US007896954B2

(12) United States Patent (10) Patent No.: US 7,896,954 B2 Wyse et al. (45) Date of Patent: *Mar. 1, 2011

(54) FLUID STORAGE AND PURIFICATION (56) References Cited METHOD AND SYSTEM U.S. PATENT DOCUMENTS (75) Inventors: Carrie L. Wyse, Longmont, CO (US); 2,201,550 A 5/1940 Van Dijcket al. Robert Torres, Jr., Parker, CO (US); 2,343,712 A * 3/1944 Ruthruff ...... 585,627 Joseph V. Vininski, Boulder, CO (US) 2,386,523 A 10/1945 Welling (73) Assignee: Matheson Tri-Gas, Inc., Basking Ridge, (Continued) NJ (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this WO WOO2,34863 A1 5, 2002 patent is extended or adjusted under 35 WO WOO3,O70667 A1 8, 2003 U.S.C. 154(b) by 0 days. This patent is Subject to a terminal dis OTHER PUBLICATIONS claimer. Weixia et al., “Reducing Sulfur Content in FCC Naphtha by Using Ionic Liquid'. Chemical Industry and Engineering Process, Issue 3, (21) Appl. No.: 12/551,627 vol. 23, 2004, pp. 297-300. Chinese first Office Action from Application No. 200680011329.1. (22) Filed: Sep. 1, 2009 English translation, 8 pages. Bates, Eleanor D. et al., “CO2 Capture by a Task-Specific Ionic (65) Prior Publication Data Liquid'. Journal of the American Chemical Society (2002), 124(6): 926-927. US 2009/0317317 A1 Dec. 24, 2009 Blanchard, Lynette A. et al., “Green Processing Using Ionic Liquids and Co2, Nature, vol. 399, May 6, 1999, pp. 28-29. Related U.S. Application Data Freemantle, Michael, “Ionic Liquids Showing Promise for Clean (63) Continuation of application No. 1 1/155,291, filed on Separation Technology”. C&EN, Aug. 24, 1998. Jun. 17, 2005, now Pat. No. 7,585,415, which is a (Continued) continuation-in-part of application No. 1 1/101,191, filed on Apr. 7, 2005, now Pat. No. 7,638,058. Primary Examiner Joseph W. Drodge (74) Attorney, Agent, or Firm Kilpatrick Townsend & (51) Int. Cl. Stockton LLP BOLD 53/00 (2006.01) (52) U.S. Cl...... 95/149; 95/151; 95/172; (57) ABSTRACT 95/173; 210/634; 210/774; 210/808: 222/1; 222/54; 137/1; 137/12: 137/14 A method of storing and dispensing a fluid includes providing (58) Field of Classification Search ...... 210/634, a vessel configured for selective dispensing of the fluid there 210/638, 639, 663, 669, 511, 774, 806, 808; from. A solvent mixture comprising an ionic liquid and a 222/1, 3, 54, 146, 146.1, 251; 137/1, 12, cosolvent is provided within the vessel. The fluid is contacted 137/14: 95/149, 151,166-169, 172-177, with the solvent mixture for take-up of the fluid by the solvent 95/187: 502/111; 510/175; 585/809, 833, mixture. The fluid is released from the ionic liquid and dis 585/843: 361/818; 422/256 259; 208/317, pensed from the vessel. 208/318 See application file for complete search history. 44 Claims, 4 Drawing Sheets

US 7,896,954 B2 Page 2

U.S. PATENT DOCUMENTS 7,022,655 B2 4/2006 Brasket al. 7,172,646 B2 2/2007 Tempel et al. 2,522,059 A 9, 1950 Gardener et al. 7,304.200 B2 12/2007 Roettger et al. 2,851,395 A 9, 1958 Kiersted, Jr. et al. 7,396.381 B2 7/2008 Graham et al. 2.941,940 A 6/1960 Chyn 7,404,845 B2 7/2008 Tempel et al. 2.943,917 A 7, 1960 Weitzel et al. 7,585,415 B2 9/2009 Wyse et al. 2,970,559 A * 2, 1961 Leroux ...... 114,74 R 7,638,058 B2 * 12/2009 Wyse et al...... 210,634

3,101,861. A * 8, 1963 Mearns et al. . 220,560.08 7,670,490 B2 3/2010 Wyse et al. 3,161,461 A * 12/1964 Deal, Jr. et al. ... 423,228 2001/0045187 A1 11, 2001 Uhlenbrock 3.256,705 A * 6/1966 Dimentberg ... 62.50.1 2002/0169071 A1 1 1/2002 Sauvage et al. 3,549,332 A 12/1970 Yoon 2003/008515.6 A1 5/2003 Schoonover 4,359,596 A 1 1/1982 Howard et al. 2003/O125599 A1 7/2003 Boudreau et al. 4,603,148 A 7, 1986 Tom 2003/0126991 A1 7/2003 Wang et al. 4,604,270 A 8, 1986 Tom 2003/0149264 A1 8/2003 Wasserscheid et al. 4,659,552 A 4, 1987 Tom 2003/0192430 A1 10, 2003 Pearlstein et al. 4,696,953. A 9, 1987 Tom 2004.0035293 A1 2/2004 Davis 4,716,181 A 12/1987 Tom 2004/0059008 A1 3/2004 Raje et al. 4,761,164 A 8, 1988 Pez et al. 2004/0106838 A1 6/2004 Smith et al. 4,867,960 A 9, 1989 Tom 2004/0206241 A1 10/2004 Tempel et al. 5,164,093 A 1 1/1992 Chilton et al. 2005/0106086 A1 5/2005 Tomlinson et al. 5,518.528 A 5, 1996 Tom et al. 2005/0154247 A1 7/2005 Jong et al. 5,827.602 A 10/1998 Koch et al. 2005/0276733 A1 12/2005 Tempel et al. 5,980,608 A 1 1/1999 Dietz et al. 2006/0008392 A1 1/2006 Graham et al. 5,985,008 A 1 1/1999 Tom et al. 2006/0060817 A1 3/2006 Tempel et al. 6,048,388 A 4/2000 Schwarz 2006/0060818 A1 3/2006 Tempel et al. 6,089,027 A 7/2000 Wang et al. 2006/008.6247 A1 4/2006 Vininski et al. 6,103,101 A 8/2000 Fragelli et al. 2006/0226074 A1 10/2006 Wyse et al. 6,110,258 A 8, 2000 Fraenkel et al. 2008, 0028170 A1 1/2008 Clinick 6,120,692 A 9/2000 Wang et al. 2008/0210633 A1 9/2008 Wyse et al. 6,187,985 B1 2/2001 Le Peltier et al. 2008, 0211118 A1 9/2008 Wyse et al. 6,274,026 B1 8/2001 Schucker et al. 2009/032O771 A1 12/2009 Torres et al. 6,339,182 B1 1/2002 Munson et al. 6,379,634 B1 4/2002 Fields et al. OTHER PUBLICATIONS 6,388,893 B1 5/2002 Calderon 6,395,070 B1 5, 2002 Bhadha et al. Medved, M. et al., “409 Ionic Liquids as Active Separation Layer in 6.425,946 B1 7/2002 Funke et al. Supported Liquid Membranes', Chemie Ingenieur Technik (73) 6,461.411 B1 10/2002 Watanabe et al. 61.2001. 6,501,000 B1 12/2002 Stibrany et al. Medved, M. et al., “Potential use of ionic liquids in membrane tech 6,531,270 B1 3/2003 Olson et al. nology applications'. Institut fur Verfahrenstechnik, AWTH-Rachen 6,531,515 B2 3/2003 Moore et al. 11-123, 8, aachener membrane colloquium 27.-29.3.2001 Cover 6,547,861 B2 4/2003 Funke et al. page and pp. 11-123 through 11-127. 6,573.405 B1 6, 2003 Abbott et al. Riddle, Jr. et al., “Spectral Shifts in Acid-Base Chemistry”, Journal of 6,579.343 B2 6/2003 Brennecke et al. the American Chemical Society, vol. 122, No. 9, Apr. 25, 1990, pp. 6,624,127 B1 9/2003 Brasket al. 3259-3264 6,703,507 B2 3/2004 Bahrmann et al. Scovazzo, Paul et al., “Supported Ionic Liquid Membranes and 6,733,734 B2 5, 2004 Watanabe et al. Facilitated Ionic Liquid Membrances”, 2002 American Chemical 6,911,065 B2 6, 2005 Watanabe et al. Society, Chapter 6, pp. 69-87. 6,998,152 B2 2/2006 Uhlenbrock 7,019, 188 B2 3, 2006 Smith et al. * cited by examiner U.S. Patent Mar. 1, 2011 Sheet 1 of 4 US 7,896,954 B2

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U.S. Patent Mar. 1, 2011 Sheet 2 of 4 US 7,896,954 B2 Fig. 2

U.S. Patent Mar. 1, 2011 Sheet 3 of 4 US 7,896,954 B2

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U.S. Patent Mar. 1, 2011 Sheet 4 of 4 US 7,896,954 B2

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US 7,896,954 B2 1. 2 FLUID STORAGE ANDPURIFICATION BRIEF SUMMARY OF THE INVENTION METHOD AND SYSTEM In one aspect of the invention, a method of storing and CROSS-REFERENCES TO RELATED dispensing a fluid is provided. The method includes providing APPLICATIONS a vessel configured for selective dispensing of the fluid there from. A solvent mixture comprising an ionic liquid and a This application is a continuation of U.S. patent applica cosolvent is provided within the vessel. The fluid is contacted tion Ser. No. 1 1/155,291, filed on Jun. 17, 2005 and entitled with the solvent mixture for take-up of the fluid by the solvent “Fluid Storage and Purification Method and System, which mixture. The fluid is released from the ionic liquid and dis is a continuation-in-part application of U.S. patent applica 10 pensed from the vessel. tion Ser. No. 1 1/101,191, filed Apr. 7, 2005 and entitled In another aspect of the invention, a method of separating “Fluid Storage and Purification Method and System, the an impurity from a fluid mixture is provided. The fluid mix entire disclosures of which are herein incorporated by refer ture includes a fluid and the impurity. A device contains an CCC. ionic liquid and a cosolvent. The fluid mixture is introduced 15 into the device. The fluid mixture is contacted with the ionic BACKGROUND OF THE INVENTION liquid and the cosolvent. A portion of the impurity is retained within the ionic liquid and/or within the cosolvent to produce Many industrial processes require a reliable source of pro a purified fluid. The purified fluid is then released from the cess gases for a wide variety of applications. Often these device. gases are stored in cylinders or vessels and then delivered to In another aspect of the invention, a method of stabilizing the process under controlled conditions from the cylinder. For an unstable fluid is provided. The method includes providing example, the silicon semiconductor manufacturing industry, a device containing an ionic liquid and a cosolvent. The fluid as well as the compound semiconductor industry, uses a num mixture is introduced into the device. The fluid mixture is ber of hazardous specialty gases such as diborane, stibene, contacted with the ionic liquid and the cosolvent. A portion of phosphine, arsine, boron trifluoride, hydrogen chloride, and 25 the impurity is retained within the ionic liquid and/or within tetrafluoromethane for doping, etching, thin-film deposition, the cosolvent to produce a purified fluid. The purified fluid is and cleaning. These gases pose significant safety and envi then released from the device. ronmental challenges due to their high toxicity and reactivity. The foregoing paragraphs have been provided by way of Additionally, storage of hazardous gases under high pressure general introduction, and are not intended to limit the scope of in metal cylinders is often unacceptable because of the pos 30 the following claims. The presently preferred embodiments, sibility of developing a leak or catastrophic rupture of the together with further advantages, will be best understood by cylinder, cylinder valve, or downstream component. reference to the following detailed description taken in con In order to mitigate Some of these safety issues associated junction with the accompanying drawings. with high pressure cylinders, there is a need for a low pressure storage and delivery system. Additionally, Some gases, such 35 BRIEF DESCRIPTION OF THE DRAWINGS as diborane, tend to decompose when stored for a period of time. Thus, it would be useful to have a way to store unstable gases in a manner that reduces or eliminates the decomposi FIG. 1 shows an embodiment of a vessel for storing a fluid tion. in an ionic liquid. It is also desirable to have a method of removing impurities 40 FIG. 2 shows another embodiment of a device for storing a from gases, particularly in the semiconductor industry. The fluid in an ionic liquid. growth of high quality thin film electronic and optoelectronic FIG. 3 shows an embodiment of a device for purifying a cells by chemical vapor deposition or other vapor-based tech fluid with an ionic liquid. niques is inhibited by a variety of low-level process impurities FIG. 4 shows another embodiment of a device for purifying which are present in gas streams involved in semiconductor 45 a fluid with an ionic liquid. manufacturing or are contributed from various components Such as piping, valves, mass flow controllers, filters, and DETAILED DESCRIPTION OF THE INVENTION similar components. These impurities can cause defects that reduce yields by increasing the number of rejects, which can The invention is described with reference to the drawings. be very expensive. 50 The relationship and functioning of the various elements of Chemical impurities may originate in the production of the this invention are better understood by the following detailed Source gas itself, as well as in its Subsequent packaging, description. However, the embodiments of this invention as shipment, storage, handling, and gas distribution system. described below are by way of example only, and the inven Although source gas manufacturers typically provide analy tion is not limited to the embodiments illustrated in the draw ses of Source gas materials delivered to the semiconductor ings. manufacturing facility, the purity of the gases may change 55 because of leakage into or outgassing of the containers, e.g. The present invention is directed to the use of ionic liquids gas cylinders, in which the gases are packaged. Impurity to store a fluid material Such as a gas or liquid. A vessel is contamination may also result from improper gas cylinder configured for the selective dispensing of the fluid and con changes, leaks into downstream processing equipment, or tains an ionic liquid. The fluid is contacted with the ionic outgassing of suchdownstream equipment. Source gases may 60 liquid for take-up of the fluid by the ionic liquid. This allows include impurities, or impurities may occur as a result of storage of the fluid for a period of time. In one embodiment, decomposition of the stored gases. Furthermore, the impurity the material in the storage vessel is at high pressure, for levels within the gas container may increase with length of example up to about 4000 psi, preferably up to at least about storage time and can also change as the container is consumed 2000 psi. In another embodiment, the pressure of the material by the end user. Thus, there remains a need to be able to 65 in the storage vessel is at around atmospheric pressure, which remove contaminants from gases, particularly to very low allows for safer storage conditions compared to high-pressure levels. storage vessels. US 7,896,954 B2 3 4 The ionic liquids may also be used to store unstable fluids 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 5 physical properties of the ionic liquid or fluids and could liquids to remove impurities from a fluid mixture. A device 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 10 structure as they were introduced into the ionic liquid. the ionic liquid to produce a purified fluid. This purification 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 15 While not intending to be bound by any particular theory, the pressure, high thermal stability, and low viscosity. Generally, 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 tight 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 20 of the anion, the cation, and the dissolved gas play a role in Suchion pairs, a wide range of gas solubilities