Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C13/00—Details of vessels or of the filling or discharging of vessels
  • F17C13/002—Details of vessels or of the filling or discharging of vessels for vessels under pressure
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
  • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
  • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
  • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/32—Hydrogen storage

Definitions

• the present i ⁇ venti ⁇ n- relates to a method for storing hydrogen in a hybrid form. More specifically, it relates to a method for storing hydrogen in two different forms within a si ⁇ gle tank.
• hybrid tanks which are specially adapte ⁇ J f ⁇ rcarryi ⁇ gOut the above ⁇ etb ⁇ d when the hydrogen is stored in liquid and solid forms-and when the hydrogen is stored in solid and gaseous forms, respectively.
• Methods for storing hydrogen can be classified in three main categories :
• category (C) is the one that makes use of metal hydride storage tanks.
• a tank of one (1) liter will contain the following amounts of hydrogen at the various-pressures indicated in Table II :
• a tank ⁇ ⁇ e (1 ) liter will contain 0.0708 kg of hydrogen si ⁇ ce the l o density of liquid hydrogen at -252.8°C (that is at the c ⁇ ventional boiling point of hydrogen) is equal to 0.0708 kg/I.
• orie may evaluate-therrraximum-percentage of hydrogen that may come from-arrothermethod of storage in the case of a tank of one liter containing a metal hydride powder (LaNisH ⁇ ). Assuming that the powder is not compacted and, therefore, occupies about half of the volume of the tank, that is about half a liter, c ⁇ rrsidering als ⁇ that the density of LaNisHs is equal to 6.59 kg/I and furtherassuming that the gaseous hydrogen within the tank (about half a liter) is at a pressure 10 bar, the am ⁇ u ⁇ t of hydrogen that is not solid within the ta ⁇ k of ⁇ ne literwill be as-reported in Table IV:
• the low temperature metal hydride allows cold starting of the-engine by providing the hydrogen at the start up.
• the heat that is generated by the same permits to inducethe desorption of hydrogen from the higlTtemperature-r ⁇ etal hydride (see column 3 of this U.S. patent No. 5,906,792 f ⁇ rm ⁇ re details).
• the method (C) for storing hydrogen in a solid form usually has a response time (loading and unloading) much-slowerthan the ⁇ ethod (A) forstoring hydrogen in a gaseous form and slowertha ⁇ the method (B) for storing hydrogen in a liquid form.
• the method for storing hydrogen in a solid for ⁇ rr hasihe- highest capacity of storage per volume unit (see again Table III heretrrabove).
• UPS uninterruptible powersupply
• a response time of about one hundred milliseconds is usually-required.
• a hydr ⁇ gerrstoring tank using metal hydride-rarnTot-satisfythis-rjarticularrequirement is usually-required.
• the very short accelerations (second) can be taken care by the batteries whereas thetraTTsitory periods-ofa l ⁇ ngerduration (a-few ⁇ r ⁇ utes) may require hydrogen stored in a gaseous-form.
• the average power which is of about 20 KW for a typical vehicle, may easily be accomodated by a metal hydride tank.
• the energy contained in the batteries of such a vehicle usually represents about 1 % of the ⁇ energy on board. Therefore, one-needs an amount of hydrogen higherthan 1% to take charge- of -the tra ⁇ sitory periods.
• An object of the present invention is to satisfy the above mentioned need by providing a new method for storing hydrogen which combines the adva ⁇ tages of at least two ofthe above-mentioned methods for o storing hydrogen, namely the-ineth ⁇ ds-forstori ⁇ g-hydrogen in a gaseous form, in a liquid f ⁇ r ⁇ rarrd in a solid form.
