WO2022096262A1 - Installation et procédé de production d'hydrogène à température cryogénique - Google Patents
Installation et procédé de production d'hydrogène à température cryogénique Download PDFInfo
- Publication number
- WO2022096262A1 WO2022096262A1 PCT/EP2021/079034 EP2021079034W WO2022096262A1 WO 2022096262 A1 WO2022096262 A1 WO 2022096262A1 EP 2021079034 W EP2021079034 W EP 2021079034W WO 2022096262 A1 WO2022096262 A1 WO 2022096262A1
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- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- flow
- oxygen
- circuit
- expansion
- Prior art date
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 179
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 179
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 238000004519 manufacturing process Methods 0.000 title description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000001301 oxygen Substances 0.000 claims abstract description 102
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 102
- 238000001816 cooling Methods 0.000 claims abstract description 81
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 56
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 15
- 238000009434 installation Methods 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 17
- 230000006835 compression Effects 0.000 claims description 13
- 238000007906 compression Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000005057 refrigeration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011176 pooling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0005—Light or noble gases
- F25J1/001—Hydrogen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
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- F25J1/0017—Oxygen
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/005—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
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- F25J1/0065—Helium
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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- F25J1/0067—Hydrogen
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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- F25J1/007—Primary atmospheric gases, mixtures thereof
- F25J1/0072—Nitrogen
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
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- F25J1/0204—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a single flow SCR cycle
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/86—Processes or apparatus using other separation and/or other processing means using electrical phenomena, e.g. Corona discharge, electrolysis or magnetic field
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/42—Nitrogen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/50—Oxygen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/62—Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/08—Cold compressor, i.e. suction of the gas at cryogenic temperature and generally without afterstage-cooler
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/20—Integrated compressor and process expander; Gear box arrangement; Multiple compressors on a common shaft
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/30—Compression of the feed stream
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/14—External refrigeration with work-producing gas expansion loop
- F25J2270/16—External refrigeration with work-producing gas expansion loop with mutliple gas expansion loops of the same refrigerant
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the invention relates to an installation and a method for producing hydrogen at cryogenic temperature.
- the invention relates more particularly to an installation for producing hydrogen at cryogenic temperature, in particular liquefied hydrogen, comprising an electrolyser provided with an oxygen outlet and a hydrogen outlet, a hydrogen circuit to be cooled comprising an upstream end connected to the hydrogen outlet and a downstream end intended to be connected to a unit for collecting cooled and/or liquefied hydrogen, the installation comprising a set of heat exchanger(s) in exchange heat with the hydrogen circuit to be cooled, the installation comprising at least one cooling device in heat exchange with at least a part of the heat exchanger assembly (s), the hydrogen circuit to be cooled comprising a hydrogen flow expansion system and at least one hydrogen compressor upstream of the hydrogen flow expansion system, the hydrogen flow expansion system comprising at least one expansion turbine.
- an installation for producing hydrogen at cryogenic temperature, in particular liquefied hydrogen comprising an electrolyser provided with an oxygen outlet and a hydrogen outlet, a hydrogen circuit to be cooled comprising an upstream end connected to the hydrogen outlet and a downstream end intended to be connected to a unit for
- the two main means of producing hydrogen are: 1 electrolysis and chemical production by vapo-reforming of methane (SMR).
- Electrolysis In the case of electrolysis, the water molecule is split, this produces hydrogen on the one hand and oxygen (02) on the other. Electrolysis technologies are made up of three main families: “DEM” (Proton Exchange Membrane), “Alkaline” and “Solid Oxide”.
- PEM technology allows operation at significant pressures without significantly impacting performance energy of 1 electrolysis.
- electrolyzers of several megawatts of power can produce hydrogen and oxygen at 30 bar abs at room temperature in the state of the art.
- An object of the present invention is to overcome all or part of the drawbacks of the prior art noted above.
- the installation according to the invention is essentially characterized in that said at least one expansion turbine and said at least one compressor are coupled to the same rotating shaft to transfer the work of expanding the flow of pressurized hydrogen to the compressor to compress the flow of hydrogen upstream of the turbine.