is conceivable, 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; 25 impact on their behavior. Ionic liquids which have been dried low viscosity, compared to other ionic materials; and recy 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 30 cially those gas components that are hydrophobic. control the release of a gas and/or its impurities via solubility The method of storing and dispensing a fluid includes control with temperature or pressure. This may enable the providing a vessel. On embodiment of a vessel 10 is shown in storage of a gas and its impurities, while selectively releasing FIG.1. The vessel 10 includes a fluid inlet 20, an ionic liquid only the desired gas by changing certain parameters. Such as inlet 30, and a fluid outlet 32. The fluid inlet 20 is connected temperature or pressure, leaving the impurities behind. Thus 35 to a fluid source 14 which is controlled by a valve 18. The there is potential for an ionic liquid system that could function ionic liquid inlet 30 is connected to an ionic liquid source 12 as a 2-in-1 system, providing both storage and purification in which is controlled by a valve 16. The fluid outlet 32 is one container. controlled by valve 26. The vessel is configured for selective Ionic liquids can have a stabilizing effect on intermediate dispensing of the fluid therefrom. The vessel is charged with reaction species in organic synthesis and catalysis. Thus, 40 an ionic liquid 22 through inlet 30. A vacuum bake procedure ionic liquids can offer stabilizing effects for unstable gas may be conducted on the vessel 10 to remove contaminants or molecules. Thus, utilization with even a small amount of other impurities from the ionic liquid, preferably by pulling a ionic liquid, can reduce or eliminate the decomposition of the vacuum while heating. This is done in order to remove any unstable fluids. Storage of a gas or other fluid in an ionic trace moisture and/or other volatile impurities from the ionic liquid may also be combined with the previously mentioned 45 liquid and the fluid distribution components. The ionic liquid purification system to provide a 3-in-1 storage, stabilization, is allowed to cool to the desired operating temperature. and purification system. The source fluid is then introduced into the vessel 10 until One potential issue in the use of ionic liquids for the storage the take-up or dissolution of the fluid by the ionic liquid is of gases is the vapor pressure of the ionic liquids. The vapor complete. The fluid may be a gas or a liquid Such as a liquefied pressure of the ionic liquid can contaminate the delivered gas 50 gas. The fluid is contacted with the ionic liquid for take-up of with ionic liquid. The present understanding is that ionic the fluid by the ionic liquid. There is substantially no chemi liquids have very low or possibly no measurable vapor pres cal change in the ionic liquid and the fluid. By “substantially sure of their own. This quality is an attractive feature of ionic no chemical change' is meant that no Substantial amount of liquids for use with storage and purification of gases. Vapor bonds in the fluid and the ionic liquid are being broken, such pressures have been reported for mixtures of ionic liquids 55 that the fluid and the ionic liquid retain their chemical iden with other dissolved liquids. The vapor pressure of the ionic tity. It is undesirable for the fluid to react with the ionic liquid liquids used in the present invention are preferably less than to any significant effect. A reaction between the fluid and the about 10 Torr at 25°C., more preferably less than about ionic liquid would be expected to generate impurities or con 10 Torr at 25° C. sume the fluid of interest. The mechanism for the dissolution of a fluid within anionic 60 The fluid may be introduced at any suitable pressure. In one liquid is believed to be due to intermolecular forces. While embodiment, the fluid is a gas at a temperature of about 5 psi. not intending to be bound by any particular theory, possible In another embodiment, the gas is introduced at a pressure of factors that influence the solubility include hydrogen bond at least about 100 psi, preferably up to about 2000 psi. The gas ing, dielectric constant, dipole moment (polarizability), high is introduced until the inlet and outlet concentrations are pi interaction, length of carbon chain, number of carbon 65 equivalent, indicating the ionic liquid is saturated and cannot double bonds, the purity of the ionic liquid, chirality, and accept any further gas under the existing conditions. At this steric hindrance. It is not believed that the fluids chemically time, the source gas flow is stopped. US 7,896,954 B2 5 6 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. 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 10 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 15 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 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 25 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 30 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 35 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 40 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 fluid to flow from the vessel to the exterior environment. The therefrom. A suitable vessel is, for example, a container that pressure conditions may involve the imposition on the ionic can hold up to 1000 liters. A typical vessel size is about 44 liquid of vacuum or Suction conditions which effect extrac 45 liters. The vessel should be able to contain fluids at a pressure tion of the gas from the vessel. of up to about 2000 psi, preferably up to about 4000 psi. In thermally-mediated evolution, the ionic liquid is heated However, the vessel may also operate at around atmospheric to cause the evolution of the gas from the ionic liquid so that pressure. Preferably, the container is made of carbon steel, the gas can be withdrawn or discharged from the vessel. stainless steel, nickel or aluminum. In some cases the vessel Typically, the temperature of the ionic liquid for thermal 50 may contain interior coatings in the form of inorganic coat mediated evolution ranges from -50° C. to 200° C., more ings such as silicon and carbon, metallic coatings such as preferably from 30° C. to 150° C. In one embodiment, the nickel, organic coatings such as paralyene or Teflon based vessel containing the fluid and the ionic liquid is transported materials. The vessel contains an ionic liquid which revers warm (i.e., around room temperature), then cooled when it is ibly takes up the fluid when contacted therewith. The fluid is stored or used at the end user's site. In this manner, the fluid 55 releasable from the ionic liquid under dispensing conditions. vapor pressure can be reduced at the end user's site and A variety of ionic liquids can be used in the present inven therefore reduce the risk of release of the gas from the vessel. tion. Additionally, two or more ionic liquids may be com Once the vessel is secured in a Suitable location, the vessel can bined for use in any of the aspects of the present invention. In be chilled and the temperature can be controlled in such a one embodiment, the ionic liquid is selected from mono manner as to limit the amount of gas pressure that is present 60 substituted imidazolium salts, di-substituted imidazolium in the container and piping. As the contents of the cylinder or salts, tri-substituted imidazolium salts, pyridinium salts, pyr other gas storage device are consumed, the temperature of the rolidinium salts, phosphonium salts, ammonium salts, cylinder can be elevated to liberate the gas from the ionic tetralkylammonium salts, guanidinium salts, isouronium liquid and to maintain the necessary amount of gas levels in salts, and mixtures thereof. In this context, the listed salts the cylinder and piping. 65 include any compound that contains the listed cation. In The vessel may also be sparged with a secondary gas, in another embodiment, the ionic liquid is selected from a Subset order to deliver the stored primary gas. In sparging, a second of the previous list and includes phosphonium salts, ammo US 7,896,954 B2 7 8 nium salts, tetralkylammonium salts, guanidinium salts, isou mide, 1-ethyl-3-methylimidiazolium cobalt-tetracarbonyl, ronium salts, and mixtures thereof. In one embodiment, the 1-propyl-3-methylimidazolium chloride, 1-butyl-3-meth ionic liquid includes a cation component selected from mono ylimidazolium hexafluoroantimonate, 1-octadecyl-3-meth Substituted imidazoliums, di-substituted imidazoliums, tri ylimidazolium bis(trifluoromethylsulfonyl)imide, 1-benzyl Substituted imidazoliums, pyridiniums, pyrrolidiniums, 3-methylimidazolium bromide, 1-phenylpropyl-3- phosphoniums, ammoniums, tetralkylammoniums, guani methylimidazolium chloride. diniums, and uroniums; and an anion component selected Tri-substituted imidazolium ionic liquids include 1-ethyl from acetate, cyanates, decanoates, halogenides, Sulfates, Sul 2,3-dimethylimidazolium chloride, 1-butyl-2,3-dimeth fonates, amides, imides, methanes, borates, phosphates, anti ylimidazolium octylsulfate, 1-propyl-2,3-dimethylimidazo monates, tetrachloroaluminate, thiocyanate, tosylate, car 10 lium chloride, 1-hexyl-2,3-dimethylimidazolium boxylate, cobalt-tetracarbonyl, trifluoroacetate and tris tetrafluoroborate, 1-hexadecyl-2,3-dimethylimidazolium (trifluoromethylsulfonyl)methide. Halogenide anions iodide. Pyridinium ionic liquids include n-ethylpyridinium include chloride, bromide, iodide. Sulfates and sulfonate chloride, n-butylpyridinium bromide, n-hexylpyridinium anions include methyl sulfate, ethyl sulfate, butyl sulfate, n-octylpyridinium chloride, 3-methyl-n-butylpyridinium hexyl Sulfate, octyl sulfate, hydrogen Sulfate, methane Sul 15 methylsulfate, 3-ethyl-n-butylpyridinium hexafluorophos fonate, dodecylbenzene Sulfonate, dimethyleneglycol phate, 4-methyl-n-butylpyridinium bromide, 3,4-dimethyl-n- monomethylether sulfate, trifluoromethane sulfonate. butylpyridinium chloride, 3,5-dimethyl-n-butylpyridinium Amides, imides, and methane anions include dicyanamide, chloride. bis(pentafluoroethylsulfonyl)imide, bis(trifluoromethylsul Pyrrolidinium ionic liquids include 1,1-dimethylpyrroli fonyl)imide, bis(trifluoromethyl)imide. Borate anions dinium tris(pentafluoroethyl)trifluorophosphate, 1-ethyl-1- include tetrafluoroborate, tetracyanoborate, bisoxalato(2-) methylpyrrolidinium dicyanamide, 1,1-dipropylpyrroli borate, bis 1,2-benzenediolato(2-)-O,O'borate, bissalicy dinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1- lato(2-)borate. Phosphate and phosphinate anions include methylpyrrolidinium bromide, 1-butyl-1-ethylpyrrolidinium hexafluorophosphate, diethylphosphate, bis(pentafluoroeth bromide, 1-octyl-1-methylpyrrolidinium dicyanamide. yl)phosphinate, tris(pentafluoroethyl)trifluorophosphate, tris 25 Phosphonium ionic liquids include tetraoctylphosphonium (nonafluorobutyl)trifluorophosphate. Anitmonate anions bromide, tetrabutylphosphonium bisoxalato(2-)-borate, tri include hexafluoroantimonate. Other anions include tetra hexyl (tetradecyl)phosphonium dicyanamide, benzyltriph chloroaluminate, acetate, thiocyanate, tosylate, carboxylate, enylphosphonium bis(trifluoromethyl)imide, tri-iso-butyl cobalt-tetracarbonyl, trifluoroacetate and tris(trifluorometh (methyl)phosphonium tosylate, ethyl(tributyl)phosphonium ylsulfonyl)methide. Various ionic liquids are available from 30 diethylphosphate, tributyl (hexadecyl)phosphonium chloride. BASF, Merck, Strem Chemicals, and Aldrich. Ammonium ionic liquids include tetramethylammonium Preferred ionic liquids used in the present invention may be bis(trifluoromethylsulfonyl)imide, tetraethylammonium bis divided into the following categories: standard, acidic, acidic salicylato-(2-)-borate, tetrabutylammonium tetracyanobo water reactive, and basic. Standard ionic liquids include but rate, methyltrioctylammonium trifluoroacetat. are not limited to 1-ethyl-3-methylimidazolium chloride, 35 Guanidinium ionic liquids include N.N.N',N',N'-pentam 1-ethyl-3-methylimidazolium methanesulfonate, 1-butyl-3- ethyl-N'-isopropylguanidinium tris(pentafluoroethyl)trif methylimidazolium chloride, 1-butyl-3-methylimidazolium luorophosphate, N.N.N',N',N'-pentamethyl-N'-isopropy methanesulfonate, methyl-tri-n-butylammonium methylsul lguanidinium tris(pentafluoroethyl) fate, 1-ethyl-2,3-dimethylimidazolium ethylsulfate, 1,2,3-tri trifluoromethanesulfonate, hexamethylguanidinium tris methylimidazolium methylsulfate. Acidic ionic liquids 40 (pentafluoroethyl)trifluorophosphate, include methylimidazolium chloride, methylimidazolium hexamethylguanidinium trifluoromethanesulfonate. hydrogensulfate, 1-ethyl-3-methylimidazolium hydrogen Uronium ionic liquids include S-methyl-N,N,N',N'-tet sulfate, 1-butyl-3-methylimidazolium hydrogensulfate. ramethylisouronium trifluoromethanesulfonate, O-methyl Acidic water reactive liquids include 1-ethyl-3-methylimida N.N.N',N'-tetramethylisouronium tris(pentafluoroethyl)trif Zolium tetrachloroaluminate and 1-butyl-3-methylimidazo 45 luorophosphate, O-ethyl-N,N,N',N'-tetramethylisouronium lium tetrachloroaluminate. Basic ionic liquids include tris(pentafluoroethyl)trifluorophosphate, S-ethyl-N,N,N',N'- 1-ethyl-3-methylimidazolium acetate and 1-butyl-3-meth tetramethylisouronium trifluoromethanesulfonate, S-ethyl ylimidazolium acetate. N.N.N',N'-tetramethylisothiouronium trifluoromethane Another way the preferred ionic liquids in the present Sulfonate. invention may be categorized is by functional group of the 50 In one embodiment, the ionic liquid used to store a fluid cation. This includes but is not limited to the following cat does not include imidazolium compounds. In another egories: mono-Substituted imidazoliums, di-substituted imi embodiment, the ionic liquid used to store a fluid does not dazoliums, tri-substituted imidazoliums, pyridiniums, pyrro include a nitrogen-containing heterocyclic cation. lidiniums, phosphoniums, ammoniums, The fluids which may be stored, purified, or stabilized in tetralkylammoniums, guanidiniums, and uroniums. Mono 55 the ionic liquids