US3230727A - Vacuum insulated storage containers having improved vacuum maintenance means - Google Patents

Vacuum insulated storage containers having improved vacuum maintenance means Download PDF

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US3230727A
US3230727A US340317A US34031764A US3230727A US 3230727 A US3230727 A US 3230727A US 340317 A US340317 A US 340317A US 34031764 A US34031764 A US 34031764A US 3230727 A US3230727 A US 3230727A
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storage compartment
space
gas
compartment
evacuable
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Ransom P Skinner
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Union Carbide Corp
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Union Carbide Corp
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    • 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
    • F17C3/00—Vessels not under pressure
    • F17C3/02—Vessels not under pressure with provision for thermal insulation
    • F17C3/08—Vessels not under pressure with provision for thermal insulation by vacuum spaces, e.g. Dewar flask
    • 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
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/03—Thermal insulations
    • F17C2203/0304—Thermal insulations by solid means
    • F17C2203/0308—Radiation shield
    • F17C2203/032—Multi-sheet layers
    • 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
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/03—Thermal insulations
    • F17C2203/0304—Thermal insulations by solid means
    • F17C2203/0329—Foam
    • F17C2203/0333—Polyurethane
    • 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
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/03—Thermal insulations
    • F17C2203/0391—Thermal insulations by vacuum
    • 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
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0612—Wall structures
    • F17C2203/0626—Multiple walls
    • F17C2203/0629—Two walls
    • 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
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0639—Steels
    • F17C2203/0643—Stainless steels
    • 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
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0646—Aluminium
    • 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
    • F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/01—Mounting arrangements
    • F17C2205/0123—Mounting arrangements characterised by number of vessels
    • F17C2205/013—Two or more vessels
    • F17C2205/0134—Two or more vessels characterised by the presence of fluid connection between vessels
    • F17C2205/0138—Two or more vessels characterised by the presence of fluid connection between vessels bundled in series
    • 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
    • F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
    • F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
    • F17C2205/0323—Valves
    • F17C2205/0326—Valves electrically actuated
    • 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
    • F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
    • F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
    • F17C2205/0323—Valves
    • F17C2205/0332—Safety valves or pressure relief valves
    • 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
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/011—Oxygen
    • 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
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/014—Nitrogen
    • 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
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0146—Two-phase
    • F17C2223/0153—Liquefied gas, e.g. LPG, GPL
    • F17C2223/0161—Liquefied gas, e.g. LPG, GPL cryogenic, e.g. LNG, GNL, PLNG
    • 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
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
    • F17C2223/033—Small pressure, e.g. for liquefied gas
    • 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
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/04—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by other properties of handled fluid before transfer
    • F17C2223/042—Localisation of the removal point
    • F17C2223/046—Localisation of the removal point in the liquid
    • F17C2223/047—Localisation of the removal point in the liquid with a dip tube
    • 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
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/04—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by other properties of handled fluid after transfer
    • F17C2225/042—Localisation of the filling point
    • F17C2225/043—Localisation of the filling point in the gas
    • F17C2225/044—Localisation of the filling point in the gas at several points, e.g. with a device for recondensing gas
    • 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
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/01—Propulsion of the fluid
    • F17C2227/0128—Propulsion of the fluid with pumps or compressors
    • F17C2227/0135—Pumps
    • 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
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • F17C2250/0439—Temperature
    • 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
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/06—Controlling or regulating of parameters as output values
    • F17C2250/0605—Parameters
    • F17C2250/0631—Temperature
    • 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
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/06—Controlling or regulating of parameters as output values
    • F17C2250/0605—Parameters
    • F17C2250/0636—Flow or movement of content
    • 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
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/01—Improving mechanical properties or manufacturing
    • F17C2260/017—Improving mechanical properties or manufacturing by calculation
    • 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
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/03—Dealing with losses
    • F17C2260/031—Dealing with losses due to heat transfer
    • F17C2260/033—Dealing with losses due to heat transfer by enhancing insulation

Definitions

  • VACUUM INSULATED STORAGE CONTAINERS HAVING IMPROVED VACUUM MAINTENANCE MEANS Filed Jan. 27, 1964 3 Sheets-Sheet 5 INVENTOR. KPJA/JOM P. JK/w A'TTORUE) 3,230,727 VACUUM INSULATED STORAGE CONTAINERS HAVING IMPROVED VACUUM MAINTENANCE MEANS Ransom P. Skinner, Indianapolis, Ind., assig'nor to Union.
  • alumina-silica powder (a conventional insulating materialused in such containers) has a thermal conductivity at 50 microns of mercury pressure of approximately 0.0016 B.t.u./hr. sq. ft. F./ft.; but if a small amount of air and/or water is present to increase the pressure to 500- microns of mercury pressure, its thermal conductivity increases to approximately-0.0054 B.t.u./h-r. sq. ft. F./ft.
  • FIGURE 1 is a front elevation view in section of an insulated container of this invention wherein a conduit joins the evacuated space of a double-walled storage compartment and the evacuated space of a double-walled cryogenic liquid container.
  • FIGURE 2 is a longitudinal view, partly in section, of an insulated container of this invention wherein a common outer wall houses both a storage compartment and a cryogenic liquid container.
  • FIGURE 3 is a sectional view of a fastening member employed in the embodiment of FIGURE 2 to fasten the storage compartment to the outer wall and to define an access conduit.
  • FIGURE 4 is a schematic diagram of conduit system which can be employed in conjunction with the embodiment of FIGURE 2.
  • FIGURE 5 is a front elevation view in section of an insulated container of this invention wherein a storage compartment and a cryogenic liquid container have separate evacuable insulating spaces.
  • the invention is based, in part, on the discovery that a vacuum can be maintained in the evacuated insulated space of a double-walled storage container used for storing materials at temperatures from about -40 F.
  • this invention provides an insulated container for storing materials at a temperature from 40 F.
  • said container comprising (a) a double walled storage compartment having an outer shell and an inner shell, said inner shell defining a space for storing said materials and said outer and inner shells defining an intervening evacuable space therebetweenj (b) a separate receptacle" which is spaced from the storage compartment and which contains a gas adsorbent that has a greater gas-adsorption capacity at temperatures below about l 5 0 F. than at about ambient temperatures, that is cooled to a tern;
  • gas-communication means pro viding gaseous communication between the. evacuable;
  • the gas adsorbent can mainta n a vacuum in the evacu-able'space.
  • the space is initially evacuated to. the desired low, pressure by any suitable means (e.g. mechanical pumps can be used to lower the pressure to a pressure slightly. above the desired pressure and then the adsorbent can be used. to further lower the pressure in the space. to the desired pressure). There-after, any gas entering the evacuated space is adsorbed by the adsorbent which thereby main;- tains the desired vacuum in the space.
