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EP4493871B1 - Method and apparatus for cooling hydrogen - Google Patents

Method and apparatus for cooling hydrogen

Info

Publication number
EP4493871B1
EP4493871B1 EP23701519.3A EP23701519A EP4493871B1 EP 4493871 B1 EP4493871 B1 EP 4493871B1 EP 23701519 A EP23701519 A EP 23701519A EP 4493871 B1 EP4493871 B1 EP 4493871B1
Authority
EP
European Patent Office
Prior art keywords
heat exchanger
intermediate fluid
cooled
flow
temperature
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.)
Active
Application number
EP23701519.3A
Other languages
German (de)
French (fr)
Other versions
EP4493871A1 (en
Inventor
Baptiste PAGES
Vanessa TURMEL
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.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP4493871A1 publication Critical patent/EP4493871A1/en
Application granted granted Critical
Publication of EP4493871B1 publication Critical patent/EP4493871B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • F25J1/0027—Oxides of carbon, e.g. CO2
    • 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
    • F25J1/003—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
    • 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
    • F25J1/003—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
    • F25J1/0052—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
    • 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
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/0062—Light or noble gases, mixtures thereof
    • 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
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/0062—Light or noble gases, mixtures thereof
    • F25J1/0065—Helium
    • 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
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/0062—Light or noble gases, mixtures thereof
    • F25J1/0067—Hydrogen
    • 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
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/007—Primary atmospheric gases, mixtures thereof
    • F25J1/0072—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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/008—Hydrocarbons
    • F25J1/0082—Methane
    • 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
    • F25J1/02—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
    • F25J1/0203—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
    • 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
    • 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
    • F25J1/02—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
    • F25J1/0203—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
    • F25J1/0205—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 dual level SCR refrigeration cascade
    • 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
    • F25J1/02—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
    • F25J1/0221—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 the cold stored in an external cryogenic component in an open refrigeration loop
    • 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
    • F25J1/02—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
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0229—Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock
    • 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
    • F25J1/02—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
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • 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
    • F25J1/02—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
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • F25J1/0236—Heat exchange integration providing refrigeration for different processes treating not the same 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—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
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0244—Operation; Control and regulation; Instrumentation
    • F25J1/0245—Different modes, i.e. 'runs', of operation; Process control
    • 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
    • F25J1/02—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
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0262—Details of the cold heat exchange system
    • F25J1/0264—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams
    • F25J1/0265—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer
    • F25J1/0268—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer using a dedicated refrigeration means
    • 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
    • F25J1/02—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
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0285—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings
    • F25J1/0288—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings using work extraction by mechanical coupling of compression and expansion of the refrigerant, so-called companders
    • 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
    • F25J1/02—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
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0292—Refrigerant compression by cold or cryogenic suction of the refrigerant gas
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop

