US3813041A - Apparatus for storing a liquid for its distribution in the gaseous state - Google Patents

Apparatus for storing a liquid for its distribution in the gaseous state Download PDF

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Publication number
US3813041A
US3813041A US00288396A US28839672A US3813041A US 3813041 A US3813041 A US 3813041A US 00288396 A US00288396 A US 00288396A US 28839672 A US28839672 A US 28839672A US 3813041 A US3813041 A US 3813041A
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liquid
polymer
gas
stored
weight
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Expired - Lifetime
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US00288396A
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English (en)
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J Kleine
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ST Dupont SA
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ST Dupont SA
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Priority claimed from FR7132946A external-priority patent/FR2154816A5/fr
Application filed by ST Dupont SA filed Critical ST Dupont SA
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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
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23Q—IGNITION; EXTINGUISHING-DEVICES
    • F23Q2/00—Lighters containing fuel, e.g. for cigarettes
    • F23Q2/16—Lighters with gaseous fuel, e.g. the gas being stored in liquid phase

Definitions

  • ABSTRACT Foreign Application Priority Data Apparatus for storing liquified gas under pressure in a Sept. 13, 1971 France 71.32946 container from which the liquid is released as a gas June 6, 1972 France 72.20346 into an atmosphere or region at a lower pressure than the storage pressure.
  • This container additionally con- [52] US. Cl. 239/55 tains a solid polymer on which the liquid acts like a [51] Int. Cl. A241 25/00, A611 9/04 swelling agent so that the polymer becomes a gel [58] Field of Search 239/53-56; which releases the liquid stored therein as a gas.
  • FIGS APPARATUS FOR STORING A LIQUID FOR ITS DISTRIBUTION IN THE GASEOUS STATE The invention relates to apparatus for storing a liquifiable product in the liquid state, with a view to its distribution in the gaseous state.
  • the vapor pressure permitting, the gaseous distribution of the liquid can be sufficiently ensured by using merely the gaseous air located at the top of the storage enclosure.
  • the outlet be provided with either a pressure reducing device or with a device limiting the rate of flow, or with both.
  • the main drawbacks of this manner of storage and distribution is that the auxiliary members considerably increase its cost price.
  • the liquid storage enclosure is filled with a porous material such as cotton or polyurethene foam.
  • a porous material such as cotton or polyurethene foam.
  • An object of the present invention is to remedy these drawbacks by providing apparatus for storing a liquifiable product in the liquid state with a view of its distribution is the gaseous state and make it possible to eliminate the auxiliary cut-off members for the gases.
  • a device for storing a liquifiable product in the liquid state and for its distribution in the gaseous state into an atmosphere whose pressure is less than the storage pressure which device comprises a storage enclosure intended to receive the liquid to be stored, at least one part of which is occupied by a solid polymer with respect to which said liquid acts like a swelling solvent, said enclosure communicating with at least one distribution aperture.
  • Certain liquid products act, with respect to certain polymers, like swelling solvents, i.e., like solvents which cause the elastomer in question to swell, by acting on the intermolecular connections (or bridges) between-chains without causing the complete dissolution of the polymer, the latter being, after the action of said swelling solvent, in the form of a gel, but again finding the integrality of its initial products after removal of said liquid product.
  • swelling solvents i.e., like solvents which cause the elastomer in question to swell
  • the polymers which can be used must have a solubility parameter which differs at the maximum by i- 2.0 and preferably by i 0.5 from that of the stored product in question.
  • the temperature for transformation to the viscous state of these polymers must be at the most equal to 50C.
  • polysiloxanes which have a solubility parameter of 7.3 can be used for storing liquified butane, the solubility parameter of which is 6.75.
  • the device according to the invention results in findings by the applicant during numerous tests which have proved that by placing, in the storage enclosure of a liquified product and in conjunction therewith, a polymer, with respect to which it acts like a swelling solvent, the
  • gel obtained has the surprising property of releasing the stored product only in its gaseous state at the moment when it is distributed into an atmosphere whose pressure is less than that of the storage enclosure.
  • a first advantage of the device according to the invention lies in the fact that the presence of a gel in the storage enclosure permits the use of the latter both as a stationary reservoir as well as a movable reservoir.
  • a second advantage lies in the fact that the discharge of the liquid in the entirely gaseous state makes it possible to remove the devices intended to transform the fuel from its liquid to its gaseous state.
  • a third advantage relates to the amount of liquid which can be stored in a given reservoir. lndeed, tests have been carried out by the applicant to determine the liquified amount of gaseous hydrocarbons which could be stored, on the one hand in an empty reservoir'and on the other hand in the same reservoir containing a porous material and thirdly in the same reservoir containing a polymer according to the invention. These tests have proved that the device according to the invention makes it possible to store greater quantities of liquified products, all things being equal.
  • the storage device according to the invention has numerous applications.