include, but are not limited to, alcohols, Substituted imidazolium ionic liquids include 1-methylimi aldehydes, amines, ammonia, aromatic hydrocarbons, dazolium tosylate, 1-methylimidazolium tetrafluoroborate, arsenic pentafluoride, arsine, borontrichloride, borontrifluo 1-methylimidazolium hexafluorophosphate, 1-methylimida ride, carbon dioxide, carbon disulfide, carbon monoxide, car Zolium trifluoromethanesulfonate, 1-butylimidazolium tosy bon Sulfide, chlorine, diborane, dichlorosilane, digermane, late, 1-butylimidazolium tetrafluoroborate, 1-methylimida 60 dimethyl disulfide, dimethyl sulfide, disilane, ethane, ethers, Zolium hexafluorophosphate, 1-methylimidazolium ethylene oxide, fluorine, germane, germanium methoxide, trifluoromethanesulfonate. germanium tetrafluoride, hafnium methylethylamide, Di-substituted imidazolium ionic liquids include 1,3-dim hafnium t-butoxide, halogenated hydrocarbons, halogens, ethylimidazolium methylsulfate, 1,3-dimethylimidiazolium hexane, hydrogen, hydrogen cyanide, hydrogen halogenides, trifluoromethanesulfonate, 1,3-dimethylimidiazolium bis 65 hydrogen selenide, hydrogen sulfide, ketones, mercaptans, (pentafluoroethyl)phosphinate, 1-ethyl-3-methylimidiazo methane, nitric oxides, nitrogen, nitrogen trifluoride, noble lium thiocyanate, 1-ethyl-3-methylimidiazolium dicyana gases, organometallics, oxygen, oxygenated-halogenated US 7,896,954 B2 10 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 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, trimethyl silane, 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 storage conditions and thus are difficult to store. the previous listed fluids and include alcohols, aldehydes, 10 Stable gases include nitrogen, argon, helium, neon, Xenon, amines, ammonia, aromatic hydrocarbons, arsenic pentafluo krypton; hydrocarbons include methane, ethane, and pro ride, arsine, boron trichloride, boron trifluoride, carbon dis panes; hydrides include silane, disilane, arsine, phosphine, ulfide, carbon monoxide, carbon Sulfide, chlorine, diborane, germane, ammonia; corrosives include hydrogen halogenides dichlorosilane, digermane, dimethyl disulfide, dimethyl Sul Such as hydrogen chloride, hydrogen bromide, and hydrogen fide, disilane, ethers, ethylene oxide, fluorine, germane, ger 15 fluoride, as well as chlorine, dichlorosilane, trichlorosilane, manium methoxide, germanium tetrafluoride, hafnium meth carbon tetrachloride, boron trichloride, tungsten hexafluo ylethylamide, hafnium t-butoxide, halogenated ride, and boron trifluoride; oxygenates include oxygen, car hydrocarbons, halogens, hexane, hydrogen, hydrogen cya bon dioxide, nitrous oxide, and carbon monoxide; and other nide, hydrogen halogenides, hydrogen selenide, hydrogen gases Such as hydrogen, deuterium, dimethyl ether, Sulfur Sulfide, ketones, mercaptains, nitric oxides, nitrogen, nitrogen hexafluoride, arsenic pentafluoride, and silicon tetrafluoride. trifluoride, organometallics, oxygenated-halogenated hydro Stable liquefied gases include inerts such as nitrogen and carbons, phosgene, phosphine, phosphorus trifluoride, n-si argon; hydrocarbons such as propane; hydrides such as lane, pentakisdimethylamino tantalum, silicon tetrachloride, silane, disilane, arsine, phosphine, germane, and ammonia; silicon tetrafluoride, stibine, styrene, sulfur dioxide, sulfur fluorinates Such as hexafluoroethane, perfluoropropane, and hexafluoride, sulfur tetrafluoride, tetramethyl cyclotetrasi 25 perfluorobutane; corrosives such as hydrogen chloride, loxane, titanium diethylamide, titanium dimethylamide, hydrogen bromide, hydrogen fluoride, chlorine, dichlorosi trichlorosilane, trimethyl silane, tungsten hexafluoride, and lane, trichlorosilane, carbon tetrachloride, boron trichloride, mixtures thereof. borontrifluoride, tungsten hexafluoride, and chlorine trifluo By way of illustration, examples of some of these classes of ride; and oxygenates such as oxygen and nitrous oxide. fluids will now be listed. However, scope of the invention is 30 Unstable gases include digermane, borane, diborane, not limited to the following examples. Alcohols include etha stibene, disilane, hydrogen selenide, nitric oxide, fluorine and nol, isopropanol, and methanol. Aldehydes include acetalde organometallics including alanes, trimethyl aluminum and hyde. Amines include dimethylamine and monomethy other similar gases. These unstable gases may also be lique lamine. Aromatic compounds include benzene, toluene, and fied. xylene. Ethers include dimethyl ether, and vinyl methyl ether. 35 In one embodiment, a fluid such as fluorine could be stored Halogens include chlorine, fluorine, and bromine. Haloge with fully fluorinated ionic liquid such as perfluorinated nated hydrocarbons include dichlorodifluoromethane, tet ammonium hexafluorophosphate. rafluoromethane, clorodifluoromethane, trifluoromethane, The present invention also provides a method of separating difluoromethane, methyl fluoride, 1,2-dichlorotetrafluoroet an impurity from a fluid mixture. In this instance, the fluid hane, hexafluoroethane, pentafluoroethane, halocarbon 134a 40 mixture includes a fluid and the impurity. FIG. 3 shows an tetrafluoroethane, difluoroethane, perfluoropropane, embodiment of a device 40 for purifying a fluid with an ionic octafluorocyclobutane, chlorotrifluoroethylene, hexafluoro liquid. A device containing the ionic liquid is configured for propylene, octafluorocyclopentane, perfluoropropane, 1,1,1- contacting the ionic liquid with the fluid mixture. A source 46 trichloroethane, 1,1,2-trichloroethane, methyl chloride, and for the fluid mixture is controlled by valve 48. The fluid methyl fluoride. Ketones include acetone. Mercaptains 45 mixture is introduced through inlet 50 into the device 40 and include ethyl mercaptan, methyl mercaptan, propyl mercap contacted with the ionic liquid. The ionic liquid is introduced tan, and n.s.t-butyl mercaptan. Nitrogen oxides include nitro through inlet 52 from ionic liquid source 42 by valve 44. A gen oxide, nitrogen dioxide, and nitrous oxide. Organometal portion of the impurities is retained within the ionic liquid to lics include trimethylaluminum, triethylaluminum, produce a purified fluid. The purified fluid is released from the dimethylethylamine alane, trimethylamine alane, dimethyla 50 device through outlet 54, which is controlled by valve 56. luminum hydride, tritertiarybutylaluminum, Tritertiarybuty FIG. 4 shows another embodiment of a device 40 for puri laluminum trimethylindium (TMI), trimethylgallium fying a fluid with an ionic liquid. Contacting the fluid with the (TMG), triethylgallium (TEG), dimethylzinc (DMZ), dieth ionic liquid comprises bubbling the fluid mixture through the ylzinc (DEZ), carbontetrabromide (CBr.), diethyltellurium ionic liquid. The vessel 60 includes a valve assembly 62, an (DETe) and magnesocene (Cp2Mg). Oxygenated-haloge 55 ionic liquid inlet 64, a fluid inlet 66, and a dip tube 78. The nated-hydrocarbons include perfluoroethylmethylether, per valve assembly 62 includes an ionic liquid inlet valve 68 and fluoromethylpropylether, perfluorodimethoxymethane, and a fluid inlet valve 70. The vessel 60 is charged with an ionic hexafluoropropylene oxide. Other fluids include vinyl acety liquid 22 through inlet 64. The vessel 60 is charged with a lene, acrylonitrile, and vinyl chloride. fluid through inlet 66 and through dip tube 78, from whence Other fluids which may be stored, purified, or stabilized in 60 it bubbles through ionic liquid 22. ionic liquids include materials used for thin film deposition Alternatively, as will be described below, the impurity may applications. Such materials include, but are not limited to, retained on a solid material that has been introduced into the tetramethyl cyclotetrasiloxane (TOMCTS), titanium dim ionic liquid. In addition, mixtures of one or more ionic liquids ethylamide (TDMAT), titanium diethylamide (TDEAT), can be used with or without the additional solid phase puri hafnium t-butoxide (Hf(OtBu)), germaniummethoxide (Ge 65 fication material to adjust the solubility of the fluid as well as (OMe)4), pentakisdimethylamino tantalum (PDMAT) the purifying ability of the ionic liquid. Additionally, non hafnium methylethylamide (TEMAH) and mixtures thereof. ionic liquids can be mixed with the ionic liquids to either US 7,896,954 B2 11 12 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 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. 5 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 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 10 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 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. 15 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. 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 20 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 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 25 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 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 30 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 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 35 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 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 40 pressures to optimize gas component separation. Sufficient to allow significant removal of targeted compo The present invention also provides a method for both nents. Thus, Systems maximizing Surface area contact storing and purifying a fluid mixture comprising a fluid and an between the ionic liquid and the fluid mixture are desirable. impurity. A vessel contains an ionic liquid and is configured In one embodiment, the device is a vessel and the step of for contacting the ionic liquid with the fluid mixture. The fluid contacting the fluid mixture with the ionic liquid comprises 45 and the ionic liquid may be any of the previously mentioned bubbling the fluid mixture through the ionic liquid, as shown fluids and ionic liquids. The fluid is contacted with the ionic in FIG. 4 and previously described. In another embodiment, a liquid for take-up of the fluid by the ionic liquid. This may be scrubbing stack is used to contact the fluid mixture with the accomplished by any of the previously described methods of ionic liquid, with the fluid mixture and the ionic liquid flow promoting intimate mixing of the liquid ionic compound and ing into the Scrubbing stack. In another embodiment, the 50 the fluid mixture, or any other suitable method. A portion of vessel containing the fluid and the ionic liquid is mechani the impurities is retained within the ionic liquid to produce a cally agitated in order to contact the fluid with the ionic liquid. purified fluid. The purified fluid can then be released from the In another embodiment, countercurrent flow of the ionic liq device. uid and the fluid is used to contact the fluid with the ionic The present invention also provides a method of storing liquid in the device. In another embodiment, the fluid is a 55 and stabilizing an unstable fluid. The unstable fluid may be liquid, and the liquid and the ionic liquid are mixed to contact any of the previously mention unstable fluids, or any other the fluid with the ionic liquid in the device. fluid that tends to decompose. The ionic liquid may be any of In another aspect of the invention, a method of separating the previously mentioned ionic liquids. The unstable fluid is an impurity from a fluid mixture is provided which used a contacted with the ionic liquid for take-up of the unstable Small amount of ionic liquid. The fluid mixture is contacted 60 fluid by the ionic liquid. The unstable fluid may be then stored with the ionic liquid for the purpose of purification only and within the ionic liquid for a period of time, during which not for uptake of the fluid by the ionic liquid. Thus, a device period of time the decomposition rate is at least reduced, and or vessel is used to contact a small amount of ionic liquid with preferably there is substantially no decomposition of the the fluid mixture. In this manner, a Substantially less amount unstable fluid. In one embodiment, the rate of decomposition of ionic liquid could be required to obtain the purification 65 is reduced by at least about 50%, more preferably at least effect compared to the previous illustration wherein the about 75%, and most preferably at least about 90%, compared unstable fluid could be taken up completely or dissolved with storage of the fluid under the same temperature and US 7,896,954 B2 13 14 pressure conditions without using an ionic liquid. In the con 6,461.411; 6,425,946; 6,547,861; and 6,733,734, the contents text of an unstable fluid, Substantially no decomposition of which are hereby incorporated by reference. Other solid means that less than 10% of the molecules of the unstable purification materials typically available from Aeronex, Mil fluid undergo a chemical change while being stored. In one lipore, Mykrolis, Saes Getters, Pall Corporation, Japan Pion embodiment, the proportion of molecules that undergo a 5 ics and used commonly in the semiconductor gas purification decomposition reaction is preferably less than 1%, more pref applications are known in the art and are intended to be erably less than 0.1%, and most preferably less than 0.01%. included within the scope of the present invention. Although it is most preferable for the decomposition rate to be Additionally, any of the previously described storage, sta less than 0.01%, it should be noted that in certain applications bilization, and purification methods and systems may becom a rate of decomposition of less than 50% over the storage 10 bined to provide multiple effects. One, two or all three meth period of the fluid would be useful. The period of time may ods can be independently combined to obtain a process that is range from a few minutes to several years, but is preferably at best suited for the application of interest. Therefore, it is least about 1 hour, more preferably at least about 24 hours, conceivable that any one method or the combination of any of even more preferably at least about 7 days, and most prefer the methods could be used for different requirements and ably at least about 1 month. 