EP3631327A1 - Method and apparatus for air separation by cryogenic distillation - Google Patents

Method and apparatus for air separation by cryogenic distillation

Info

Publication number
EP3631327A1
EP3631327A1 EP18736971.5A EP18736971A EP3631327A1 EP 3631327 A1 EP3631327 A1 EP 3631327A1 EP 18736971 A EP18736971 A EP 18736971A EP 3631327 A1 EP3631327 A1 EP 3631327A1
Authority
EP
European Patent Office
Prior art keywords
air
column
pressure
compressor
liquid
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.)
Granted
Application number
EP18736971.5A
Other languages
German (de)
French (fr)
Other versions
EP3631327B1 (en
Inventor
Jean-Pierre Tranier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP3631327A1 publication Critical patent/EP3631327A1/en
Application granted granted Critical
Publication of EP3631327B1 publication Critical patent/EP3631327B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • F25J3/04054—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 of air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/0015—Nitrogen
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
    • F25J1/0037—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work of a return stream
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0045—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by vaporising a liquid return stream
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop
    • F25J1/0224—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop in combination with an internal quasi-closed refrigeration loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0234—Integration with a cryogenic air separation unit
    • 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
    • F25J3/04006—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
    • F25J3/0406—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 of 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
    • 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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    • 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
    • F25J3/0409—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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    • 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
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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
    • F25J3/04151—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
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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
    • F25J3/04151—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
    • F25J3/04218—Parallel arrangement of the main heat exchange line in cores having different functions, e.g. in low pressure and high pressure cores
    • F25J3/04224—Cores associated with a liquefaction or refrigeration cycle
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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
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    • 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
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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
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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
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
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    • 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
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    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
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    • F25J3/04351—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams of nitrogen
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    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04333—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/04351—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams of nitrogen
    • F25J3/04357—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams of nitrogen and comprising a gas work expansion loop
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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
    • F25J3/04472—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
    • F25J3/04503—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 by exchanging "cold" between at least two different cryogenic liquids, e.g. independently from the main heat exchange line of the air fractionation and/or by using external alternating storage systems
    • F25J3/04509—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 by exchanging "cold" between at least two different cryogenic liquids, e.g. independently from the main heat exchange line of the air fractionation and/or by using external alternating storage systems within the cold part of the air fractionation, i.e. exchanging "cold" within the fractionation and/or main heat exchange line
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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
    • F25J3/04472—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
    • F25J3/04503—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 by exchanging "cold" between at least two different cryogenic liquids, e.g. independently from the main heat exchange line of the air fractionation and/or by using external alternating storage systems
    • F25J3/04509—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 by exchanging "cold" between at least two different cryogenic liquids, e.g. independently from the main heat exchange line of the air fractionation and/or by using external alternating storage systems within the cold part of the air fractionation, i.e. exchanging "cold" within the fractionation and/or main heat exchange line
    • F25J3/04515—Simultaneously changing air feed and products output
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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
    • F25J3/04666—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system
    • F25J3/04672—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser
    • F25J3/04678—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser cooled by oxygen enriched liquid from high pressure column bottoms
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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
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    • F25J3/04721—Producing pure argon, e.g. recovered from a crude argon column
    • F25J3/04727—Producing pure argon, e.g. recovered from a crude argon column using an auxiliary pure argon column for nitrogen rejection
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    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
    • F25J2200/06—Processes or apparatus using separation by rectification in a dual pressure main column system in a classical double column flow-sheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
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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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    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
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    • F25J2210/00—Processes characterised by the type or other details of the feed stream
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    • 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
    • F25J2240/10—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid being air
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    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
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    • F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
    • F25J2250/42—One fluid being nitrogen
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    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
    • F25J2250/58—One fluid being argon or crude argon
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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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration

Definitions

  • the present invention relates to a method and an apparatus for the separation of air by cryogenic distillation.
  • it relates to methods and apparatus for producing oxygen and / or nitrogen under high pressure.