- Such an installation makes it possible to effectively enhance the pressure of the hydrogen (in particular at high pressure) produced by an electrolyser to pre-cool or cool a flow of hydrogen to a cryogenic temperature.
- This solution makes it possible to reduce the investment expenditure of such an installation, in particular by eliminating or reducing the cooling down to 80 to 130K of the hydrogen to be liquefied. This makes it possible, for example, to reduce or dispense with a liquid nitrogen pre-cooling system with a nitrogen compression station such as in the prior art.
- embodiments of the invention may comprise one or more of the following characteristics: the assembly comprising the expansion turbine and the compressor coupled to the same rotary shaft is a passive mechanical system, i.e. - say that it does not include a rotary shaft drive motor other than the hydrogen flow or an active mechanical system, i.e.
- the hydrogen circuit comprises several hydrogen compressors arranged in series and/or in parallel upstream of the hydrogen flow expansion system, the hydrogen flow expansion system comprising a plurality of expansion turbines arranged in series and/or in parallel and in that each of the compressors is coupled to a rotating shaft to which is also coupled at least one turbine, the hydrogen circuit to be cooled comprises several compressors arranged in series upstream of the flow expansion system of hydrogen, the hydrogen flow expansion system comprising a plurality of expansion turbines arranged in series and in that the compressors and turbines are coupled in pairs on respective rotating shafts, the turbines are arranged in series in the circuit of hydrogen to be cooled, the hydrogen circuit to be cooled comprising separate respective heat exchange portions between at least a part of the heat exchanger assembly (s) and the flow of hydrogen at the outlet of each turbine, heat exchanger assembly (s) comprises several heat exchangers arranged in series and in heat exchange with the hydrogen circuit to be cooled between the upstream and downstream ends of the hydrogen circuit to be cooled, the installation comprises
- the invention also relates to a method for producing hydrogen at cryogenic temperature, in particular liquefied hydrogen, using an installation according to any one of the preceding characteristics, the method comprising a step of supplying, by the electrolyser, a flow of hydrogen at the upstream end of the hydrogen circuit, for example at a pressure of between 15 and 150 bar, a step of supplying, by one electrolyser, a flow of oxygen to the upstream end of the oxygen circuit, for example at a pressure of between 15 and 150 bar, the method comprising a step of compressing then expanding the flow of hydrogen in which the expansion is carried out by at least one turbine coupled to a shaft, the shaft also being coupled to at least one compressor ensuring the compression of the hydrogen flow before its expansion;
- the invention may also relate to any alternative device or method comprising any combination of the characteristics above or below within the scope of the claims.
- FIG. 1 represents a schematic and partial view illustrating a first embodiment of the structure and operation of an installation according to the invention
- FIG. 2 represents a schematic and partial view illustrating a second embodiment of the structure and operation of an installation according to the invention
- FIG. 3 represents a schematic and partial view illustrating a third embodiment of the structure and operation of an installation according to the invention
- FIG. 4 represents a schematic and partial view illustrating a fourth embodiment of structure and operation of an installation according to the invention.
- the hydrogen production installation 1 represented is a device for producing hydrogen at cryogenic temperature, in particular liquefied hydrogen.
- This installation 1 comprises an electrolyser 2, preferably of the “PEM” (proton exchange membrane) type operating at high pressure, that is to say producing gaseous hydrogen and oxygen at pressures between 15 and 150 bar, for example equal to 30 bar.
- PEM proto exchange membrane
- the electrolyser 2 has an oxygen outlet and a hydrogen outlet.
- the installation 1 comprises a circuit 3 (or pipe(s)) of hydrogen to be cooled having an upstream end connected to the hydrogen outlet of the electrolyser 2 and a downstream end intended to be connected to a member 23 for collecting cooled and/or liquefied hydrogen (storage and/or user application for example).
- a circuit 3 or pipe(s) of hydrogen to be cooled having an upstream end connected to the hydrogen outlet of the electrolyser 2 and a downstream end intended to be connected to a member 23 for collecting cooled and/or liquefied hydrogen (storage and/or user application for example).
