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J. Chem. Thermodynamics 46 (2012) 62–71

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Application of gas hydrate formation in separation processes: A review
of experimental studies
Ali Eslamimanesh a, Amir H. Mohammadi a,b,⇑, Dominique Richon a, Paramespri Naidoo b,
Deresh Ramjugernath b,⇑
a
b

MINES ParisTech, CEP/TEP – Centre Énergétique et Procédés, 35 Rue Saint Honoré, 77305 Fontainebleau, France
Thermodynamics Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4041, South Africa

a r t i c l e

i n f o

Article history:
Available online 14 October 2011
Keywords:
Gas hydrate
Review
Separation
Greenhouse gases
Carbon dioxide
Positive application
Flue gas

a b s t r a c t
There has been a dramatic increase in gas hydrate research over the last decade. Interestingly, the
research has not focussed on only the inhibition of gas hydrate formation, which is of particular relevance
to the petroleum industry, but has evolved into investigations on the promotion of hydrate formation as a
potential novel separation technology. Gas hydrate formation as a separation technology shows tremendous potential, both from a physical feasibility (in terms of effecting difficult separations) as well as an
envisaged lower energy utilization criterion. It is therefore a technology that should be considered as a
future sustainable technology and will find wide application, possibly replacing a number of current commercial separation processes. In this article, we focus on presenting a brief description of the positive
applications of clathrate hydrates and a comprehensive survey of experimental studies performed on
separation processes using gas hydrate formation technology. Although many investigations have been
undertaken on the positive application of gas hydrates to date, there is a need to perform more theoretical, experimental, and economic studies to clarify various aspects of separation processes using clathrate/semi-clathrate hydrate formation phenomena, and to conclusively prove its sustainability.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
Gas hydrates (clathrate hydrates) are crystalline solid structures
consisting of water and small molecules such as CO2, N2, CH4, H2,
etc. which are formed under conditions of low temperature and
specified (generally high) pressure [1–3]. A clathrate is a structure
composed of a molecule or molecules of one or several components
(guest molecules) which are enclosed within a cage built from molecules of another component (host molecules) [1–3].
The discovery of hydrate structures is attributed to Sir Humphry
Davy who first reported the formation of chlorine hydrates in the
early 19th century [1,2]. He observed that the ice-like solid formed
at temperatures above the freezing point of water and that it was
composed of more than just water. Michael Faraday also undertook
hydrate investigations [1,2] and in 1823 he measured and reported
the composition of chlorine hydrates; the first quantitative study.
Early efforts in the 19th century concentrated mainly on searching
⇑ Corresponding authors at: Thermodynamics Research Unit, School of Chemical
Engineering, University of KwaZulu-Natal, Howard College Campus, King George V

Avenue, Durban 4041, South Africa. Tel.: +27 312603128; fax: +27 312601118
(D. Ramjugernath), tel.: +33 1 64 69 49 70; fax: +33 1 64 69 49 68 (A.H.
Mohammadi).
E-mail addresses: (A.H. Moham
madi), (D. Ramjugernath).
0021-9614/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2011.10.006

for different kinds of hydrate formers and the conditions for
hydrate formation. Although during 19th century researchers measured the hydrate formation conditions for a wide range of substances, it was not until the 20th century that the industrial
significance of hydrates was demonstrated [1,2].
The first hydrates of hydrocarbons were discovered by Villard
and de Forcrand who undertook studies in the late 19th and early
20th century, respectively [1,2]. Villard reported the existence of
methane, ethane, and propane hydrates and Forcrand measured
the equilibrium temperature of 15 different substances including
natural gas species at atmospheric pressure. These primary studies
in the field of hydrates were mainly concerned with the estimation
of the number of water molecules per guest molecule in a hydrate
crystalline structure (hydration number) e.g. Villard reported a hydrate structure that contained six water molecules per guest molecule. It was later proposed by Schroeder that the early work with
regard to the hydrate structure was limited to only 15 substances.
It is now obvious that clathrate hydrates are non-stoichiometric
compounds and different from ice which has a hexagonal structure. In earlier studies, the difference between ice and hydrate
was determined by using the different effects the two structures
have on polarized light [1,2]. The majority of gas hydrates are
known to form three typical hydrate crystal structures, viz.
structure I (sI), structure II (sII), and structure H (sH) [1–3]. The


