WO2005080892A1 - Liquefaction d'hydrogene - Google Patents
Liquefaction d'hydrogene Download PDFInfo
- Publication number
- WO2005080892A1 WO2005080892A1 PCT/EP2005/050608 EP2005050608W WO2005080892A1 WO 2005080892 A1 WO2005080892 A1 WO 2005080892A1 EP 2005050608 W EP2005050608 W EP 2005050608W WO 2005080892 A1 WO2005080892 A1 WO 2005080892A1
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- WIPO (PCT)
- Prior art keywords
- stream
- refrigerant
- hydrogen
- pressure
- gaseous
- Prior art date
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 98
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003507 refrigerant Substances 0.000 claims abstract description 135
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 21
- 239000003949 liquefied natural gas Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 230000006835 compression Effects 0.000 claims abstract description 9
- 238000007906 compression Methods 0.000 claims abstract description 9
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 7
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005057 refrigeration 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
- F25J1/006—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
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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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- 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
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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
- F25J1/003—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
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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
- F25J1/02—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
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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
- F25J1/02—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
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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
- F25J1/02—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
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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
- F25J1/02—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
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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
- 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]
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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
- 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
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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
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/30—Compression of the feed stream
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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
- F25J2250/00—Details related to the use of reboiler-condensers
- F25J2250/02—Bath type boiler-condenser using thermo-siphon effect, e.g. with natural or forced circulation or pool boiling, i.e. core-in-kettle heat exchanger
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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
- 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
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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
- 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
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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
- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/12—Particular process parameters like pressure, temperature, ratios
Definitions
- the present invention relates to a method of liquefying hydrogen.
- a method of liquefying a gas such as hydrogen
- the method of liquefying a gas, which is at elevated pressure disclosed in this publication comprises the steps of:
- the intermediate pressure is a pressure between the refrigerant pressure and the high pressure.
- the refrigerant is hydrogen, similar to the gas to be liquefied.
- the known process comprises six heat exchange stages and three expansion stages; thus the ratio of heat exchange stage to expansion stages is two.
- An improvement of this method is described in asserstoff-Energietechnik II, VDI Berichte No. 725, 1989, pages 163-177.
- the hydrogen feed is precooled with evaporating liquid nitrogen, which has a boiling temperature that is higher than the condensation temperature of hydrogen, the gas to be liquefied. Precooling with liquid nitrogen has the advantage that two heat exchange stages and one expansion stage can be omitted.
- WO 90/08295 is disclosed in Figure 2 a method for liquefying hydrogen with a ratio of heat exchange stages to expansion stages of one.
- Helium gas is used as refrigerant.
- hydrogen at 35 bar and 300 K (20) is cooled in three heat exchangers (100A-C) arranged in series, each having at least a first warm side, a second warm side and a cold side, and one further heat exchanger (100D) having a warm side and a cold side.
- Hydrogen at 35 bar (20) is first passed through the first warm sides of the three heat exchangers (100A-C) and then through the warm side of the further heat exchanger (100D) , wherein heat is transferred to helium passing through the cold sides of the heat exchangers at refrigerant pressure (1 bar) , to obtain a cooled gaseous hydrogen stream (24), which is expanded to a low pressure to obtain an expanded fluid hydrogen stream (27), which expanded stream (27) is then liquefied in a final heat exchanger by indirect heat exchange with helium to obtain liquefied hydrogen (28).
- the helium (3), leaving the cold side of the first heat exchanger (100A) is compressed in compressor 108 and recycled via the three heat exchangers (100A-C) and an expander (HOD) to the final heat exchanger.
- a side stream is withdrawn from the compressed helium and expanded to refrigerant pressure in an expander (110A-C) and the expanded helium is added to the refrigerant downstream of the heat exchanger (100A-C) .
- AIAA American Institute of Aeronautics and Astronautics
- the liquefier of Figure 2 of WO 90/08295 or of Figure 1 of the above-mentioned AIAA publication can be improved by using evaporating liquefied natural gas for 1) precooling the hydrogen to be liquefied to a temperature well below ambient temperature and 2) removing the heat of compression from the refrigerant stream.
- evaporating liquefied natural gas for 1) precooling the hydrogen to be liquefied to a temperature well below ambient temperature and 2) removing the heat of compression from the refrigerant stream.
- the resultant pre-cooling has the advantage that at least one heat exchanger/expansion stage can be omitted and that the liquefier can also be used with hydrogen as refrigerant with an acceptable number of expanders.
