EP1877153A1 - Procede et systeme de stockage et de purification de fluide - Google Patents

Procede et systeme de stockage et de purification de fluide

Info

Publication number
EP1877153A1
EP1877153A1 EP06740623A EP06740623A EP1877153A1 EP 1877153 A1 EP1877153 A1 EP 1877153A1 EP 06740623 A EP06740623 A EP 06740623A EP 06740623 A EP06740623 A EP 06740623A EP 1877153 A1 EP1877153 A1 EP 1877153A1
Authority
EP
European Patent Office
Prior art keywords
fluid
ionic liquid
gas
canister
salts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP06740623A
Other languages
German (de)
English (en)
Other versions
EP1877153A4 (fr
Inventor
Carrie L. Wyse
Robert Torres, Jr
Joseph V. Vininski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Matheson Tri-Gas Inc
Original Assignee
Matheson Tri-Gas Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/101,191 external-priority patent/US7638058B2/en
Application filed by Matheson Tri-Gas Inc filed Critical Matheson Tri-Gas Inc
Publication of EP1877153A1 publication Critical patent/EP1877153A1/fr
Publication of EP1877153A4 publication Critical patent/EP1877153A4/fr
Pending legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/10778—Purification
    • C01B33/10784—Purification by adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • C01B6/065—Hydrides of arsenic or antimony
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • C01B6/10—Monoborane; Diborane; Addition complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/34—Purification; Stabilisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/024—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels

