US20240053094A1 - Method and apparatus for liquefying hydrogen - Google Patents

Method and apparatus for liquefying hydrogen Download PDF

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Publication number
US20240053094A1
US20240053094A1 US18/277,796 US202218277796A US2024053094A1 US 20240053094 A1 US20240053094 A1 US 20240053094A1 US 202218277796 A US202218277796 A US 202218277796A US 2024053094 A1 US2024053094 A1 US 2024053094A1
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hydrogen
heat exchanger
rich
cooled
rich gas
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Axelle GAERTNER
Marie-Khuny Khy
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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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
    • 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
    • F25J1/0237—Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural 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
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis 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
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • 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
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of 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
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0261—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon monoxide
    • 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/76—Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • 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
    • F25J2210/02—Multiple feed streams, e.g. originating from different sources
    • 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
    • F25J2210/18—H2/CO mixtures, i.e. synthesis gas; Water gas, shifted synthesis gas or purge gas from HYCO synthesis
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/02—Separating impurities in general from the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/60—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being (a mixture of) hydrocarbons
    • 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
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/20—Integration in an installation for liquefying or solidifying a fluid stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F25J2270/06—Internal refrigeration with work-producing gas expansion loop with multiple gas expansion loops
    • 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
    • F25J2270/24—Quasi-closed internal or closed external carbon monoxide refrigeration cycle