  • any suitable means e.g. mechanical pumps can be used to lower the pressure to a pressure slightly. above the desired pressure and then the adsorbent can be used. to further lower the pressure in the space. to the desired pressure).
  • any gas entering the evacuated space is adsorbed by the adsorbent which thereby main;- tains the desired vacuum in the space.
  • One more specific embodiment of this invention pro.- vides an insulated container comprising (1) a doublewalled storage compartment and (2) a double-walled cryogenic liquid container. associated therewith.
  • the storage compartment has an outer shell and: an inner. shell defining an intervening first evacuab'le space there between, a storage space within the inner shell, insulation in the first evacuable space for insulatingv the storage space and access means for introducing materials to be stored into the storage space and for withdrawing said materials from the storage space.
  • the double-walled cryogenic liquid container has outer and; inner walls defining an intervening second evacuable space therebe tween that is in gaseous communication with the first evaouable space, a cryogenic liquid storage space within the inner wall, insulation in the second evacuable' space for insulating the cryogenic liquid storage space, access" means for introducing a cryogenic. liquid into the cryogenie liquid storage space and a-mass of; a gas adsorbent whose gas absorbing properties are better at cryogenic temperatures than at ambient temperatures disposedin the second evacuable space.
  • the adsorbent is in thermal contact with a cryogenic liquid introduced into and main' tained in the cryogenic liquid storage space and theadsorbent is in gaseous communication with boththe first and second evaeuab'le spaces for maintaining a vacuum in each space after they have been evacuated.
  • any gas adsorbent whose gas adsorption properties are better at cryogenic temperatures than at about ambient temperatures can be employed in the insulated containers of this invention.
  • the adsorbent can be a material such as charcoal (preferably coconut charcoal) or silica gel.
  • it is preferred thatflth'e adsorbent be a crystalline zeolitic molecular sieve. Suitable zeolitic molecular sieves include both the naturally: occurring zeoliticmolecular sieves and the synthetic. ze0 litic molecular sieves.
  • zeolitic molecular sieves include chabazite, erionite, mordenite and faujasite, these being adequately described in the chemical art.
  • Synthetic zeolitic molecular sieves include zeolites The cooling of the adsorbent is readily accomplished with A, D, L, R, S, T, X and Y, as Well as the mordenite-type material known commercially as Zeolon and described in Chemical and Engineering News, March 12, 1956, pages 5254.
  • the pore size of the zeolitic molecular sieves may be varied by employing different metal cations.
  • sodium zeolite A has a pore size of about 4 angstrom units whereas when calcium cations have been exchanged for at least about 40 percent of the sodium cations calcium zeolite A has a pore size of about angstrom units.
  • Zeolite A is a crystalline zeolitic molecular sieve which may be represented by the formula:
  • n is the valence of M and y may have any value up to about 6.
  • the as-synthesized Zeolite A contains primarily sodium ions and is designated sodium zeolite A, described in more detail in U.S. Patent No. 2,882,243, issued April 14, 1959.
  • Zeolite X is a synthetic crystalline zeolitic molecular sieve which may be represented by the formula:
  • M represents a metal, particularly alkali and alkaline earth metals
  • n is the valence of M
  • y may have any value up to about 8, depending on the identity of M and the degree of hydration of the crystalline Zeolite.
  • Sodium zeolite X has an apparent pore size of about angstrom units.
  • vZeolite X, its X-ray diifraction pattern, its properties and methods for its preparation are described in detail in U.S. Patent No..2,882,244, issued April 14, 1959.
  • Zeolite Y is described and claimed in U.S. Patent application Serial No. 109,487, filed May 12, 1961, now Patent No. 3,130,007, in the name of D. W. Breck and issued as U.S. Patent N0. 3,130,007 on April 21, 1964.
  • Agglomerates comprising both zeolitic molecular sieves and finely divided metal particles can also be employed as the gas adsorbent in the containers of this invention. More specifically, such agglomerates comprise zeolitic molecular sieve crystals of less than 10 microns individual size and metal bodies having at least one dimension less than 50 microns, the ratio of the metal body size to the zeolitic molecular sieve crystal size being at least 5 to 1.
  • the metal bodies are uniformly dispersed throughout the agglomerate in quantity sufiicient to constitute between about -5 and 30 percent by weight of the agglomerate and are sintered to the outer surface of the molecular sieve crystals.
  • the metal should have a melting point over 300'C.”and is employed primarily as a structural component in the multi-crystalline agglomerate but probably also enters into the formation of a chemical bond with the molecular sieve crystals by virtue of the sintering.
  • the metals suitable for use in the multicrystalline agglomerate are those of groups Ib, IIb, IIIa, Va, Vb, VIb, VIIv and VII of the Periodic Table (Handbook of Chemistry and Physics, thirty-eighth edition, page 394, Chemical Rubber Publishing Co., 1956). Silicon, germanium, lead and tellurium are also suitable.
  • Exemplary metals include, but are not limited to, copper, silver and gold of group Ib, magnesium of group Ila, zinc of group IIb, boron and aluminum of group IIIa, yttrium of group IIIb, antimony of group Va, Vanadium of group Vb, chromimum of group VIb, manganese of group VHb and iron, nickel, platinum and palladium of group VIII. Mixtures and alloys of these metals may also be employed. Such agglomerates are disclosed and claimed in U.S. Patent application Serial No. 300,163, filed August 6, 1963.'
  • the amount of gas adsorbent employed in the insulated containers of this invention will depend on such factors as the particular cryogenic liquid and adsorbent used, the amount of gas to be adsorbed, the size of the vacuum 4 space, the length of time that the vacuum is to be maintained and the like.
  • cryogenic fluids include inert liquids having boiling points at atmospheric pressure below -320 F. Such liquids include liquid nitrogen, liquid oxygen and the like.
  • liquefied gas and liquefied refrigerant gas are used as synonyms for the term cryogenic liquid. Cold gaseous nitrogen is also useful.
  • cryogenic liquid container can be insulated with composite insulating materials such as those composed of alternate layers of thin metallic sheets (e.g. aluminum foil) and glass fiber sheets (e.g. in the form of paper or;
  • Suitable composite insulating materials are disclosed in U.S. Patents 3,007,596, 3,018,016, 3,007,576, 3,009,600 and 3,009,602.
  • the storage compartment can be insulated with the latter-mentioned composite insulating materials or with polyurethane foam.
  • FIG- URE 1 shows an insulated container of the presentinvention composed of cryogenic liquid container 2 and storage compartment 3.
  • the walls 4 and 5 of cryogenic liquid container 2 are spaced apart so as to define an intervening evacuable space 6.
  • the outer shell 7 and inner shell 8 of the storage compartment 3 are spaced apart so as to define intervening evacuable space 9.
