EP1203194A1 - Systeme de stockage d'hydrogene dans un hydrure metallique, a auto-chauffage - Google Patents

Systeme de stockage d'hydrogene dans un hydrure metallique, a auto-chauffage

Info

Publication number
EP1203194A1
EP1203194A1 EP99928784A EP99928784A EP1203194A1 EP 1203194 A1 EP1203194 A1 EP 1203194A1 EP 99928784 A EP99928784 A EP 99928784A EP 99928784 A EP99928784 A EP 99928784A EP 1203194 A1 EP1203194 A1 EP 1203194A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
metal
hydride
storage
primary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99928784A
Other languages
German (de)
English (en)
Inventor
Ned T. Stetson
Krishna Sapru
Heidi Vankirk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Energy Conversion Devices Inc
Original Assignee
Energy Conversion Devices Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Energy Conversion Devices Inc filed Critical Energy Conversion Devices Inc
Priority claimed from PCT/US1999/013766 external-priority patent/WO2000079201A1/fr
Publication of EP1203194A1 publication Critical patent/EP1203194A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C3/00—Vessels not under pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • 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 invention deals with metal-hydride hydrogen storage system. More specifically the present invention deals with a self-heating metal-hydride hydrogen storage system.
  • Hydrogen may be used, for example, as fuel for internal-combustion engines in place of hydrocarbons. In this case it has the advantage of eliminating atmospheric pollution through the formation of oxides of carbon or of sulfur upon combustion of the hydrocarbons. Hydrogen may also be used to fuel hydrogen-air fuel cells for production of the electricity needed for electric motors.
  • Hydrogen may be stored under high pressure in steel cylinders, but this approach has the drawback of requiring hazardous and heavy containers which are difficult to handle (in addition to having a low storage capacity of about 1% by weight) .
  • Hydrogen may also be stored in cryogenic containers, but this entails the disadvantages associated with the use of cryogenic liquids; such as, for example, the high cost of the containers, which also require careful handling. There are also "boil off" losses of about 2-5% per day.
  • Another method of storing hydrogen is to store it in the form of a hydride, which then is decomposed at the proper time to furnish hydrogen.
  • the hydrides of iron-titanium, lanthanum-nickel, vanadium, and magnesium have been used in this manner, as described in French Pat. No. 1,529,371.
  • the MgH 2 -Mg system is the most appropriate of all known metal-hydride and metal systems that can be used as reversible hydrogen-storage systems because it has the highest percentage by weight (7.65% by weight) of theoretical capacity for hydrogen storage and hence the highest theoretical energy density (2332 h/kg; Reilly & Sandrock, Spektrum dermaschine, Apr. 1980, 53) per unit of storage material. Although this property and the relatively low price of magnesium make the MgH 2 -Mg seem the optimum hydrogen storage system for transportation, for hydrogen-powered vehicles that is, its unsatisfactory kinetics have prevented it from being used up to the present time. It is known for instance that pure magnesium can be hydrided only under drastic conditions, and then only very slowly and incompletely.
  • the dehydriding rate of the resulting hydride is also unacceptable for a hydrogen storage material (Genossar & Rudman, Z. f. Phys . Chem., Neue Folge 116, 215 [1979], and the literature cited therein) .
  • the hydrogen storage capacity of a magnesium reserve diminishes during the decomposition-reconstitution cycles. This phenomenon may be explained by a progressive poisoning of the surface, which during the reconstitution renders the magnesium atoms located in the interior of the reserve inaccessible to the hydrogen.
  • U.S. Pat. No. 4,111,689 has disclosed a storage alloy which comprises 31 to 46% by weight of titanium, 5 to 33% by weight of vanadium and 36 to 53% by weight of iron and/or manganese.
  • alloys of this type have a greater storage capacity for hydrogen than the alloy according to U.S. Pat. No. 4,160,014, hereby incorporated by reference, they have the disadvantage that temperatures of at least 250°C are necessary in order to completely expel the hydrogen. At temperatures of up to about 100°C, about 80% of the hydrogen content can be discharged in the best case.
  • a high discharge capacity, particularly at low temperatures is frequently necessary in industry because the heat required for liberating the hydrogen from the hydride stores is often available only at a low temperature level.
  • magnesium is preferred for the storage of hydrogen not only because of its lower material costs, but above all, because of its lower specific weight as a storage material.
  • Mg + H 2 - MgH 2 is, in general, more difficult to achieve with magnesium, inasmuch as the surface of the magnesium will rapidly oxidize in air so as to form stable MgO and/or Mg(OH) 2 surface layers. These layers inhibit the dissociation of hydrogen molecules, as well as the absorption of produced hydrogen atoms and their diffusion from the surface of the granulate particles into the magnesium storage mass.
  • the apparent gravimetric H 2 density of the system would be approximately 2/3 the actual H 2 density.
  • an alloy with 6 wt . % H 2 density would have an apparent H 2 density of about 4 wt . % .
  • the instant invention provides such a system.
  • An objective of the present invention is to provide a metal-hydride hydrogen storage system that can be used to store hydrogen in a high-temperature, high-capacity metal- hydride hydrogen storage material.