  • the gaseous oxygen produced by the air separation units is usually at a high pressure of about 20 to 50 bar.
  • the basic distillation scheme is usually a double column process producing oxygen at the bottom of the second column operated at a pressure of 1 to 4 bar.
  • Oxygen must be compressed at a higher pressure, thanks to an oxygen compressor or the liquid pumping process. Because of the safety issues associated with oxygen compressors, the newer oxygen production units use the liquid pumping process.
  • an additional booster is required to elevate a portion of the air or feed nitrogen to a higher pressure in the range of 40 to 80 bar. . In essence, the booster replaces the oxygen compressor.
  • One of the goals of developing new process cycles is to reduce the energy consumption of an oxygen generating unit.
  • FIG. 1 This prior art is illustrated in FIG.
  • a double column 2 is used in an air separation unit 1, comprising a first column 8 and a second column 9 operating at a lower pressure than the first column, thermally connected by a reboiler / condenser 10.
  • the entire supply air is compressed in a compressor 6 at the pressure of the first column 8, purified in the purification unit 7, and subdivided into three .
  • a flow 502 is sent to a booster 503, cooled in a water cooler (not shown), and further cooled in the heat exchanger 5, then expanded in a turbine 501 coupled to the booster 503.
  • the expanded air 502 is sent to the second column.
  • Another part of the air is sent to the heat exchanger 5 substantially under the same pressure as the first column 8.
  • the third flow is compressed in a compressor 230 and sent to the heat exchanger, where it condenses.
  • the liquefied air is subdivided between the first column 8 and the second column 9.
  • An oxygen enriched liquid flow LR is expanded and sent from the first column to the second column.
  • the nitrogen-enriched liquid flow LP is relaxed and sent from the first column to the second column.
  • Pure liquid nitrogen NLMP is produced by the first column, then cooled again in the heat exchanger 24 and expanded in the valve 143 and sent to a storage 144.
  • the high pressure nitrogen gas 39 is withdrawn at the top of the the first column and heated in the heat exchanger to form a product flow 40.
  • the liquid oxygen OL is withdrawn from the bottom of the second column 9, pressurized by a pump 37 and sent partly in the form of a flow rate 38 to the heat exchanger 5, where it vaporizes by heat exchange with the pressurized air to form a pressurized oxygen gas.
  • the remainder of the liquid oxygen 52 is withdrawn as a liquid product.
  • a nitrogen-enriched head gas stream NR is withdrawn from the second column 9, heated in the heat exchanger 5 in the form of a flow rate 33.
  • Argon is produced using a column of impure argon 3 and pure argon 4.
  • the impure argon column is fed with a flow 16 from the second column 9.
  • a flow of liquid 17 is sent from the bottom of the impure argon column 3 to the second column 9.
  • a rich liquid is sent to the top condenser 12 of the column 3 through the valve 26 and is evaporated to form a flow 27 which is returned to the second column .
  • a product flow 19 is sent to the condenser 20 and hence the flow 19.
  • the flow 19 is condensed in the heat exchanger 20 and subdivided into the flow 48 which is sent to the waste flow 33 at the point of intersection 50 , and another flow.
  • the other flow is sent by the valve 21 to the column 4.
  • the pure argon column 4 produces a product flow 45.
  • a purge flow 46 is also withdrawn.
  • the condenser 20 is fed by the nitrogen-rich liquid LP through the valve 31, and the vaporized liquid is sent by the valve 32 to the waste flow 33.
  • Figure 2 shows the relationship between heat exchange in kcal / h and temperature for fluids cooling and heating in exchanger 5.
  • a cold compression process as described in US-A-5,475,980, provides a technique for controlling an oxygen generating unit with a single air compressor.
  • the air to be distilled is cooled in the heat exchanger, and is then compressed again by a booster controlled by an expansion machine whose effluent is sent to the first column of a double column process. which operates at the highest pressure.
  • the discharge pressure of the air compressor is of the order of 15 bar, which is likewise very advantageous for the purification unit.
