US20160216013A1 - Method and device for separation at sub-ambient temperature - Google Patents

Method and device for separation at sub-ambient temperature Download PDF

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Publication number
US20160216013A1
US20160216013A1 US15/021,031 US201415021031A US2016216013A1 US 20160216013 A1 US20160216013 A1 US 20160216013A1 US 201415021031 A US201415021031 A US 201415021031A US 2016216013 A1 US2016216013 A1 US 2016216013A1
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Prior art keywords
column
zone
heat
heat pump
fluid
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US15/021,031
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Inventor
Guillaume CARDON
Antony CORREIA ANACLETO
Benoît Davidian
Clement LIX
Bernard Saulnier
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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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Priority claimed from FR1358666A external-priority patent/FR3010509A1/fr
Priority claimed from FR1358668A external-priority patent/FR3010511B1/fr
Priority claimed from FR1358667A external-priority patent/FR3010510B1/fr
Application filed by LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Publication of US20160216013A1 publication Critical patent/US20160216013A1/en
Assigned to L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude reassignment L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SAULNIER, BERNARD, LIX, CLEMENT, CARDON, Guillaume, CORREIA ANACLETO, Antony, DAVIDIAN, BENOIT
Abandoned legal-status Critical Current

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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
    • 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
    • F25J3/04—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 for air
    • F25J3/04406—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 for air using a dual pressure main column system
    • F25J3/04412—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 for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • 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
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B30/00—Heat pumps
    • F25B30/06—Heat pumps characterised by the source of low potential heat
    • 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
    • F25J3/04—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 for air
    • F25J3/04636—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 for air using a hybrid air separation unit, e.g. combined process by cryogenic separation 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
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00—Machines, plants or systems, using electric or magnetic effects
    • 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
    • F25J3/04—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 for air
    • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
    • F25J3/04187—Cooling of the purified feed air by recuperative heat-exchange; Heat-exchange with product streams
    • F25J3/04193—Division of the main heat exchange line in consecutive sections having different functions
    • 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
    • F25J3/04—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 for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04278—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using external refrigeration units, e.g. closed mechanical or regenerative refrigeration units
    • 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
    • F25J3/04—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 for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
    • F25J3/04303—Lachmann expansion, i.e. expanded into oxygen producing or low pressure column
    • 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
    • F25J3/04—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 for air
    • F25J3/044—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 for air using a single pressure main column system only
    • 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
    • F25J3/04—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 for air
    • F25J3/04642—Recovering noble gases from air
    • F25J3/04648—Recovering noble gases from air argon
    • F25J3/04654—Producing crude argon in a crude argon column
    • F25J3/0466—Producing crude argon in a crude argon column as a parallel working rectification column or auxiliary column system in a single pressure main column system
    • 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
    • F25J3/04—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 for air
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
    • F25J3/04872—Vertical layout of cold equipments within in the cold box, e.g. columns, heat exchangers etc.
    • F25J3/04884—Arrangement of reboiler-condensers
    • 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
    • F25J2200/40—Features relating to the provision of boil-up in the bottom of a column
    • 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
    • F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
    • 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
    • F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead 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
    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
    • 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
    • F25J2250/20—Boiler-condenser with multiple exchanger cores in parallel or with multiple re-boiling or condensing streams
    • 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
    • F25J2270/908—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by regenerative chillers, i.e. oscillating or dynamic systems, e.g. Stirling refrigerator, thermoelectric ("Peltier") or magnetic refrigeration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]