Definitions

  • the present invention relates to a method and apparatus for cooling hydrogen.
  • the present invention proposes a solution for the first stage of pre-cooling hydrogen using the cooling power of a flow of liquefied natural gas that vaporizes.
  • the process uses a cycle to transfer the heat of vaporization from the liquefied natural gas to the hydrogen which cools, this cycle including a compressor with an inlet temperature preferably below -90°C and possibly an expansion turbine.
  • a hydrogen cooling process is provided. according to claim 1.
  • a hydrogen cooling device is provided. according to claim 13.
  • the apparatus may include a phase separator to separate a fluid from the turbine, the gas flow being the overhead gas and/or the vaporized liquid from the separator.
  • a hydrogen liquefaction apparatus comprising a hydrogen cooling apparatus as described above, as well as means for liquefying the hydrogen cooled in the cooling apparatus.
  • the cold from an LNG terminal located far from the H2 liquefaction unit can be utilized. via an intermediate fluid (to avoid importing/exporting natural gas from the LNG terminal).
  • the LNG vaporization takes place in a single exchanger and the intermediate fluid distributes the cold to the various consumers.
  • a dedicated heat exchanger E1 is used to recover the cooling capacity of liquefied natural gas 1 at -150°C using an intermediate fluid that is cooled by liquid 1 in the exchanger E1.
  • the exchanger E1 can be a brazed plate and fin heat exchanger made of stainless steel or steel.
  • the exchanger E1 can be a shell and tube heat exchanger.
  • Liquid 1 is heated, for example to 15°C and possibly vaporized to cool fluid 5 to a temperature below -50°C, preferably below -120°C. In the example, it is cooled to -140°C.
  • Gas 1 enters the cold end of the exchanger E1 and exits the hot end as fluid 3.
  • fluid 5 is nitrogen. It could, for example, be natural gas or methane.
  • fluid 5 is inert. Fluid 5 is preferably at a pressure between 3 and 70 bar abs if the intermediate fluid is not nitrogen, and between 3 and 25 bar if the intermediate fluid is nitrogen.
  • Nitrogen 13 exits heat exchanger E2 at a temperature below -90°C, for example -120°C, or even between -150°C and -110°C, and is compressed in a compressor C, for example a centrifugal compressor, to approximately 20 bar.
  • the nitrogen at 20 bar is then optionally divided into two parts 15 and 17, part 17 not necessarily being present.
  • Part 17 can be partially cooled in heat exchanger E1 and then sent to a cooling element 31.
  • the heated part 19 is sent to the hot end of heat exchanger E1.
  • the portion 15, 21 is sent at 20°C to the hot end of the heat exchanger E1 and cools there to -140°C, forming a gas 5 which is sent to the heat exchanger E2 at a temperature of -140°C, therefore colder than the temperature at which the gas 13 is drawn from the heat exchanger E2.
  • the gas 5 heats up in the heat exchanger E2 to 20°C and is then cooled against the LNG in the heat exchanger E1.
  • the gas cooled to -140°C is sent to cool, in this example first by passing through the heat exchanger E2 and then by expansion in a turbine T having an inlet temperature below -100°C, for example -120°C.
  • the expanded fluid (7 to 1.5 bar) in turbine T is two-phase and is sent to a phase separator where it forms a liquid (9) and a gas (11).
  • the liquid is vaporized in a heat exchanger (E3) and rejoins the gas (11) to be heated. in the exchanger E2 constituting the flow 13 to be sent to the cold compressor C.
  • the flow 13 can consist of the vaporized liquid 9 and/or the gas 11.
  • nitrogen or another fluid for example helium or a mixed refrigerant, circulates in a closed cycle, taking cooling from the LNG.
  • the hydrogen-25 is then cooled and liquefied in another heat exchanger using a known method.
  • a cycle of hydrogen, helium, or mixed refrigerants, possibly including noble gases, provides the necessary cooling capacity.
  • LNG provides at least a portion of the cooling required for pre-cooling gaseous hydrogen to -190°C.
  • This fraction can be at least 50%, 75%, or 99% of the cooling required for cooling gaseous hydrogen to -190°C.
  • LNG can even provide all the necessary cooling except for that supplied by the T turbine.
  • the LNG can be vaporized in a separate vaporizer, for example, an "open rack vaporizer," by exchanging heat with water, possibly seawater.
  • This vaporizer consists of a series of vertical tubes through which the LNG circulates and vaporizes, with water flowing over the outside of the tubes.
  • Other types of heat exchangers can obviously be considered.
  • the process can also provide cooling to another element 31, cooled by the cycle.
  • a portion 17 of the gas compressed in compressor C is cooled in the heat exchanger to an intermediate temperature, here -50°C, drawn from the exchanger into a central zone of the heat exchanger, and used to cool element 31 while being itself heated to form gas 19.
  • This gas then rejoins the compressed flow 15 in compressor C to form flow 21, which enters exchanger E1 at 20°C. Since the pressure losses for flow 18 and 19 are limited, a small expansion of flow 15 through a valve will suffice to allow flow 15 and 19 to mix.
  • Element 31 can for example be a liquefier of another gas or a separation apparatus by distillation and/or partial condensation at a temperature below 0°C, for example a carbon dioxide liquefier.
  • a heater for example an electric heater or a heat exchanger heated by hot water, will be used to heat fraction 17 to form flow 19.
  • [ Fig. 2 ] shows a variant of the [ Fig.1 where gas 5 is not cooled in the exchanger E2 but only in the turbine E.
  • gas 5 enters the turbine E at the temperature at which it exits the heat exchanger E1.
  • the gas 13 is compressed in the cold compressor 1 and then in a booster C1 coupled to the turbine E. It is the gas compressed in the booster C1 that is sent to the exchanger E1 to recover the cold from the LNG 1.
  • the natural gas produced can be sent to a hydrocarbon conversion unit for further processing and/or use as fuel.
  • the unit can be of the POX, ATR, or SMR type.
  • the hydrogen to be liquefied can obviously come from this unit.

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Description

La présente invention est relative à un procédé et à un appareil de refroidissement d'hydrogène.The present invention relates to a method and apparatus for cooling hydrogen.

Il est connu d'optimiser un procédé de refroidissement d'hydrogène en récupérant des frigories de la vaporisation de gaz naturel liquéfié (LNG).It is known to optimize a hydrogen cooling process by recovering cooling from the vaporization of liquefied natural gas (LNG).

Il est connu de liquéfier l'hydrogène en deux étapes :

  • Une première étape de prérefroidissement utilisant un cycle d'azote ou un cycle de réfrigérants mixtes suivie de
  • Une deuxième étape de liquéfaction de l'hydrogène refroidi avec un cycle d'hydrogène, d'hélium ou de réfrigérants mixtes y compris des gaz rares.
It is known that hydrogen can be liquefied in two steps:
  • A first pre-cooling stage using a nitrogen cycle or a mixed refrigerant cycle followed by
  • A second stage of liquefaction of the cooled hydrogen with a cycle of hydrogen, helium or mixed refrigerants including rare gases.

La présente invention propose une solution pour la première étape de préfroi-dissement de l'hydrogène en utilisant les frigories d'un débit de gaz naturel liquéfié qui se vaporise.The present invention proposes a solution for the first stage of pre-cooling hydrogen using the cooling power of a flow of liquefied natural gas that vaporizes.