  • a particularly important application relates to stored gas combustion devices such as lighters for smokers, luminous gas lamps or gas heating apparatuses wherein liquified hydrocarbons, particularly aliphatic hydrocarbons such as butane, propane, pentrane or the like are used individually or in combination as a fuel, these hydrocarbons having the property of causing certain polymers to swell.
  • liquified hydrocarbons particularly aliphatic hydrocarbons such as butane, propane, pentrane or the like are used individually or in combination as a fuel, these hydrocarbons having the property of causing certain polymers to swell.
  • Another application relates to the transportation, over great distances, by vehicles provided with tanks or by ships of the type designed to carry liquified natural gas, of these liquified hydrocarbons the importance of which is becoming increasingly greater.
  • Another application relating to other types of liquified compounds distributed in the gaseous state into the ambient atmosphere relates for example, to deodorizing products or insecticides.
  • polysiloxanes (so-called polymers of silicons);
  • polyisoprenes natural (latex) or synthetic
  • polyolefins with transverse connections obtained by action of radiation or peroxides
  • block polymers at least one constituent part of which has a maximum affinity forthe solvent; polymethylpentenes;
  • the polymer used may be introduced into the storage enclosure in the solid state. It may also possibly be polymerized in the storage enclosure before it is filled with the compound in the liquid state intended to be distributed in the gaseous state. This latter modification for carrying out the invention may be found to be advantageous for certain applications (formation of liquified fuel gas cartridges which cannot be refilled for gas lighters, for example).
  • EXAMPLE I This example is intended to illustrate the fact that only polymers with weak transverse connections (weakly linked polymers) may be used for carrying out the invention.
  • EXAMPLE II This example illustrates different ways of carrying out the invention with the polymers each belonging to the above-mentioned classes as capable of being used in the case where the stored liquid in a hydrocarbon in the liquid state.
  • the following polymers have bee used:
  • 3a cross-linking by peroxide: polyethylene manufactured by Sekisui, Japan (commercial name Softlon BN-30).
  • 3b cross-linking under radiations: polyethylene manufactured by Furakawa Electric, Japan (commercial name: Minicel L-200);
  • Polyalkylstyrenes with cross-links poly-tertbutylstyrene, manufactured by DOW (commercial name: lmbiber Bead XE0100.3 l) with 0.025% transverse connections;
  • Block polymers olefin styrene manufactured by Shell, of the type of the products Kraton of this Company (commercial name GXT 0650). 6. Polymethylpentene: product sold by l.C.l. under the commercial name TPV RT 20. 7. Butyl rubber with weak linking: product sold by Polysar Polymer Corp. Ltd., Canada,
  • the operation which consists of heating the polymer used, three times with excess butane, until complete saturation, before it is used for storage, whether the liquid to be stored is butane or not, is termed extraction.
  • the treated polymer is termed the extracted polymer.
  • EXAMPLE lll This example relates to the case where the stored product is butane in the liquid state.
  • Rhodorsil 10558 Catalyst 10052 (14% by weight of the preceding) Rhodorsil Oil Y-V-20 indicated above by weight of Rhodorsil 10558).
  • Extract Weight g Apparent Volume: 97 cm Shape: cylinders having a diameter of 6mm and a length of 20 mm. Swelling liquid presented (butane) Weight: 300g Volume: 520 cm Characteristics of the polymer after absorption:
  • Extract Weight 100g Apparent Volume: 98 cm Shape: cylinder: diameter 6mm length 20mm Swelling liquid presented (pentane):
  • Weight 127g Volume: 203 cm 2. NOT EXTRACTED RTV FOAM Characteristics of the solid polymer before absorption: Weight: 100g Apparent Volume: 286 cm Shape: diabolos: large diameter 12mm small diameter 8mm length 20 mm with skin on each base. Swelling liquid presented (pentane).
  • Example V In order to determine if the amount of liquid which can be stored in a given macromolecular product is an inverse function not only of the dimensions of the storage container which may hinder swelling but also of stresses peculiar to its structure, two series of tests were also carried out which were made from solid products of identical material, but whose outer characteristics were different.
  • the foam with closed cells which constituted the solid products had each of its two bases constituted by a skin, i.e., from a plane surface, evidently less flexible than an alveolar surface, while in the second case Example Vl) only one of its bases was constituted by a skin, the other being constituted by an alveolar surface.
  • Apparent Volume 143 cm Shape: diabolos: large diameter 12mm small diameter 8mm height 20mm with skin on each base.
  • outer diameter 10mm inner diameter: 3mm thickness: 3mm Swelling liquid presented:
  • outer diameter 10mm inner diameter: 3mm thickness: 3mm Swelling liquid presented:
  • one of the most important and most advantageous applications of the process according to the invention relates to liquified fuel gases, in particular liquified, gaseous aliphatic hydrocarbons.
  • the storage device according to the invention has surprising advantages which were not evident to the man skilled in the art. These advantages will now be revealed.
  • the process according to the invention retains the advantages of processes for storing liquids with spongy supports, namely stabilization of the stored liquid and possiblity of using the storage container in any position whatsoever.
  • the apparatus according to the invention also has the advantage of improving the checking of the distribution, which in the case of easily combustible liquids, reduces the risks of explosion.
  • a second advantage made by the invention lies in the fact that the pressure of the gaseous air above the liquid stored in the storage container is less than that of the gaseous air in a container with liquified gas alone or in a container with gas and cotton or gas and alveolar foam with open cells.