  • Evacuable spaces 6 and 9 are, in a preferred embodiment of this invention, in gaseous communication through double-walled insulated conduit 10. However, it is not essential that conduit 10 be a double-walled, insulated connecting means.
  • Cryogenic liquid container 2 contains a cryogenic liquid 11 (e.g.
  • Cryogenic liquid container 2 is provided with an accessmeans (not shown) for introducing the cryogenic liquid therein.
  • the storage compartment 3 is provided withan access means (not shown) for introducing materials to be stored therein and for removing such materials.
  • Walls 5 and 6 are composed of aluminum or other suitable material and outer shell 7 and inner shell 8 are composed of stainless steel or other suitable materiaL. Insulating materials 12 are provided in the evacuable spaces around inner walls 5, the inner wall of conduit 10 and inner shell 8.
  • FIGURE 2 depicts an insulated container of this invention having an outer shell 50 within which are located two separate compartments, liquefied gas storage compartment 51 and perishable food storage compartment 52.
  • Outer shell 50 and compartments 51 and 52 can be composed of any suitable material such as stainless steel or aluminum.
  • liquefied gas storage compartment 51 and perishable food storage compartment 52 together with the inner surface of outer shell 50 define an intervening evacuable space 53.
  • Evacuable space 53 also extends between the adjacent walls of liquefied gas storage compartment 51 and perishable food storage compartment 52. Accordingly, both compartmentfil and compartment 52 are surrounded by common evacuable space 53.
  • a plurality of solid cylindrical load-supporting pegs'54 or other load-supporting means are disposed in evacuable space 53 between the liquefied gas storage compartment 51 and the adjacent portion of the outer shell 50 so as to support the atmospheric load on the outer shell. Suitable loadsupport means are described and claimed in U.S. Patent Application Serial No. 340,311, filed January 27, 1964, in the names of W. L. Berner, C. P. Mulcahey and R. P. Skinner, entitled Load Support Means for Thermally In;
  • pegs that are disposed between the, bottom surfaces of the compartments 51 and 52 and the outer shell 50 so as to also support the weight of compartments 51 and 52. Additionally, pegs 54 are disposed between liquefied gas storage compartment 51 and perishable food storage compartment 52 in order to maintain these compartments at a distance from each other equal to the length of the pegs so as to stabilize the compartments against relative movement and prevent thermal contact between the walls of the compartments. Compression-sensitive insulating material 55 (e.g.
  • insulation such as is described in the above-mentioned United States patents
  • the thickness of the insulating material 55 around liquefied gas storage compartment 51 may be as shown in FIGURE 2, greater than the thick-.
  • insulating material 55 around perishable food storage compartment 52.
  • Insulating material 55 is provided with holes through which pass pegs 54.
  • a liquefied refrigerant gas 5511 (such as liquid nitrogen) is provided in liquefied gas storage compartment 51 and this liquefied gas 55a is in thermal communication with a mass of a zeolitic molecular sieve gas adsorbent 56 which is retained in a perforated metal blister 57 depending from the bottom of liquefied gas storage compartment 51.
  • the liquefied gas 55 cools the molecular sieve 56 thereby improving the gas adsorbing properties of the sieve.
  • the perforations in the blister 57 provides gaseous communication between the zeolitic molecular sieve gas adsorbent 56 and evacuable space 53 and serves to maintain a vacuum in the evacuable space after the evacuable space is evacuated;
  • Strips of gas-impervious organic polymer 58 having low thermal conductivity join the top, bottom and side walls of perishable food storage compartment 52 to outer wall 50. These strips of organic polymer 58 serve to prevent the passage of gas into evacuable space 53 and serve to prevent heat leak into perishable food storage compartment 52 while at the same time defining an access conduit for introducingfood into perishable food storage compartment 52.
  • Insulated storage compartment door 59 provides access'to perishable food storage compartment 52.
  • Door 59 can be insulated with polyurethane foam or other suitable insulating material. Alternately, the desired degree of insulating can be achieved by using a vacuum panel door.
  • the floor of perishable food storage compartment 52 is provided with cover plate 60 rotatable about hinge 61 which can be positioned over the strip of organic polymer 58 connecting the floor of compartment 52 to outer shell 50.
  • Cover plate 60 prevents damage to the strip of .organic polymer 58 when perishable food is being introduced into perishable food storage compartment 52.
  • cover plate 60 is charged so thatit can be rotated into the position shown in FIG- URE 2 when not needed to protect lower strip of organic polymer 58.
  • Low heat conducting filling tube 63 is provided for introducing liquefied gas 55a into liquefied gas storage compartment 51 and transfer conduit 64 is provided for transporting liquefied gas 55a from liquefied gas storage compartment 51 to perishable food storage compartment 62 in order to provide refrigeration for perishable food stored in perishable food storage compartment 52.
  • Perforations are provided in the portion of the transfer conduit 64 located within perishable food storage compartment 52 to allow the liquefied gas 55 to be sprayed from the transfer conduit 64 as a fine mist on the perishable food within perishable food storage compartment 52.
  • Suitable means are provided for regulating the fiow of liquefied gas 55a into perishable food storage, compartment 52 so as to maintain the perishable food at a predetermined desired temperature.
  • the temperature in compartment 52 will be dependent on thetype material being stored (e.g. fruit, meat, vegetables etc.) and will usually be between 40 F. and +60 F.
  • Such flow-regulating means include the feature of discontinuing the transfer of the liquefied gas into perishable food storage compartment 52 when insulated storage compartment door 59 is opened. This latter feature prevents a waste of the liquefied gas when the insulated storage compartment door 59 is opened to introduce perishable food into perishable food storage compartment 52 or to withdraw the food.
  • the pressure required to transfer the liquefied gas 55a from liquefied gas storage compartment 51 through transfer conduit 54 in which perishable food storage compartment 52 can be created in any convenient manner.
  • the pressure can be created by a heating coil in the bottom of liquefied storage compartment 51 which creates the desired pressure by vaporizing a portion of the liquelied gas 55a in response to a temperature sensing element in perishable food storage compartment 52.
  • the pressure is created initially by charging the liquefied gas to the liquefied gas storage compartment 51 along with vapor of the gas at a pressure sufficient to insure. the transfer of the gas during the desired period of .operation.
  • a pressure from 5 p.s.i.g. to 25 p.s.i.g. is maintained in compartment 51.
  • Liquefied gas storage compartment 51 is preferably provided with internal bracing means or supports to assist in carrying loads imposed on compartment 51.
  • the expansion and contraction of the. outer shell 50 is readily provided for by employing corrugated walls as illustrated by corrugated wall 50a in FIGURE 4.