• the present invention basically-consists in coupli ⁇ ga ⁇ d using in a singletank hereinafter called « hybrid tankfor storing hydrogen » at least two of the methods foi sloriMg-hydrogerrmentio ⁇ ed herei ⁇ above, namely : 5 A) the-method-forstori ⁇ g- hydrogen in a gaseous form ;
• each- ⁇ f the above methods is used for o storing at least 5% by weight of the total amount-of hydrogen- within the tank.
• the invention as claimed is directed to a method for storing hydrogen-in-ar ⁇ -hybrid-fo ⁇ m, which omprises the step of coupling and using within a single tank at least two hydrogen storage rneans selected from the group consisting of : 5 a) means forstori ⁇ g-hydrogen in a gaseous form ; b) mea ⁇ s-forstoring-hydrogen i ⁇ a liquid form ; and c) means forstoring hydrogen in a solid form by absorption or adsorption, with the proviso that each of the storing means that are used, is o sized to store at least 5% by weight of the total amount of hydrogen stored within the tank.
• the means mentioned hereinab ⁇ ve for storing hydrogen in different forms are those comr ⁇ only used f ⁇ rcarryi ⁇ g out each of the above mentioned methods. They are very conventional and need not be further described in detail.
• The-only ⁇ equiremenf isthatthey beooupled within the same 5 tank in ⁇ rderto be-used-stmultaneously for-each storing at least 5% by weight of the hydrogen.
• ArrotherObjectOftrre-present invention is to provide a hybrid tank for storing hydrogen- in- both liquid and solid -forms, comprising two concentric containers, one of the containers herei ⁇ aftercalled “inner” container is located l o within the other one which ⁇ s hereinafter called “outer container", the containers being separated by an i ⁇ sulating-sleeve f ⁇ r-rrrairrtai ⁇ i ⁇ g the inrrer container at low temperature.
• the irtnerc ⁇ ntai ⁇ er is used forstoring hydrogen in a liquid form.
• a furtherobjectOf the present invention is to provide a hybrid tank for storing hydrogerrin-both-solid and gaseous-forms, comprising:
• Figure 1 is a diagram illustrating the equilibrium plateau of the hydride used in a hybrid gas-solid storage-tank disclosed in example 1
• Figure 2 is a schematic cross-sectional view of the hybrid liquid- solid storage tank disclosed in example 2 ;
• Figure 3 is a diagram illustratf ⁇ g-the equilibrium plateau of the hydride used in the hybrid gas-solid -storage-tank disclosed in example 3 ;
• Figure 4 is a schematic-cr ⁇ ss-secti ⁇ al view of the hybrid gas-solid storage tank disclosed in example 3.
• Figures 5 and 6 are diagrams givrng the equilibrium plateaux of several hydrides as : afurrrtron of thetemperature-a ⁇ d indicating which one could be used in the hybrid gas ⁇ solid-storage tank disclosed in examples 1 and 3.
• a hydrogerrstoragetank-having-a-volume of 1 liter has beerrfilled up with a powderof ⁇ a ⁇ oparticles of a hydride of LaNis having an average diameter of 5 nanometers.
• the powder ⁇ ccupied 50% by volume of the tank, that is 0.5 liter, si ⁇ ce it was ⁇ ot-coTrrpacted.
• the tank disclosed ⁇ n example 1 is illustrative ⁇ fa tankthat can be used in a "back up" system based on a fuel cell or a hydrogen source generator.
• the hydrogen in the gaseous phase will irritially supply the fuel cell orthe generator that will slowly warm up.
• the pressure within the tank will be reduced.
• the pressure reaches the equilibrium plateau of the hydride, that is about 2 bars for a AB 5 alloy at room temperature, there will be almost no more hydrogen in the gaseous phase. Then, the hydride will take over by providing hydrogen to the system thanks to he heat-generated by the fuel cell or the generator.
• a hybrid-tank 1 for storing hydrogen-having a total volume of one liter has been devised from two corrcerrtric-containers 3,5 (see Fig.2).
• the inner container 3 had a volume of 0.8 literwhereas the outer container 5 had a volume of 0.2 liter.