A. Eslamimanesh et al. / J. Chem. Thermodynamics 46 (2012) 62–71

type of crystal structure generally depends on the size of the guest
molecule(s) [1–3]. Detailed descriptions about different hydrate
structures, and their physico-chemical properties have been
well-established [1,2].
The first industrial and theoretical research activities on gas hydrates, which were initiated in the early 20th century, are attributed to the requirement from the petroleum industry for a better
understanding of the effects of water in the operation of gas pipelines, and petroleum and gas processing. Water is often associated
with natural gas in reservoirs and therefore extracted natural gas is
always saturated with water. As the temperature and pressure
change during the production of the gas, water can condense from
the gas stream. Water is also often used in processes to sweeten
natural gas (i.e. to remove hydrogen sulfide and carbon dioxide,
the so-called ‘‘acid gases’’) in the form of aqueous solutions [1,2].
The sweet gas (i.e. the product of the sweetening process) from
these processes is saturated with water. This association of water
and natural gas means that hydrates may be encountered in all aspects of the production and processing of natural gas. Consequently, engineers working in the natural gas industry need to
know whether hydrates would occur and as a result cause problems in their applications [1,2]. In the 1930s, Hammerschmidt [4]
found that natural gas hydrates might result in blockage of gas
transmission lines. The formation of hydrates leads to a reduction
in the pipelines’ cross sectional area and consequently increases
the pressure drop in the processing of natural gases leading to
higher production, processing, and transportation costs and the
corresponding lower flow rates. Inhibition of gas hydrate formation in pipelines has therefore attracted the attention of engineers
in the field over the past century [1–6]. The phenomena may occur
in pipelines well below sea level where the pressure is high, or in
cold areas where the temperature is suitably low for its formation.
Gas hydrate formation has also been reported to occur in drilling
muds [7–9], oil reservoirs [10–14], from water content of natural
gas [14–26], inside the earth’s crust [27–30], and outside the
earth’s atmosphere (Mars and Saturn) [31,32]. Wherever gas hydrate tends to be formed, significant care should be taken to prevent/solve/use the harmful or useful features of these chemical

structures. Engineers encountering problems with gas hydrates
generally have to employ one of the following methods to overcome the issue of pipeline blockages: mechanical removal of the
clathrates; warming up the pipelines; prediction of the dissociation conditions via thermodynamic/kinetic models; and modifying
the dew point of water in dehydration units.
Gas hydrate formation, even though it is something that has negative connotations in the petroleum and gas processing industry,
also has the potential for numerous positive applications, e.g. the
use of clathrate hydrates as means of gas storage. Many positive
applications of clathrate hydrates such as in carbon dioxide capture
and sequestration, gas storage, air-conditioning systems in the form
of hydrate slurry, water desalination/treatment technology, concentration of dilute aqueous solutions, separation of different gases
from flue gas streams, and many other examples have been reported,
especially in recent years [1,2,33–35]. In this review article, a brief
study of the various positive applications of gas hydrates is presented, focusing on a comprehensive review of studies undertaken
to date with regard to the application of clathrate/semi-clathrate hydrate formation as a novel approach for separation processes.

63

energy needed by the world economy. The estimated amount of
methane in situ gas reserves is approximately 1016 m3 [36,37]. Furthermore, there are estimations showing that there are more organic carbon reserves present globally as methane hydrates than
all other forms of fossil fuels [38]. It is currently believed that if
only about 1% of the estimated reserves of methane from methane
hydrate reserves are recovered, it may be enough for the United
States to satisfy its energy demands for the next eight decades [39].
There are generally three methods of methane production form
these hydrate reserves:
1. Pressure reduction in the reservoirs to conditions below the gas
hydrate equilibrium pressure;
2. Increasing the temperature of the reservoir by heating up to a
temperature above that needed for equilibrium (or hydrate dissociation temperature);
3. Addition of alternate gases or inhibitors such as CO2 or methanol

which would replace methane within the hydrate structures or
change the stability conditions of the corresponding hydrates [40].
Although methane/natural gas has not yet been produced from
gas hydrate reserves on a commercial scale and also interestingly it
has not been included in the EPPA model in MITEI’s Future of Natural Gas report, it is still considered as a promising approach which
should begin to be exploited within the next 15 years, mainly due
to the fact that conventional natural gas reservoirs are being depleted very rapidly [41]. Detailed experimental and theoretical
studies (e.g. thermodynamic and kinetic models, effects of the
physical parameters on the gas hydrate reservoirs, exploitation of
the reserves, methods of gas recovery, economical study of the process of extraction of methane/natural gas from gas hydrate reserves) have been well-established in the literature [38–86].
2.2. Gas storage
Several studies show that the gas hydrate structures have considerable potential as storage media for various gases. For instance, they can
be used for natural gas/hydrogen storage and transportation, as cool
storage media in air conditioning systems, etc. [87–168]. Storage and
transportation in the form of gas hydrates have the advantage of safety
for the corresponding processes, as well as much lower process volumes
in comparison with conventional storage methods like liquefaction. Detailed economical studies show that the capital cost for natural gas transportation in the form of gas hydrates is lower than that for the liquefied
natural gas (LNG) technique, mainly because of lower investment in
infrastructure and equipment [101]. However, LNG-type gas transportation is currently preferred for distant markets or transportation of natural gases produced from huge gas fields because of expensive capital
investment [101]. There is evidence, on the other hand (e.g. Mitsui Shipbuilding & Engineering Company Pilot Plant, Hiroshima, Japan) showing
that gas hydrates are economically more cost effective for storage and
transportation of standard gas (gas streams of small quantity, especially
those far from the pipeline) compared to the LNG method [102–
105,110]. A comprehensive review on application of gas hydrates for
hydrogen storage has been published by Strobel and coworkers [157].
In addition, use of this technique for cool storage in air conditioning
processes has been well-discussed by Chatti et al. [32].
3. Application of clathrate/semi-clathrate hydrates in
separation processes

