EP3980705A1 - Procédé et installation de décomposition d'air à basse température - Google Patents

Procédé et installation de décomposition d'air à basse température

Info

Publication number
EP3980705A1
EP3980705A1 EP20727147.9A EP20727147A EP3980705A1 EP 3980705 A1 EP3980705 A1 EP 3980705A1 EP 20727147 A EP20727147 A EP 20727147A EP 3980705 A1 EP3980705 A1 EP 3980705A1
Authority
EP
European Patent Office
Prior art keywords
column
liquid
fed
gas
evaporation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20727147.9A
Other languages
German (de)
English (en)
Inventor
Dimitri GOLUBEV
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of EP3980705A1 publication Critical patent/EP3980705A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • F25J3/04436—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 at least a triple 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
    • F25J3/04248—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
    • F25J3/04327—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 argon or argon enriched 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
    • 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
    • F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04048—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) 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
    • 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
    • F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
    • F25J3/04084—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
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    • 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
    • F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
    • F25J3/0409—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of oxygen
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    • 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
    • F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
    • F25J3/04096—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of argon or argon enriched 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
    • 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
    • F25J3/04163—Hot end purification of the feed air
    • F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
    • F25J3/04181—Regenerating the adsorbents
    • 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
    • F25J3/0423—Subcooling of liquid process 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
    • 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
    • F25J3/04236—Integration of different exchangers in a single core, so-called integrated cores
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • 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
    • F25J3/04375—Details relating to the work expansion, e.g. process parameter etc.
    • F25J3/04393—Details relating to the work expansion, e.g. process parameter etc. using multiple or multistage gas work expansion
    • 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
    • F25J3/04472—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 the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages
    • F25J3/04496—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 the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages for compensating variable air feed or variable product demand by alternating between periods of liquid storage and liquid assist
    • 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
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    • 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
    • F25J3/04709—Producing crude argon in a crude argon column as an auxiliary column system in at least a dual pressure main column system
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    • F25J3/04642—Recovering noble gases from air
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    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
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    • 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
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation gas
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    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/50—Oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/58—Argon
    • 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
    • F25J2215/50—Oxygen or special cases, e.g. isotope-mixtures or low purity O2
    • F25J2215/52—Oxygen production with multiple purity O2
    • 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
    • F25J2215/50—Oxygen or special cases, e.g. isotope-mixtures or low purity O2
    • F25J2215/56—Ultra high purity oxygen, i.e. generally more than 99,9% O2
    • 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
    • F25J2230/52—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being oxygen enriched compared to air, e.g. "crude oxygen"
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/42—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • F25J2240/28—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid being argon or crude argon
    • 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
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/40—Expansion without extracting work, i.e. isenthalpic throttling, e.g. JT valve, regulating valve or venturi, or isentropic nozzle, e.g. Laval
    • F25J2240/44—Expansion without extracting work, i.e. isenthalpic throttling, e.g. JT valve, regulating valve or venturi, or isentropic nozzle, e.g. Laval the fluid being nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/50—Processes or apparatus involving steps for recycling of process streams the recycled stream being oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • 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
    • F25J2270/02—Internal refrigeration with liquid vaporising loop

Definitions

  • the present invention relates to a method and a system for
  • Air separation plants have rectification column systems that
  • Multi-column systems can be formed.
  • rectification columns for obtaining nitrogen and / or oxygen in liquid and / or gaseous state, i.e. the rectification columns for nitrogen-oxygen separation
  • rectification columns can be provided for obtaining further air components, in particular the noble gases krypton, xenon and / or argon.
  • the terms “rectification” and “distillation” and “column” and “column” or terms composed of these are often used synonymously.
  • the rectification columns of the mentioned rectification column systems are operated at different pressure levels.
  • Known double column systems have a so-called high pressure column (also referred to as a pressure column, medium pressure column or lower column) and a so-called low pressure column (also referred to as an upper column).
  • the high pressure column is typically on a
  • the low-pressure column is operated at a pressure level of typically 1 to 2 bar, in particular about 1.4 bar. In certain cases, both
  • Rectification columns can also be used at higher pressure levels. With the here and The pressures given below are absolute pressures at the top of the columns given.
  • liquid argon can be delivered or evaporated on site, or gaseous argon can be obtained on site.
  • the delivery of liquid argon not only brings economic disadvantages (transport costs, refueling losses, cold losses when evaporating against ambient air), but also makes high demands on the
  • the nitrogen produced should typically only contain about 1 ppb, a maximum of 1000 ppb, oxygen, be essentially free of particles, and be able to be supplied at a pressure level that is clearly above atmospheric.
  • Figures in ppb or ppm relate to the molar proportion.
  • Air separation plants are typically used to extract argon
  • Rectification columns are designed accordingly. Pure argon can then be withdrawn from the crude argon column or a comparable column typically somewhat further below than the fluid conventionally transferred into the pure argon column.
  • the present invention therefore sets itself the task of specifying a method and an air separation plant by means of which, in addition to larger amounts of high-purity, gaseous nitrogen on a clearly
  • argon can also be advantageously provided.
  • Liquids and gases can be rich or poor in one or more components in the parlance used here, with "rich” for a content of at least 75%, 90%, 95%, 99%, 99.5%, 99.9% or 99.99% and “poor” can mean a content of no more than 25%, 10%, 5%, 1%, 0.1% or 0.01% on a mole, weight or volume basis.