- the installation 1 comprises a set of heat exchanger(s) 4, 5, 6, 7, 8 in heat exchange with the hydrogen circuit 3 to be cooled, with the aim of reaching a temperature favorable to the liquefaction of hydrogen.
- At least one separate heat exchanger 25 may be provided at the outlet of one electrolyser 2 to cool the flow of hydrogen (for example by heat exchange with a coolant such as water or air for example ) to bring it back to a temperature close to room temperature.
- a coolant such as water or air for example
- the electrochemical reaction for the production of hydrogen by electrolysis generally leads to a temperature rise of a few tens of degrees.
- the installation 1 further comprises at least one device 9, 10 for cooling in heat exchange with at least part of the heat exchanger assembly(s) 4, 5, 6, 7, 8.
- the installation 1 may include an oxygen circuit 190 (at least one pipe) comprising an upstream end connected to the oxygen outlet of one electrolyzer 2 and a downstream end.
- the downstream end can be connected for example to a device 27 for collecting and/or using oxygen.
- This collection device may include, for example: an oxygen liquefaction system, an oxygen (pre)cooling system, an oxygen compression and conditioning system in cylinders or pressurized storage , a combustion system, a venting system, etc.
- the hydrogen circuit 3 to be cooled comprises a hydrogen flow expansion system 18 and at least one hydrogen compressor 19 upstream of the hydrogen flow expansion system 18.
- all (the entirety) of the hydrogen stream to be cooled/liquefied is expanded in the turbine expansion system(s) 18. That is to say, the entire stream to be cooled/liquefied is expanded in the turbine or turbines 18 and this expanded flow is cooled by the cooling device in the exchanger assembly (s) to be liquefied, for example.
- the hydrogen flow expansion system 18 comprises at least one hydrogen flow expansion turbine 18 and said expansion turbine 18 and said compressor 19 are coupled to the same rotary shaft 20 to transfer hydrogen flow expansion work. pressurized hydrogen to the compressor 19 to compress the flow of hydrogen upstream of the turbine 18.
- the expansion turbine 18 and compressor 19 assembly coupled to the same rotating shaft 20 is a preferably passive mechanical system, that is to say that is, it does not include a motor driving the rotary shaft 20 other than the flow of hydrogen.
- the hydrogen circuit 3 preferably comprises several hydrogen compressors 19 arranged in series upstream of the system 18 for expanding the flow of hydrogen.
- the hydrogen flow expansion system preferably comprises as many expansion turbines 18 arranged in series, each of the compressors 19 being coupled to a rotating shaft 20 to which is also coupled at least one turbine 18.
- the compressors 19 and turbines are associated in pairs on distinct respective rotary shafts 20 (for example first compressor 19 upstream coupled with first turbine 20 upstream, etc.).
- the expanded hydrogen flow may optionally pass through separate heat exchangers respectively from upstream to downstream of the first group of heat exchanger(s) 4, 5, 6, 7, to ensure pre-cooling of the hydrogen.
- expansion stages 18 make it possible to enhance the pressure of the hydrogen flow (with cooling (s) intermediate (s) or not). This makes it possible to replace or supplement the pre-cooling described above.
- This cold provided without energy consumption makes it possible to reduce the work required to cool the hydrogen down to its target temperature (for example via a second cooling device 10 as described in more detail below).
- this mode of expansion and recovery of the pressure of the hydrogen flow is not limited to this example.
- the expansion of hydrogen from ambient temperature to a determined pre-cooling temperature could be carried out in several radial expansion stages or else in a single expansion stage, for example via a volumetric expansion valve, in particular to reduce the costs.
- This pre-cooling of the hydrogen can be completed downstream of the circuit 3 by a second cooling device 10 in heat exchange with the circuit 3 of hydrogen to be cooled.
- the aforementioned first cooling device 9 expansion of the hydrogen with precompression
- the second cooling device 10 can itself be placed in heat exchange with a second group of heat exchangers 8 downstream (symbolized here by a single heat exchanger but several heat exchangers in series and/or in parallel can be considered).