  • the expansion and contraction of perishable food storage compartment 52 can be provided for by constructing wall 65 of relativelythin and resilient material so that it will tend to buckle under stress (e.g. a 7.5 ft. x 7.5 ft. wall can be made 0.100 inch thick for this purpose
  • the expansion and contraction of perishable food storage compartment 52 can be provided for by employing an elastic material also possessing low thermal'conductivity and gasimpervious properties as organic polymer strip 58.
  • wall65 ca nbe made thicker and, therefore, more rigid (e.g. a 7.5 ft. x 7.5 ft. wall can be made 0.50 inch thick for this purpose).
  • Organic polymer strips suitable for this use include those composed of butyl rubber.
  • FIG- URE 3 The manner in which the strips of organic polymer 58 can be attached to the walls of perishable food storage compartment 52 and outer shell 50 is illustrated by FIG- URE 3.
  • the strip of organic polymer 58 is provided with enlarged end portions 58a which are adapted to fit into bracket 52a attached to the floor of inner compartment 52 and into bracket 50a attached to outer shell 50.
  • Enlarged end portions 58a of organic polymer strip 58 are maintained in brackets 52a and 50a b-y plates 52b and 50b held in place by means of screws 52c and 500.
  • FIGURE 4 illustrates a conduit arrangement suitable for use in transferring a cryogenic liquid from storage compartment 51 of FIGURE 2 to storage compartment 52 of FIGURE 2 in order to refrigerate the contents of compartment 52 of FIGURE 2.
  • Compartment 51 is filled with 'a cryogenic liquid through conduit 63 and then the interior of compartment 51 is pressurized by conventional means to a pressure of about 5 p.s.i.g. to 25 p.s.i.g.
  • Conduit 64 is provided with a solenoid valve 64a which is connected to a suitable temperature controller (not shown).
  • Conduit 66 is provided With a relief valve and safety valve (not shown). When the temperature in compartment 52 arises above a predetermined point, the controller energizes a solenoid 64a to open it.
  • the cryogenic liquid then flows from compartment 51 into compartment 52 through conduit 64 because of the pressure differential (compartment 52 is at about atmospheric pressure).
  • the cryogenic liquid is sprayed into compartment 52 through perforations in conduit 64 until the temperature in compartment 52 decreases to the predetermined point.
  • solenoid valve 64a closes, terminating the flow of the cryogenic liquid.
  • the container consisted of (1) a standard commercially available double-walled dewar used for storing liquid nitrogen and (2) a storage compartment.
  • the storage compartment was similar to-the storage compartment 3 of FIGURE 1.
  • the storage compartment had a storage capacity of 39,300 cubic inches and the evacuable space in the storage compartment was one inch wide.
  • the evacuable space in the storage compartment was evacuated to about one micron of mercury pressure employing conventional pumping means.
  • compartment was maintained at about -10" F. by purging the interior of the compartment with liquid nitrogen.
  • Ten liters of liquid nitrogen were maintained in the dewar.
  • Five pounds of zeolite A were placed in an air-tight aluminum can which was air-tightly fitted with a plastic hose.
  • the can was inserted in the dewar so that it was immersed in the liquid nitrogen and the hose extended out of the top of the dewar through the necktube of the dewar.
  • the hose was air-tightly attached to an opening in the outer shell ofthe storage compartment so as to provide gaseous communication between the liquid nitrogen-cooled zeolite A and the evacuable space of the storage compartment.
  • a vacuum of about one micron of mercury pressure was maintained in the evacuable space of the storage compartment for one year in this manner.
  • the liquid nitrogenin the dewar was replenished at a rate of about 10 liters of liquid-nitrogen per day. The above-described.
  • container is illustrative of a container of this invention WhBI'ClIl-thfi adsorbent used to maintain a vacuum in the evacuable space in the storage compartment is not also used to maintain a vacuum in the evacuable space in the cryogenic liquid container and wherein the evacuable space of the container is not in gaseous communication with the evacuable space of the dewar.
  • This container is depicted byFIG- URE 5 wherein storage compartment 1 has stainless steel or aluminum Walls 2 and 3 spaced apart to define intervening evacuable insulating space 4. Space 4 is in gaseous communication with a mass of adsorbent 5 (Zeolite A) through plastic conduit 6.
  • Adsorbent 5 is retained in air-tight aluminum can 7 which is immersed in liquid nitrogen 8 that is in dewar 9.
  • Compartment 1 is provided with low heat conducting plug 10 through which pass thermistor lead 11 and liquid nitrogen conduit 12 that communicates with a liquid nitrogen reservoir (not shown).
  • thermistor 13 activates a valve (not shown) in conduit 12 permitting liquid nitrogen to pass through conduit 12 and purge storage space 14 till the temperature therein falls to another predetermined temperature at which point the valve is closed.
  • Conduit 6 has pinch-off tube 18 for use in evacuating the conduit, can 7 and space 4. Stainless.
  • steel inner shell 15 and stainless steel outer shell 16 of dewar 9 define another intervening evacuable insulating space 17.
  • the storage compartments in the containers of this The temperature withinvthe storage 8 invention are useful for storing meat, fish, fowl, vegetables, fruits and the like.-
  • An insulated container for storing materials at a temperature from .40 F. to +60 F., said container comprising (a) a double-walled storage compartment having an outer shell and an inner shell, said inner shell defining a space for storing said materials and said outer and inner shells defining an intervening evacuable space therebetween; (b) a separate receptacle which is spaced from the storage compartment and which contains a gas adsorbent that has a greater gas-adsorption capacity at temperatures .below about 150 F. than at about ambient temperatures, that is cooled to a temperature below about 150 F. and that is sealed from the atmosphere; and (c) gas-communication means providing gaseous communication between the evacuable space and the gas adsorbent so that the gas adsorbent can maintain a vacuum in the evacuable space.
  • An insulated container comprising (1) a storage compartment for storing materials at a temperature from about 40 F. to about +60 F., said compartment having (a) an outer shell and an inner shell defining an intervening first evacuable space therebetween, said inner shell defining a storage space for storing said materials, a storage space within the inner shell, (b) thermal insulating material in the first evacuable space for insulating the storage space.
  • said adsorbent being in thermal contact with a cryogenic liquid in the cryogenic liquid storage space and said adsorbent being in gaseous communication with both the first and second. evacuable spaces for maintaining a vacuum in each space after evacuation thereof.
  • the container of claim 2 having means for withdrawing a portion of the cryogenic liquid from cryogenic liquid storage space for cooling materials stored in the storage space of the storage compartment.