15 applications. The basic steps of these combined methods will The unstable fluid may be selected from categories such as now be set forth. It will be apparent that the information dopants, dielectrics, etchants, thin film growth, cleaning, and previously described for the individual methods will also be other semiconductor processes. Examples of unstable fluids applicable for the combined methods described below. The include, but are not limited to, digermane, borane, diborane, fluids and the ionic liquids used in the combined processes disilane, fluorine, halogenated oxy-hydrocarbons, hydrogen 20 may be any of the previously mentioned fluids and ionic Selenide, Stilbene, nitric oxide, organometallics and mixtures liquids. thereof. The storage method may be combined with the method of The present invention also provides a method of storing purifying using a purifying Solid. In this method, a vessel and purifying a fluid mixture. The storage vessel is provided containing an ionic liquid is provided. The fluid mixture is with a purifying solid or liquid for contact with the fluid 25 contacted with the ionic liquid for take-up of the fluid by the mixture. The purifying Solid or liquid retains at least a portion ionic liquid. There is Substantially no chemical change in the of the impurity in the fluid mixture to produce a purified fluid ionic liquid and the fluid. A purifying solid is provided for when the fluid is released from the storage vessel. The puri contact with the fluid mixture. A portion of the impurity is fying Solid or liquid may be used with any of the previously retained by the purifying solid to produce a purified fluid. mentioned fluids and ionic liquids. 30 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 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 35 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 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, 40 the unstable fluid. amorphous silica-alumina, silica (SiO2), aluminosilicate The methods of storage, stabilizing, and purifying using molecular sieves, titania (TiO), Zirconia (ZrO2), and carbon. the ionic liquid may also be combined. A device containing an The materials are commercially available in a variety of ionic liquid and configured for contacting the ionic liquid shapes of different sizes, including, but not limited to, beads, with the fluid mixture is provided. The fluid mixture is intro sheets, extrudates, powders, tablets, etc. The surface of the 45 duced into the device. The fluid mixture is contacted with the materials can be coated with a thin layer of a particular form ionic liquid. The fluid mixture may then be stored within the of the metal (e.g., a metal oxide or a metal salt) using methods ionic liquid for a period of time of at least about 1 hour, during known to those skilled in the art, including, but not limited to, which period of time there is substantially no degradation of incipient wetness impregnation techniques, ion exchange the unstable fluid. A portion of the impurities are retained methods, vapor deposition, spraying of reagent Solutions, 50 within the ionic liquid to produce a purified unstable fluid, co-precipitation, physical mixing, etc. The metal can consist and the purified unstable fluid may then be released from the of alkali, alkaline earth or transition metals. Commercially device. available purification materials includes a Substrate coated The two purification methods may also be combined. A with a thin layer of metal oxide (known as NHX-PlusTM) for device containing an ionic liquid and a purifying Solid therein removing HO, CO and O, HS and hydride impurities, 55 for contact with the fluid mixture is provided. The fluid mix Such as silane, germane and siloxanes; ultra-low emission ture is introduced into the device. The fluid mixture is con (ULE) carbon materials (known as HCXTM) designed to tacted with the ionic liquid and with the purifying solid. A first remove trace hydrocarbons from inert gases and hydrogen; portion of the impurity is retained within the ionic liquid and macroreticulate polymer scavengers (known as OMATM and a second portion of the impurity is retained by the purifying OMX-PlusTM) for removing oxygenated species (H2O, O, 60 solid, to produce a purified fluid. The purified fluid may then CO, CO., NO, SO, etc.) and non-methane hydrocarbons; be released from the device. and inorganic silicate materials (known as MTXTM) for The storage method may be combined with both methods removing moisture and metals. All of these are available from of purifying. A vessel containing an ionic liquid and a puri Matheson Tri-Gas(R), Newark, Calif. Further information on fying solid therein for contact with the fluid mixture is pro these purifying materials and other purification materials is 65 vided. The fluid is contacted with the ionic liquid for take-up disclosed in U.S. Pat. Nos. 4,603,148; 4,604270; 4,659,552; of the fluid by the ionic liquid. A first portion of the impurity 4,696,953; 4,716,181; 4,867,960; 6,110,258; 6,395,070; is retained within the ionic liquid and a second portion of the US 7,896,954 B2 15 16 impurity is retained by the purifying solid, to produce a puri the decomposition reaction and shift the reaction Such that fied fluid. The purified fluid may then be released from the decomposition of the fluid is not favored. device. Thus, a cosolvent may be used with an ionic liquid for any The storage and stabilization methods may be combined of the processes described herein in order to enhance the with both methods of purifying. A vessel containing an ionic 5 performance of the process. For example, to store an ionic liquid and a purifying solid therein for contact with the fluid mixture is provided. The fluid mixture is introduced into the fluid, a solvent mixture comprising an ionic liquid and a device. The fluid is contacted with the ionic liquid for take-up cosolvent is provided within a suitable vessel. The fluid is of the fluid by the ionic liquid. The fluid mixture is stored contacted with the solvent mixture for take-up of the fluid by within the ionic liquid for a period of time of at least about 1 10 the solvent mixture. The fluid is released from the ionic liquid hour, during which period of time there is substantially no and dispensed from the vessel. In one embodiment, the solu degradation of the unstable fluid. A first portion of the impu bility of the fluid in the solvent mixture is greater than the rity is retained within the ionic liquid and a second portion of solubility of the fluid in the ionic liquid under the operating the impurity is retained by the purifying Solid, to produce a conditions of the vessel. purified unstable fluid. The purified fluid may then be 15 As another example, to purify a fluid mixture containing a released from the device. fluid and an impurity, a device containing an ionic liquid and The stabilization methods may be combined with both a cosolvent is provided. The fluid mixture is introduced into methods of purifying. A vessel containing an ionic liquid and the device. The fluid mixture is contacted with the ionic liquid a purifying solid therein for contact with the fluid mixture is and the cosolvent. A portion of the impurity is retained within provided. The unstable fluid mixture is introduced into the the ionic liquid, within the cosolvent, or within the mixture of device. The unstable fluid is contacted with the ionic liquid the cosolvent and the ionic liquid, to produce a purified fluid. primarily for the purposes of stabilization and purification The purified fluid is then released from the device. only, and not for the purposes of uptake of the fluid by the As another example, to stabilize a fluid mixture including ionic liquid. Thus, a device or vessel is used to contact a small an unstable fluid, an ionic liquid and a cosolvent are provided amount of ionic liquid with the fluid. In this manner, a Sub 25 within a vessel. The fluid mixture is introduced into the ves stantially less amount of ionic liquid could be required to sel. The fluid mixture is contacted with the ionic liquid and the obtain the stabilization effect and the purification effect com cosolvent. The fluid mixture is stored within the vessel for a pared to the previous illustrations wherein the unstable fluid period of time, during which period of time there is substan could be taken up completely or dissolved within the ionic tially no decomposition of the unstable fluid. liquid. No decomposition products, or Substantially less 30 The cosolvents and ionic liquids can be used in various decomposition products, are produced as a result of the con combinations for the various methods described herein. For tact of the unstable fluid with the ionic liquid, producing a example, one type of ionic liquids and cosolvents can be used stabilized fluid. The fluid mixture is stored within the ionic for storage and a second type of ionic liquids and cosolvents liquid for a period of time of at least about 1 hour, during used for purification, in a process for both storage and puri which period of time there is substantially no degradation of 35 fication. Similarly, one type of ionic liquids and cosolvents the unstable fluid. A portion of the impurity is retained within can be used for storage, a second type of ionic liquids and the ionic liquid to produce a purified fluid. The purified fluid cosolvents used for purification and a third type of ionic may then be released from the device. liquids and cosolvents used for stabilization, in a process In another aspect of the present invention, cosolvents can including storage, purification, and Stabilization. Various be combined with the ionic liquids. Cosolvency, also known 40 other combinations of the processes disclosed herein will be as solvent blending, is a process used to increase the solubility apparent. It is intended that the elements of these processes of a chemical compound in a given solvent. This is achieved and the ionic liquids and cosolvents can be mixed, matched by adding a portion of a different solvent (cosolvent) to the and combined in a variety of combinations for different appli given solvent. In general, the more interaction between the cations and different requirements. cosolvent and the given solvent, Such as miscibility, the more 45 effective the cosolvency is. Conventionally, cosolvents are Additionally, steps may be taken to remove the cosolvent used to increase the water solubility of substances that nor from the ionic liquid and/or from the fluid mixture in later mally have poor water solubility, by adding water-miscible stages of the process. For example, after a fluid mixture is organic solvents. released from Storage in the ionic fluid-cosolvent mixture, In the present invention, cosolvents can be combined with 50 traces of cosolvent may be retained by the fluid mixture. ionic liquids in the methods of storage, purification, stabili These traces of cosolvent may be removed by any conven zation, and combinations thereof. The solubility of the fluid in tional purification process known in the art. the ionic liquid is increased by adding a particular cosolvent In one embodiment, the amount of cosolvent used is less for the purpose of storing the fluid. The solubility of fluid than the amount of ionic liquid used in the process. The impurities in the ionic liquid could also be increased by add 55 amount of cosolvent is preferably between about 0.1% and ing a particular cosolvent for the purpose of purifying the about 100% of the amount of ionic liquid used. More prefer fluid. The solubility of decomposition species could be ably, the amount of cosolvent is less than about 50% of the decreased or increased by the use of cosolvents with the ionic ionic liquid, and most preferably, less than about 25% of the liquid for the purpose of preventing decomposition. The solu ionic liquid. In various other embodiments, the amount of bility of stabilizing species could be increased by the use of 60 cosolvent used relative to the amount of ionic liquid used may cosolvents with the ionic liquid, for the purpose of stabiliza be less than about 10%, 5%, and 1%. The relative amount of tion. The intermolecular distances found between two mol the cosolvent will depend on the ionic liquid and fluid mix ecules of the fluid taken up by the ionic liquid could be ture, as well as the operating conditions of the process. increased by the addition of a particular cosolvent. This In another embodiment, the amount of ionic liquid used is would prevent condensation reactions between molecules of 65 less than the amount of cosolvent used in the process. The the fluid in the ionic liquid, providing stabilization. Addition amount of ionic liquid is preferably between about 1% and ally, the presence of cosolvents can alter the equilibrium of about 100% of the amount of cosolvent used. In various other US 7,896,954 B2 17 18 embodiments, the amount of ionic liquid used relative to the canister to measure head pressure. This canister is connected amount of cosolvent used may be less than about 50%, 25%, to a manifold with vacuum capability and to a gas source. The 5%, and 1%. canister is also connected to an analyzer (such as FT-IR, GC, A variety of cosolvents can be used in the present inven APIMS, etc.). tion. Additionally, two or more cosolvents may be combined A vacuum bake procedure is conducted on the canister for use in any aspects of the present invention. In one embodi charged with the ionic liquid and the manifold up to the gas ment, the cosolvent is selected from liquid phase compounds. cylinder, by pulling a vacuum while heating. This removes In another embodiment, the cosolvent is selected from gas any trace moisture and other Volatile impurities from the ionic phase compounds. The cosolvents can be used in combina liquid and the gas distribution components. The ionic liquid is tion with an ionic liquid or mixtures of ionic liquids. 