- the second cooling device 10 After this pre-cooling of the hydrogen circuit 3 to a temperature of 80 to 100K for example, the second cooling device 10 provides additional cooling of the hydrogen, for example to a temperature of the order of 20K for example, in order to liquefy it.
- the second cooling device 10 may comprise a refrigerator with a refrigeration cycle of a cycle gas (comprising for example hydrogen or helium, or neon or an optimized combination of the latter three) for improve the efficiency of the device 10 for the final cooling of the hydrogen.
- this refrigerator of the second cooling device 10 may comprise, arranged in series in a cycle circuit: a mechanism 15 for compressing the second cycle gas (one or more compressors, a member 24 for cooling the second cycle gas (exchanger (s) for example), a mechanism 16 for expanding the second cycle gas (turbine(s) and/or expansion valve(s)) and a member 8 for heating the second expanded cycle gas (heat exchangers and especially heat exchanger(s) in exchange with the hydrogen flow to be cooled) .
- the installation 1 may comprise a third device 17 for cooling in heat exchange at least part of the heat exchangers 4, 5, 6, 7.
- This third cooling device 17 (optional) may comprise a fluid loop of cooling (liquid nitrogen, liquefied natural gas, oxygen or other for example) circulating against the current) which supplies cold to the heat exchanger(s) 4, 5, 6, 7 to also ensure part of the pre- hydrogen cooling.
- the pre-cooling carried out via the expansion of hydrogen as described above can in particular make it possible to reduce (in particular halve) the consumption of such a cooling fluid (liquid nitrogen type or with a gas mixing cycle for example ) .
- the oxygen circuit 190 may also optionally comprise a system 13 for expanding the oxygen flow and at least one heat exchange between the expanded oxygen flow (and therefore cooled by the expansion) and the circuit 3 hydrogen to be cooled.
- This heat exchange can in particular be used to pre-cool the hydrogen in its refrigeration and/or liquefaction process.
- the oxygen circuit 190 may comprise at least one oxygen compressor 12 arranged upstream of the system 13 for expanding the oxygen flow.
- the oxygen flow expansion system 13 comprises at least one expansion turbine 13 .
- Said oxygen expansion turbine 13 and said oxygen upstream compressor 12 are coupled to the same rotary shaft 14 to transfer the work of expanding the oxygen flow under pressure to the compressor 12 to compress the oxygen flow by upstream of the expansion turbine 13.
- the assembly comprising the expansion turbine 13 and the compressor 12 coupled to the same rotary shaft 14 is preferably a passive mechanical system, that is to say it does not include a shaft drive motor. 14 rotary other than oxygen flow.
- the expansion turbine 13 is mechanically braked by the compressor 12 coupled to the same shaft 14.
- this is not limiting, it could thus be envisaged to provide a system with a motor whose shaft and coupled to the turbine (s) and compressor (s) (to improve the efficiency of the installation if appropriate).
- this transfer of work from the flow of oxygen achieves a "supercharging" ("turbo boosting”) which therefore consists in integrating one or more cryogenic expansion turbines 13 for which the working fluid is oxygen previously produced by one electrolyser 2.
- the braking system of these turbines is one or more compressors 12 coupled on the same shaft 14. This makes it possible to inject the work of expansion of this gas flow as a flow booster upstream at ambient temperature .
- the integration of the expanded oxygen flow in the battery of heat exchangers 4, 5, 6, 7 of the refrigeration/hydrogen liquefaction system makes it possible in particular to reduce its volume. Costs are also reduced by pooling the heat exchange lines in a single piece of equipment.
- a typically inert intermediate coolant, helium, nitrogen, argon for example, so as not to risk bringing hydrogen and oxygen into contact in the same equipment.
- the hydrogen is cooled down to a target temperature of around 20K for example.
- the hydrogen flow can be pre-cooled between the temperature at the outlet of one electrolyser to a temperature between 220 and 90K and for example of the order of 100K.
