EP2427687A2 - Method for storing industrial gases and corresponding accumulator - Google Patents

Method for storing industrial gases and corresponding accumulator

Info

Publication number
EP2427687A2
EP2427687A2 EP10726881A EP10726881A EP2427687A2 EP 2427687 A2 EP2427687 A2 EP 2427687A2 EP 10726881 A EP10726881 A EP 10726881A EP 10726881 A EP10726881 A EP 10726881A EP 2427687 A2 EP2427687 A2 EP 2427687A2
Authority
EP
European Patent Office
Prior art keywords
storage
gas
pressure
container
bar
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Withdrawn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
EP10726881A
Other languages
German (de)
French (fr)
Inventor
Gunter Kaiser
Jürgen Klier
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.)
Institut fuer Luft und Kaeltetechnik Gemeinnuetzige GmbH
Original Assignee
Institut fuer Luft und Kaeltetechnik Gemeinnuetzige GmbH
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 DE102010010108A external-priority patent/DE102010010108B4/en
Application filed by Institut fuer Luft und Kaeltetechnik Gemeinnuetzige GmbH filed Critical Institut fuer Luft und Kaeltetechnik Gemeinnuetzige GmbH
Publication of EP2427687A2 publication Critical patent/EP2427687A2/en
Withdrawn legal-status Critical Current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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01B3/0021—Carbon, e.g. active carbon, carbon nanotubes, fullerenes; Treatment thereof
    • 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
    • C01B3/0026—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 of one single metal or a rare earth metal; Treatment thereof
    • 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
    • F17C3/00—Vessels not under pressure
    • F17C3/02—Vessels not under pressure with provision for thermal insulation
    • F17C3/04—Vessels not under pressure with provision for thermal insulation by insulating 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
    • F17C7/00—Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
    • 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
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0104—Shape cylindrical
    • 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
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0138—Shape tubular
    • 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
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0147—Shape complex
    • F17C2201/0166—Shape complex divided in several chambers
    • 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
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0147—Shape complex
    • F17C2201/0171—Shape complex comprising a communication hole between chambers
    • 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
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/054—Size medium (>1 m3)
    • 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
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/056—Small (<1 m3)
    • 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
    • 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
    • F17C2203/0312—Radiation shield cooled by external means
    • 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
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0612—Wall structures
    • F17C2203/0626—Multiple walls
    • F17C2203/0631—Three or more 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
    • 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
    • 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
    • F17C2205/0142—Two or more vessels characterised by the presence of fluid connection between vessels bundled in parallel
    • 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
    • F17C2205/0149—Vessel mounted inside another one
    • 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
    • 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
    • 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
    • F17C2221/03—Mixtures
    • F17C2221/032—Hydrocarbons
    • F17C2221/033—Methane, e.g. natural gas, CNG, LNG, GNL, GNC, 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
    • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0107—Single phase
    • F17C2223/0115—Single phase dense or supercritical, i.e. at high pressure and high density
    • 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
    • F17C2223/036—Very high pressure (>80 bar)
    • 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
    • F17C2225/01—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the phase
    • F17C2225/0107—Single phase
    • F17C2225/0115—Single phase dense or supercritical, i.e. at high pressure and high density
    • 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
    • F17C2225/01—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the phase
    • F17C2225/0107—Single phase
    • F17C2225/0123—Single phase gaseous, e.g. CNG, GNC
    • 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
    • F17C2225/01—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the phase
    • F17C2225/0146—Two-phase
    • F17C2225/0153—Liquefied gas, e.g. LPG, GPL
    • F17C2225/0161—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
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/03—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the pressure level
    • F17C2225/033—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
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/03—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the pressure level
    • F17C2225/035—High pressure, i.e. between 10 and 80 bars
    • 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
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0337—Heat exchange with the fluid by cooling
    • F17C2227/0339—Heat exchange with the fluid by cooling using the same fluid
    • 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
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0337—Heat exchange with the fluid by cooling
    • F17C2227/0341—Heat exchange with the fluid by cooling using another fluid
    • F17C2227/0353—Heat exchange with the fluid by cooling using another fluid using cryocooler
    • 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
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0337—Heat exchange with the fluid by cooling
    • F17C2227/0358—Heat exchange with the fluid by cooling by expansion
    • F17C2227/036—"Joule-Thompson" effect
    • 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
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0367—Localisation of heat exchange
    • F17C2227/0369—Localisation of heat exchange in or on a vessel
    • F17C2227/0376—Localisation of heat exchange in or on a vessel in wall contact
    • F17C2227/0379—Localisation of heat exchange in or on a vessel in wall contact inside the vessel
    • 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
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0367—Localisation of heat exchange
    • F17C2227/0369—Localisation of heat exchange in or on a vessel
    • F17C2227/0376—Localisation of heat exchange in or on a vessel in wall contact
    • F17C2227/0381—Localisation of heat exchange in or on a vessel in wall contact integrated in the wall
    • 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
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0367—Localisation of heat exchange
    • F17C2227/0369—Localisation of heat exchange in or on a vessel
    • F17C2227/0376—Localisation of heat exchange in or on a vessel in wall contact
    • F17C2227/0383—Localisation of heat exchange in or on a vessel in wall contact outside the vessel
    • 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
    • F17C2260/02—Improving properties related to fluid or fluid transfer
    • F17C2260/021—Avoiding over pressurising
    • 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
    • F17C2260/02—Improving properties related to fluid or fluid transfer
    • F17C2260/027—Making transfer independent of vessel orientation
    • 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
    • F17C2260/04—Reducing risks and environmental impact
    • F17C2260/046—Enhancing energy recovery
    • 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
    • F17C2265/00—Effects achieved by gas storage or gas handling
    • F17C2265/06—Fluid distribution
    • F17C2265/065—Fluid distribution for refueling vehicle fuel tanks
    • 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
    • F17C2265/00—Effects achieved by gas storage or gas handling
    • F17C2265/06—Fluid distribution
    • F17C2265/066—Fluid distribution for feeding engines for propulsion
    • 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
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0134—Applications for fluid transport or storage placed above the ground
    • F17C2270/0139—Fuel stations
    • 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
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0165—Applications for fluid transport or storage on the road
    • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
    • 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
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0165—Applications for fluid transport or storage on the road
    • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
    • F17C2270/0178—Cars
    • 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
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0165—Applications for fluid transport or storage on the road
    • F17C2270/0184—Fuel cells
    • 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
    • F17C2270/00—Applications
    • F17C2270/05—Applications for industrial use
    • F17C2270/0509—"Dewar" vessels
    • 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
    • F17C2270/00—Applications
    • F17C2270/05—Applications for industrial use
    • F17C2270/0581—Power plants
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to a process for the storage of industrial gases, which makes it possible to increase the density of stored under pressure technical gases without pressure increase significantly.
  • the store is suitable for the storage and transport of industrial gases in general, for the storage of technical fuel gases, such as. Hydrogen or natural gas, at service stations and for use as a fuel-gas vehicle tank.
  • natural gas has been used as fuel for automobiles for many years, and accordingly there is also a well-developed network of filling stations.
  • the natural gas is typically kept ready at a pressure of 200 bar; at this pressure, it has a density of about 155 kg / m 3 or a calorific value of about 6.25 MJ / I.
  • the energy density of compressed natural gas (200 bar) compared to other fossil fuels, such as gasoline with an energy density of 32 MJ / I or diesel fuel with an energy density of 36 MJ / I or regenerative fuels, such as bio-diesel with 32 MJ / I or bioethanol at 21 MJ / I, very low.
  • Liquefied Natural Gas has only about 1 / 600th of the volume of gaseous natural gas, very high storage densities can be achieved with the storage of LNG.
  • the natural gas must be cooled to about 110 K for liquefaction;
  • energy is required for its phase transformation from gaseous to. liquid.
  • the LNG due to the comparatively low storage temperature
  • the LNG must be constantly cooled with high refrigeration capacities in order to avoid vaporization of the LNG.