  • Liquids and gases can also be enriched or depleted in one or more components, these terms referring to a content in a starting liquid or a starting gas from which the liquid or the gas was obtained. Be the liquid or the gas
  • pressure range and "temperature range” to characterize pressures and temperatures, which is intended to express that corresponding pressures and temperatures in a corresponding system do not have to be used in the form of exact pressure or temperature values to realize the inventive concept.
  • pressures and temperatures typically move in certain ranges, for example ⁇ 1%, 5%, 10% or 20% around a mean value.
  • Corresponding pressure ranges and temperature ranges can be in disjoint areas or in areas that overlap one another.
  • pressure ranges include, for example, unavoidable or expected pressure losses.
  • the values specified in bar for the pressure ranges are absolute pressures.
  • expansion machines are mentioned here, this is typically understood to mean known turboexpander. These expansion machines can in particular also be coupled to compressors. These compressors can in particular be turbo compressors.
  • a corresponding combination of Turboexpander and turbo-compressor is typically also referred to as “turbine booster". In a turbine booster, the turbo-expander and the turbo-compressor are mechanically coupled, the coupling being able to take place at the same speed (for example via a common shaft) or at different speeds (for example via a suitable transmission gear).
  • compressor is used here in general.
  • a “cold compressor” here denotes a compressor to which a fluid flow is fed in a temperature range well below 0 ° C, in particular below -50, -75 or -100 ° C and down to -150 or -200 ° C.
  • a corresponding fluid flow is particularly cooled to a temperature in this temperature range by means of a main heat exchanger (see below).
  • a “main air compressor” is characterized by the fact that it compresses all of the air that is fed to the air separation plant and separated there. In contrast, in one or more optionally provided further compressors, for example booster compressors, only a portion of this air that has already been previously compressed in the main air compressor is further compressed.
  • the "main heat exchanger" of an air separation plant represents the heat exchanger in which at least the
  • a “heat exchanger” for use in the context of the present invention can be designed in a manner customary in the art. It serves for the indirect transfer of heat between at least two e.g. fluid flows guided in countercurrent to one another, for example a warm compressed air flow and one or more cold ones
  • Fluid flows or a cryogenic liquid air product and one or more warm or warmer, but possibly also cryogenic fluid flows.
  • Heat exchanger can be formed from a single or several heat exchanger sections connected in parallel and / or in series, e.g. from one or more plate heat exchanger blocks. For example, it is one
  • Such a heat exchanger has "passages" which are separated from each other as fluid channels
  • Heat exchange surfaces formed and separated in parallel and by other passages are united to "passage groups".
  • a heat exchanger is characterized by the fact that heat is exchanged between two mobile media in it at a time, namely at least one fluid flow to be cooled and at least one fluid flow to be heated.
  • a “condenser evaporator” is a heat exchanger in which a first, condensing fluid flow enters into indirect heat exchange with a second, evaporating fluid flow.
  • Each condenser evaporator has one
  • Evaporation chambers have liquefaction or evaporation passages.
  • the condensation (liquefaction) of the first fluid flow is carried out in the liquefaction space, and the evaporation of the second fluid flow in the vaporization space.
  • the evaporation and the liquefaction space are formed by groups of passages which are in a heat exchange relationship with one another.
  • This pressure can be generated, for example, by a column of liquid in the feed line to the evaporation chamber. The height of this liquid column corresponds to the pressure loss in the
  • downstream device forwarded and in particular not in a
  • Components "one above the other” is understood here to mean that the upper end of the lower of the two components is at a lower or the same geodetic height as the lower end of the upper of the two components and that the projections of the two apparatus parts intersect in a horizontal plane.
  • the two components are arranged exactly one above the other, that is, the axes of the two components run vertically on the same
  • the axes of the two components do not have to be exactly perpendicular, but can also be offset from one another, especially if one of the two components, for example a rectification column or a column part with a smaller diameter, is to have the same distance from the sheet metal jacket of a coldbox as another with a larger one Diameter.
  • the present invention proposes a method for
  • Cryogenic separation of air in which an air separation plant is used with a column system comprising a first column, a second column, a third column and a fourth column.
  • the first to third columns in the air separation plant according to the invention emerge in particular from the expansion of a classic double column system known from the prior art by an additional column operated at a higher pressure than the conventionally present high pressure column.
  • the first column can be provided in particular structurally separate from the second and third column, wherein the second and third column can in particular be part of a double column and by means of a corresponding one Condenser evaporator, the so-called main condenser, can be in heat-exchanging connection with one another.
  • the second and third column can in particular be part of a double column and by means of a corresponding one Condenser evaporator, the so-called main condenser, can be in heat-exchanging connection with one another.
  • main condenser the so-called main condenser
  • Double columns are formed, can also be supplemented by an additional column in a corresponding multiple column system, or the second and third columns can be provided as separate columns.
  • the main capacitor can be provided as an internal or external main capacitor, as is basically known from the prior art. At Using an internal main condenser, this is at least partially submerged in a bottom liquid in the bottom of the third column and an overhead gas to be condensed from the second column is passed through a
  • a first bottom liquid is formed in the first column
  • a second bottom liquid is formed in the second column
  • a third is formed in the third column
  • Bottom liquid is formed and a fourth bottom liquid is formed in the fourth column.
  • the fourth column in the context of the present invention is used in particular for argon production or
  • the fourth column can in particular be a conventional crude argon column of a known arrangement with crude and pure argon column, but it can also be a modified argon column from which argon is withdrawn in the pure state below the top without using an additional pure argon column.
  • the first column is in a first
  • the second column is operated in a second pressure range below the first pressure range and the third column is operated in a third pressure range below the second (and thus also the first) pressure range.