Definitions

  • Source gas manufacturers typically provide analyses of source gas materials delivered to the semiconductor manufacturing facility, the purity of the gases may change because of leakage into or outgassing of the containers, e.g. gas cylinders, in which the gases are packaged. Impurity contamination may also result from improper gas cylinder changes, leaks into downstream processing equipment, or outgassing of such downstream equipment.
  • Source gases may include impurities, or impurities may occur as a result of decomposition of the stored gases.
  • the impurity levels within the gas container may increase with length of storage time and can also change as the container is consumed by the end user. Thus, there remains a need to be able to remove contaminants from gases, particularly to very low levels.
  • a method of storing and dispensing a fluid includes providing a vessel configured for selective dispensing of the fluid therefrom.
  • a solvent mixture comprising an ionic liquid and a cosolvent is provided within the vessel.
  • the fluid is contacted with the solvent mixture for take-up of the fluid by the solvent mixture.
  • the fluid may be released from the ionic liquid and dispensed from the vessel.
  • the present invention provides a method of storing and dispensing a fluid.
  • the method includes contacting the fluid with a solvent mixture within a vessel and dispensing the fluid from the vessel.
  • the solvent mixture includes an ionic liquid and a cosolvent.
  • a method of separating an impurity from a fluid mixture includes a fluid and the impurity.
  • a device contains an ionic liquid and a cosolvent.
  • the fluid mixture is introduced into the device.
  • the fluid mixture is contacted with the ionic liquid and the cosolvent.
  • a portion of the impurity is retained within the ionic liquid and/or within the cosolvent to produce a purified fluid.
  • the purified fluid is then released from the device.
  • a method of stabilizing an unstable fluid includes providing a device containing an ionic liquid and a cosolvent.
  • the fluid mixture is introduced into the device.
  • the fluid mixture is contacted with the ionic liquid and the cosolvent.
  • a portion of the impurity is retained within the ionic liquid and/or within the cosolvent to produce a purified fluid.
  • the purified fluid is then released from the device.
  • a method of storing and dispensing a fluid includes the use of a vessel configured for dispensing (e.g. selective dispensing) of the fluid therefrom.
  • the vessel contains an ionic liquid therein.
  • the fluid is contacted with the ionic liquid for take-up of the fluid by the ionic liquid.
  • the fluid is released from the ionic liquid and dispensed from the vessel.
  • the fluid may be selected from alcohols, aldehydes, amines, ammonia, aromatic hydrocarbons, arsenic pentafluoride, arsine, boron trichloride, boron trifluoride, carbon disulfide, carbon monoxide, carbon sulfide, diborane, dichlorosilane, digermane, dimethyl disulfide, dimethyl sulfide, disilane, ethers, ethylene oxide, fluorine, germane, germanium methoxide, germanium tetrafluoride, hafnium methylethylamide, hafnium t-butoxide, halogenated hydrocarbons, halogens, hexane, hydrogen, hydrogen cyanide, hydrogen halogenides, hydrogen selenide, hydrogen sulfide, ketones, mercaptans, nitric oxides, nitrogen, nitrogen trifluoride, organometallics, oxygenated-halogenated hydrocarbon
  • the ionic liquid may be selected from mono-substituted imidazolium salts, di- substituted imidazolium salts, tri-substituted imidazolium salts, pyridinium salts, phosphonium salts, ammonium salts, tetralkylammonium salts, guanidinium salts, isouronium salts, and mixtures thereof.
  • the fluid is a dispersed phase fluid (e.g. solid particles dispersed in gas, tow immiscible liquids, etc.).
  • the fluid is a fluid mixture (e.g. a fluid comprising more than one discrete chemical entity).
  • a method of separating an impurity from a fluid mixture includes a fluid and the impurity.
  • a device contains an ionic liquid and is configured for contacting the ionic liquid with the fluid mixture.
  • the fluid mixture is introduced into the device.
  • the fluid mixture is contacted with the ionic liquid.
  • a portion of the impurity is retained within the ionic liquid to produce a purified fluid.
  • a method of storing and stabilizing an unstable fluid includes providing a vessel containing an ionic liquid therein.
  • the unstable fluid is contacted with the ionic liquid for take-up of the unstable fluid by the ionic liquid.
  • the unstable fluid is then stored within the ionic liquid for a period of time, during which period of time there is substantially no decomposition of the unstable fluid.
  • the unstable fluid may be selected from digermane, disilane, hydrogen selenide, borane, diborane, stibene, nitric oxide, organometallics, and halogenated oxy- hydrocarbons.
  • FIG. 1 shows an embodiment of a vessel for storing a fluid in an ionic liquid.
  • FIG. 2 shows another embodiment of a device for storing a fluid in an ionic liquid.
  • FIG. 3 shows an embodiment of a device for purifying a fluid with an ionic liquid.
  • FIG. 4 shows another embodiment of a device for purifying a fluid with an ionic liquid.
  • the present invention is directed to the use of ionic liquids to store a fluid material such as a gas or liquid.
  • a vessel may be configured for the selective dispensing of the fluid and contains an ionic liquid.
  • the fluid is contacted with the ionic liquid for take-up of the fluid by the ionic liquid. This allows storage of the fluid for a period of time.
  • the material in the storage vessel is at high pressure, for example up to about 4000 psi, preferably up to at least about 2000 psi.
  • the pressure of the material in the storage vessel is at around atmospheric pressure, which allows for safer storage conditions compared to high-pressure storage vessels.
  • the ionic liquids may also be used to store unstable fluids such as diborane which tend to decompose.
  • the storage in the ionic liquid can reduce or eliminate the decomposition of the unstable fluids.
  • the present invention is also directed to the use of ionic liquids to remove impurities from a fluid mixture.
  • a device may be employed containing an ionic liquid and is configured for contacting the ionic liquid with the fluid mixture.
  • the fluid mixture is introduced into the device and the fluid mixture is contacted with the ionic liquid.
  • a portion of the impurities are retained within the ionic liquid to produce a purified fluid.
  • This purification method may be combined with the previously described storage method and/or other embodiments described herein, such as the fluid stabilization methods.
  • the present invention provides a method of storing and dispensing a fluid.
  • the method includes contacting the fluid with a solvent mixture within a vessel, and dispensing the fluid from the vessel.
  • the solvent mixture includes an ionic liquid and a cosolvent.
  • the fluid and/or solvent mixture includes an impurity, hi this case, the method may be combined with purification techniques disclose herein.
  • the method further includes the step of allowing the impurity to be retained within the ionic liquid and/or within the cosolvent thereby producing a purified fluid upon dispensing.
  • the method may be combined with methods disclosed herein to stabilize and unstable liquid.
  • the method further includes storing the fluid (e.g.
  • Ionic liquids are a relatively new class of materials which can offer such physical properties as extremely low vapor pressure, high thermal stability, and low viscosity. Generally, ionic liquids consist of a bulky, asymmetric cation and an inorganic anion.
  • the bulky, asymmetric nature of the cation prevents tight packing, which decreases the melting point. Due to the wide variety of cations and anions possible for such ion pairs, a wide range of gas solubilities is conceivable, for a variety of inorganic and organic materials.
  • the physical properties of ionic liquids can include good dissolution properties for most organic and inorganic compounds; high thermal stability; non-flammability; negligible vapor pressure; low viscosity, compared to other ionic materials; and recyclability.
  • ionic liquids may provide the capability to control the release of a gas and/or its impurities via solubility control with temperature or pressure. This may enable the storage of a gas and its impurities, while selectively releasing only the desired gas by changing certain parameters, such as temperature or pressure, leaving the impurities behind.
  • ionic liquid system that could function as a 2-in-l system, providing both storage and purification in one container.
  • Ionic liquids can have a stabilizing effect on intermediate reaction species in organic synthesis and catalysis.
  • ionic liquids can offer stabilizing effects for unstable gas molecules.
  • utilization with even a small amount of ionic liquid can reduce or eliminate the decomposition of the unstable fluids relative the amount of decomposition in the absence of the ionic liquid.
  • Storage of a gas or other fluid in an ionic liquid may also be combined with the previously mentioned purification system to provide a 3-in-l storage, stabilization, and purification system.
  • ionic liquids for the storage of gases.
  • the vapor pressure of the ionic liquid can contaminate the delivered gas with ionic liquid.
  • the present understanding is that ionic liquids have very low or possibly no measurable vapor pressure of their own. This quality is an attractive feature of ionic liquids for use with storage and purification of gases. Vapor pressures have been reported for mixtures of ionic liquids with other dissolved liquids.
  • the vapor pressure of the ionic liquids used in the present invention are preferably less than about 10-4 Torr at 25 0 C, more preferably less than about 10-6 Torr at 25°C.
  • the mechanism for the dissolution of a fluid within an ionic liquid is due to intermolecular forces. While not intending to be bound by any particular theory, possible factors that influence the solubility include hydrogen bonding, dielectric constant, dipole moment (polarizability), high pi interaction, length of carbon chain, number of carbon double bonds, the purity of the ionic liquid, chirality, and steric hindrance.
  • the fluids dissolve within the ionic liquid without the breaking of high energy (e.g. irreversible) chemical bonds (e.g. covalent bonding).
  • the ionic liquid does not interact with the fluid through an electron donation interaction, or vice versa (i.e.
  • the fluid and ionic liquid are not a Lewis Acid - Lewis Base pair).
  • the ionic liquid interacts with the fluid via ion-dipole moment interactions, polarizability interaction, van der Waals interactions, hydrogen bonding interactions, and/or pi bonding interactions.
  • the fluids simply dissolve in the ionic liquid.
  • the solubility of the fluid in the ionic liquid is influenced by the dipole and/or quadrapole moments of the fluid and/or ionic liquid. It is the intention of this invention to store the fluid of interest in an ionic liquid wherein the fluid molecules remain intact and are removed from the ionic liquid with the same molecular structure as they were introduced into the ionic liquid.
  • the solubility of a gas in an ionic liquid varies with physical parameters such as temperature and pressure.
  • the gas solubilities obtained depends on the ionic liquid used, particularly the anion and cation used.
  • the anion has a strong influence on gas solubility. Specifically, the more interaction between the anion, the more dissolution appears to occur. Thus, several properties of the anion, the cation, and the dissolved gas play a role in these interactions.
  • mixtures of different ionic liquids could result in unexpected high solubilities of various fluids.
  • Ionic liquids which have been dried or baked, thus leaving them substantially anhydrous, may exhibit greater increased capacity for taking up fluid components, hi addition, the presence of water or other impurities may decrease the solubility of certain fluid components, especially those gas components that are hydrophobic.
  • the method of storing and dispensing a fluid includes providing a vessel. On embodiment of a vessel 10 is shown in FIG. 1.
  • the vessel 10 includes a fluid inlet 20, an ionic liquid inlet 30, and a fluid outlet 32.
  • the fluid inlet 20 is connected to a fluid source 14 which is controlled by a valve 18.
  • the ionic liquid inlet 30 is connected to an ionic liquid source 12 which is controlled by a valve 16.
  • the fluid outlet 32 is controlled by valve 26.
  • the vessel is configured for selective dispensing of the fluid therefrom.
  • the vessel is charged with an ionic liquid 22 through inlet 30.
  • a vacuum bake procedure may be conducted on the vessel 10 to remove contaminants or other impurities from the ionic liquid, preferably by pulling a vacuum while heating. This is done in order to remove any trace moisture and/or other volatile impurities from the ionic liquid and the fluid distribution components.
  • the ionic liquid is allowed to cool to the desired operating temperature.
  • the source fluid is then introduced into the vessel 10 until the take-up or dissolution of the fluid by the ionic liquid is complete.
  • the fluid may be a gas or a liquid such as a liquefied gas, or mixtures thereof.
  • the fluid is contacted with the ionic liquid for take-up of the fluid by the ionic liquid, hi some embodiments, there is substantially no chemical change in the ionic liquid and the fluid.
  • substantially no chemical change is meant that the fluid and the ionic liquid retain their chemical identity. It is undesirable for the fluid to irreversibly react with the ionic liquid to a significant level. A reaction between the fluid and the ionic liquid forming a high energy chemical bond would be expected to generate impurities or consume the fluid of interest.
  • the fluid may be introduced at any suitable pressure.
  • the fluid is a gas at a temperature of about 5 psi.
  • the gas is introduced at a pressure of at least about 100 psi, preferably up to about 2000 psi. The gas is introduced until the inlet and outlet concentrations are equivalent, indicating the ionic liquid is saturated and cannot accept any further gas under the existing conditions. At this time, the source gas flow is stopped.
  • contacting the fluid with the ionic liquid comprises bubbling the fluid mixture through the ionic liquid, as shown in FIG. 1.
  • the vessel 10 is charged with a fluid through inlet 28 and through dip tube 20, from whence it bubbles through ionic liquid 22.
  • Fig. 2 shows an embodiment of a vessel 80 for storing a fluid in an ionic liquid.
  • the ionic liquid 22 is put into the vessel before valve assembly 82 is inserted unto the vessel 80.
  • the fluid is then added to the vessel 80 containing the ionic liquid in the conventional fashion through inlet port 84 in valve assembly 82.
