US 8083945 B2 Jun. 17, 2005, Now Pat. No. 7670490, Which Is A

US008O83945B2

(12) United States Patent (10) Patent No.: US 8,083,945 B2 Wyse et al. (45) Date of Patent: *Dec. 27, 2011

(54) FLUID STORAGE AND PURIFICATION 585/860–862; 208/219, 223; 141/1, 70; METHOD AND SYSTEM 222/1; 96/108,243; 588/249; 137/1 (75) Inventors: Carrie L. Wyse, Longmont, CO (US); See application file for complete search history. Robert Torres, Jr., Parker, CO (US); (56) References Cited Tadaharu Watanabe, Saitama (JP); Joseph V. Vininski, Boulder, CO (US) U.S. PATENT DOCUMENTS (73) Assignee: Matheson Tri-Gas, Inc., Basking Ridge, 3.59 A 5:3. R et al. NJ (US) 2,386,523 A 10/1945 Welling 2.522,059 A 9, 1950 Gard tal. (*) Notice: Subject to any disclaimer, the term of this 2.851.395 A 9, 1958 E. al. patent is extended or adjusted under 35 2.941,940 A 6/1960 Duog U.S.C. 154(b) by 0 days. 2.943,917 A 7, 1960 Weitzel et al. This patent is Subject to a terminal dis- (Continued) claimer. FOREIGN PATENT DOCUMENTS (21) Appl. No.: 12/716,016 WO WOO2,34863 A1 5, 2002 Continued (22) Filed: Mar. 2, 2010 ( ) OTHER PUBLICATIONS (65) Prior Publication Data Bates, Eleanor D. et al., “CO2 Capture by a Task-Specific Ionic US 2010/022.3208A1 Sep. 2, 2010 Liquid'. Journal of the American Chemical Society (2002), 124(6): 926-927. Related U.S. Application Data (Continued) (63) ContinuationJun. 17, 2005, of now application Pat. No. No. 7,670,490, 1 1/155,303, which filed is on a Primary Examiner Joseph Drodge continuation of application No. 1 1/101,191, filed on (74) Attorney, Agent, or Firm — Kilpatrick Townsend & Apr. 7, 2005, now Pat. No. 7,638,058. Stockton LLP (51) Int. Cl. (57) ABSTRACT BOLD II/00 (2006.01) A method of storing and dispensing a fluid includes providing (52) U.S. Cl 210/63495/1499.5/1519.5/155: a vessel configured for selective dispensing of the fluid there AV 55.241,952ss. 1371. 210,774. 222/1: 141/1. from. The vessel contains an ionic liquid therein. The fluid is s s s 141770.588,249 contacted with the ionic liquid for take-up of the fluid by the (58) Field of Classification Search 210f634 ionic liquid. There is Substantially no chemical change in the 210/638,639, 660, 663, 669, 774; 95/51, ionic liquid and the fluid. The fluid is released from the ionic 95/149, 151,166-169, 172-177,90, 155, liquid and dispensed from the vessel. 95/156, 158,241, 254, 288: 585/809, 843-850, 23 Claims, 4 Drawing Sheets

SS

US 8,083,945 B2 Page 2

U.S. PATENT DOCUMENTS 2002/0169071 A1 1 1/2002 Sauvage et al. 2003/008515.6 A1 5/2003 Schoonover 2,970.559 2, 1961 LeRoux 2003/O125599 A1* 7/2003 Boudreau et al...... 585,809 3,101,861 8, 1963 Mearns, III et al. 2003/O126991 A1 7/2003 Wang et al. 3, 161461 12, 1964 Deal, Jr. et al. 2003. O149264 A1 8, 2003 Wasserscheid et al. 3,256,705 6, 1966 Dimentberg 2003/0192430 A1 10, 2003 Pearlstein et al. 3,549,332 12, 1970 Yoon 2004.0035293 A1 2/2004 Davis 4,359,596 11, 1982 Howard et al. 2004/0059008 A1 3/2004 Rajeet al. 4,603,148 T. 1986 Tom 2004/0106838 A1 6/2004 Smith et al. 4,604,270 8, 1986 Tom 2004/0206241 A1 10/2004 Tempel et al. 4,659,552 4, 1987 Tom 2005/0106086 A1 5/2005 Tomlinson et al. 4,696,953 9, 1987 Tom 2005/O154247 A1 7/2005 Jong et al. 4,716, 181 12, 1987 Tom 2005/0276733 A1 12/2005 Tempel et al. 4,761,164 8, 1988 Pez et al. 2006,0008392 A1 1/2006 Graham et al. 4,867,960 9, 1989 Tom 2006,0060817 A1 3/2006 Tempel et al. 5,164,093 11, 1992 Chilton et al. 2006,0060818 A1 3/2006 Tempel et al. 5,518,528 5, 1996 Tom et al. 2006, OO86247 A1 4/2006 Vininski et al. 5,827,602 10, 1998 Koch et al. 2006/0226074 A1 10/2006 Wyse et al. 5,980,608 11, 1999 Dietz et al. 2008, 0028170 A1 3/2008 Cleary et al. 5,985,008 11, 1999 Tom et al. 2008, 0210633 A1 9/2008 Wyse et al. 6,048,388 4, 2000 Schwarz 2008, 0211118 A1 9/2008 Wyse et al. 6,089,027 T/2000 Wang et al. 2009/0317317 A1 12/2009 Wyse et al. 6,103,101 8, 2000 Fragelli et al. 2009/032O771 A1 12/2009 Torres et al. 6,110,258 8, 2000 Fraenkel et al. 6,120,692 9, 2000 Wang et al. FOREIGN PATENT DOCUMENTS 6,187,985 2, 2001 Le Peltier et al. 6,274,026 8, 2001 Schucker et al. WO WOO3,O70667 A1 8, 2003 6,339, 182 1, 2002 Munson et al. OTHER PUBLICATIONS 6,379,634 4, 2002 Fields et al. 6,388,893 5, 2002 Calderon Blanchard, Lynette A. et al., “Green Processing Using Ionic Liquids 6,395,070 5, 2002 Bhadha et al. 6.425,946 T/2002 Funke et al. and Co2, Nature, vol. 399, May 6, 1999, pp. 28-29. 6,461.411 10, 2002 Watanabe et al. Freemantle, Michael, “Ionic Liquids Showing Promise for Clean 6,501,000 12, 2002 Stibrany et al. Separation Technology”. C&EN, Aug. 24, 1998. 6,531,270 3, 2003 Olson et al. Medved, M. et al., “409 Ionic Liquids as Active Separation Layer in 6,531,515 3, 2003 Moore et al. Supported Liquid Membranes', Chemie Ingenieur Technik (73) 6,547,861 4, 2003 Funke et al. 61.2001. 6,573.405 6, 2003 Abbott et al. Medved, M. et al., "Potential use of ionic liquids in membrane tech 6,579,343 6, 2003 Brennecke et al. nology applications'. Institut fur Verfahrenstechnik, AWTH-Rachen 6,624,127 9, 2003 Brasket al. 11-123, 8, aachener membrane colloquium 27.-29.3.2001 Cover 6,703,507 3, 2004 Bahrmann et al. page and pp. 11-123 through 11-127. 6,733,734 5, 2004 Watanabe et al. Riddle, Jr. et al., “Spectral Shifts in Acid-Base Chemistry”, Journal of 6,911,065 6, 2005 Watanabe et al. the American Chemical Society, vol. 122, No. 9, Apr. 25, 1990, pp. 6,998, 152 2, 2006 Uhlenbrock 3259-3264 7,019,188 3, 2006 Smith et al. Scovazzo, Paul et al., “Supported Ionic Liquid Membranes and 7,022,655 4, 2006 Brasket al. Facilitated Ionic Liquid Membrances”, 2002 American Chemical 7,172,646 2, 2007 Tempel et al. Society, Chapter 6, pp. 69-87. 7,304.200 12, 2007 Roettger et al...... 585,833 Weixia et al., “Reducing Sulfur Content in FCC Naphtha by Using 7,396.381 T/2008 Graham et al. Ionic Liquid'. Chemical Industry and Engineering Process, Issue 3, 7,404,845 T/2008 Tempel et al. vol. 23, 2004, pp. 297-300. 7,585,415 9, 2009 Wyse et al...... 210/639

Chinese first Office Action from Application No. 200680011329.1. 7,638,058 12, 2009 Wyse et al. . 210,634 English translation, 8 pages. 7,670.490 3, 2010 Wyse et al...... 210,634 2001/OO45187 11, 2001 Uhlenbrock * cited by examiner

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U.S. Patent Dec. 27, 2011 Sheet 4 of 4 US 8,083,945 B2

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+ + ! + * * * * + ! * ! + * u * ! * * * W W * * w * ? ! US 8,083,945 B2 1. 2 FLUID STORAGE ANDPURIFICATION BRIEF SUMMARY METHOD AND SYSTEM In one aspect of the invention, a method of storing and RELATED APPLICATIONS dispensing a fluid is provided. The method includes providing a vessel configured for selective dispensing of the fluid there This application is a continuation of prior U.S. patent from. The vessel contains an ionic liquid therein. The fluid is application Ser. No. 1 1/155.303 filed Jun. 17, 2005, now U.S. contacted with the ionic liquid for take-up of the fluid by the Pat. No. 7,670,490 which is a continuation of prior U.S. ionic liquid. There is Substantially no chemical change in the patent application Ser. No. 1 1/101.191, filed Apr. 7, 2005, ionic liquid and the fluid. The fluid is released from the ionic now U.S. Pat. No. 7,638,058. The entire contents of these 10 liquid and dispensed from the vessel. The fluid may be selected from alcohols, aldehydes, amines, ammonia, aro applications is herein incorporated by reference for all pur matic hydrocarbons, arsenic pentafluoride, arsine, boron poses. trichloride, boron trifluoride, carbon disulfide, carbon mon BACKGROUND oxide, carbon Sulfide, diborane, dichlorosilane, digermane, 15 dimethyl disulfide, dimethylsulfide, disilane, ethers, ethylene oxide, fluorine, germane, germanium methoxide, germanium Many industrial processes require a reliable source of pro tetrafluoride, hafnium methylethylamide, hafnium t-butox cess gases for a wide variety of applications. Often these ide, halogenated hydrocarbons, halogens, hexane, hydrogen, gases are stored in cylinders or vessels and then delivered to hydrogen cyanide, hydrogen halogenides, hydrogen selenide, the process under controlled conditions from the cylinder. For hydrogen Sulfide, ketones, mercaptains, nitric oxides, nitro example, the silicon semiconductor manufacturing industry, gen, nitrogen trifluoride, organometallics, oxygenated-halo as well as the compound semiconductor industry, uses a num genated hydrocarbons, phosgene, phosphorus trifluoride, ber of hazardous specialty gases such as diborane, stibene, n-silane, pentakisdimethylamino tantalum, silicon tetrachlo phosphine, arsine, boron trifluoride, hydrogen chloride, and ride, silicon tetrafluoride, stibine, styrene, sulfur dioxide, sul tetrafluoromethane for doping, etching, thin-film deposition, 25 fur hexafluoride, sulfur tetrafluoride, tetramethyl cyclotet and cleaning. These gases pose significant safety and envi rasiloxane, titanium diethylamide, titanium dimethylamide, ronmental challenges due to their high toxicity and reactivity. trichlorosilane, trimethylsilane, tungsten hexafluoride, and Additionally, storage of hazardous gases under high pressure mixtures thereof. The ionic liquid may be selected from in metal cylinders is often unacceptable because of the pos mono-Substituted imidazolium salts, di-substituted imidazo sibility of developing a leak or catastrophic rupture of the 30 lium salts, tri-substituted imidazolium salts, pyridinium salts, cylinder, cylinder valve, or downstream component. phosphonium salts, ammonium salts, tetralkylammonium In order to mitigate some of these safety issues associated salts, guanidinium salts, isouronium salts, and mixtures with high pressure cylinders, there is a need for a low pressure thereof. storage and delivery system. Additionally, Some gases, such In another aspect of the invention, a method of separating as diborane, tend to decompose when stored for a period of 35 an impurity from a fluid mixture is provided. The fluid mix time. Thus, it would be useful to have a way to store unstable ture includes a fluid and the impurity. A device contains an gases in a manner that reduces or eliminates the decomposi ionic liquid and is configured for contacting the ionic liquid tion. with the fluid mixture. The fluid mixture is introduced into the It is also desirable to have a method of removing impurities device. The fluid mixture is contacted with the ionic liquid. A from gases, particularly in the semiconductor industry. The 40 portion of the impurity is retained within the ionic liquid to growth of high quality thin film electronic and optoelectronic produce a purified fluid. cells by chemical vapor deposition or other vapor-based tech In another aspect of the invention, a method of storing and niques is inhibited by a variety of low-level process impurities stabilizing an unstable fluid is provided. The method includes which are present in gas streams involved in semiconductor providing a vessel containing an ionic liquid therein. The manufacturing or are contributed from various components 45 unstable fluid is contacted with the ionic liquid for take-up of Such as piping, valves, mass flow controllers, filters, and the unstable fluid by the ionic liquid. The unstable fluid is then similar components. These impurities can cause defects that stored within the ionic liquid for a period of time, during reduce yields by increasing the number of rejects, which can which period of time there is substantially no decomposition be very expensive. of the unstable fluid. The unstable fluid may be selected from Chemical impurities may originate in the production of the 50 digermane, disilane, hydrogen selenide, borane, diborane, Source gas itself, as well as in its Subsequent packaging, stibene, nitric oxide, organometallics, and halogenated oxy shipment, storage, handling, and gas distribution system. hydrocarbons. Although source gas manufacturers typically provide analy The foregoing paragraphs have been provided by way of ses of Source gas materials delivered to the semiconductor general introduction, and are not intended to limit the scope of manufacturing facility, the purity of the gases may change 55 the following claims. The presently preferred embodiments, because of leakage into or outgassing of the containers, e.g. together with further advantages, will be best understood by gas cylinders, in which the gases are packaged. Impurity reference to the following detailed description taken in con contamination may also result from improper gas cylinder junction with the accompanying drawings. changes, leaks into downstream processing equipment, or outgassing of suchdownstream equipment. Source gases may 60 BRIEF DESCRIPTION OF THE DRAWINGS include impurities, or impurities may occur as a result of decomposition of the stored gases. Furthermore, the impurity FIG. 1 shows an embodiment of a vessel for storing a fluid levels within the gas container may increase with length of in an ionic liquid. storage time and can also change as the container is consumed FIG. 2 shows another embodiment of a device for storing a by the end user. Thus, there remains a need to be able to 65 fluid in an ionic liquid. remove contaminants from gases, particularly to very low FIG. 3 shows an embodiment of a device for purifying a levels. fluid with an ionic liquid. US 8,083,945 B2 3 4 FIG. 4 shows another embodiment of a device for purifying unstable fluids. Storage of a gas or other fluid in an ionic a fluid with an ionic liquid. liquid may also be combined with the previously mentioned purification system to provide a 3-in-1 storage, stabilization, DETAILED DESCRIPTION and purification system. One potential issue in the use of ionic liquids for the storage The invention is described with reference to the drawings. of gases is the vapor pressure of the ionic liquids. The vapor The relationship and functioning of the various elements of pressure of the ionic liquid can contaminate the delivered gas this invention are better understood by the following detailed with ionic liquid. The present understanding is that ionic description. However, the embodiments of this invention as liquids have very low or possibly no measurable