Definitions

  • the present invention relates to a method and to a device for separation by separating at sub-ambient, or even cryogenic, temperature.
  • the separation may be a separation by distillation and/or by dephlegmation and/or by absorption.
  • the equipment used for this separation will be referred to as a “column”.
  • a column may for example be a distillation or absorption column. Reduced to its simplest expression, it may be a phase separator. Otherwise, a column may also be a device in which dephlegmation takes place.
  • Magnetic refrigeration relies on the use of magnetic materials that exhibit a magnetocaloric effect. Reversible, this effect is manifested by a variation in temperature when subjected to the application of an external magnetic field.
  • the optimum ranges within which these materials are used lie in the vicinity of their Curie temperature (Tc). This is because the greater the variations in magnetization and, therefore, the changes in magnetic entropy, the greater the changes in temperature.
  • the magnetocaloric effect is said to be direct when the temperature of the material increases when placed in a magnetic field, and indirect when it cools when placed in a magnetic field. The remainder of the description will be given for the direct case, but it is obvious to a person skilled in the art how to reapply this to the indirect case. There are many thermodynamic cycles based on this principle.
  • a conventional magnetic refrigeration cycle consists i) in magnetizing the material in order to increase its temperature, ii) in cooling the material for a constant magnetic field in order to dissipate heat, iii) in demagnetizing the material in order to cool it and iv) in heating the material in a constant (generally zero) magnetic field in order to absorb heat.
  • a magnetic refrigeration device employs elements made of magnetocaloric material, which generate heat when magnetized and absorb heat when demagnetized. They may employ a magnetocaloric material regenerator to amplify the temperature difference between the “hot source” and the “cold source”: the magnetic refrigeration is then said to be magnetic refrigeration employing active regeneration.
  • U.S. Pat. No. 6,502,404 describes the use of the magnetocaloric effect to supply cold (needed to provide the refrigeration balance of the method) to a cryogenic method for separating the gas of the air, the separation energy being conventionally supplied by pressurized air allows the operation of the vaporizer-condenser of the double column (it being possible for the low-pressure column to be reduced to a simple vaporizer in the case of a nitrogen generator).
  • the present invention tackles the problem of the transfer of heat from one place in a device for separation by distillation and/or by dephlegmation and/or by absorption at sub-ambient temperature, which place is considered to be a cold source, to another place of said device considered to be a hot source.
  • a heat pump is a thermodynamic device that allows a quantity of heat to be transferred from a medium considered to be the “emitter” and referred to as the “cold source” from which heat is extracted, to a medium considered to be the “receiver” and referred to as the “hot source” to which the heat is supplied, the cold source being at a colder temperature than the hot source.
  • thermodynamic cycle of compressing—cooling (condensing)—expanding—reheating (vaporizing) a refrigeration fluid.
  • FIG. 12 of the document entitled “TECHNIQUES DE L'INGENIEUR—Réfrigération magnically [Engineering techniques—Magnetic refrigeration] 2005” shows a twofold improvement in the coefficient of performance of a refrigeration system using a magnetic cycle as compared with the conventional cycle.
  • An ambient temperature is the temperature of the ambient air in which the method is situated or, alternatively, a temperature of a cooling water circuit connected with the air temperature.
  • a sub-ambient temperature is at least 10° C. below ambient temperature.
  • U.S. Pat. No. 4,987,744 describes a cryogenic distillation method in which a heat pump transfers heat from one point of one column, which is at a cryogenic temperature, to another point on the column, which is likewise at a cryogenic temperature.
  • the heat pump comprises two closed refrigerant circuits thermally connected to one another, each of the circuits comprising a compression step and a cooling step using a fluid at ambient temperature (air, water).
  • One subject of certain embodiments of the invention provide a method for separation at sub-ambient, or even cryogenic, temperature, in which a mixture of fluid at sub-ambient, or even cryogenic, temperature is sent into a system of separation columns comprising at least one separation column, a fluid enriched in a lighter component of the mixture leaves the top of one column of the system and a fluid enriched in a heavier component is withdrawn from the bottom of one column of the system, in which the cold source of a heat pump using the magnetocaloric effect is directly or indirectly thermally connected to a first zone of a column of the system and the hot source of the same heat pump is directly or indirectly thermally connected to a second zone of the same or of another column of the system, the minimum temperature of the first zone being lower than the maximum temperature of the second zone.
  • Another subject of the invention is a device for separation at sub-ambient, or even cryogenic, temperature, comprising a system of separation columns comprising at least one separation column to which a mixture of fluid at sub-ambient, or even cryogenic, temperature is sent, a pipe for withdrawing a fluid enriched with a lighter component of the mixture from the top of one column of the system and a pipe for withdrawing a fluid enriched in a heavier component from the bottom of one column of the system, in which the cold source of a heat pump using the magnetocaloric effect is directly or indirectly thermally connected to a first zone of a column of the system and the hot source of the same heat pump being directly or indirectly thermally connected to a second zone of the same or of another column of the system, the arrangement of the first and second zones in the column or columns being such that the minimum temperature of the first zone is lower than the maximum temperature of the second zone.