2. Some positive uses of gas hydrates
3.1. Separation of greenhouse gases
2.1. Gas supply
Natural reserves of gas hydrates in the earth can be used as a
gas/natural gas supply by providing the increasing amounts of

The ever-growing energy needs of human beings which resulted from rapid industrialization and population growth, has to
date been satisfied by using fossil fuels such as coal, oil, and natural


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gas [32,36,37,169–174]. Several comprehensive studies demonstrate that large amounts of carbon dioxide, carbon monoxide,
and hydrogen sulfide (called ‘‘greenhouse gases’’) are emitted
every year into the atmosphere [32,36,37,169–174] due to combustion of fossil fuels and fossil-based fuels. Over the last few decades there has been growing concern as to the effects of the
increased concentration of these gases in the earth’s atmosphere
and their contribution to global warming. Due to the potential
for harmful environmental effects, including climate change, there
has been public and political pressure to reduce the amount of
‘‘greenhouse’’ gas emitted. Therefore, separation of these gases
from their corresponding gas mixtures, generally found in flue
gas streams of most industrial processes, has generated great interest and a number of research studies recently.
3.1.1. Separation of CO2
The capture of CO2 and sequestration (CCS) has become an
important area of research to mitigate CO2 emissions worldwide.
Approximately 64% of the greenhouse gas effects in the atmosphere are related to carbon dioxide emissions [33,34,36,37,170–
174]. As CO2 separation is the most expensive step of the CCS
[33,34,175–180] process, the challenge is to evaluate and develop

energy efficient and environmental friendly technologies to capture the CO2 produced in large scale power-plants, where flue
gas typically contains mostly CO2 and N2 [33,34].
One novel approach to separate carbon dioxide from combustion flue gas is through gas hydrate crystallization techniques
[33,34,173–202]. Due to the difference in affinity between CO2
and other gases in the hydrate cages when hydrate crystals are
formed from a binary mixture of these gases, the hydrate phase
is enriched in CO2 while the concentration of other gases is increased in the gas phase. The hydrate phase can be later dissociated by depressurization and/or heating and consequently CO2
can be recovered [33,34,173]. Detailed experimental results indicate that CO2 selectivity in the hydrate phase would be at least four
times higher than that in the gas phase [177]. For efficient design of
such processes, reliable phase equilibrium data are required.
Table 1 reports most of the corresponding experimental studies
undertaken to date on gas hydrates for the (CO2 + other gas/gases + water) systems in the absence of hydrate promoters.
Gas hydrate promoters are typically used as chemical additives
in hydrate formation processes. The promoter generally reduces
the required hydrate formation pressure and increases the formation rate and/or temperature, as well as modifies the selectivity of
hydrate cages to absorb various gas molecules. Current gas hydrate
formation promoters can be categorized into two groups:
1. Chemical additives that have no effect on the structures of the water
cages e.g. tetrahydrofuran (THF), anionic/non-ionic surfactants,
cyclopentane, acetone etc. [152–157,165,168,203–209], and
2. Additives that change the structures of the ordinary water cages
in the traditional clathrates structures such as tetra-n-butylammonium salts and [(n-C4H9)4NBH4] [35,159,209–238].
The material THF from the first, and TBAB (tetra-n-butylammonium bromide) from the second category are well known thermodynamic promoters that have been employed recently [33]. As a matter
of fact, the second group of promoters consists mainly of environmentally friendly tetra-n-butylammonium ionic liquids (they are
not liquid at room temperature) and form semi-clathrate hydrates,
in which a part of the cage structure is broken in order to trap the
large tetra-n-butyl ammonium molecule [33]. This characteristic
of the semi-clathrate hydrates may lead to the structure having
more gas storage capacity than that produced from promoters such
as THF. Although promoters like THF can significantly decrease the

hydrate formation pressure, they are volatile and this may lead to

non-negligible amounts of loss of these promoters during the corresponding storage/separation/transportation processes [33]. Experimental studies performed to date on the separation of CO2 from
different gas mixtures via clathrate/semi-clathrate hydrates in the
presence of promoters are reported in table 2.
Assuming that there are no losses of gas hydrate promoters (such
as TBAB) and water (if water is re-circulated in the corresponding
process); an 80% efficiency for pumps, compressors, and expanders;
a typical economic study shows the energy cost of CO2 capture using
gas hydrates would be approximately 30 € per tonne of CO2 [177].
The cost is comparable to conventional CO2 capture methods such
as application of membranes, amine absorption, etc. Further simulation results suggest that other costs associated with carbon dioxide
separation processes using gas hydrate crystallization, such as
equipment, total capital investment, maintenance and depreciation,
would lead to estimated capture cost of approximately 40.8 € per
tonne of CO2 from a conventional blast furnace (CBF) flue gas
[177]. Two points should however be kept in mind regarding the
costing of hydrate separation processes: firstly, there is the possibility for designing more efficient and economical separation processes
through suitable utilization of the energy available in the fluid
streams of the processes (i.e. pinch technology can be applied to
re-design the aforementioned processes); and secondly, economic
simulation results show that gas separation by hydrate formation
techniques may be more competitive in applications where there
are high pressure feed gas streams to the separation process, such
as the oil and gas industry. Hydrates separation is however still considered as a long-term capturing technology [236].
3.1.2. Separation of methane
Methane (CH4) is a greenhouse gas with a greenhouse effect 21
times greater than that of CO2 and it contributes to 18% of the global
greenhouse effects [208,243]. This component is the major constituent of natural gas streams and natural gas reserves in the form of
hydrates in the earth, as well as emissions in the form of cold bed