  • the fourth column can in particular be operated in the third pressure range or in a pressure range which is slightly below this and which can result in particular from pressure losses via the lines connecting the third and fourth columns.
  • Sump liquid is formed and the third sump liquid is formed with a higher oxygen content and a lower argon content than the second sump liquid.
  • the higher argon content of the second sump liquid compared to that of the first sump liquid results from the different
  • the lower argon content in the third column results in particular from the fact that an argon-enriched gas is withdrawn from this third column, as will be explained below.
  • the first oxygen content can be at 28 to 40%, in particular at approx. 34%, the second oxygen content at approx. 45 to 65%, in particular at approx. 55%, and the third oxygen content at approx. 0 to 99.9%, in particular around 99.5%.
  • the respective percentages relate to the molar content of oxygen in a corresponding one
  • the third column is therefore used in the context of the present invention as a pure oxygen column and a corresponding pure oxygen product can be withdrawn from it.
  • the first and the second sump liquid are typically not used as a product, but are further processed in the plant.
  • fluid is generally fed from the first column at least into the second column.
  • the fluid fed into the second column from the first column can in particular comprise bottom liquid from the first column, which is evaporated, expanded and introduced into the second column.
  • fluid can be fed from the first column into the second and into the third column. Fluid from the second column is fed into at least the third column, fluid from the third column is fed into at least the fourth column, and fluid from the fourth column is fed into at least the third column.
  • fluid is “at least” fed into another column from one column, in particular a direct or indirect one
  • the transferred fluids can include overhead gases, bottom liquids and / or side streams of corresponding columns. Under a "side stream" is a
  • a sump liquid is discharged in particular in the form of a liquid substance flow, and an overhead gas in particular in the form of a gaseous substance flow.
  • liquid or gaseous material flows can also be withdrawn, for example, directly above the sump, but still below the lowest separating section or the lowest separating tray.
  • a liquid side stream can, for example, be removed from a liquid retention device or from a storage floor.
  • the fluid fed into the fourth column from the third column comprises at least part of a side stream which is withdrawn from the third column with a lower oxygen content and a higher argon content than the third bottom liquid.
  • the side stream is withdrawn from the third column in particular in the area of the argon transition already explained above, but it can also be withdrawn below the argon transition.
  • a corresponding side stream represents a gas mixture in particular, which has a higher argon content than the bottom liquid and a lower argon content than the top gas.
  • An essential aspect of the present invention is that a reflux liquid is formed by condensing top gas of the first column, and that this reflux liquid is returned in liquid form to the first column.
  • the formation of the reflux liquid “using” the top gas can in particular include removing top gas in gaseous form from the first column, at least this in a condenser evaporator which is also explained in detail below partially liquefied, and a liquid portion at least partially returned to the first column.
  • a liquid cooling stream is evaporated or partially evaporated in indirect heat exchange with the top gas.
  • Gas formed in the cooling stream (any remaining liquid can be separated off beforehand) is furthermore, according to the invention, work-producing to a pressure in the second pressure range, ie the operating pressure of the second column, expanded and fed into the second column.
  • the correspondingly expanded gas can be part of the gas formed during the evaporation or partial evaporation or also only a part thereof.
  • the liquid cooling stream can in particular be provided at a pressure in the first pressure range and before evaporation or
  • Partial evaporation for example by means of a valve, can be expanded to a somewhat lower pressure, for example in a region between the first pressure range and the second pressure range. Another relaxation after the
  • the present invention creates a method with lower energy consumption than methods currently under development. This applies in particular in comparison to known so-called SPECTRA processes and variants thereof.
  • the present invention can, however, as explained for example in connection with FIG. 4, be used in connection with such a SPECTRA method or a variant thereof.
  • a SPECTRA method is known, for example, from EP 2 789 958 A1 and the patent literature cited there. In its simplest form, it is a single-column process. A SPECTRA process can also be expanded to include oxygen and argon production by providing additional columns. SPECTRA processes enable a relatively high nitrogen yield.
  • Condensation of at least a portion of the top gas of the same column is used.
  • Condensed top gas is at least partially returned to the column from which it was previously taken.
  • the fluid to be evaporated can be passed through the condenser evaporator in the form of just one material flow or in the form of two or more separate first material flows.
  • the correspondingly vaporized fluid is partially cold, i.e. using one or more compressors. at a temperature level well below 0 ° C, in particular at a temperature level of -50 ° C or less, compressed and then fed back into the column from which it was previously removed.
  • the one or more compressors can or can with one or more
  • Relaxation machines in particular with one of two relaxation machines arranged in parallel, be coupled and at least partially driven using them.
  • expansion machine or machines a further part of the evaporated fluid is expanded and discharged from the air separation plant.
  • the present invention is based on the knowledge that the potential of a method of the generic type cannot be fully exploited without the measures proposed according to the invention.
  • An indicator for this is or was a still relatively high temperature difference present in such generic processes in a condenser which condenses overhead gas of the first rectification column operating under the highest pressure.
  • this condenser was used as a bath condenser with a relatively high hydrostatic level because of the requirements for the nitrogen product pressure and thus the first pressure level (for example 11 bar; the feed air is correspondingly highly compressed)
  • the process topology with several rectification columns is based on the generation Injection of air (approx. 10-15% of the amount of air used) into the medium-pressure unit, provided for the cooling capacity
  • the present invention proposes that not (or at least not exclusively) a feed air stream into the second rectification column is used to generate the process cooling capacity, but rather one in one
  • Condenser evaporator top condenser of the first rectification column evaporating stream, namely the stream referred to here as "cooling stream".