- the oxygen Before expansion (downstream of the compressors 12) the oxygen can for example be brought to a pressure of between 15 and 150 and to a temperature close to ambient temperature, thanks to inter-stage compression (then terminal) cooling exchangers which have a cold source of the industrial water type. All or part of this pre-cooling can be carried out via expanded oxygen as described above.
- the inventors have determined in particular that this enhancement of the pressure of oxygen and/or hydrogen with overpressure makes it possible to save approximately 45% of the consumption of liquid nitrogen (saving of electrical energy consumed to produce liquid nitrogen ) for an installation producing 25 tons of hydrogen per day to be cooled from 300K to 85K.
- the oxygen circuit 190 may comprise several oxygen compressors 12 arranged in series upstream of the system 13 for expanding the oxygen flow.
- the oxygen flow expansion system comprises a plurality of expansion turbines 13 and each of the compressors 12 is coupled to a rotating shaft 14 to which at least one turbine 13 is also coupled.
- all or part of these elements could be integrated into a (for example single) turbomachine having n turbines and n compressors mounted on either side of the same shaft.
- the oxygen circuit 190 comprises as many compressors 12 arranged in series upstream as expansion turbines 13 arranged in series downstream, the compressors and turbines 13 are coupled in pairs on rotating shafts 14 respective.
- the first turbine (upstream) is coupled with the first compressor (upstream), the second turbine with the second compressor etc...
- the invention is not limited to this configuration comprising only “turboboosters”, it is possible to provide “turboboosters” of this type and, in addition, one or more conventional turbines (idem for the system of compression/expansion of the aforementioned hydrogen flow).
- an oxygen cooling system 21 is provided at the outlet of at least part of the compressors 12.
- a cooler cooling exchanger in exchange with a fluid such as air or water
- a fluid such as air or water
- the set of heat exchanger(s) 4, 5, 6, 7, 8 thus preferably comprises several heat exchangers arranged in series and in heat exchange with the circuit 3 of hydrogen to be cooled between the ends upstream and downstream of the hydrogen circuit 3 to be cooled.
- the oxygen flow passes through the heat exchangers 4, 5, 6, 7 respectively in series from upstream to downstream.
- This passage through the exchangers thus forms a cooling or heating of the oxygen flow after each expansion stage (cooling or heating according to the pressure conditions of the oxygen flow and the temperature of the exchanger 4, 5, 6, 7 concerned).
- the [Fig. 2] represents another possible embodiment which differs from that of [Fig. 1] essentially in that it additionally comprises a system for enhancing the pressure of the oxygen flow.
- the same elements are not described again and are designated by the same reference numerals (idem for the following embodiments).
- the compressors 19 of the hydrogen flow are located upstream of the first group of pre-cooling exchangers 4, 5, 6, 7 (for example at ambient temperature) and the turbines 18 in the pre-cooling part (Heat exchange at the outlet of the turbines 18 with these heat exchangers 4, 5, 6, 7 for precooling).
- This arrangement is not limiting.
- the embodiment of [FIG. 3] differs from that of [Fig. 2] essentially in that the compressors 19 of the hydrogen flow are located downstream of the first group of pre-cooling exchangers 4, 5, 6 and upstream of the second group of cooling exchangers 8 (in the part of the circuit 3 where the hydrogen is already pre-ref stiffened). That is to say, the compression of the hydrogen stream is carried out after precooling and before final cooling. this allows to obtain a higher compression rate on a very light H2 molecule (molar mass of approximately 2 g/mol).
- the expansion turbines 18 are interposed in the cooling part (exchange of heat at the outlet of the turbines 18 with these heat exchangers 8 of the second group).
- FIG. 3 illustrates the optional possibility (and which can be applied to other embodiments) of providing a cooling 26 of the flow of oxygen leaving the electrolyser 2 upstream of the first compressor 12.
- the compressors 19 of the hydrogen flow are located upstream of the first group of pre-cooling exchangers 4, 5, 6, 7 and the turbines in the pre-cooling part (heat exchange at the outlet of the turbines 18 with these heat exchangers 4, 5, 6,
- the compression of the hydrogen stream is carried out after pre-cooling and before cooling.