vapor pres described below are by way of example only, and the inven 10 sure of their own. This quality is an attractive feature of ionic tion is not limited to the embodiments illustrated in the draw liquids for use with storage and purification of gases. Vapor ings. pressures have been reported for mixtures of ionic liquids The present invention is directed to the use of ionic liquids with other dissolved liquids. The vapor pressure of the ionic to store a fluid material Such as a gas or liquid. A vessel is liquids used in the present invention are preferably less than configured for the selective dispensing of the fluid and con 15 about 10 Torr at 25°C., more preferably less than about tains an ionic liquid. The fluid is contacted with the ionic 10 Torr at 25° C. liquid for take-up of the fluid by the ionic liquid. This allows The mechanism for the dissolution of a fluid within anionic storage of the fluid for a period of time. In one embodiment, liquid is believed to be due to intermolecular forces. While the material in the storage vessel is at high pressure, for not intending to be bound by any particular theory, possible example up to about 4000 psi, preferably up to at least about factors that influence the solubility include hydrogen bond 2000 psi. In another embodiment, the pressure of the material ing, dielectric constant, dipole moment (polarizability), high in the storage vessel is at around atmospheric pressure, which pi interaction, length of carbon chain, number of carbon allows for safer storage conditions compared to high-pressure double bonds, the purity of the ionic liquid, chirality, and storage vessels. steric hindrance. It is not believed that the fluids chemically The ionic liquids may also be used to store unstable fluids 25 react with the ionic liquid; rather, it is believed that the fluids Such as diborane which tend to decompose. The storage in the simply dissolve in the ionic liquid without the breaking of ionic liquid can reduce or eliminate the decomposition of the bonds. The breaking of bonds in either the ionic liquid or the unstable fluids. fluids being stored therein would change the chemical and The present invention is also directed to the use of ionic physical properties of the ionic liquid or fluids and could liquids to remove impurities from a fluid mixture. A device 30 cause the new species to be considered a new impurity. It is contains an ionic liquid and is configured for contacting the the intention of this invention to store the fluid of interest in an ionic liquid with the fluid mixture. The fluid mixture is intro ionic liquid wherein the fluid molecules remains intact and duced into the device and the fluid mixture is contacted with are removed from the ionic liquid with the same molecular the ionic liquid. A portion of the impurities are retained within structure as they were introduced into the ionic liquid. the ionic liquid to produce a purified fluid. This purification 35 The solubility of a gas in an ionic liquid varies with physi method may be combined with the previously described stor cal parameters such as temperature and pressure. However, it age method. is also evident that the gas solubilities obtained depends on Ionic liquids are a relatively new class of materials which the ionic liquid used, particularly the anion and cation used. can offer Such physical properties as extremely low vapor While not intending to be bound by any particular theory, the pressure, high thermal stability, and low viscosity. Generally, 40 current understanding is that the anion has a strong influence ionic liquids consist of a bulky, asymmetric cation and an on gas solubility. Specifically, the more interaction between inorganic anion. The bulky, asymmetric nature of the cation the anion, the more dissolution appears to occur. The cation prevents light packing, which decreases the melting point. seems to be of secondary influence. Thus, several properties Due to the wide variety of cations and anions possible for of the anion, the cation, and the dissolved gas play a role in Suchion pairs, a wide range of gas solubilities is conceivable, 45 these interactions. In addition, mixtures of different ionic for a variety of inorganic and organic materials. The physical liquids could result in unexpected high solubilities of various properties of ionic liquids can include good dissolution prop fluids. erties for most organic and inorganic compounds; high ther The purity of an ionic liquid is also believed to have an mal stability; non-flammability; negligible vapor pressure; impact on their behavior. Ionic liquids which have been dried low viscosity, compared to other ionic materials; and recy 50 or baked, thus leaving them Substantially anhydrous, may clability. exhibit greater increased capacity for taking up fluid compo The wide range of chemical functionalities available with nents. In addition, the presence of water or other impurities ionic liquids offers possibilities for gas delivery and control. may decrease the Solubility of certain fluid components, espe For example, ionic liquids may provide the capability to cially those gas components that are hydrophobic. control the release of a gas and/or its impurities via solubility 55 The method of storing and dispensing a fluid includes control with temperature or pressure. This may enable the providing a vessel. One embodiment of a vessel 10 is shown storage of a gas and its impurities, while selectively releasing in FIG. 1. The vessel 10 includes a fluid inlet 20, an ionic only the desired gas by changing certain parameters. Such as liquid inlet 30, and a fluid outlet 32. The fluid inlet 20 is temperature or pressure, leaving the impurities behind. Thus connected to a fluid source 14 which is controlled by a valve there is potential for an ionic liquid system that could function 60 18. The ionic liquid inlet 30 is connected to an ionic liquid as a 2-in-1 system, providing both storage and purification in source 12 which is controlled by a valve 16. The fluid outlet one container. 32 is controlled by valve 26. The vessel is configured for Ionic liquids can have a stabilizing effect on intermediate selective dispensing of the fluid therefrom. The vessel is reaction species in organic synthesis and catalysis. Thus, charged with an ionic liquid 22 through inlet 30. A vacuum ionic liquids can offer stabilizing effects for unstable gas 65 bake procedure may be conducted on the vessel 10 to remove molecules. Thus, utilization with even a small amount of contaminants or other impurities from the ionic liquid, pref ionic liquid, can reduce or eliminate the decomposition of the erably by pulling a vacuum while heating. This is done in US 8,083,945 B2 5 6 order to remove any trace moisture and/or other volatile fluid to flow from the vessel to the exterior environment. The impurities from the ionic liquid and the fluid distribution pressure conditions may involve the imposition on the ionic components. The ionic liquid is allowed to cool to the desired liquid of vacuum or Suction conditions which effect extrac operating temperature. tion of the gas from the vessel. The source fluid is then introduced into the vessel 10 until In thermally-mediated evolution, the ionic liquid is heated the take-up or dissolution of the fluid by the ionic liquid is to cause the evolution of the gas from the ionic liquid so that complete. The fluid may be a gas or a liquid Such as a liquefied the gas can be withdrawn or discharged from the vessel. gas. The fluid is contacted with the ionic liquid for take-up of Typically, the temperature of the ionic liquid for thermal the fluid by the ionic liquid. There is substantially no chemi mediated evolution ranges from -50° C. to 200° C., more cal change in the ionic liquid and the fluid. By “substantially 10 preferably from 30° C. to 150° C. In one embodiment, the no chemical change' is meant that no Substantial amount of vessel containing the fluid and the ionic liquid is transported bonds in the fluid and the ionic liquid are being broken, such warm (i.e., around room temperature), then cooled when it is that the fluid and the ionic liquid retain their chemical iden stored or used at the end user's site. In this manner, the fluid tity. It is undesirable for the fluid to react with the ionic liquid vapor pressure can be reduced at the end user's site and to any significant effect. A reaction between the fluid and the 15 therefore reduce the risk of release of the gas from the vessel. ionic liquid would be expected to generate impurities or con Once the vessel is secured in a suitable location, the vessel can sume the fluid of interest. be chilled and the temperature can be controlled in such a The fluid may be introduced at any suitable pressure. In one manner as to limit the amount of gas pressure that is present embodiment, the fluid is a gas at a temperature of about 5 psi. in the container and piping. As the contents of the cylinder or In another embodiment, the gas is introduced at a pressure of other gas storage device are consumed, the temperature of the at least about 100 psi, preferably up to about 2000 psi. The gas cylinder can be elevated to liberate the gas from the ionic is introduced until the inlet and outlet concentrations are liquid and to maintain the necessary amount of gas levels in equivalent, indicating the ionic liquid is saturated and cannot the cylinder and piping. accept any further gas under the existing conditions. At this The vessel may also be sparged with a secondary gas, in time, the source gas flow is stopped. 25 order to deliver the stored primary gas. In sparging, a second In one embodiment, contacting the fluid with the ionic ary gas is introduced into the vessel in order to force the liquid comprises bubbling the fluid mixture through the ionic primary gas out of the ionic liquid and out of the storage liquid, as shown in FIG. 1. The vessel 10 is charged with a container. Sparging of a container can take place wherein the fluid through inlet 28 and through dip tube 20, from whence secondary gas is selected from a group of gases that has it bubbles through ionic liquid 22. 30 relatively low solubility in the ionic liquid. The secondary gas In another embodiment, the fluid is first introduced and is introduced into the ionic liquid in a manner wherein the then the vessel is mechanically agitated in order to contact the secondary gas bubbles through the ionic liquid and displaces fluid with the ionic liquid. FIG. 2 shows an embodiment of a the primary gas from the ionic liquid. The resultant gas mix vessel 80 for storing a fluid in an ionic liquid. The ionic liquid ture of primary gas and secondary gas then exit the gas storage 22 is put into the vessel before valve assembly 82 is inserted 35 container and are delivered to a downstream component in the unto the vessel 80. The fluid is then added to the vessel 80 gas distribution system. The sparging parameters should be containing the ionic liquid in the conventional fashion selected Such that the maximum amount of primary gas is through inlet port 84 in valve assembly 82. The vessel 80 removed from the ionic liquid. This includes selection of the would then be mechanically agitated to contact the fluid with appropriate geometry of the sparging vessel Such that the the ionic liquid 22. The fluid may be removed through outlet 40 secondary gas has an enhanced pathway for the interaction or port 86. contact between the secondary fluid and the ionic liquid. In In one embodiment, the fluid is a liquid. The vessel 80 practice, this could be use of a long and narrow storage shown in FIG.2 may also be used to store a liquid in the ionic container wherein the secondary fluid is introduced at the liquid. The ionic liquid 22 is put into the vessel before valve bottom of the container and the outlet of the container is near assembly 82 is inserted into the vessel 80. The liquid is then 45 the top. Additionally, a device such as a diffuser can be used added to the vessel 80 in the conventional fashion through within the storage container that causes the bubbles of the inlet port 84 in valve assembly 82. The vessel 80 would then secondary gas to be very small and numerous. In this manner, be mechanically agitated to contact the liquid with the ionic the surface area or contact area of the bubbles of the second liquid 22. The liquid may be removed through outlet port 86. ary gas is enhanced with the ionic liquid. Finally, the param In another embodiment, countercurrent flow of the ionic 50 eters oftemperature and pressure within the sparging Storage liquid and the fluid is used to contact the fluid with the ionic container can be adjusted Such that the desired concentration liquid. In another embodiment, the fluid is a liquid, and the of the secondary gas and primary gas are constant and fall liquid and the ionic liquid are mixed to contact the fluid with within a desired range. In this example, the sparging vessel the ionic liquid. can be a separate container from the typical storage container The fluid stored within the ionic liquid may be removed 55 Such as a gas cylinder, or the typical storage container can be from the ionic liquid by any suitable method. The fluid is used as the sparging vessel depending on the requirements of released from the ionic liquid in a substantially unreacted the specific application. state. Pressure-mediated and thermally-mediated methods When released from the ionic liquid, the gas flows out of and sparging, alone or in combination, are preferred. In pres the vessel, by Suitable means such as a discharge port or Sure-mediated evolution, a pressure gradient is established to 60 opening 24 in FIG.1. A flow control valve 26 may be joined cause the gas to evolve from the ionic liquid. In one embodi in fluid communication with the interior volume of the vessel. ment, the pressure gradient is in the range of about atmo A pipe, conduit, hose, channel or other Suitable device or spheric pressure to about 4000 psig. In a more preferred assembly by which the fluid can be flowed out of the vessel embodiment, the pressure gradient is typically in the range may be connected to the