  • the vessel 80 would then be mechanically agitated to contact the fluid with the ionic liquid 22.
  • the fluid may be removed through outlet port 86.
  • the fluid is a liquid.
  • the vessel 80 shown in Fig. 2 may also be used to store a liquid in the ionic liquid.
  • the ionic liquid 22 is put into the vessel before valve assembly 82 is inserted into the vessel 80.
  • the liquid is then added to the vessel 80 in the conventional fashion through inlet port 84 in valve assembly 82.
  • the vessel 80 would then be mechanically agitated to contact the liquid with the ionic liquid 22.
  • the liquid may be removed through outlet port 86.
  • countercurrent flow of the ionic liquid and the fluid is used to contact the fluid with the ionic liquid.
  • the fluid is a liquid, and the liquid and the ionic liquid are mixed to contact the fluid with the ionic liquid.
  • the fluid stored within the ionic liquid may be removed from the ionic liquid by any suitable method.
  • the fluid is released from the ionic liquid in a substantially unreacted state.
  • Pressure-mediated and thermally-mediated methods and sparging, alone or in combination, are preferred, hi pressure-mediated evolution, a pressure gradient is established to cause the gas to evolve from the ionic liquid.
  • the pressure gradient is in the range of about atmospheric pressure to about 4000 psig. hi a more preferred embodiment, the pressure gradient is typically in the range from 10-7 to 600 Torr at 25° C.
  • the pressure gradient may be established between the ionic liquid in the vessel, and the exterior environment of the vessel, causing the fluid to flow from the vessel to the exterior environment.
  • the pressure conditions may involve the imposition on the ionic liquid of vacuum or suction conditions which effect extraction of the gas from the vessel.
  • the methods of the present invention further include the step of creating a pressure differential between the ionic liquid and an outlet of the vessel before dispensing the fluid from the vessel.
  • the ionic liquid is heated to cause the evolution of the gas from the ionic liquid so that the gas can be withdrawn or discharged from the vessel.
  • the methods of the present invention further include the step of heating the ionic liquid before dispensing the fluid from the vessel.
  • the temperature of the ionic liquid for thermal-mediated evolution ranges from -50° C to 200° C, more preferably from 30° C to 150° C.
  • the vessel containing the fluid and the ionic liquid is transported warm (i.e., around room temperature), then cooled when it is stored or used at the end user's site.
  • the fluid vapor pressure can be reduced at the end user's site and therefore reduce the risk of release of the gas from the vessel.
  • the vessel can be chilled and the temperature can be controlled in such a manner as to limit the amount of gas pressure that is present in the container and piping.
  • the temperature of the cylinder can be elevated to liberate the gas from the ionic liquid and to maintain the necessary amount of gas levels in the cylinder and piping.
  • the vessel may also be sparged with a secondary gas, in order to deliver the stored primary gas.
  • the step of dispensing includes sparging the vessel with a secondary gas.
  • a secondary gas is introduced into the vessel in order to force the primary gas out of the ionic liquid and out of the storage container. Sparging of a container can take place wherein the secondary gas is selected from a group of gases that has relatively low solubility in the ionic liquid.
  • the secondary gas is introduced into the ionic liquid in a manner wherein the secondary gas bubbles through the ionic liquid and displaces the primary gas from the ionic liquid.
  • the resultant gas mixture of primary gas and secondary gas then exit the gas storage container and are delivered to a downstream component in the gas distribution system.
  • the sparging parameters should be selected such that the maximum amount of primary gas is removed from the ionic liquid. This includes selection of the appropriate geometry of the sparging vessel such that the secondary gas has an enhanced pathway for the interaction or contact between the secondary fluid and the ionic liquid. In practice, this could be use of a long and narrow storage container wherein the secondary fluid is introduced at the bottom of the container and the outlet of the container is near the top. Additionally, a device such as a diffuser can be used within the storage container that causes the bubbles of the secondary gas to be very small and numerous. In this manner, the surface area or contact area of the bubbles of the secondary gas is enhanced with the ionic liquid.
  • the parameters of temperature and pressure within the sparging storage container can be adjusted such that the desired concentration of the secondary gas and primary gas are constant and fall within a desired range.
  • the sparging vessel can be a separate container from the typical storage container such as a gas cylinder, or the typical storage container can be used as the sparging vessel depending on the requirements of the specific application.
  • the fluid may be a solid at the time it is taken up by the ionic liquid and/or the cosolvent.
  • the gas flows out of the vessel, by suitable means such as a discharge port or opening 24 in FIG. 1.
  • a flow control valve 26 may be joined in fluid communication with the interior volume of the vessel.
  • a pipe, conduit, hose, channel or other suitable device or assembly by which the fluid can be flowed out of the vessel may be connected to the vessel.
  • the present invention also provides a fluid storage and dispensing system.
  • the system includes a fluid storage and dispensing vessel configured to selectively dispense a fluid therefrom.
  • a suitable vessel is, for example, a container that can hold up to 1000 liters.
  • a typical vessel size is about 44 liters.
  • the vessel should be able to contain fluids at a pressure of up to about 2000 psi, preferably up to about 4000 psi. However, the vessel may also operate at around atmospheric pressure.
  • the container is made of carbon steel, stainless steel, nickel or aluminum.
  • the vessel may contain interior coatings in the form of inorganic coatings such as silicon and carbon, metallic coatings such as nickel, organic coatings such as paralyene or Teflon based materials.
  • the vessel contains an ionic liquid which reversibly takes up the fluid when contacted therewith. The fluid is releasable from the ionic liquid under dispensing conditions.
  • the ionic liquid is selected from mono-substituted imidazolium salts, di-substituted imidazolium salts, tri-substituted imidazolium salts, pyridinium salts, pyrrolidinium salts, phosphonium salts, ammonium salts, tetralkylammonium salts, guanidinium salts, isouronium salts, and mixtures thereof.
  • the listed salts include any compound that contains the listed cation.
  • the ionic liquid is selected from a subset of the previous list and includes phosphonium salts, ammonium salts, tetralkylammonium salts, guanidinium salts, isouronium salts, and mixtures thereof.
  • the ionic liquid includes a cation component selected from mono-substituted imidazoliums, di-substituted imidazoliums, tri-substituted imidazoliums, pyridiniums, pyrrolidiniums, phosphoniums, ammoniums, tetralkylammoniums, guanidiniums, and uraniums; and an anion component selected from acetate, cyanates, decanoates, halogenides, sulfates, sulfonates, amides, imides, methanes, borates, phosphates, antimonates, tetrachoroaginanate, thiocyanate, tosylate, carboxylate, cobalt-tetracarbonyl, trifluoroacetate and tris(trifluoromethylsulfonyl)methide.
  • a cation component selected from mono-substituted imidazol
  • Halogenide anions include chloride, bromide, iodide.
  • Sulfates and sulfonate anions include methyl sulfate, ethyl sulfate, butyl sulfate, hexyl sulfate, octyl sulfate, hydrogen sulfate, methane sulfonate, dodecylbenzene sulfonate, dimethyleneglycolmonomethylether sulfate, trifluoromethane sulfonate.
  • Amides, imides, and methane anions include dicyanamide, bis(pentafluoroethylsulfonyl)imide, bis(trifluoromethylsulfonyl)imide, bis(trifluoromethyl)imide.
  • Borate anions include tetrafluoroborate, tetracyanoborate, bis[oxalato(2-)]borate, bis[l,2-benzenediolato(2-)- O,O']borate, bis[salicylato(2-)]borate.
  • Phosphate and phosphinate anions include hexafluorophosphate, diethylphosphate, bis(pentafluoroethyl)phosphinate, tris(pentafluoroethyl)trifluorophosphate, tris(nonafluorobutyl)trifluorophosphate.
  • Anitmonate anions include hexafluoroantimonate.
  • Other anions include tetrachoroaluminate, acetate, thiocyanate, tosylate, carboxylate, cobalt-tetracarbonyl, trifluoroacetate and tris(trifluoromethylsulfonyl)methide.
  • Various ionic liquids are available from BASF, Merck, Strem Chemicals, and Aldrich.
  • Preferred ionic liquids used in the present invention may be divided into the following categories: standard, acidic, acidic water reactive, and basic.
  • Standard ionic liquids include but are not limited to l-ethyl-3-methylimidazolium chloride, l-ethyl-3- methylimidazolium methanesulfonate, l-butyl-3-methylimidazolium chloride, l-butyl-3- methylimidazolium methanesulfonate, methyl-tri-n-butylammonium methylsulfate, 1-ethyl- 2,3-dimethylimidazolium ethylsulfate, 1,2,3-trimethylimidazolium methylsulfate.
  • Acidic ionic liquids include methylimidazolium chloride, methylimidazolium hydrogensulfate, 1- ethyl-3 -methylimidazolium hydrogensulfate, l-butyl-3-methylimidazolium hydrogensulfate.
  • Acidic water reactive liquids include l-ethyl-3-methylimidazolium tetrachloroaluminate and l-butyl-3-methylimidazolium tetrachloroaluminate.
  • Basic ionic liquids include l-ethyl-3- methylimidazolium acetate and l-butyl-3-methylimidazolium acetate.
  • Another way the preferred ionic liquids in the present invention may be categorized is by functional group of the cation. This includes but is not limited to the following categories: mono-substituted imidazoliums, di-substituted imidazoliums, tri- substituted imidazoliums, pyridmiums, pyrrolidiniums, phosphoniums, ammoniums, • tetralkylammoniums, guanidiniums, and uroniums.
  • Mono-substituted imidazolium ionic liquids include 1 -methylimidazolium tosylate, 1 -methylimidazolium tetrafluoroborate, 1- methylimidazolium hexafluorophosphate, 1-methylimidazolium tifluoromethanesullonate, 1-butylimidazolium tosylate, 1-butylimidazolium tetrafluoroborate, 1-methylimidazolium hexafluorophosphate, 1-methylimidazolium tifluoromethanesulfonate.
  • Di-substituted imidazolium ionic liquids include 1,3-dimethylimidiazolium methylsulfate, 1,3-dimethylimidiazolium trifluoromethanesulfonate, 1,3- dimethylimidiazolium bis(pentafluoroethyl)phosphinate, l-ethyl-3-methylimidiazolium thiocyanate, l-ethyl-3-methylimidiazolium dicyanamide, l-ethyl-3-methylimidiazolium cobalt-tetracarbonyl, l-propyl-3 -methylimidazolium chloride, l-butyl-3 -methylimidazolium hexafluoroantimonate, 1 -octadecyl-3 -methylimidazolium bis(trifluoromethylsulfonyl)imide, 1 -benzyl-3 -methylimidazolium bromid
  • Tri-substituted imidazolium ionic liquids include l-ethyl-2,3-dimethylimidazolium chloride, l-butyl-2,3-dimethylimidazolium octylsulfate, l-propyl-2,3-dimethylimidazolium chloride, l-hexyl-2,3-dimethylimidazolium tetrafluoroborate, l-hexadecyl-2,3- dimethylimidazolium iodide.
  • Pyridinium ionic liquids include n-ethylpyridinium chloride, n-butylpyridinium bromide, n-hexylpyridinium n-octylpyridinium chloride, 3-methyl-n- butylpyridinium methylsulfate, 3-ethyl-n-butylpyridinium hexafluorophosphate, 4-methyl- n-butylpyridinium bromide, 3,4-dimemyl-n-butylpyridmium chloride, 3,5-dimethyl-n- butylpyridinium chloride.
  • Pyrrolidinium ionic liquids include 1,1-dimethylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 1 -ethyl- 1-methylpyrrolidinium dicyanamide, 1,1- dipropylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1 -butyl- 1 -methylpyrrolidinium bromide, 1 -butyl- 1-ethylpyrrolidinium bromide, 1-octyl- 1-methylpyrrolidinium dicyanamide.
  • Phosphonium ionic liquids include tetraoctylphosphonium bromide, tetrabutylphosphonium bis[oxalato(2-)]-borate, trihexyl(tetradecyl)phosphonium dicyanamide, benzyltriphenylphosphonium bis(trifluoromethyl)imide, tri-iso- butyl(methyl)phosphonium tosylate, ethyl(tributyl)phosphonium diethylphosphate, tributyl(hexadecyl)phosphonium chloride.
  • Ammonium ionic liquids include tetramethylammonium bis(trifluoromethylsulfonyl)imide, tetraethylammonium bis-[salicylato-(2-)]-borate, tetrabutylammonium tetracyanoborate, methyltrioctylammonium trifluoroacetat.
  • Guanidinium ionic liquids include N,N,N',N',N"-pentametliyl-JN"- isopropylguanidimuni tris(pentafluoroethyl)trifluoropliospliate, N 5 N 5 N' ,N',N"-pentamethyl- N"-isopropylguanidinium tris(pentafluoroeth.yl)trifluoroniethanesulfonate, hexamethylguanidinium trs(pentafluoroethyl)trifluorophosphate 5 hexamethylguanidinium trifluoromethanesulfonate.
  • Uronium ionic liquids include S-methyl-N,N 5 N' 5 N'-tetramethylisouronium trifluoromethanesulfonate, O-methyl-N,N,N' 5 N'-tetramethylisouronium tris(pentafluoroethyl)trifluorophosphate, O-ethyl-N,N,N' , N'-tetramethylisouronium tris(pentafluoroethyl)trifluorophosphate, S-ethyl-N,N,N' 5 N'-tetramethylisouronium trifluoromethanesulfonate, S-ethyl-N,N,N', N'-tetramethylisothiouronium trifluoromethanesulfonate.
  • the ionic liquid used to store a fluid does not include imidazolium compounds. In another embodiment, the ionic liquid used to store a fluid does not include a nitrogen-containing heterocyclic cation.
  • the fluids which may be stored, purified, and/or stabilized in the ionic liquids include, but are not limited to, alcohols, aldehydes, amines, ammonia, aromatic hydrocarbons, arsenic pentafluoride, arsine, boron trichloride, boron trifluoride, carbon dioxide, carbon disulfide, carbon monoxide, carbon sulfide, chlorine, diborane, dichlorosilane, digermane, dimethyl disulfide, dimethyl sulfide, disilane, ethane, ethers, ethylene oxide, fluorine, germane, germanium methoxide, germanium tetrafluoride, hafnium methylethylamide, hafnium t-butoxide, halogenated hydrocarbons, unsubstituted hydrocarbons, oxygenated hydrocarbons, halogens, hexane, hydrogen, hydrogen cyanide, hydrogen halogenides
  • the fluids which may be stored, purified, or stabilized in the ionic liquids includes a subset of the previous listed fluids and include alcohols, aldehydes, amines, ammonia, aromatic hydrocarbons, arsenic pentafluoride, arsine, boron trichloride, boron trifluoride, carbon disulfide, carbon monoxide, carbon sulfide, cniorme, diborane, dichlorosilane, digermane, dimethyl disulfide, dimethyl sulfide, disilane, ethers, ethylene oxide, fluorine, germane, germanium methoxide, germanium tetrafluoride, hafnium methylethylamide, hafnium t-butoxide, halogenated hydrocarbons, halogens, hexane, hydrogen, hydrogen cyanide, hydrogen halogenides, hydrogen selenide, hydrogen sulfide
  • Alcohols include ethanol, isopropanol, and methanol.