En particulier le procédé utilise un cycle pour transférer la chaleur de vaporisation du gaz naturel liquéfie vers l'hydrogène qui se refroidit, ce cycle comprenant un compresseur à température d'entrée de préférence inférieure à -90°C et éventuellement une turbine de détente.In particular, the process uses a cycle to transfer the heat of vaporization from the liquefied natural gas to the hydrogen which cools, this cycle including a compressor with an inlet temperature preferably below -90°C and possibly an expansion turbine.

« Large scale hydrogen liquefaction in combination with LNG re-gasification" de Kündig et al, 16th World Hydrogen Energy Conference, 2006 décrit un procédé selon le préambule de la revendication 1." Large scale hydrogen liquefaction in combination with LNG re-gasification" by Kündig et al, 16th World Hydrogen Energy Conference, 2006 describes a method according to the preamble of claim 1.

Selon un objet de l'invention, il est prévu un procédé de refroidissement d'hydrogène selon la revendication 1.According to one aspect of the invention, a hydrogen cooling process is provided. according to claim 1.

Selon d'autres aspects facultatifs de l'invention :

  • l'écart de température maximal dans le premier échangeur entre fluides à contre-courant est inférieure à 25°C, de préférence inférieure à 20°C, voire inférieure à 15°C.
  • le fluide intermédiaire contient plus que 50% mol d'azote, de préférence au moins 90% mol d'azote, voire au moins 99% mol d'azote.
  • le gaz naturel liquéfié se vaporise dans le premier échangeur de chaleur et de préférence s'y réchauffe jusqu'à une température supérieure à 0°C.
  • le débit d'hydrogène gazeux refroidi dans le deuxième échangeur de chaleur se condense dans un autre échangeur de chaleur suite à un refroidissement jusqu'à sa température de liquéfaction.
  • du gaz naturel liquéfié vaporisé ou du gaz naturel réchauffé dans le premier échangeur de chaleur est envoyé dans une unité de conversion pour être converti en hydrogène.
  • pour le démarrage le gaz naturel liquéfié se vaporise dans un échangeur de chaleur par échange de chaleur avec de l'eau, par exemple de l'eau de mer.
  • une partie du fluide intermédiaire comprimé est refroidie d'abord dans le premier échangeur de chaleur jusqu'à une température intermédiaire du premier échangeur de chaleur, par exemple entre -40°C et -90°C, de préférence entre -45°C et -70°C, et est envoyée refroidir un échangeur de chaleur auxiliaire et ensuite est envoyée après être réchauffée dans l'échangeur de chaleur auxiliaire se refroidir dans le premier échangeur de chaleur.
  • l'échangeur de chaleur auxiliaire sert à refroidir un débit de gaz contenant du dioxyde de carbone et au moins un autre composant dans un appareil de séparation et/ou de liquéfaction de dioxyde de carbone.
  • on réchauffe la partie du fluide intermédiaire comprimé avec des moyens de réchauffage connectés en parallèle avec l'échangeur de chaleur auxiliaire.
  • une partie du froid généré par du gaz naturel liquéfié soit du gaz naturel vaporisé sert à refroidir de l'eau de refroidissement d'un compresseur du procédé et/ou refroidir le débit d'hydrogène gazeux en amont d'une étape de séchage et/ou du deuxième échangeur de chaleur.
  • le débit d'hydrogène est d'abord refroidi selon un procédé selon une des revendications précédentes et ensuite liquéfié par échange de chaleur avec un cycle de réfrigération.
  • le débit d'hydrogène se refroidit dans le deuxième échangeur de chaleur par échange de chaleur avec un débit de fluide intermédiaire qui se réchauffe en amont de la compression froide et un débit de fluide intermédiaire qui se réchauffe en aval de la compression froide
  • seuls le gaz naturel liquéfié et le fluide intermédiaire échangent de la chaleur dans le premier échangeur de chaleur.
  • seuls le débit d'hydrogène et le fluide intermédiaire échangent de la chaleur dans le deuxième échangeur de chaleur
  • la température d'approche entre le gaz naturel liquéfié et le fluide intermédiaire est inférieure à 7°C.
  • le débit de fluide intermédiaire à une température égale ou supérieure à - 145°C est refroidi en l'introduisant à cette température dans un deuxième échangeur de chaleur où il se refroidit par échange de chaleur indirect et/ou
  • le débit de fluide intermédiaire à une température égale ou supérieure à - 145°C est refroidi par détente dans une turbine, éventuellement entraînant un compresseur du procédé, ou une vanne
  • le débit de fluide intermédiaire à une température égale ou supérieure à - 145°C est refroidi uniquement par détente dans une turbine, éventuellement entraînant un compresseur du procédé, ou une vanne.
According to other optional aspects of the invention:
  • the maximum temperature difference in the first counter-current fluid exchanger is less than 25°C, preferably less than 20°C, or even less than 15°C.
  • the intermediate fluid contains more than 50 mol% nitrogen, preferably at least 90 mol% nitrogen, or even at least 99 mol% nitrogen.
  • The liquefied natural gas vaporizes in the first heat exchanger and preferably heats up there to a temperature above 0°C.
  • The flow of cooled gaseous hydrogen in the second heat exchanger condenses in another heat exchanger following cooling to its liquefaction temperature.
  • Vaporized liquefied natural gas or natural gas heated in the first heat exchanger is sent to a conversion unit to be converted into hydrogen.
  • For startup, liquefied natural gas is vaporized in a heat exchanger by exchanging heat with water, for example seawater.
  • A portion of the compressed intermediate fluid is first cooled in the first heat exchanger to an intermediate temperature of the first heat exchanger, for example between -40°C and -90°C, preferably between -45°C and -70°C, and is sent to cool an auxiliary heat exchanger and then, after being reheated, is sent into The auxiliary heat exchanger cools down in the first heat exchanger.
  • The auxiliary heat exchanger is used to cool a flow of gas containing carbon dioxide and at least one other component in a carbon dioxide separation and/or liquefaction apparatus.
  • The portion of the compressed intermediate fluid is heated with heating means connected in parallel with the auxiliary heat exchanger.
  • Part of the cold generated by liquefied natural gas or vaporized natural gas is used to cool the cooling water of a process compressor and/or to cool the flow of hydrogen gas upstream of a drying stage and/or the second heat exchanger.
  • the hydrogen flow is first cooled according to a process according to one of the preceding claims and then liquefied by heat exchange with a refrigeration cycle.
  • The hydrogen flow is cooled in the second heat exchanger by exchanging heat with an intermediate fluid flow that is heated upstream of the cold compression and an intermediate fluid flow that is heated downstream of the cold compression.
  • only liquefied natural gas and the intermediate fluid exchange heat in the first heat exchanger.
  • Only the hydrogen flow and the intermediate fluid exchange heat in the second heat exchanger
  • the approach temperature between the liquefied natural gas and the intermediate fluid is less than 7°C.
  • The intermediate fluid flow at a temperature equal to or greater than -145°C is cooled by introducing it at this temperature into a second heat exchanger where it is cooled by indirect heat exchange and/or
  • The intermediate fluid flow at a temperature equal to or greater than -145°C is cooled by expansion in a turbine, possibly driving a process compressor, or a valve
  • The intermediate fluid flow at a temperature equal to or greater than -145°C is cooled solely by expansion in a turbine, possibly driving a process compressor, or a valve.