Description

Jan. 25, 1966 R. P. SKINNER 3,230,727
VACUUM INSULATED STORAGE CONTAINERS HAVING IMPROVED VACUUM MAINTENANCE MEANS Filed Jan. 27, 1964 s Sheets-Sheet 1 IN VEN TOR. 04445044 AJK/N/VEB A TI'OF/VE) Jan. 25, 1966 R. P. SKINNER 3,230,727
VACUUM INSULATED STORAGE CONTAINERS HAVING IMPROVED VACUUM MAINTENANCE MEANS Filed Jan. 27, 1964 3 Sheets-Sheet 2 147 TOE/V5 y Jan. 25, 1966 R. P. SKINNER 3,230,727
VACUUM INSULATED STORAGE CONTAINERS HAVING IMPROVED VACUUM MAINTENANCE MEANS Filed Jan. 27, 1964 3 Sheets-Sheet 5 INVENTOR. KPJA/JOM P. JK/w A'TTORUE) 3,230,727 VACUUM INSULATED STORAGE CONTAINERS HAVING IMPROVED VACUUM MAINTENANCE MEANS Ransom P. Skinner, Indianapolis, Ind., assig'nor to Union.
Carbide Corporation, a corporation of New York Filed-Jan. 27, 1964, Ser. No. 340,317 Claims. (Cl. 62 48) This invention relates to.v'acuum insulated'storage containers.
It has becomeucomm-on. practice to store materials at sub-ambient: temperatures in double-walled. storage. containers having insulating materialsin. an evacuatedv space. It has been found that the thermal.
between the walls. conductivity of many insulating. materials used in such containers increases sharply if even a. relatively small amount of gas (eg. water vaporand/or air). are present.
in the evacuated space between the double walls of the container. By way of: illustration, alumina-silica powder (a conventional insulating materialused in such containers) has a thermal conductivity at 50 microns of mercury pressure of approximately 0.0016 B.t.u./hr. sq. ft. F./ft.; but if a small amount of air and/or water is present to increase the pressure to 500- microns of mercury pressure, its thermal conductivity increases to approximately-0.0054 B.t.u./h-r. sq. ft. F./ft.
It has been found that undesirable small amounts of gases in the insulating spaces in the above-described containers cannot be removed effectively by providing gas adsorbents in such spaces since gas adsorbents do not possess adequate gas adsorbent properties at the temperatures (e.g. from --40 F. to +60 F.) often prevailing in such spaces.
It is an object of this invention to provide means for maintaining the vacuum in evacuated insulated spaces of double walled storage containers in which materials are stored at temperatures from 40 F. to +60 F.
Other objects and advantages of this invention will be apparent from the ensuing enclosure and the appended claims.
In the drawings,
FIGURE 1 is a front elevation view in section of an insulated container of this invention wherein a conduit joins the evacuated space of a double-walled storage compartment and the evacuated space of a double-walled cryogenic liquid container.
FIGURE 2 is a longitudinal view, partly in section, of an insulated container of this invention wherein a common outer wall houses both a storage compartment and a cryogenic liquid container.
FIGURE 3 is a sectional view of a fastening member employed in the embodiment of FIGURE 2 to fasten the storage compartment to the outer wall and to define an access conduit.
FIGURE 4 is a schematic diagram of conduit system which can be employed in conjunction with the embodiment of FIGURE 2.
FIGURE 5 is a front elevation view in section of an insulated container of this invention wherein a storage compartment and a cryogenic liquid container have separate evacuable insulating spaces.
The invention is based, in part, on the discovery that a vacuum can be maintained in the evacuated insulated space of a double-walled storage container used for storing materials at temperatures from about -40 F.
. to +60 F. by providing a mass of a gas adsorbent that is cooled to cryogenic temperatures (e.g. temperatures below 320 F.) and that is in gaseous communication with the evacuated space. The improved gas adsorption capacity of the gas absorbent at cryogenic temperatures "ice allows for the ready adsorption of any small amountof gas in the evacuated space. Accordingly, this invention provides an insulated container for storing materials at a temperature from 40 F. to +60 F., said container comprising (a) a double walled storage compartment having an outer shell and an inner shell, said inner shell defining a space for storing said materials and said outer and inner shells defining an intervening evacuable space therebetweenj (b) a separate receptacle" which is spaced from the storage compartment and which contains a gas adsorbent that has a greater gas-adsorption capacity at temperatures below about l 5 0 F. than at about ambient temperatures, that is cooled to a tern;
perature below about F. and that is sealed from the atmosphere; and (c) gas-communication means pro viding gaseous communication between the. evacuable;
space and the gas adsorbent so, that the gas adsorbent can mainta n a vacuum in the evacu-able'space.
The space is initially evacuated to. the desired low, pressure by any suitable means (e.g. mechanical pumps can be used to lower the pressure to a pressure slightly. above the desired pressure and then the adsorbent can be used. to further lower the pressure in the space. to the desired pressure). There-after, any gas entering the evacuated space is adsorbed by the adsorbent which thereby main;- tains the desired vacuum in the space.
One more specific embodiment of this invention pro.- vides an insulated container comprising (1) a doublewalled storage compartment and (2) a double-walled cryogenic liquid container. associated therewith. The storage compartment has an outer shell and: an inner. shell defining an intervening first evacuab'le space there between, a storage space within the inner shell, insulation in the first evacuable space for insulatingv the storage space and access means for introducing materials to be stored into the storage space and for withdrawing said materials from the storage space. The double-walled cryogenic liquid container has outer and; inner walls defining an intervening second evacuable space therebe tween that is in gaseous communication with the first evaouable space, a cryogenic liquid storage space within the inner wall, insulation in the second evacuable' space for insulating the cryogenic liquid storage space, access" means for introducing a cryogenic. liquid into the cryogenie liquid storage space and a-mass of; a gas adsorbent whose gas absorbing properties are better at cryogenic temperatures than at ambient temperatures disposedin the second evacuable space. The adsorbent is in thermal contact with a cryogenic liquid introduced into and main' tained in the cryogenic liquid storage space and theadsorbent is in gaseous communication with boththe first and second evaeuab'le spaces for maintaining a vacuum in each space after they have been evacuated.
In general, any gas adsorbent whose gas adsorption properties are better at cryogenic temperatures than at about ambient temperatures can be employed in the insulated containers of this invention. Thus, the adsorbent can be a material such as charcoal (preferably coconut charcoal) or silica gel. However, it is preferred thatflth'e adsorbent be a crystalline zeolitic molecular sieve. Suitable zeolitic molecular sieves include both the naturally: occurring zeoliticmolecular sieves and the synthetic. ze0= litic molecular sieves. Among the naturally-occurring zeolitic molecular sieves are chabazite, erionite, mordenite and faujasite, these being adequately described in the chemical art. Synthetic zeolitic molecular sieves include zeolites The cooling of the adsorbent is readily accomplished with A, D, L, R, S, T, X and Y, as Well as the mordenite-type material known commercially as Zeolon and described in Chemical and Engineering News, March 12, 1956, pages 5254.
The pore size of the zeolitic molecular sieves may be varied by employing different metal cations. For example, sodium zeolite A has a pore size of about 4 angstrom units whereas when calcium cations have been exchanged for at least about 40 percent of the sodium cations calcium zeolite A has a pore size of about angstrom units.
