WO2017004680A1 - Remplissage à densité variable d'hydrure de métal dans un récipient de stockage d'hydrogène - Google Patents

Remplissage à densité variable d'hydrure de métal dans un récipient de stockage d'hydrogène Download PDF

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Publication number
WO2017004680A1
WO2017004680A1 PCT/AU2016/050596 AU2016050596W WO2017004680A1 WO 2017004680 A1 WO2017004680 A1 WO 2017004680A1 AU 2016050596 W AU2016050596 W AU 2016050596W WO 2017004680 A1 WO2017004680 A1 WO 2017004680A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen storage
region
internal volume
density
storage material
Prior art date
Application number
PCT/AU2016/050596
Other languages
English (en)
Inventor
Jordan Christopher Pierce
Krista DUMUR
Matthew Campbell Greaves
Original Assignee
Hydrexia Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2015902695A external-priority patent/AU2015902695A0/en
Application filed by Hydrexia Pty Ltd filed Critical Hydrexia Pty Ltd
Publication of WO2017004680A1 publication Critical patent/WO2017004680A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • 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
    • F17C2221/012—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

  • This invention relates to the use of metal hydrides for hydrogen storage and in particular to metal hydride storage vessels and methods of managing the density within a vessel.
  • a safer and more compact method of hydrogen storage and transportation as compared to compressed gas cylinders is through the storage of hydrogen within solid materials such as metal hydrides.
  • metal hydrides When exposed to hydrogen at relatively low pressures, metal hydrides can absorb large quantities of hydrogen in a safe solid form. Stored hydrogen can then be released from the metal hydride when required by heating the material to a temperature above the pressure equilibrium temperature.
  • the storage of hydrogen as a solid hydride has the additional potential to provide greater weight percentage storage than compressed gas.
  • Hydrogen storage units typically include an enclosed volume containing a bed of hydrogen storage material such as catalysed MgH 2 or other metal hydride.
  • thermal challenges associated with such storage units particularly with high temperature hydrides. As an example magnesium hydride must be held within a narrow range of operating temperature in the vicinity of 365°C to operate effectively during the emptying process.
  • the metal hydride that is closest to the cooling surface/surfaces starts to absorb first.
  • the hydrogen is absorbed into the material the hydride expands and begins to impart a load not only on the shell of the vessel but on the unreacted metal hydride.
  • This mechanical stress on the unreacted hydride leads to its compaction and densification.
  • the metal hydride that is closest to the cooling surfaces may decrease in density and material further away from the cooling surfaces may significantly increase in density.
  • this density redistribution may result in a material density that is significantly higher than the average density. This increase in density may result in bed permeability problems as well as having the potential to damage the internal or external structures of the containment vessel where the high density material is located.
  • the method employed in most metal hydride cylinders to minimise the stress on the wall of the cylinder is to introduce structures within the bed to attempt to minimize movement and redistribution of metal hydride material. These structures may take the form of a series of regular dividers to compartmentalise the material bed. These compartments can additionally assist in increasing the thermal conductivity of the bed and reduce the thermal gradient, but at the expense of increased complexity and weight.
  • One possible way to minimise the stress on the wall of the cylinder is to minimise the movement of the material.
  • One solution employed in many metal hydride cylinders is to introduce dividers longitudinally along the hydride bed to minimise the distance the powder can travel.
  • the radial length of the vessel may be decreased to reduce stress. While the use of dividers can limit the movement of particles, they cannot reduce the density of the material at the wall which is produced as a consequence of the absorption process.
  • hydrogen storage units utilising high temperature metal hydrides such as catalysed MgH 2 have stringent requirements to accomplish at least one of minimising the stress on the cylinder wall induced by hydride expansion forces; minimising density redistribution which may lead to excessive high or low densities; and ensure the metal hydride bed behaves as a uniform thermal load.
  • the invention provides, a method of filling a hydrogen storage vessel with a hydrogen storage material, the hydrogen storage vessel comprising an internal volume having at least a first and second region and an outer shell, the internal volume containing a hydrogen storage material; the method including the steps of filling the region of the internal volume in proximity to the inner surface of the outer shell with hydrogen storage material which has a lower density than hydrogen storage material within the internal volume in the second region which is positioned closer to the centre of the internal volume.
  • the region of lower density is separated from the higher density region by a barrier formed within the storage vessel. This barrier may be structural or non-structural whereby it acts as a division between regions to provide partial separation of different density material during the initial material filling process.
  • the lower density in the region in proximity to the inner surface of the outer shell may be produced by providing hydrogen storage material in a form which has a lower packing density than hydrogen storage material used on the inner region of the internal volume.
  • the density in the lower density region is preferably in the range of 350 to 600 g/l compared to a density in the inner regions of 700 to 1200g/l
  • the vessel is filled with the desired profile with two or more different filling densities using internal structures as a separation or partial separation barrier inside the internal volume.
  • the region of the internal volume closest to the shell is filled to a lower density using hydrogen storage material which may be shaped into a lower density form or mixed with a material which is non expansive at the conditions experienced in the storage vessel and the inner sections are filled with denser material. In this way, the vessel shell is not subjected to high expansion forces during the initial absorption cycles.
  • a hydrogen storage vessel comprising an internal volume and an outer shell, the internal volume containing a hydrogen storage material; the internal volume having a region of the internal volume in proximity to the inner surface of the outer shell with hydrogen storage material which has a lower density than hydrogen storage material within the internal volume in a second region which is positioned closer to the centre of the internal volume.
  • at least one barrier is formed between the region of lower density and the region of higher density within the storage vessel. Multiple barriers may be provided in the internal volume of the storage vessel to create multiple regions of different density providing a varying density profile of storage material in the vessel. Preferably the profile is from the lower density to the higher density towards or at the centre of the internal volume.
  • the lower density region in proximity to the inner surface of the outer shell may be provided with hydrogen storage material initially provided in a lower density form. This may be achieved by providing hydrogen storage material in a form which has a lower packing density than hydrogen storage material used on the inner region or regions of the internal volume.
  • the vessel is provided with the desired profile with two or more different filling densities using internal structures such as a longitudinal separation barrier or barriers inside the internal volume.
  • the region of the internal volume closest to the shell is filled to a low density using hydrogen storage material which may be shaped into a lower density form or mixed with a non-expansive material.
  • This vessel may be provided with internal oil tubes and preferably provided with oil at the same time so that all regions are absorb hydrogen simultaneously.
  • Figure 1 is cross section of a hydrogen storage vessel according to the invention.
  • Figure 2 is cross section of a hydrogen storage vessel during the material loading process according to the invention.
  • the vessel 10 includes an internal volume 1 1 and an outer shell. At least one barrier 12 is provided to divide the internal volume into two or more internal regions. Multiple barriers may be provided in the internal volume of the storage vessel to create multiple regions. The barriers may be provided with apertures or holes to allow the passage of hydrogen storage material to balance stresses on either side of the barrier but significant migration of hydrogen storage material and variation from the original density profile may not be desirable. These regions are loaded with hydrogen storage material at different densities providing a varying density profile of storage material in the vessel. In order to reduce mechanical stresses at the wall, the profile is from the lower density to higher density towards or at the centre of the internal volume.
  • the lower density region in proximity to the inner surface of the outer shell is provided by loading the vessel with hydrogen storage material initially provided in a lower density form. This is achieved by providing hydrogen storage material in a form which either has a lower packing density than hydrogen storage material used in the inner region or regions of the internal volume. Lower density might also be achieved by inserting weak structures onto the inner surface of the outer shell that are easily deformed and crushed as the material expands during the first or subsequent absorptions.
  • the vessel is provided with the desired profile with material of two or more different filling densities using internal structures such as a longitudinal separation barrier or barriers inside the internal volume to separate or maintain the material in a bed in or with minimal, but planned migration from its original form.
  • the region of the internal volume closest to the shell is filled to a low density using hydrogen storage material which is processed into a lower density form or alternatively mixed with a material such as graphite which is non expansive at the conditions experienced in the storage vessel. In this way, the vessel shell is not subjected to high expansion forces during absorption and the inner sections are filled with denser material.
  • the vessel 10 is filled by loading high density material 21 into the inner region of the vessel.
  • the divider 25 maintains the bed in position during the filling process.
  • Low density material 22 is then loaded into the outer region of the internal volume 22 to fill all of the outer region and preferably other unfilled space 20 in the vessel in proximity to the outer shell 23.
  • This vessel shown in figure 1 is provided with internal oil tubes 13, 14, 15, 16 and preferably provided with oil to cool the regions as hydrogen is absorbed.
  • the hydrogen storage material is heated to absorption temperature. The heaters are turned off and hydrogen supplied at the pressure required for absorption.
  • cooling of the material in region or regions closer to the centre of the storage vessel can be commenced by circulating cooling fluid to tubes 14, 15, 16 within these sections of the storage bed. This can occur in tubes 14, 14, 16 simultaneously or sequentially from the outermost tubes 14 to the inner most tubes 16.
  • the cooling fluid circulating through tubes 16 may be sequentially passed to tubes 14, 15 and 16 to provide different rates of cooling around these respective tubes due to the gradual heating of the cooling fluid passing therethrough.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