methane (CBM) discharging from coal seams [1,2,33,207,244]. Consequently, separation of methane from emitted industrial gas
streams has attracted significant attention in the last few decades.
Recently, novel separation processes using gas hydrate formation
phenomena have been proposed in the literature. Table 3 lists corresponding experimental studies undertaken and available in open literature. Economic studies for such processes would focus mainly on
the price of the promoters needed to reduce the pressure and increase the temperature of the separation steps because the design
of other required equipment is generally simple. It seems that the
industry will be interested in such investments whenever the environmental regulations are rigid and when the natural gas reserves
tend to reach their half-lives.
3.1.3. Separation of other greenhouse gases
Beside carbon dioxide and methane, gas hydrate separation
processes have been investigated for other greenhouse gases such
as hydrogen sulfide (H2S), sulfur hexafluoride (SF6), and 1,1,1,2tetrafluoroethane (R-134a). Separation of hydrogen sulfide from
gas streams is an imperative task for the petroleum industry because high hydrogen sulfide concentration in gas streams increases
the possibility of solid sulfur precipitation during the production of
sour natural gases in the formation, in well bores, and in production facilities especially at high temperatures and pressures
[250]. Sulfur hexafluoride SF6-containing gases are widely used
in industry because SF6 has good electrical insulating properties
[251]. Its mixtures with N2 are used as an insulating filler gas for
underground cables, a protective, and an etching agent in the semiconductor industry [251]. Because it has a very long lifetime in the
atmosphere (3200 years) and significant global warming potential,
separation of this component is of great interest. Utilization of gas


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65

TABLE 1
Experimental studies for gas hydrates of carbon dioxide + gas/gas mixture systems in the presence of pure liquid water.
Author(s)

Gas system

Study

Ohgaki et al. [190]

(CO2 + CH4)

PVT studies on dissociation conditions + compositions of vapor and hydrate phases

Seo and Kang [184]

(CO2 + CH4)

PVT studies on dissociation conditions + composition of vapor and hydrate phases

Bruusgaard et al. [192]

(CO2 + CH4)

PVT studies on dissociation conditions + composition of vapor phase in equilibrium with hydrate phase

Belandria et al. [239]

(CO2 + CH4)

PVT studies on dissociation conditions of gas hydrates

Belandria et al. [240]

(CO2 + CH4)

PVT studies on dissociation conditions + compositions of vapor, liquid, and hydrate phases through
measurements by a new designed apparatus and a mass balance approach

Unruh and Katz [186]

(CO2 + CH4)

PVT studies on dissociation conditions of gas hydrates

Adisasmito et al. [187]

(CO2 + CH4)

PVT studies on dissociation conditions of gas hydrates

Hachikubo et al. [189]

(CO2 + CH4)

PVT studies on dissociation conditions of gas hydrates

Seo et al. [183]

(CO2 + CH4)

PVT studies on dissociation conditions of gas hydrates

Uchida et al. [119]

(CO2 + CH4)

Kinetic study: investigation of the change of vapor-phase composition and cage occupancies using gas
chromatography and Raman spectroscopy

Seo et al. [183]

(CO2 + N2)

PVT studies on dissociation conditions + compositions of vapor and hydrate phases

Kang et al. [193]

(CO2 + N2)

PVT studies on dissociation conditions + compositions of vapor and hydrate phases

Seo and Lee [194]

(CO2 + N2)

PVT studies on dissociation conditions + compositions of vapor and hydrate phases

Bruusgaard et al. [195]

(CO2 + N2)

PVT studies on dissociation conditions + compositions of vapor in equilibrium with gas hydrate

Park et al. [182]

(CO2 + N2)

PVT studies in an equilibrium cell for measurements of gas hydrate phase equilibria and NMR spectroscopy for
measurements of the cage occupancies of CO2 and consequently the molar compositions of hydrate phase

Belandria et al. [34]

(CO2 + N2)

PVT studies on dissociation conditions + compositions of vapor, liquid, and hydrate phases through
measurements by a new designed apparatus and a mass balance approach

Sugahara et al. [196]

(CO2 + H2)

Raman spectroscopy using quartz windows on cage occupancy by hydrogen molecules and direct gas release method