vessel. from 107 to 600 Torr at 25° C. For example, the pressure 65 The present invention also provides a fluid storage and gradient may be established between the ionic liquid in the dispensing system. The system includes a fluid storage and vessel, and the exterior environment of the vessel, causing the dispensing vessel configured to selectively dispense a fluid US 8,083,945 B2 7 8 therefrom. A Suitable vessel is, for example, a container that sulfate, 1-butyl-3-methylimidazolium hydrogensulfate. can hold up to 1000 liters. A typical vessel size is about 44 Acidic water reactive liquids include 1-ethyl-3-methylimida liters. The vessel should be able to contain fluids at a pressure Zolium tetrachloroaluminate and 1-butyl-3-methylimidazo of up to about 2000 psi, preferably up to about 4000 psi. lium tetrachloroaluminate. Basic ionic liquids include However, the vessel may also operate at around atmospheric 1-ethyl-3-methylimidazolium acetate and 1-butyl-3-meth pressure. Preferably, the container is made of carbon steel, ylimidazolium acetate. stainless steel, nickel or aluminum. In some cases the vessel Another way the preferred ionic liquids in the present may contain interior coatings in the form of inorganic coat invention may be categorized is by functional group of the ings such as silicon and carbon, metallic coatings Such as cation. This includes but is not limited to the following cat nickel, organic coatings such as paralyene or Teflon based 10 materials. The vessel contains an ionic liquid which revers egories: mono-Substituted imidazoliums, di-substituted imi ibly takes up the fluid when contacted therewith. The fluid is dazoliums, tri-substituted imidazoliums, pyridiniums, pyrro releasable from the ionic liquid under dispensing conditions. lidiniums, phosphoniums, ammoniums, A variety of ionic liquids can be used in the present inven tetralkylammoniums, guanidiniums, and uraniums. Mono tion. Additionally, two or more ionic liquids may be com 15 Substituted imidazolium ionic liquids include 1-methyl imi bined for use in any of the aspects of the present invention. In dazolium tosylate, 1-methylimidazolium tetrafluoroborate, one embodiment, the ionic liquid is selected from mono 1-methylimidazolium hexafluorophosphate, 1-methylimida substituted imidazolium salts, di-substituted imidazolium Zolium tifluoromethanesulfonate, 1-butylimidazolium tosy salts, tri-substituted imidazolium salts, pyridinium salts, pyr late, 1-butylimidazolium tetrafluoroborate, 1-methylimida rolidinium salts, phosphonium salts, ammonium salts, Zolium hexafluorophosphate, 1-methylimidazolium tetralkylammonium salts, guanidinium salts, isouronium trifluoromethanesulfonate. salts, and mixtures thereof. In this context, the listed salts Di-substituted imidazolium ionic liquids include 1,3-dim include any compound that contains the listed cation. In ethylimidiazolium methylsulfate, 1,3-dimethylimidiazolium another embodiment, the ionic liquidis selected from a Subset trifluoromethanesulfonate, 1,3-dimethylimidiazolium bis of the previous list and includes phosphonium salts, ammo 25 (pentafluoroethyl)phosphinate, 1-ethyl-3-methylimidiazo nium salts, tetralkylammonium salts, guanidinium salts, isou lium thiocyanate, 1-ethyl-3-methylimidiazolium dicyana ronium salts, and mixtures thereof, in one embodiment, the mide, 1-ethyl-3-methylimidiazolium cobalt-tetracarbonyl, ionic liquid includes a cation component selected from mono 1-propyl-3-methylimidazolium chloride, 1-butyl-3-meth Substituted imidazoliums, di-substituted imidazoliums, tri ylimidazolium hexafluoroantimonate, 1-octadecyl-3-meth Substituted imidazoliums, pyridiniums, pyrrolidiniurns, 30 ylimidazolium bis(trifluoromethylsulfonyl)imide, 1-benzyl phosphoniums, ammoniums, tetralkylammoniums, guani 3-methylimidazolium bromide, 1-phenylpropyl-3- diniums, and uroniums; and an anion component selected methylimidazolium chloride. from acetate, cyanates, decanoates, halogenides, Sulfates, Sul Tri-substituted imidazolium ionic liquids include 1-ethyl fonates, amides, imides, methanes, borates, phosphates, anti 2,3-dimethylimidazolium chloride, 1-butyl-2,3-dimeth monates, tetrachloroaluminate, thiocyanate, tosylate, car 35 ylimidazolium octylsulfate, 1-propyl-2,3-dimethylimidazo boxylate, cobalt-tetracarbonyl, trifluoroacetate and tris lium chloride, 1-hexyl-2,3-dimethylimidazolium (trifluoromethylsulfonyl)methide. Halogenide anions tetrafluoroborate, 1-hexadecyl-2,3-dimethylimidazolium include chloride, bromide, iodide. Sulfates and sulfonate iodide. Pyridinium ionic liquids include n-ethylpyridinium anions include methyl sulfate, ethyl sulfate, butyl sulfate, chloride, n-butylpyridinium bromide, n-hexylpyridinium hexyl Sulfate, octyl sulfate, hydrogen Sulfate, methane Sul 40 n-octylpyridinium chloride, 3-methyl-n-butylpyridinium fonate, dodecylbenzene Sulfonate, dimethyleneglycol methylsulfate, 3-ethyl-n-butylpyridinium hexafluorophos monomethylether sulfate, trifluoromethane sulfonate. phate, 4-methyl-n-butylpyridinium bromide, 3,4-dimethyl-n- Amides, imides, and methane anions include dicyanamide, butylpyridinium chloride, 3,5-dimethyl-n-butylpyridinium bis(pentafluoroethylsulfonyl)imide, bis(trifluoromethylsul chloride. fonyl)imide, bis(trifluoromethyl)imide. Borate anions 45 Pyrrolidinium ionic liquids include 1,1-dimethylpyrroli include tetrafluoroborate, tetracyanoborate, bisoxalato(2-) dinium tris(pentafluoroethyl)trifluorophosphate, 1-ethyl-1- borate, bis 1,2-benzenediolato(2-)-O,O'borate, bissalicy methylpyrrolidinium dicyanamide, 1,1-dipropylpyrroli lato(2-)borate. Phosphate and phosphinate anions include dinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1- hexafluorophosphate, diethylphosphate, bis(pentafluoroeth methylpyrrolidinium bromide, 1-butyl-1-ethylpyrrolidinium yl)phosphinate, tris(pentafluoroethyl)trifluorophosphate, tris 50 bromide, 1-octyl-1-methylpyrrolidinium dicyanamide. (nonafluorobutyl)trifluorophosphate. Anitmonate anions Phosphonium ionic liquids include tetraoctylphosphonium include hexafluoroantimonate. Other anions include tetra bromide, tetrabulylphosphonium bisoxalato(2-)-borate, tri chloroaluminate, acetate, thiocyanate, tosylate, carboxylate, hexyl (tetradecyl)phosphonium dicyanamide, benzyltriph cobalt-tetracarbonyl, trifluoroacetate and tris(trifluorometh enylphosphonium bis(trifluoromethyl)imide, tri-iso-butyl ylsulfonyl)methide. Various ionic liquids are available from 55 (methyl)phosphonium tosylate, ethyl(tributyl)phosphonium BASF, Merck, Strem Chemicals, and Aldrich. diethylphosphate, tributyl (hexadecyl)phosphonium chloride. Preferred ionic liquids used in the present invention may be Ammonium ionic liquids include tetramethylammonium divided into the following categories: standard, acidic, acidic bis(trifluoromethylsulfonyl)imide, tetraethylammonium bis water reactive, and basic. Standard ionic liquids include but salicylato-(2-)-borate, tetrabutylammonium tetracyanobo are not limited to 1-ethyl-3-methylimidazolium chloride, 60 rate, methyltrioctylammonium trifluoroacetat. 1-ethyl-3-methylimidazolium methanesulfonate, 1-butyl-3- Guanidinium ionic liquids include N.N.N',N',N'-pentam methylimidazolium chloride, 1-butyl-3-methylimidazolium ethyl-N'-isopropylguanidinium tris(pentafluoroethyl)trif methanesulfonate, methyl-tri-n-butylammonium methylsul luorophosphate, N.N.N',N',N'-pentamethyl-N'-isopropy fate, 1-ethyl-2,3-dimethylimidazolium ethylsulfate, 1,2,3-tri lguanidinium tris(pentafluoroethyl) methylimidazolium methylsulfate. Acidic ionic liquids 65 trifluoromethanesulfonate, hexamethyl guanidinium tris include methylimidazolium chloride, methylimidazolium (pentafluoroethyl)trifluorophosphate, hydrogensulfate, 1-ethyl-3-methylimidazolium hydrogen hexamethylguanidinium trifluoromethanesulfonate. US 8,083,945 B2 10 Uronium ionic liquids include S-methyl-N,N,N',N'-tet octafluorocyclobutane, chlorotrifluoroethylene, hexafluoro ramethylisouronium trifluoromethanesulfonate, O-methyl propylene, octafluorocyclopentane, perfluoropropane, 1,1,1- N.N.N',N'-tetramethylisouronium tris(pentafluoroethyl)trif. trichloroethane, 1,1,2-trichloroethane, methyl chloride, and luorophosphate, O-ethyl-N,N,N',N'-tetramethylisouronium methyl fluoride. Ketones include acetone. Mercaptains tris(pentafluoroethyl)trifluorophosphate, S-ethyl-N,N,N',N'- include ethyl mercaptan, methyl mercaptan, propyl mercap tetramethylisouronium trifluoromethanesulfonate, S-ethyl tan, and n.s.t-butyl mercaptan. Nitrogen oxides include nitro N.N.N',N'-tetramethylisothiouronium trifluoromethane gen oxide, nitrogen dioxide, and nitrous oxide. Organometal Sulfonate. lics include trimethylaluminum, triethylaluminum, In one embodiment, the ionic liquid used to store a fluid dimethylethylamine alane, trimethylamine alane, dimethyla does not include imidazolium compounds. In another 10 luminum hydride, tritertiarybutylaluminum, Tritertiarybuty embodiment, the ionic liquid used to store a fluid does not laluminum trimethylindium (TMI), trimethylgallium include a nitrogen-containing heterocyclic cation. (TMG), triethylgallium (TEG), dimethylzinc (DMZ), dieth The fluids which may be stored, purified, or stabilized in ylzinc (DEZ), carbontetrabromide (CBra), diethyltellurium the ionic liquids include, but are not limited to, alcohols, (DETe) and magnesocene (CpMg). Oxygenated-haloge aldehydes, amines, ammonia, aromatic hydrocarbons, 15 nated-hydrocarbons include perfluoroethylmethylether, per arsenic pentafluoride, arsine, borontrichloride, borontrifluo fluoromethylpropylether, perfluorodimethoxymethane, and ride, carbon dioxide, carbon disulfide, carbon monoxide, car hexafluoropropylene oxide. Other fluids include vinyl acety bon Sulfide, chlorine, diborane, dichlorosilane, digermane, lene, acrylonitrile, and vinyl chloride. dimethyl disulfide, dimethyl sulfide, disilane, ethane, ethers, Other fluids which may be stored, purified, or stabilized in ethylene oxide, fluorine, germane, germanium methoxide, ionic liquids include materials used for thin film deposition germanium tetrafluoride, hafnium methylethylamide, applications. Such materials include, but are not limited to, hafnium t-butoxide, halogenated hydrocarbons, halogens, tetramethyl cyclotetrasiloxane (TOMCTS), titanium dim hexane, hydrogen, hydrogen cyanide, hydrogen halogenides, ethylamide (TDMAT), titanium diethylamide (TDEAT), hydrogen selenide, hydrogen sulfide, ketones, mercaptains, hafnium t-butoxide (Hf(OtBu)4), germanium methoxide (Ge methane, nitric oxides, nitrogen, nitrogen trifluoride, noble 25 (OMe)4), pentakisdimethylamino tantalum (PDMAT) gases, organometallics, oxygen, oxygenated-halogenated hafnium methylethylamide (TEMAH) and mixtures thereof. hydrocarbons, phosgene, phosphine, phosphorus trifluoride, The fluids which may be stored in the ionic liquids may be n-silane, pentakisdimethylamino tantalum, propane, silicon divided into categories including include stable gases, stable tetrachloride, silicon tetrafluoride, stibine, styrene, sulfur liquefied gases, unstable gases, and unstable liquefied gases. dioxide, sulfur hexafluoride, sulfur tetrafluoride, tetramethyl 30 The term stable is relative and includes gases which do not cyclotetrasiloxane, titanium diethylamide, titanium dimethy substantially decompose over the shelflife of a storage vessel lamide, trichlorosilane, trimethylsilane, tungsten hexafluo at the typical temperatures and pressures at which those ride, water, and mixtures thereof. skilled in the art would store the gases. Unstable refers to In another embodiment, the fluids which may be stored, materials which are prone to decomposition under typical purified, or stabilized in the ionic liquids includes a subset of 35 storage conditions and thus are difficult to store. the previous listed fluids and include alcohols, aldehydes, Stable gases include include nitrogen, argon, helium, neon, amines, ammonia, aromatic hydrocarbons, arsenic pentafluo Xenon, krypton; hydrocarbons include methane, ethane, and ride, arsine, boron trichloride, boron trifluoride, carbon dis propanes; hydrides include silane, disilane, arsine, phos ulfide, carbon monoxide, carbon Sulfide, chlorine, diborane, phine, germane, ammonia; corrosives include hydrogen halo dichlorosilane, digermane, dimethyl disulfide, dimethyl Sul 40 genides Such as hydrogen chloride, hydrogen bromide, and fide, disilane, ethers, ethylene oxide, fluorine, germane, ger hydrogen fluoride, as well as chlorine, dichlorosilane, trichlo manium methoxide, germanium tetrafluoride, hafnium meth rosilane, carbon tetrachloride, boron trichloride, tungsten ylethylamide, hafnium t-butoxide, halogenated hexafluoride, and boron trifluoride; oxygenates include oxy hydrocarbons, halogens, hexane, hydrogen, hydrogen cya gen, carbon dioxide, nitrous oxide, and carbon monoxide; and nide, hydrogen halogenides, hydrogen selenide, hydrogen 45 other gases such as hydrogen, deuterium, dimethyl ether, Sulfide, ketones, mercaptains, nitric oxides, nitrogen, nitrogen Sulfur hexafluoride, arsenic pentafluoride, and silicon tet trifluoride, organometallics, oxygenated-halogenated hydro rafluoride. carbons, phosgene, phosphine, phosphorus trifluoride, n-si Stable liquefied gases include inerts such as nitrogen and lane, pentakisdimethylamino tantalum, silicon tetrachloride, argon; hydrocarbons such as propane; hydrides such as silicon tetrafluoride, stibine, styrene, sulfur dioxide, sulfur 50 silane, disilane, arsine, phosphine, germane, and ammonia; hexafluoride, sulfur tetrafluoride, tetramethyl cyclotetrasi fluorinates Such as hexafluoroethane, perfluoropropane, and loxane, titanium diethylamide, titanium dimethylamide, perfluorobutane; corrosives such as hydrogen chloride, trichlorosilane, trimethyl silane, tungsten hexafluoride, and hydrogen bromide, hydrogen fluoride, chlorine, dichlorosi mixtures thereof. lane, trichlorosilane, carbon tetrachloride, boron trichloride, By way of illustration, examples of some of these classes of 55 borontrifluoride, tungsten hexafluoride, and chlorine trifluo fluids will now be listed. However, scope of the invention is ride; and oxygenates such as oxygen and nitrous oxide. not limited to the following