  • Aldehydes include acetaldehyde.
  • Amines include dimethylamine and monomethylamine.
  • Aromatic compounds include benzene, toluene, and xylene.
  • Ethers include dimethyl ether, and vinyl methyl ether.
  • Halogens include chlorine, fluorine, and bromine.
  • Halogenated hydrocarbons include dichlorodifluorornethane, tetrafluoromethane, clorodifluoromethane, trifluoromethane, difluoromethane, methyl fluoride, 1,2-dichlorotetrafluoroethane, hexafluoroethane, pentafluoroethane, halocarbon 134a tetrafluoroethane, difluoroethane, perfluoropropane, octafluorocyclobutane, chlorotrifluoroethylene, hexafluoropropylene, octafluorocyclopentane, perfluoropropane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, methyl chloride, and methyl fluoride.
  • Ketones include acetone.
  • Mercaptans include ethyl mercaptan, methyl mercaptan, propyl mercaptan, and n,s,t-butyl mercaptan.
  • Nitrogen oxides include nitrogen oxide, nitrogen dioxide, and nitrous oxide.
  • Organometallics include trimethylaluminurn, triethylaluminum, dimethylethylamine alane, trimethylamine alane, dimethylaluminum hydride, tritertiarybutylaluminum, Tritertiarybutylaluminum trimethylindium (TMI), trimethylgallium (TMG), triethylgallium (TEG), dimethylzinc (DMZ), diethylzinc (DEZ), carbontetrabromide (CBr 4 ), diethyltellurium (DETe) and magnesocene (Cp 2 Mg).
  • Oxygenated-halogenated-hydrocarbons include perfluoroethyhnethylether, perfluoromethylpropylether, perfluorodimethoxymethane, and hexafluoropropylene oxide.
  • Other fluids include vinyl acetylene, acrylonitrile, and vinyl chloride.
  • Other fluids which may be stored, purified, or stabilized m ionic liquids include materials used for thin film deposition applications.
  • Such materials include, but are not limited to, tetramethyl cyclotetrasiloxane (TOMCTS), titanium dimethylamide (TDMAT), titanium diethylamide (TDEAT), hafnium t-butoxide (Hf(OtBu)4), germaniummethoxide (Ge(OMe)4), pentakisdimethylamino tantalum (PDMAT) hafnium methylethylamide (TEMAH) and mixtures thereof.
  • TOMCTS tetramethyl cyclotetrasiloxane
  • TDMAT titanium dimethylamide
  • TDEAT titanium diethylamide
  • Hf(OtBu)4 hafnium t-butoxide
  • Ge(OMe)4 germaniummethoxide
  • PDMAT pentakisdimethylamino tantalum hafnium methylethylamide
  • TEMAH pentakisdimethylamino tantalum
  • the fluids which may be stored in the ionic liquids may be divided into categories including include stable gases, stable liquefied gases, unstable gases, and unstable liquefied gases.
  • stable is relative and includes gases which do not substantially decompose over the shelf life of a storage vessel at the typical temperatures and pressures at which those skilled in the art would store the gases.
  • Unstable refers to materials which are prone to decomposition under typical storage conditions and thus are difficult to store.
  • Stable gases include nitrogen, argon, helium, neon, xenon, krypton; hydrocarbons include methane, ethane, and propanes; hydrides include silane, disilane, arsine, phosphine, germane, ammonia; corrosives include hydrogen halogenides such as hydrogen chloride, hydrogen bromide, and hydrogen fluoride, as well as chlorine, dichlorosilane, trichlorosilane, carbon tetrachloride, boron trichloride, tungsten hexafluoride, and boron trifluoride; oxygenates include oxygen, carbon dioxide, nitrous oxide, and carbon monoxide; and other gases such as hydrogen, deuterium, dimethyl ether, sulfur hexafluoride, arsenic pentafluoride, and silicon tetrafluoride.
  • Stable liquefied gases include inerts such as nitrogen and argon; hydrocarbons such as propane; hydrides such as silane, disilane, arsine, phosphine, germane, and ammonia; fiuorinates such as hexafluoroethane, perfluoropropane, and perfluorobutane; corrosives such as hydrogen chloride, hydrogen bromide, hydrogen fluoride, chlorine, dichlorosilane, trichlorosilane, carbon tetrachloride, boron trichloride, boron trifluoride, tungsten hexafluoride, and chlorine trifluoride; and oxygenates such as oxygen and nitrous oxide.
  • inerts such as nitrogen and argon
  • hydrocarbons such as propane
  • hydrides such as silane, disilane, arsine, phosphine, germane, and ammonia
  • fiuorinates such as hexafluoro
  • Unstable gases include digermane, borane, diborane, stibene, disilane, hydrogen selenide, nitric oxide, fluorine and organometallics including alanes, trimethyl aluminum and other similar gases. These unstable gases may also be liquefied.
  • a fluid such as fluorine could be stored with a fully fluorinated ionic liquid such as perfluorinated ammonium hexafluorophosphate.
  • the present invention also provides a method of separating an impurity lrom a fluid mixture.
  • the fluid mixture includes a fluid and the impurity.
  • FIG. 3 shows an embodiment of a device 40 for purifying a fluid with an ionic liquid.
  • a device containing the ionic liquid is configured for contacting the ionic liquid with the fluid mixture.
  • a source 46 for the fluid mixture is controlled by valve 48.
  • the fluid mixture is introduced through inlet 50 into the device 40 and contacted with the ionic liquid.
  • the ionic liquid is introduced through inlet 52 from ionic liquid source 42 by valve 44. A portion of the impurities is retained within the ionic liquid to produce a purified fluid. The purified fluid is released from the device through outlet 54, which is controlled by valve 56.
  • FIG. 4 shows another embodiment of a device 40 for purifying a fluid with an ionic liquid.
  • Contacting the fluid with the ionic liquid comprises bubbling the fluid mixture through the ionic liquid.
  • the vessel 60 includes a valve assembly 62, an ionic liquid inlet 64, a fluid inlet 66, and a dip tube 78.
  • the valve assembly 62 includes an ionic liquid inlet valve 68 and a fluid inlet valve 70.
  • the vessel 60 is charged with an ionic liquid 22 through inlet 64.
  • the vessel 60 is charged with a fluid through inlet 66 and through dip tube 78, from whence it bubbles through ionic liquid 22.
  • the impurity may retained on a solid material that has been introduced into the ionic liquid.
  • mixtures of one or more ionic liquids can be used with or without the additional solid phase purification material to adjust the solubility of the fluid as well as the purifying ability of the ionic liquid.
  • non-ionic liquids can be mixed with the ionic liquids to either capture impurities present in the fluid or to substantially modify the impurities into a form that is retained by the purifying liquid or ionic liquid. The net effect is that the impurities are separated from the fluid and the purified fluid is then released from the device.
  • the fluid and fluid mixture may include liquids, vapors (volatilized liquids), gaseous compounds, and/or gaseous elements.
  • purified may include purification to be essentially free of one or more impurities, or simply lowering the lower level of impurities in the fluid mixture.
  • Impurities include any substance that may be desirable to have removed from the fluid mixture, or are undesirable within the fluid mixture. Impurities can be undesirable variants or analogs of the fluid itself.
  • Impurities that would typically be desired to be removed may include but are not limited to water, CO 2 , oxygen, CO, NO, NO 2 N 2 O 4 , SO 2 , SO 3 , SO, S 2 O 2 , SO 4 , and mixtures thereof. Additionally, impurities include out are not limited to derivatives of the fluid of interest. For example, higher boranes are considered impurities within diborane. Disilane is considered an impurity in silane. Phosphine could be considered an impurity in arsine, and HF could be considered an impurity in BF 3 .
  • the ionic liquid used in the purification process may be any of the previously mentioned ionic liquids. However, it should be understood that certain ionic liquids will be better suited to removing certain impurities. It should also be understood that certain ionic liquids will be better suited to working with certain fluids.
  • the ionic liquid used for purification does not comprise a nitrogen-containing heterocyclic cation.
  • the fluid which may be purified includes any of the previously mentioned fluids. In one embodiment, the method is not used to purify one or more of the following fluids: carbon dioxide, water, methane, ethane, propane, noble gases, oxygen, nitrogen, or hydrogen.
  • Contacting the ionic liquid with the fluid mixture may be accomplished in any of the variety of ways.
  • the process is selected to promote intimate mixing of the liquid ionic compound and the fluid mixture and is conducted for a time sufficient to allow significant removal of targeted components.
  • systems maximizing surface area contact between the ionic liquid and the fluid mixture are desirable.
  • the device is a vessel and the step of contacting the fluid mixture with the ionic liquid comprises bubbling the fluid mixture through the ionic liquid, as shown in FIG. 4 and previously described.
  • a scrubbing stack is used to contact the fluid mixture with the ionic liquid, with the fluid mixture and the ionic liquid flowing into the scrubbing stack.
  • the vessel containing the fluid and the ionic liquid is mechanically agitated in order to contact the fluid with the ionic liquid.
  • countercurrent flow of the ionic liquid and the fluid is used to contact the fluid with the ionic liquid in the device.
  • the fluid is a liquid, and the liquid and the ionic liquid are mixed to contact the fluid with the ionic liquid in the device.
  • a method of separating an impurity from a fluid mixture includes the fluid and at least one impurity.
  • the method may employ only a small amount of ionic liquid relative to the amount of fluid.
  • the fluid mixture may be contacted with the ionic liquid for the purpose of purification only and not for uptake or dissolvation of the fluid by the ionic liquid.
  • a ⁇ evice or vessel is used to contact a small amount of ionic liquid with the fluid mixture.
  • a substantially less amount of ionic liquid could be required to obtain the purification effect compared to the previous illustration wherein the unstable fluid could be taken up completely or dissolved within the ionic liquid.
  • a portion of the impurity is retained within the ionic liquid to produce a purified fluid.
  • a method of stabilizing an unstable fluid which uses a small amount of ionic liquid relative to the amount of fluid.
  • the unstable fluid is contacted with the ionic liquid for the purpose of stabilization only and not for uptake of the fluid by the ionic liquid.
  • a device or vessel is used to contact a small amount of ionic liquid with the fluid.
  • a substantially less amount of ionic liquid could be required to obtain the stabilization effect compared to an illustration wherein the unstable fluid could be taken up completely or dissolved within the ionic liquid.
  • No decomposition products, or substantially less decomposition products are produced as a result of the contact of the unstable fluid with the ionic liquid, producing a stabilized fluid.
  • Ionic liquids which have been dried or baked, thus leaving them substantially anhydrous may exhibit greater overall capacity for removing gaseous components.
  • the presence of water or other impurities in the ionic liquid may reduce the capacity of the ionic liquid for dissolving fluid components.
  • the presence of water or other impurities may decrease the solubility of certain fluid components, especially those fluid components that are hydrophobic.
  • Dried baked ionic liquid may exhibit differential selectivities between various fluid components when compared to those ionic liquids containing measurable amounts of dissolved water, such as ionic liquids having been exposed to humid atmospheres.
  • Ionic liquids may be dried by conventional methods, such as by heat treatment, exposure to a reduced pressure environment, or a combination of heat and reduced pressure.
  • gas solubility in various liquids is dependent upon temperature and pressure. Different gas components may each elicit a different sensitivity to temperature and/or pressure changes as pertains to the solubility of the gas component in the ionic liquids. This differential temperature and/or temperature dependence may be advantageously exploited by conducting variations of the process of the 12836 present invention at different temperatures and pressures to optimize gas component separation.
  • the present invention also provides a method for both storing and purifying a fluid mixture comprising a fluid and an impurity.
  • a vessel contains an ionic liquid and is configured for contacting the ionic liquid with the fluid mixture.
  • the fluid and the ionic liquid may be any of the previously mentioned fluids and ionic liquids.
  • the fluid is contacted with the ionic liquid for take-up of the fluid by the ionic liquid. This may be accomplished by any of the previously described methods of promoting intimate mixing of the liquid ionic compound and the fluid mixture, or any other suitable method.
  • a portion of the impurities is retained within the ionic liquid to produce a purified fluid.
  • the purified fluid can then be released from the device.
  • the present invention also provides a method of storing and stabilizing an unstable fluid.
  • the unstable fluid may be any of the previously mention unstable fluids, or any other fluid that tends to decompose.
  • the ionic liquid may be any of the previously mentioned ionic liquids.
  • the unstable fluid is contacted with the ionic liquid for take-up of the unstable fluid by the ionic liquid.
  • the unstable fluid may be then stored within the ionic liquid for a period of time, during which period of time the decomposition rate is at least reduced, and preferably there is substantially no decomposition of the unstable fluid.
  • the rate of decomposition is reduced by at least about 50%, more preferably at least about 75%, and most preferably at least about 90%, compared with storage of the fluid under the same temperature and pressure conditions without using an ionic liquid.
  • substantially no decomposition means that less than 10% of the molecules of the unstable fluid undergo a chemical change while being stored.
  • the proportion of molecules that undergo a decomposition reaction is preferably less than 1%, more preferably less than 0.1%, and most preferably less than 0.01%. Although it is most preferable for the decomposition rate to be less than 0.01%, it should be noted that in certain applications a rate of decomposition of less than 50% over the storage period of the fluid would be useful.
  • the period of time may range from a few minutes to several years, but is preferably at least about 1 hour, more preferably at least about 24 hours, even more preferably at least about 7 days, and most preferably at least about 1 month.
  • the unstable fluid may be selected from categories such as dopants, dielectrics, etchants, thin film growth, cleaning, and other semiconductor processes. Examples of unstable fluids include, but are not limited to, digermane, borane, diborane, disilane, fluorine, halogenated oxy-hydrocarbons, hydrogen selenide, stibene, nitric oxide, organometallics and mixtures thereof.