10 allowed to cool to the desired operating temperature. The The cosolvents may include organic and inorganic com mass of the vacuum baked canister and ionic liquid is pounds. The cosolvents may be in the liquid phase or the gas recorded. phase. Cosolvents include but are not limited to hydrocar bons, cycloalkanes, aromatic hydrocarbons, halogenated Example 1 hydrocarbons, alcohols, aldehydes, ketones, furans, amines, 15 amides, imides, nitriles, ethers, esters, epoxides, pyridiniums, Storage of an Unstable Gas in Ionic Liquid-BH pyrrolidiniums, phenols, sulfates, sulfites, Sulfides, Sulfox Stored in BMIMPF) ides, thiols, carbonyls, hydrides, halogens, water, carbon dioxide, oxygen, noble gases, organometallics and mixtures A canister of BMIMPF) is prepared as described above. thereof. Cosolvents also include, but are not limited to, inor The source gas, BH or a gas mixture containing B.H., is ganic compounds comprising alkaline salts, alkaline earth then introduced into the canister, at 5 psig, until the uptake of metal salts, transition metal complexes, lanthanide com BHe is complete. The uptake can be determined gravimetri plexes, actinide complexes. Cosolvents also include, but are cally, or by analytical methods. For example, the concentra not limited to, inorganic acids comprised of the following tion or absolute amount of the BH can be measured at the anions: Sulfates, nitrates, chlorates, phosphates, borates, car 25 inlet of the canister and the outlet of the canister. B.H. will bonates, acetates, and halides. Cosolvents also include, but continue to be introduced until the inlet and outlet concentra are not limited to, inorganic bases comprised of hydroxide tions are equivalent, indicating the BMIMPF) fluid is satu anions. CoSolvents also include, but are not limited to, rated and cannot accept any further B.H. under the existing organic acids. conditions. At this time, the source gas flow is stopped. Preferred cosolvents used in the present invention include 30 The BMIMIPF-charged canister is then heated, a pres alkaline halogenated salts, alkaline earth halogenated salts, Sure differential is applied, or it is sparged with an inert gas, in transition metal halogenated salts, lanthanide metal haloge order to deliver the stored B.H. The delivered gas is analyzed nated salts, actinide metal halogenated salts, alcohols, alde for BH content. This can be determined gravimetrically or hydes, amines, ammonia, aromatic hydrocarbons, arsenic analytically. The total amount introduced is compared to the pentafluoride, arsine, borontrichloride, borontrifluoride, car 35 total amount removed to determine the loading factor of the bon dioxide, carbon disulfide, carbon monoxide, carbon Sul cylinder. fide, chlorine, diborane, dichlorosilane, digermane, dimethyl Example 2 disulfide, dimethyl sulfide, disilane, ethane, ethers, ethylene oxide, fluorine, germane, germanium methoxide, germanium Storage of a Stable Gas in Ionic Liquid SiF Stored tetrafluoride, hafnium methylethylamide, hafnium t-butox 40 ide, halogenated hydrocarbons, halogens, hexane, hydrogen, in BMIMPF) hydrogen cyanide, hydrogenhalogenides, hydrogen selenide, A canister of BMIMPF) is prepared as described above. hydrogen Sulfide, ketones, mercaptains, methane, nitric The source gas, SiF or a gas mixture containing SiF, is oxides, nitrogen, nitrogen trifluoride, noble gases, organome then introduced into the canister, at 5 psig, until the uptake of tallics, oxygen, oxygenated-halogenated hydrocarbons, 45 SiF is complete. The uptake can be determined gravimetri phosgene, phosphine, phosphorus trifluoride, n-silane, pen cally, or by analytical methods. For example, the concentra takisdimethylamino tantalum, propane, silicon tetrachloride, tion or absolute amount of the SiF can be measured at the silicon tetrafluoride, stibine, styrene, sulfur dioxide, sulfur inlet of the canister and the outlet of the canister. SiF will hexafluoride, sulfur tetrafluoride, tetramethyl cyclotetrasi continue to be introduced until the inlet and outlet amounts loxane, titanium diethylamide, titanium dimethylamide, 50 are equivalent, indicating the BMIMPF) fluid is saturated trichlorosilane, trimethyl silane, tungsten hexafluoride, and cannot accept any further SiF under the existing condi water, and mixtures thereof. tions. At this time, the Source gas flow is stopped. Most preferred cosolvents include alcohols, water, hydro The BMIMIPF-charged canister is stored for a period of gen, ammonia, carbon dioxide, carbonyls, cyanides, Sulfides, time. It is then heated, a pressure differential is applied, or it oxygen, hydrocarbons, halogenated hydrocarbons, oxygen 55 is sparged with an inert gas, in order to deliver the stored SiF. ated hydrocarbons, hydrides, hydrogen halogenides, halides, The delivered gas is analyzed for SiF content. This can be and mixtures thereof. determined gravimetrically or analytically. The total amount introduced is compared to the total amount removed to deter EXAMPLES mine the loading factor of the cylinder. 60 For all the following Examples, a canister of ionic liquid is Example 3 prepared by the following method. A stainless steel canister with a dip tube is charged with a known quantity of the ionic Storage of an Unstable Compressed Liquefied Gas in liquid. The charged canister is thermally controlled by a PID Ionic Liquid SbH. Stored in MTBS temperature controller or variac with a heating element and a 65 thermocouple. The canister is placed on a gravimetric load A canister of MTBS (methyl-tri-n-butylammonium meth cell or weight scale and a pressure gauge is connected to the ylsulfate) is prepared as described above. US 7,896,954 B2 19 20 The source gas, SbH or a gas mixture containing SbH, is Example 6 then introduced into the canister, at 5 psig, until the uptake of SbH is complete. The uptake can be determined gravimetri Purification of an Unstable Gas with Ionic Liquid cally, or by analytical methods. For example, the concentra BH with BMIMPF) tion or absolute amount of the SbH can be measured at the inlet of the canister and the outlet of the canister. SbH will A canister of BMIMPF) is prepared as described above. continue to be introduced until the inlet and outlet amounts The source gas, BH or a gas mixture containing B.H., is are equivalent, indicating the MTBS fluid is saturated and then analyzed while by-passing the BMIMIPF-charged cannot accept any further SbH under the existing conditions. canister, in order to determine the concentration of impurities. Once the impurity concentrations in the source gas have been At this time, the Source gas flow is stopped. 10 established, source gas is flowed into the canister containing The MTBS-charged canister is then stored for a period of BMIMPF) at a pressure of 5 psig. The delivered gas from time. It is then heated, a pressure differential is applied, or it the outlet of the canister is analyzed for impurities. is sparged with an inert gas, in order to deliver the stored Purification of the source BH is determined by the lack SbH. The delivered gas is analyzed for SbH content. This of or a decrease in the impurities detected in the delivered gas can be determined gravimetrically or analytically. The total 15 compared to the source gas. The capacity of the BMIMPF) amount introduced is compared to the total amount removed for impurities is calculated by measuring the total moles of to determine the loading factor of the cylinder. impurities removed for the moles of BMIMPF) with which Example 4 the canister was charged. Example 7 Storage of a Stable Compressed Liquefied Hydride Gas in Ionic Liquid PH in BMIMPF) Purification of a Stable Gas with Ionic Liquid SiF with BMIMPF) A canister of BMIMPF) is prepared as described above. The source gas. PH or a gas mixture containing PH, is 25 A canister of BMIMPF) is prepared as described above. then introduced into the canister, at 5 psig, until the uptake of The source gas, SiF or a gas mixture containing SiF, is PH is complete. The uptake can be determined gravimetri then analyzed while by-passing the BMIMIPF-charged cally, or by analytical methods. For example, the concentra canister, in order to determine the concentration of impurities. Once the impurity concentrations in the source gas have been tion or absolute amount of the PH can be measured at the established, source gas is flowed into the canister containing inlet of the canister and the outlet of the canister. PH will 30 BMIMPF) at a pressure of 5 psig. The delivered gas from continue to be introduced until the inlet and outlet amounts the outlet of the canister is analyzed for impurities are equivalent, indicating the BMIMPF) fluid is saturated Purification of the source SiF is determined by the lack of and cannot accept any further PH under the existing condi or a decrease in the impurities detected in the delivered gas tions. At this time, the source gas flow is stopped. compared to the source gas. The capacity of the BMIMPF) The BMIMIPF-charged canister is then heated, a pres 35 for impurities is calculated by measuring the total moles of Sure differential is applied, or it is sparged with an inert gas, in impurities removed for the moles of BMIMPF) with which order to deliver the stored PH. The delivered gas is analyzed the canister was charged. for PH content. This can be determined gravimetrically or analytically. The total amount introduced is compared to the Example 8 total amount removed to determine the loading factor of the 40 cylinder. Purification of an Unstable Compressed Liquefied Gas with Ionic Liquid SbH, with MTBS Example 5 A canister of MTBS is prepared as described above. Storage of a Stable Compressed Liquefied Acid Gas 45 The source gas, SbH or a gas mixture containing SbH, is in Acidic Ionic Liquid HCl in EMIMAICl. then analyzed while by-passing the MTBS-charged canister, in order to determine the concentration of impurities. Once A canister of EMIMAlCl is prepared as described the impurity concentrations in the Source gas have been estab above. lished, source gas is flowed into the canister containing The source gas, HCl or a gas mixture containing HCl, is 50 MTBS at a pressure of 5 psig. The delivered gas from the then introduced into the canister, at the vapor pressure of HCl, outlet of the canister is analyzed for impurities. until the uptake of HCl is complete. The uptake can be deter Purification of the source SbH is determined by the lack of or a decrease in the impurities detected in the delivered gas mined gravimetrically, or by analytical methods. For compared to the source gas. The capacity of the MTBS for example, the concentration or absolute amount of the HCl can impurities is calculated by measuring the total moles of impu be measured at the inlet of the canister and the outlet of the 55 rities removed for the moles of MTBS with which the canister canister. HCl will continue to be introduced until the inlet and was charged. outlet amounts are equivalent, indicating the EMIMAlCl4] fluid is saturated and cannot accept any further HCl under the Example 9 existing conditions. At this time, the source gas flow is stopped. 60 Purification of an Unstable Compressed Liquefied The EMIMAIC1-charged canister is then heated, a pres Gas in the Liquid Phase with Ionic Liquid SbH Sure differential is applied, or it is sparged with an inert gas, in with MTBS order to deliver the stored HC1. The delivered gas is analyzed for HCl content. This can be determined gravimetrically or A canister of MTBS is prepared as described above. analytically. The total amount introduced is compared to the 65 The liquid phase source material, SbH, is flowed through total amount removed to determine the loading factor of the the apparatus, by-passing the MTBS-charged canister, vapor cylinder. ized, and analyzed in order to determine the concentration of US 7,896,954 B2 21 22 impurities. Once the impurity levels in the source fluid have Source fluid have been established, liquid phase source mate been established, liquid phase source material is flowed into rial is flowed into the canister containing EMIMAcetat, at the canister containing MTBS, at the vapor pressure of SbH. the vapor pressure of NH. The delivered liquid from the The delivered liquid from the outlet of the canister is vapor outlet of the canister is vaporized and analyzed to determine ized and analyzed to determine the concentration of the impu the concentration of the impurities. rities. Purification of the source NH is determined by the lack of Purification of the source SbH is determined by the lack or a decrease in the impurities detected in the delivered liquid of, or a decrease in the impurities detected in the delivered when compared to the source liquid, as determined by analy liquid when compared to the source liquid, as determined by sis in the vapor phase. The capacity of the EMIMLAcetat for analysis in the vapor phase. The capacity of the MTBS for 10 impurities is calculated by measuring the total moles of impu impurities is calculated by measuring the total moles of impu rities removed for the moles of EMIMAcetat with which the rities removed for the moles of MTBS with which the canister canister was charged. was charged. Example 13 Example 10 15 Stabilization of an Unstable Gas with Ionic Liquid Purification of a Stable Compressed Liquefied BH with BMIMPF) Hydride Gas with Ionic Liquid PH with A canister of BMIMPF) is prepared as described above. BMIMPF) The source gas, BH or a gas mixture containing B.H., is A canister of BMIMPF) is prepared as described above. analyzed while by-passing the BMIMIPF-charged canister, The source gas, PH or a gas mixture containing PH, is in order to determine the concentration of BH and decom analyzed while by-passing the BMIMIPF-charged canister, position products. Once these concentrations in the Source in order to determine the concentration of impurities. Once gas have been established, Source gas is flowed into the can the impurity concentrations in the Source gas have been estab ister containing BMIMPF) until it has equilibrated to a lished, source gas is flowed into the canister containing 25 pressure of 5 psig. At this time, the flow of the source material BMIMPF at the vapor pressure of PH. The delivered gas is stopped. from the outlet of the canister is analyzed for impurities. With the source gas flow off, the gas from the outlet of the Purification of the stored PH is determined by the lack of canister containing the BMIMPFI is then analyzed for BH or a decrease in the impurities detected in the delivered gas and decomposition products. compared to the source gas. The capacity of the BMIMPF) 30 Stabilization of the source BH is determined by the lack for impurities is calculated by measuring the total moles of of or a decrease in the decomposition products detected in the impurities removed for the moles of BMIMPF) with which delivered gas compared to the source gas, in addition to the canister was charged. quantitative recovery of BH. Example 11 Example 14 35 Purification of a Stable Compressed Liquefied Acid Stabilization of an Unstable Compressed Liquefied Gas in the Liquid Phase with Ionic Liquid SbH Gas with Ionic Liquid HCl with EMIMAlCl with MTBS A canister of EMIMAlCl is prepared as described above. 