- the present invention relates to a method of liquefying hydrogen at elevated pressure comprising: (a) precooling the hydrogen by indirect heat exchange with evaporating liquefied natural gas to obtain a precooled gaseous hydrogen stream at elevated pressure; (b) cooling in at least two heat exchangers arranged in series, each having a first warm side, a second warm side and a cold side, the gaseous hydrogen stream at elevated pressure by passing the gaseous hydrogen stream at elevated pressure through the first warm sides of the heat exchangers, wherein the heat is transferred to a refrigerant stream passing through the cold sides of the heat exchangers at refrigerant pressure, to obtain a cooled gaseous hydrogen stream at elevated pressure and a warm refrigerant stream; (c) liquefying the cooled gaseous hydrogen stream at a low pressure by heat exchange with evaporating liquefied refrigerant to obtain a liquefied hydrogen stream and a gaseous refrigerant stream; (d) withdrawing the liquefied hydrogen
- Hydrogen to be liquefied is supplied through conduit 5 to a first heat exchanger 7.
- the hydrogen is precooled by indirect heat exchange with evaporating liquefied natural gas to obtain a precooled gaseous hydrogen stream.
- the liquefied natural gas is supplied through conduit 10.
- the precooled gaseous hydrogen stream is compressed in compressor 12 to an elevated pressure.
- the gaseous hydrogen stream at elevated pressure is supplied through conduit 15 to a second heat exchanger 17, where the heat of compression is removed by indirect heat exchange with evaporating liquefied natural gas to obtain a precooled gaseous hydrogen stream at elevated pressure.
- the liquefied natural gas is supplied through conduit 18. If gaseous hydrogen is supplied through conduit 5 at elevated pressure, then compressor 12 and the heat- exchanger 17 for removal of the heat of compression may be omitted in the method according to the invention.
- the precooled gaseous hydrogen stream at elevated pressure thus-obtained preferably has a temperature below 200K, more preferably has a temperature in the range of from 115 to 150K.
- the evaporating liquefied natural gas used for the precooling is preferably at elevated pressure, i.e.
- the precooled gaseous hydrogen stream at elevated pressure is supplied through connection conduit 19 to a set of at least two heat exchangers for cooling.
- the precooled gaseous hydrogen stream at elevated pressure is supplied through connection conduit 19 to a set of at least two heat exchangers for cooling.
- the heat exchangers 20, 21 and 23 have a first warm side 20a, 21a and 23a, a second warm side 20b, 21b and 23b, and a cold side 20c, 21c and 23c.
- the heat exchangers 21, 22 and 23 each represent a heat exchange stage.
- each heat exchanger 20, 21 and 23 the gaseous hydrogen stream at elevated pressure passes through the first warm sides 20a, 21a and 23a and is cooled by indirect heat exchange with a refrigerant passing through the cold sides 20c, 21c and 23c.
- the connection conduits connecting the warm sides of the heat exchangers are referred to with reference numeral 19.
- the reference numeral 19 is used to refer to all conduits through which the hydrogen to be liquefied passes.
- a cooled gaseous hydrogen stream is obtained from the first warm side 23a of the last heat exchanger 23 of the set of at least two heat exchangers.
- a warm refrigerant stream is removed from the cold side 20c of the first heat exchanger 20 of the set of at least two heat exchangers through conduit 25.
- the next step is liquefying the cooled gaseous hydrogen stream at a low pressure by heat exchange with evaporating liquefied refrigerant to obtain a liquefied hydrogen stream and a gaseous refrigerant stream.
- the cooled gaseous hydrogen stream is expanded to a low pressure in a suitably expansion device, such as a Joule-Thompson valve 27, to obtain an expanded fluid hydrogen stream.
- This expanded fluid hydrogen stream may be partially liquid.
- the expanded fluid hydrogen stream is supplied through connection conduit 19 to the warm side 30a of a final heat exchanger 30.
- the expanded fluid hydrogen stream is further liquefied by indirect heat exchange with evaporating liquefied refrigerant in the cold side 30c of the final heat exchanger 30 to obtain a liquefied hydrogen stream and a gaseous refrigerant stream.
- the liquefied hydrogen stream is withdrawn from the warm side 30a of the final heat exchanger 30 through connection conduit 19 as product stream.
- Reference herein to elevated pressure of the gaseous hydrogen stream is to a pressure above the critical pressure for hydrogen, i.e. above 1.3 MPa.
- the elevated pressure at which the precooled gasous stream is passed through the first warm sides of the heat exchangers is in the range of from 1.3 to 5.0 MPa, more preferably of from 2.0 to 4.0 MPa.
- the low pressure to which the cooled gaseous hydrogen stream is expanded in expansion device 27 is the product pressure.