  • a self-heating metal- hydride hydrogen storage system comprising: a primary metal- hydride storage container housing a metal-hydride hydrogen storage material, the primary storage container having a hydrogen outlet port; a hydrogen combustor housed within the primary metal-hydride storage container and surrounded by the high-temperature storage material, the combustor having a hydrogen inlet port gaseously connected to the hydrogen outlet port of the primary storage container; and means for supplying hydrogen gaseously connected to the hydrogen inlet port of the combustor.
  • Figure 1 is a highly stylized view of the metal-hydride hydrogen storage system of the present invention.
  • the high-temperature metal-hydride hydrogen storage system of the present invention comprises a primary metal-hydride hydrogen storage container 5.
  • the metal-hydride hydrogen storage container 5 is preferably made from a thermally nonconductive material. Heat is transferred away from a metal hydride material during the hydrogen absorption process (exothermic) and transferred into the metal hydride material during the hydrogen desorption process (endothermic) .
  • a metal- hydride hydrogen storage material housed within the primary storage container 5 is a metal- hydride hydrogen storage material.
  • the metal- hydride hydrogen storage material housed within the primary storage container 5 is a high-temperature metal-hydride hydrogen storage material.
  • a high-temperature metal-hydride hydrogen storage material is a metal-hydride hydrogen storage material which will have a 1 atmosphere equilibrium plateau pressure at temperatures at or above 100°C.
  • the high-temperature storage material may be a magnesium-based hydride alloy (also known as an "Mg-based" hydride alloy) such as MgH 2 .
  • Mg-based hydride alloy also known as an "Mg-based" hydride alloy
  • Other examples of Mg-based hydrides that can be used as the high-temperature storage material are discussed in commonly assigned U.S. Patent Application No. 08/730,274, the disclosure of which is incorporated by reference herein.
  • the metal-hydride hydrogen storage material housed within the primary storage container may be physically bonded to a support means.
  • the support means can take the form of any structure than can hold the hydridable material.
  • Examples of support means include, but are not limited to mesh, grid, matte, foil, foam and plate. Each may exist as either a metal or a non-metal.
  • the support means may be formed from a variety of materials with the appropriate thermodynamic characteristics that can provide the necessary heat transfer mechanism. These include both metals and non- metals.
  • Preferable metals include those from the group consisting of Ni, Al, Cu, Fe and mixtures or alloys thereof.
  • Examples of support means that can be formed from metals include wire mesh, expanded metal and foamed metal.
  • the metal-hydride hydrogen storage material may be physically bonded to the support means by compaction and sintering processes.
  • the hydridable material is first converted into a fine hydridable power.
  • the hydridable powder is then compacted onto the support means.
  • the compaction process causes the hydridable powder to adhere to and become an integral part of the support means.
  • the support means that has been impregnated with hydridable powder is preheated and then sintered.
  • the preheating process liberates excess moisture and discourages oxidation of the hydridable powder.
  • Sintering is carried out in a high temperature, substantially inert atmosphere containing hydrogen. The temperature is sufficiently high to promote particle-to-particle bonding of the hydridable material as well as the bonding of the hydridable material to the support means .
  • the support means/hydridable material can be packaged within the primary storage container in many different configurations. Examples are provided in commonly assigned U.S. Patent Application 08/623,497, the disclosure of which is incorporated by reference herein.
  • the hydrogen that is stored in the hydridable metal-hydride storage material may flow out of the primary storage container 5 via the hydrogen outlet port 8. This port permits the flow of hydrogen gas into and out of the primary container 5.
  • the primary metal-hydride hydrogen storage container of the present invention also comprises at least one hydrogen combustor that is housed within the primary storage container 5.
  • the primary metal- hydride hydrogen storage container houses a single hydrogen combustor 30.
  • the hydrogen combustor 30 has a hydrogen inlet port 31 which is gaseously connected to the hydrogen outlet port 8 of the storage container 5 via an external manifold 23.
  • the hydrogen combustor 30 is surrounded by the metal-hydride storage material and provides an internal heat source for heating the material.
  • the combustor 30 comprises a nonporous chamber 32.
  • the chamber 32 is made from a "nonporous" material which does not permit the flow of either oxygen, hydrogen or water between the interior of the combustor and the metal-hydride material.
  • the chamber 32 is formed from a nonporous, thermally conductive material.
  • a catalyst 30 Housed within the chamber 32 is a catalyst 30.
  • the catalyst 30 is one which can lower the activation energy of hydrogen combustion.
  • the catalyst 30 comprises Pd. More preferably, the catalyst 30 is Pd which is supported on alumina. Most preferably, the catalyst 30 is a mixture of (1) 50% by volume of 5% Pd supported on gamma-alumina mixed with (2) 50% by volume of gamma-alumina.
  • a hydrogen distribution tube 35 housed within the chamber 32 is a hydrogen distribution tube 35.
  • the hydrogen tube 35 is positioned so that it is surrounded by the catalyst 34.
  • the hydrogen distribution tube 35 is gaseously connected to the hydrogen inlet port 31. Hence, hydrogen gas from the metal-hydride material within the primary storage container 5 is transported into the hydrogen distribution tube 35 via the external manifold 23.