Selon un autre objet de l'invention, il est prévu un appareil de refroidissement d'hydrogène selon la revendication 13.According to another object of the invention, a hydrogen cooling device is provided. according to claim 13.

L'appareil peut comprendre un séparateur de phases pour séparer un fluide provenant de la turbine, le débit gazeux étant le gaz de tête et/ou le liquide vaporisé du séparateur.The apparatus may include a phase separator to separate a fluid from the turbine, the gas flow being the overhead gas and/or the vaporized liquid from the separator.

Selon un autre objet de l'invention, il est prévu un appareil de liquéfaction d'hydrogène comprenant un appareil de refroidissement d'hydrogène tel que décrit ci-dessus ainsi que des moyens pour liquéfier l'hydrogène refroidi dans l'appareil de refroidissement,According to another object of the invention, a hydrogen liquefaction apparatus is provided, comprising a hydrogen cooling apparatus as described above, as well as means for liquefying the hydrogen cooled in the cooling apparatus.

L'utilisation d'un fluide intermédiaire permet de mieux contrôler l'intégration en différenciant les réseaux d'hydrogène et de LNG.The use of an intermediate fluid allows for better control of the integration by differentiating between the hydrogen and LNG networks.

Ainsi le risque de fuite vers le H2 est réduit.Thus, the risk of leakage into H2 is reduced.

Il est possible de modifier les paramètres (pression, débit) du cycle de fluide intermédiaire pour pallier les fluctuations du LNG.It is possible to modify the parameters (pressure, flow rate) of the intermediate fluid cycle to compensate for fluctuations in LNG.

La régulation précise des conditions de sortie du LNG vaporisé / de l'H2 refroidi de façon indépendante est possible.Precise regulation of the outlet conditions of vaporized LNG / cooled H2 independent method is possible.

On peut valoriser du froid d'un terminal LNG éloigné de l'unité de liquéfaction H2 via un fluide intermédiaire (pour éviter d'importer / exporter du gaz naturel depuis le terminal LNG).The cold from an LNG terminal located far from the H2 liquefaction unit can be utilized. via an intermediate fluid (to avoid importing/exporting natural gas from the LNG terminal).

La vaporisation du LNG se fait dans un unique échangeur et le fluide intermédiaire distribue le froid vers les différents consommateurs.The LNG vaporization takes place in a single exchanger and the intermediate fluid distributes the cold to the various consumers.

Le cycle intermédiaire permet de produire un fluide froid plus bas en température que le LNG.

  • [Fig.1] illustre un procédé de liquéfaction selon l'invention.
  • [Fig.2] illustre un autre procédé de liquéfaction selon l'invention.
The intermediate cycle makes it possible to produce a cold fluid at a lower temperature than LNG.
  • [ Fig.1 ] illustrates a liquefaction process according to the invention.
  • [ Fig. 2 ] illustrates another liquefaction process according to the invention.