  • the present invention also provides a method of storing and purifying a fluid mixture.
  • the storage vessel is provided with a purifying solid or liquid for contact with the fluid mixture.
  • the purifying solid or liquid retains at least a portion of the impurity in the fluid mixture to produce a purified fluid when the fluid is released from the storage vessel.
  • the purifying solid or liquid may be used with any of the previously mentioned fluids and ionic liquids.
  • purifying materials may be used with the present invention.
  • the purification or impurity removal can be used to remove impurities from the ionic liquid which could change the solubility of a fluid in the ionic liquid.
  • the purification material could remove only impurities present in the incoming gas or contributed from the fluid storage vessel that will be stored in the ionic liquid.
  • the purification material could have the ability to remove impurities from both the fluid of interest and the ionic liquid simultaneously.
  • the purification materials include, but are not limited to, alumina, amorphous silica-alumina, silica (SiO 2 ), aluminosilicate molecular sieves, titania (TiO 2 ), zirconia (ZrO 2 ), and carbon.
  • the materials are commercially available in a variety of shapes of different sizes, including, but not limited to, beads, sheets, extrudates, powders, tablets, etc.
  • the surface of the materials can be coated with a thin layer of a particular form of the metal (e.g., a metal oxide or a metal salt) using methods known to those skilled in the art, including, but not limited to, incipient wetness impregnation techniques, ion exchange methods, vapor deposition, spraying of reagent solutions, co-precipitation, physical mixing, etc.
  • the metal can consist of alkali, alkaline earth or transition metals.
  • purification materials includes a substrate coated with a thin layer of metal oxide (known as NHX-PlusTM) for removing H 2 O, CO 2 and O 2 , H 2 S and hydride impurities, such as silane, germane and siloxanes; ultra- low emission (ULE) carbon materials (known as HCXTM) designed to remove trace hydrocarbons from inert gases and hydrogen; macroreticulate polymer scavengers (known as OMATM and OMX-PlusTM) for removing oxygenated species (H 2 O, O 2 , CO, CO 2 , NO x , SO x , etc.) and non-methane hydrocarbons; and inorganic silicate materials (known as MTXTM) for removing moisture and metals.
  • NHX-PlusTM metal oxide
  • HCXTM ultra- low emission carbon materials
  • OMATM and OMX-PlusTM macroreticulate polymer scavengers
  • OMATM and OMX-PlusTM for removing oxygenated species
  • any of the previously described storage, stabilization, and/or purification methods and systems may be combined to provide multiple effects.
  • One, two or all three methods can be independently combined to obtain a process that is best suited for the application of interest. Therefore, it is conceivable that any one method or the combination of any of the methods could be used for different requirements and applications.
  • the basic steps of these combined methods will now be set forth. It will be apparent that the information previously described for the individual methods will also be applicable for the combined methods described below.
  • the fluids and the ionic liquids used in the combined processes may be any of the previously mentioned fluids and ionic liquids.
  • the storage method may be combined with the method of purifying using a purifying solid.
  • a vessel containing an ionic liquid is provided.
  • the fluid mixture is contacted with the ionic liquid for take-up of the fluid by the ionic liquid.
  • a purifying solid is provided for contact with the fluid mixture. A portion of the impurity is retained by the purifying solid to produce a purified fluid.
  • the methods of storage, stabilizing, and purifying using a purifying solid may also be combined.
  • a vessel containing an ionic liquid is provided.
  • the fluid mixture fluid is contacted with the ionic liquid for take-up of the fluid mixture by the ionic liquid.
  • a purifying solid is provided for contact with the fluid mixture.
  • a portion of the impurity is retained by the purifying solid to produce a purified fluid.
  • the ionic liquid is stored for a period of time of at least about 1 hour, during which period of time there is substantially no degradation of the unstable fluid.
  • the methods of storage, stabilizing, and/or purifying using the ionic nqui ⁇ ana/ or cosolvent may also be combined.
  • a device containing an ionic liquid and configured for contacting the ionic liquid with the fluid mixture is provided.
  • the fluid mixture is introduced into the device.
  • the fluid mixture is contacted with the ionic liquid.
  • the fluid mixture may then be stored within the ionic liquid for a period of time of at least about 1 hour, during which period of time there is substantially no degradation of the unstable fluid.
  • a portion of the impurities are retained within the ionic liquid a to produce a purified unstable fluid, and the purified unstable fluid may then be released from the device.
  • the two purification methods may also be combined.
  • a device containing an ionic liquid and a purifying solid therein for contact with the fluid mixture is provided.
  • the fluid mixture is introduced into the device.
  • the fluid mixture is contacted with the ionic liquid and with the purifying solid.
  • a first portion of the impurity is retained within the ionic liquid and a second portion of the impurity is retained by the purifying solid, to produce a purified fluid.
  • the purified fluid may then be released from the device.
  • the storage method may be combined with both methods of purifying.
  • a vessel containing an ionic liquid and a purifying solid therein for contact with the fluid mixture is provided.
  • the fluid is contacted with the ionic liquid for take-up of the fluid by the ionic liquid.
  • a first portion of the impurity is retained within the ionic liquid and a second portion of the impurity is retained by the purifying solid, to produce a purified fluid.
  • the purified fluid may then be released from the device.
  • the storage and stabilization methods may be combined with both methods of purifying.
  • a vessel containing an ionic liquid and a purifying solid therein for contact with the fluid mixture is provided.
  • the fluid mixture is introduced into the device.
  • the fluid is contacted with the ionic liquid for take-up of the fluid by the ionic liquid.
  • the fluid mixture is stored within the ionic liquid for a period of time of at least about 1 hour, during which period of time there is substantially no degradation of the unstable fluid..
  • a first portion of the impurity is retained within the ionic liquid and a second portion of the impurity is retained by the purifying solid, to produce a purified unstable fluid.
  • the purified fluid may then be released from the device.
  • the stabilization methods may be combined with both methods of purifying.
  • a vessel containing an ionic liquid and a purifying solid therein for contact with the fluid mixture is provided.
  • the unstable fluid mixture is introduced into the device.
  • the unstable fluid is contacted with the ionic liquid primarily for the purposes of stabilization and purification only, and not for the purposes of uptake of the fluid by the ionic liquid.
  • a device or vessel is used to contact a small amount of ionic liquid with the fluid. In this manner, a substantially less amount of ionic liquid could be required to obtain the stabilization effect and the purification effect compared to the previous illustrations wherein the unstable fluid could be taken up completely or dissolved within the ionic liquid.
  • No decomposition products, or substantially less decomposition products, are produced as a result of the contact of the unstable fluid with the ionic liquid, producing a stabilized fluid.
  • the fluid mixture is stored within the ionic liquid for a period of time of at least about 1 hour, during which period of time there is substantially no degradation of the unstable fluid.
  • a portion of the impurity is retained within the ionic liquid to produce a purified fluid.
  • the purified fluid may then be released from the device.
  • cosolvents can be combined with the ionic liquids.
  • Cosolvency also known as solvent blending, is a process used to increase the solubility of a chemical compound in a given solvent. This is achieved by adding a portion of a different solvent (cosolvent) to the given solvent.
  • solvent solvent
  • cosolvents are used to increase the water solubility of substances that normally have poor water solubility, by adding water-miscible organic solvents.
  • the cosolvent forms part of a mixture.
  • cosolvents can be combined with ionic liquids in the methods of storage, purification, and/or stabilization described above.
  • the solubility of the fluid in the ionic liquid may be increased by adding a particular cosolvent for the purpose of storing the fluid.
  • cosolvents employed in the present invention are typically fluid- solubilizing cosolvents.
  • the fluid-solubilizing cosolvent is of lower viscosity than the fluid, thereby allowing fore more facile loading and unloading rates.
  • the solubility of fluid impurities in the ionic liquid could also be increased by adding a particular cosolvent for the purpose of purifying the fluid.
  • the solubility of decomposition species could be decreased or increased by the use of cosolvents with the ionic liquid for the purpose of preventing decomposition.
  • the solubility of stabilizing species could be increased by the use of cosolvents with the ionic liquid, for the purpose of stabilization.
  • the intermolecular distances found between two molecules of the fluid taken up by the ionic liquid could be increased by the addition of a particular cosolvent. This would prevent condensation reactions between molecules of the fluid in the ionic liquid, providing stabilization.
  • the presence of cosolvents can alter the equilibrium of the decomposition reaction and shift the reaction such that decomposition of the fluid is not favored.
  • a cosolvent may be used with an ionic liquid for any of the processes described herein in order to enhance the performance of the process.
  • a solvent mixture comprising an ionic liquid and a cosolvent is provided within a suitable vessel.
  • the fluid is contacted with the solvent mixture for take-up of the fluid by the solvent mixture.
  • the fluid is released from the ionic liquid and dispensed from the vessel, hi one embodiment, the solubility of the fluid in the solvent mixture is greater than the solubility of the fluid in the ionic liquid under the operating conditions of the vessel.
  • a device containing an ionic liquid and a cosolvent is provided.
  • the fluid mixture is introduced into the device.
  • the fluid mixture is contacted with the ionic liquid and the cosolvent.
  • a portion of the impurity is retained within the ionic liquid, within the cosolvent, or within the mixture of the cosolvent and the ionic liquid, to produce a purified fluid.
  • the purified fluid is then released from the device.
  • an ionic liquid and a cosolvent are provided within a vessel.
  • the fluid mixture is introduced into the vessel.
  • the fluid mixture is contacted with the ionic liquid and the cosolvent.
  • the fluid mixture is stored within the vessel for a period of time, during which period of time there is substantially no decomposition of the unstable fluid.
  • the cosolvents and ionic liquids can be used in various combinations for the various methods described herein.
  • one type of ionic liquids and cosolvents can be used for storage and a second type of ionic liquids and cosolvents used for purification, in a process for both storage and purification.
  • one type of ionic liquids and cosolvents can be used for storage, a second type of ionic liquids and cosolvents used for purification and a third type of ionic liquids and cosolvents used for stabilization, in a process including storage, purification, and stabilization.
  • Various other combinations of the processes disclosed herein will be apparent. It is intended that the elements of these processes and the ionic liquids and cosolvents can be mixed, matcne ⁇ ana comomea in a variety of combinations for different applications and different requirements.
  • steps may be taken to remove the cosolvent from the ionic liquid and/or from the fluid mixture in later stages of the process. For example, after a fluid mixture is released from storage in the ionic fluid-cosolvent mixture, traces of cosolvent may be retained by the fluid mixture. These traces of cosolvent may be removed by any conventional purification process known in the art.
  • the amount of cosolvent used is less than the amount of ionic liquid used in the process.
  • the amount of cosolvent is preferably between about 0.1% and about 100% of the amount of ionic liquid used. More preferably, the amount of cosolvent is less than about 50% of the ionic liquid, and most preferably, less than about 25% of the ionic liquid.
  • the amount of cosolvent used relative to the amount of ionic liquid used may be less than about 10%, 5%, and 1%. The relative amount of the cosolvent will depend on the ionic liquid and fluid mixture, as well as the operating conditions of the process .
  • the amount of ionic liquid used is less than the amount of cosolvent used in the process.
  • the amount of ionic liquid is preferably between about 1% and about 100% of the amount of cosolvent used, hi various other embodiments, the amount of ionic liquid used relative to the amount of cosolvent used may be less than about 50%, 25%, 5%, and 1%.
  • cosolvents can be used in the present invention. Additionally, two or more cosolvents may be combined for use in any aspects of the present invention, hi one embodiment, the cosolvent is selected from liquid phase compounds. In another embodiment, the cosolvent is selected from gas phase compounds. The cosolvents can be used in combination with an ionic liquid or mixtures of ionic liquids.
  • the cosolvents may include organic and inorganic compounds.
  • the cosolvents may be in the liquid phase or the gas phase.
  • Cosolvents include but are not limited to hydrocarbons, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, aldehydes, ketones, furans, amines, amides, imides, nitriles, ethers, esters, epoxides, pyridiniums, pyrrolidiniums, phenols, sulfates, sulfites, sulfides, sulfoxides, thiols, carbonyls, hydrides, halogens, water, carbon dioxide, oxygen, noble gases, organometallics and mixtures thereof.
  • Cosolvents also include, but are not limited to, inorganic compounds comprising alkaline salts, alkaline earth metal salts, transition metal complexes, lanmam ⁇ e complexes, actinide complexes.