examples. Alcohols include etha Unstable gases include digermane, borane, diborane, nol, isopropanol, and methanol. Aldehydes include acetalde stibene, disilane, hydrogen selenide, nitric oxide, fluorine and hyde. Amines include dimethylamine and monomethy organometallics including alanes, trimethyl aluminum and lamine. Aromatic compounds include benzene, toluene, and 60 other similar gases. These unstable gases may also be lique xylene. Ethers include dimethyl ether, and vinyl methyl ether. fied. Halogens include chlorine, fluorine, and bromine. Haloge In one embodiment, a fluid such as fluorine could be stored nated hydrocarbons include dichlorodifluoromethane, tet with fully fluorinated ionic liquid such as perfluorinated rafluoromethane, chlorodifluoromethane, trifluoromethane, ammonium hexafluorophosphate. difluoromethane, methyl fluoride, 1,2-dichlorotetrafluoroet 65 The present invention also provides a method of separating hane, hexafluoroethane, pentafluoroethane, halocarbon 134a an impurity from a fluid mixture. In this instance, the fluid tetrafluoroethane, difluoroethane, perfluoropropane, mixture includes a fluid and the impurity. FIG. 3 shows an US 8,083,945 B2 11 12 embodiment of a device 40 for purifying a fluid with an ionic Sufficient to allow significant removal of targeted compo liquid. A device containing the ionic liquid is configured for nents. Thus, Systems maximizing Surface area contact contacting the ionic liquid with the fluid mixture. A source 46 between the ionic liquid and the fluid mixture are desirable. for the fluid mixture is controlled by valve 48. The fluid In one embodiment, the device is a vessel and the step of mixture is introduced through inlet 50 into the device 40 and 5 contacting the fluid mixture with the ionic liquid comprises contacted with the ionic liquid. The ionic liquid is introduced bubbling the fluid mixture through the ionic liquid, as shown through inlet 52 from ionic liquid source 42 by valve 44. A in FIG. 4 and previously described. In another embodiment, a portion of the impurities is retained within the ionic liquid to scrubbing stack is used to contact the fluid mixture with the produce a purified fluid. The purified fluid is released from the ionic liquid, with the fluid mixture and the ionic liquid flow device through outlet 54, which is controlled by valve 56. 10 ing into the scrubbing stack. In another embodiment, the FIG. 4 shows another embodiment of a device 40 for puri vessel containing the fluid and the ionic liquid is mechani fying a fluid with an ionic liquid. Contacting the fluid with the cally agitated in order to contact the fluid with the ionic liquid. ionic liquid comprises bubbling the fluid mixture through the In another embodiment, countercurrent flow of the ionic liq ionic liquid. The vessel 60 includes a valve assembly 62, an uid and the fluid is used to contact the fluid with the ionic ionic liquid inlet 64, a fluid inlet 66, and a dip tube 78. The 15 liquid in the device. In another embodiment, the fluid is a valve assembly 62 includes an ionic liquid inlet valve 68 and liquid, and the liquid and the ionic liquid are mixed to contact a fluid inlet valve 70. The vessel 60 is charged with an ionic the fluid with the ionic liquid in the device. liquid 22 through inlet 64. The vessel 60 is charged with a In another aspect of the invention, a method of separating fluid through inlet 66 and through dip tube 78, from whence an impurity from a fluid mixture is provided which used a it bubbles through ionic liquid 22. Small amount of ionic liquid. The fluid mixture is contacted Alternatively, as will be described below, the impurity may with the ionic liquid for the purpose of purification only and retained on a solid material that has been introduced into the not for uptake of the fluid by the ionic liquid. Thus, a device ionic liquid. In addition, mixtures of one or more ionic liquids or vessel is used to contact a small amount of ionic liquid with can be used with or without the additional solid phase puri the fluid mixture. In this manner, a Substantially less amount fication material to adjust the solubility of the fluid as well as 25 of ionic liquid could be required to obtain the purification the purifying ability of the ionic liquid. Additionally, non effect compared to the previous illustration wherein the ionic liquids can be mixed with the ionic liquids to either unstable fluid could be taken up completely or dissolved capture impurities present in the fluid or to substantially within the ionic liquid. A portion of the impurity is retained modify the impurities into a form that is retained by the within the ionic liquid to produce a purified fluid. purifying liquid or ionic liquid. The net effect is that the 30 In another aspect of the invention, a method of stabilizing impurities are separated from the fluid and the purified fluid is an unstable fluid is provided which uses a small amount of then released from the device. ionic liquid. The unstable fluid is contacted with the ionic It is understood that the fluid and fluid mixture may include liquid for the purpose of stabilization only and not for uptake liquids, vapors (volatilized liquids), gaseous compounds, of the fluid by the ionic liquid. Thus, a device or vessel is used and/or gaseous elements. Furthermore, while reference is 35 to contact a small amount of ionic liquid with the fluid. In this made to “purified, it is understood that purified may include manner, a substantially less amount of ionic liquid could be purification to be essentially free of one or more impurities, or required to obtain the stabilization effect compared to an simply lowering the lower level of impurities in the fluid illustration wherein the unstable fluid could be taken upcom mixture. Impurities include any Substance that may be desir pletely or dissolved within the ionic liquid. No decomposition able to have removed from the fluid mixture, or are undesir 40 products, or Substantially less decomposition products, are able within the fluid mixture. Impurities included can be produced as a result of the contact of the unstable fluid with variants or analogs of the fluid itself if they are undesirable. the ionic liquid, producing a stabilized fluid. Impurities that would typically be desired to be removed Ionic liquids which have been dried or baked, thus leaving include but are not limited to water, CO, oxygen, CO., NO, them Substantially anhydrous, may exhibit greater overall NO NO, SO, SO, SO, S.O., SO, and mixtures thereof. 45 capacity for removing some gaseous components. The pres Additionally, impurities include but are not limited to deriva ence of water or other impurities in the ionic liquid may tives of the fluid of interest. For example, higher boranes are reduce the capacity of the ionic liquid for dissolving fluid considered impurities within diborane. Disilane is considered components. In addition, the presence of water or other impu an impurity in silane. Phosphine could be considered an rities may decrease the solubility of certain fluid components, impurity in arsine, and HF could be considered an impurity in 50 especially those fluid components that are hydrophobic. BF. Dried baked ionic liquid may exhibit differential selectivities The ionic liquid used in the purification process may be any between various fluid components when compared to those of the previously mentioned ionic liquids. However, it should ionic liquids containing measurable amounts of dissolved be understood that certain ionic liquids will be better suited to water, such as ionic liquids having been exposed to humid removing certain impurities. It should also be understood that 55 atmospheres. Ionic liquids may be dried by conventional certain ionic liquids will be better suited to working with methods, Such as by heat treatment, exposure to a reduced certain fluids. In one embodiment, the ionic liquid used for pressure environment, or a combination of heat and reduced purification does not comprise a nitrogen-containing hetero pressure. cyclic cation. The fluid which may be purified includes any of It is known that gas solubility in various liquids, including the previously mentioned fluids. In one embodiment, the 60 ionic liquids, is dependent upon temperature and pressure. method is not used to purify any of the following fluids: Different gas components may each elicit a different sensi carbon dioxide, water, methane, ethane, propane, noble tivity to temperature and/or pressure changes as pertains to gases, oxygen, nitrogen, or hydrogen. the Solubility of the gas component in the ionic liquids. This Contacting the ionic liquid with the fluid mixture may be differential temperature and/or temperature dependence may accomplished in any of the variety of ways. The process is 65 be advantageously exploited by conducting variations of the selected to promote intimate mixing of the liquid ionic com process of the present invention at different temperatures and pound and the fluid mixture and is conducted for a time pressures to optimize gas component separation. US 8,083,945 B2 13 14 The present invention also provides a method for both amorphous silica-alumina, silica (SiO2), aluminosilicate storing and purifying a fluid mixture comprising a fluid and an molecular sieves, titania (TiO), Zirconia (ZrO2), and carbon. impurity. A vessel contains an ionic liquid and is configured The materials are commercially available in a variety of for contacting the ionic liquid with the fluid mixture. The fluid shapes of different sizes, including, but not limited to, beads, and the ionic liquid may be any of the previously mentioned 5 sheets, extrudates, powders, tablets, etc. The surface of the fluids and ionic liquids. The fluid is contacted with the ionic materials can be coated with a thin layer of a particular form liquid for take-up of the fluid by the ionic liquid. This may be of the metal (e.g., a metal oxide or a metal salt) using methods accomplished by any of the previously described methods of known to those skilled in the art, including, but not limited to, promoting intimate mixing of the liquid ionic compound and incipient wetness impregnation techniques, ion exchange the fluid mixture, or any other suitable method. A portion of 10 the impurities is retained within the ionic liquid to produce a methods, vapor deposition, spraying of reagent Solutions, purified fluid. The purified fluid can then be released from the co-precipitation, physical mixing, etc. The metal can consist device. of alkali, alkaline earth or transition metals. Commercially The present invention also provides a method of storing available purification materials includes a Substrate coated and stabilizing an unstable fluid. The unstable fluid may be 15 with a thin layer of metal oxide (known as NHX-PlusTM) for any of the previously mention unstable fluids, or any other removing H2O, CO and O2, H2S and hydride impurities, fluid that tends to decompose. The ionic liquid may be any of Such as silane, germane and siloxanes; ultra-low emission the previously mentioned ionic liquids. The unstable fluid is (ULE) carbon materials (known as HCXTM) designed to contacted with the ionic liquid for take-up of the unstable remove trace hydrocarbons from inert gases and hydrogen; fluid by the ionic liquid. The unstable fluid may be then stored macroreticulate polymer scavengers (known as OMATM and within the ionic liquid for a period of time, during which OMX-PlusTM) for removing oxygenated species (HO, O, period of time the decomposition rate is at least reduced, and CO, CO., NO, SO, etc.) and non-methane hydrocarbons; preferably there is substantially no decomposition of the and inorganic silicate materials (known as MTXTM) for unstable fluid. In one embodiment, the rate of decomposition removing moisture and metals. All of these are available from is reduced by at least about 50%, more preferably at least 25 Matheson Tri-Gas(R), Newark, Calif. Further information on about 75%, and most preferably at least about 90%, compared these purifying materials and other purification materials is with storage of the fluid under the same temperature and disclosed in U.S. Pat. Nos. 4,603,148; 4,604270; 4,659,552; pressure conditions without using an ionic liquid. In the con 4,696,953; 4,716,181; 4,867,960; 6,110,258; 6,395,070; text of an unstable fluid, Substantially no decomposition 6,461.411; 6,425,946; 6,547,861; and 6,733,734, the contents means that less than 10% of the molecules of the unstable 30 of which are hereby incorporated by reference. Other solid fluid undergo a chemical change while being stored. In one purification materials typically available from Acronex, Mil embodiment, the proportion of molecules that undergo a lipore, Mykrolis, Saes Getters, Pall Corporation, Japan Pion decomposition reaction is preferably less than 1%, more pref ics and used commonly in the semiconductor gas purification erably less than 0.1%, and most preferably less than 0.01%. applications are known in the art and are intended to be Although it is most preferable for the decomposition rate to be 35 included within the scope of the present invention. less than 0.01%, it should be noted that in certain applications Additionally, any of the previously described storage, sta a rate of decomposition of less than 50% over the storage bilization, and purification methods and systems may becom period of the fluid would be useful. The period of time may bined to provide multiple effects. One, two or all three meth range from a few minutes to several years, but is preferably at ods can be independently combined to obtain a process that is least about 1 hour, more preferably at least about 24 hours, 40 best suited for the application of interest. Therefore, it is even more preferably at least about 7 days, and most prefer conceivable that any one method or the combination of any of ably at least about 1 month. the methods could be used for different requirements and The unstable fluid may be selected from categories such as applications. The basic steps of these combined methods will dopants, dielectrics, etchants, thin film growth, cleaning, and