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J Chem Thermodynamics 46 (2012) 6271 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 ẫnergộtique et Procộdộs, 35 Rue Saint Honorộ, 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 difcult 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 nd 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 ể 2011 Elsevier Ltd All rights reserved 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 specied (generally high) pressure [13] 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) [13] The discovery of hydrate structures is attributed to Sir Humphry Davy who rst 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 rst 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 64 69 49 70; fax: +33 64 69 49 68 (A.H Mohammadi) E-mail addresses: amir-hossein.mohammadi@mines-paristech.fr (A.H Moham madi), ramjuger@ukzn.ac.za (D Ramjugernath) 0021-9614/$ - see front matter ể 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 signicance of hydrates was demonstrated [1,2] The rst 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 eld 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) [13] The A Eslamimanesh et al / J Chem Thermodynamics 46 (2012) 6271 type of crystal structure generally depends on the size of the guest molecule(s) [13] Detailed descriptions about different hydrate structures, and their physico-chemical properties have been well-established [1,2] The rst 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 sulde 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 ow rates Inhibition of gas hydrate formation in pipelines has therefore attracted the attention of engineers in the eld over the past century [16] 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 [79], oil reservoirs [1014], from water content of natural gas [1426], inside the earths crust [2730], and outside the earths atmosphere (Mars and Saturn) [31,32] Wherever gas hydrate tends to be formed, signicant 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 ue gas streams, and many other examples have been reported, especially in recent years [1,2,3335] 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: Pressure reduction in the reservoirs to conditions below the gas hydrate equilibrium pressure; Increasing the temperature of the reservoir by heating up to a temperature above that needed for equilibrium (or hydrate dissociation temperature); 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 MITEIs 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 [3886] 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 [87168] 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 liqueed 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 elds 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] Application of clathrate/semi-clathrate hydrates in separation processes 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 satised by using fossil fuels such as coal, oil, and natural 64 A Eslamimanesh et al / J Chem Thermodynamics 46 (2012) 6271 gas [32,36,37,169174] Several comprehensive studies demonstrate that large amounts of carbon dioxide, carbon monoxide, and hydrogen sulde (called greenhouse gases) are emitted every year into the atmosphere [32,36,37,169174] 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 earths 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 ue 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 [33,34,175180] process, the challenge is to evaluate and develop energy efcient and environmental friendly technologies to capture the CO2 produced in large scale power-plants, where ue gas typically contains mostly CO2 and N2 [33,34] One novel approach to separate carbon dioxide from combustion ue gas is through gas hydrate crystallization techniques [33,34,173202] Due to the difference in afnity 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 efcient design of such processes, reliable phase equilibrium data are required Table 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 modies the selectivity of hydrate cages to absorb various gas molecules Current gas hydrate formation promoters can be categorized into two groups: Chemical additives that have no effect on the structures of the water cages e.g tetrahydrofuran (THF), anionic/non-ionic surfactants, cyclopentane, acetone etc [152157,165,168,203209], and 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] [35,159,209238] The material THF from the rst, 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 signicantly 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 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% efciency 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) ue gas [177] Two points should however be kept in mind regarding the costing of hydrate separation processes: rstly, there is the possibility for designing more efcient and economical separation processes through suitable utilization of the energy available in the uid 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 signicant attention in the last few decades Recently, novel separation processes using gas hydrate formation phenomena have been proposed in the literature Table 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 sulde (H2S), sulfur hexauoride (SF6), and 1,1,1,2tetrauoroethane (R-134a) Separation of hydrogen sulde from gas streams is an imperative task for the petroleum industry because high hydrogen sulde 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 hexauoride 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 ller 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 signicant global warming potential, separation of this component is of great interest Utilization of gas A Eslamimanesh et al / J Chem Thermodynamics 46 (2012) 6271 65 TABLE 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 ue 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 benecial 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 ue 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 ue 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 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 [39,170174,177,208,243] 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 [197199] 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 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 ue gas emitted from power-plants [33,34,183], efcient processes should be proposed for its separation from the accompanied gases Gas hydrate forma- 66 A Eslamimanesh et al / J Chem Thermodynamics 46 (2012) 6271 TABLE Experimental studies on clathrate/semi-clathrate hydrate for the carbon dioxide + gas/gases systems in the presence of hydrate promoters Authors System Study Beltrỏn 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 ue 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 ue 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 efciency, gas consumption, and induction time for a CO2 capture process from a ue 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 ue 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 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 ỉstergaard 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 [261263] can perform well when compared with traditional desalination processes [261265] 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 efciently and economically via formation of gas hydrates [266282] 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 [261265] Though, it is obvious that an appropriate hydrate promoter can signicantly reduce the energy cost of the process and nally lead to a lower fresh water production cost A Eslamimanesh et al / J Chem Thermodynamics 46 (2012) 6271 67 TABLE 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 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 ue 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 eld [283295] 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) 6271 TABLE 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 ue 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 ue 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 efciency of the proposed process has been reported TABLE 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 efcient 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 efcient processes and products [299] Non-ammability, 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 purication 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 benecial 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 eld 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 signicant 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 signicant 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 nancially supported by the Agence Nationale de la Recherche (ANR) as part of the SECOHYA project The nancial support of Orientation Stratộgique des Ecoles des Mines (OSEM) is also acknowledged Conclusion In this communication, we have focussed on reviewing the application of 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