- the product pressure is in the range of from 0.2 to 0.5 MPa.
- the reference numeral 25 is used to refer to all conduits through which the gaseous refrigerant stream passes.
- the gaseous refrigerant stream is returned via the cold sides 23c, 21c and 20c of the at least two heat exchangers to obtain warm refrigerant.
- the gaseous refrigerant is warmed by the heat removed from the gaseous hydrogen stream at elevated pressure that is being cooled.
- the warm refrigerant steam exiting the cold side 20c of the first heat exchanger 20 is passed to a refrigerant compressor 33.
- the warm refrigerant stream is compressed to obtain a compressed refrigerant stream at high pressure that is supplied to the heat exchangers 20, 21 and 23 through connection conduit 35.
- heat exchanger 37 the heat of compression is removed from the compressed refrigerant stream by indirect heat exchange with evaporating liquefied natural gas.
- the liquefied natural gas is supplied through conduit 38.
- the heat of compression is preferably removed to such extent that the temperature of the after-cooled compressed refrigerant is substantially the same as that of the warm refrigerant stream exiting the cold side 20c of the first heat exchanger 20.
- the after- cooled compressed refrigerant has a temperature which is 1 to 5K above the temperature of the warm refrigerant stream.
- the liquefied natural gas supplied through conduit 38 preferably has the same pressure as the liquefied natural gas used for the precooling of the hydrogen in step (a) .
- the after-cooled compressed refrigerant stream is cooled by passing the stream at high pressure through the second warm sides 20b, 21b and 23b of the at least two heat exchangers 20, 21 and 23 to obtain a cooled refrigerant stream.
- Cooling is effected by indirect heat exchange with the refrigerant passing through the cold sides 20c, 21c and 23c.
- the connection conduits through which the refrigerant stream passes at high pressure are referred to with reference numeral 35.
- the cooled refrigerant stream exiting the last heat exchanger 23 is expanded in a suitably expansion device, such as a Joule-Thompson valve 39, to a pressure at which the refrigerant is liquefied to obtain liquefied refrigerant.
- the liquefied refrigerant is evaporated in the cold side 30c of the final heat exchanger 30 to liquefy the expanded fluid stream passing through the warm side 30a of the final heat exchanger 30.
- the pressure at which the liquefied refrigerant evaporates is the refrigerant pressure.
- the refrigerant pressure is so selected that the temperature at which the refrigerant evaporates is below the temperature at which the hydrogen becomes liquefied at the low pressure.
- the refrigerant pressure is 50 to 90% of the low pressure.
- the reference for the relative terms upstream and downstream is the direction of flow of the gaseous hydrogen stream to be liquefied.
- refrigerant is compressed from refrigerant pressure to high pressure in compressor 37 and expanded from high pressure to refrigerant pressure in each of expanders 45, 46, 47.
- the ratio between high pressure and refrigerant pressure depends inter alia on the number of heat exchanger/expander stages in the process, the refrigerant used, and the temperature of the pre-cooled gaseous hydrogen stream, since the pressure difference over the expander is preferably such that the resultant temperature drop matches the temperature difference over the heat exchanger in the same stage.
- the ratio is preferably in the range of from 5 to 11, for a two-stage process and hydrogen as refrigerant the ratio is preferably in the range of from 10 to 20.
- the method according to the invention has two to four heat exchanger/expander stages in step (b) , more preferably two or three such stages.
- the hydrogen is compressed in compressor 12 to a pressure of 2.5 MPa, and cooled in heat exchanger 17 by indirect heat exchange with evaporating liquefied natural gas to a temperature of 115 K.
- the temperature of the gaseous hydrogen stream downstream the first warm side 20a of the first heat exchanger 20 is 76 K
- downstream the first warm side 21a of the second heat exchanger 21 the temperature of the hydrogen stream is 48 K
- downstream the first warm side 23a of the third heat exchanger 23 the temperature of the hydrogen stream is 31 K.
- the temperature of the expanded hydrogen stream leaving expansion device 27 is 27 K and its pressure is
- the temperature of the liquefied hydrogen stream leaving the final heat exchanger 30 is 26 K and its pressure is 0.4 MPa.
- the temperature of the liquefied hydrogen refrigerant entering into the cold side 30c of the final heat exchanger 30 is 25 K and its pressure is 0.3 MPa.
- the temperature of the hydrogen refrigerant before it enters into the cold side 23c is 28 K, before it enters into the cold side 21c its temperature is 45 K and before it enters into the cold side 20c its temperature is 73 K.