now be set forth. It will be apparent that the information other semiconductor processes. Examples of unstable fluids 45 previously described for the individual methods will also be include, but are not limited to, digermane, borane, diborane, applicable for the combined methods described below. The disilane, fluorine, halogenated oxy-hydrocarbons, hydrogen fluids and the ionic liquids used in the combined processes Selenide, Stilbene, nitric oxide, organometallics and mixtures may be any of the previously mentioned fluids and ionic thereof. liquids. The present invention also provides a method of storing 50 The storage method may be combined with the method of and purifying a fluid mixture. The storage vessel is provided purifying using a purifying Solid. In this method, a vessel with a purifying solid or liquid for contact with the fluid containing an ionic liquid is provided. The fluid mixture is mixture. The purifying Solid or liquid retains at least a portion contacted with the ionic liquid for take-up of the fluid by the of the impurity in the fluid mixture to produce a purified fluid ionic liquid. There is Substantially no chemical change in the when the fluid is released from the storage vessel. The puri 55 ionic liquid and the fluid. A purifying solid is provided for fying Solid or liquid may be used with any of the previously contact with the fluid mixture. A portion of the impurity is mentioned fluids and ionic liquids. retained by the purifying solid to produce a purified fluid. Various purifying materials may be used with the present The methods of storage, stabilizing, and purifying using a invention. The purification or impurity removal can be used to purifying Solid may also be combined. A vessel containing an remove impurities from the ionic liquid which could change 60 ionic liquid is provided. The fluid mixture fluid is contacted the solubility of a fluid in the ionic liquid. Alternatively, the with the ionic liquid for take-up of the fluid mixture by the purification material could remove only impurities present in ionic liquid. A purifying solid is provided for contact with the the incoming gas or contributed from the fluid storage vessel fluid mixture. A portion of the impurity is retained by the that will be stored in the ionic liquid. Finally, the purification purifying solid to produce a purified fluid. The ionic liquid is material could have the ability to remove impurities from both 65 stored for a period of time of at least about 1 hour, during the fluid of interest and the ionic liquid simultaneously. The which period of time there is substantially no degradation of purification materials include, but are not limited to, alumina, the unstable fluid. US 8,083,945 B2 15 16 The methods of storage, stabilizing, and purifying using with a dip tube is charged with a known quantity of the ionic the ionic liquid may also be combined. A device containing an liquid. The charged canister is thermally controlled by a PID ionic liquid and configured for contacting the ionic liquid temperature controller or variac with a heating element and a with the fluid mixture is provided. The fluid mixture is intro thermocouple. The canister is placed on a gravimetric load duced into the device. The fluid mixture is contacted with the ionic liquid. The fluid mixture may then be stored within the cell or weight scale and a pressure gauge is connected to the ionic liquid for a period of time of at least about 1 hour, during canister to measure head pressure. This canister is connected which period of time there is substantially no degradation of to a manifold with vacuum capability and to a gas source. The the unstable fluid. A portion of the impurities are retained canister is also connected to an analyzer (such as FT-IR, GC, within the ionic liquid to produce a purified unstable fluid, APIMS, etc.). and the purified unstable fluid may then be released from the 10 A vacuum bake procedure is conducted on the canister device. charged with the ionic liquid and the manifold up to the gas The two purification methods may also be combined. A cylinder, by pulling a vacuum while heating. This removes device containing an ionic liquid and a purifying solid therein any trace moisture and other Volatile impurities from the ionic for contact with the fluid mixture is provided. The fluid mix ture is introduced into the device. The fluid mixture is con 15 liquid and the gas distribution components. The ionic liquid is tacted with the ionic liquid and with the purifying solid. A first allowed to cool to the desired operating temperature. The portion of the impurity is retained within the ionic liquid and mass of the vacuum baked canister and ionic liquid is a second portion of the impurity is retained by the purifying recorded. solid, to produce a purified fluid. The purified fluid may then be released from the device. Example 1 The storage method may be combined with both methods of purifying. A vessel containing an ionic liquid and a puri Storage of An Unstable Gas In Ionic Liquid-BH fying solid therein for contact with the fluid mixture is pro Stored In BMIMPF) vided. The fluid is contacted with the ionic liquid for take-up of the fluid by the ionic liquid. A first portion of the impurity 25 A canister of BMIMPF) is prepared as described above. is retained within the ionic liquid and a second portion of the impurity is retained by the purifying solid, to produce a puri The source gas, BH or a gas mixture containing B.H., is fied fluid. The purified fluid may then be released from the then introduced into the canister, at 5 psig, until the uptake of device. BHe is complete. The uptake can be determined gravimetri The storage and stabilization methods may be combined cally, or by analytical methods. For example, the concentra with both methods of purifying. A vessel containing an ionic 30 tion or absolute amount of the BH can be measured at the liquid and a purifying solid therein for contact with the fluid inlet of the canister and the outlet of the canister. B.H. will mixture is provided. The fluid mixture is introduced into the continue to be introduced until the inlet and outlet concentra device. The fluid is contacted with the ionic liquid for take-up tions are equivalent, indicating the BMIMPF) fluid is satu of the fluid by the ionic liquid. The fluid mixture is stored rated and cannot accept any further B.H. under the existing within the ionic liquid for a period of time of at least about 1 35 hour, during which period of time there is substantially no conditions. At this time, the source gas flow is stopped. degradation of the unstable fluid. A first portion of the impu The BMIMIPF-charged canister is then heated, a pres rity is retained within the ionic liquid and a second portion of Sure differential is applied, or it is sparged with an inert gas, in the impurity is retained by the purifying Solid, to produce a order to deliver the stored B.H. The delivered gas is analyzed purified unstable fluid. The purified fluid may then be 40 for BH content. This can be determined gravimetrically or released from the device. analytically. The total amount introduced is compared to the The stabilization methods may be combined with both total amount removed to determine the loading factor of the methods of purifying. A vessel containing an ionic liquid and cylinder. a purifying solid therein for contact with the fluid mixture is provided. The unstable fluid mixture is introduced into the 45 Example 2 device. The unstable fluid is contacted with the ionic liquid primarily for the purposes of stabilization and purification Storage of A Stable Gas In Ionic Liquid SiF only, and not for the purposes of uptake of the fluid by the ionic liquid. Thus, a device or vessel is used to contact a small Stored In BMIMPF) amount of ionic liquid with the fluid. In this manner, a Sub stantially less amount of ionic liquid could be required to 50 A canister of BMIMPF) is prepared as described above. obtain the stabilization effect and the purification effect com The source gas, SiF or a gas mixture containing SiF, is pared to the previous illustrations wherein the unstable fluid then introduced into the canister, at 5 psig, until the uptake of could be taken up completely or dissolved within the ionic SiF is complete. The uptake can be determined gravimetri liquid. No decomposition products, or Substantially less cally, or by analytical methods. For example, the concentra decomposition products, are produced as a result of the con 55 tion or absolute amount of the SiF can be measured at the tact of the unstable fluid with the ionic liquid, producing a inlet of the canister and the outlet of the canister. SiF will stabilized fluid. The fluid mixture is stored within the ionic continue to be introduced until the inlet and outlet amounts liquid for a period of time of at least about 1 hour, during are equivalent, indicating the BMIMPF) fluid is saturated which period of time there is substantially no degradation of and cannot accept any further SiF under the existing condi the unstable fluid. A portion of the impurity is retained within 60 tions. At this time, the Source gas flow is stopped. the ionic liquid to produce a purified fluid. The purified fluid The BMIMIPF-charged canister is stored for a period of may then be released from the device. time. It is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored SiF. EXAMPLES The delivered gas is analyzed for SiF content. This can be 65 determined gravimetrically or analytically. The total amount For all the following Examples, a canister of ionic liquid is introduced is compared to the total amount removed to deter prepared by the following method. A stainless steel canister mine the loading factor of the cylinder. US 8,083,945 B2 17 18 Example 3 The EMIMAlCl4]-charged canister is then heated, a pres Sure differential is applied, or it is sparged with an inert gas, in Storage of An Unstable Compressed Liquefied Gas order to deliver the stored HC1. The delivered gas is analyzed In Ionic Liquid SbH. Stored In MTBS for HCl content. This can be determined gravimetrically or analytically. The total amount introduced is compared to the A canister of MTBS (methyl-tri-n-butylammonium meth total amount removed to determine the loading factor of the ylsulfate) is prepared as described above. cylinder. The source gas, SbH or a gas mixture containing SbH, is then introduced into the canister, at 5 psig, until the uptake of Example 6 SbH is complete. The uptake can be determined gravimetri 10 cally, or by analytical methods. For example, the concentra Purification of An Unstable Gas With Ionic tion or absolute amount of the SbH can be measured at the Liquid B.H. With BMIMPF) inlet of the canister and the outlet of the canister. SbH will continue to be introduced until the inlet and outlet amounts A canister of BMIMPF) is prepared as described above. are equivalent, indicating the MTBS fluid is saturated and 15 The source gas, BH or a gas mixture containing B.H., is cannot acceptany further SbH under the existing conditions. then analyzed while by-passing the BMIMIPF-charged At this time, the Source gas flow is stopped. The MTBS-charged canister is then stored for a period of canister, in order to determine the concentration of impurities. time. It is then heated, a pressure differential is applied, or it Once the impurity concentrations in the source gas have been is sparged with an inert gas, in order to deliver the stored established, source gas is flowed into the canister containing SbH. The delivered gas is analyzed for SbH content. This BMIMPF at a pressure of 5 psig. The delivered gas from can be determined gravimetrically or analytically. The total the outlet of the canister is analyzed for impurities. amount introduced is compared to the total amount removed Purification of the source BH is determined by the lack to determine the loading factor of the cylinder. of or a decrease in the impurities detected in the delivered gas 25 compared to the source gas. The capacity of the BMIMPF) Example 4 for impurities is calculated by measuring the total moles of impurities removed for the moles of BMIMPF) with which Storage of A Stable Compressed Liquefied Hydride the canister was charged. Gas In Ionic Liquid PH. In BMIMPF) 30 Example 7 A canister of BMIMPF) is prepared as described above. The source gas, PH, or a gas mixture containing PH, is Purification of A Stable Gas With Ionic then introduced into the canister, at 5 psig, until the uptake of Liquid SiF. With BMIMPF) PH is complete. The uptake can be determined gravimetri cally, or by analytical methods. For example, the concentra 35 A canister of BMIMPF) is prepared as described above. tion or absolute amount of the PH can be measured at the The source gas, SiF or a gas mixture containing SiF, is inlet of the canister and the outlet of the canister. PH will then analyzed while by-passing the BMIMIPF-charged continue to be introduced until the inlet and outlet amounts canister, in order to determine the concentration of impurities. are equivalent, indicating the BMIMPF) fluid is saturated Once the impurity concentrations in the source gas have been and cannot accept any further PH under the existing condi 40 established, source gas is flowed into the canister containing tions. At this time, the source gas flow is stopped. BMIMPF at a pressure of 5 psig. The delivered gas from The BMIMIPF-charged canister is then heated, a pres the outlet of the canister is analyzed for impurities. Sure differential is applied, or it is sparged with an inert gas, in Purification of the source SiF is determined by the lack of, order to deliver the stored PH. The delivered gas is analyzed or a decrease in the impurities detected in the delivered gas for PH content. This can be determined gravimetrically or 45 compared to the source gas. The capacity of the BMIMPF) analytically. The total amount introduced is compared to the for impurities is calculated by measuring the total moles of total amount removed to determine the loading factor of the impurities removed for the moles of BMIMPF) with which cylinder. the canister was charged.