  • DE 25 36 993 C2 and US Pat. No. 6,672,077 B1 propose storing hydrogen at temperatures far below the ambient temperature in absorbent or nanostructured material.
  • EP 1 130 06 A1 and WO 00/01980 solutions are shown, in which hydrogen is also stored at low temperatures, but in addition by means of an adjuvant in the storing material quasi "encapsulated" is.
  • DE 103 92 240 T5 a solution is presented in which hydrogen is stored under increased pressure in an absorbent material.
  • WO 97/26082 A1 and WO 01/13032 A1 show hydrogen storage devices which have a special layer or film structure
  • US 2004/0250552 A1 proposes the use of a liquid storage material.
  • DE 10 2005 023 036 A1 shows a method for hydrogen storage in which hydrogen is stored in gaseous, cooled and compressed form under high pressure on a physically adsorbing material, in particular carbon powder.
  • the invention has for its object to find a method for storing industrial gases, which makes it possible to increase the density of stored under pressure technical gases, in particular natural gas and hydrogen, without pressure increase and with low energy use significantly.
  • the technical gas is stored in a storage container which, depending on the gas stored therein, has to withstand pressures of up to 1200 bar, above its critical pressure and above the critical temperature, or in the compressible phase range below the critical temperature.
  • the storage above the critical temperature is preferably used when the storage is carried out at pressures which are substantially greater than the critical pressure. At pressures that are only slightly above the critical pressure, the storage is preferably applied in the compressible phase range. Materials which are suitable for adsorption or absorption of the technical gas in appreciable amount, ie in a larger amount than in the case of virtually all materials occurring surface absorption or absorption, are not used.
  • the gas can advantageously be throttled when it is withdrawn from the storage container, the gas remaining in the container being removed by means of the exiting gas, whose temperature drops sharply during the relaxation due to the Joule-Thomson effect, is cooled.
  • the storage of hydrogen takes place at a temperature above 33 K and at a pressure above 13 bar. Again, a storage in the compressible phase range at a temperature below 33 K in the same pressure range is possible.
  • the hydrogen is stored at a temperature of 33 to 100 K and above the critical pressure at 13 to 1200 bar.
  • a hydrogen density of 100 kg / m 3 can be achieved.
  • the storage density at the same pressure drops by only 12%, ie to 88 kg / m 3 .
  • storage densities above that of the liquid hydrogen and about three times the high pressure hydrogen at ambient temperature are achievable.
  • the storage tank for the technical gas consists of a thermally insulated, pressure-tight container with a closable opening for removal and filling.
  • the container is equipped with a refrigerating machine, which is mounted on the container so that it can deliver the cold produced by it to the natural gas in the container, and / or equipped with the throttled relaxing the leaking technical glass relaxation device, which in thermal Contact with the stored in the storage tank technical gas is.
  • the cold part / the cold finger of the chiller must be in thermal contact with the technical gas in the interior of the container.
  • the basic structure of the Speicherbefflel- ter 's thin-walled tubes (0.1 to 30 mm wall thickness) with small inner diameters (0.1 to 100 mm), which are thermally connected to each other and possibly with other structural elements of the memory , Due to the thin walls of the tubes, a good thermal connection of the technical gas stored in the tube bundles to the tubes and structural elements serving as heat storage is achieved.
  • the small inner diameters of the tubes make it possible, despite the comparatively low wall thicknesses, to achieve the required storage pressures of up to 1200 bar.
  • the expansion device which serves to reduce the release of technical gases during removal, consists either of at least one capillary larrohr or it is designed as at least one porous element which covers the at least one outlet opening for the technical gas (eg hydrogen).
  • technical gas eg hydrogen
  • a particularly good heat transfer between the exiting and in the Spei- rather remaining technical gas is achieved with an embodiment in which the basic structure of the storage container consists of thin-walled tube bundles, wherein the capillary tubes are integrated into the thin-walled tube bundles.
  • the storage container may additionally be equipped with at least one latent storage element, for which storage elements based on the Gibbs-Thomson effect are particularly suitable.
  • the memory can be used particularly advantageously in conjunction with natural gas or hydrogen as a motor vehicle tank.
  • the thermal insulation of the storage container is carried out as a multilayer vacuum superinsulation, which is equipped with actively cooled radiant screens.
  • the radiation screens can be thermally connected to the gas outlet, whereby the sensible heat of the escaping technical gas is used to cool the radiation shields.
  • FIG. 1 shows a memory, preferably for supercritical and transcritical natural gas, in a schematic representation
  • Fig. 2 the diagram of the temperature dependence of density and calorific value for natural gas at different pressures
  • 3 shows a memory, preferably for supercritical and transcritical hydrogen, in a schematic representation; 4 shows various embodiments of the expansion device.
  • the storage for natural gas consists of the container 1 and the refrigerating machine 2.
  • the container 1 has a closable by means of a valve 3 opening 4, which serves for filling with and for the removal of natural gas.
  • the container 1 is equipped with an insulation layer 5 designed either as a solid or vacuum insulation, which minimizes the heat transfer from the environment into the supercritical natural gas 6 in the reservoir.
  • the chiller 2 has a cooling capacity which is sufficient to compensate for the thermal losses and is either as a compression refrigeration cascade or as
  • the cold part 7 of the refrigerator 2 communicates with the interior 8 of the container 1 and thus with the supercritical natural gas 6 in thermal contact. It does not matter at which point of the container 1, the chiller 2 is arranged (up or down), since the supercritical natural gas 6 evenly fills the interior space 8 (no liquid phase).
  • the storage of natural gas at a pressure above the critical pressure (46 bar) and a temperature of 190 K results in an increase in the density of the stored supercritical natural gas.
  • the density of natural gas compared to that at ambient temperature (at 200 bar) from 155 kg / m 3 to 330 kg / m 3 , ie increased to 2.13 times become.
  • the volumetric energy density increases in the same ratio from 6.25 MJ / I to 13.3 MJ / I, which saves more than twice as much energy when the tank is used as a vehicle tank with the same tank volume and consequently increases the range of the vehicle.
  • the container 11 of the hydrogen storage (Fig. 3) consists of numerous, parallel arranged storage tubes 12, wherein one side of the tubes 12 with a Collecting device 13 is connected, which connects all tubes 12 with the hydrogen outlet 14.
  • the storage container 11 composed of the tube bundles is surrounded by a multilayer vacuum superinsulation 15, which is surrounded by radiation shields 16 for further improvement of the thermal insulation.
  • the radiation screens 16 are thermally connected to the hydrogen outlet line 14 so that the radiation screens 16 are actively cooled by the sensible heat of the exiting hydrogen.
  • the entire assembly is located in a Dewar vessel 17, which ensures a first thermal insulation against the comparatively high ambient temperature.
  • Fig. 4 are arranged from top to bottom, several embodiments of relaxation devices 18.
  • the capillary tubes 19 are arranged coaxially in the interior of the storage tubes 12. When hydrogen is withdrawn, the hydrogen remaining in the respective storage tube 12 is cooled directly through the capillary tube 19.
  • the cross sections of the storage tubes 12 are chosen so small with an inner diameter of about 1 mm that they simultaneously take over the function of the capillary 19, while in the third variant, the storage tubes 12 are spirally surrounded by the capillary tubes 18.
  • outlet openings of the storage tubes 12 are each covered with porous plugs 20, which serve as an alternative to the capillary tubes 19 for the throttled relaxation of the hydrogen.

Abstract

The invention relates to a method for storing industrial gases which allows the density of the industrial gases stored under pressure to be increased without increasing the pressure. The accumulator is especially suitable for use as a tank of vehicles that are operated with combustible gases, such as natural gas or hydrogen. The industrial gas is stored at a temperature close to its critical point and at a pressure higher than its critical pressure up to a maximum of 1200 bar. The accumulator operating according to the method of the invention comprises a thermally insulated, pressure-tight container (1, 10) which has a closable opening (4) for withdrawal and filling and which is designed for internal pressures up to a maximum of 1200 bar. The industrial gas is cooled by means of a refrigerating machine (2) and/or by means of a relaxation unit (18) which is used to relax the emerging industrial gas in a controlled manner.