Zeolite A is a crystalline zeolitic molecular sieve which may be represented by the formula:
wherein M represents a metal, n is the valence of M and y may have any value up to about 6. The as-synthesized Zeolite A contains primarily sodium ions and is designated sodium zeolite A, described in more detail in U.S. Patent No. 2,882,243, issued April 14, 1959.
Zeolite X is a synthetic crystalline zeolitic molecular sieve which may be represented by the formula:
wherein M represents a metal, particularly alkali and alkaline earth metals, n is the valence of M and y may have any value up to about 8, depending on the identity of M and the degree of hydration of the crystalline Zeolite. Sodium zeolite X has an apparent pore size of about angstrom units. vZeolite X, its X-ray diifraction pattern, its properties and methods for its preparation are described in detail in U.S. Patent No..2,882,244, issued April 14, 1959.
Zeolite Y is described and claimed in U.S. Patent application Serial No. 109,487, filed May 12, 1961, now Patent No. 3,130,007, in the name of D. W. Breck and issued as U.S. Patent N0. 3,130,007 on April 21, 1964.
Agglomerates comprising both zeolitic molecular sieves and finely divided metal particles can also be employed as the gas adsorbent in the containers of this invention. More specifically, such agglomerates comprise zeolitic molecular sieve crystals of less than 10 microns individual size and metal bodies having at least one dimension less than 50 microns, the ratio of the metal body size to the zeolitic molecular sieve crystal size being at least 5 to 1. The metal bodies are uniformly dispersed throughout the agglomerate in quantity sufiicient to constitute between about -5 and 30 percent by weight of the agglomerate and are sintered to the outer surface of the molecular sieve crystals. The metal should have a melting point over 300'C."and is employed primarily as a structural component in the multi-crystalline agglomerate but probably also enters into the formation of a chemical bond with the molecular sieve crystals by virtue of the sintering. Among the metals suitable for use in the multicrystalline agglomerate are those of groups Ib, IIb, IIIa, Va, Vb, VIb, VIIv and VII of the Periodic Table (Handbook of Chemistry and Physics, thirty-eighth edition, page 394, Chemical Rubber Publishing Co., 1956). Silicon, germanium, lead and tellurium are also suitable. Exemplary metals-include, but are not limited to, copper, silver and gold of group Ib, magnesium of group Ila, zinc of group IIb, boron and aluminum of group IIIa, yttrium of group IIIb, antimony of group Va, Vanadium of group Vb, chromimum of group VIb, manganese of group VHb and iron, nickel, platinum and palladium of group VIII. Mixtures and alloys of these metals may also be employed. Such agglomerates are disclosed and claimed in U.S. Patent application Serial No. 300,163, filed August 6, 1963.'
The amount of gas adsorbent employed in the insulated containers of this invention will depend on such factors as the particular cryogenic liquid and adsorbent used, the amount of gas to be adsorbed, the size of the vacuum 4 space, the length of time that the vacuum is to be maintained and the like.
The gas adsorbents employed in the insulated containers of this invention are in thermal contact with a cryogenic fluid when the container is in use. Suitable cryogenic fluids include inert liquids having boiling points at atmospheric pressure below -320 F. Such liquids include liquid nitrogen, liquid oxygen and the like. As used herein, the terms liquefied gas and liquefied refrigerant gas are used as synonyms for the term cryogenic liquid. Cold gaseous nitrogen is also useful.
Any suitable insulating material can be used to insulate the cryogenic liquidcontainer and the storage compartment in the insulated containers of this invention. Thus, the cryogenic liquid container can be insulated with composite insulating materials such as those composed of alternate layers of thin metallic sheets (e.g. aluminum foil) and glass fiber sheets (e.g. in the form of paper or;
webbing). Suitable composite insulating materials are disclosed in U.S. Patents 3,007,596, 3,018,016, 3,007,576, 3,009,600 and 3,009,602. The storage compartment can be insulated with the latter-mentioned composite insulating materials or with polyurethane foam. I
Referring now more specifically to the drawings, FIG- URE 1 shows an insulated container of the presentinvention composed of cryogenic liquid container 2 and storage compartment 3. The walls 4 and 5 of cryogenic liquid container 2 are spaced apart so as to define an intervening evacuable space 6. Similarly, the outer shell 7 and inner shell 8 of the storage compartment 3 are spaced apart so as to define intervening evacuable space 9. Evacuable spaces 6 and 9 are, in a preferred embodiment of this invention, in gaseous communication through double-walled insulated conduit 10. However, it is not essential that conduit 10 be a double-walled, insulated connecting means. Cryogenic liquid container 2 contains a cryogenic liquid 11 (e.g. liquid nitrogen) which is in thermal contact with adsorbent 12 that is retained in the perforated metal blister 13 welded or otherwise attached to wall 5. The perforations in metal blister 13. provide gaseous communication among the adsorbent 12, evacuable space 6 and (through conduit 10) evacuable space 9. Cryogenic liquid container 2 is provided with an accessmeans (not shown) for introducing the cryogenic liquid therein. Similarly, the storage compartment 3 is provided withan access means (not shown) for introducing materials to be stored therein and for removing such materials. Walls 5 and 6 are composed of aluminum or other suitable material and outer shell 7 and inner shell 8 are composed of stainless steel or other suitable materiaL. Insulating materials 12 are provided in the evacuable spaces around inner walls 5, the inner wall of conduit 10 and inner shell 8.
FIGURE 2 depicts an insulated container of this invention having an outer shell 50 within which are located two separate compartments, liquefied gas storage compartment 51 and perishable food storage compartment 52. Outer shell 50 and compartments 51 and 52 can be composed of any suitable material such as stainless steel or aluminum.
The outer surfaces of liquefied gas storage compartment 51 and perishable food storage compartment 52 together with the inner surface of outer shell 50 define an intervening evacuable space 53. Evacuable space 53 also extends between the adjacent walls of liquefied gas storage compartment 51 and perishable food storage compartment 52. Accordingly, both compartmentfil and compartment 52 are surrounded by common evacuable space 53. A plurality of solid cylindrical load-supporting pegs'54 or other load-supporting means are disposed in evacuable space 53 between the liquefied gas storage compartment 51 and the adjacent portion of the outer shell 50 so as to support the atmospheric load on the outer shell. Suitable loadsupport means are described and claimed in U.S. Patent Application Serial No. 340,311, filed January 27, 1964, in the names of W. L. Berner, C. P. Mulcahey and R. P. Skinner, entitled Load Support Means for Thermally In;
sulated Container. Those pegs that are disposed between the, bottom surfaces of the compartments 51 and 52 and the outer shell 50 so as to also support the weight of compartments 51 and 52. Additionally, pegs 54 are disposed between liquefied gas storage compartment 51 and perishable food storage compartment 52 in order to maintain these compartments at a distance from each other equal to the length of the pegs so as to stabilize the compartments against relative movement and prevent thermal contact between the walls of the compartments. Compression-sensitive insulating material 55 (e.g. insulation such as is described in the above-mentioned United States patents) is disposed in the evacuable space 53 around compartments 51 and 52 so as to minimize the heat leak from outside the outer shell 50 into the compartments 51 and 52 and to minimize heat leak from perishable food storage compartment 52 to liquefied gas storage compartment 51. Inasmuch as the temperature difference between a liquefied gas storage compartment 51 and the surfaces surrounding it is much greater than the temperature difference between perishable food storage compartment 52 and the surfaces surrounding it, the thickness of the insulating material 55 around liquefied gas storage compartment 51 may be as shown in FIGURE 2, greater than the thick-.