  • a disadvantage of this approach is the increased size of the heat exchanger due to the additional recycling of the flow, which is representative of a cold pressing unit. It is possible to reduce the size of the exchanger by opening the temperature approaches of the exchanger. However, this would lead to inefficient use of energy, and higher compressor discharge pressure, which would increase the cost.
  • US-A-5,596,885 a portion of the feed air is further compressed in a hot booster, while at least a portion of the air is still compressed in a cold booster. .
  • the air from both boosters is liquefied, and some of the cold compressed air is expanded in a Claude turbine.
  • US-A-5,901,576 discloses various arrangements of cold compression schemes using the expansion of a vaporized rich liquid from the bottom of the first column, or the expansion of the high pressure nitrogen to drive the compressor cold. In some cases, motor-driven cold compressors have also been used. These processes also operate with feed air at approximately the pressure of the first column and, in most cases, a booster is also required.
  • US-A-6,626,008 discloses a heat pump cycle using a cold compressor to improve the distillation process for the production of low purity oxygen for a double vaporizer oxygen production process. Low air pressure, and a booster, are also representative of this type of process.
  • EP-A-1 972 872 discloses means for improving the above processes using a cold compressor, in particular by introducing all the feed air flows into the columns at a temperature close to the temperature. of the column at the point where the flow is introduced, in order to reduce the thermodynamic irreversibility of the system. But it requires the addition of at least one additional compression stage.
  • the present invention therefore aims at solving the disadvantages of these processes, in particular by introducing all the feed air flow rates into the columns at a temperature close to the temperature of the column at the point where the flow is introduced, in the goal of reducing the thermodynamic irreversibility of the system without adding an additional compression stage.
  • the overall cost of the products of an oxygen production unit can therefore be reduced.
  • the main improvement is due to the use of an air booster (Booster Air Compressor (BAC)) to recycle air once it has been used to recover the heat produced by the vaporization of a liquid high pressure in the main heat exchanger.
  • Booster Air Compressor BAC
  • a process according to the preamble of claim 1 is known from US6336345.
  • a method for separating air by cryogenic distillation in a column system comprising a first column and a second column operating at a lower pressure than the first column, comprising the steps of:
  • Clean, cooled air is sent from the first compressor to the column system to separate.
  • the expansion is performed in at least one valve.
  • the expansion is performed in at least one turbine and produces work.
  • the temperature of the at least one fraction before expansion is less than the sum of the temperature of the vaporization of the liquid and the minimum temperature approach in the heat exchanger.
  • the second compressor is a multi-stage compressor.
  • said at least one third pressure is at least the inlet pressure of one of the stages of the second compressor.
  • a stage of the second compressor is driven by a machine for expanding a process fluid.
  • the inlet temperature of the expansion machine is lower than the ambient temperature.
  • At least one stage of the second compressor has a suction temperature lower than the ambient temperature.
  • the suction temperature is higher than the vaporization temperature of the liquid, but is close to it.
  • the liquid is a flow enriched in oxygen
  • the liquid is a flow enriched in nitrogen.
  • the production rate of the liquid product or products is not greater than 10% of the supply air, preferably not more than 5% of the supply air.
  • an apparatus for separating air by cryogenic distillation in a column system comprising a first column and a second column operating at a lower pressure than the first column, further comprising:
  • a first compressor for compressing the supply air to a first outlet pressure of at least one bar greater than the pressure of the first column, preferably substantially equal to the pressure of the first column
  • iv means for withdrawing the liquid from a column of the column system, means for pressurizing the liquid, means for supplying the pressurized liquid to the heat exchanger, and means for withdrawing the vaporized liquid from the exchanger heat,
  • the apparatus comprises an expansion turbine of the auxiliary flow rate fraction compressed in the second compressor.
  • FIGS. 3, 5 and 6 are fluid flow schemes showing cryogenic air separation methods according to the invention, and FIG. heat exchange diagram for the exchanger 5 of FIG. 3.
  • a double column 2 comprising a first column 8 and a second column 9 made available, thermally connected by a reboiler / condenser 10.