Un échangeur de chaleur dédié E1 sert à récupérer les frigories du gaz naturel liquéfié 1 à -150°C en utilisant un fluide intermédiaire qui est refroidi par le liquide 1 dans l'échangeur E1. L'échangeur E1 peut être un échangeur brasé à plaques et à ailettes en acier inoxydable ou en acier. Sinon l'échangeur E1 peut être un échangeur à tubes et à calandre.A dedicated heat exchanger E1 is used to recover the cooling capacity of liquefied natural gas 1 at -150°C using an intermediate fluid that is cooled by liquid 1 in the exchanger E1. The exchanger E1 can be a brazed plate and fin heat exchanger made of stainless steel or steel. Alternatively, the exchanger E1 can be a shell and tube heat exchanger.

Le liquide 1 est réchauffé, par exemple jusqu'à 15°C et éventuellement vaporisé pour refroidir le fluide 5 jusqu'à une température inférieure à -50°C, de préférence inférieure à -120°C. Dans l'exemple il est refroidi jusqu'à -140°C.Liquid 1 is heated, for example to 15°C and possibly vaporized to cool fluid 5 to a temperature below -50°C, preferably below -120°C. In the example, it is cooled to -140°C.

Le gaz 1 rentre au bout froid de l'échangeur E1 et sort au bout chaud comme fluide 3.Gas 1 enters the cold end of the exchanger E1 and exits the hot end as fluid 3.

Dans l'exemple, le fluide 5 est de l'azote. Il peut, par exemple, être du gaz naturel ou du méthane. De préférence le fluide 5 est inerte. Le fluide 5 se trouve de préférence à une pression entre 3 et 70 bars abs si le fluide intermédiaire n'est pas l'azote et entre 3 et 25 bars si le fluide intermédiaire est l'azote.In the example, fluid 5 is nitrogen. It could, for example, be natural gas or methane. Preferably, fluid 5 is inert. Fluid 5 is preferably at a pressure between 3 and 70 bar abs if the intermediate fluid is not nitrogen, and between 3 and 25 bar if the intermediate fluid is nitrogen.

L'azote 13 sort de l'échangeur E2 à une température inférieure à -90°C, par exemple à -120°C, voire entre -150°C et -110°C, et est comprimé dans un compresseur C, par exemple un compresseur centrifuge, jusqu'à environ 20 bars. Ensuite l'azote à 20 bars est optionnellement divisé en deux parties 15, 17, la partie 17 n'étant pas nécessairement présente. La partie 17 peut se refroidir partiellement dans l'échangeur E1 puis est envoyé à un élément à refroidir 31. Ainsi la partie 19 réchauffée est envoyée au bout chaud de l'échangeur E1. La partie 15, 21 est envoyée à 20°C au bout chaud de l'échangeur E1 et s'y refroidit jusqu'à -140°C formant un gaz 5 qui est envoyé à l'échangeur E2 à une température de -140°C, donc plus froide que la température à laquelle le gaz 13 est soutiré de l'échangeur E2. Le gaz 5 se réchauffe dans l'échangeur E2 jusqu'à 20°C puis est refroidi contre le LNG dans l'échangeur E1. Le gaz refroidi à -140°C est envoyé se refroidir, dans cet exemple d'abord en passant dans l'échangeur E2 et ensuite par détente dans une turbine T ayant une température d'entrée inférieure à -100°C, par exemple -120°C. Le fluide détendu 7 à 1,5 bars dans la turbine T est di-phasique et est envoyé à un séparateur de phases où il forme un liquide 9 et un gaz 11. Le liquide est vaporisé dans un échangeur de chaleur E3 et rejoint le gaz 11 pour se réchauffer dans l'échangeur E2 constituant le débit 13 à envoyer au compresseur froid C. Le débit 13 peut être constitué par le liquide 9 vaporisé et/ou le gaz 11.Nitrogen 13 exits heat exchanger E2 at a temperature below -90°C, for example -120°C, or even between -150°C and -110°C, and is compressed in a compressor C, for example a centrifugal compressor, to approximately 20 bar. The nitrogen at 20 bar is then optionally divided into two parts 15 and 17, part 17 not necessarily being present. Part 17 can be partially cooled in heat exchanger E1 and then sent to a cooling element 31. Thus, the heated part 19 is sent to the hot end of heat exchanger E1. The portion 15, 21 is sent at 20°C to the hot end of the heat exchanger E1 and cools there to -140°C, forming a gas 5 which is sent to the heat exchanger E2 at a temperature of -140°C, therefore colder than the temperature at which the gas 13 is drawn from the heat exchanger E2. The gas 5 heats up in the heat exchanger E2 to 20°C and is then cooled against the LNG in the heat exchanger E1. The gas cooled to -140°C is sent to cool, in this example first by passing through the heat exchanger E2 and then by expansion in a turbine T having an inlet temperature below -100°C, for example -120°C. The expanded fluid (7 to 1.5 bar) in turbine T is two-phase and is sent to a phase separator where it forms a liquid (9) and a gas (11). The liquid is vaporized in a heat exchanger (E3) and rejoins the gas (11) to be heated. in the exchanger E2 constituting the flow 13 to be sent to the cold compressor C. The flow 13 can consist of the vaporized liquid 9 and/or the gas 11.