Description

Verfahren zur Speicherung von und Speicher für technische Gase Method of storing and storage of technical gases
Die Erfindung betrifft ein Verfahren zur Speicherung von technischen Gasen, das es ermöglicht, die Dichte von unter Druck gelagerten technischen Gasen ohne Druck- Steigerung wesentlich zu erhöhen. Der Speicher eignet sich für die Lagerung und für Transporte von technischen Gasen im Allgemeinen, für die Speicherung von technischen Brenngasen, wie z.B. Wasserstoff oder Erdgas, an Tankstellen und für den Einsatz als Tank von mit Brenngasen betriebenen Fahrzeugen.The invention relates to a process for the storage of industrial gases, which makes it possible to increase the density of stored under pressure technical gases without pressure increase significantly. The store is suitable for the storage and transport of industrial gases in general, for the storage of technical fuel gases, such as. Hydrogen or natural gas, at service stations and for use as a fuel-gas vehicle tank.
Die effektive Speicherung der technischen Gase Erdgas und Wasserstoff ist von großer wirtschaftlicher Relevanz , da beide Brenngase direkt zum Antrieb von Kraftfahrzeugen eingesetzt werden können.The effective storage of the technical gases natural gas and hydrogen is of great economic relevance, since both fuel gases can be used directly for propulsion of motor vehicles.
So wird Erdgas bereits seit Jahren als Treibstoff für Kraftfahrzeuge benutzt und ent- sprechend gibt es auch ein gut ausgebautes Tankstellennetz. Das Erdgas wird typischerweise bei einem Druck von 200 bar bereit gehalten; bei diesem Druck hat es eine Dichte von ca. 155 kg/m3 bzw. einen Heizwert von ca. 6.25 MJ/I. Damit ist die Energiedichte von komprimiertem Erdgas (200 bar) im Vergleich zu anderen fossilen Kraftstoffen, wie z.B. Benzin mit einer Energiedichte von 32 MJ/I oder Dieselkraftstoff mit einer Energiedichte von 36 MJ/I oder regenerativen Kraftstoffen, wie z.B. Bio- Diesel mit 32 MJ/I oder Bioethanol mit 21 MJ/I, sehr gering.For example, natural gas has been used as fuel for automobiles for many years, and accordingly there is also a well-developed network of filling stations. The natural gas is typically kept ready at a pressure of 200 bar; at this pressure, it has a density of about 155 kg / m 3 or a calorific value of about 6.25 MJ / I. Thus, the energy density of compressed natural gas (200 bar) compared to other fossil fuels, such as gasoline with an energy density of 32 MJ / I or diesel fuel with an energy density of 36 MJ / I or regenerative fuels, such as bio-diesel with 32 MJ / I or bioethanol at 21 MJ / I, very low.
Eine Erhöhung der Energiedichte des Erdgases ist zwar prinzipiell durch eine Erhöhung des Speicherdrucks möglich, die technischen und insbesondere die sicherheits- technischen Anforderungen an die eingesetzten Druckbehälter nehmen bei Drücken über 200 bar jedoch unverhältnismäßig zu, wodurch eine solche Lagerung nicht mehr wirtschaftlich ist.Although an increase in the energy density of the natural gas is possible in principle by increasing the accumulator pressure, the technical and in particular the safety requirements for the pressure vessels used take at pressures above 200 bar but disproportionately, whereby such storage is no longer economical.
Weiterhin ist bekannt, das Erdgas in flüssiger Form zu speichern. Da flüssiges Erd- gas (LNG - Liquified Natural Gas) nur etwa ein 1/600stel des Volumens von gasförmigem Erdgas hat, sind mit der Speicherung von LNG sehr hohe Speicherdichten erreichbar. Allerdings muss das Erdgas zur Verflüssigung auf ca. 110 K abgekühlt werden; zudem benötigt man Energie für dessen Phasenumwandlung von gasförmig zu. flüssig. Hinzu kommt, dass aufgrund der vergleichsweise tiefen Lagertemperatu- ren, auch wenn sich das LNG in thermisch gut isolierten Behältern befindet, das LNG ständig mit hohen Kälteleistungen gekühlt werden muss, wenn ein Verdampfen des LNG vermieden werden soll.Furthermore, it is known to store the natural gas in liquid form. Since Liquefied Natural Gas (LNG) has only about 1 / 600th of the volume of gaseous natural gas, very high storage densities can be achieved with the storage of LNG. However, the natural gas must be cooled to about 110 K for liquefaction; In addition, energy is required for its phase transformation from gaseous to. liquid. In addition, due to the comparatively low storage temperature Even if the LNG is in thermally insulated containers, the LNG must be constantly cooled with high refrigeration capacities in order to avoid vaporization of the LNG.
Die Speicherung von Erdgas in Form von LNG wird zurzeit in größerem Maßstab nur bei LNG-Tankschiffen (siehe DE 10 2006 056 821 A1) eingesetzt. Obwohl die Speicher der Tankschiffe ein wesentlich besseres Verhältnis von Volumen zur Oberfläche haben als z.B. die Tanks von Kraftfahrzeugen, geht dennoch beim Transport des Erdgases ungefähr ein Viertel der transportierten Energie verloren, da das Erdgas zuerst verflüssigt und während der Fahrt gekühlt werden muss bzw. ein Teil des Erdgases während der Fahrt verdampft. Für einen Einsatz in Kraftfahrzeugen ist diese Methode jedoch völlig ungeeignet, da das LNG ständig, also auch in Zeiten, in denen das Kraftfahrzeug nicht bewegt wird, auf 110 K gekühlt werden muss.The storage of natural gas in the form of LNG is currently used on a larger scale only in LNG tankers (see DE 10 2006 056 821 A1). Although the tanks of tankers have a much better volume to surface ratio than e.g. However, the tanks of motor vehicles, is lost in the transport of natural gas about a quarter of the transported energy, since the natural gas must first be liquefied and cooled while driving or part of the natural gas evaporates while driving. However, this method is completely unsuitable for use in motor vehicles, since the LNG must be cooled constantly to 110 K, even in times when the motor vehicle is not being moved.
Des Weiteren sind aus der Patentliteratur (CN 2389281 Y, US 5,709,203 A, US 5,582,016 A, CA 2, 113,774 A1, EP 0 670 452 A1, US 6,089,226 A, US 6,513,521 B1) Lösungen bekannt, bei denen eine Flüssig-Erdgas-Speicherung bei Drücken im überkritischen Bereich als unterkühlte Flüssigkeit angewandt, und folglich die Verdampfung des flüssigen Erdgases unterbunden wird. Hierdurch kann gegenüber der oben beschriebenen LNG-Speicherung zwar die während der Lagerung erforderliche Energie etwas gesenkt werden, jedoch muss auch hier eine große Energiemenge für die Phasenumwandlung des Erdgases von der gasförmigen in die flüssige Phase aufgebracht werden.Furthermore, from the patent literature (CN 2389281 Y, US 5,709,203 A, US 5,582,016 A, CA 2, 113,774 A1, EP 0 670 452 A1, US 6,089,226 A, US 6,513,521 B1) solutions are known in which a liquid-natural gas storage is applied as supercooled liquid at pressures in the supercritical range, and thus the evaporation of the liquid natural gas is suppressed. As a result, while the energy required during storage may be somewhat reduced compared to the above-described LNG storage, but here too, a large amount of energy for the phase transformation of the natural gas must be applied from the gaseous to the liquid phase.
Mit Wasserstoff betriebene Fahrzeuge werden zwar, im Gegensatz zu den mit Erdgas betriebenen, zurzeit nur in geringem Umfang eingesetzt, jedoch ist zu erwarten, dass sie in Zukunft an Bedeutung gewinnen, da unter Einsatz von Energie vergleichsweise einfach Wasserstoff (Wasserelektrolyse) gewonnen werden kann.Although hydrogen-powered vehicles are currently used only to a limited extent, unlike those fueled by natural gas, they are expected to become more important in the future because hydrogen can be obtained relatively easily by using energy (water electrolysis).