  • Cosolvents also include, but are not limited to, inorganic acids comprised of the following anions: sulfates, nitrates, chlorates, phosphates, borates, carbonates, acetates, and halides.
  • Cosolvents also include, but are not limited to, inorganic bases comprised of hydroxide anions.
  • Cosolvents also include, but are not limited to, organic acids.
  • Preferred cosolvents used in the present invention include alkaline halogenated salts, alkaline earth halogenated salts, transition metal halide salts (e.g. FeCl 3 , CuCl, etc.), lanthanide metal halide salts, actinide metal halide salts, alcohols, aldehydes, amines, ammonia, aromatic hydrocarbons, arsenic pentafluoride, arsine, boron trichloride, boron trifluoride, carbon dioxide, carbon disulfide, carbon monoxide, carbon sulfide, chlorine, diborane, dichlorosilane, digermane, dimethyl disulfide, dimethyl sulfide, disilane, ethane, ethers, ethylene oxide, fluorine, germane, germanium methoxide, germanium tetrafluoride, hafnium methylethylamide, hafnium t-butoxide
  • cosolvents include alcohols (e.g. ethanol), water, hydrogen, ammonia, carbon dioxide, carbonyls, cyanides, sulfides, oxygen, hydrocarbons, halogenated hydrocarbons, oxygenated hydrocarbons, hydrides, hydrogen halogenides, halides, and mixtures thereof, hi some embodiments, the cosolvent is carbon dioxide, ethanol, or hydrogen gas. hi other embodiments, the cosolvent is carbon dioxide.
  • a canister of ionic liquid is prepared by the following method.
  • a stainless steel canister with a dip tube is charged with a known quantity of the ionic liquid.
  • the charged canister is thermally controlled by a PID temperature controller or variac with a heating element and a thermocouple.
  • the canister is US2006/012836 placed on a gravimetric load cell or weight scale and a pressure gauge is connected to tne canister to measure head pressure.
  • This canister is connected to a manifold with vacuum capability and to a gas source.
  • the canister is also connected to an analyzer (such as FT-IR, GC, APIMS, etc.).
  • a vacuum bake procedure is conducted on the canister charged with the ionic liquid and the manifold up to the gas cylinder, by pulling a vacuum while heating. This removes any trace moisture and other volatile impurities from the ionic liquid and the gas distribution components. The ionic liquid is allowed to cool to the desired operating temperature. The mass of the vacuum baked canister and ionic liquid is recorded.
  • a canister OfBMBVI[PF 6 ] is prepared as described above.
  • the source gas, B 2 H 6 or a gas mixture containing B 2 H 6 is then introduced into the canister, at 5 psig, until the uptake OfB 2 H 6 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the B 2 H 6 can be measured at the inlet of the canister and the outlet of the canister. B 2 H 6 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the BMIM[PF 6 ] fluid is saturated and cannot accept any further B 2 H 6 under the existing conditions. At this time, the source gas flow is stopped.
  • the BMIM[PF 6 ] -charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored B 2 H 6 .
  • the delivered gas is analyzed for B 2 H 6 content. This can be determined gravimetrically or analytically.
  • the total amount introduced is compared to the total amount removed to determine the loading factor of the cylinder.
  • a canister OfBMEvI[PF 6 ] is prepared as described above.
  • the source gas, SiF 4 or a gas mixture containing SiF 4 is then introduced into the canister, at 5 psig, until the uptake of SiF 4 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the SiF 4 can be measured at the inlet of the canister and the outlet of the canister. SiF 4 will continue to be introduced until the inlet and outlet amounts are equivalent, indicating the BMIM[PF 6 ] fluid is saturated and cannot accept any further SiF 4 under the existing conditions. At this time, the source gas flow is stopped.
  • the BMIM[PF 6 ] -charged canister is stored for a period of time. It is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored SiF 4 .
  • the delivered gas is analyzed for SiF 4 content. This can be determined gravimetrically or analytically. The total amount introduced is compared to the total amount removed to determine the loading factor of the cylinder.
  • a canister of MTBS (methyl-tri-n-butylammonium methylsulfate) is prepared as described above.
  • the source gas, SbH 3 or a gas mixture containing SbH 3 is then introduced into the canister, at 5 psig, until the uptake of SbH 3 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the SbH 3 can be measured at the inlet of the canister and the outlet of the canister. SbH 3 will continue to be introduced until the inlet and outlet amounts are equivalent, indicating the MTBS fluid is saturated and cannot accept any further SbH 3 under the existing conditions. At this time, the source gas flow is stopped.
  • the MTBS-charged canister is then stored for a period of time. It is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored SbH 3 .
  • the delivered gas is analyzed for SbH 3 content. This can be determined gravimetrically or analytically. The total amount introduced is compared to the total amount removed to determine the loading factor of the cylinder.
  • a canister OfBMBvI[PF 6 ] is prepared as described above.
  • the source gas, PH 3 or a gas mixture containing PH 3 is then introduced into me canister, at 5 psig, until the uptake of PH 3 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the PH 3 can be measured at the inlet of the canister and the outlet of the canister.
  • PH 3 will continue to be introduced until the inlet and outlet amounts are equivalent, indicating the BMIM[PF 6 ] fluid is saturated and cannot accept any further PH 3 under the existing conditions. At this time, the source gas flow is stopped.
  • the BMIM[PF 6 ] -charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored PH 3 .
  • the delivered gas is analyzed for PH 3 content. This can be determined gravimetrically or analytically.
  • the total amount introduced is compared to the total amount removed to determine the loading factor of the cylinder.
  • a canister of EMIM[AlCl 4 ] is prepared as described above.
  • the source gas, HCl or a gas mixture containing HCl is then introduced into the canister, at the vapor pressure of HCl, until the uptake of HCl is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the HCl can be measured at the inlet of the canister and the outlet of the canister. HCl will continue to be introduced until the inlet and outlet amounts are equivalent, indicating the EMIM[AlCl 4 ] fluid is saturated and cannot accept any further HCl under the existing conditions. At this time, the source gas flow is stopped.
  • the EMIM[AlCl 4 ]-charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored HCl.
  • the delivered gas is analyzed for HCl content. This can be determined gravimetrically or analytically.
  • the total amount introduced is compared to the total amount removed to determine the loading factor of the cylinder.
  • a canister OfBMIM[PF 6 ] is prepared as described above.
  • the source gas, B 2 H 6 or a gas mixture containing B 2 H 6 is then analyzed while bypassing the BMM[PF 6 ]-charged canister, in order to determine the concentration of impurities.
  • source gas is flowed into the canister containing BMIM[PF 6 ] at a pressure of 5 psig.
  • the delivered gas from the outlet of the canister is analyzed for impurities.
  • Purification of the source B 2 H 6 is determined by the lack of, or a decrease in the impurities detected in the delivered gas compared to the source gas.
  • the capacity of the BMIM[PF 6 ] for impurities is calculated by measuring the total moles of impurities removed for the moles of BMIM[PF 6 ] with which the canister was charged.
  • a canister OfBMIM[PF 6 ] is prepared as described above.
  • the source gas, SiF 4 or a gas mixture containing SiF 4 is then analyzed while by- passing the BMBvI[PF 6 ] -charged canister, in order to determine the concentration of impurities.
  • source gas is flowed into the canister containing BMIM[PF 6 ] at a pressure of 5 psig.
  • the delivered gas from the outlet of the canister is analyzed for impurities
  • Purification of the source SiF 4 is determined by the lack of, or a decrease in the impurities detected in the delivered gas compared to the source gas.
  • the capacity of the BMIM[PF 6 ] for impurities is calculated by measuring the total moles of impurities removed for the moles OfBMIM[PF 6 ] with which the canister was charged.
  • a canister of MTBS is prepared as described above.
  • the source gas, SbH 3 or a gas mixture containing SbH 3 is then analyzed while bypassing the MTBS-charged canister, in order to determine the concentration of impurities. Once the impurity concentrations in the source gas have been established, source gas is flowed into the canister containing MTBS at a pressure of 5 psig. The delivered gas from the outlet of the canister is analyzed for impurities.
  • Purification of the source SbH 3 is determined by the lack of, or a decrease in the impurities detected in the delivered gas compared to the source gas.
  • the capacity of the MTBS for impurities is calculated by measuring the total moles of impurities removed for the moles of MTBS with which the canister was charged.
  • a canister of MTBS is prepared as described above.
  • liquid phase source material SbH 3
  • SbH 3 The liquid phase source material is flowed through the apparatus, bypassing the MTBS-charged canister, vaporized, and analyzed in order to determine the concentration of impurities.
  • liquid phase source material is flowed into the canister containing MTBS, at the vapor pressure of SbH 3 .
  • the delivered liquid from the outlet of the canister is vaporized and analyzed to determine the concentration of the impurities.
  • Purification of the source SbH 3 is determined by the lack of, or a decrease in the impurities detected in the delivered liquid when compared to the source liquid, as determined by analysis in the vapor phase.
  • the capacity of the MTBS for impurities is calculated by measuring the total moles of impurities removed for the moles of MTBS with which the canister was charged.
  • a canister OfBMIM[PF 6 ] is prepared as described above.
  • the source gas, PH 3 or a gas mixture containing PH 3 is analyzed while by-passing the BMM[PF 6 ]-charged canister, in order to determine the concentration of impurities. Once the impurity concentrations in the source gas have been established, source gas is flowed into the canister containing BMIM[PF 6 ] at the vapor pressure of PH 3 . The delivered gas from the outlet of the canister is analyzed for impurities.
  • Purification of the stored PH 3 is determined by the lack of, or a decrease in tne impurities detected in the delivered gas compared to the source gas.
  • the capacity of the BMIM[PF 6 ] for impurities is calculated by measuring the total moles of impurities removed for the moles OfBMIM[PF 6 ] with which the canister was charged.
  • a canister of EMIM[AlCl 4 ] is prepared as described above.
  • the source gas, HCl or a gas mixture containing HCl, is analyzed while by- passing the EMIM[AlCl 4 ] -charged canister, in order to determine the concentration of moisture.
  • source gas is flowed into the canister containing EMIM[AlCl 4 ] at a pressure of 5 psig.
  • the gas is bubbled through the EMIM[AlCU] inside the canister and the delivered gas at the outlet of the canister is analyzed to measure the moisture content.
  • Purification of the stored HCl is determined by the lack of, or a decrease in the H 2 O impurity concentration detected in the delivered gas compared to the source gas.
  • the capacity of the EMIM[AlCU] for impurities is calculated by measuring the total moles of H 2 O removed for the moles of EMIM[AlCl 4 ]with which the canister was charged.
  • a canister of EMIM[Acetat] is prepared as described above.
  • liquid phase source material NH 3
  • EMIM[Acetat] -charged canister vaporized, and analyzed in order to determine the concentration of impurities.
  • liquid phase source material is flowed into the canister containing EMIM[Acetat], at the vapor pressure OfNH 3 .
  • the delivered liquid from the outlet of the canister is vaporized and analyzed to determine the concentration of the impurities.
  • Purification of the source NH 3 is determined by the lack of, or a decrease in the impurities detected in the delivered liquid when compared to the source liquid, as determined by analysis in the vapor phase.
  • the capacity of the EMIM[AcetatJ tor impurities is calculated by measuring the total moles of impurities removed for the moles of EMIM[Acetat] with which the canister was charged.
  • a canister OfBMBVI[PF 6 ] is prepared as described above.
  • the source gas, B 2 H 6 or a gas mixture containing B 2 H 6 is analyzed while bypassing the BMDVI[PFo] -charged canister, in order to determine the concentration OfB 2 H 6 and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into the canister containing BMBVI[PF O ] until it has equilibrated to a pressure of 5 psig. At this time, the flow of the source material is stopped.
  • Stabilization of the source B 2 H 6 is determined by the lack of, or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery OfB 2 H 6 .
  • a canister of MTBS is prepared as described above.
  • liquid phase source material SbH 3
  • SbH 3 The liquid phase source material is flowed through the apparatus, bypassing the MTBS-charged canister, vaporized, and analyzed in order to determine the concentration of decomposition products.
  • liquid phase source material is flowed into the canister containing MTBS, at the vapor pressure of SbH 3 . At this time, the flow of the source material is stopped.
  • the delivered liquid from the outlet of the canister is vaporized and analyzed for SbH 3 and decomposition products.
  • Stabilization of the source SbH 3 is determined by the lack ot, or a decrease in me decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery of SbH 3 .
  • a canister OfBMIM[PF 6 ] is prepared as described above.
  • the source gas, B 2 H 6 or a gas mixture containing B 2 H 6 is analyzed while bypassing the BMIM[PF 6 ]-charged canister, in order to determine the concentration of impurities.
  • source gas is flowed into the canister containing BMIM[PF 6 ] at a pressure of 5 psig, until the uptake OfB 2 H 6 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the B 2 H 6 can be measured at the inlet of the canister and the outlet of the canister. B 2 H 6 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the BMIM[PF 6 ] fluid is saturated and cannot accept any further B 2 H 6 under the existing conditions. At this time, the source gas flow is stopped.
  • the BMIM[PF 6 ] -charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored B 2 H 6 .
  • the delivered gas from the outlet of the canister is analyzed for impurities.