  • the hydrogen distribution tube 35 is formed from a material which permits the passage of hydrogen gas into the high-temperature storage material.
  • the hydrogen distribution tube 35 is formed from a porous metal such as a porous stainless steel.
  • the hydrogen distribution tube is adapted to have alternating areas of high and low porosity, thereby providing for a more uniform distribution of hydrogen gas into the metal-hydride hydrogen storage material.
  • the hydrogen distribution tube 35 is formed from porous stainless steel. This tube is coated with spiral bands of a high- temperature steel-like sealant (i.e., Thermo Seal) thereby forming the desired alternating pattern of high-porous and low-porous areas on the distribution tube.
  • a high- temperature steel-like sealant i.e., Thermo Seal
  • the embodiment of the hydrogen combustor 30 shown in Figure 1 includes an oxygen inlet port 37 which provides a means of allowing oxygen to enter the combustor 30. More specifically, the oxygen inlet port 37 is positioned so that oxygen can enter the region of the combustor 30 housing the catalyst 34.
  • the embodiment of the combustor 30 also includes an exhaust outlet port 39. Combustor exhaust collects in the exhaust region 38 of the combustor 30 and exists the exhaust outlet port 39. The exhaust is transported from the combustor and out of the primary metal-hydride container via the exhaust tube 25 which is gaseously connected to the exhaust outlet port 39. In the embodiment shown in Figure 1, the exhaust tube 25 is a short and straight piece of tubing.
  • the exhaust tube 25 is adapted so that it is coiled and wound through the metal-hydride material. This permits the heat from the exhaust to transfer into the metal- hydride material in the primary container. Further, in another embodiment of the invention, the exhaust tube is additionally wound around the outside of the primary storage container after exiting said primary storage container.
  • the metal-hydride hydrogen storage system of the present invention further comprises means for supplying hydrogen which is gaseously connected to the hydrogen inlet port 31 of the hydrogen combustor 30.
  • the means for supplying hydrogen can be any source of hydrogen that can supply the necessary quantity of hydrogen to the combustor.
  • the "necessary" quantity of hydrogen is that amount sufficient to heat the metal-hydride storage material of the primary storage container to a temperature enabling hydrogen desorption from said material.
  • the means for supplying hydrogen include, but are not limited to hydrogen storage as a gas in a high-pressure hydrogen storage tank, hydrogen storage as a liquid in a cryogenic container, and hydrogen storage in a solid in the form of a metal-hydride.
  • the means for supplying hydrogen is a secondary metal-hydride hydrogen storage container 50 which houses a second metal-hydride hydrogen storage material.
  • the second metal-hydride storage material housed in the secondary storage container is a "low-temperature" metal hydride hydrogen storage material.
  • a low-temperature metal-hydride hydrogen storage material is a metal-hydride hydrogen storage material which will have a 1 atmosphere equilibrium plateau pressure at temperatures below 100°C. Examples of compounds that may be used to form low- temperature metal hydrides include, but are not limited to, the alloys from the AB 5 (e.g. LaNi 5 ) , AB (e.g.
  • metal hydrides can be formed readily and reversibly (i.e. hydrogenated and dehydrogenated) in the vicinity of ordinary temperatures and at modest hydrogen pressures.
  • the second metal-hydride hydrogen storage material may be physically bonded to the same type of support means described above in reference to the primary metal-hydride storage container.
  • the secondary storage container is gaseously connected to the hydrogen inlet port 31 of the hydrogen combustor 30. Hence, hydrogen gas can flow from the secondary container 50 and into the combustor 30. Furthermore, as shown in Figure 1, the secondary storage container 50 is gaseously connected to the hydrogen outlet port 8 of the primary container 5 via the external manifold 23, thereby permitting the flow of hydrogen gas from the primary container 5 to the secondary container 50.
  • hydrogen from the secondary storage container 50 enters the hydrogen inlet port 31 of the combustor 30.
  • the hydrogen passes through the porous chamber 35 and into the catalyst 34.
  • Compressed air, which includes oxygen, is passed into the catalyst via the oxygen inlet port 37.
  • the Pd catalyst catalyzes the reaction between the hydrogen and the oxygen in the compressed air. The reaction is
  • the heat generated from the hydrogen combustion is initially used to heat the high-temperature metal-hydride storage material in the primary storage module up to a temperature at which the hydride material starts to desorb hydrogen. This temperature is typically greater than or equal to about 250°C.
  • the heat produced by the hydrogen combustor 30 does two things: (1) it maintains the temperature of the metal-hydride storage material (i.e., compensates for heat transfer out of the material), and (2) provides the heat of desorption of hydrogen from the metal- hydride material.
  • the reaction describing said desorption of hydrogen is
  • the self-heating metal-hydride hydrogen storage system of the present invention may further comprise temperature sensors for detecting the temperature of the hydrogen storage materials in both the primary and the secondary storage containers.
  • the storage system of the present invention may further include prssure sensors for detecting the pressure of hydrogen released from the primary and well as the secondary storage containers.