40 A canister of MTBS is prepared as described above. The source gas, HCl or a gas mixture containing HCl, is The liquid phase source material, SbH, is flowed through analyzed while by-passing the EMIMAlCl4]-charged canis the apparatus, by-passing the MTBS-charged canister, vapor ter, in order to determine the concentration of moisture. Once ized, and analyzed in order to determine the concentration of the H2O concentration in the source gas have been estab decomposition products. Once the decomposition levels in lished, source gas is flowed into the canister containing 45 the source fluid have been established, liquid phase source EMIMAlCl4 at a pressure of 5 psig. The gas is bubbled material is flowed into the canister containing MTBS, at the through the EMIMAICl inside the canister and the deliv vapor pressure of SbH. At this time, the flow of the source ered gas at the outlet of the canister is analyzed to measure the material is stopped. moisture content. With the source flow off, the delivered liquid from the outlet of the canister is vaporized and analyzed for SbH and Purification of the stored HCl is determined by the lack of 50 or a decrease in the H2O impurity concentration detected in decomposition products. the delivered gas compared to the source gas. The capacity of Stabilization of the source SbH is determined by the lack the EMIMAlCl for impurities is calculated by measuring of or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to the total moles of HO removed for the moles of EMIM quantitative recovery of SbH. AlCl with which the canister was charged. 55 Example 12 Example 15 Purification of a Stable Compressed Liquefied Gas in Storage and Purification of an Unstable Gas in Ionic the Liquid Phase with Ionic Liquid NH with Liquid B.H. with BMIMPF) EMIMAcetat 60 A canister of BMIMPF) is prepared as described above. A canister of EMIMLAcetat is prepared as described The source gas, BH or a gas mixture containing B.H., is above. analyzed while by-passing the BMIMIPF-charged canister, The liquid phase source material, NH, is flowed through in order to determine the concentration of impurities. Once the apparatus, by-passing the EMIMAcetat-charged canis 65 the impurity concentrations in the Source gas have been estab ter, vaporized, and analyzed in order to determine the con lished, source gas is flowed into the canister containing centration of impurities. Once the impurity levels in the BMIMPF at a pressure of 5 psig, until the uptake of BH US 7,896,954 B2 23 24 is complete. The uptake can be determined gravimetrically, or absolute amount of the SbH can be measured at the inlet of by analytical methods. For example, the concentration or the canister and the outlet of the canister. SbH will continue absolute amount of the BH can be measured at the inlet of to be introduced until the inlet and outlet concentrations are the canister and the outlet of the canister. B.H. will continue equivalent, indicating the MTBS fluid is saturated and cannot to be introduced until the inlet and outlet concentrations are 5 accept any further SbH under the existing conditions. At this equivalent, indicating the BMIMPF) fluid is saturated and time, the source gas flow is stopped. cannot accept any further B.H. under the existing conditions. The MTBS-charged canister is then heated, a pressure At this time, the Source gas flow is stopped. 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 SbH. The delivered gas from the Sure differential is applied, or it is sparged with an inert gas, in 10 outlet of the canister is analyzed for impurities. order to deliver the stored B.H. The delivered gas from the Purification of the source SbH is determined by the lack outlet of the canister is analyzed for impurities. of or a decrease in the impurities detected in the delivered gas The canister is then stored for a period of time. Samples of from the canister compared to the Source gas. The capacity of BH are taken at time intervals in order to determined the the MTBS for impurities is calculated by measuring the total stability of the BH in the BMIMPF). Purification of the 15 moles of impurities removed for the moles of MTBS with source BH is determined by the lack of, or a decrease in the which the canister was charged. impurities detected in the delivered gas from the canister compared to the source gas. The capacity of the BMIMPF) Example 18 for impurities is calculated by measuring the total moles of impurities removed for the moles of BMIMPF6 with which Storage and Purification of a Stable Compressed the canister was charged. Liquefied Gas in Ionic Liquid PH with BMIMPF) Example 16 A canister of BMIMPF) is prepared as described above. Storage and Purification of a Stable Gas in Ionic 25 The source gas, PH or a gas mixture containing PH, is Liquid SiF with BMIMPF) analyzed while by-passing the BMIMIPF-charged canister, in order to determine the concentration of impurities. Once A canister of BMIMPF) is prepared as described above. the impurity concentrations in the Source gas have been estab The source gas, SiF or a gas mixture containing SiF, is lished, source gas is flowed into the canister containing analyzed while by-passing the BMIMIPF-charged canister, 30 BMIMPF) at a pressure of 5 psig, until the uptake of PH is in order to determine the concentration of impurities. Once complete. The uptake can be determined gravimetrically, or the impurity concentrations in the source gas have been estab by analytical methods. For example, the concentration or lished, source gas is flowed into the canister containing absolute amount of the PH can be measured at the inlet of the BMIMPF at a pressure of 5 psig, until the uptake of SiF is canister and the outlet of the canister. PH will continue to be complete. The uptake can be determined gravimetrically, or 35 introduced until the inlet and outlet concentrations are by analytical methods. For example, the concentration or equivalent, indicating the BMIMPF) liquid is saturated and absolute amount of the SiF can be measured at the inlet of the cannot accept any further PH under the existing conditions. canister and the outlet of the canister. SiF will continue to be At this time, the source gas flow is stopped. introduced until the inlet and outlet concentrations are The BMIMIPF-charged canister is then heated, a pres equivalent, indicating the BMIMPF) fluid is saturated and 40 Sure differential is applied, or it is sparged with an inert gas, in cannot accept any further SiF under the existing conditions. order to deliver the stored PH. The delivered gas from the At this time, the Source gas flow is stopped. outlet of the canister is analyzed for impurities. The BMIMIPF-charged canister is then heated, a pres Purification of the source PH is determined by the lack of, Sure differential is applied, or it is sparged with an inert gas, in or a decrease in the impurities detected in the delivered gas order to deliver the stored SiF. The delivered gas from the 45 from the canister compared to the Source gas. The capacity of outlet of the canister is analyzed for impurities. the BMIMPF) for impurities is calculated by measuring the Purification of the source SiF is determined by the lack of total moles of impurities removed for the moles of BMIM or a decrease in the impurities detected in the delivered gas IPF with which the canister was charged. from the canister compared to the Source gas. The capacity of the BMIMPF) for impurities is calculated by measuring the 50 Example 19 total moles of impurities removed for the moles of BMIM IPF with which the canister was charged. Storage and Purification of a Stable Compressed Liquefied Gas in Acidic Ionic Liquid HCl with Example 17 EMIMAlCl 55 Storage and Purification of an Unstable Compressed A canister of EMIMAICl is prepared as described Liquefied Gas in Ionic Liquid SbH with MTBS above. The source gas, HCl or a gas mixture containing HCl, is A canister of MTBS is prepared as described above. analyzed while by-passing the EMIMAlCl4]-charged canis The source gas, SbH or a gas mixture containing SbH, is 60 ter, in order to determine the concentration of impurities. analyzed while by-passing the MTBS-charged canister, in Once the impurity concentrations in the source gas have been order to determine the concentration of impurities. Once the established, source gas is flowed into the canister containing impurity concentrations in the Source gas have been estab EMIMAlCl at a pressure of 5 psig, until the uptake of HCl lished, source gas is flowed into the canister containing is complete. The uptake can be determined gravimetrically, or MTBS at a pressure of 5 psig, until the uptake of SbH is 65 by analytical methods. For example, the concentration or complete. The uptake can be determined gravimetrically, or absolute amount of the HCl can be measured at the inlet of the by analytical methods. For example, the concentration or canister and the outlet of the canister. HCl will continue to be US 7,896,954 B2 25 26 introduced until the inlet and outlet concentrations are The MTBS-charged canister is then heated, a pressure equivalent, indicating the EMIMAlCl liquid is saturated differential is applied, or it is sparged with an inert gas, in and cannot accept any further HCl under the existing condi order to deliver the stored SbH. The delivered gas from the tions. At this time, the source gas flow is stopped. outlet of the canister is analyzed for SbH and decomposition The EMIMAIC1-charged canister is then heated, a pres products. Sure differential is applied, or it is sparged with an inert gas, in Stabilization of the source SbH is determined by the lack order to deliver the stored HC1. The delivered gas from the of or a decrease in the decomposition products detected in the outlet of the canister is analyzed for impurities. delivered gas compared to the source gas, in addition to Purification of the source HCl is determined by the lack of, quantitative recovery of SbH. or a decrease in the impurities detected in the delivered gas 10 from the canister compared to the Source gas. The capacity of Example 22 the EMIMAICl for impurities is calculated by measuring the total moles of impurities removed for the moles of EMIM Stabilization and Purification of an Unstable Gas AlCl with which the canister was charged. with Ionic Liquid B.H. with BMIMPF) 15 Example 20 A canister of BMIMPF) is prepared as described above. The source gas, BH or a gas mixture containing B.H., is Storage and Stabilization of an Unstable Gas in Ionic analyzed while by-passing the BMIMIPF-charged canister, Liquid B.H. with BMIMPF) in order to determine the concentration of BH, impurities, and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into A canister of BMIMPF) is prepared as described above. the canister containing BMIMPF) until it has equilibrated at The Source gas, BH or a gas mixture containing B2H6, is a pressure of 5 psig. At this time, the Source gas flow is analyzed while by-passing the BMIMIPF-charged canister, stopped. in order to determine the concentration of BH and decom position products. Once these concentrations in the Source 25 With the source gas flow off, the gas from the outlet of the gas have been established, Source gas is flowed into the can canister containing the BMIMPF) is then analyzed for ister containing BMIMPF) at a pressure of 5 psig, until the BH, impurities, and decomposition products. uptake of BHe is complete. The uptake can be determined Stabilization of the source BH is determined by the lack 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 BH can be mea 30 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 BH. BH will continue to be introduced until the inlet and outlet Purification of the source BH is determined by the lack concentrations are equivalent, indicating the BMIMPF) of or a decrease in the impurities detected in the delivered gas fluid is saturated and cannot accept any further B.H. under from the canister compared to the Source gas. The capacity of the existing conditions. At this time, the source gas flow is 35 the BMIMPF) for impurities is calculated by measuring the stopped. total moles of impurities removed for the moles of BMIM The BMIMIPF-charged canister is then heated, a pres |PF with which the canister was charged. Sure differential is applied, or it is sparged with an inert gas, in Example 23 order to deliver the stored B.H. The delivered gas from the 40 outlet of the canister is analyzed for BH and decomposition Stabilization and Purification of an Unstable products. Compressed Liquefied Gas with Ionic Stabilization of the source BH is determined by the lack Liquid SbH3 with MTBS of or a decrease in the decomposition products detected in the delivered gas compared to the Source gas, in addition to 45 A canister of MTBS is prepared as described above. quantitative recovery to the source material. The source gas, SbH or a gas mixture containing SbH, is analyzed while by-passing the MTBS-charged canister, in Example 21 order to determine the concentration of SbH, impurities, and decomposition products. Once these concentrations in the