  • the canister is then stored for a period of time. Samples OfB 2 H 6 are taken at time intervals in order to determined the stability of the B 2 H 6 in the BMIM[PF 6 ]. Purification of the source B 2 H 6 is determined by the lack of, or a decrease in the impurities detected in the delivered gas from the canister compared to the source gas. The capacity of the BMIM[PF 6 ] for impurities is calculated by measuring the total moles of impurities removed for the moles OfBMEVI[PF 6 ] with which the canister was charged.
  • a canister OfBMIM[PF 6 ] is prepared as described above.
  • the source gas, SiF 4 or a gas mixture containing SiF 4 is analyzed while by- passing the BMIM[PF 6 ]-charged canister, in order to determine the concentration of impurities.
  • source gas is flowed into the canister containing BMIM[PF 6 ] at a pressure of 5 psig, until the uptake of SiF 4 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the SiF 4 can be measured at the inlet of the canister and the outlet of the canister. SiF 4 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the BMIM[PF 6 ] fluid is saturated and cannot accept any further SiF 4 under the existing conditions. At this time, the source gas flow is stopped.
  • the BMIM[PF 6 ] -charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored SiF 4 .
  • the delivered gas from the outlet of the canister is analyzed for impurities.
  • Purification of the source SiF 4 is determined by the lack of, or a decrease in the impurities detected in the delivered gas from the canister compared to the source gas.
  • the capacity of the BMIM[PF 6 ] for impurities is calculated by measuring the total moles of impurities removed for the moles OfBMEVI[PF 6 ] with which the canister was charged.
  • a canister of MTBS is prepared as described above.
  • the source gas, SbH 3 or a gas mixture containing SbH 3 is analyzed while bypassing the MTBS-charged canister, in order to determine the concentration of impurities.
  • source gas is flowed into the canister containing MTBS at a pressure of 5 psig, until the uptake Of SbH 3 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the SbH 3 can be measured at the inlet of the canister and the outlet of the canister.
  • SbH 3 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the MTBS fluid is saturated and cannot accept any further SbH 3 under the existing conditions. At this time, the source gas flow is stopped. [0158] The MTBS-charged canister is then heated, a pressure di ⁇ terential is applied, or ix is sparged with an inert gas, in order to deliver the stored SbH 3 . The delivered gas from the outlet of the canister is analyzed for impurities.
  • Purification of the source SbH 3 is determined by the lack of, or a decrease in the impurities detected in the delivered gas from the canister compared to the source gas.
  • the capacity of the MTBS for impurities is calculated by measuring the total moles of impurities removed for the moles of MTBS with which the canister was charged.
  • a canister OfBMIM[PF 6 ] is prepared as described above.
  • the source gas, PH 3 or a gas mixture containing PH 3 is analyzed while by-passing the BMIM[PF 6 ] -charged canister, in order to determine the concentration of impurities.
  • source gas is flowed into the canister containing BMIM[PF 6 ] at a pressure of 5 psig, until the uptake of PH 3 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the PH 3 can be measured at the inlet of the canister and the outlet of the canister. PH 3 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the BMIM[PF 6 ] liquid is saturated and cannot accept any further PH 3 under the existing conditions. At this time, the source gas flow is stopped.
  • the BMIM[PF 6 ] -charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored PH 3 .
  • the delivered gas from the outlet of the canister is analyzed for impurities.
  • Purification of the source PH 3 is determined by the lack of, or a decrease in the impurities detected in the delivered gas from the canister compared to the source gas.
  • the capacity of the BMIM[PF 6 ] for impurities is calculated by measuring the total moles of impurities removed for the moles OfBMIM[PF 6 ] with which the canister was charged.
  • a canister of EMIM[AlCl 4 ] is prepared as described above.
  • the source gas, HCl or a gas mixture containing HCl, is analyzed while by- passing the EMIM[AlCl 4 ]-charged canister, in order to determine the concentration of impurities.
  • source gas is flowed into the canister containing EMIM[AlCl 4 ] at a pressure of 5 psig, until the uptake of HCl is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the HCl can be measured at the inlet of the canister and the outlet of the canister. HCl will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the EMIM[AlCl 4 ] liquid is saturated and cannot accept any further HCl under the existing conditions. At this time, the source gas flow is stopped.
  • the EMIM[AlCl 4 ] -charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored HCl.
  • the delivered gas from the outlet of the canister is analyzed for impurities.
  • Purification of the source HCl is determined by the lack of, or a decrease in the impurities detected in the delivered gas from the canister compared to the source gas.
  • the capacity of the EMIM[AlCl 4 ] for impurities is calculated by measuring the total moles of impurities removed for the moles of EMIM[AlCl 4 ] with which the canister was charged.
  • a canister OfBMDVI[PF 6 ] is prepared as described above.
  • the source gas, B 2 H 6 or a gas mixture containing B 2 H 6 is analyzed while by- passing the BMIM[PF 6 ]-charged canister, in order to determine the concentration OfB 2 H 6 and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into the canister containing BMIM[PF 6 ] at a pressure of 5 psig, until the uptake OfB 2 H 6 is complete. The uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the B 2 H 6 can be measured at the inlet of the canister and the outlet of the canister. B 2 H 6 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating me BMIM[PF 6 ] fluid is saturated and cannot accept any further B 2 H 6 under the existing conditions. At this time, the source gas flow is stopped.
  • the BMIM[PF 6 ] -charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored B 2 H 6 .
  • the delivered gas from the outlet of the canister is analyzed for B 2 H 6 and decomposition products.
  • Stabilization of the source B 2 H 6 is determined by the lack of, or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery to the source material.
  • a canister of MTBS is prepared as described above.
  • the source gas, SbH 3 or a gas mixture containing SbH 3 is analyzed while by- passing the MTBS-charged canister, in order to determine the concentration of SbH 3 and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into the canister containing MTBS at a pressure of 5 psig, until the uptake of SbH 3 is complete. The uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the SbH 3 can be measured at the inlet of the canister and the outlet of the canister. SbH 3 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the MTBS fluid is saturated and cannot accept any further SbH 3 under the existing conditions. At this time, the source gas flow is stopped.
  • the MTBS-charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored SbH 3 .
  • the delivered gas from the outlet of the canister is analyzed for SbH 3 and decomposition products.
  • Stabilization of the source SbH 3 is determined by the lack of, or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery OfSbH 3 .
  • a canister of BMIM[PF 6 ] is prepared as described above.
  • the source gas, B 2 H 6 or a gas mixture containing B 2 H 6 is analyzed while by- passing the BMIM[PF 6 ] -charged canister, in order to determine the concentration OfB 2 H 6 , impurities, and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into the canister containing BMIM[PF 6 ] until it has equilibrated at a pressure of 5 psig. At this time, the source gas flow is stopped.
  • Stabilization of the source B 2 H 6 is determined by the lack of, or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery OfB 2 H 6 .
  • Purification of the source B 2 H 6 is determined by the lack of, or a decrease in the impurities detected in the delivered gas from the canister compared to the source gas.
  • the capacity of the BMIM[PF 6 ] for impurities is calculated by measuring the total moles of impurities removed for the moles OfBMEVI[PF 6 ] with which the canister was charged.
  • a canister of MTBS is prepared as described above.
  • the source gas, SbH 3 or a gas mixture containing SbH 3 is analyzed while bypassing the MTBS-charged canister, in order to determine the concentration OfSbH 3 , impurities, and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into the canister containing MTBS until it has equilibrated at 5 psig. At this time, the source gas flow is stopped.
  • the gas from the outlet of the canister containing the MTBS is then analyzed for SbH 3 , impurities, and decomposition products.
  • the MTBS-charged canister is then heated, a pressure dii ⁇ erential is applied, or ii is sparged with an inert gas, in order to deliver the stored SbH 3 .
  • the delivered gas from the outlet of the canister is analyzed for SbH 3 , impurities, and decomposition products.
  • Stabilization of the source SbH 3 is determined by the lack of, or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery Of SbH 3 .
  • Purification of the source SbH 3 is determined by the lack of, or a decrease in the impurities detected in the delivered gas from the canister compared to the source gas.
  • the capacity of the MTBS for impurities is calculated by measuring the total moles of impurities removed for the moles of MTBS with which the canister was charged.
  • a canister OfBMIM[PF 6 ] is prepared as described above.
  • the source gas, B 2 H 6 or a gas mixture containing B 2 H 6 is analyzed while bypassing the BMEVI[PF 6 ]-charged canister, in order to determine the concentration OfB 2 H 6 , impurities, and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into the canister containing BMIM[PF 6 ] at a pressure of 5 psig, until the uptake OfB 2 H 6 is complete.
  • the uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the B 2 H 6 can be measured at the inlet of the canister and the outlet of the canister. B 2 H 6 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the BMIM[PF 6 ] fluid is saturated and cannot accept any further B 2 H 6 under the existing conditions. At this time, the source gas flow is stopped.
  • the BMIM[PF 6 ]-charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored B 2 H 6 .
  • the delivered gas from the outlet of the canister is analyzed for B 2 H 6 , impurities, and decomposition products.
  • Stabilization of the source B 2 H 6 is determined by the lack of, or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery of B 2 H 6 . 36
  • Purification of the source B 2 H 6 is determined by the lack ot, or a decrease in me impurities detected in the delivered gas from the canister compared to the source gas.
  • the capacity of the BMM[PF 6 ] for impurities is calculated by measuring the total moles of impurities removed for the moles OfBMIM[PF 6 ] with which the canister was charged.
  • a canister of MTBS is prepared as described above.
  • the source gas, SbH 3 or a gas mixture containing SbH 3 is analyzed while by- passing the MTBS-charged canister, in order to determine the concentration of SbH 3 , impurities, and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into the canister containing MTBS at a pressure of 5 psig, until the uptake of SbH 3 is complete. The uptake can be determined gravimetrically, or by analytical methods. For example, the concentration or absolute amount of the SbH 3 can be measured at the inlet of the canister and the outlet of the canister. SbH 3 will continue to be introduced until the inlet and outlet concentrations are equivalent, indicating the MTBS fluid is saturated and cannot accept any further SbH 3 under the existing conditions. At this time, the source gas flpw is stopped.
  • the MTBS-charged canister is then heated, a pressure differential is applied, or it is sparged with an inert gas, in order to deliver the stored SbH 3 .
  • the delivered gas from the outlet of the canister is analyzed for SbH 3 , impurities, and decomposition products.
  • Stabilization of the source SbH 3 is determined by the lack of, or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery OfSbH 3 .
  • Purification of the source SbH 3 is determined by the lack of, or a decrease in the impurities detected in the delivered gas from the canister compared to the source gas.
  • the capacity of the MTBS for impurities is calculated by measuring the total moles of impurities removed for the moles of MTBS with which the canister was charged.
  • a canister OfBMM[PF 6 ] is prepared as described above.
  • the canister is charged with the cosolvent, CO 2 , by bubbling the CO 2 into the ionic liquid until the desired pressure is obtained in the canister.
  • the source gas, CS 2 or a gas mixture containing CS 2 is then introduced into the canister at 5 psig, until the uptake of CS 2 is complete.
  • the uptake can be determined gravimetrically.
  • the charged canister is stored for a period of time. It is heated, a pressure differential is applied, or it is sparged with an inert gas in order to deliver the stored CS 2 .
  • the total amount of CS 2 introduced into to the canister is compared to the total amount removed to determine the loading factor of the cylinder.
  • a canister OfBMEVI[PF 6 ] is prepared as described above.
  • the canister is charged with a gravimetrically determined amount of the cosolvent, ethanol.
  • the source gas, CH 4 or a gas mixture containing CH 4 is then introduced into the canister at 5 psig, until the uptake of CH 4 is complete.
  • the uptake can be determined gravimetrically.
  • the charged canister is stored for a period of time. It is heated, a pressure differential is applied, or it is sparged with an inert gas in order to deliver the stored CH 4 .
  • the total amount of CH 4 introduced into to the canister is compared to the total amount removed to determine the loading factor of the cylinder.
  • a canister OfBMEVI[PF 6 ] is prepared as described above.
  • the canister is charged with the cosolvent, hydrogen gas, by bubbling the gas into the ionic liquid until the desired pressure is obtained in the canister.
  • the source gas, B 2 H 6 or a gas mixture containing B 2 H 6 is analyzed while bypassing the charged canister, in order to determine the concentration OfB 2 H 6 and decomposition products. Once these concentrations in the source gas have been established, source gas is flowed into the canister containing BMEVI[PF 6 ] and hydrogen cosolvent at a pressure of 5 psig, until the uptake OfB 2 H 6 is complete. The uptake can be determined gravimetrically.
  • Stabilization of the source B 2 H 6 is determined by the lack of, or a decrease in the decomposition products detected in the delivered gas compared to the source gas, in addition to quantitative recovery to the source material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