Definitions

  • the present invention relates to a process and to an apparatus for the liquefaction of hydrogen, preferably integrated with the cryogenic separation of a mixture of carbon monoxide and hydrogen.
  • the hydrogen is cooled and then liquefied in three stages:
  • the passages corresponding to the stream of gas to be liquefied contain catalyst and make it possible to carry out a continuous conversion of the hydrogen until a parahydrogen content of greater than 95% is achieved.
  • the cooling down to approximately 80K is carried out in a chamber thermally insulated with perlite.
  • This cooling is carried out using a closed nitrogen cycle or with the cold of an addition of cryogenic liquid (generally liquid nitrogen) called “boosting”, both consuming a great deal of energy.
  • cryogenic liquid generally liquid nitrogen
  • the cooling from approximately 80K to 20K is carried out in a vacuum chamber maintained at approximately 10 ⁇ 6 mmHg, with the items of equipment of the chamber being surrounded by multilayer insulation.
  • This cooling which comprises the liquefaction, is carried out using a hydrogen or helium cycle.
  • a nitrogen cycle in particular, could not be used at such low temperatures.
  • An aim of the present invention is to reduce the energy consumption of the process and possibly to eliminate a portion of the equipment by eliminating the precooling stage.
  • a hydrogen liquefaction apparatus comprising a liquefier comprising a first heat exchanger, an apparatus for separation by distillation and/or stripping and/or partial condensation, means for sending a hydrogen-rich gas originating from the apparatus for separation by distillation and/or stripping and/or partial condensation at a temperature of at most 103K containing at least 99.9 mol % of hydrogen, preferably at least 99.99 mol % of hydrogen, indeed even at least 99.999 mol % of hydrogen and at a pressure between 20 and 30 bar to the hydrogen liquefier, without having heated the hydrogen-rich gas to a temperature above 0° C., and means for sending the hydrogen-rich gas to be cooled from the temperature of at most 103K and at the pressure between 20 and 30 bar in the first heat exchanger, characterized in that it comprises a second heat exchanger, means for sending a hydrogen-rich flow to be cooled in the second heat exchanger, means for mixing the hydrogen-rich gas with the hydrogen-rich
  • the first exchanger is preferably located in a first thermally insulated chamber and the second exchanger is located in a second thermally insulated chamber, the point where the hydrogen-rich gas and the hydrogen-rich flow mix being located outside the first and second chambers.
  • the apparatus can comprise comprising a refrigeration cycle using helium or hydrogen in order to cool and optionally to liquefy the second mixture.
  • the means for liquefying the cooled gas in order to form liquid hydrogen can be constituted by the first heat exchanger and/or by expansion means downstream of the latter.
  • the expansion means are preferably located in the same insulated chamber as the heat exchanger but may be in a dedicated thermally insulated chamber.
  • FIG. 1 illustrates a cryogenic separation process for producing hydrogen.
  • FIG. 2 and FIG. 3 very diagrammatically illustrate processes for the liquefaction of hydrogen originating, for example, from the process of FIG. 1 .
  • FIG. 1 shows a process using a phase separator 9 , a methane scrubbing column 15 , a stripping column 25 and a column for the separation of carbon monoxide and methane 45 , containing for example structured packings for the columns and which are capable of operating at cryogenic temperatures.
  • the synthesis gas 1 containing carbon monoxide, methane and carbon monoxide is purified of water and/or of carbon dioxide in the purification unit 3 before arriving at the heat exchanger 7 , where it is cooled down to a cryogenic temperature and partially condensed.
  • the two phases are separated in a phase separator 9 , in order to form a gas 11 enriched in hydrogen and a liquid depleted in hydrogen 13 .
  • the gas 11 is sent to the bottom of the methane scrubbing column 15 , which produces a gas 19 enriched in hydrogen which is heated in the exchanger. A part of this gas 19 serves to regenerate the purification unit 3 .
  • At least one intermediate gas 210 , 211 withdrawn from the column 15 is cooled in a heat exchanger 23 by heat exchange with a fluid of the process, in this instance the liquid 51 .
  • the bottom liquid 17 from the column 15 joins the liquid 13 from the separator 9 and the mixture 91 , containing between 1 mol % and 3 mol % of hydrogen, is sent to the top of a stripping column 25 .
  • An overhead gas 27 from the stripping column contains at least 95 mol % of hydrogen and also carbon monoxide, nitrogen and methane. It is at between 20 and 30 bar, which is the operating pressure of the column 25 , and has a temperature between 103K and 120K.
  • the gas 27 is not heated but is purified in an adsorption unit 29 operating at cryogenic temperatures in order to remove carbon monoxide and/or methane and/or nitrogen in order to provide a gas 31 capable of being liquefied containing at least 99.9 mol % of hydrogen, preferably at least 99.99 mol % of hydrogen, indeed even at least 99.999 mol % of hydrogen.
  • a purification of this type is described in “The low temperature removal of small quantities of nitrogen or methane from hydrogen gas by physical adsorption on a synthetic zeolite”, Kidnay et al., AIChE Journal, Vol. 12, No. 1, January 1966.
  • a liquid 33 taken at the bottom of the stripping column 25 is cooled in the exchanger 7 and is sent to the separation column 45 .
  • Another part of the same liquid 35 is vaporized in a bottom reboiler 37 and is returned at the bottom of the stripping column.
  • the separation column comprises several sections for separation by distillation and optionally a vessel 99 . It has a bottom reboiler 73 which serves to heat the bottom liquid 75 , the gas formed being returned to the bottom.
  • the bottom liquid 77 enriched in methane is divided into two.
  • a part 83 is evaporated in the exchanger 7 in order to form fuel.
  • the remainder 85 is pressurized by a pump 87 and is sent to the top of the scrubbing column 15 .
  • the overhead gas from the column 43 enriched in carbon monoxide is sent to a product compressor 57 , which produces a gas enriched in carbon monoxide 57 .
  • a part of the gas enriched in carbon monoxide 61 is cooled and is divided into two.
  • a part 65 is expanded in a turbine 67 in order to provide cold.
  • the expanded gas 89 is returned to the inlet of the compressor 57 .
  • the remainder of the gas 69 continues its cooling in the exchanger 7 and serves to heat the reboilers 73 and 37 (flows 93 and 73 ).
  • the gas which has served for the reboiling is thus partially condensed and feeds, as flow 97 , the vessel 99 at the top of the separation column 45 .
  • the gas 41 from the vessel 99 feeds the compressor 57 .
  • the liquid 47 from the vessel 99 is sent to a phase separator 49 , the liquid 51 from the separator serves as refrigerant in the heat exchanger 23 in order to cool the intermediate gases 21 A, 21 B, 21 C as well as the overhead gas 27 from the stripping column.
  • a liquid withdrawn from the separation section of the separation column can replace the liquid 47 or another liquid of the process.
  • hydrogen 27 can be produced by a phase separator at between 20 and 30 bar abs in a partial condensation process optionally combined with a distillation.
  • separation processes are also capable of supplying hydrogen at a cryogenic temperature and at a pressure between 20 and 30 bar, for example the separation of purge gas from an ammonia production process.
  • the hydrogen produced at low temperature and at a pressure between 20 and 30 bar can be purified in the thermally insulated chamber in which the separation column and/or the phase separator from which it originates is/are located. Otherwise, and in particular in the case of the modification of an existing apparatus, the hydrogen can exit from the chamber where the separation column and/or the phase separator from which it originates is/are located and be sent by at least one thermally insulated pipe into a chamber 102 containing the purification apparatus in order to reduce its content of impurities, for example at least one of carbon monoxide, methane and nitrogen.
  • impurities for example at least one of carbon monoxide, methane and nitrogen.
  • the “cold” purification is a necessary stage in order to remove all the impurities which might freeze along the exchange line which goes down to approximately 20K, and consequently clog the heat exchangers.
  • FIG. 2 shows a first alternative form of the process according to the invention where the flow 27 of [ FIG. 1 ] feeds a liquefaction process as sole feed fluid.
  • the gaseous purified hydrogen 27 exits either from the thermally insulated chamber E in which the separation column and/or the phase separator C from which it originates is/are located or from a dedicated purification chamber 102 at a pressure between 20 and 30 bar abs.
  • This chamber 104 contains a brazed aluminum multipass plate heat exchanger 101 .
  • the passages corresponding to the stream of gas to be liquefied contain catalyst and make it possible to carry out a continuous conversion of the hydrogen until a parahydrogen content of greater than 95% is achieved.
  • the chamber 104 is under vacuum maintained at approximately 10 ⁇ 6 mmHg, the items of equipment inside the chamber being surrounded by multilayer insulation.
  • This cooling which is carried out therein comprises the liquefaction and is carried out using a hydrogen or helium cycle.
  • the exchanger 101 can simply contain at least one passage for cooling and liquefying the hydrogen, all the hydrogen being produced in liquid form and removed as product 111 , and also the passages necessary for the refrigeration cycle or cycles.
  • the purified hydrogen can be introduced at the hot end of the heat exchanger 101 .
  • the purified hydrogen is the only source of hydrogen to be liquefied or if all the hydrogen to be liquefied is available at the temperature of the hydrogen to be purified, no precooling will be necessary and the second conventional exchanger for cooling the hydrogen down to approximately 120K with its nitrogen cycle or other refrigerant cycle will not be required.
  • the second exchanger 103 will be present but preferably the purified hydrogen 27 coming from the low-temperature separation will be mixed with the hydrogen-rich flow 127 cooled in the second exchanger outside the chamber 106 of the second exchanger 103 and subsequently the mixture formed will be cooled in the liquefaction heat exchanger 101 inside the chamber 104 .
  • the hydrogen-rich flow 127 is cooled by traversing the second exchanger 103 from the hot end to the cold end and a common cycle 105 provides cold for the first and second exchangers while a cycle 107 provides cold solely for the second exchanger 103 .
  • the liquefaction of hydrogen as such can be:
  • the invention can also be used by modifying an existing apparatus for the separation of synthesis gas. It would be necessary to provide for increasing the size of the refrigeration cycle, the size of the turbines and the size of the cycle compressor coolers.
  • the synthesis gas 1 can be cooled at least partially in the heat exchanger 103 upstream of the separation.
  • At least a part of the apparatus for separation by distillation and/or stripping and/or partial condensation can be arranged in the same thermally insulated chamber as the second heat exchanger.
  • the hydrogen to be liquefied is usually expanded at the end of cooling in a turbine and/or a valve. This last stage is not illustrated.
  • “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms “consisting essentially of” and “consisting of” unless otherwise indicated herein.
  • Providing in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.
  • Optional or optionally means that the subsequently described event or circumstances may or may not occur.
  • the description includes instances where the event or circumstance occurs and instances where it does not occur.
  • Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation By Low-Temperature Treatments (AREA)
US18/277,796 2021-02-18 2022-02-14 Method and apparatus for liquefying hydrogen Pending US20240053094A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FRFR2101587 2021-02-18
FR2101587A FR3119883B1 (fr) 2021-02-18 2021-02-18 Procédé et appareil de liquéfaction d’hydrogène
PCT/EP2022/053519 WO2022175204A1 (fr) 2021-02-18 2022-02-14 Procédé et appareil de liquéfaction d'hydrogène