- the mass flow rate of the refrigerant supplied through conduit 25 to the compressor 33 is 7.43 kg/s and its pressure is 0.3 MPa. In the compressor 33, the pressure is increased to 2.0 MPa.
- the mass flow rate of the first side stream, withdrawn through conduit 40 is 1.56 kg/s
- the mass flow rate of the second side stream, withdrawn through conduit 41 is 2.66 kg/s
- the mass flow rate of the third side stream, withdrawn through conduit 42 is 3.07 kg/s.
- the method of the present invention further comprises further cooling the cooled gaseous hydrogen stream in additional heat exchanger 55 before expanding this stream in expansion device 27 by indirect heat exchange with the gaseous refrigerant stream exiting the last heat exchanger 30.
- the refrigerant in conduit 38 is evaporating liquefied natural gas, i.e. the same refrigerant as the one supplied through conduits 10 and 18.
- the liquefied hydrogen stream can pass through one or more o-p conversion reactors that are suitably included in the heat exchangers .
- compression of the refrigerant stream in compressor 33 can be done in more than one stage with inter-stage cooling.
- connection conduit 35 is hydrogen, i.e. the same gas as the gas to be liquefied.
- An advantage of the use of hydrogen as refrigerant is that no contamination of the hydrogen to be liquefied with refrigerant will take place in case of leaks in the refrigerant system.
- Hydrogen liquefaction is suitably carried out at a mass flow rate between 0.1 and 10 kg hydrogen per second (which corresponds to a production of between about 10 and 1 000 ton liquefied hydrogen per day) .
- the method of liquefying hydrogen according to the present invention provides an efficient liquefaction process .
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Abstract
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WO2005080892A1 true WO2005080892A1 (fr) | 2005-09-01 |
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PCT/EP2005/050608 WO2005080892A1 (fr) | 2004-02-23 | 2005-02-11 | Liquefaction d'hydrogene |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007144078A2 (fr) * | 2006-06-12 | 2007-12-21 | Linde Aktiengesellschaft | Procédé de liquéfaction d'hydrogène |
NO331153B1 (no) * | 2007-02-26 | 2011-10-24 | Kanfa Aragon As | Fremgangsmåte og system for nedkjøling av gass. |
WO2012069342A1 (fr) | 2010-11-22 | 2012-05-31 | Shell Internationale Research Maatschappij B.V. | Procédé de production d'hydrogène liquide et d'électricité |
CN107940895A (zh) * | 2017-11-30 | 2018-04-20 | 中国科学院理化技术研究所 | 气体液化系统 |
CN108036582A (zh) * | 2017-12-29 | 2018-05-15 | 上海启元空分技术发展股份有限公司 | 一种生产液氢的方法及其装置 |
WO2023174601A1 (fr) * | 2022-03-18 | 2023-09-21 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil de refroidissement d'hydrogène |
EP4325150A1 (fr) * | 2022-08-16 | 2024-02-21 | L'Air Liquide, société anonyme pour l'Étude et l'Exploitation des procédés Georges Claude | Procédé et appareil de refroidissement d'hydrogène |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007144078A2 (fr) * | 2006-06-12 | 2007-12-21 | Linde Aktiengesellschaft | Procédé de liquéfaction d'hydrogène |
WO2007144078A3 (fr) * | 2006-06-12 | 2008-01-17 | Linde Ag | Procédé de liquéfaction d'hydrogène |
NO331153B1 (no) * | 2007-02-26 | 2011-10-24 | Kanfa Aragon As | Fremgangsmåte og system for nedkjøling av gass. |
WO2012069342A1 (fr) | 2010-11-22 | 2012-05-31 | Shell Internationale Research Maatschappij B.V. | Procédé de production d'hydrogène liquide et d'électricité |
CN107940895A (zh) * | 2017-11-30 | 2018-04-20 | 中国科学院理化技术研究所 | 气体液化系统 |
CN108036582A (zh) * | 2017-12-29 | 2018-05-15 | 上海启元空分技术发展股份有限公司 | 一种生产液氢的方法及其装置 |
WO2023174601A1 (fr) * | 2022-03-18 | 2023-09-21 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil de refroidissement d'hydrogène |
FR3133664A1 (fr) * | 2022-03-18 | 2023-09-22 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil de refroidissement d’hydrogène |
EP4325150A1 (fr) * | 2022-08-16 | 2024-02-21 | L'Air Liquide, société anonyme pour l'Étude et l'Exploitation des procédés Georges Claude | Procédé et appareil de refroidissement d'hydrogène |
FR3138939A1 (fr) * | 2022-08-16 | 2024-02-23 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil de refroidissement d’hydrogène |
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