Bekannte Methoden zur Speicherung von Wasserstoff sind erstens die Speicherung bei Umgebungstemperatur unter Hochdruck, zweitens die Speicherung als Flüssigwasserstoff im Verdampfungsgleichgewicht bei tiefen Temperaturen und drittens Ad- bzw. Absorption von Wasserstoff an bzw. in Festkörpern, wie z.B. Metallhydriden oder Graphit. Mit allen drei Methoden können bislang nur unzureichende volumetrische Speicherdichten erzielt werden. So beträgt die Speicherdichte des Wasserstoffs bei Umgebungstemperatur und einem Druck von 700 bar lediglich 39 kg/m3; flüssiger Wasser- stoff (am kritischen Punkt) hat sogar nur eine Dichte von 31 kg/m3. Bei der festkörpergebundenen Speicherung von Wasserstoff sind die Speicherdichten üblicherweise wesentlich geringer.Well-known methods for the storage of hydrogen are first storage at ambient temperature under high pressure, secondly storage as liquid hydrogen in the evaporation equilibrium at low temperatures and third ad- or absorption of hydrogen on or in solids, such as metal hydrides or graphite. With all three methods only insufficient volumetric storage densities can be achieved so far. Thus, the storage density of the hydrogen at ambient temperature and a pressure of 700 bar only 39 kg / m 3 ; liquid hydrogen (at the critical point) even has a density of only 31 kg / m 3 . In the case of solid-state storage of hydrogen, the storage densities are usually much lower.
Eine Ausnahme bildet die Speicherung von Wasserstoff an Graphit-Nanotubes, mit der in Laborversuchen Speicherdichten von bis zu 75% der Kohlenstoffdichte erreicht wurden. Allerdings ist die Be- und Entladung sehr zeitaufwendig, da sie 4 bis 24 Stunden dauert; zudem ist sie nicht vollständig reversibel. In den Versuchen wurden lediglich 4 bis 5 befriedigende Ladezyklen erreicht. Danach nimmt, da der adsorbierte Wasserstoff dem Kohlenstoff nicht mehr vollständig entnommen werden kann, die nutzbare Speicherdichte rapide ab. Bei wesentlich mehr Lade-/Entlade-Zyklen sind schätzungsweise nur noch 0,5 bis 1 % der Kohlenstoffdichte nutzbar.An exception is the storage of hydrogen on graphite nanotubes, which has been used in laboratory experiments to achieve storage densities of up to 75% of the carbon density. However, the loading and unloading is very time consuming, since it takes 4 to 24 hours; Moreover, it is not completely reversible. In the experiments, only 4 to 5 satisfactory charging cycles were achieved. Thereafter, since the adsorbed hydrogen can not be completely removed from the carbon, the usable storage density decreases rapidly. With significantly more charge / discharge cycles, it is estimated that only 0.5 to 1% of the carbon density can be used.
Neuere Entwicklungen zielen insbesondere auf die Verbesserung der Speicherdichten von Speichern, die auf dem Prinzip der Ad- beziehungsweise Absorption von Wasserstoff an bzw. in anderen Materialien beruhen.More recent developments are aimed in particular at improving the storage densities of storage systems based on the principle of adsorption or absorption of hydrogen on or in other materials.
So wird in DE 25 36 993 C2 und US 6,672,077 B1 vorgeschlagen, Wasserstoff bei Temperaturen weit unterhalb der Umgebungstemperatur in absorbierendem bzw. nanostrukturiertem Material einzulagern. In EP 1 130 06 A1 und WO 00/01980 wer- den Lösung aufgezeigt, bei denen Wasserstoff ebenfalls bei tiefen Temperaturen eingelagert, jedoch zusätzlich mittels eines Hilfsstoffes im speichernden Material quasi "eingekapselt" wird. In DE 103 92 240 T5 wird hingegen eine Lösung vorgestellt, bei der Wasserstoff unter erhöhtem Druck in einem absorbierenden Material gespeichert wird.For example, DE 25 36 993 C2 and US Pat. No. 6,672,077 B1 propose storing hydrogen at temperatures far below the ambient temperature in absorbent or nanostructured material. In EP 1 130 06 A1 and WO 00/01980 solutions are shown, in which hydrogen is also stored at low temperatures, but in addition by means of an adjuvant in the storing material quasi "encapsulated" is. In DE 103 92 240 T5, however, a solution is presented in which hydrogen is stored under increased pressure in an absorbent material.
In WO 97/26082 A1 und WO 01/13032 A1 werden Wasserstoffspeicher gezeigt, die eine spezielle Schicht- bzw. Folienstruktur besitzen, und in US 2004/0250552 A1 wird der Einsatz eines flüssigen Speichermaterials vorgeschlagen. Schließlich wird in DE 10 2005 023 036 A1 ein Verfahren zur Wasserstoffspeiche- rung gezeigt, bei dem Wasserstoff in gasförmiger, gekühlter und komprimierter Form unter Hochdruck an einem physikalisch adsorbierenden Material, insbesondere Kohlenstoffpulver, gespeichert wird.WO 97/26082 A1 and WO 01/13032 A1 show hydrogen storage devices which have a special layer or film structure, and US 2004/0250552 A1 proposes the use of a liquid storage material. Finally, DE 10 2005 023 036 A1 shows a method for hydrogen storage in which hydrogen is stored in gaseous, cooled and compressed form under high pressure on a physically adsorbing material, in particular carbon powder.
Mit diesen Lösungen kann zwar eine gewisse Erhöhung der volumetrischen Energiedichten der Wasserstoffspeicher erzielt werden, beim Einsatz von nanostrukturiertem Kohlenstoff bzw. von Kohlenstoffpulver als Speichermaterial tritt jedoch nach wie vor das Problem auf, dass eingelagerter Wasserstoff nur sehr langsam und/oder nicht vollständig aus dem Speicher entnommen werden kann und/oder die maximaleAlthough a certain increase in the volumetric energy densities of the hydrogen storage can be achieved with these solutions, the use of nanostructured carbon or of carbon powder as a storage material is still the problem that stored hydrogen only very slowly and / or not completely from the memory can be taken and / or the maximum
Speicherkapazität stark abnimmt mit der Zahl der Beladezyklen, wohingegen bei den Lösungen, die andere Speichermaterialien einsetzen, nur wesentlich geringere volu- metrische Energiedichten erreicht werden können, als solche von fossilen Brennstoffen.Storage capacity decreases sharply with the number of loading cycles, whereas in the solutions using other storage materials, only much lower volumetric energy densities can be achieved than those of fossil fuels.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Speicherung von technischen Gasen zu finden, das es ermöglicht, die Dichte von unter Druck gelagerten technischen Gasen, insbesondere von Erdgas und Wasserstoff, ohne Drucksteigerung und mit geringem Energieeinsatz signifikant zu erhöhen.The invention has for its object to find a method for storing industrial gases, which makes it possible to increase the density of stored under pressure technical gases, in particular natural gas and hydrogen, without pressure increase and with low energy use significantly.
Diese Aufgabe wird erfindungsgemäß durch die kennzeichnenden Merkmale der Ansprüche 1 und 7 gelöst. Weitere vorteilhafte Ausführungen ergeben sich aus den Ansprüchen 2 bis 6 sowie 8 bis 16.This object is achieved by the characterizing features of claims 1 and 7. Further advantageous embodiments will become apparent from the claims 2 to 6 and 8 to 16.
Nach Maßgabe der Erfindung wird das technische Gas in einem Speicherbehälter, der abhängig vom darin gelagerten Gas Drücken bis 1200 bar standhalten muss, oberhalb seines kritischen Druckes und oberhalb der kritischen Temperatur, bzw. im kompressiblen Phasenbereich unterhalb der kritischen Temperatur gelagert.According to the invention, the technical gas is stored in a storage container which, depending on the gas stored therein, has to withstand pressures of up to 1200 bar, above its critical pressure and above the critical temperature, or in the compressible phase range below the critical temperature.