  • the device according to the invention is found to be very superior to the conventional devices. This is proved by the following numbers which relate to the value, in bars, at a temperature of 25C, of the relative pressure of the gaseous air in a storage container con- 'taining a mixture of liquified hydrocarbons comprising (in by weight) 79.0% n-butane, 19.0% isobutane, 1.0% propane, 0.5% ethane and 0.5% pentane and butene:
  • Another advantage peculiar to this application is due to the fact that the device limiting the rate of flow may be removed, which is usually mounted on the supply line of the combustion device so as to keep only a regulating device at the users disposal.
  • FIG. 1 is a vertical section showing a first embodiment according to the invention
  • FIGS. 2, 3, and 6 are respectively views similar to FIG. 1 of four variations.
  • FIG. 4 and 7 are detail views illustrating other variations.
  • a hollow body 1 which cannot be refilled, contains a plurality of pieces 2 of a solid elastomer with respect to which the liquified fuel gas to be stored acts like a swelling solvent.
  • An aperture 3 formed at the top of the body 1 makes it possible to supply a burner with fuel gas without the interposition of a cut-off system.
  • the hollow body 4 is divided into two separate chambers 5 and 6 respectively by a grid, latticework or more usually a support 7 provided with apertures, secured in the body 1 and through which communication between the two chambers is effected.
  • a filling valve 8 provided in the base of the body 4 makes it possible to fill the chamber 5 with a liquified fuel gas, the liquid passing through the support 7 so as to impregnate a solid polymeric material contained in the chamber 6.
  • a burner (not shown) is supplied with fuel gas by way of the aperture 9 formed at the top of the body 4.
  • the embodiment according to FIG. 3 is derived directly from that of FIG. 2.
  • the hollow body 10 is-divided into two chambers 11 and 12 by a grid 13 or the like, however, the elastomer intended to be impregnated with liquified gas is constituted by a simple membrane 14 held against the grid 13 by a ring 15 force fitted into an inner groove of the body 1, the grid itself bearing against a shoulder of the inner walls of the container.
  • the chamber 11 which may be filled with liquified gas by a valve 16 has a much greater volume than in the case of the embodiment shown in FIG. 2, whereas the chamber 12 has a minimum volume in communication with the distribution aperture 17.
  • the membrane 14 ensures a continuous distribution of gas, releasing the latter through the face located opposite the aperture 17, whereas through the opposite face, it absorbs an amount of liquified gas which may or may not be equal to the amount of gas released.
  • FIG. 4 is a detail view of a modification of the device of FIG. 3, wherein the elastomeric membrane 14a surrounds the grid 13a.
  • the hollow body 18 comprises a main chamber 1.9 which can be filled with liquified gas by the valve 20.
  • the liquified gas impregnates a polymeric material which fills a tubular member 21 made of gridding and connected to the distribution aperture 22.
  • tubular element 21 made of gridding may be replaced by a tube 23 of any material containing no polymer, but having perforations closed by a suitable macromolecular material 24.
  • the storage enclosure 25 comprises no more than one single chamber 26, whose inner walls, with the exception of the part adjacent the filling aperture 27, are covered with a layer 28 of a solid polymer so as to form a kind of pocket which receives the liquid by way of the aperture 27, the gas being released directly through the membrane 28 on a level with the distribution aperture 29.
  • a storage chamber of the type which has just been described is intended to supply a gas combustion device, it may be made integral with the device and may be filled with liquified gas either directly by way of the filling aperture or by means of a refill constituted by an element of a macromolecular product having a suitable shape and volume, and previously saturated with liquified gas.
  • Detachable enclosures may also be used constituting disposable refills.
  • a device for storing a liquefiable product in the liquid state with a view to its distribution in the gaseous state comprising a storage enclosure, at least one part of which is occupied by a solid polymer with respect to which the liquid to be stored acts like a swelling solvent, this part of the enclosure communicating with one or more distribution apertures, said polymer being absorbative of the liquefied gas and having a limited solubility parameter with respect to said liquefied gas so as to undergo swelling and form a gel which releases the liquid only in gaseous state.
  • a device in which said polymer comprises a membrane covering at least one part of the inner walls of the storage enclosure.
  • a device comprising a tubular member connected to said one or more distribution apertures, said tubular member having at least one aperture closed by said polymer.
  • a gas lighter in which ignition means and combustion means for the gas is supplied by a device according to claim 1 without the interposition of a member ensuring the cutting off of the gas.
  • the liquid to be stored comprises a major part of at least one liquefied saturated hydrocarbon and the solid polymer is selected from the group consisting of polysiloxanes; natural polyisoprenes; synethtic polyisoprenes; polyolefins with cross-links, obtained by action of radiation orperoxides; polyalkylstyrenes, with cross-links; block polymers having at least one constituent part with a maximum affinity for the solvent; polymethylpentenes; and butyl rubbers with weak bridging between chains.
  • the solid polymer is selected from the group consisting of polysiloxanes; natural polyisoprenes; synethtic polyisoprenes; polyolefins with cross-links, obtained by action of radiation orperoxides; polyalkylstyrenes, with cross-links; block polymers having at least one constituent part with a maximum affinity for the solvent; polymethylpentenes; and butyl rubbers with weak bridging between chains.
  • bustion means for the gaseous product