Kumar et al. [180]

(CO2 + H2)

Powder X-ray diffraction on cage occupancy by hydrogen molecules, gas chromatography of released gas
from hydrate, 13C NMR, Raman spectroscopy

Seo and Kang [184]

(CO2 + H2)

13

Kim and Lee [198]

(CO2 + H2)

1H MAS NMR on cage occupancy by hydrogen molecules, gas chromatography of released gas from hydrate
on cage occupancy by hydrogen molecules

Rice [199]

(CO2 + H2)

Designing a process in which methane is burnt to produce energy and H2 and CO2. Later, CO2 can be
separated from a flue containing H2 using gas hydrate formation process

Belandria et al. [255]

(CO2 + H2)

PVT studies on dissociation conditions + compositions of vapor phase through measurements by a new
designed apparatus

Zhang et al. [200]

(CO2 + H2 + cyclopentane)

The (hydrate + liquid water + liquid hydrocarbon + vapor) equilibria of a pre-combustion gas sample have

been measured using a high pressure DSC technique. Cyclopentane has been added to the system as a more
beneficial promoter than THF

Surovtseva et al. [201]

(CO2 + H2 + N2 + CH4 + Ar)

Combination of a gas hydrate formation process with a low temperature cryogenic one for capturing CO2
from a coal gas stream. The operational conditions and the amount of captured CO2 have been reported

Tajima et al. [202]

(CO2 + N2 + O2 + H2O
(vapor))

Design of a process for separation of CO2 from a flue gas sample using a hydrate forming reactor. The kinetic
and energy consumption parameters of the process have been also measured and calculated

Lee et al. [241]

(CO2 + NOx + SOx)

A separation process has been presented to separate CO2 from flue gas. Thermodynamic and kinetic studies
have been performed on the hydrate formation process

C NMR on cage occupancy by hydrogen molecules in hydrate formed in silica gel particles

hydrates for the separation of refrigerant gases, which have extreme greenhouse effects, has also been recently studied in literature. Table 4 reports experimental studies available in the open
literature on separation of the aforementioned gases from their
corresponding mixtures via gas hydrate formation processes.

Careful attention should be paid to materials of construction and
health and safety issues in the design of process equipment for separation of these gases, especially H2S and SF6, because they are toxic
and corrosive. Therefore, the main factor in an economic study
would be focused on these issues. From studies performed to date,
it seems that these types of separations, through gas hydrate formation, would only be considered as economical alternative approach
by industry by the end of this decade [39,170–174,177,208,243].

be designed to replace the current pressure swing adsorption (PSA)
method, for capture of CO2 and H2 separation simultaneously from
the generated gas stream after the steam reforming operation
[33,240,255]. Very high pressures (100 to 360 MPa) [197,240,255]
are required to stabilize the sII H2 clathrate hydrate though CO2 is enclathrated in hydrate cages at moderate pressure conditions [1,2,33,197,
240,255]. The difference between hydrate formation pressures of these
two substances is the main reason for considering the potential of gas
hydrate technology for the aforementioned process [197–199]. However, the capacity of the clathrate hydrate cages to absorb hydrogen
must be determined, or at least estimated, before starting industrial design of the related processes. Phase equilibrium studies undertaken to
date on the separation of hydrogen from different gas mixtures
through gas hydrate crystallization processes are reported in table 5.

3.2. Hydrogen separation
3.3. Nitrogen separation
Hydrogen is considered as a clean and novel energy resource. Consequently, separation, storage, and transportation of this component
are among the latest industrial technology developments. For instance,
applying gas hydrate formation processes, a double-effect process can

Since N2 is one of the major components of flue gas emitted from
power-plants [33,34,183], efficient processes should be proposed
for its separation from the accompanied gases. Gas hydrate forma-

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TABLE 2
Experimental studies on clathrate/semi-clathrate hydrate for the carbon dioxide + gas/gases systems in the presence of hydrate promoters.
Authors

System

Study

Beltrán and Servio [191]

(CO2 + CH4 + water/neohexane emulsion)

PVT studies on dissociation conditions + composition of vapor phase in equilibrium with
hydrate phase

Linga et al. [185]

(CO2 + N2 + THF aqueous solution)

PVT and kinetic studies on CO2 capture from its mixture with N2 via clathrate hydrate
structures. Induction times, hydrate formation rates, CO2 uptake amount accompanied
with molar compositions of hydrate and vapor phases have also been measured

Fan et al. [188]

(CO2 + CH4 + water/aqueous sodium

chloride solution)

PVT studies on dissociation conditions of gas hydrates
PVT studies on dissociation conditions of gas hydrates

Lu et al. [206]

(CO2 + N2 + TBAB/THF aqueous solutions)

Mohammadi et al. [303]

(CO2 + N2 + TBAB aqueous solution)

PVT studies on dissociation conditions of gas hydrates

Deschamps and
Dalmazzone [220]

(CO2 + N2 + TBAB aqueous solution and
CO2 + CH4 +
TBAB aqueous solution)