L'invention concerne un procédé de remplissage d'un récipient de stockage d'hydrogène (10) avec un matériau de stockage d'hydrogène, le récipient de stockage d'hydrogène (10) comprenant un volume interne (11) ayant au moins une première région, au moins une seconde région et une coque externe, le volume interne contenant un matériau de stockage d'hydrogène ; le procédé comprenant les étapes consistant à remplir la première région du volume interne à proximité de la surface interne de la coque externe avec le matériau de stockage d'hydrogène qui a une densité inférieure au matériau de stockage d'hydrogène dans le volume interne dans au moins une seconde région qui est positionnée plus près du centre du volume interne que la première région.
PCT/AU2016/050596 2015-07-08 2016-07-07 Remplissage à densité variable d'hydrure de métal dans un récipient de stockage d'hydrogène WO2017004680A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2015902695A AU2015902695A0 (en) 2015-07-08 Variable density filling of metal hydride in a hydrogen storage vessel
AU2015902695 2015-07-08

Publications (1)

Publication Number Publication Date
WO2017004680A1 true WO2017004680A1 (fr) 2017-01-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2016/050596 WO2017004680A1 (fr) 2015-07-08 2016-07-07 Remplissage à densité variable d'hydrure de métal dans un récipient de stockage d'hydrogène

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WO (1) WO2017004680A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6318453B1 (en) * 2000-04-26 2001-11-20 Energy Conversion Devices, Inc. Hydrogen cooled hydrogen storage unit having maximized cooling efficiency
US20060051638A1 (en) * 2004-09-03 2006-03-09 Gross Karl J Hydrogen storage and integrated fuel cell assembly
US20070077463A1 (en) * 2005-10-05 2007-04-05 Paul Adams Fuel cartridge of a fuel cell with fuel stored outside fuel liner

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6318453B1 (en) * 2000-04-26 2001-11-20 Energy Conversion Devices, Inc. Hydrogen cooled hydrogen storage unit having maximized cooling efficiency
US20060051638A1 (en) * 2004-09-03 2006-03-09 Gross Karl J Hydrogen storage and integrated fuel cell assembly
US20070077463A1 (en) * 2005-10-05 2007-04-05 Paul Adams Fuel cartridge of a fuel cell with fuel stored outside fuel liner

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