Die Lagerung oberhalb der kritischen Temperatur wird dabei vorzugsweise dann angewendet, wenn die Lagerung bei Drücken erfolgt, welche wesentlich größer als der kritische Druck sind. Bei Drücken, die nur unwesentlich über dem kritischen Druck liegen, wird vorzugsweise die Lagerung im kompressiblen Phasenbereich angewandt. Materialien, die geeignet sind das technische Gas in merklicher Menge, d.h. in größerer Menge als bei der bei praktisch allen Materialien auftretenden Oberflächenabsorption bzw. -absorption, zu ad- oder zu absorbieren, kommen dabei nicht zum Einsatz.The storage above the critical temperature is preferably used when the storage is carried out at pressures which are substantially greater than the critical pressure. At pressures that are only slightly above the critical pressure, the storage is preferably applied in the compressible phase range. Materials which are suitable for adsorption or absorption of the technical gas in appreciable amount, ie in a larger amount than in the case of virtually all materials occurring surface absorption or absorption, are not used.
In der untenstehenden Tabelle sind exemplarisch die kritischen Temperaturen und kritischen Drücke von Gasen aufgeführt, die vorteilhaft mit dem erfindungsgemäßen Verfahren gespeichert werden können.In the table below, the critical temperatures and critical pressures of gases are listed by way of example, which can advantageously be stored with the method according to the invention.
Die Eigenschaften von Erdgas, das zu circa 95 % aus Methan besteht, entsprechen weitgehend denen des reinen Methans.The properties of natural gas, which is about 95% methane, are very similar to those of pure methane.
Bei technischen Gasen, die bei der Lagertemperatur und möglichst auch bei weit darüber liegenden Temperaturen einen positiven Joule-Thomson-Koeffizienten aufweisen, kann das Gas vorteilhafterweise bei der Entnahme aus dem Speicherbehälter gedrosselt entspannt werden, wobei das im Behälter verbleibende Gas mittels des austretenden Gases, dessen Temperatur während der Entspannung aufgrund des Joule-Thomson-Effekts stark absinkt, gekühlt wird.In the case of industrial gases, which have a positive Joule-Thomson coefficient at the storage temperature and, if possible, also at far higher temperatures, the gas can advantageously be throttled when it is withdrawn from the storage container, the gas remaining in the container being removed by means of the exiting gas, whose temperature drops sharply during the relaxation due to the Joule-Thomson effect, is cooled.
Es ist vorgesehen, Erdgas bei einer Temperatur oberhalb von 190 K und einem Druck oberhalb von 46 bar zu lagern. Weiterhin ist die Lagerung von Erdgas im kom- pressiblen Phasenbereich bei einer Temperatur unterhalb von 190 K im gleichen Druckbereich vorteilhaft möglich. Weiterhin vorteilhaft ist auch die Lagerung des Erdgases bei einem Druck oberhalb des kritischen Drucks bei 46 bar bis ca. 200 bar und einer Temperatur von 180 bis 190 K, d.h. unterhalb der kritischen Temperatur. Die Dichte des Erdgases beträgt dann ca. 330 kg/m3, d.h., gegenüber der Speicherung bei Umgebungstemperatur (unter 200 bar), bei der die Dichte des gespeicherten Erdgases lediglich 155 kg/m3 beträgt, wird die Speicherdichte auf etwa das Doppelte erhöht.It is intended to store natural gas at a temperature above 190 K and a pressure above 46 bar. Furthermore, the storage of natural gas in the compressible phase range at a temperature below 190 K in the same pressure range is advantageously possible. Also advantageous is the storage of natural gas at a pressure above the critical pressure at 46 bar to about 200 bar and a temperature of 180 to 190 K, ie below the critical temperature. The density of the natural gas is then about 330 kg / m 3 , ie, compared to the storage at ambient temperature (below 200 bar), in which the density of the stored natural gas is only 155 kg / m 3 , the storage density is increased to about double ,
Systeme mit einem Maximaldruck von 200 bar sind kostengünstig erhältlich (die gängigen Gasflaschen sowie die daran angeschlossenen Systeme haben üblicherweise einen Maximaldruck von 200 bar) und außerdem sind die Sicherheitsanforderungen geringer als die für mit höheren Drücken arbeitende Systeme. Für das Abkühlen des Erdgases wird wesentlich weniger Energie benötigt als bei der Speicherung des Erdgases als LNG, da erstens das Erdgas weit weniger abgekühlt und zweitens auch keine Kondensationsenergie abgeführt werden muss.Systems with a maximum pressure of 200 bar are available at low cost (common gas cylinders and their connected systems usually have a maximum pressure of 200 bar) and safety requirements are lower than those for higher pressure systems. For the cooling of natural gas much less energy is needed than for the storage of natural gas as LNG, because firstly, the natural gas cooled much less and secondly no condensation energy must be dissipated.
Die Lagerung von Wasserstoff erfolgt bei einer Temperatur oberhalb von 33 K und bei einem Druck oberhalb von 13 bar. Auch hier ist eine Lagerung im kompressiblen Phasenbereich bei einer Temperatur unterhalb von 33 K im gleichen Druckbereich möglich.The storage of hydrogen takes place at a temperature above 33 K and at a pressure above 13 bar. Again, a storage in the compressible phase range at a temperature below 33 K in the same pressure range is possible.
Bevorzugt wird der Wasserstoff bei einer Temperatur von 33 bis 100 K und oberhalb des kritischen Drucks bei 13 bis 1200 bar gespeichert. Exemplarisch kann bei 850 bar und einer Temperatur von 33 K eine Wasserstoffdichte von 100 kg/m3 erreicht werden. Bei einer Erwärmung auf 70 K sinkt die Speicherdichte bei gleichem Druck um lediglich 12 %, d.h. auf 88 kg/m3, ab. Somit sind Speicherdichten, die über der des Flüssigwasserstoffs und ungefähr bei dem dreifachen des Hochdruckwasserstoffs bei Umgebungstemperatur liegen, erreichbar.Preferably, the hydrogen is stored at a temperature of 33 to 100 K and above the critical pressure at 13 to 1200 bar. By way of example, at 850 bar and a temperature of 33 K, a hydrogen density of 100 kg / m 3 can be achieved. When heated to 70 K, the storage density at the same pressure drops by only 12%, ie to 88 kg / m 3 . Thus, storage densities above that of the liquid hydrogen and about three times the high pressure hydrogen at ambient temperature are achievable.
Da dieses Speicherprinzip von Wasserstoff Erwärmungen von 33 K auf 100 K ohne wesentliche Veränderungen des Speicherdrucks toleriert, ist es, hochwertige Speicherbehälter vorausgesetzt, bei regelmäßiger Wasserstoffentnahme durch Ausnutzung des Joule-Thomson-Effekts möglich, den Speicher für Wasserstoff ohne zusätzliche kryogene Kühlung zu betreiben. Weiterhin ist es aber auch vorgesehen, das technische Gas bei längeren Zeiten ohne Entnahme mittels eines Kryokühlers geringfügig, d.h. abhängig von der Temperaturregelung bis 5 K, unterhalb der maximal zulässigen Speichertemperatur zu halten.Since this storage principle of hydrogen tolerates heatings from 33 K to 100 K without significant changes in storage pressure, it is possible for high-quality storage tanks with regular hydrogen extraction by utilizing the Joule-Thomson effect to operate the storage for hydrogen without additional cryogenic cooling. Furthermore, it is also intended to keep the technical gas at longer times without removal by means of a cryocooler slightly, ie, depending on the temperature control to 5 K, below the maximum allowable storage temperature.