Example 5 50 Example 8 Storage of A Stable Compressed Liquefied Acid Gas Purification of An Unstable Compressed Liquefied Gas In Acidic Ionic Liquid HCl In EMIMAlCla With Ionic Liquid SbH. With MTBS A canister of MTBS is prepared as described above. A canister of EMIMAlCl is prepared as described 55 The source gas, SbH or a gas mixture containing SbH, is above. then analyzed while by-passing the MTBS-charged canister, The source gas, HCl or a gas mixture containing HCl, is in order to determine the concentration of impurities. Once then introduced into the canister, at the vapor pressure of HCl, the impurity concentrations in the Source gas have been estab until the uptake of HCl is complete. The uptake can be deter lished, source gas is flowed into the canister containing mined gravimetrically, or by analytical methods. For 60 MTBS at a pressure of 5 psig. The delivered gas from the example, the concentration or absolute amount of the HCl can outlet of the canister is analyzed for impurities. be measured at the inlet of the canister and the outlet of the Purification of the source SbH is determined by the lack canister. HCl will continue to be introduced until the inlet and of or a decrease in the impurities detected in the delivered gas outlet amounts are equivalent, indicating the EMIMAlCl4] compared to the source gas. The capacity of the MTBS for fluid is saturated and cannot accept any further HCl under the 65 impurities is calculated by measuring the total moles of impu existing conditions. At this time, the source gas flow is rities removed for the moles of MTBS with which the canister stopped. was charged. US 8,083,945 B2 19 20 Example 9 the total moles of HO removed for the moles of EMIM AlCl with which the canister was charged. Purification of An Unstable Compressed Liquefied Gas In the Liquid Phase With Ionic Liquid SbH Example 12 With MTBS Purification of A Stable Compressed Liquefied Gas A canister of MTBS is prepared as described above. In the Liquid Phase With Ionic Liquid NH With The liquid phase source material, SbH, is flowed through EMIMAcetat the apparatus, by-passing the MTBS-charged canister, vapor ized, and analyzed in order to determine the concentration of 10 A canister of EMIMAcetat is prepared as described impurities. Once the impurity levels in the source fluid have above. been established, liquid phase source material is flowed into The liquid phase source material, NH, is flowed through the canister containing MTBS, at the vapor pressure of SbH. the apparatus, by-passing the EMIMAcetat-charged canis The delivered liquid from the outlet of the canister is vapor 15 ter, vaporized, and analyzed in order to determine the con ized and analyzed to determine the concentration of the impu centration of impurities. Once the impurity levels in the rities. Source fluid have been established, liquid phase source mate Purification of the source SbH is determined by the lack rial is flowed into the canister containing EMIMAcetat, at of, or a decrease in the impurities detected in the delivered the vapor pressure of NH). The delivered liquid from the liquid when compared to the source liquid, as determined by outlet of the canister is vaporized and analyzed to determine analysis in the vapor phase. The capacity of the MTBS for the concentration of the impurities. impurities is calculated by measuring the total moles of impu Purification of the source NH is determined by the lack of, rities removed for the moles of MTBS with which the canister or a decrease in the impurities detected in the delivered liquid was charged. when compared to the source liquid, as determined by analy 25 sis in the vapor phase. The capacity of the EMIMLAcetat for Example 10 impurities is calculated by measuring the total moles of impu rities removed for the moles of EMIMAcetat with which the Purification of A Stable Compressed Liquefied canister was charged. Hydride Gas With Ionic Liquid PH. With BMIMPF) 30 Example 13 A canister of BMIMPF) is prepared as described above. Stabilization of An Unstable Gas With Ionic The source gas, PH or a gas mixture containing PH, is Liquid B.H. With BMIMPF) analyzed while by-passing the BMIMIPF-charged canister, in order to determine the concentration of impurities. Once 35 A canister of BMIMPF) is prepared as described above. the impurity concentrations in the Source gas have been estab The source gas, BH or a gas mixture containing B.H., is lished, source gas is flowed into the canister containing analyzed while by-passing the BMIMIPF-charged canister, BMIMPF at the vapor pressure of PH. The delivered gas in order to determine the concentration of BH and decom from the outlet of the canister is analyzed for impurities. 40 position products. Once these concentrations in the Source Purification of the stored PH is determined by the lack of gas have been established, Source gas is flowed into the can or a decrease in the impurities detected in the delivered gas ister containing BMIMPF) until it has equilibrated to a compared to the source gas. The capacity of the BMIMPF) pressure of 5 psig. At this time, the flow of the source material for impurities is calculated by measuring the total moles of is stopped. impurities removed for the moles of BMIMPF) with which 45 With the source gas flow off, the gas from the outlet of the the canister was charged. canister containing the BMIMPF) is then analyzed for BH and decomposition products. Example 11 Stabilization of the source BH is determined by the lack of or a decrease in the decomposition products detected in the Purification of A Stable Compressed Liquefied Acid 50 delivered gas compared to the source gas, in addition to Gas With Ionic Liquid-HCl with EMIMAlCl quantitative recovery of BH. A canister of EMIMAlCl is prepared as described Example 14 above. The source gas, HCl or a gas mixture containing HCl, is 55 Stabilization of An Unstable Compressed Liquefied analyzed while by-passing the EMIMAIC1-charged canis Gas In the Liquid Phase With Ionic Liquid SbH ter, in order to determine the concentration of moisture. Once With MTBS the H2O concentration in the source gas have been estab lished, source gas is flowed into the canister containing A canister of MTBS is prepared as described above. EMIMAlCl4 at a pressure of 5 psig. The gas is bubbled 60 The liquid phase source material, SbH, is flowed through through the EMIMAICl inside the canister and the deliv the apparatus, by-passing the MTBS-charged canister, vapor ered gas at the outlet of the canister is analyzed to measure the ized, and analyzed in order to determine the concentration of moisture content. decomposition products. Once the decomposition levels in Purification of the stored HCl is determined by the lack of the source fluid have been established, liquid phase source or a decrease in the H2O impurity concentration detected in 65 material is flowed into the canister containing MTBS, at the the delivered gas compared to the source gas. The capacity of vapor pressure of SbH. At this time, the flow of the source the EMIMAlCl for impurities is calculated by measuring material is stopped. US 8,083,945 B2 21 22 With the source flow off, the delivered liquid from the from the canister compared to the Source gas. The capacity of outlet of the canister is vaporized and analyzed for SbH and the BMIMPF) for impurities is calculated by measuring the decomposition products. total moles of impurities removed for the moles of BMIM Stabilization of the source SbH is determined by the lack IPF with which the canister was charged. of or a decrease in the decomposition products detected in the 5 delivered gas compared to the Source gas, in addition to Example 17 quantitative recovery of SbH. Storage And Purification of An Unstable Example 15 Compressed Liquefied Gas In Ionic Liquid-SbH 10 With MTBS Storage And Purification of An Unstable Gas In Ionic Liq uid B.H. With BMIMPF) A canister of MTBS is prepared as described above. A canister of BMIMPF) is prepared as described above. The source gas, SbH or a gas mixture containing SbH, is The source gas, BH or a gas mixture containing B.H., is analyzed while by-passing the MTBS-charged canister, in analyzed while by-passing the BMIMIPF-charged canister, 15 in order to determine the concentration of impurities. Once order to determine the concentration of impurities. Once the the impurity concentrations in the Source gas have been estab impurity concentrations in the Source gas have been estab lished, source gas is flowed into the canister containing lished, source gas is flowed into the canister containing BMIMPF) at a pressure of 5 psig, until the uptake of BH MTBS at a pressure of 5 psig, until the uptake of SbH is is complete. The uptake can be determined gravimetrically, or complete. The uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or by analytical methods. For example, the concentration or absolute amount of the BH can be measured at the inlet of absolute amount of the SbH can be measured at the inlet of the canister and the outlet of the canister. B.H. will continue the canister and the outlet of the canister. SbH will continue to be introduced until the inlet and outlet concentrations are to be introduced until the inlet and outlet concentrations are equivalent, indicating the BMIMPF) fluid is saturated and 25 equivalent, indicating the MTBS fluid is saturated and cannot cannot accept any further B.H. under the existing conditions. accept any further SbH under the existing conditions. At this At this time, the Source gas flow is stopped. time, the source gas flow is stopped. The BMIMIPF-charged canister is then heated, a pres The MTBS-charged canister is then heated, a pressure Sure differential is applied, or it is sparged with an inert gas, in differential is applied, or it is sparged with an inert gas, in order to deliver the stored B.H. The delivered gas from the 30 order to deliver the stored SbH. The delivered gas from the outlet of the canister is analyzed for impurities. outlet of the canister is analyzed for impurities. The canister is then stored for a period of time. Samples of Purification of the source SbH is determined by the lack BH are taken at time intervals in order to determined the of or a decrease in the impurities detected in the delivered gas stability of the BH in the BMIMPF). Purification of the from the canister compared to the Source gas. The capacity of source BH is determined by the lack of, or a decrease in the 35 the MTBS for impurities is calculated by measuring the total impurities detected in the delivered gas from the canister moles of impurities removed for the moles of MTBS with compared to the source gas. The capacity of the BMIMPF) which the canister was charged. for impurities is calculated by measuring the total moles of impurities removed for the moles of BMIMPF) with which Example 18 the canister was charged. 40 Storage And Purification of A Stable Compressed Example 16 Liquefied Gas In Ionic Liquid PH. With BMIMPF) Storage And Purification of A Stable Gas In Ionic Liquid SiF. With BMIMPF) 45 A canister of BMIMPF) is prepared as described above. The source gas, PH or a gas mixture containing PH, is A canister of BMIMPF) is prepared as described above. analyzed while by-passing the BMIMIPF-charged canister, The source gas, SiF or a gas mixture containing SiF, is in order to determine the concentration of impurities. Once analyzed while by-passing the BMIMIPF-charged canister, the impurity concentrations in the Source gas have been estab in order to determine the concentration of impurities. Once 50 lished, source gas is flowed into the canister containing the impurity concentrations in the Source gas have been estab BMIMPF at a pressure of 5 psig, until the uptake of PH is lished, source gas is flowed into the canister containing complete. The uptake can be determined gravimetrically, or BMIMPF at a pressure of 5 psig, until the uptake of SiF is by analytical methods. For example, the concentration or complete. The uptake can be determined gravimetrically, or absolute amount of the PH can be measured at the inlet of the by analytical methods. For example, the concentration or 55 canister and the outlet of the canister. PH will continue to be absolute amount of the SiF can be measured at the inlet of the introduced until the inlet and outlet concentrations are canister and the outlet of the canister. SiF will continue to be equivalent, indicating the BMIMPF) liquid is saturated and introduced until the inlet and outlet concentrations are cannot accept any further PH under the existing conditions. equivalent, indicating the BMIMPF) fluid is saturated and At this time, the source gas flow is stopped. cannot accept any further SiF under the existing conditions. 60 The BMIMIPF-charged canister is then heated, a pres At this time, the Source gas flow is stopped. Sure differential is applied, or it is sparged with an inert gas, in The BMIMIPF-charged canister is then heated, a pres order to deliver the stored PH. The delivered gas from the Sure differential is applied, or it is sparged with an inert gas, in outlet of the canister is analyzed for impurities. order to deliver the stored SiF. The delivered gas from the Purification of the source PH is determined by the lack of, outlet of the canister is analyzed for impurities. 