ness of insulating material 55 around perishable food storage compartment 52. Insulating material 55 is provided with holes through which pass pegs 54. A liquefied refrigerant gas 5511 (such as liquid nitrogen) is provided in liquefied gas storage compartment 51 and this liquefied gas 55a is in thermal communication with a mass of a zeolitic molecular sieve gas adsorbent 56 which is retained in a perforated metal blister 57 depending from the bottom of liquefied gas storage compartment 51. The liquefied gas 55 cools the molecular sieve 56 thereby improving the gas adsorbing properties of the sieve. The perforations in the blister 57 provides gaseous communication between the zeolitic molecular sieve gas adsorbent 56 and evacuable space 53 and serves to maintain a vacuum in the evacuable space after the evacuable space is evacuated; Strips of gas-impervious organic polymer 58 having low thermal conductivity join the top, bottom and side walls of perishable food storage compartment 52 to outer wall 50. These strips of organic polymer 58 serve to prevent the passage of gas into evacuable space 53 and serve to prevent heat leak into perishable food storage compartment 52 while at the same time defining an access conduit for introducingfood into perishable food storage compartment 52. Insulated storage compartment door 59 provides access'to perishable food storage compartment 52. Door 59 can be insulated with polyurethane foam or other suitable insulating material. Alternately, the desired degree of insulating can be achieved by using a vacuum panel door. The floor of perishable food storage compartment 52 is provided with cover plate 60 rotatable about hinge 61 which can be positioned over the strip of organic polymer 58 connecting the floor of compartment 52 to outer shell 50. Cover plate 60 prevents damage to the strip of .organic polymer 58 when perishable food is being introduced into perishable food storage compartment 52. In order to minimize heat leak into compartment 52 through cover plate 60, cover plate 60 is charged so thatit can be rotated into the position shown in FIG- URE 2 when not needed to protect lower strip of organic polymer 58. Low heat conducting filling tube 63 is provided for introducing liquefied gas 55a into liquefied gas storage compartment 51 and transfer conduit 64 is provided for transporting liquefied gas 55a from liquefied gas storage compartment 51 to perishable food storage compartment 62 in order to provide refrigeration for perishable food stored in perishable food storage compartment 52. Perforations are provided in the portion of the transfer conduit 64 located within perishable food storage compartment 52 to allow the liquefied gas 55 to be sprayed from the transfer conduit 64 as a fine mist on the perishable food within perishable food storage compartment 52.
Suitable means are provided for regulating the fiow of liquefied gas 55a into perishable food storage, compartment 52 so as to maintain the perishable food at a predetermined desired temperature. The temperature in compartment 52 will be dependent on thetype material being stored (e.g. fruit, meat, vegetables etc.) and will usually be between 40 F. and +60 F. Such flow-regulating means include the feature of discontinuing the transfer of the liquefied gas into perishable food storage compartment 52 when insulated storage compartment door 59 is opened. This latter feature prevents a waste of the liquefied gas when the insulated storage compartment door 59 is opened to introduce perishable food into perishable food storage compartment 52 or to withdraw the food.
The pressure required to transfer the liquefied gas 55a from liquefied gas storage compartment 51 through transfer conduit 54 in which perishable food storage compartment 52 can be created in any convenient manner. Thus, the pressure can be created by a heating coil in the bottom of liquefied storage compartment 51 which creates the desired pressure by vaporizing a portion of the liquelied gas 55a in response to a temperature sensing element in perishable food storage compartment 52. Preferably, the pressure is created initially by charging the liquefied gas to the liquefied gas storage compartment 51 along with vapor of the gas at a pressure sufficient to insure. the transfer of the gas during the desired period of .operation. Preferably, a pressure from 5 p.s.i.g. to 25 p.s.i.g. is maintained in compartment 51.
Liquefied gas storage compartment 51 is preferably provided with internal bracing means or supports to assist in carrying loads imposed on compartment 51.
It is desirable to provide for the expansion and contraction of the outer shell 50 and-the perishable food storage compartment 52 of the insulated container of FIGURE 2. The expansion and contraction of the. outer shell 50 is readily provided for by employing corrugated walls as illustrated by corrugated wall 50a in FIGURE 4. The expansion and contraction of perishable food storage compartment 52 can be provided for by constructing wall 65 of relativelythin and resilient material so that it will tend to buckle under stress (e.g. a 7.5 ft. x 7.5 ft. wall can be made 0.100 inch thick for this purpose Alternately, the expansion and contraction of perishable food storage compartment 52 can be provided for by employing an elastic material also possessing low thermal'conductivity and gasimpervious properties as organic polymer strip 58. In the latter case, wall65 ca nbe made thicker and, therefore, more rigid (e.g. a 7.5 ft. x 7.5 ft. wall can be made 0.50 inch thick for this purpose). Organic polymer strips suitable for this use include those composed of butyl rubber.
The manner in which the strips of organic polymer 58 can be attached to the walls of perishable food storage compartment 52 and outer shell 50 is illustrated by FIG- URE 3. In FIGURE 3, the strip of organic polymer 58 is provided with enlarged end portions 58a which are adapted to fit into bracket 52a attached to the floor of inner compartment 52 and into bracket 50a attached to outer shell 50. Enlarged end portions 58a of organic polymer strip 58 are maintained in brackets 52a and 50a b-y plates 52b and 50b held in place by means of screws 52c and 500.