Der Speicher für das technische Gas besteht aus einem thermisch isolierten, druckdichten Behälter, der über eine verschließbare Öffnung zur Entnahme und Befüllung verfügt. Erfindungsgemäß ist der Behälter mit einer Kältemaschine ausgestattet, die derart am Behälter angebracht ist, dass sie die von ihr erzeugte Kälte an das Erdgas im Behälter abgeben kann, und/oder mit einer dem gedrosselten Entspannen des austretenden technischen Glases dienenden Entspannungseinrichtung ausgestattet, die in thermischem Kontakt mit dem im Speicherbehälter gelagerten technischen Gas steht.The storage tank for the technical gas consists of a thermally insulated, pressure-tight container with a closable opening for removal and filling. According to the invention, the container is equipped with a refrigerating machine, which is mounted on the container so that it can deliver the cold produced by it to the natural gas in the container, and / or equipped with the throttled relaxing the leaking technical glass relaxation device, which in thermal Contact with the stored in the storage tank technical gas is.
Als Kältemaschinen sind je nach Temperaturbereich insbesondere Stirlingkühler, Kompressionskältemaschinen oder Gemisch-Joule-Thomson-Kühler einsetzbar. Um eine Übertragung der von den Kältemaschinen erzeugten Kälte an das technischeDepending on the temperature range, in particular Stirling coolers, compression refrigerating machines or mixture Joule-Thomson coolers can be used as refrigerating machines. In order to transfer the cold generated by the refrigerators to the technical
Gas im Tank zu ermöglichen, muss das Kaltteil/der Kühlfinger der Kältemaschine mit dem technischen Gas im Innenraum des Behälters in thermischem Kontakt stehen.To allow gas in the tank, the cold part / the cold finger of the chiller must be in thermal contact with the technical gas in the interior of the container.
Da sich im Behälter nur eine Phase ausbildet, ist es unerheblich, an welcher Stelle das Kaltteil/der Kühlfinger in den Behälter geführt ist.Since only one phase forms in the container, it is irrelevant at which point the cold part / the cold finger is guided into the container.
In einer vorteilhaften Ausführungsform besteht die Grundstruktur des Speicherbehäl- ter's aus dünnwandigen Rohren (0,1 bis 30 mm Wandstärke) mit kleinen Innendurchmessern (0,1 bis 100 mm), die thermisch miteinander und ggf. mit weiteren Strukturelementen des Speichers verbunden sind. Durch die dünnen Wände der Rohre wird eine gute thermische Anbindung des in den Rohrbündeln gespeicherten technischen Gases an die als Wärmespeicher dienenden Rohre und Strukturelemente erreicht. Die kleinen Innendurchmesser der Rohre ermöglichen es, trotz der vergleichsweise geringen Wandstärken, die erforderlichen Speicherdrücke bis 1200 bar zu realisieren.In an advantageous embodiment, the basic structure of the Speicherbehäl- ter 's thin-walled tubes (0.1 to 30 mm wall thickness) with small inner diameters (0.1 to 100 mm), which are thermally connected to each other and possibly with other structural elements of the memory , Due to the thin walls of the tubes, a good thermal connection of the technical gas stored in the tube bundles to the tubes and structural elements serving as heat storage is achieved. The small inner diameters of the tubes make it possible, despite the comparatively low wall thicknesses, to achieve the required storage pressures of up to 1200 bar.
Die Entspannungseinrichtung, die zur gedrosselten Entspannung der technischen Gase während ihrer Entnahme dient, besteht entweder aus mindestens einem Kapil- larrohr oder sie ist als mindestens ein poröses Element ausgeführt, das die mindestens eine Austrittsöffnung für das technische Gas (z.B. Wasserstoff) bedeckt.The expansion device, which serves to reduce the release of technical gases during removal, consists either of at least one capillary larrohr or it is designed as at least one porous element which covers the at least one outlet opening for the technical gas (eg hydrogen).
Ein besonders guter Wärmeübertrag zwischen dem austretenden und dem im Spei- eher verbleibenden technischen Gas wird mit einer Ausführungsform erreicht, bei der die Grundstruktur des Speicherbehälters aus dünnwandigen Rohrbündeln besteht , wobei die Kapillarrohre in die dünnwandigen Rohrbündel integriert sind.A particularly good heat transfer between the exiting and in the Spei- rather remaining technical gas is achieved with an embodiment in which the basic structure of the storage container consists of thin-walled tube bundles, wherein the capillary tubes are integrated into the thin-walled tube bundles.
Zur weiteren Erhöhung der Wärmekapazität kann der Speicherbehälter zusätzlich mit mindestens einem Latentspeicherelement ausgestattet sein, wofür auf dem Gibbs- Thomson-Effekt basierende Speicherelemente besonders geeignet sind.To further increase the heat capacity, the storage container may additionally be equipped with at least one latent storage element, for which storage elements based on the Gibbs-Thomson effect are particularly suitable.
Der Speicher kann besonders vorteilhaft in Verbindung mit Erdgas bzw. Wasserstoff als Kraftfahrzeugtank eingesetzt werden.The memory can be used particularly advantageously in conjunction with natural gas or hydrogen as a motor vehicle tank.
Insbesondere für die Speicherung von technischen Gasen mit sehr niedrigen Verdampfungstemperaturen, wie z.B. Wasserstoff oder Helium, ist es vorgesehen, die thermische Isolierung des Speicherbehälters als Multilagen-Vakuum-Superisolation auszuführen, die mit aktiv gekühlten Strahlungsschirmen ausgestattet ist. Zur aktiven Kühlung können die Strahlungsschirme thermisch mit dem Gasauslass verbunden sein, wodurch die fühlbare Wärme des austretenden technischen Gases zur Kühlung der Strahlungsschirme genutzt wird.In particular for the storage of technical gases with very low evaporation temperatures, e.g. Hydrogen or helium, it is intended to carry out the thermal insulation of the storage container as a multilayer vacuum superinsulation, which is equipped with actively cooled radiant screens. For active cooling, the radiation screens can be thermally connected to the gas outlet, whereby the sensible heat of the escaping technical gas is used to cool the radiation shields.
Die Erfindung wird nachfolgend anhand mehrerer Ausführungsbeispiele näher erläu- tert; hierzu zeigen:The invention will be explained in more detail below with reference to several exemplary embodiments; show:
Fig. 1 : einen Speicher, vorzugsweise für über- und transkritisches Erdgas, in schematischer Darstellung;1 shows a memory, preferably for supercritical and transcritical natural gas, in a schematic representation;
Fig. 2: das Diagramm der Temperaturabhängigkeit von Dichte und Heizwert für Erdgas bei unterschiedlichen Drücken;Fig. 2: the diagram of the temperature dependence of density and calorific value for natural gas at different pressures;
Fig. 3: einen Speicher, vorzugsweise für über- und transkritischen Wasserstoff, in schematischer Darstellung; Fig. 4: verschiedene Ausführungsformen der Entspannungseinrichtung.3 shows a memory, preferably for supercritical and transcritical hydrogen, in a schematic representation; 4 shows various embodiments of the expansion device.
Wie aus Fig. 1 ersichtlich, besteht der Speicher für Erdgas aus dem Behälter 1 und der Kältemaschine 2.As can be seen from FIG. 1, the storage for natural gas consists of the container 1 and the refrigerating machine 2.
Der Behälter 1 weist eine mittels eines Ventils 3 verschließbare Öffnung 4 auf, die zur Befüllung mit und zur Entnahme von Erdgas dient. Der Behälter 1 ist mit einer entweder als Feststoff- oder Vakuumisolierung ausgeführten Isolationsschicht 5 ausgestattet, die den Wärmeübertrag von der Umgebung in das überkritsche Erdgas 6 im Speicher minimiert.The container 1 has a closable by means of a valve 3 opening 4, which serves for filling with and for the removal of natural gas. The container 1 is equipped with an insulation layer 5 designed either as a solid or vacuum insulation, which minimizes the heat transfer from the environment into the supercritical natural gas 6 in the reservoir.