Ainsi l'azote, ou un autre fluide par exemple de l'hélium ou un réfrigérant mixte, circule dans un cycle fermé, prenant des frigories du LNG.Thus nitrogen, or another fluid for example helium or a mixed refrigerant, circulates in a closed cycle, taking cooling from the LNG.

L'hydrogène gazeux 23 à température ambiante, par exemple 20°C rentre au bout chaud de l'échangeur de chaleur E2 qu'il parcourt d'un bout à l'autre pour se refroidir jusqu'à -180°C Il est ensuite refroidi dans l'échangeur de chaleur E3 contre le liquide du séparateur de phases pour former de l'hydrogène gazeux 25 à -190°C.Gaseous hydrogen 23 at room temperature, for example 20°C, enters the hot end of the heat exchanger E2, which it travels through from one end to the other to cool down to -180°C. It is then cooled in the heat exchanger E3 against the liquid of the phase separator to form gaseous hydrogen 25 at -190°C.

L'hydrogène 25 est ensuite refroidi et liquéfié dans un autre échangeur de chaleur de manière connue. Un cycle d'hydrogène, d'hélium ou de réfrigérants mixtes éventuellement y compris des gaz rares fournit les frigories nécessaires.The hydrogen-25 is then cooled and liquefied in another heat exchanger using a known method. A cycle of hydrogen, helium, or mixed refrigerants, possibly including noble gases, provides the necessary cooling capacity.

Ainsi le LNG fournit au moins une partie des frigories nécessaires pour le prérefroidissement de l'hydrogène gazeux jusqu'à -190°C. Cette fraction peut être au moins 50%, au moins 75% ou au moins 99% des frigories nécessaires pour le refroidissement de l'hydrogène gazeux jusqu'à -190°C. Le LNG peut même fournir toutes les frigories nécessaires à part celles provenant de la turbine T.Thus, LNG provides at least a portion of the cooling required for pre-cooling gaseous hydrogen to -190°C. This fraction can be at least 50%, 75%, or 99% of the cooling required for cooling gaseous hydrogen to -190°C. LNG can even provide all the necessary cooling except for that supplied by the T turbine.

Pendant le démarrage de l'appareil, le LNG peut être vaporisé dans un vaporiseur indépendant par exemple du type « Open Rack Vaporizer » par échange de chaleur avec de l'eau, éventuellement de l'eau de mer. Ce vaporiseur comprend une série de tubes verticaux dans lequel circule le LNG qui se vaporise, l'eau coulant sur l'extérieur des tubes. D'autre types d'échangeur peuvent évidemment être envisagés.During the device's startup, the LNG can be vaporized in a separate vaporizer, for example, an "open rack vaporizer," by exchanging heat with water, possibly seawater. This vaporizer consists of a series of vertical tubes through which the LNG circulates and vaporizes, with water flowing over the outside of the tubes. Other types of heat exchangers can obviously be considered.

Le procédé peut également fournir du froid à un autre élément 31, refroidi par le cycle. Dans la figure, on voit qu'une partie 17 du gaz comprimé dans le compresseur C est refroidie dans l'échangeur de chaleur jusqu'à une température intermédiaire, ici - 50°C, est soutirée de l'échangeur dans une zone centrale de l'échangeur de chaleur et sert à refroidir l'élément 31 en étant soi-même réchauffée pour former le gaz 19 qui rejoint le débit 15 comprimé dans le compresseur C pour former le débit 21 qui rentre dans l'échangeur E1 à 20°C. Comme les pertes de charge pour le débit 18, 19 sont limitées, une petite détente du débit 15 dans une vanne suffira pour permettre aux débits 15, 19 de se mélanger.The process can also provide cooling to another element 31, cooled by the cycle. In the figure, a portion 17 of the gas compressed in compressor C is cooled in the heat exchanger to an intermediate temperature, here -50°C, drawn from the exchanger into a central zone of the heat exchanger, and used to cool element 31 while being itself heated to form gas 19. This gas then rejoins the compressed flow 15 in compressor C to form flow 21, which enters exchanger E1 at 20°C. Since the pressure losses for flow 18 and 19 are limited, a small expansion of flow 15 through a valve will suffice to allow flow 15 and 19 to mix.

L'élément 31 peut par exemple être un liquéfacteur d'un autre gaz ou un appareil de séparation par distillation et/ou condensation partielle à une température inférieure à 0°C, par exemple un liquéfacteur de dioxyde de carbone.Element 31 can for example be a liquefier of another gas or a separation apparatus by distillation and/or partial condensation at a temperature below 0°C, for example a carbon dioxide liquefier.