FIGURE 4 illustrates a conduit arrangement suitable for use in transferring a cryogenic liquid from storage compartment 51 of FIGURE 2 to storage compartment 52 of FIGURE 2 in order to refrigerate the contents of compartment 52 of FIGURE 2. Compartment 51 is filled with 'a cryogenic liquid through conduit 63 and then the interior of compartment 51 is pressurized by conventional means to a pressure of about 5 p.s.i.g. to 25 p.s.i.g. Conduit 64 is provided with a solenoid valve 64a which is connected to a suitable temperature controller (not shown). Conduit 66 is provided With a relief valve and safety valve (not shown). When the temperature in compartment 52 arises above a predetermined point, the controller energizes a solenoid 64a to open it. The cryogenic liquid then flows from compartment 51 into compartment 52 through conduit 64 because of the pressure differential (compartment 52 is at about atmospheric pressure). The cryogenic liquid is sprayed into compartment 52 through perforations in conduit 64 until the temperature in compartment 52 decreases to the predetermined point. At the latter point, solenoid valve 64a closes, terminating the flow of the cryogenic liquid.
The following description illustrates another form of the insulated containers of this invention. The container consisted of (1) a standard commercially available double-walled dewar used for storing liquid nitrogen and (2) a storage compartment. The storage compartment was similar to-the storage compartment 3 of FIGURE 1. The storage compartment had a storage capacity of 39,300 cubic inches and the evacuable space in the storage compartment was one inch wide. The evacuable space in the storage compartment was evacuated to about one micron of mercury pressure employing conventional pumping means. compartment was maintained at about -10" F. by purging the interior of the compartment with liquid nitrogen. Ten liters of liquid nitrogen were maintained in the dewar. Five pounds of zeolite A were placed in an air-tight aluminum can which was air-tightly fitted with a plastic hose. The can was inserted in the dewar so that it was immersed in the liquid nitrogen and the hose extended out of the top of the dewar through the necktube of the dewar. The hose was air-tightly attached to an opening in the outer shell ofthe storage compartment so as to provide gaseous communication between the liquid nitrogen-cooled zeolite A and the evacuable space of the storage compartment. A vacuum of about one micron of mercury pressure was maintained in the evacuable space of the storage compartment for one year in this manner. During this period, the liquid nitrogenin the dewar was replenished at a rate of about 10 liters of liquid-nitrogen per day. The above-described. container is illustrative of a container of this invention WhBI'ClIl-thfi adsorbent used to maintain a vacuum in the evacuable space in the storage compartment is not also used to maintain a vacuum in the evacuable space in the cryogenic liquid container and wherein the evacuable space of the container is not in gaseous communication with the evacuable space of the dewar. This container is depicted byFIG- URE 5 wherein storage compartment 1 has stainless steel or aluminum Walls 2 and 3 spaced apart to define intervening evacuable insulating space 4. Space 4 is in gaseous communication with a mass of adsorbent 5 (Zeolite A) through plastic conduit 6. Adsorbent 5 is retained in air-tight aluminum can 7 which is immersed in liquid nitrogen 8 that is in dewar 9. Compartment 1 is provided with low heat conducting plug 10 through which pass thermistor lead 11 and liquid nitrogen conduit 12 that communicates with a liquid nitrogen reservoir (not shown). When the temperature in storage space 14 rises above a predetermined temperature, thermistor 13 activates a valve (not shown) in conduit 12 permitting liquid nitrogen to pass through conduit 12 and purge storage space 14 till the temperature therein falls to another predetermined temperature at which point the valve is closed. Conduit 6 has pinch-off tube 18 for use in evacuating the conduit, can 7 and space 4. Stainless.
steel inner shell 15 and stainless steel outer shell 16 of dewar 9 define another intervening evacuable insulating space 17.
The storage compartments in the containers of this The temperature withinvthe storage 8 invention are useful for storing meat, fish, fowl, vegetables, fruits and the like.-
What is claimed is:
1. An insulated container for storing materials at a temperature from .40 F. to +60 F., said container comprising (a) a double-walled storage compartment having an outer shell and an inner shell, said inner shell defining a space for storing said materials and said outer and inner shells defining an intervening evacuable space therebetween; (b) a separate receptacle which is spaced from the storage compartment and which contains a gas adsorbent that has a greater gas-adsorption capacity at temperatures .below about 150 F. than at about ambient temperatures, that is cooled to a temperature below about 150 F. and that is sealed from the atmosphere; and (c) gas-communication means providing gaseous communication between the evacuable space and the gas adsorbent so that the gas adsorbent can maintain a vacuum in the evacuable space.
2. An insulated container comprising (1) a storage compartment for storing materials at a temperature from about 40 F. to about +60 F., said compartment having (a) an outer shell and an inner shell defining an intervening first evacuable space therebetween, said inner shell defining a storage space for storing said materials, a storage space within the inner shell, (b) thermal insulating material in the first evacuable space for insulating the storage space. and (c) access'means for introducing materials to be stored into said storage space and for withdrawing said material from the storage space and (2) a separate double-walled cryogenic liquid container which is spaced from the compartment and which has (a) outer and inner Walls defining an intervening second evacuable space therebetween that is in gaseous communication with'the first evacuable space, said inner walls defining a storage space for a' cryogenic liquid, (b) thermal insulating material in thesecond evacuable space for insulating the cryogenic liquid storage space, (c) access means for introducing a cryogenic liquid into the cryogenic liquid storage space and (d) a mass of a gas adsorbent whose gas adsorption capacity is greater at temperatures below about 150 F .than at about am bient temperatures disposed in the second evacuable space,
, said adsorbent being in thermal contact with a cryogenic liquid in the cryogenic liquid storage space and said adsorbent being in gaseous communication with both the first and second. evacuable spaces for maintaining a vacuum in each space after evacuation thereof.
3. The container of claim 2 having means for withdrawing a portion of the cryogenic liquid from cryogenic liquid storage space for cooling materials stored in the storage space of the storage compartment.
4. The container of claim 2Wherein the outer shell of the storage compartment is corrugated.
5. The container of claim 1 wherein theadsorbent is a crystalline zeolitic molecular sieve.
References Cited by the Examiner UNITED. STATES PATENTS ROBERT A. OLEARY, Primary Examiner.
LLOYD L. KING, Examiner.

Claims (1)

1. AN INSULATED CONTAINER FOR STORING MATERIALS AT A TEMPERATURE FROM -40*F. TO +60*F., SAID CONTAINER COMPRISING (A) A DOUBLE-WALLED STORAGE COMPARTMENT HAVING AN OUTER SHELL AND AN INNER SHELL, SAID INNER SHELL DEFINING A SPACE FOR STORING SAID MATERIALS AND SAID OUTER AND INNER SHELLS DEFINING AN INTERVENING EVACUABLE SPACE THEREBETWEEN; (B) A SEPARATE RECEPTACLE WHICH IS SPACED FROM THE STORAGE COMPARTMENT AND WHICH CONTAINS A GAS ADSORBENT THAT HAS A GREATER GAS-ADSORPTION CAPACITY AT TEMPERATURES BELOW ABOUT -150*F. THAN AT ABOUT
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US4856297A (en) * 1987-09-30 1989-08-15 Mitsubishi Denki Kabushiki Kaisha Transfer vessel device and method of transfer using the device

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