Die Kältemaschine 2 hat eine Kühlleistung die zur Kompensation der thermischen Verluste ausreichend ist und ist entweder als Kompressionskälte-Kaskade oder alsThe chiller 2 has a cooling capacity which is sufficient to compensate for the thermal losses and is either as a compression refrigeration cascade or as
Gemisch-Joule-Thomson-Kühler ausgeführt. Das Kaltteil 7 der Kältemaschine 2 steht mit dem Innenraum 8 des Behälters 1 und damit mit dem überkritischen Erdgas 6 im thermischen Kontakt. Dabei spielt es keine Rolle, an welcher Stelle des Behälters 1 die Kältemaschine 2 angeordnet (oben oder unten) ist, da das überkritische Erdgas 6 den Innenraum 8 gleichmäßig ausfüllt (keine flüssige Phase).Mixture Joule-Thomson cooler performed. The cold part 7 of the refrigerator 2 communicates with the interior 8 of the container 1 and thus with the supercritical natural gas 6 in thermal contact. It does not matter at which point of the container 1, the chiller 2 is arranged (up or down), since the supercritical natural gas 6 evenly fills the interior space 8 (no liquid phase).
Wie aus Fig. 2 ersichtlich, erfolgt bei der Speicherung von Erdgas bei einem Druck oberhalb des kritischen Drucks (46 bar) und einer Temperatur von 190 K ein Anstieg der Dichte des gespeicherten überkritischen Erdgases. Infolgedessen kann bei ei- nem Druck von 200 bar und einer Temperatur von 190 K die Dichte von Erdgas gegenüber derjenigen bei Umgebungstemperatur (bei 200 bar) von 155 kg/m3 auf 330 kg/m3, also auf das 2,13 fache gesteigert werden. Die volumetrische Energiedichte steigt im gleichen Verhältnis von 6.25 MJ/I auf 13.3 MJ/I, wodurch sich beim Einsatz des Speichers als Fahrzeugtank bei gleichem Tankvolumen mehr als das Doppelte an Energie speichern und entsprechend die Reichweite des Fahrzeugs erhöhen lässt.As can be seen from FIG. 2, the storage of natural gas at a pressure above the critical pressure (46 bar) and a temperature of 190 K results in an increase in the density of the stored supercritical natural gas. As a result, at a pressure of 200 bar and a temperature of 190 K, the density of natural gas compared to that at ambient temperature (at 200 bar) from 155 kg / m 3 to 330 kg / m 3 , ie increased to 2.13 times become. The volumetric energy density increases in the same ratio from 6.25 MJ / I to 13.3 MJ / I, which saves more than twice as much energy when the tank is used as a vehicle tank with the same tank volume and consequently increases the range of the vehicle.
Der Behälter 11 des Wasserstoffspeichers (Fig. 3) besteht aus zahlreichen, parallel angeordneten Speicherrohren 12, wobei jeweils eine Seite der Rohre 12 mit einer Sammeleinrichtung 13 verbunden ist, die alle Rohre 12 mit der Wasserstoff- Auslassleitung 14 verbindet.The container 11 of the hydrogen storage (Fig. 3) consists of numerous, parallel arranged storage tubes 12, wherein one side of the tubes 12 with a Collecting device 13 is connected, which connects all tubes 12 with the hydrogen outlet 14.
Der aus den Rohrbündeln zusammengesetzte Speicherbehälter 11 ist von einer MuI- tilagen-Vakuum-Superisolation 15 umgeben, die zur weiteren Verbesserung der thermischen Isolierung mit Strahlungsschirmen 16 umgeben ist. Die Strahlungsschirme 16 sind thermisch mit der Auslassleitung 14 für den Wasserstoff verbunden, sodass die Strahlungsschirme 16 über die fühlbare Wärme des austretenden Wasserstoffs aktiv gekühlt werden. Die gesamte Anordnung befindet sich in einem Dewar-Gefäß 17, das eine erste thermische Isolierung gegenüber der vergleichsweise hohen Umgebungstemperatur sicherstellt.The storage container 11 composed of the tube bundles is surrounded by a multilayer vacuum superinsulation 15, which is surrounded by radiation shields 16 for further improvement of the thermal insulation. The radiation screens 16 are thermally connected to the hydrogen outlet line 14 so that the radiation screens 16 are actively cooled by the sensible heat of the exiting hydrogen. The entire assembly is located in a Dewar vessel 17, which ensures a first thermal insulation against the comparatively high ambient temperature.
In Fig. 4 sind von oben nach unten angeordnet mehrere Ausführungsvarianten von Entspannungseinrichtungen 18 dargestellt.In Fig. 4 are arranged from top to bottom, several embodiments of relaxation devices 18.
Bei der ersten Variante sind die Kapillarrohre 19 koaxial im Innern der Speicherrohre 12 angeordnet. Bei der Entnahme von Wasserstoff wird so der im jeweiligen Speicherrohr 12 verbleibende Wasserstoff direkt durch das Kapillarrohr 19 gekühlt.In the first variant, the capillary tubes 19 are arranged coaxially in the interior of the storage tubes 12. When hydrogen is withdrawn, the hydrogen remaining in the respective storage tube 12 is cooled directly through the capillary tube 19.
Bei der zweiten Variante sind die Querschnitte der Speicherrohre 12 mit einem Innendurchmesser von ca. 1 mm so klein gewählt, dass sie gleichzeitig auch die Funktion der Kapillarrohre 19 übernehmen, während bei der dritten Variante die Speicherrohre 12 spiralförmig von den Kapillarrohren 18 umgeben sind.In the second variant, the cross sections of the storage tubes 12 are chosen so small with an inner diameter of about 1 mm that they simultaneously take over the function of the capillary 19, while in the third variant, the storage tubes 12 are spirally surrounded by the capillary tubes 18.
Bei der vierten Variante sind die Austrittsöffnungen der Speicherrohre 12 jeweils mit porösen Stopfen 20, die alternativ zu den Kapillarrohren 19 zur gedrosselten Entspannung des Wasserstoffs dienen, bedeckt. Liste der verwendeten BezugszeichenIn the fourth variant, the outlet openings of the storage tubes 12 are each covered with porous plugs 20, which serve as an alternative to the capillary tubes 19 for the throttled relaxation of the hydrogen. List of reference numbers used
I Speicherbehälter (vorzugsweise für Erdgas) 2 KältemaschineI storage tank (preferably for natural gas) 2 chiller
3 Ventil3 valve
4 Öffnung4 opening
5 Isolation5 isolation
6 trans- oder überkritisches Erdgas 7 Kaltteil der Kältemaschine6 trans- or supercritical natural gas 7 Cold part of the chiller
8 Innenraum des Behälters8 Interior of the container
I 1 Speicherbehälter (vorzugsweise für Wasserstoff) 12 Speicherrohr 13 SammeleinrichtungI 1 storage tank (preferably for hydrogen) 12 storage pipe 13 collecting device
14 Auslassleitung14 outlet pipe
15 Multilagen-Vakuum-Superisolation15 multi-layer vacuum superinsulation
16 Strahlungsschirm16 radiation screen
17 Dewar-Gefäß 18 Entspannungseinrichtung17 Dewar vessel 18 Relaxation device
19 Kapillarrohr19 capillary tube
20 poröses Element / poröser Stopfen 20 porous element / porous plug

Claims

Patentansprüche claims
1. Verfahren zur Speicherung von technischen Gasen in einem thermisch isolier- ten Speicherbehälter, dadurch gekennzeichnet, dass das technische Gas bei einer Temperatur nahe seines kritischen Punkts und oberhalb seines kritischen Drucks bis zu einem Druck von 1200 bar gelagert wird, ohne Einsatz von Materialien, die geeignet sind^das technische Gas zu ad- oder zu absorbieren.1. A method for storing industrial gases in a thermally insulated storage container, characterized in that the technical gas is stored at a temperature near its critical point and above its critical pressure up to a pressure of 1200 bar, without the use of materials, which are suitable ^ ad- or absorb the technical gas.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das technische Gas bei der Entnahme aus dem Speicherbehälter (1 , 10) gedrosselt entspannt wird, wobei das im Behälter (1 , 10) verbleibende technische Gas mittels des austretenden technischen Gases, dessen Temperatur während der Entspan- nung aufgrund des Joule-Thomson-Effekts bei gedrosselter Entspannung absinkt, gekühlt wird.2. The method according to claim 1, characterized in that the technical gas at the removal from the storage container (1, 10) is throttled relaxed, wherein the in the container (1, 10) remaining technical gas by means of the escaping technical gas whose temperature during The relaxation decreases due to the Joule-Thomson effect at reduced relaxation, is cooled.