Measurements of enthalpy of dissociations via differential scanning calorimetry (DSC)
under pressure

Fan et al. [230]

(CO2 + H2 + TBAB aqueous solution and
CO2 + H2 +
THF aqueous solution)

Measurements of semi-clathrate hydrate formation conditions and the effects of different
additives through using equilibrium cell

Li et al. [224]

(CO2 + N2 + TBAB aqueous solution in the
presence
of dodecyl trimethyl ammonium chloride
(DTAC))

Measurement of induction time, pressure drop, split fraction via a crystallizer cell

Ma et al. [234]

(H2 + CH4, H2 + N2 + CH4, CH4 + C2H4,
CH4 + C2H4 in
the presence of water and aqueous
solution of THF)

Measurements of gas and liquid phases compositions in equilibrium with gas hydrates
through an equilibrium cell

Fan et al. [230]

(CO2 + N2 + TBAB/TBAF aqueous solution)

PVT studies on measurement of induction time, dissociation conditions, space velocity,
and vapor and hydrate compositions using a two- stage hybrid hydrate membrane
separation process

Meysel et al. [302]

(CO2 + N2 + TBAB aqueous solution)

PVT studies on equilibrium conditions of semi-clathrate hydrate in a jacketed isochoric
cell reactor

Li et al. [225]

(CO2 + H2 + TBAB aqueous solution)

Measurement of dissociation condition, gas consumption, induction time of semiclathrate gas hydrates of a flue gas containing CO2 + H2 in a hydrate crystallizer. The effect
of water memory has been also studied

Kim et al. [235]

(CO2 + H2 + TBAB aqueous solution)

PVT and kinetic studies on hydrate formation conditions, gas consumption, induction
time of semi-clathrate gas hydrates of a flue gas containing CO2+H2 in a hydrate formation
reactor. Enclathration of the semi-clathrate hydrate with the CO2 molecules have been
also observed using Raman Spectroscopy

Li et al. [236]

(CO2 + H2 + TBAB aqueous solution/
cyclopentane)

Measurements of CO2 separation efficiency, gas consumption, and induction time for a

CO2 capture process from a flue gas of CO2 + H2 in a hydrate crystallizer

Kamata et al. [237]

(CO2 + H2S + TBAB aqueous solution)

Constructing a high pressure equilibrium cell for separation of mixtures of different gases
through semi-clathrate hydrate formation processes

Li et al. [242]

(CO2 + N2 + cyclopentane/water emulsion)

The kinetics of hydrate formation in a flue gas sample containing CO2 + N2 have been studied in
a reactor along with measurements of vapor and hydrate compositions at equilibrium

tion processes have been studied as an alternative nitrogen separation process in industry. Table 6 summarizes experimental studies
undertaken in this area which are available in open literature.
3.4. Oil and gas separation
Due to the fact that the composition of a hydrate-forming mixture is
different from the composition of the hydrate phase, gas hydrate formation can be applied as an alternative approach to conventional
gas-liquid separation (fractionation) technique [37,259]. A lowtemperature extraction (LTX) process designed by Dorsett [260] and
separation of oil and gas in a hydrate rig by Østergaard et al. [259] using
the gas hydrate crystallization method, in which the kinetic parameters of the proposed process have been reported, may be the only
two proposed processes for this purpose to date.
3.5. Desalination process
Water desalination/treatment technology using clathrate hydrates with different hydrate formers e.g. refrigerants [261–263]
can perform well when compared with traditional desalination
processes [261–265]. The technique is of particular interest be-

cause only water and an appropriate refrigerant can form clathrate hydrates at ambient temperature and atmospheric pressure.
The clathrate hydrate can then be dissociated and pure water
phase can be produced while the released refrigerant may be
recycled in the hydrate formation unit. From the 1940s to date,
numerous studies have been undertaken to design desalination
processes efficiently and economically via formation of gas hydrates [266–282]. For instance, a detailed economical study
[263] including total capital investment, operational and maintenance costs, and depreciation (amortized) costs demonstrates
that the total cost of potable water production through the propane hydrate formation method is between 2.8 and 4.2 US$ per
ton of fresh water depending on the yield (number of moles of
the potable water produced by the process per mole of seawater
fed to the process) and temperature of the seawater. These results
indicate that formation of the gas hydrates in the absence of any
hydrate promoters may not be an economical method for a desalination process compared with traditional methods [261–265].
Though, it is obvious that an appropriate hydrate promoter can
significantly reduce the energy cost of the process and finally lead
to a lower fresh water production cost.