La présente invention concerne des procédés de stockage, de distribution, de purification et/ou de stabilisation d'un fluide. Les procédés comprennent typiquement l'utilisation d'un récipient qui contient un liquide ionique ou un mélange à base d'un liquide ionique.
EP06740623A 2005-04-07 2006-04-07 Procede et systeme de stockage et de purification de fluide Pending EP1877153A4 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11/101,191 US7638058B2 (en) 2005-04-07 2005-04-07 Fluid storage and purification method and system
US11/155,291 US7585415B2 (en) 2005-04-07 2005-06-17 Fluid storage and purification method and system
US11/155,303 US7670490B2 (en) 2005-04-07 2005-06-17 Fluid storage and purification method and system
PCT/US2006/012836 WO2006110450A1 (fr) 2005-04-07 2006-04-07 Procede et systeme de stockage et de purification de fluide

Publications (2)

Publication Number Publication Date
EP1877153A1 true EP1877153A1 (fr) 2008-01-16
EP1877153A4 EP1877153A4 (fr) 2011-12-21

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EP (1) EP1877153A4 (fr)
KR (1) KR20080009708A (fr)
WO (1) WO2006110450A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2008005906A2 (fr) * 2006-07-03 2008-01-10 Matheson Tri-Gas, Inc. Procédé et système de stockage et de purification de liquide
DE102006060061A1 (de) * 2006-12-19 2008-06-26 Linde Ag Versiegelung mittels ionischer Flüssigkeiten
KR100975897B1 (ko) * 2009-01-05 2010-08-13 경희대학교 산학협력단 트리알콕시히드록시포스포늄 카복실레이트계 이온성 액체를포함하는 이산화탄소 흡수제
DE102009012298A1 (de) 2009-03-11 2010-05-12 Linde Aktiengesellschaft Vorrichtung und Verfahren zur Gewinnung von hochreinen Edelgasen
EP2785436B1 (fr) 2011-11-29 2016-01-13 Danmarks Tekniske Universitet - DTU Absorption et oxydation d'azote dans les liquides ioniques
CN108395448B (zh) * 2018-05-23 2023-08-04 福建久策气体股份有限公司 一种乙硼烷制备装置及其制备方法

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US20040206241A1 (en) * 2003-04-15 2004-10-21 Tempel Daniel Joseph Reactive liquid based gas storage and delivery systems
WO2005014547A1 (fr) * 2003-07-17 2005-02-17 Novartis Ag Melanges de liquides ioniques avec des acides de lewis
WO2005019137A1 (fr) * 2003-07-21 2005-03-03 Basf Aktiengesellschaft Procede pour extraire des impuretes au moyen de liquides ioniques
EP1607674A1 (fr) * 2004-06-14 2005-12-21 Air Products And Chemicals, Inc. Liquide contenant un acide de Lewis pour le stockage et la fourniture de bases de Lewis gazeuses

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US5164093A (en) * 1991-11-29 1992-11-17 Motorola, Inc. Apparatus and method for removing metallic contamination from fluids using silicon beads
EP2243539A3 (fr) * 2002-04-05 2011-06-01 University Of South Alabama Liquides ioniques fonctionnalisés et leurs procédés d'utilisation
US20030192430A1 (en) * 2002-04-11 2003-10-16 Pearlstein Ronald Martin Helical built-in purifier for gas supply cylinders
US6624127B1 (en) * 2002-11-15 2003-09-23 Intel Corporation Highly polar cleans for removal of residues from semiconductor structures

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Publication number Priority date Publication date Assignee Title
US20040206241A1 (en) * 2003-04-15 2004-10-21 Tempel Daniel Joseph Reactive liquid based gas storage and delivery systems
WO2005014547A1 (fr) * 2003-07-17 2005-02-17 Novartis Ag Melanges de liquides ioniques avec des acides de lewis
WO2005019137A1 (fr) * 2003-07-21 2005-03-03 Basf Aktiengesellschaft Procede pour extraire des impuretes au moyen de liquides ioniques
EP1607674A1 (fr) * 2004-06-14 2005-12-21 Air Products And Chemicals, Inc. Liquide contenant un acide de Lewis pour le stockage et la fourniture de bases de Lewis gazeuses

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See also references of WO2006110450A1 *

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WO2006110450A9 (fr) 2006-11-23
WO2006110450A1 (fr) 2006-10-19
EP1877153A4 (fr) 2011-12-21
KR20080009708A (ko) 2008-01-29

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