3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, dass das technische Gas bei längeren Zeiten ohne Entnahme mittels eines Kryokühlers bis 5 K unterhalb der maximal zulässigen Speichertemperatur gehalten wird.3. The method according to claim 1 and 2, characterized in that the technical gas is kept at longer times without removal by means of a cryocooler to 5 K below the maximum allowable storage temperature.
4. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, dass als technisches Gas Wasserstoff verwendet und dieser bei einer Temperatur von 33 bis 100 K und oberhalb des kritischen Drucks bei 13 bis 1200 bar gespeichert wird.4. The method according to claim 1 to 3, characterized in that used as the technical gas hydrogen and this is stored at a temperature of 33 to 100 K and above the critical pressure at 13 to 1200 bar.
5. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, dass als technisches Gas Erdgas verwendet und dieses oberhalb der kritischen Temperatur bei 190 bis 220 K und oberhalb des kritischen Drucks bei 46 bar bis 300 bar gespeichert wird.5. The method of claim 1 to 3, characterized in that used as a technical gas natural gas and this is stored above the critical temperature at 190 to 220 K and above the critical pressure at 46 bar to 300 bar.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass das Erdgas im kompressiblen Flüssigkeitsbereich bei einer Temperatur von 180 bis 190 K und einem Druck oberhalb des kritischen Drucks bei 46 bar bis ca. 200 bar gespeichert wird.6. The method according to claim 5, characterized in that the natural gas in the compressible liquid region at a temperature of 180 to 190 K. and a pressure above the critical pressure at 46 bar to about 200 bar is stored.
7. Speicher für ein technisches Gas, arbeitend nach dem Verfahren nach An- spruch 1, mit einem thermisch isolierten, druckdichten Behälter (1 , 10), der über eine verschließbare Öffnung (4) zur Entnahme und Befüllung verfügt, dadurch gekennzeichnet, dass der Behälter (1, 10) für Innendrücke bis maximal 1200 bar ausgelegt ist und mit einer Kältemaschine (2), die derart am Behälter (1 , 10) angebracht ist, dass sie die von ihr erzeugte Kälte an das Erd- gas im Behälter (1 , 10) abgeben kann, und/oder mit einer dem gedrosselten7. A storage tank for a technical gas, working according to the method of claim 1, comprising a thermally insulated, pressure-tight container (1, 10), which has a closable opening (4) for removal and filling, characterized in that the Container (1, 10) for internal pressures to a maximum of 1200 bar is designed and with a chiller (2) which is mounted on the container (1, 10), that it generates the cold generated by it to the natural gas in the container (1 , 10), and / or with a throttled
Entspannen des austretenden technischen Glases dienenden Entspannungseinrichtung (18) ausgestattet ist, die in thermischem Kontakt mit dem im Speicherbehälter (1, 10) gelagerten technischen Gas steht.Relaxing the escaping technical glass serving relaxation device (18) is provided, which is in thermal contact with the stored in the storage container (1, 10) technical gas.
8. Speicher nach Anspruch 7, dadurch gekennzeichnet, dass als Kältemaschine8. A storage according to claim 7, characterized in that as a refrigerator
(2) eine Kompressionskälte-Kaskade eingesetzt ist.(2) a compression refrigeration cascade is used.
9. Speicher nach Anspruch 7, dadurch gekennzeichnet, dass als Kältemaschine (2) ein Gemisch-Joule-Thomson-Kühler eingesetzt ist.9. A storage according to claim 7, characterized in that a mixture Joule Thomson cooler is used as the refrigerator (2).
10. Speicher nach Anspruch 7, dadurch gekennzeichnet, dass als Kältemaschine (2) ein Stirling-Kühler eingesetzt ist.10. A storage according to claim 7, characterized in that a Stirling cooler is used as a chiller (2).
11. Speicher nach Anspruch 7 bis 10, dadurch gekennzeichnet, dass sich der Speicherbehälter (1, 10) aus Rohrbündeln zusammensetzt, wobei die einzelnen Rohre (12) Innendurchmesser von 0,1 bis 100 mm und Wandstärken von 0,1 bis 30 mm aufweisen .11. The storage of claim 7 to 10, characterized in that the storage container (1, 10) composed of tube bundles, wherein the individual tubes (12) have inner diameter of 0.1 to 100 mm and wall thicknesses of 0.1 to 30 mm ,
12. Speicher nach Anspruch 7 bis 11 , dadurch gekennzeichnet, dass der Spei- cherbehälter (1 , 10) mit mindestens einem auf dem Gibbs-Thomson-Effekt basierenden Latentspeicherelement ausgestattet ist. 12. The memory of claim 7 to 11, characterized in that the storage container (1, 10) is equipped with at least one based on the Gibbs-Thomson effect latent storage element.
13. Speicher nach Anspruch 7 bis 12, dadurch gekennzeichnet, dass die thermische Isolierung (5, 15) des Speicherbehälters eine Multilagen-Vakuum- Superisolation ist.13. The memory of claim 7 to 12, characterized in that the thermal insulation (5, 15) of the storage container is a multilayer vacuum super insulation.
5 14. Speicher nach Anspruch 7 bis 13, dadurch gekennzeichnet, dass die thermische Isolierung (5, 15) mit aktiv gekühlten Strahlungsschirmen (16) ausgestattet ist und/oder die Strahlungsschirme (16) zur Kühlung mit Hilfe der fühlbaren Wärme des technischen Gases thermisch mit der Gasauslassleitung (14) verbunden sind.14. Memory according to claim 7 to 13, characterized in that the thermal insulation (5, 15) with actively cooled radiation screens (16) is equipped and / or the radiation screens (16) for cooling by means of the sensible heat of the technical gas thermally are connected to the gas outlet line (14).
00
15. Speicher nach Anspruch 7 bis 14, dadurch gekennzeichnet, dass die Entspannungseinrichtung (18) mindestens ein poröses Element (20) umfasst oder mindestens ein Kapillarrohr (19) aufweist, das entweder in die dünnwandigen Rohre (12) des Speicherbehälters (1 , 10) integriert ist oder bei der gedrossel-15. The storage of claim 7 to 14, characterized in that the expansion device (18) comprises at least one porous element (20) or at least one capillary tube (19) which either in the thin-walled tubes (12) of the storage container (1, 10 ) is integrated or in the throttling
[5 ten Entspannung des technischen Glases die Funktion des Speicherrohrs (12) übernimmt.[5] relaxation of the technical glass, the function of the storage tube (12) takes over.
16. Speicher nach Anspruch 7 bis 15, dadurch gekennzeichnet, dass dieser mit einem Kryokühler ausgestattet ist, der mittels einer Brennstoffzelle mit Elekt-0 roenergie versorgt ist. 16. The memory of claim 7 to 15, characterized in that it is equipped with a cryocooler, which is supplied by means of a fuel cell with Elekt-0 roenergie.
EP10726881A 2009-05-06 2010-05-05 Method for storing industrial gases and corresponding accumulator Withdrawn EP2427687A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102009020138A DE102009020138B3 (en) 2009-05-06 2009-05-06 Method for storing industrial gas in thermally insulated, pressure-tight storage tank of motor vehicle, involves using accumulator to store gas at temperature close to critical point and at pressure higher than given critical pressure
DE102010010108A DE102010010108B4 (en) 2010-02-23 2010-03-04 Method of storing and storing natural gas
PCT/DE2010/000537 WO2010127671A2 (en) 2009-05-06 2010-05-05 Method for storing industrial gases and corresponding accumulator

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DE (1) DE102009020138B3 (en)
WO (1) WO2010127671A2 (en)

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