A. Eslamimanesh et al. / J. Chem. Thermodynamics 46 (2012) 62–71

67

TABLE 3
Experimental studies on clathrate/semi-clathrate hydrates for the methane + gas/gas mixture systems in the presence/absence of hydrate promoters.
Author(s)

System

Study

Zhao et al. [208]

(CH4 + oxygen-containing coal bed gas + THF
aqueous solution)

Separation of CH4 using a reactor in different concentration of feed gas and
pressures

Lu et al. [206]

(CH4 + N2 + TBAB/THF aqueous solutions)

PVT studies on dissociation conditions

Zhang and Wu [205]

(CH4 + N2 + O2 + THF aqueous solution)

Separation of methane from a coal mine methane using a high pressure
reactor

Kondo et al. [245]

(CH4 + C2H6 + C3H8 + pure water)

Measurements of dissociation conditions the composition of vapor phases
in equilibrium with gas hydrate in a high pressure cell

Ng [246]

(CH4 + C3H8, CH4 + C2H6 + C3H8,
CH4 + C3H8 + C4H10 + CO2,
CH4 + C2H6 + C3H8 + C4H10 + CO2,
CH4 + C2H6 + C3H8 + C4H10 + CO2 in the presence of
water)

Measurements of compositions of hydrate phase by gas chromatography in
an equilibrium variable volume cell

Sun et al. [203]

(CH4 + C2H6 + THF aqueous solution)

Measurements of hydrate formation conditions of a sample consisting of
CH4 and C2H6 for observing the appropriate conditions of a separation
process of CH4. The structures of the formed hydrates have been also
investigated using Raman spectroscopy

Ma et al. [247]

(CH4 + C2H6 + THF aqueous solution,
CH4 + C2H4 + THF aqueous solution)

PVT study on hydrate formation conditions and molar compositions of
vapor and hydrate phases for separation of methane form its mixture with
ethane and ethylene in a high pressure equilibrium cell

Lee et al. [248]

(CH4 + N2 + water)

PVT studies and 13C solid-state NMR spectroscopy along with powder XRD
measurement have been performed for investigation of the equilibrium
conditions and phase transitions of clathrate hydrates of mixture of
CH4 + N2

Sun et al. [249]

(CH4 + N2 + TBAB/(TBAB + SDS(sodium dodecyl
sulfate)) aqueous solutions)

Measurement of phase equilibrium conditions of semi-clathrate hydrates of
mixtures of methane + nitrogen + TBAB aqueous solution in a hydrate
forming reactor. Gas storage capacity and recovery factor of CH4 have also
been reported

Kamata et al. [237]

(CH4 + C2H6 + TBAB aqueous solution,
CH4 + H2 + TBAB aqueous solution, CH4 + N2)

High pressure equilibrium studies for separation of methane from its
mixtures with different gases

TABLE 4
Experimental studies on clathrate/semi-clathrate hydrates for mixtures of greenhouse gases with other gases in the presence/absence of hydrate promoters.
Authors

System

Study

Shiojiri et al. [252]

(HFC-134a (R-134a) + N2 + water)

Measurements of hydrate formation conditions and vapor and hydrate
molar compositions in a porous media for separation of R-134a greenhouse
gas

Tajima et al. [202]

(HFC-134a (R-134a) + air + water,
SF6 + N2 + water)

Design of a process for separation of R-134a refrigerant from air, and SF6
from N2 using a hydrate forming reactor. The kinetic and energy
consumption parameters of the process have been also measured and
calculated

Tajima et al. [253]

(R-134a + N2 + water)

Study on the effects of concentration of feed gas on kinetic parameters of
HFC hydrate formation and its separation from its mixture with N2 in a
hydrate forming reactor

Vorotyntsev et al. [181]

(SF6 + SO2 + water, SF6 + CCl2F2 + water)

Dong et al. [254]

(CH4 + NH3 + water/THF aqueous solution)

Separation of SF6 greenhouse gas from its corresponding mixtures in a
batch isobaric gas hydrate crystallization process. The separation factors of
the compounds have been reported along with relevant kinetic study.
Measurements of equilibrium conditions, vapor phase compositions in
equilibrium with gas hydrates in a hydrate forming reactor for separation of
ammonia form methane (synthesis vent gas)

Cha et al. [251]

(SF6 + N2 + water)

Hydrate dissociation conditions of mixture of SF6 + N2 in the presence of
pure water and Raman Spectroscopy of cage occupancies by the
corresponding hydrate formers in a high pressure equilibrium cell

Kamata et al. [238]

(CH4 + H2S + TBAB aqueous solution,
CO2 + H2S + TBAB aqueous solution,
CH4 + CO2 + H2S + TBAB aqueous solution)

A high pressure cell has been designed and constructed to separate H2S
from a flue gas via gas hydrate formation process. The effects of different
operational parameters on recovery of H2S have been reported

3.6. Biotechnology
The possible formation of clathrate hydrates in animal/plant tissues and gas hydrate formation in protein containing micellar solutions, as well as applications in controlling enzymes in biological

systems, recovery of proteins, application in drug delivery systems,
etc. are just some examples of importance of gas hydrate formation
in the bioengineering/biotechnology field [283–295]. This area is
relatively new and has the potential for tremendous growth in
terms of the study of applications.