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US00288396A 1971-09-13 1972-09-12 Apparatus for storing a liquid for its distribution in the gaseous state Expired - Lifetime US3813041A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7132946A FR2154816A5 (en) 1971-09-13 1971-09-13 Liquefied gas storage - for subsequent distribution in gaseous form from eg cartridges
FR7220346A FR2188095B2 (cs) 1971-09-13 1972-06-06

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US3813041A true US3813041A (en) 1974-05-28

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US (1) US3813041A (cs)
JP (1) JPS5442086B2 (cs)
AR (1) AR204502A1 (cs)
AT (1) AT359052B (cs)
BE (1) BE788513A (cs)
CA (1) CA980742A (cs)
CH (1) CH551592A (cs)
DE (1) DE2244390C3 (cs)
ES (1) ES406616A1 (cs)
FR (1) FR2188095B2 (cs)
GB (1) GB1384578A (cs)
IT (1) IT972443B (cs)
NL (1) NL153991B (cs)
NO (1) NO133462C (cs)
OA (1) OA04169A (cs)
SE (1) SE374596B (cs)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285468A (en) * 1977-06-03 1981-08-25 Sy Hyman Article for the dispensing of volatiles
AU623501B2 (en) * 1989-03-02 1992-05-14 Rocep Lusol Holdings Limited Gas storage and dispensing system
US5301851A (en) * 1991-03-02 1994-04-12 Rocep-Lusol Holdings Limited Gas storage and dispensing system
EP1273530A4 (de) * 2000-02-29 2003-05-21 World Lab Complex Technology A Gaspatrone und verfahren zum füllen
EP1458330A1 (en) * 2001-12-26 2004-09-22 The Gillette Company Packaging means for personal care products
CN106855246A (zh) * 2015-12-08 2017-06-16 深圳市华晋源环境投资控股有限公司 一种戊烷转化成气体供给燃烧系统
EP3916302A1 (en) * 2020-05-29 2021-12-01 Société BIC Lighter comprising container with liquefied gas and a compressible member to prevent overfilling of the container