  • An essential aspect of the present invention consists inter alia in the utilization of the differential pressure between the operating pressure of the second
  • Rectification column i.e. the corresponding to the second pressure range
  • evaporation pressure in the one used for condensing the top gas
  • Condenser for generating the cold and reducing the air "blown amount" into the second rectification column.
  • the evaporation pressure in the condenser mentioned becomes higher (and thus the better for the process of refrigeration), the lower the temperature difference in the condenser.
  • the capacitor is therefore advantageously not as
  • Bath condenser but in particular designed as a forced flow condenser with the lowest possible minimum temperature difference.
  • a forced flow condenser evaporator is advantageously used.
  • forced-flow condenser evaporator express reference is made to the explanations above.
  • a further liquid cooling stream is evaporated or partially evaporated in indirect heat exchange against the top gas to condense the top gas of the first column, with the further cooling stream coming out above the bottom taken from the first column and after evaporation or
  • Partial evaporation is at least partially compressed and returned to the first column.
  • the vaporized further cooling flow or a part thereof is compressed in particular in one or more compressors that are mechanically coupled to one or more expansion machines and, in particular, are additionally braked.
  • the compression takes place in particular on one
  • Expansion machines compress, in particular, a remainder of the cooling flow formed from the bottom liquid of the first column, which is not compressed and is returned to the second column. This compressed remainder is in particular compressed to a pressure in the first pressure range and into the first column
  • the mentioned first pressure range is in particular from 9 to 12 bar
  • the second pressure range in particular from 4 to 6.5 bar
  • the third pressure range in particular from 1 to 2 bar.
  • the third pressure range can, however, also be reduced further, in particular by 50 to 200 mbar, for example compared to the pressure value of 1.4 bar mentioned at the beginning with regard to conventional air separation plants.
  • the second pressure range can also be reduced by 120 to 500 mbar, for example compared to the value of 5.3 bar mentioned at the beginning.
  • a corresponding pressure reduction is possible in particular when, as explained below, gas from an evaporation chamber
  • Condenser evaporator the top gas of the fourth column condensed as Regeneration gas is used. The driving temperature difference in this condenser evaporator is also reduced.
  • the refrigeration capacity can be increased accordingly by increasing the pressure difference between the first pressure range and the second pressure range or lowering the outlet pressure during expansion.
  • the pressure specifications here denote absolute pressures at the top of the columns.
  • the first pressure range is thus above a pressure which is conventionally used for a high pressure column in an air separation plant.
  • the second column can in particular be operated at a lower pressure range than that conventionally in one
  • High pressure column used in the air separation plant In principle, however, it can also be the same pressure.
  • Cooling stream used cooling stream is formed using the first bottom liquid of the first column, no pump is necessary for pumping liquid nitrogen due to the existing pressure conditions. This means that there is less heat input into the low-temperature system and, in contrast to the use of a fluid that is more oxygen-rich, there is a higher driving temperature difference due to the lower oxygen content in the evaporating liquid. This enables a higher evaporation pressure and the turbine output is increased accordingly.
  • an energy advantage of 5-6%, based on the performance of the main air compressor, can be achieved by increasing the yield of nitrogen product and the recovery of turbine power compared to the aforementioned, likewise possible expansion of feed air instead of the evaporated cooling stream .
  • This can correspond to a reduced energy consumption of, for example, approx. 500 kW and thus a TCO (Total Cost of Ownership) cost reduction of over EUR 1 million.
  • TCO Total Cost of Ownership
  • a smaller amount of air is required overall, which leads to a smaller “warm” part of the system.
  • a smaller main heat exchanger can also be used (the kF value is approx. 6% lower with the same MTD value). If a forced flow condenser evaporator is used, there is no enrichment of flammable hydrocarbons due to the relatively high evaporation pressure (typically more than 7 bar).
  • the present invention can provide different possibilities for temperature control or non-temperature control of the cooling stream, each of which can offer certain energetic advantages. This can be done with the evaporation or partial evaporation of the
  • Cooling stream formed gas which is expanded to perform work and fed into the second column, are heated before the expansion.
  • the main heat exchanger of the air separation plant can be used for this purpose.
  • the feed streams can be cooled by means of appropriate cold and the heat exchanger profile can be adapted accordingly. That at the
  • Evaporation or partial evaporation of the cooling stream which is expanded to perform work and is fed into the second column, but can also be supplied to the expansion at a temperature at which it is present after the evaporation or partial evaporation; so there is no further temperature control in this embodiment.
  • Evaporation or partial evaporation of the cooling stream which is expanded to perform work and is fed into the second column, but can also be supplied to the expansion at a temperature at which it is present after the evaporation or partial evaporation; so there is no further temperature control in this embodiment.
  • Boundary conditions can also offer energetic advantages, the gas formed during the evaporation or partial evaporation of the cooling stream, which is expanded to perform work and fed into the second column, can be fed into the second column at a temperature at which it is taken from an expansion machine used for expansion will. Alternatively, you can warm up after relaxation.
  • Overhead gas of the fourth column is particularly preferred in the context of a
  • Condensation space of a condenser evaporator condenses, its
  • a gas mixture is removed from the evaporation chamber.
  • Part of this gas mixture and / or also at least part of the residual gas from the upper region of the third column, i.e. at least part of a gas mixture which is withdrawn from the third column, can be used in one embodiment of the present invention to form a recycle stream and thereby heated, compressed, cooled and fed into the second column.