65 or a decrease in the impurities detected in the delivered gas Purification of the source SiF is determined by the lack of from the canister compared to the Source gas. The capacity of or a decrease in the impurities detected in the delivered gas the BMIMPF) for impurities is calculated by measuring the US 8,083,945 B2 23 24 total moles of impurities removed for the moles of BMIM Example 21 IPF with which the canister was charged. Storage And Stabilization of An Unstable Example 19 Compressed Liquefied Gas With Ionic Liquid SbH. With MTBS Storage And Purification of A Stable Compressed Liquefied Gas In Acidic Ionic Liquid HCl With A canister of MTBS is prepared as described above. EMIMAlCl The source gas, SbH or a gas mixture containing SbH, is analyzed while by-passing the MTBS-charged canister, in A canister of EMIMAlCl is prepared as described 10 order to determine the concentration of SbH and decompo above. sition products. Once these concentrations in the Source gas The source gas, HCl or a gas mixture containing HCl, is have been established, source gas is flowed into the canister analyzed while by-passing the EMIMAIC1-charged canis containing MTBS at a pressure of 5 psig, until the uptake of ter, in order to determine the concentration of impurities. SbH is complete. The uptake can be determined gravimetri 15 cally, or by analytical methods. For example, the concentra Once the impurity concentrations in the Source gas have been tion or absolute amount of the SbH can be measured at the established, Source gas is flowed into the canister containing inlet of the canister and the outlet of the canister. SbH will EMIMAlCl4 at a pressure of 5 psig, until the uptake of HCl continue to be introduced until the inlet and outlet concentra is complete. The uptake can be determined gravimetrically, or tions are equivalent, indicating the MTBS fluid is saturated by analytical methods. For example, the concentration or and cannot accept any further SbH under the existing con absolute amount of the HCl can be measured at the inlet of the ditions. At this time, the source gas flow is stopped. canister and the outlet of the canister. HCl will continue to be The MTBS-charged canister is then heated, a pressure introduced until the inlet and outlet concentrations are differential is applied, or it is sparged with an inert gas, in equivalent, indicating the EMIMAlCl liquid is saturated order to deliver the stored SbH. The delivered gas from the outlet of the canister is analyzed for SbH and decomposition and cannot accept any further HCl under the existing condi 25 products. tions. At this time, the source gas flow is stopped. Stabilization of the source SbH is determined by the lack The EMIMAlCl4]-charged canister is then heated, a pres of or a decrease in the decomposition products detected in the Sure differential is applied, or it is sparged with an inert gas, in delivered gas compared to the source gas, in addition to order to deliver the stored HC1. The delivered gas from the quantitative recovery of SbH. outlet of the canister is analyzed for impurities. 30 Purification of the source HCl is determined by the lack of, Example 22 or a decrease in the impurities detected in the delivered gas from the canister compared to the Source gas. The capacity of Stabilization And Purification of An Unstable Gas the EMIMAlCl for impurities is calculated by measuring With Ionic Liquid B.H. With BMIMPF) the total moles of impurities removed for the moles of EMIM 35 AlCl with which the canister was charged. A canister of BMIMPF) is prepared as described above. The source gas, BH or a gas mixture containing B.H., is Example 20 analyzed while by-passing the BMIMIPF-charged canister, in order to determine the concentration of BH, impurities, Storage And Stabilization of An Unstable Gas In 40 and decomposition products. Once these concentrations in Ionic Liquid B.H. With BMIMPF) the source gas have been established, source gas is flowed into the canistercontaining BMIMPFI until it has equilibrated at A canister of BMIMPF) is prepared as described above. a pressure of 5 psig. At this time, the Source gas flow is The source gas, BH or a gas mixture containing B.H., is stopped. analyzed while by-passing the BMIMIPF-charged canister, 45 With the source gas flow off, the gas from the outlet of the in order to determine the concentration of BH and decom canister containing the BMIMPFI is then analyzed for position products. Once these concentrations in the Source BH, impurities, and decomposition products. Stabilization of the source BH is determined by the lack gas have been established, Source gas is flowed into the can of or a decrease in the decomposition products detected in the ister containing BMIMPF) at a pressure of 5 psig, until the delivered gas compared to the source gas, in addition to uptake of BHe is complete. The uptake can be determined 50 quantitative recovery of BH. gravimetrically, or by analytical methods. For example, the Purification of the source BH is determined by the lack concentration or absolute amount of the BH can be mea of or a decrease in the impurities detected in the delivered gas sured at the inlet of the canister and the outlet of the canister. from the canister compared to the Source gas. The capacity of BH will continue to be introduced until the inlet and outlet the BMIMPF) for impurities is calculated by measuring the concentrations are equivalent, indicating the BMIMPF) 55 total moles of impurities removed for the moles of BMIM fluid is saturated and cannot accept any further B.H. under IPF with which the canister was charged. the existing conditions. At this time, the source gas flow is stopped. Example 23 The BMIMIPF-charged canister is then heated, a pres Sure differential is applied, or it is sparged with an inert gas, in 60 Stabilization And Purification of An Unstable order to deliver the stored B.H. The delivered gas from the Compressed Liquefied Gas With Ionic outlet of the canister is analyzed for BH and decomposition Liquid SbH. With MTBS products. Stabilization of the source BH is determined by the lack A canister of MTBS is prepared as described above. of or a decrease in the decomposition products detected in the 65 The source gas, SbH or a gas mixture containing SbH, is delivered gas compared to the Source gas, in addition to analyzed while by-passing the MTBS-charged canister, in quantitative recovery to the source material. order to determine the concentration of SbH, impurities, and US 8,083,945 B2 25 26 decomposition products. Once these concentrations in the Example 25 Source gas have been established, source gas is flowed into the canister containing MTBS until it has equilibrated at 5 psig. Storage, Purification, And Stabilization of An At this time, the Source gas flow is stopped. Unstable Compressed Liquefied Gas With Ionic With the source gas flow off, the gas from the outlet of the Liquid SbH. With MTBS canister containing the MTBS is then analyzed for SbH, A canister of MTBS is prepared as described above. impurities, and decomposition products. The source gas, SbH or a gas mixture containing SbH, is The MTBS-charged canister is then heated, a pressure analyzed while by-passing the MTBS-charged canister, in differential is applied, or it is sparged with an inert gas, in 10 order to determine the concentration of SbH, impurities, and order to deliver the stored SbH. The delivered gas from the decomposition products. Once these concentrations in the outlet of the canister is analyzed for SbH, impurities, and Source gas have been established, Source gas is flowed into the decomposition products. canister containing MTBS at a pressure of 5 psig, until the Stabilization of the source SbH is determined by the lack uptake of SbH is complete. The uptake can be determined 15 gravimetrically, or by analytical methods. For example, the of or a decrease in the decomposition products detected in the concentration or absolute amount of the SbH can be mea delivered gas compared to the Source gas, in addition to sured at the inlet of the canister and the outlet of the canister. quantitative recovery of SbH. SbH will continue to be introduced until the inlet and outlet Purification of the source SbH is determined by the lack concentrations are equivalent, indicating the MTBS fluid is of or a decrease in the impurities detected in the delivered gas saturated and cannot accept any further SbH under the exist from the canister compared to the Source gas. The capacity of ing conditions. At this time, the source gas flow is stopped. The MTBS-charged canister is then heated, a pressure the MTBS for impurities is calculated by measuring the total differential is applied, or it is sparged with an inert gas, in moles of impurities removed for the moles of MTBS with order to deliver the stored SbH. The delivered gas from the which the canister was charged. 25 outlet of the canister is analyzed for SbH, impurities, and decomposition products. Example 24 Stabilization of the source SbH is determined by the lack of or a decrease in the decomposition products detected in the Storage, Purification, And Stabilization of An delivered gas compared to the source gas, in addition to Unstable Gas With Ionic Liquid B.H. With 30 quantitative recovery of SbH. BMIMPF) Purification of the source SbH is determined by the lack of, or a decrease in the impurities detected in the delivered gas A canister of BMIMPF) is prepared as described above. from the canister compared to the Source gas. The capacity of The source gas, BH or a gas mixture containing B.H., is the MTBS for impurities is calculated by measuring the total analyzed while by-passing the BMIMIPF-charged canister, 35 moles of impurities removed for the moles of MTBS with which the canister was charged. in order to determine the concentration of BH, impurities, The embodiments described above and shown herein are and decomposition products. Once these concentrations in illustrative and not restrictive. The scope of the invention is the Source gas have been established, Source gas is flowed into indicated by the claims rather than by the foregoing descrip the canister containing BMIMPF) at a pressure of 5 psig, 40 tion and attached drawings. The invention may be embodied until the uptake of BH is complete. The uptake can be in other specific forms without departing from the spirit of the determined gravimetrically, or by analytical methods. For invention. Accordingly, these and any other changes which come within the scope of the claims are intended to be example, the concentration or absolute amount of the BH embraced therein. can be measured at the inlet of the canister and the outlet of the 45 canister. B.H. will continue to be introduced until the inlet What is claimed is: and outlet concentrations are equivalent, indicating the 1. A method of stabilizing an unstable fluid for shipment to BMIMPF) fluid is saturated and cannot accept any further an end user, comprising: BH under the existing conditions. At this time, the Source providing a cylinder containing an ionic liquid therein gas flow is stopped. 50 wherein said cylinder consists of a single storage space that is formed by inserting a valve assembly into said The BMIMIPF-charged canister is then heated, a pres cylinder, wherein said valve assembly is operable to Sure differential is applied, or it is sparged with an inert gas, in introduce the unstable fluid into said cylinder; order to deliver the stored B.H. The delivered gas from the contacting the unstable fluid with said ionic liquid wherein outlet of the canister is analyzed for B.H., impurities, and 55 said ionic liquid is not substantially chemically reactive decomposition products. with said unstable fluid; and Stabilization of the source BH is determined by the lack shipping said cylinder containing a mixture of the unstable of or a decrease in the decomposition products detected in the fluid and said ionic liquid to an end user wherein the delivered gas compared to the Source gas, in addition to unstable fluid may be dispensed from said cylinder 60 while said ionic liquid remains in said cylinder. quantitative recovery of B.H. 2. The method of claim 1 wherein the unstable fluid is Purification of the source BH is determined by the lack selected from the group consisting of digermane, borane, of or a decrease in the impurities detected in the delivered gas diborane, disilane, fluorine, halogenated oxy-hydrocarbons, from the canister compared to the Source gas. The capacity of hydrogen selenide, Stilbene, nitric oxide, organometallics and the BMIMPF) for impurities is calculated by measuring the 65 mixtures thereof. total moles of impurities removed for the moles of BMIM 3. The method of claim 1 wherein the unstable fluid is IPF with which the canister was charged. contacted with said ionic liquid for at least about 24 hours. US 8,083,945 B2 27 28 4. The method of claim 1 wherein the unstable fluid is N',N',N'-pentamethyl-N'-isopropylguanidinium tris contacted with said ionic liquid for at least about 7 days. (pentafluoroethyl)trifluoromethanesulfonate, hexam