Si la fraction 17 est présente mais l'élément 31 ne fonctionne pas, un réchauffeur, par exemple un chauffage électrique ou un échangeur de chaleur réchauffé par de l'eau chaude, servira à chauffer la fraction 17 pour former le débit 19.If fraction 17 is present but element 31 is not working, a heater, for example an electric heater or a heat exchanger heated by hot water, will be used to heat fraction 17 to form flow 19.

[Fig.2] montre une variante de la [Fig.1] où le gaz 5 n'est pas refroidi dans l'échangeur E2 mais seulement dans la turbine E. Ainsi le gaz 5 rentre dans la turbine E à la température à laquelle il sort de l'échangeur de chaleur E1. Le gaz 13 est comprimé dans le compresseur froid 1 et ensuite dans un surpresseur C1 couplé à la turbine E. C'est le gaz comprimé dans le surpresseur C1 qui est envoyé à l'échangeur E1 pour récupérer le froid du LNG 1.[ Fig. 2 ] shows a variant of the [ Fig.1 where gas 5 is not cooled in the exchanger E2 but only in the turbine E. Thus, gas 5 enters the turbine E at the temperature at which it exits the heat exchanger E1. The gas 13 is compressed in the cold compressor 1 and then in a booster C1 coupled to the turbine E. It is the gas compressed in the booster C1 that is sent to the exchanger E1 to recover the cold from the LNG 1.

Le gaz naturel 3 produit peut être envoyé à une unité de conversion d'hydrocarbures pour être converti et/ou comme carburant. L'unité peut être du type POX, ATR ou SMR.The natural gas produced can be sent to a hydrocarbon conversion unit for further processing and/or use as fuel. The unit can be of the POX, ATR, or SMR type.

L'hydrogène à liquéfier peut évidemment provenir de cette unité.The hydrogen to be liquefied can obviously come from this unit.

Claims (15)