  • the main heat exchanger can be used for heating and cooling the recycle stream mentioned
  • Air separation plant can be used.
  • a (further) part of the gas mixture from the evaporation chamber of the condenser evaporator can also be used as a regeneration gas for an adsorber, in which feed air that is fed to the column system is processed. This can take place in particular with a corresponding evaporation pressure.
  • the aforementioned adsorber is operated in particular without the use of regeneration gas, which is taken from the third column and fed to the adsorber in the same composition as there.
  • gas from the upper region of the third column and gas from the lower region of this column can be combined and heated as a common stream in the main heat exchanger and as
  • Regeneration gas can be used.
  • At least part of the gas mixture that is in the evaporation space of the condenser evaporator is taken, used as a first regeneration gas portion, and at least part of the gas or the gas mixture mentioned, which is withdrawn from the third column, is used as a second regeneration gas portion.
  • the second regeneration gas component is provided at a lower pressure than the first, compressed and combined with the first regeneration gas component before it is fed to the adsorber. So it is combined residual gas from the third column and gas from a top condenser of the argon column.
  • the embodiment just explained has advantages in particular when no refrigeration machine is used for pre-cooling and therefore the need for regeneration gas is comparatively high. In such cases it can happen that the amount of gas from the condenser evaporator is insufficient as the amount of regeneration gas. Therefore, a partial flow of the residual gas from the low-pressure column (i.e. the third column) is recompressed (the pressure difference is approx. 50 to 200 mbar) and combined with the other flow. There are also advantages if the
  • the air inlet temperature into the molecular sieve i.e. the adsorber
  • the hydrogen removal on the special layer provided for this with a catalyst in the adsorber
  • the amount of gas from the condenser evaporator is not sufficient as the amount of regeneration gas.
  • the evaporation chamber of the condenser evaporator in whose condensation chamber the top gas of the fourth column is at least partially condensed, is supplied with a portion of the first bottom liquid and subjected to partial evaporation, the aforementioned gas mixture being formed in this partial evaporation.
  • a top condenser of a crude argon column or the only existing argon column is cooled using bottom liquid from the first column. If a pure argon column is available as the fifth column, its top condenser can also be cooled using a corresponding bottom liquid, as explained below.
  • evaporated and non-evaporated portions of the bottom liquid from the first column which are in the condenser evaporator or evaporators of the fourth or fourth column and fifth column were used, then also at least partially transferred into the third column (possibly minus the portion used in the adsorber), namely at a position which corresponds to the oxygen content and argon content of these fluids.
  • the vaporized and non-vaporized fractions can therefore be fed into the third column at essentially the same point.
  • the streams mentioned can be combined or transferred separately from one another into the third column.
  • the fluid transferred from the first column to the third column thus comprises corresponding liquid, ie at least part of the first bottom liquid which was used to cool the top condenser or condensers of the fourth or fourth and fifth columns. If necessary, it is also possible to dispense with feeding vaporized fractions from the top condenser or condensers and these vaporized fractions are carried out from the process without being fed into the third column, as mentioned for the case of the recycle stream and the fraction used in the adsorber. In this case, too, part of the first bottom liquid is fed into the third column with the non-evaporated liquid.
  • the fluid fed from the second column into the third column can comprise at least part of the second bottom liquid which is transferred from the second column to the third column without using a pump.
  • corresponding bottom liquid can be transferred into the third column only on the basis of the pressure difference between the second and the third column. However, it can be subcooled beforehand or during the transfer against further currents using a subcooling countercurrent.
  • Top gas can be withdrawn from the first column at a defined withdrawal position and discharged from the air separation plant as a nitrogen pressure product in a corresponding pressure range.
  • the present invention can be used in combination with a
  • Pure argon column can be used, that is to say a fifth column into which the fluid from the fourth column is transferred, the fluid transferred from the fourth column having an argon content which is higher than that from the third column
  • the fifth column is therefore used in the context of the present invention, as is fundamentally known from the field of air separation technology, to obtain a corresponding argon product.
  • the top gas of the fifth column is condensed by means of a further condenser evaporator, in which a further portion of the second
  • the side stream which in the context of the present invention is formed with a lower oxygen content and a higher argon content than the third bottom liquid and is withdrawn from the third column, can, in particular, obtain an oxygen-depleted gas mixture and an oxygen-rich one
  • Liquid are subjected to processing in a further column, with at least a portion of the oxygen-depleted gas mixture from the further column being able to be fed into the fourth column.
  • part of the side stream reaches the fourth column via the detour of the further column.
  • the further column is in particular designed in two parts and comprises two parts arranged one above the other, which are separated by a fluid-tight separating tray, the oxygen-depleted gas mixture at least at the top of the upper part, but possibly also at the top of the lower part, and the oxygen-rich liquid is taken from the sump of the lower part.
  • the side stream from the third column is fed, in particular in gaseous form, into a lower region of the upper part.
  • liquid is withdrawn from the bottom of the upper part and returned to the third column.
  • Bottom liquid from the fourth column is given up as reflux, in particular at the top of the upper part, but can also be partly given up as reflux on the lower part.
  • the lower part fulfills the function of a (high-purity) oxygen column.
  • Air separation plant set up to carry out a process as previously described in different configurations has been explained, and this has each set up means.
  • Air separation plant is expressly referred to the explanations relating to the method according to the invention.
  • FIGS. 1 to 4 air separation plants are shown which each correspond to configurations of the present invention insofar as they fall under the scope of the patent claims and otherwise relate to the technical background and / or configurations not according to the invention.