ethylguanidinium trs(pentafluoroethyl)trifluorophos 5. The method of claim 1 wherein said ionic liquid is phate, hexamethylguanidinium selected from the group consisting of pyridinium salts, pyr trifluoromethanesulfonate, S-methyl-N,N,N',N'-tetram rolidinium salts, phosphonium salts, ammonium salts, 5 ethylisouronium trifluoromethanesulfonate, O-methyl tetralkylammonium salts, guanidinium salts, uronium salts, N.N.N',N'-tetramethylisouronium tris(pentafluoroet and compounds comprising: hyl)trifluorophosphate, O-ethyl-N,N,N',N'- a cation component selected from the group consisting of tetramethylisouronium tris(pentafluoroethyl) mono-Substituted imidazoliums, di-substituted imida trifluorophosphate, S-ethyl-N,N,N',N'- Zoliums, tri-substituted imidazoliums, pyridiniums, pyr 10 tetramethylisouronium trifluoromethanesulfonate, rolidinium salts, phosphoniums, ammoniums, tetralky S-ethyl-N,N,N',N'-tetramethylisothiouronium trifluo romethanesulfonate; and lammoniums, guanidiniums, and uroniums; and an anion component selected from the group consisting of an anion component selected from the group consisting of chloride, bromide, iodide, methyl sulfate, ethyl sulfate, acetate, cyanates, decanoates, halogenides, Sulfates, Sul butyl sulfate, hexyl sulfate, octyl sulfate, hydrogen sul fonates, amides, imides, methanes, antimonates, tetra 15 fate, methane Sulfonate, dodecylbenzene Sulfonate, chloroaluminate, thiocyanate, tosylate, carboxylate, dimethyleneglycolmonomethylether sulfate, trifluo cobalt-tetracarbonyl, trifluoroacetate and tris(trifluo romethane Sulfonate, dicyanamide, bis(pentafluoroeth romethylsulfonyl)methide; and ylsulfonyl)imide, bis(trifluoromethylsulfonyl)imide, mixtures thereof. bis(trifluoromethyl)imide, tetrafluoroborate, tetracy 6. The method of claim 1 wherein said ionic liquid com anoborate, bisoxalato(2-)borate, bis 1,2-benzene prises: diolato(2-)-O,O'borate, bissalicylato(2-)borate, a cation component selected from the group consisting of hexafluorophosphate, diethylphosphate, bis(pentafluo 1-methylimidazolium tosylate, 1-methylimidazolium roethyl)phosphinate, tetrafluoroborate, 1-methylimidazolium hexafluoro tris(pentafluoroethyl)trifluorophosphate, tris(nonafluorobu phosphate, 1-methylimidazolium trifluoromethane 25 tyl)trifluorophosphate, hexafluoroantimonate. sulfonate, 1-butylimidazolium tosylate, 1-butylimida 7. The method of claim 1 wherein said cylinder is config Zolium tetrafluoroborate, 1-methylimidazolium ured to bubble the unstable fluid through said ionic liquid. hexafluorophosphate, 1-methylimidazolium trifluo 8. The method of claim 1 wherein said cylinder is config romethanesulfonate, 1,3-dimethylimidiazolium meth ured to mechanically agitate the unstable fluid and said ionic ylsulfate, 1,3-dimethylimidiazolium trifluoromethane 30 liquid. Sulfonate, 1,3-dimethylimidiazolium bis 9. The method of claim 1 wherein dispensing the unstable (pentafluoroethyl)phosphinate, 1-ethyl-3- fluid from said cylinder separately from said ionic liquid methylimidiazolium thiocyanate, 1-ethyl-3- occurs by controlling either the temperature and/or the pres methylimidiazolium dicyanamide, 1-ethyl-3- Sure gradient of said ionic liquid. methylimidiazolium cobalt-tetracarbonyl, 1-propyl-3- 10. A method of dispensing an unstable fluid in contact methylimidazolium chloride, 1-butyl-3- 35 with an ionic liquid all of which has been stored within a methylimidazolium hexafluoroantimonate, cylinder having a valve assembly by a source gas manufac 1-octadecyl-3-methylimidazolium bis(trifluoromethyl turer and shipped to an end user, comprising: sulfonyl)imide, 1-benzyl-3-methylimidazolium bro receiving the cylinder consisting of a single storage space, mide, 1-phenylpropyl-3-methylimidazolium chloride, wherein said single storage space contains a mixture of 1-ethyl-2,3-dimethylimidazolium chloride, 1-butyl-2,3- 40 the unstable fluid and the ionic liquid wherein the dimethylimidazolium octylsulfate, 1-propyl-2,3-dim unstable fluid is contacted for a controllable period of ethylimidazolium chloride, 1-hexyl-2,3-dimethylimida time with the ionic liquid for take-up of the unstable fluid Zolium tetrafluoroborate, 1-hexadecyl-2,3- by the ionic liquid that is not substantially chemically dimethylimidazolium iodide, pyridinium ionic liquids reactive with the unstable fluid; include n-ethylpyridinium chloride, n-butylpyridinium 45 placing the cylinder in fluid communication with a gas dis bromide, n-hexylpyridinium n-octylpyridinium chlo tribution system wherein the unstable fluid has undergone ride, 3-methyl-n-butylpyridinium methylsulfate, relatively no decomposition within the cylinder while in con 3-ethyl-n-butylpyridinium hexafluorophosphate, 4-me tact with the ionic liquid; and thyl-n-butylpyridinium bromide, 3,4-dimethyl-n-bu releasing the unstable fluid from the cylinder through the tylpyridinium chloride, 3,5-dimethyl-n-butylpyri 50 valve assembly which is operable to introduce and release the dinium chloride, 1,1-dimethylpyrrolidinium tris unstable fluid into and from the single storage space of the (pentafluoroethyl)trifluorophosphate, 1-ethyl-1- cylinder separately from the ionic liquid by controlling either methylpyrrolidinium dicyanamide, 1,1- the temperature and/or the pressure gradient of the ionic dipropylpyrrolidinium bis(trifluoromethylsulfonyl) liquid. imide, 1-butyl-1-methylpyrrolidinium bromide, 11. The method of claim 10 wherein the unstable fluid is 1-butyl-1-ethylpyrrolidinium bromide, 1-octyl-1-meth 55 selected from the group consisting of digermane, borane, ylpyrrolidinium dicyanamide, tetraoctylphosphonium diborane, disilane, fluorine, halogenated oxy-hydrocarbons, bromide, tetrabutylphosphonium bisoxalato(2-)-bo hydrogen selenide, Stilbene, nitric oxide, organometallics and rate, trihexyl(tetradecyl)phosphonium dicyanamide, mixtures thereof. benzyltriphenylphosphonium bis(trifluoromethyl) 12. The method of claim 10 wherein the unstable fluid is imide, tri-iso-butyl(methyl)phosphonium tosylate, ethyl 60 contacted with the ionic liquid for at least about 24 hours. (tributyl)phosphonium diethylphosphate, tributyl(hexa 13. The method of claim 10 wherein the unstable fluid is decyl)phosphonium chloride, tetramethylammonium contacted with the ionic liquid for at least about 7 days. bis(trifluoromethylsulfonyl)imide, tetraethylammo 14. The method of claim 10 wherein the ionic liquid is nium bis-Salicylato-(2-)-borate, tetrabutylammonium selected from the group consisting of pyridinium salts, pyr tetracyanoborate, methyltrioctylammonium trifluoroac 65 rolidinium salts, phosphonium salts, ammonium salts, etat, N.N.N',N',N'-pentamethyl-N'-isopropylguani tetralkylammonium salts, guanidinium salts, uronium salts, dinium tris(pentafluoroethyl)trifluorophosphate, N.N. and compounds comprising: US 8,083,945 B2 29 30 a cation component selected from the group consisting of sulfonate, S-methyl-N,N,N',N'-tetramethylisouronium mono-Substituted imidazoliums, di-substituted imida trifluoromethanesulfonate, O-methyl-N,N,N',N'-tet Zoliums, tri-substituted imidazoliums, pyridiniums, pyr ramethylisouronium tris(pentafluoroethyl)trifluoro rolidinium salts, phosphoniums, ammoniums, tetralky phosphate, O-ethyl-N,N,N',N'-tetramethylisouronium lammoniums, guanidiniums, and uroniums; and 5 tris(pentafluoroethyl)trifluorophosphate, S-ethyl-N,N. an anion component selected from the group consisting of N',N'-tetramethylisouronium trifluoromethane acetate, cyanates, decanoates, halogenides, Sulfates, Sul sulfonate, S-ethyl-N,N,N',N'-tetramethylisothiouro fonates, amides, imides, methanes, antimonates, tetra nium trifluoromethanesulfonate; and chloroaluminate, thiocyanate, tosylate, carboxylate, an anion component selected from the group consisting of cobalt-tetracarbonyl, trifluoroacetate and tris(trifluo 10 chloride, bromide, iodide, methyl sulfate, ethyl sulfate, romethylsulfonyl)methide; and butyl sulfate, hexyl sulfate, octyl sulfate, hydrogen sul mixtures thereof. fate, methane Sulfonate, dodecylbenzene Sulfonate, 15. The method of claim 10 wherein the ionic liquid com dimethyleneglycolmonomethylether sulfate, trifluo prises romethane Sulfonate, dicyanamide, bis(pentafluoroeth a cation component selected from the group consisting of 15 ylsulfonyl)imide, bis(trifluoromethylsulfonyl)imide, 1-methylimidazolium tosylate, 1-methylimidazolium bis(trifluoromethyl)imide, tetrafluoroborate, tetracy tetrafluoroborate, 1-methylimidazolium hexafluoro anoborate, bisoxalato(2-)borate, bis 1,2-benzene phosphate, 1-methylimidazolium trifluoromethane diolato(2-)-O,O'borate, bissalicylato(2-)borate, sulfonate, 1-butylimidazolium tosylate, 1-butylimida hexafluorophosphate, diethylphosphate, bis(pentafluo Zolium tetrafluoroborate, 1-methylimidazolium roethyl)phosphinate, tris(pentafluoroethyl)trifluoro hexafluorophosphate, 1-methylimidazolium trifluo phosphate, tris(nonafluorobutyl)trifluorophosphate, romethanesulfonate, 1,3-dimethylimidiazolium meth hexafluoroantimonate. ylsulfate, 1,3-dimethylimidiazolium trifluoromethane 16. The method of claim 10 wherein the cylinder is con Sulfonate, 1,3-dimethylimidiazolium bis figured to bubble the unstable fluid through the ionic liquid. (pentafluoroethyl)phosphinate, 1-ethyl-3- 25 17. The method of claim 10 wherein the cylinder is con methylimidiazolium thiocyanate, 1-ethyl-3- figured to mechanically agitate the unstable fluid and the methylimidiazolium dicyanamide, 1-ethyl-3- ionic liquid. methylimidiazolium cobalt-tetracarbonyl, 1-propyl-3- 18. The method of claim 10 wherein the unstable fluid is a methylimidazolium chloride, 1-butyl-3- gaS. methylimidazolium hexafluoroantimonate, 30 19. The method of claim 10 wherein the unstable fluid is a 1-octadecyl-3-methylimidazolium bis(trifluoromethyl liquid. sulfonyl)imide, 1-benzyl-3-methylimidazolium bro 20. The method of claim 10 wherein contacting the mide, 1-phenylpropyl-3-methylimidazolium chloride, unstable fluid with the ionic liquid comprises spraying the 1-ethyl-2,3-dimethylimidazolium chloride, 1-butyl-2,3- unstable fluid through the ionic liquid. dimethylimidazolium octylsulfate, 1-propyl-2,3-dim 35 21. A method of Stabilizing an unstable fluid, comprising: ethylimidazolium chloride, 1-hexyl-2,3-dimethylimida providing a cylinder consisting of a single storage space Zolium tetrafluoroborate, 1-hexadecyl-2,3- that is formed by inserting a valve assembly into said dimethylimidazolium iodide, pyridinium ionic liquids cylinder, wherein said valve assembly is configured for include n-ethylpyridinium chloride, n-butylpyridinium selectively dispensing the unstable fluid; bromide, n-hexylpyridinium n-octylpyridinium chlo 40 providing anionic liquid within said single storage space of ride, 3-methyl-n-butylpyridinium methylsulfate, said cylinder wherein said ionic liquid is selected based 3-ethyl-n-butylpyridinium hexafluorophosphate, 4-me on the solubility of the unstable fluid and is not substan thyl-n-butylpyridinium bromide, 3,4-dimethyl-n-bu tially chemically reactive with the unstable fluid; tylpyridinium chloride, 3,5-dimethyl-n-butylpyri introducing the unstable fluid into said single storage space dinium chloride, 1,1-dimethylpyrrolidinium tris 45 of said cylinder through said valve assembly which is (pentafluoroethyl)trifluorophosphate, 1-ethyl-1- operable to introduce the unstable fluid into said cylin methylpyrrolidinium dicyanamide, 1,1- der; dipropylpyrrolidinium bis(trifluoromethylsulfonyl) contacting the unstable fluid with said ionic liquid wherein imide, 1-butyl-1-methylpyrrolidinium bromide, the unstable fluid is taken up by said ionic liquid in a 1-butyl-1-ethylpyrrolidinium bromide, 1-octyl-1-meth 50 manner in which no chemical bonds are broken; and ylpyrrolidinium dicyanamide, tetraoctylphosphonium shipping said cylinder containing a mixture of the unstable bromide, tetrabutylphosphonium bisoxalato(2-)-bo fluid and said ionic liquid to an end user wherein the rate, trihexyl(tetradecyl)phosphonium dicyanamide, unstable fluid may be dispensed from said cylinder, benzyltriphenylphosphonium bis(trifluoromethyl) separately from said ionic liquid, by controlling either imide, tri-iso-butyl(methyl)phosphonium tosylate, ethyl 55 the temperature and/or the pressure gradient of the ionic (tributyl)phosphonium diethylphosphate, tributyl(hexa liquid. decyl)phosphonium chloride, tetramethylammonium 22. The method of claim 21 wherein the amount of said bis(trifluoromethylsulfonyl)imide, tetraethylammo ionic liquid within said cylinder is Small compared to the nium bis-Salicylato-(2-)-borate, tetrabutylammonium amount of the unstable fluid within said cylinder. tetracyanoborate, methyltrioctylammonium trifluoroac 60 23. The method of claim 21 wherein the unstable fluid is etat, N.N.N',N',N'-pentamethyl-N'-isopropylguani selected from the group consisting of digermane, borane, dinium tris(pentafluoroethyl)trifluorophosphate, N.N. diborane, disilane, fluorine, halogenated oxy-hydrocarbons, N',N',N'-pentamethyl-N'-isopropylguanidinium tris hydrogen selenide, Stilbene, nitric oxide, organometallics, and (pentafluoroethyl)trifluoromethanesulfonate, mixtures thereof. hexamethylguanidinium trs(pentafluoroethyl)trifluoro 65 phosphate, hexamethylguanidinium trifluoromethane