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4862897U (cs) * 1971-11-15 1973-08-09
JPS5343278B2 (cs) * 1974-06-24 1978-11-17
JPS5589401U (cs) * 1979-12-06 1980-06-20
EP0167783B1 (de) * 1984-06-28 1988-10-19 ZELLER PLASTIK Koehn, Gräbner & Co. Verschliessvorrichtung für die Entnahmeöffnung eines Behälters und zugehöriger Behälter
JP4078522B2 (ja) 2002-01-31 2008-04-23 Ｊｆｅスチール株式会社 ハイブリッド型水素貯蔵容器および容器への水素貯蔵方法
DE112006002110B4 (de) * 2005-08-08 2010-08-26 Toyota Jidosha Kabushiki Kaisha, Toyota-shi Wasserstoffspeichervorrichtung

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129888A (en) * 1959-05-19 1964-04-21 Interstate Sanitation Corp Air odor control device
US3729289A (en) * 1970-01-06 1973-04-24 Dupont S T Cigarette lighter

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129888A (en) * 1959-05-19 1964-04-21 Interstate Sanitation Corp Air odor control device
US3729289A (en) * 1970-01-06 1973-04-24 Dupont S T Cigarette lighter

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285468A (en) * 1977-06-03 1981-08-25 Sy Hyman Article for the dispensing of volatiles
EP0019010B1 (en) * 1979-05-10 1984-09-26 Sy Hyman Article for the dispersion of a volatile substance and an article of manufacture comprising a plurality of said articles
AU623501B2 (en) * 1989-03-02 1992-05-14 Rocep Lusol Holdings Limited Gas storage and dispensing system
US5301851A (en) * 1991-03-02 1994-04-12 Rocep-Lusol Holdings Limited Gas storage and dispensing system
EP1273530A4 (de) * 2000-02-29 2003-05-21 World Lab Complex Technology A Gaspatrone und verfahren zum füllen
EP1458330A1 (en) * 2001-12-26 2004-09-22 The Gillette Company Packaging means for personal care products
CN106855246A (zh) * 2015-12-08 2017-06-16 深圳市华晋源环境投资控股有限公司 一种戊烷转化成气体供给燃烧系统
EP3916302A1 (en) * 2020-05-29 2021-12-01 Société BIC Lighter comprising container with liquefied gas and a compressible member to prevent overfilling of the container
WO2021239725A1 (en) * 2020-05-29 2021-12-02 Societe Bic Lighter comprising a container suitable for liquefied gas and a compressible member to prevent overfilling of the container
US12474050B2 (en) 2020-05-29 2025-11-18 SOCIéTé BIC Lighter comprising a container suitable for liquefied gas and a compressible member to prevent overfilling of the container

Also Published As

Publication number Publication date
OA04169A (fr) 1979-12-15
NL153991B (nl) 1977-07-15
DE2244390A1 (de) 1973-05-03
SE374596B (cs) 1975-03-10
CA980742A (en) 1975-12-30
NO133462B (cs) 1976-01-26
JPS5442086B2 (cs) 1979-12-12
AT359052B (de) 1980-10-27
DE2244390C3 (de) 1980-04-03
JPS4837717A (cs) 1973-06-04
NO133462C (cs) 1976-05-05
DE2244390B2 (de) 1979-08-02
AU4654472A (en) 1974-03-21
BE788513A (fr) 1973-01-02
ATA784372A (de) 1980-03-15
ES406616A1 (es) 1976-01-16
IT972443B (it) 1974-05-20
CH551592A (fr) 1974-07-15
AR204502A1 (es) 1976-02-12
FR2188095A2 (cs) 1974-01-18
FR2188095B2 (cs) 1975-08-29
NL7212373A (cs) 1973-03-15
GB1384578A (en) 1975-02-19

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