  • the air separation plants according to FIGS. 1 to 4 are each designated as a whole with the reference numerals 100 to 400.
  • the air separation plant 500 illustrated in FIG. 5 is shown as a variant of the air separation plant 100 illustrated in FIG. 1.
  • the aspects illustrated here can nevertheless also be implemented in other systems, in particular systems 200 to 400.
  • All of the air separation plants 100 to 400 shown in FIGS. 1 to 4 are equipped with a column system which, regardless of the different design and possibly different number of columns, is each designated overall by 10.
  • the column systems 10 each have a first column 11, a second column 12, a third column 13 and a fourth column 14.
  • the second column 12 and the third column 13 are each part of one
  • Double column basically of a known type.
  • the first column 11 is formed separately from the second column 12 and the third column 13.
  • the first column 11 is equipped with a condenser-evaporator 111 which is used for the condensation of top gas from the first column 11 and, in the configurations according to FIGS. 1 to 3, is more classic
  • Head capacitor is formed.
  • bottom liquid from the first column 11 is fed into the condenser evaporator 111, which is designed as a forced flow condenser evaporator in the illustrated examples, and is conveyed without the use of a pump.
  • Bottom liquid is formed from the first column 11, evaporated against the top gas of the first column 11 or partially evaporated.
  • Partial evaporation of the cooling flow is formed by means of a
  • Expansion machine 5 expanded to a pressure in the second pressure range, performing work, and fed into the second column 12.
  • the second column 12 and the third column 13 stand in via an internal condenser-evaporator 121, the so-called main condenser
  • the main condenser 121 serves on the one hand to condense an overhead gas of the second column 12 and
  • the second column 12 and the third column 13 can also be formed separately.
  • the main capacitor 121 can alternatively also be formed on the outside. Different types of
  • Condenser evaporators can be used as the main condensers 121.
  • the fourth column 14 is used in all air separation plants 100 to 400 according to FIGS. 1 to 4 for the extraction of argon.
  • the systems 100 to 400 are each designed to remove an argon product from the fourth column 14.
  • Crude argon columns and corresponding modifications reference is also made to the above citations from the specialist literature.
  • the fourth column is equipped with a condenser-evaporator (top condenser) 141 which condenses top gas.
  • this is cooled with part of the bottom liquid from the first column 11, whereas in the configuration according to FIG. 4, bottom liquid from the second column 12 is used for this purpose.
  • the sump liquid used in each case is subcooled beforehand by a subcooling countercurrent 18.
  • Head condenser 141 unevaporated portion is illustrated in the here
  • a vaporized portion is used to regenerate an adsorber and, in the case of the air separation plant 300 according to FIG. 3, to form a return flow, as will be explained below.
  • a further column 15 is provided in which a mass transfer between a portion of a bottom stream from the fourth column 14 and a side stream from the third column 13 and a portion of the bottom stream from the fourth Column 14 is depleted in more volatile components.
  • the further column 15 has an upper and a lower area which are functionally completely separated from one another. Further details are explained below.
  • the further column 15 is designed with a condenser evaporator 152, which is heated with top gas from the second column 12.
  • Air separation plants 100 to 300 according to FIGS. 1 to 3 have a pump 19 which conveys bottom liquid from the fourth column 14 back into the further column 15.
  • a bottom liquid is formed in the first column 11, which here is the first
  • Sump liquid is called.
  • the second column 12 are accordingly a second bottom liquid, a third bottom liquid in the third column 13 and a fourth bottom liquid in the fourth column 14.
  • the first column 11 is in a first pressure range, the second column 12 in a second
  • the second sump liquid will have a higher oxygen content and a higher one
  • fluid is transferred from the first column 11 into the second column 12 (and in the air separation plants 100 to 300 according to FIGS. 1 to 3 also into the third column 13) fed in. Furthermore, fluid is fed from the second column 12 into the third column 13 and fluid is fed from the fourth column 14 into the third column 13.
  • the fluid fed from the third column 13 into the fourth column 14 comprises at least a part of a side stream which has a lower oxygen content and a higher argon content than the second bottom liquid from the third column 13 is removed.
  • a feed air stream a is sucked in from the atmosphere generally designated here by A by means of a main air compressor 1 via a filter which is not separately designated and is shown hatched, in FIG an aftercooler, also not separately designated, and fed to a direct contact cooler 2, which is operated with cooling water W.
  • the feed air stream is freed from water and carbon dioxide in an adsorption device 3 in a manner which has been described many times in the literature.
  • Adsorption device 3 previously also generally referred to as "adsorber" can be regenerated by means of a regeneration gas flow z. The formation of the
  • the correspondingly treated and thus purified feed air stream is fed to a main heat exchanger 4 on the warm side.
  • the feed air stream a is withdrawn from the main heat exchanger 4 on the cold side or near its cold end and fed into the first column 11.
  • the bottom liquid of the first column 11 is withdrawn from this and divided into two substreams d and e in the air separation plants 100 to 300 according to FIGS. 1 to 3.
  • the substream d is fed into the condenser evaporator 111 and evaporated in the process.
  • the vaporized substream d is then partially heated in the main heat exchanger 4 and then expanded to the operating pressure of the second column 12 in an expansion machine 5, which is coupled to a generator G, and fed into this second column 12 in a lower region.
  • the treatment of the sump liquid in the air separation plant 400 according to FIG. 4 differs from this. Please refer to the specific explanations below.