  1. A method for cooling hydrogen wherein
    i) Either liquefied natural gas (1) or vaporized natural gas, the vaporized natural gas being at a temperature below -50°C, is reheated by indirect heat exchange in a first heat exchanger (E1) with a flow of intermediate fluid (5) at a pressure between 3 and 70 bars abs which is cooled to a temperature equal to or greater than -145°C,
    ii) The flow of intermediate fluid at a temperature equal to or greater than -145°C is cooled
    a) by introducing it at this temperature into a second heat exchanger (E2) where it is cooled by indirect heat exchange and/or
    b) by expansion in a turbine (E) possibly driving a compressor of the process (C, C1), or a valve,
    iii) a flow of gaseous hydrogen (23) is cooled in the second heat exchanger without condensing,
    iv) a gaseous flow (11, 13) derived from the intermediate fluid cooled in step a) and/or b) is reheated in the second heat exchanger (E2) to a temperature between -150°C and -90°C, is withdrawn from the second heat exchanger at this temperature and compressed in a compressor (C) with an inlet temperature between -150°C and -90°C and at least a part (15, 17) of the compressed intermediate fluid is first cooled in the first heat exchanger and then reheats from a temperature of at most -110°C and
    v) at least a part (15) of the reheated intermediate fluid constitutes the flow of intermediate fluid of step i) the at least one part (15, 17) of the compressed intermediate fluid, first cooled in the first heat exchanger, then reheating from the temperature of at most -110°C to constitute the flow of intermediate fluid of step i), characterized in that the liquefied natural gas or, as the case may be, the vaporized gas is reheated to a temperature above 0°C by indirect heat exchange in the first heat exchanger (E1) with the flow of intermediate fluid (5) at a pressure between 3 and 70 bars abs if the intermediate fluid is not nitrogen and between 3 and 25 bars if the intermediate fluid is nitrogen, and in that the compressed and cooled intermediate fluid in the first heat exchanger is reheated in the second heat exchanger.
  2. The method according to claim 1, wherein the maximum temperature difference between counter-current fluids in the first heat exchanger (E1) is less than 25°C, preferably less than 20°C, or even less than 15°C.
  3. The method according to any one of the preceding claims, wherein the intermediate fluid (5) contains more than 50 mol% nitrogen, preferably at least 90 mol% nitrogen, or even at least 99 mol% nitrogen.
  4. The method according to any one of the preceding claims, wherein the liquefied natural gas (1) vaporizes in the first heat exchanger (E1).
  5. The method according to any one of the preceding claims, wherein the flow of gaseous hydrogen cooled in the second heat exchanger (E2) condenses in another heat exchanger following cooling to its liquefaction temperature.
  6. The method according to any one of the preceding claims, wherein vaporized liquefied natural gas or reheated natural gas in the first heat exchanger (E1) is sent to a conversion unit to be converted into hydrogen.
  7. The method according to any one of the preceding claims, wherein for start-up the liquefied natural gas (1) is vaporized in a heat exchanger by heat exchange with water, for example sea water.
  8. The method according to any one of the preceding claims, wherein a part of the compressed intermediate fluid (17) is first cooled in the first heat exchanger to an intermediate temperature of the first heat exchanger, for example between - 40°C and -90°C, preferably between 45°C and -70°C, and is sent to cool an auxiliary heat exchanger (31) and is then sent after being reheated in the auxiliary heat exchanger to be cooled in the first heat exchanger.
  9. The method according to claim 8, wherein the auxiliary heat exchanger (31) is used to cool a flow of gas containing carbon dioxide and at least one other component in a carbon dioxide separation and/or liquefaction apparatus.
  10. The method according to claim 8 or 9, wherein the part of the compressed intermediate fluid (18) is reheated with reheating means connected in parallel with the auxiliary heat exchanger (31).
  11. The method according to any one of the preceding claims, wherein a part of the cold generated by liquefied natural gas (1) or vaporized natural gas is used to cool the cooling water of a compressor of the process and/or to cool the flow of gaseous hydrogen (23) upstream of a drying step and/or of the second heat exchanger.
  12. A method for liquefying hydrogen, wherein the flow of hydrogen (23) is first cooled according to a method according to one of the preceding claims and then liquefied by heat exchange with a refrigeration cycle.
  13. An apparatus for cooling hydrogen comprising a first heat exchanger (E1), a second heat exchanger (E2), a compressor (C), optionally a turbine (E) or a valve, means for sending either liquefied natural gas (1) or vaporized natural gas, the vaporized natural gas being at a temperature below -50°C, to be reheated to a temperature above 0°C by indirect heat exchange in the first heat exchanger (E1) with a flow of intermediate fluid (5), means for sending the flow of intermediate fluid (5) at a pressure between 3 and 70 bars abs if the intermediate fluid is not nitrogen and between 3 and 25 bars if the intermediate fluid is nitrogen to be cooled in the first heat exchanger to a temperature equal to or greater than -145°C, means for sending the flow of intermediate fluid at a temperature equal to or greater than -145°C to be cooled
    a) by introducing it at this temperature into the second heat exchanger (E2) where it is cooled by indirect heat exchange and/or
    b) by expansion, as the case may be, in the turbine (E) optionally configured to drive a compressor of the apparatus (C, C1), or the valve,
    means for sending a flow of gaseous hydrogen (23) to be cooled in the second heat exchanger without condensing, means for sending a gaseous flow (11, 13) derived from the intermediate fluid cooled in step a) and/or b) to be reheated in the second heat exchanger (E2) to a temperature between -150°C and -90°C, means for withdrawing the gaseous flow from the second heat exchanger at this temperature, means for sending the withdrawn gaseous flow to the compressor (C) with an inlet temperature between -150°C and -90°C to be compressed, means for sending at least a part (15, 17) of the compressed intermediate fluid to be first cooled in the first heat exchanger, means for sending the at least one part of the intermediate fluid cooled in the first heat exchanger to be reheated from a temperature of at most -110°C, and for sending the at least one part (15) of the reheated intermediate fluid to the first heat exchanger (E1) constituting the flow of intermediate fluid to be cooled, the means for sending the at least one part (15, 17) of the intermediate fluid to be reheated are connected so that the at least one part is reheated in the second heat exchanger from the temperature of at most -110°C to constitute the flow of intermediate fluid to be cooled in the first heat exchanger.
  14. The apparatus according to claim 13, comprising the turbine (E) for cooling by expansion the flow of intermediate fluid and a phase separator (S) for separating a fluid (7) coming from the turbine (E), the gaseous flow (13) being the overhead gas (11) and/or the vaporized liquid of the separator.
  15. An apparatus for liquefying hydrogen comprising a hydrogen cooling apparatus according to claim 13 or 14 as well as means for liquefying the cooled hydrogen in the cooling apparatus,
EP23701519.3A 2022-03-18 2023-01-24 Method and apparatus for cooling hydrogen Active EP4493871B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR2202427A FR3133664B1 (en) 2022-03-18 2022-03-18 Hydrogen cooling method and apparatus
FR2204918 2022-05-23
PCT/EP2023/051625 WO2023174601A1 (en) 2022-03-18 2023-01-24 Method and apparatus for cooling hydrogen

Publications (2)

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EP4493871B1 true EP4493871B1 (en) 2025-11-05

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US (1) US20250207851A1 (en)
EP (1) EP4493871B1 (en)
JP (1) JP2025506692A (en)
KR (1) KR20240165971A (en)
CN (1) CN118765364A (en)
FR (1) FR3133664B1 (en)
WO (1) WO2023174601A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3398545A (en) * 1965-03-19 1968-08-27 Conch Int Methane Ltd Hydrogen recovery from a refinery tail gas employing two stage scrubbing
WO2005080892A1 (en) * 2004-02-23 2005-09-01 Shell Internationale Research Maatschappij B.V. Liquefying hydrogen
JP7488093B2 (en) * 2020-04-14 2024-05-21 川崎重工業株式会社 Liquefied hydrogen production facility

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FR3133664B1 (en) 2024-02-02
EP4493871A1 (en) 2025-01-22
FR3133664A1 (en) 2023-09-22
US20250207851A1 (en) 2025-06-26
WO2023174601A1 (en) 2023-09-21
JP2025506692A (en) 2025-03-13
KR20240165971A (en) 2024-11-25
CN118765364A (en) 2024-10-11

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