• Arri ⁇ sulating:sleeve 7 was-p ⁇ siti ⁇ ed betweerrthe inner and o the outercontainers 3,5 to keep the irr ⁇ er c ⁇ ntai ⁇ er 3 at low temperature.
• the total amount-of hydrogen-stored within trie-tank 1 was equal to 0.0658 kg (14% in the outertank and 86% in the innertank).
• hydrides are TiCr-i. ⁇ which has an equilibrium plateau at ruoin temperature much higher than 100 bars (see Fig.6).
• hydrides 5 with equilibrium-plateau attiigh pressures like TiMn 2-y , Hf 2 Cu, Zr 2 Pd, TiCu 3 or Vo.855 Cr 0 . ⁇ 5 which can be of ⁇ nterest f ⁇ rthis kind of application (see Figs. 5 and 6).
• the gaseous system of the storage tank will permit to accommodate such a o request with a very-short response time (t1 ) ofabout one second (forexample in the case of a carthataccelerates).
• t1 very-short response time
• the pressure-withirrthe tank drops and changes from a value (1 ) to a value (2) (see Fig. 3)
• the hydride will regenerate the gaseous syste ⁇ rwith a lowerresp ⁇ nse-time (t2) of a few minutes, until the next acceleration.
• FIG. 4 shows a hybrid tank 11 for storing hydrogen in both-solid-and-gaseous form.
• the tank 11 comprises a container 5 having a metallic liner ⁇ rir ⁇ nerwall 15 covered with a polymeric outer shell 13.
• This type of container is conventional and commonly used forstoring hydrogen in gaseous form at high pressure. It is preferably cylindrical in shape and provided with an axial opening 17.
• the liner 15 is usually made of aluminium whereas its outershell is made of a composite-material reinforced with carbon 0 fibers.
• thexontainer of the hybrid'tank 11 is intended to be used for storing hydr ⁇ gen ⁇ n gaseous forrrrat a pressure usually hignerthan 40 bar and simultaneously to receive ⁇ and-store ⁇ ametal hydride in ordertostore hydrogen in solid form as well.
• At least-one heat pipe 19 is mounted withi ⁇ the contai ⁇ erto allow the circulati ⁇ -of a tieat carrying fluidwithirrthe container 11.
• the tank 11 preferably comprises only one heat pipe 19 which is inserted into the co ⁇ tai ⁇ erthr ⁇ ugh-the-ope ⁇ i ⁇ g 17 and exterrds axially within the same.
• the tank 11 further comprrses a- heat exchanger located within the container to ensure thermal connection between the heat pipe 19 and the hydride.
• This heat exchanger preferablyoorrsistsOfat least ⁇ e metallic grid, or a porous metallic structure orfibers 21 which-extends transversally withirrthe container and is in direct contact withtheaxial treat " pipe 19, themetal li ⁇ erwall 15 of the container, and the hydride stored within the-same.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Inorganic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Filling Or Discharging Of Gas Storage Vessels (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Fuel Cell (AREA)

Applications Claiming Priority (3)

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• 2001
  • 2001-06-29 US US09/894,010 patent/US20030042008A1/en not_active Abandoned
• 2002
  • 2002-06-28 RU RU2004101771/15A patent/RU2004101771A/ru not_active Application Discontinuation
  • 2002-06-28 BR BR0210764-3A patent/BR0210764A/pt not_active IP Right Cessation
  • 2002-06-28 JP JP2003508644A patent/JP2004530628A/ja active Pending
  • 2002-06-28 KR KR10-2003-7017070A patent/KR20040012993A/ko not_active Application Discontinuation
  • 2002-06-28 CN CNA02813219XA patent/CN1522224A/zh active Pending
  • 2002-06-28 WO PCT/CA2002/000998 patent/WO2003002451A1/en not_active Application Discontinuation
  • 2002-06-28 MX MXPA03011759A patent/MXPA03011759A/es not_active Application Discontinuation
  • 2002-06-28 CA CA002452067A patent/CA2452067A1/en not_active Abandoned
  • 2002-06-28 EP EP02744993A patent/EP1404611A1/en not_active Withdrawn

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