  • the partial flow e is conducted in the air separation plants 100 to 300 according to FIGS. 1 to 3 through the subcooling countercurrent 18 and then through the condenser evaporator 141.
  • a part can also, as in the form of a
  • Linkage f illustrated are fed into the second column 12.
  • Gas generated in the top condenser 141 may be different from that already mentioned
  • Regeneration gas stream z can be used. This is done first in the
  • the top gas of the first column 11 is partly conducted in the form of a stream h through the condensation space of the top condenser 111 and returned to the first column 11 as a liquid reflux. Another portion is in the form of a
  • the bottom liquid of the second column 12 is withdrawn therefrom in the form of a stream j, passed through the subcooling countercurrent 18, and fed into the third column 13.
  • the material flow j is passed through the condenser evaporator 141 for cooling as an alternative to the material flow e (see above).
  • Gas formed in the air separation plant 400 can also be used here as a regeneration gas stream, which is also designated with z for the sake of simplicity.
  • gas from the top condenser 141 or its evaporation space is also fed into the third column 13.
  • a portion which remains liquid is fed into the third column 13, as also illustrated in FIG. 4 in the form of a stream g.
  • the top gas of the second column 12 is partly conducted in the form of a stream k through the condensation space of the main condenser 121, liquefied there and partly returned to the second column 12 as a liquid reflux. Another part is in the form of a material flow I in the condensation chamber of the
  • Condensation chamber of the main condenser 121 combined liquefied portion, as illustrated in the form of link I.
  • Corresponding liquid can also be fed into the first column 11 as return flow by means of a pump 6.
  • the pump 6 conveys a liquid, nitrogen-rich stream b, which is withdrawn from the second column 12 in an upper region.
  • Another portion of overhead gas from the second column 12 is in the examples according to Figures 1 to 3 carried out in the form of a stream c from the plant.
  • the liquefied portion of the stream k and the stream I are not combined. Rather, portions of the stream k are fed separately to the second column 12 and the third column 13 after liquefaction. The stream I is fed into the third column 13 separately.
  • the bottom liquid of the third column 13 is withdrawn from this in the form of a material flow o, brought to liquid pressure by means of an internal compression pump 7, converted into the gaseous or critical state by heating in the main heat exchanger 4 and as a gaseous oxygen pressure product from the
  • Air separation unit 100 diverted or otherwise used.
  • gas withdrawn from the third column 13 in the form of a stream p above the sump becomes one with residual gas from the third column 13 (see below)
  • the top gas of the third column 13 is passed in the form of a stream r through the subcooling countercurrent 18 and combined in the air separation plants 100 to 300 according to FIGS. 1 to 3 with the stream o, as mentioned, to form the collective stream q.
  • a separate one takes place in the air separation plant 400 according to FIG. 4, a separate one takes place
  • a side stream t is also withdrawn in gaseous form from the third column 13 and initially fed into an upper part of the further column 15.
  • a material flow u is returned in liquid form to the third column 13.
  • In the upper part of the further column 15 is a
  • Substance exchange is carried out with bottom liquid from the fourth column 14, which is applied in liquid form in the air separation plants 100 to 300 according to FIGS. 1 to 3 in the form of a mass flow v into the upper and lower part of the further column 15.
  • the air separation plant 400 according to FIG. 1 is applied in liquid form in the air separation plants 100 to 300 according to FIGS. 1 to 3 in the form of a mass flow v into the upper and lower part of the further column 15.
  • Stream w is fed into the fourth column 14.
  • the fourth column 14 is only fed with a gas stream w ′ from the upper part of the further column 15.
  • Liquid exchange between the upper and lower part of the further column 15 takes place here in the form of the streams w "and w '".
  • part of the side stream t is ultimately fed into the fourth column 14 and from this part of the bottom liquid is ultimately returned to the third column 13.
  • the further column 15 can, for example, also be arranged above the top condenser 111 of the first column 11.
  • a material flow also designated by x for the sake of clarity, is taken from the tank system T, evaporated in the main heat exchanger 4 and implemented as a highly pure, gaseous oxygen product.
  • argon-rich liquid is withdrawn in the form of a substance flow y by means of a further internal compression pump 8, brought to liquid pressure, converted into the gaseous or critical state by heating in the main heat exchanger 4, and as a gaseous argon pressure product from
  • Air separation unit 100 diverted or otherwise used.
  • Air separation plant 400 according to FIG. 4 also shows a corresponding tank system T ′ in this context.
  • Liquid nitrogen, liquid oxygen (possibly also with different purities) and liquid argon can be provided as further products of the system 100, as is known in principle and shown for example in the form of a partial flow of the liquefied top gas h of the first column 11.
  • liquid nitrogen, liquid oxygen (possibly also with different purities) and liquid argon can be provided as further products of the system 100, as is known in principle and shown for example in the form of a partial flow of the liquefied top gas h of the first column 11.
  • Air separation plant 400 according to FIG. 4 also shows a liquid nitrogen feed into the condenser evaporator 111 based on a material flow h '.
  • the air separation plant 200 constructed in this way differs from the air separation plant shown in FIG. 1 essentially in that the material flow d is not heated before it is expanded in the expansion machine 8.
  • the air separation plant 300 illustrated in FIG. 3 differs from the air separation plant 200 shown in FIG Main heat exchanger 4 is cooled and fed into the second column 12.
  • the air separation plant 300 can otherwise also be the same as the air separation plant 100 illustrated in FIG. 1.
  • the air separation plant 400 shown in FIG. 4 illustrates the
  • Part of the stream d is expanded in the expansion machine 5, which is coupled to a generator G, and, as mentioned (see link D), is fed into the second column 12.