  • the device comprises:
  • FIG. 1 represents an embodiment of the present invention.
  • FIG. 2 represents an embodiment of the present invention.
  • FIG. 3 represents a process flow diagram in accordance with an embodiment of the present invention.
  • FIG. 4 represents a process flow diagram in accordance with an embodiment of the present invention.
  • FIG. 5 represents a process flow diagram in accordance with an embodiment of the present invention.
  • FIG. 6 represents a process flow diagram in accordance with an embodiment of the present invention.
  • FIG. 7 represents a process flow diagram in accordance with an embodiment of the present invention.
  • FIG. 8 represents a process flow diagram in accordance with an embodiment of the present invention.
  • a mixture containing at least components A, B cooled to a sub-ambient, or even cryogenic, temperature is separated in a column 3 to form a fluid, possibly gaseous, rich in volatile components A and a fluid, possibly liquid, rich in less-volatile components B.
  • first zone 1 is directly or indirectly thermally connected to the cold source of the heat pump MC using the magnetocaloric effect
  • the second zone 2 is directly or indirectly thermally connected to the hot source of the same heat pump MC using the magnetocaloric effect.
  • a mixture containing at least components A, B cooled to a sub-ambient, or even cryogenic, temperature is separated in a column 3 to form a fluid, possibly gaseous, rich in volatile components A and a fluid, possibly liquid, rich in less-volatile components B.
  • a mixture containing at least C, D, cooled to a sub-ambient, or even cryogenic, temperature is separated in a column 5 to form a fluid, possibly gaseous, rich in volatile components C and a fluid, possibly liquid, rich in less-volatile components D.
  • first zone 1 is directly or indirectly thermally connected to the cold source of the heat pump using the magnetocaloric effect MC
  • the second zone 2 is directly or indirectly thermally connected to the hot source of the same heat pump MC using the magnetocaloric effect.
  • a compressor 7 compresses a flow A, B (for example of air considered to be a mixture mainly of oxygen and nitrogen).
  • the compressed flow is cooled in a cooler 9 and purified in a purification unit 11 to remove the impurities (if present).
  • the purified flow is cooled in a heat exchanger 13 to a cryogenic temperature and is split into two flows 23 , 25 .
  • One flow 23 is sent to the column 3 in gaseous form and the rest 25 is cooled or, at least partially liquefied, in an exchanger 27 .
  • the cooled or at least partially liquefied flow is sent to the column 3 .
  • the column 3 has a top end condenser 15 and a bottom end reboiler 17 .
  • the condenser 15 is considered to be the first zone 1 and the reboiler 17 is the second zone 2 , the heat being transferred from the first zone 1 to the second zone 2 by means of a heat pump using the magnetocaloric effect MC 1 .
  • the cooling or at least partial liquefaction of the flow 25 which in part compensates for the electrical or mechanical energy introduced by the operation of the heat pump using the magnetocaloric effect MC 1 , can be performed directly or indirectly by means of a heat pump using the magnetocaloric effect MC 4 using a cooling fluid 51 , typically ambient air or cooling water or any other refrigeration system, for example a compression/expansion thermodynamic cycle.
  • FIGS. 4 and 5 heat is transferred from the top of the medium-pressure column of a double air separation column to the bottom of the low-pressure column thereof.
  • a compressor 7 compresses a flow A, B (for example air considered to be a mixture mainly of oxygen and nitrogen).
  • the compressed flow is cooled in a cooler 9 and purified in a purification unit 11 to remove the impurities (if present).
  • the purified flow is split into two.
  • a part 23 cooled in a heat exchanger 13 to a cryogenic temperature is sent to the bottom of the medium-pressure column 3 .
  • the rest 123 has its pressure boosted in a pressure booster 41 , is partially cooled in the heat exchanger 13 , and is then expanded in an inlet turbine 43 , driving the pressure booster 41 .
  • the expanded air is sent to the low-pressure column 5 , directly or indirectly thermally connected to the medium-pressure column 3 through a heat pump using the magnetocaloric effect MC.
  • Other means of producing cold other than the intake turbine may be considered.
  • a liquid flow 61 enriched in B (oxygen) and a liquid flow 63 enriched in A (nitrogen) are withdrawn from the medium-pressure column 3 and sent to the low-pressure column 5 .
  • the column 3 has no top end condenser in the column and the column 5 has no bottom reboiler in the column.
  • Gaseous nitrogen 47 is withdrawn from the column 3 and split into two. One part 49 is heated up in the exchanger 13 .
  • the rest 51 is sent to the heat pump using the magnetocaloric effect MC where it condenses (possibly partially) and the condensed nitrogen is sent to the top of the column 3 .
  • Liquid oxygen from the bottom of the column 5 is also sent to the heat pump using the magnetocaloric effect MC where it vaporizes (possibly partially) before being sent back to the column 5 .
  • the heat pump using the magnetocaloric effect MC replaces both the top condenser and the bottom reboiler, making it possible in particular to reduce the overall height of the system of columns 3 , 5 .