Storage and Stabilization of an Unstable Compressed 50 Source gas have been established, Source gas is flowed into the Liquefied Gas with Ionic Liquid SbH with MTBS canister containing MTBS until it has equilibrated at 5 psig. At this time, the source gas flow is stopped. A canister of MTBS is prepared as described above. With the source gas flow off, the gas from the outlet of the The source gas, SbH or a gas mixture containing SbH, is canister containing the MTBS is then analyzed for SbH, analyzed while by-passing the MTBS-charged canister, in 55 impurities, and decomposition products. order to determine the concentration of SbH and decompo The MTBS-charged canister is then heated, a pressure sition products. Once these concentrations in the Source gas differential is applied, or it is sparged with an inert gas, in have been established, source gas is flowed into the canister order to deliver the stored SbH. The delivered gas from the containing MTBS at a pressure of 5 psig, until the uptake of outlet of the canister is analyzed for SbH, impurities, and SbH is complete. The uptake can be determined gravimetri 60 decomposition products. cally, or by analytical methods. For example, the concentra Stabilization of the source SbH is determined by the lack tion or absolute amount of the SbH can be measured at the of or a decrease in the decomposition products detected in the inlet of the canister and the outlet of the canister. SbH will delivered gas compared to the source gas, in addition to continue to be introduced until the inlet and outlet concentra quantitative recovery of SbH. tions are equivalent, indicating the MTBS fluid is saturated 65 Purification of the source SbH is determined by the lack and cannot accept any further SbH under the existing con of or a decrease in the impurities detected in the delivered gas ditions. At this time, the source gas flow is stopped. from the canister compared to the Source gas. The capacity of US 7,896,954 B2 27 28 the MTBS for impurities is calculated by measuring the total Stabilization of the source SbH is determined by the lack moles of impurities removed for the moles of MTBS with of or a decrease in the decomposition products detected in the which the canister was charged. delivered gas compared to the source gas, in addition to Example 24 quantitative recovery of SbH. Purification of the source SbH is determined by the lack of or a decrease in the impurities detected in the delivered gas Storage, Purification, and Stabilization of an from the canister compared to the Source gas. The capacity of Unstable Gas with Ionic Liquid B.H. with BMIM the MTBS for impurities is calculated by measuring the total PF moles of impurities removed for the moles of MTBS with A canister of BMIMPF) is prepared as described above. 10 which the canister was charged. The source gas, BH or a gas mixture containing B2H6, is analyzed while by-passing the BMIMIPF-charged canister, Example 26 in order to determine the concentration of BH, impurities, Storage of CS in BMIMPF) using CO as a and decomposition products. Once these concentrations in Cosolvent the Source gas have been established, Source gas is flowed into 15 the canister containing BMIMPF) at a pressure of 5 psig, A canister of BMIMPF) is prepared as described above. until the uptake of BH is complete. The uptake can be The canister is charged with the cosolvent, CO., by bub determined gravimetrically, or by analytical methods. For bling the CO into the ionic liquid until the desired pressure is example, the concentration or absolute amount of the BH obtained in the canister. can be measured at the inlet of the canister and the outlet of the The source gas, CS or a gas mixture containing CS, is canister. B.H. will continue to be introduced until the inlet then introduced into the canister at 5 psig, until the uptake of and outlet concentrations are equivalent, indicating the CS is complete. The uptake can be determined gravimetri BMIMPF) fluid is saturated and cannot accept any further cally. The charged canister is stored for a period of time. It is BH under the existing conditions. At this time, the Source 25 heated, a pressure differential is applied, or it is sparged with gas flow is stopped. an inert gas in order to deliver the stored CS. The total The BMIMIPF-charged canister is then heated, a pres amount of CS introduced into to the canister is compared to Sure differential is applied, or it is sparged with an inert gas, in the total amount removed to determine the loading factor of order to deliver the stored B.H. The delivered gas from the the cylinder. outlet of the canister is analyzed for B.H., impurities, and 30 decomposition products. Example 27 Stabilization of the source BH is determined by the lack of or a decrease in the decomposition products detected in the Storage of CH in BMIMPF. Using Ethanol as a delivered gas compared to the Source gas, in addition to Cosolvent quantitative recovery of BH. 35 Purification of the source BH is determined by the lack A canister of BMIMPF) is prepared as described above. of or a decrease in the impurities detected in the delivered gas The canister is charged with a gravimetrically determined from the canister compared to the Source gas. The capacity of amount of the cosolvent, ethanol. the BMIMPF) for impurities is calculated by measuring the The source gas, CH or a gas mixture containing CH, is total moles of impurities removed for the moles of BMIM 40 then introduced into the canister at 5 psig, until the uptake of IPF with which the canister was charged. CH is complete. The uptake can be determined gravimetri Example 25 cally. The charged canister is stored for a period of time. It is heated, a pressure differential is applied, or it is sparged with Storage, Purification, and Stabilization of an an inert gas in order to deliver the stored CH. The total Unstable Compressed Liquefied Gas with Ionic 45 amount of CH introduced into to the canister is compared to Liquid SbH with MTBS the total amount removed to determine the loading factor of the cylinder. A canister of MTBS is prepared as described above. The source gas, SbH or a gas mixture containing SbH, is Example 28 analyzed while by-passing the MTBS-charged canister, in 50 order to determine the concentration of SbH, impurities, and Storage and Stabilization of BH in BMIMPF) decomposition products. Once these concentrations in the Using H2 as a Cosolvent Source gas have been established, source gas is flowed into the canister containing MTBS at a pressure of 5 psig, until the A canister of BMIMPF) is prepared as described above. uptake of SbH is complete. The uptake can be determined 55 The canister is charged with the cosolvent, hydrogen gas, gravimetrically, or by analytical methods. For example, the by bubbling the gas into the ionic liquid until the desired concentration or absolute amount of the SbH can be mea pressure is obtained in the canister. sured at the inlet of the canister and the outlet of the canister. The source gas, BH or a gas mixture containing B.H., is SbH will continue to be introduced until the inlet and outlet analyzed while by-passing the charged canister, in order to concentrations are equivalent, indicating the MTBS fluid is 60 determine the concentration of BH and decomposition saturated and cannot accept any further SbH under the exist products. Once these concentrations in the Source gas have ing conditions. At this time, the source gas flow is stopped. been established, Source gas is flowed into the canister con The MTBS-charged canister is then heated, a pressure taining BMIMPF) and hydrogen cosolvent at a pressure of differential is applied, or it is sparged with an inert gas, in 5 psig, until the uptake of BHe is complete. The uptake can be order to deliver the stored SbH. The delivered gas from the 65 determined gravimetrically. outlet of the canister is analyzed for SbH, impurities, and Stabilization of the source BH is determined by the lack decomposition products. of or a decrease in the decomposition products detected in the US 7,896,954 B2 29 30 delivered gas compared to the Source gas, in addition to 7. The method of claim 1 wherein said impurity is retained quantitative recovery to the source material. within the cosolvent. The embodiments described above and shown herein are 8. The method of claim 1 wherein said impurity is retained illustrative and not restrictive. The scope of the invention is within the ionic liquid. indicated by the claims rather than by the foregoing descrip 9. The method of claim 1 wherein the fluid is selected from tion and attached drawings. The invention may be embodied the group consisting of alcohols, aldehydes, amines, ammo in other specific forms without departing from the spirit of the nia, aromatic hydrocarbons, arsenic pentafluoride, arsine, invention. Accordingly, these and any other changes which boron trichloride, boron trifluoride, carbon disulfide, carbon come within the scope of the claims are intended to be monoxide, carbon Sulfide, diborane, dichlorosilane, diger embraced therein. 10 mane, dimethyl disulfide, dimethyl sulfide, disilane, ethers, What is claimed is: ethylene oxide, germane, germanium methoxide, germanium 1. A method of separating an impurity from a fluid mixture tetrafluoride, hafnium methylethylamide, hafnium t-butox wherein the fluid mixture comprises a fluid in contact with a ide, halogenated hydrocarbons, halogens, hexane, hydrogen solvent mixture all of which have been stored within a vessel cyanide, hydrogen halogenides, hydrogen selenide, hydrogen by a source gas manufacturer and shipped to an end user, 15 Sulfide, ketones, mercaptains, nitric oxides, nitrogen trifluo comprising: ride, organometallics, oxygenated-halogenated hydrocar receiving the vessel containing the fluid and the Solvent bons, phosgene, phosphorus trifluoride, n-silane, pentakis mixture wherein the fluid may or may not contain an dimethylamino tantalum, phosphine, silicon tetrachloride, impurity and wherein the solvent mixture comprises an silicon tetrafluoride, stibine, styrene, sulfur dioxide, sulfinur ionic liquid and a cosolvent; hexafluoride, sulfur tetrafluoride, tetramethyl cyclotetrasi placing the vessel in fluid communication with a gas dis loxane, titanium diethylamide, titanium dimethylamide, tribution system wherein the fluid within the vessel con trichlorosilane, trimethylsilane, tungsten hexafluoride, and tains an impurity; mixtures thereof. retaining said impurity within the solvent mixture to pro 10. The method of claim 1 wherein the fluid comprises a duce a purified fluid; and 25 gaS. releasing said purified fluid from the vessel separately from 11. The method of claim 1 wherein the fluid comprises a said solvent mixture. liquid. 2. The method of claim 1 wherein the fluid contains said 12. The method of claim 1 wherein the fluid is selected impurity prior to placing the vessel in fluid communication from the group consisting of arsenic pentafluoride, arsine, with said gas distribution system. 30 borontrichloride, borontrifluoride, germanium tetrafluoride, 3. The method of claim 1 wherein the fluid becomes con hydrogen selenide, phosphine, phosphorustrifluoride, silicon taminated with said impurity upon placing the vessel in fluid tetrafluoride, chlorine, fluorine, ammonia, silane, and mix communication with said gas distribution system. tures thereof. 4. The method of claim 1 wherein the cosolvent is selected 13. The method of claim 1 wherein the fluid is selected from the group consisting of alkaline halogenated salts, alka 35 from the group consisting of digermane, Stilbene, diborane, line earth halogenated salts, transition metal halogenated borane, nitric oxide, disilane, and hydrogen selenide. salts, lanthanide metal halogenated salts, actinide metal halo 14. The method of claim 1 wherein the ionic liquid is genated salts, alcohols, aldehydes, amines, ammonia, aro selected from the group consisting of mono-Substituted imi matic hydrocarbons, arsenic pentafluoride, arsine, boron dazolium salts, di-substituted imidazolium salts, tri-substi trichloride, boron trifluoride, carbon dioxide, carbon disul 40 tuted imidazolium salts, pyridinium salts, pyrrolidinium fide, carbon monoxide, carbon Sulfide, chlorine, diborane, salts, phosphonium salts, ammonium salts, tetralkylammo dichlorosilane, digermane, dimethyl disulfide, dimethyl Sul nium salts, guanidinium salts, uronium salts, and mixtures fide, disilane, ethane, ethers, ethylene oxide, fluorine, ger thereof. mane, germanium methoxide, germanium tetrafluoride, 15. The method of claim 1 wherein the ionic liquid is hafnium methylethylamide, hafnium t-butoxide, halogenated 45 selected from the group consisting of pyridinium salts, pyr hydrocarbons, halogens, hexane, hydrogen, hydrogen cya rolidinium salts, phosphonium salts, ammonium salts, nide, hydrogen halogenides, hydrogen selenide, hydrogen tetralkylammonium salts, guanidinium salts, uronium salts, Sulfide, ketones, mercaptains, methane, nitric oxides, nitro and mixtures thereof. gen, nitrogen trifluoride, noble gases, organometallics, oxy 16. The method of claim 1 wherein said impurity is selected gen, oxygenated-halogenated hydrocarbons, phosgene, 50 from the group consisting of water, CO, oxygen, CO., NO. phosphine, phosphorus trifluoride, n-silane, pentakisdim NO, NO, SO, SO, SO, S.O., SO, and mixtures thereof. ethylamino tantalum, propane, silicon tetrachloride, silicon 17. The method of claim 1 wherein said impurity has an tetrafluoride, stibine, styrene, sulfur dioxide, sulfur hexafluo affinity which is greater towards said ionic liquid than for the ride, sulfur tetrafluoride, tetramethyl cyclotetrasiloxane, tita fluid. nium diethylamide, titanium dimethylamide, trichlorosilane, 55 trimethylsilane, tungsten hexafluoride, water, and mixtures 18. The method of claim 1 wherein there is substantially no thereof. chemical change in said ionic liquid. 