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

Abstract

L'invention concerne un système de stockage d'hydrogène dans un hydrure métallique, à auto-chauffage comprenant : un récipient de stockage primaire d'hydrure métallique contenant un matériau de stockage d'hydrogène dans un hydrure métallique, ledit récipient de stockage primaire possédant un orifice de sortie d'hydrogène ; un dispositif de combustion d'hydrogène placé dans le récipient de stockage primaire d'hydrure métallique et entouré par un matériau de stockage haute température, le dispositif de combustion possédant un orifice d'admission d'hydrogène relié pour la circulation du gaz à l'orifice de sortie d'hydrogène du récipient de stockage primaire ; et des moyens pour fournir de l'hydrogène, raccordés pour la circulation du gaz à l'orifice d'admission d'hydrogène du dispositif de combustion.
EP99928784A 1999-06-17 1999-06-17 Systeme de stockage d'hydrogene dans un hydrure metallique, a auto-chauffage Withdrawn EP1203194A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1999/013766 WO2000079201A1 (fr) 1998-02-13 1999-06-17 Systeme de stockage d'hydrogene dans un hydrure metallique, a auto-chauffage

Publications (1)

Publication Number Publication Date
EP1203194A1 true EP1203194A1 (fr) 2002-05-08

Family

ID=22273001

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99928784A Withdrawn EP1203194A1 (fr) 1999-06-17 1999-06-17 Systeme de stockage d'hydrogene dans un hydrure metallique, a auto-chauffage

Country Status (6)

Country Link
EP (1) EP1203194A1 (fr)
JP (1) JP2003502610A (fr)
KR (1) KR20020047052A (fr)
AU (1) AU4577299A (fr)
CA (1) CA2375392A1 (fr)
MX (1) MXPA01012999A (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0079201A1 *

Also Published As

Publication number Publication date
CA2375392A1 (fr) 2000-12-28
KR20020047052A (ko) 2002-06-21
MXPA01012999A (es) 2002-07-30
JP2003502610A (ja) 2003-01-21
AU4577299A (en) 2001-01-09

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