  • Gaseous oxygen 53 is withdrawn from the column 5 by way of product, is heated up in the exchanger 13 and compressed in the compressor 55 . It is obvious to a person skilled in the art that liquid oxygen may be withdrawn from the column either by way of liquid product or so that it can be pumped and then vaporized in the exchange line 13 against the pressure-boosted air.
  • Nitrogen 57 is withdrawn from the top of the low-pressure column 5 , heated up in the subcooler 45 and in the exchanger 13 before being used at least in part for the regeneration of the unit 11 .
  • FIG. 5 shows a more conventional alternative form in which the column 3 has a top end condenser 15 and the column 5 has a bottom end reboiler 17 .
  • the transfer of heat between the two takes place indirectly by means of a heat pump using the magnetocaloric effect MC, a heat-transfer fluid, for example a liquid, coming from the heat pump using the magnetocaloric effect MC being supplied to the condenser, a heat-transfer fluid, for example a liquid, coming from the heat pump using the magnetocaloric effect MC being supplied to the vaporizer, it being possible for the two heat-transfer fluids to be the same.
  • a heat-transfer fluid for example a liquid
  • FIG. 6 shows a device similar to that of FIG. 3 , except that it comprises an argon-producing column 103 supplied from the column 3 .
  • This argon column 103 may actually produce an argon-enriched fluid or alternatively may output the argon-enriched fluid in a residual flow.
  • the condenser of the argon column 103 is supplied with a liquid coming from the column 3 , withdrawn on the “distillation equivalent plates” around the introduction of liquid air, above the introduction of air 23 . Said liquid is vaporized (at least partially) in the condenser of the argon column 103 in order to refrigerate the argon column 103 , and is then reintroduced into the column 3 underneath the air supply 23 .
  • the argon column 103 is connected to the column 3 underneath the reintroduction of said vaporized liquid. In that case, the oxygen 29 withdrawn from the bottom of the column 3 may have a purity of more than 97 mol %.
  • FIG. 7 shows a device similar to that of FIG. 6 , in which the heat pumps using the magnetocaloric effect MC 2 , MC 3 replace the argon production column 103 and the top condenser thereof. Some of the heat exchanged at the condenser 15 of the column 3 is transferred directly or indirectly to the cold source of the heat pump using the magnetocaloric effect MC 3 .
  • the heat pump using the magnetocaloric effect MC 3 has by way of hot source a liquid withdrawn between the liquid air inlet and the gaseous air inlet 23 , which is at least partially vaporized and reintroduced into the column 3 under the gaseous air supply 23 .
  • the heat pump using the magnetocaloric effect MC 2 has as its cold source a gas withdrawn below the level of said reintroduction, which is at least partially condensed and reintroduced at the level of said reintroduction.
  • Some of the heat exchanged at the vaporizer 17 of the column 3 comes directly or indirectly from the hot source of the heat pump using the magnetocaloric effect MC 2 .
  • the remaining heat exchanged at the condenser 15 of the column 3 is transferred directly or indirectly to the cold source of the heat pump using the magnetocaloric effect MC 1 .
  • the remainder of the heat exchanged at the vaporizer 17 of the column 3 comes directly or indirectly from the hot source of the heat pump using the magnetocaloric effect MC 1 .
  • the heat pumps using the magnetocaloric effect MC 1 , MC 2 and/or MC 3 may be fully or partially combined into one and the same device.
  • the method in FIG. 7 has an energy performance identical to FIG. 6 in the case where the argon-enriched fluid is discharged in a residual flow. It allows an energy saving of around 7% in comparison with FIG. 3 . In that case, the oxygen 29 withdrawn at the bottom of the column 3 may have a purity of more than 97 mol %.
  • FIG. 8 depicts a device similar to that of FIG. 3 but comprising an intermediate reboiler.
  • heat is transferred indirectly from the condenser 15 to both the two reboilers 17 , 71 through two heat pumps using the magnetocaloric effect MC 1 , MC 2 .
  • Part of the heat exchanged at the condenser 15 of the column 3 is transferred directly or indirectly to the cold source of the heat pump using the magnetocaloric effect MC 2 .
  • the heat exchanged at the intermediate reboiler 71 situated below the gaseous air inlet 23 comes directly or indirectly from the hot source of the heat pump using the magnetocaloric effect MC 2 .
  • the remainder of the heat exchanged at the condenser 15 of the column 3 is transferred directly or indirectly to the cold source of the heat pump using the magnetocaloric effect MC 1 .
  • the heat exchanged at the vaporizer 17 of the column 3 comes directly or indirectly from the heat pump using the magnetocaloric effect MC 1 .
  • the oxygen 29 withdrawn at the bottom of the column 3 may have a purity of less than 96.5 mol %.
  • the heat pumps using the magnetocaloric effect MC 1 and MC 2 may be fully or partially combined within one and the same device.
  • “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)
  • Separation By Low-Temperature Treatments (AREA)
US15/021,031 2013-09-10 2014-09-10 Method and device for separation at sub-ambient temperature Abandoned US20160216013A1 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
FR1358666A FR3010509A1 (fr) 2013-09-10 2013-09-10 Procede et appareil de separation a temperature subambiante
FR1358667 2013-09-10
FR1358668A FR3010511B1 (fr) 2013-09-10 2013-09-10 Procede et appareil de separation d'un melange gazeux a temperature subambiante
FR1358666 2013-09-10
FR1358668 2013-09-10
FR1358667A FR3010510B1 (fr) 2013-09-10 2013-09-10 Procede et appareil de separation a temperature subambiante
PCT/FR2014/052241 WO2015036697A2 (fr) 2013-09-10 2014-09-10 Procédé et appareil de séparation à température subambiante