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CN (1) CN116724208A (fr)
FR (1) FR3119883B1 (fr)
WO (1) WO2022175204A1 (fr)

Family Cites Families (10)

* 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
DE2460515B2 (de) * 1974-12-20 1976-10-28 ^i/vtaimvti ·«* fvnYtMumg -zur IaU- Verfahren und vorrichtung zur entfernung von gasfoermigen verunreinigungen aus wasserstoff
CR7129A (es) * 2003-10-29 2003-11-17 Carlos Eduardo Rold N Villalobos Metodo y aparato para almacenar gases a baja temperatura utilizando un sistema de recuperacion de refrigeracion
FR2934581B1 (fr) * 2008-08-04 2011-02-18 Air Liquide Procede et appareil de generation et de purification de gaz de synthese.
EP3163236A1 (fr) 2015-10-27 2017-05-03 Linde Aktiengesellschaft Liquéfaction d'hydrogène à grande échelle au moyen d'un cycle de réfrigération d'hydrogène haute pression combiné à un nouveau pré-refroidissement unique avec mélange de réfrigérants
EP3162871A1 (fr) 2015-10-27 2017-05-03 Linde Aktiengesellschaft Cycle de réfrigération pour mélange hydrogène-néon pour refroidissement et liquéfaction d'hydrogène à grande échelle
EP3162870A1 (fr) 2015-10-27 2017-05-03 Linde Aktiengesellschaft Réfrigérant mélangé basse température pour pré-refroidissement d'hydrogène à grande échelle
EP3163235A1 (fr) 2015-10-27 2017-05-03 Linde Aktiengesellschaft Nouveau procédé en cascade de refroidissement et de liquéfaction d'hydrogène à grande échelle
EP3339605A1 (fr) 2016-12-23 2018-06-27 Linde Aktiengesellschaft Procédé de compression d'un mélange de gaz comprenant néon
GB2571569A (en) 2018-03-02 2019-09-04 Linde Ag Cooling system

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CN116724208A (zh) 2023-09-08
FR3119883B1 (fr) 2023-03-31
FR3119883A1 (fr) 2022-08-19
WO2022175204A1 (fr) 2022-08-25

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