  • the remainder of the material flow d is partially heated in the main heat exchanger 4 and then in another
  • Relaxation machine 401 which is coupled to a compressor 402 and a brake 403, relaxes. Subsequently, a diversion from the
  • Air separation plant 400 Part of the liquefied material flow h is discharged in liquid form and, if necessary, subcooled against part of the same material flow in a subcooler 404. The portion used for subcooling can be combined with the relaxed remainder of the stream d.
  • Condenser evaporator 111 at least in part, a compression in the compressor 402 subjected, cooled again in the main heat exchanger 4 and returned to the first column 11.
  • the air separation plant 500 shown in FIG. 5 is illustrated as a variant of the air separation plant 100 according to FIG. She stands out

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

L'invention concerne un procédé de décomposition d'air à basse température, dans lequel une installation de décomposition d'air (100-500) pourvue d'un système de colonnes (10) est utilisée, lequel comporte une première colonne (11), une deuxième colonne (12), une troisième colonne (13) et une quatrième colonne (14). Du fluide provenant de la première colonne (11) est injecté au moins dans la deuxième colonne (12), du fluide provenant de la deuxième colonne (12) est injecté au moins dans la troisième colonne (13), du fluide provenant de la troisième colonne (13) est injecté au moins dans la quatrième colonne (14), et du fluide provenant de la quatrième colonne (14) est injecté au moins dans la troisième colonne (13). Le fluide injecté depuis la troisième colonne (13) dans la quatrième colonne (14) comprend au moins une partie d'un soutirage latéral, qui est soutiré avec une teneur en oxygène plus faible et une teneur en argon plus élevée que le troisième liquide de puits provenant de la troisième colonne (13). L'invention prévoit qu'un liquide de reflux est formé par une condensation de gaz de tête de la première colonne (11), lequel est retourné à l'état liquide à la première colonne (11). Pour condenser le gaz de tête de la première colonne (11), un flux de refroidissement liquide est fourni et est évaporé ou évaporé en partie lors de l'échange de chaleur indirect contre le gaz de tête, et le gaz formé lors de l'évaporation ou de l'évaporation partielle du flux de refroidissement est détendu avec production de travail sur une pression dans la deuxième plage de pressions et est injecté dans la deuxième colonne (12). L'invention concerne également une installation (100-500) correspondante.
EP20727147.9A 2019-06-04 2020-05-06 Procédé et installation de décomposition d'air à basse température Withdrawn EP3980705A1 (fr)

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EP19020361 2019-06-04
PCT/EP2020/025207 WO2020244801A1 (fr) 2019-06-04 2020-05-06 Procédé et installation de décomposition d'air à basse température

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EP (1) EP3980705A1 (fr)
KR (1) KR20220015406A (fr)
CN (1) CN113874669A (fr)
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WO (1) WO2020244801A1 (fr)

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Publication number Priority date Publication date Assignee Title
US20240035743A1 (en) 2022-08-01 2024-02-01 Air Products And Chemicals, Inc. Process and apparatus for recovery of at least nitrogen and argon
US20240125550A1 (en) 2022-10-18 2024-04-18 Air Products And Chemicals, Inc. Process and Apparatus for Improved Recovery of Argon

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR610024A (fr) * 1924-11-18 1926-08-28 Procédé de liquéfaction et de séparation des mélanges gazeux, particulièrementde l'air
GB688550A (en) * 1950-03-29 1953-03-11 British Oxygen Co Ltd Improvements in or relating to the low temperature separation of gas mixtures by rectification
FR1496217A (fr) * 1966-08-19 1967-09-29 Air Liquide Procédé de séparation et de purification d'un mélange gazeux riche en éthylène
US4533375A (en) * 1983-08-12 1985-08-06 Erickson Donald C Cryogenic air separation with cold argon recycle
US4769055A (en) * 1987-02-03 1988-09-06 Erickson Donald C Companded total condensation reboil cryogenic air separation
US5098456A (en) * 1990-06-27 1992-03-24 Union Carbide Industrial Gases Technology Corporation Cryogenic air separation system with dual feed air side condensers
GB9414939D0 (en) * 1994-07-25 1994-09-14 Boc Group Plc Air separation
GB9513765D0 (en) * 1995-07-06 1995-09-06 Boc Group Plc Production of argon
GB9619687D0 (en) * 1996-09-20 1996-11-06 Boc Group Plc Air separation
US5966967A (en) * 1998-01-22 1999-10-19 Air Products And Chemicals, Inc. Efficient process to produce oxygen
EP2789958A1 (fr) 2013-04-10 2014-10-15 Linde Aktiengesellschaft Procédé de décomposition à basse température de l'air et installation de décomposition de l'air
EP2980514A1 (fr) * 2014-07-31 2016-02-03 Linde Aktiengesellschaft Procédé de séparation cryogénique de l'air et installation de séparation d'air
EP3059536A1 (fr) * 2015-02-19 2016-08-24 Linde Aktiengesellschaft Procédé et dispositif destinés à la production d'un produit d'azote pressurisé
EP3290843A3 (fr) * 2016-07-12 2018-06-13 Linde Aktiengesellschaft Procédé et dispositif destiné à fabriquer de l'azote pressurisé et liquide par décomposition à basse température de l'air

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WO2020244801A1 (fr) 2020-12-10
TW202108222A (zh) 2021-03-01
CN113874669A (zh) 2021-12-31
KR20220015406A (ko) 2022-02-08

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