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US15/021,035 Abandoned US20160223253A1 (en) 2013-09-10 2014-09-10 Method and device for separation at cryogenic temperature

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US20120067082A1 (en) * 2009-06-03 2012-03-22 L'air Liquide Societe Anonyme Pour L'etude Et Expl Method and apparatus for producing at least one argon-enriched fluid and at least one oxygen-enriched fluid from a residual fluid

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DE19529681C2 (de) * 1995-08-11 1997-05-28 Linde Ag Verfahren und Vorrichtung zur Luftzerlegung durch Tieftemperaturrektifikation
US6082135A (en) * 1999-01-29 2000-07-04 The Boc Group, Inc. Air separation method and apparatus to produce an oxygen product
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DE102005029274A1 (de) * 2004-08-17 2006-02-23 Linde Ag Verfahren und Vorrichtung zur Gewinnung eines gasförmigen Druckprodukts durch Tieftemperatur-Zerlegung von Luft

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US4987744A (en) * 1990-01-26 1991-01-29 Union Carbide Industrial Gases Technology Corporation Cryogenic distillation with unbalanced heat pump
US6502404B1 (en) * 2001-07-31 2003-01-07 Praxair Technology, Inc. Cryogenic rectification system using magnetic refrigeration
US7481064B2 (en) * 2002-12-24 2009-01-27 Haute Ecole D'ingenierie Et De Gestion Du Canton De Vaud (Heig-Vd) Method and device for continuous generation of cold and heat by means of the magneto-calorific effect
US20080016907A1 (en) * 2006-07-18 2008-01-24 John Arthur Barclay Active gas regenerative liquefier system and method
US20120067082A1 (en) * 2009-06-03 2012-03-22 L'air Liquide Societe Anonyme Pour L'etude Et Expl Method and apparatus for producing at least one argon-enriched fluid and at least one oxygen-enriched fluid from a residual fluid

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EP3044522A2 (fr) 2016-07-20
CN105705884B (zh) 2019-03-29
EP3071910A2 (fr) 2016-09-28
CN105705893A (zh) 2016-06-22
CN105705884A (zh) 2016-06-22
US20160223253A1 (en) 2016-08-04

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