68

A. Eslamimanesh et al. / J. Chem. Thermodynamics 46 (2012) 62–71

TABLE 5
Experimental studies on clathrate/semi-clathrate hydrates for the hydrogen + gas/gas mixture systems in the presence/absence of hydrate promoters.
Authors

System

Study

Wang et al. [256]

(H2 + CH4 + diesel oil + THF aqueous
solution + anti-agglomeration system)

Measurements of gas-hydrate phase equilibria in a variable-volume cell for
observing the conditions of separation of H2 from a flue sample. A

surfactant has been added to the system to disperse hydrate particles into
the condensate phase

Lee et al. [257]

(H2 + CH4 + water)

Hydrate formation conditions for a mixture of pre-combustion flue gas
containing H2 + CH4 have been investigated in a semi-batch stirred vessel

Sun et al. [244]

(H2 + CH4 + water/THF aqueous solution)

A one-stage hydrogen separation unit has been constructed based on
hydrate formation process. In addition, the separation efficiency of the
proposed process has been reported

TABLE 6
Experimental studies on clathrate hydrates for the nitrogen + gas/gas mixtures.
Author

System

Study

Johnson et al. [258]

(N2 + industrial gas mixtures + water)

Designing a new economical and efficient process for separation of N2 from gas mixtures in a
constructed multi-stage reactor to form gas hydrates

Happel et al. [243]

(N2 + CH4 + water)

A novel apparatus for separation of N2 from its mixture with CH4 using a hydrate forming
reactor has been constructed, in which the vapor and hydrate molar compositions and kinetic
parameters like the rate of hydrate formation can be measured

3.7. Food engineering
The concentration of dilute aqueous solutions using clathrate
hydrate formation is, similar to but, more economically feasible
than freeze concentration because clathrate hydrates can be
formed at temperatures above the normal freezing point of water
[37,296]. The characteristics of refrigerant hydrates in a variety
of aqueous solutions containing carbohydrates, proteins, or lipids
and the concentration of apple, orange, and tomato juices via hydrate formation have already been reported [297,298].
3.8. Separation of ionic liquids
Ionic liquids are organic salts which are generally liquid at room
temperatures [299]. They are normally composed of a large organic
cation and organic or inorganic anions [299]. The applications of ionic liquids have generated numerous discussions and studies in the
past decade. This is mainly due to their physico-chemical properties
which are able to be adjusted through combination of cations and
anions. This phenomenon can be utilized to design particular solvents for application in the development of efficient processes and
products [299]. Non-flammability, high thermal stability, a wide liquid range, and their electric conductivity are all physical properties
[299] which make ionic liquids very attractive in terms of application as separating solvents and catalysts. In the synthesis of ionic liquids, one of the key steps is the purification of the ionic liquid. Ionic
liquids are also expensive to synthesize and therefore recovery of
the ionic liquid via regeneration is essential. Therefore, recovery of

these solvents from aqueous solutions will certainly be beneficial
for the future potential of these solvents in the separation industry
[299,300]. Recently, a novel separation technique has been proposed
regarding the separation of ionic liquids from dilute aqueous solutions using clathrate hydrates of carbon dioxide [301]. The fundamental concept of this method is based on the phenomenon of
hydrophobic hydration taking place when a gas dissolves in water
and results in formation of both structured water and gas hydrates
under suitable operational conditions [301].

separation of hydrogen and nitrogen; oil and gas fractionation; desalination processes; separation of different substances from living
organisms; and separation of ionic liquids from their dilute aqueous
solutions. The studies preformed to date show a diverse field of research in chemistry, physics, earth and environmental sciences, bioengineering, and pharmaceutical processes to name a few. It is
evident that gas hydrate formation technology will play a significant
role in the future in separation processes and has the potential to be,
perhaps, a more sustainable technique than current comparable
commercial technologies for separation.
It should be noted that one of the significant factors in decision
making for alternative technologies is the economical aspect. The
novel proposed techniques or methods which are meant to replace
the traditional processes should be economically feasible. However, there are very few detailed economic studies on separation
processes using gas hydrate formation technology available in
the open literature. Hence, it is imperative that more studies of this
nature are undertaken in near future to truly ascertain the sustainability of gas hydrate technology.
To recapitulate, this review demonstrates the importance of
experimental measurements (phase behavior, induction times, formation rates, etc.) on separation processes utilizing gas hydrate crystallization. It should be noted that these experimental studies
should be accompanied by theoretical investigations (thermodynamic/kinetic modeling, molecular simulation, etc.) and economical
studies (production cost, capital investment etc.) in order to clarify
different novel aspects and applications of gas clathrate/semi-clathrate hydrates in separation technologies and consequently persuade
the industry to invest in this in the future.

Acknowledgements

Ali Eslamimanesh is grateful to Mines ParisTech for providing
him a Ph.D. scholarship. This work was financially supported by
the Agence Nationale de la Recherche (ANR) as part of the SECOHYA project. The financial support of Orientation Stratégique des
Ecoles des Mines (OSEM) is also acknowledged.

4. Conclusion
In this communication, we have focussed on reviewing the application of clathrate/semi-clathrate hydrates for separation processes,
including experimental studies on separation of greenhouse gases;

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JCT-11-401