- the expansion turbines 18 are interposed in the cooling part (exchange of heat at the outlet of the turbines 18 with these heat exchangers
- FIG. 4 differs from that of [Fig. 3] essentially in that the compressors 19 of the hydrogen flow are located upstream of the first group of exchangers 4, 5, 6 for pre-cooling. That is to say that the compression of the hydrogen stream is carried out before precooling (at room temperature for example) while the expansion is carried out in the cold cooling part (after pre-cooling).
- the second refrigeration device 10 may comprise one or more turbines 16 in series and/or in parallel.
- the flows upstream and downstream of the compressor(s) 15 can exchange heat against the current in the same heat exchanger 150.
- the flow(s) leaving the turbine(s) can optionally exchange in the exchanger(s) 8 of heat of the second group (representation in dotted lines).
- the turbines are preferably of the radial and centripetal technology type. This allows pooling of expansion technologies throughout the liquefaction installation.
- the compressors are preferably of the centrifugal type.
- the oxygen circuit 190 produces liquefied oxygen downstream which is recovered.
- all or part of the flow of oxygen can pass through heat exchangers separate from the exchangers 4, 5, 6, 7, 8 in exchange with the flow of hydrogen.
- compressors or turbines may not be coupled to a shaft on which is also coupled another wheel of a turbine (or respectively of a compressor). That is to say that all turbines (or compressors) are not necessarily coupled to the same shaft as a compressor and vice versa. Similarly, more than two wheels (compressors and/or turbines) can be coupled to the same shaft.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US18/036,127 US20230408189A1 (en) | 2020-11-09 | 2021-10-20 | Plant and method for producing hydrogen at cryogenic temperature |
JP2023521353A JP2023548753A (ja) | 2020-11-09 | 2021-10-20 | 極低温で水素を製造するためのプラント及び方法 |
EP21798334.5A EP4241028A1 (fr) | 2020-11-09 | 2021-10-20 | Installation et procédé de production d'hydrogène à température cryogénique |
KR1020237017377A KR20230104898A (ko) | 2020-11-09 | 2021-10-20 | 극저온에서 수소를 생성하기 위한 설비 및 방법 |
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FRFR2011491 | 2020-11-09 | ||
FR2011491A FR3116107B1 (fr) | 2020-11-09 | 2020-11-09 | Installation et procédé de production d’hydrogène à température cryogénique |
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WO2022096262A1 true WO2022096262A1 (fr) | 2022-05-12 |
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PCT/EP2021/079034 WO2022096262A1 (fr) | 2020-11-09 | 2021-10-20 | Installation et procédé de production d'hydrogène à température cryogénique |
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US (1) | US20230408189A1 (fr) |
EP (1) | EP4241028A1 (fr) |
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US20220205714A1 (en) * | 2020-12-28 | 2022-06-30 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Method for efficient cold recovery in o2-h2 combustion turbine power generation system |
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2020
- 2020-11-09 FR FR2011491A patent/FR3116107B1/fr active Active
-
2021
- 2021-10-20 WO PCT/EP2021/079034 patent/WO2022096262A1/fr active Application Filing
- 2021-10-20 EP EP21798334.5A patent/EP4241028A1/fr active Pending
- 2021-10-20 JP JP2023521353A patent/JP2023548753A/ja active Pending
- 2021-10-20 KR KR1020237017377A patent/KR20230104898A/ko unknown
- 2021-10-20 US US18/036,127 patent/US20230408189A1/en active Pending
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JP2004210597A (ja) * | 2003-01-06 | 2004-07-29 | Toshiba Corp | 排熱利用水素・酸素システムおよび液体水素の製造方法 |
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Also Published As
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FR3116107B1 (fr) | 2022-12-16 |
FR3116107A1 (fr) | 2022-05-13 |
EP4241028A1 (fr) | 2023-09-13 |
JP2023548753A (ja) | 2023-11-21 |
KR20230104898A (ko) | 2023-07-11 |
US20230408189A1 (en) | 2023-12-21 |
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