19. A method of stabilizing an unstable fluid for an end user 5. The method of claim 1 wherein the step of releasing said that can be shipped, stored, handled and dispensed, compris purified fluid from the solvent mixture is achieved by control 1ng: ling either the temperature and/or the pressure gradient of the 60 Solvent mixture. providing a vessel configured for selectively dispensing the 6. The method of claim 1 wherein the cosolvent is selected unstable fluid thereform; from the group consisting of alcohols, water, hydrogen, providing an ionic liquid and a cosolvent within the vessel; ammonia, carbon dioxide, carbonyls, cyanides, sulfides, oxy introducing the unstable fluid into the vessel; gen, hydrocarbons, halogenated hydrocarbons, oxygenated 65 contacting the unstable fluid with said ionic liquid and said hydrocarbons, hydrides, hydrogen halogenides, halides, and cosolvent wherein said cosolvent changes the solubility mixtures thereof. of the unstable fluid to said ionic liquid; and US 7,896,954 B2 31 32 shipping the vessel containing the unstable fluid to the end dispensing a purified fluid from the vessel separately from user wherein there is substantially no decomposition of the solvent mixture by controlling either the temperature the unstable fluid prior the release of the unstable fluid. and/or the pressure gradient of the solvent mixture. 20. The method of claim 19 wherein said cosolvent is 31. The method of claim 30 wherein the cosolvent is selected from the group consisting of alkaline halogenated 5 selected from the group consisting of alkaline halogenated salts, alkaline earth halogenated salts, transition metal halo salts, alkaline earth halogenated salts, transition metal halo genated salts, lanthanide metal halogenated salts, actinide genated salts, lanthanide metal halogenated salts, actinide metal halogenated salts, alcohols, aldehydes, amines, ammo metal halogenated salts, alcohols, aldehydes, amines, ammo nia, aromatic hydrocarbons, arsenic pentafluoride, arsine, nia, aromatic hydrocarbons, arsenic pentafluoride, arsine, boron trichloride, boron trifluoride, carbon dioxide, carbon 10 boron trichloride, boron trifluoride, carbon dioxide, carbon disulfide, carbon monoxide, carbon sulfide, chlorine, dibo disulfide, carbon monoxide, carbon sulfide, chlorine, dibo rane, dichlorosilane, digermane, dimethyl disulfide, dimethyl rane, dichlorosilane, digermane, dimethyl disulfide, dimethyl Sulfide, disilane, ethane, ethers, ethylene oxide, fluorine, ger Sulfide, disilane, ethane, ethers, ethylene oxide, fluorine, ger mane, germanium methoxide, germanium tetrafluoride, mane, germanium methoxide, germanium tetrafluoride, hafnium methylethylamide, hafnium t-butoxide, halogenated hafiium methylethylamide, hafnium t-butoxide, halogenated hydrocarbons, halogens, hexane, hydrogen, hydrogen cya 15 hydrocarbons, halogens, hexane, hydrogen, hydrogen cya nide, hydrogen halogenides, hydrogen selenide, hydrogen nide, hydrogen halogenides, hydrogen selenide, hydrogen Sulfide, ketones, mercaptains, methane, nitric oxides, nitro Sulfide, ketones, mercaptains, methane, nitric oxides, nitro gen, nitrogen trifluoride, noble gases, organometallics, oxy gen, nitrogen trifluoride, noble gases, organometallics, oxy gen, oxygenated-halogenated hydrocarbons, phosgene, gen, oxygenated-halogenated hydrocarbons, phosgene, phosphine, phosphorus trifluoride, n-silane, pentakisdim phosphine, phosphorus trifluoride, n-silane, pentakisdim ethylamino tantalum, propane, silicon tetrachloride, silicon ethylamino tantalum, propane, silicon tetrachloride, silicon tetrafluoride, stibine, styrene, sulfur dioxide, sulfur hexafluo tetrafluoride, stibine, styrene, sulfur dioxide, sulfur hexafluo ride, sulfur tetrafluoride, tetramethyl cyclotetrasiloxane, tita ride, sulfinur tetrafluoride, tetramethyl cyclotetrasiloxane, nium diethylamide, titanium dimethylamide, trichlorosilane, titanium diethylamide, titanium dimethylamide, trichlorosi trimethylsilane, tungsten hexafluoride, water, and mixtures 25 lane, trimethylsilane, tungsten hexafluoride, water, and mix thereof. tures thereof. 21. The method of claim 19 wherein said cosolvent is 32. The method of claim 30 wherein the cosolvent is selected from the group consisting of alcohols, water, hydro selected from the group consisting of alcohols, water, hydro gen, ammonia, carbon dioxide, carbonyls, cyanides, Sulfides, gen, ammonia, carbon dioxide, carbonyls, cyanides, sulfides, oxygen, hydrocarbons, halogenated hydrocarbons, oxygen 30 oxygen, hydrocarbons, halogenated hydrocarbons, oxygen ated hydrocarbons, hydrides, hydrogen halogenides, halides, ated hydrocarbons, hydrides, hydrogen halogenides, halides, and mixtures thereof. and mixtures thereof. 22. The method of claim 19 wherein said ionic liquid is 33. The method of claim 30 wherein the fluid is selected selected from the group consisting of mono-Substituted imi from the group consisting of alcohols, aldehydes, amines, dazolium salts, di-substituted imidazolium salts, tri-Substi ammonia, aromatic hydrocarbons, arsenic pentafluoride, ars tuted imidazolium salts, pyridinium salts, pyrrolidinium 35 ine, borontrichloride, borontrifluoride, carbon disulfide, car salts, phosphonium salts, ammonium salts, tetralkylammo bon monoxide, carbon Sulfide, diborane, dichlorosilane, nium salts, guanidinium salts, uronium salts, and mixtures digermane, dimethyl disulfide, dimethyl sulfide, disilane, thereof. ethers, ethylene oxide, germane, germanium methoxide, ger 23. The method of claim 19 wherein said ionic liquid is manium tetrafluoride, hafiiium methylethylamide, hafnium selected from the group consisting of pyridinium salts, pyr 40 t-butoxide, halogenated hydrocarbons, halogens, hexane, rolidinium salts, phosphonium salts, ammonium salts, hydrogen cyanide, hydrogen halogenides, hydrogen selenide, tetralkylammonium salts, guanidinium salts, uronium salts, hydrogen Sulfide, ketones, mercaptains, nitric oxides, nitrogen and mixtures thereof. trifluoride, organometallics, oxygenated-halogenated hydro 24. The method of claim 19 wherein the unstable fluid is carbons, phosgene, phosphorus trifluoride, n-silane, pentak 45 isdimethylamino tantalum, phosphine, silicon tetrachloride, selected from the group consisting of digermane, borane, silicon tetrafluoride, stibine, styrene, sulfur dioxide, sulfur diborane, disilane, fluorine, halogenated oxy-hydrocarbons, hexafluoride, sulfur tetrafluoride, tetramethyl cyclotetrasi hydrogen selenide, Stilbene, nitric oxide, organometallics and loxane, titanium diethylamide, titanium dimethylamide, mixtures thereof. trichlorosilane, trimethylsilane, tungsten hexafluoride, and 25. The method of claim 19 wherein the unstable fluid mixtures thereof. mixture comprises a gas. 50 34. The method of claim 30 wherein the ionic liquid is 26. The method of claim 19 wherein the unstable fluid selected from the group consisting of phosphonium salts, mixture comprises a liquid. ammonium salts, tetralkylammonium salts, guanidinium 27. The method of claim 19 wherein the shipment time is at salts, uronium salts, and mixtures thereof. least about 24 hours. 35. A method of storing, stabilizing and dispensing an 28. The method of claim 19 wherein the shipment time is at 55 unstable fluid in contact with a solvent mixture all of which least about 7 days. has been stored within a vessel by a source gas manufacturer 29. The method of claim 19 wherein there is substantially and shipped to an end user, comprising: no chemical change in said ionic liquid. receiving the vessel containing the unstable fluid in contact 30. A method of storing, purifying, and dispensing a fluid with the solvent mixture wherein the solvent mixture mixture wherein the fluid mixture comprises a fluid having an 60 comprises an ionic liquid and a cosolvent and wherein impurity in contact with a solvent mixture all of which have the unstable fluid is contacted for a controllable period been stored within a vessel by a source gas manufacturer and of time with the solvent mixture for take-up of the shipped to an end user, comprising: unstable fluid by the solvent mixture wherein said cosol receiving the vessel containing the fluid and the Solvent vent changes the solubility of the unstable fluid to the mixture wherein the solvent mixture comprises an ionic 65 ionic liquid; liquid and a cosolvent; storing the unstable fluid within the solvent mixture during attaching the vessel to a gas distribution system; and which period of time there is substantially no decompo US 7,896,954 B2 33 34 sition of the unstable fluid prior to the unstable fluid 42. A method of separating an impurity from a fluid mix being released from the vessel separately from said sol ture wherein the fluid mixture comprises a fluid in contact vent mixture by controlling either the temperature and/ with a solvent mixture all of which have been stored within a or the pressure gradient of the ionic liquid; vessel by a source gas manufacturer and shipped to an end placing the vessel in fluid communication with a gas dis 5 user, comprising: tribution system wherein the fluid within the vessel con receiving the vessel containing the fluid and the solvent tains an impurity; mixture wherein the fluid is selected from the group retaining said impurity within said solvent mixture to pro consisting of arsenic pentafluoride, arsine, boron duce a purified fluid; and trichloride, boron trifluoride, germanium tetrafluoride, releasing said purified fluid from the vessel separately from 10 hydrogen selenide, phosphine, phosphorus trifluoride, silicon tetrafluoride, chlorine, fluorine, ammonia, silane, said solvent mixture. and mixtures thereof and may or may not contain an 36. The method of claim 35 wherein the cosolvent is impurity and wherein the solvent mixture comprises an selected from the group consisting of alkaline halogenated ionic liquid and a cosolvent; salts, alkaline earth halogenated salts, transition metal halo 15 placing the vessel in fluid communication with a gas dis genated salts, lanthanide metal halogenated salts, actinide tribution system wherein the fluid within the vessel con metal halogenated salts, alcohols, aldehydes, amines, ammo tains an impurity; nia, aromatic hydrocarbons, arsenic pentafluoride, arsine, retaining said impurity within the solvent mixture to pro boron trichloride, boron trifluoride, carbon dioxide, carbon duce a purified fluid; and disulfide, carbon monoxide, carbon sulfide, chlorine, dibo releasing said purified fluid from the vessel separately from rane, dichlorosilane, digermane, dimethyl disulfide, dimethyl said solvent mixture. Sulfide, disilane, ethane, ethers, ethylene oxide, fluorine, ger mane, germanium methoxide, germanium tetrafluoride, 43. A method of separating an impurity from a fluid mix hafnium methylethylamide, hafnium t-butoxide, halogenated ture wherein the fluid mixture comprises a fluid in contact hydrocarbons, halogens, hexane, hydrogen, hydrogen cya with a solvent mixture all of which have been stored within a 25 vessel by a source gas manufacturer and shipped to an end nide, hydrogen halogenides, hydrogen selenide, hydrogen user, comprising: Sulfide, ketones, mercaptains, methane, nitric oxides, nitro receiving the vessel containing the fluid and the solvent gen, nitrogen trifluoride, noble gases, organometallics, oxy mixture wherein the fluid is selected from the group gen, oxygenated-halogenated hydrocarbons, phosgene, consisting digermane, Stilbene, borane, diborane, nitric phosphine, phosphorus trifluoride, n-silane, pentakisdim 30 oxide, disilane, hydrogen selenide, and mixtures thereof ethylamino tantalum, propane, silicon tetrachloride, silicon and may or may not contain an impurity and wherein the tetrafluoride, stibine, styrene, sulfur dioxide, sulfinur solvent mixture comprises an ionic liquid and a cosol hexafluoride, sulfur tetrafluoride, tetramethyl cyclotetrasi vent; loxane, titanium diethylamide, titanium dimethylamide, placing the vessel in fluid communication with a gas dis trichlorosilane, trimethyl silane, tungsten hexafluoride, 35 tribution system wherein the fluid within the vessel con water, and mixtures thereof. tains an impurity; and 37. The method of claim 35 wherein the cosolvent is retaining said impurity within the solvent mixture to pro selected from the group consisting of alcohols, water, hydro duce a purified fluid; and gen, ammonia, carbon dioxide, carbonyls, cyanides, Sulfides, releasing said purified fluid from the vessel separately from oxygen, hydrocarbons, halogenated hydrocarbons, oxygen 40 said solvent mixture. ated hydrocarbons, hydrides, hydrogen halogenides, halides, 44. A method of stabilizing an unstable fluid for an end user and mixtures thereof. that can be shipped, stored, handled and dispensed, compris 38. The method of claim 35 wherein the unstable fluid is ing: selected from the group consisting of digermane, borane, providing a vessel configured for selectively dispensing the diborane, disilane, fluorine, halogenated oxy-hydrocarbons, 45 unstable fluid therefrom wherein the unstable fluid is hydrogen selenide, Stilbene, nitric oxide, organometallics and Selected from the group consisting of digermane, mixtures thereof. borane, diborane, disilane, fluorine, halogenated oxy 39. The method of claim35 wherein the period of time is at hydrocarbons, hydrogen selenide, Stilbene, nitric oxide, least about 24 hours. organometallics and mixtures thereof; 40. The method of claim 35 wherein the period of time is at 50 providing an ionic liquid and a cosolvent within the vessel; least about 7 days. introducing the unstable fluid into the vessel; 41. The method of claim 35 wherein the ionic liquid is contacting the unstable fluid with said ionic liquid and said selected from the group consisting of mono-Substituted imi cosolvent wherein said cosolvent changes the solubility dazolium salts, di-substituted imidazolium salts, tri-Substi of the unstable fluid to said ionic liquid; and tuted imidazolium salts, pyridinium salts, pyrrolidinium 55 shipping the vessel containing the unstable fluid to the end salts, phosphonium salts, ammonium salts, tetralkylammo user wherein there is substantially no decomposition of nium salts, guanidinium salts, uronium salts, and mixtures the unstable fluid prior the release of the unstable fluid. thereof. k k k k k