  • the entire supply air is compressed in the compressor 6 at a pressure of at least one bar greater than the pressure of the first column 8, preferably substantially equal to the pressure of the first column 8, allowing a pressure drop in the intermediate pipes, purified in the purification unit 7 and subdivided into three.
  • a flow 502 is sent to a booster 503, cooled in a water cooler (not shown), then further cooled in the heat exchanger 5, then expanded in a turbine 501, coupled to the booster 503.
  • the air relaxed 502 is sent to the second column.
  • Another part 507 of the air is sent to the heat exchanger 5 under a pressure substantially equal to that of the first column 8.
  • the third flow 505 is compressed in a compressor 230 and sent to the heat exchanger, where it condenses.
  • the compressor 230 is a four-stage centrifugal compressor 230A, 230B, 230C and 230D, for example of the integrated speed-multiplication type cooled by intermediate water coolers 232A, 232B, 232C and a cooler. final 232D.
  • the compressor suction pressure is 5.5 bar abs
  • the intermediate pressures are 10.2 bar abs, 18.9 bar abs and 35.1 bar abs
  • the final outlet pressure is 65 bar abs.
  • the suction flow rate is 26.5% of the total air flow.
  • the liquefied air is subdivided between the first column 8, the second column 9, and the fractions to be expanded in the valves 1 16A, 1 16B and 1 16C.
  • An oxygen enriched liquid flow LR is expanded and sent from the first column to the second column.
  • An LP-enriched liquid flow rate is expanded and fed from the first column to the second column.
  • NLMP pure liquid nitrogen is produced by the first column 8, cooled again in the heat exchanger 24 and expanded in the valve 143 and sent to the storage 144.
  • the high pressure nitrogen gas 39 is withdrawn at the top of the first column and heated in the heat exchanger to form a product flow 40.
  • the liquid oxygen OL is withdrawn from the bottom of the second column 9, pressurized by a pump 37 and sent partly as a flow 38 to the heat exchanger 5, where it vaporizes by heat exchange with the pressurized air to form pressurized gaseous oxygen.
  • the remainder of the liquid oxygen 52 is withdrawn as a liquid product.
  • a nitrogen-enriched top-stream gas stream NR is withdrawn from the second column 9, heated in the heat exchanger 5 in the form of a flow 33.
  • Argon is produced by using the column of impure argon 3 and pure argon 4.
  • the impure argon column is fed by the flow 16 from the second column 9.
  • a flow of liquid 17 is sent from the base of the impure argon column 3 to the second column 9.
  • the oxygen enriched liquid is sent to the top condenser 12 of the column 3 by the valve 26 and evaporated to form the flow 27, which is returned to the second column.
  • a product flow 19 is sent to the condenser 20, and from there, forms the flow 19.
  • the flow 19 is condensed in the heat exchanger 20 and subdivided into a flow 48 which is sent to the waste flow 33 at the point d intersection 50, and another flow.
  • the other flow is sent by the valve 21 to the column 4.
  • the pure argon column 4 produces a product flow 45.
  • the overhead condenser 13 of the pure argon column 4 is fed by the nitrogen-rich LP liquid from the first column via the valve 34, and the vaporized nitrogen is withdrawn by the valve 35 in the form of a flow 33 and cooled in the subcooler 24.
  • the bottom reboiler 14 of the pure argon column is heated by using air, and the liquefied air 23 is sent to the first column.
  • a purge flow 46 is likewise withdrawn.
  • Nitrogen-rich liquid 43 is collected via valve 143 into storage 144.
  • the condenser 20 is fed with the LP liquid rich in nitrogen through the valve 31, and the vaporized liquid is sent by the valve 32 to the waste flow 33.
  • the air flow 505 at 65 bar is subdivided into two. Part of the air is expanded in the valve 231 and sent to the columns 8 and 9 in liquid form.
  • the remainder of the air 107 is subdivided into three fractions 107A, 107B, 107C.
  • the fraction of air 107A recycled between the first stage 230A and the second stage 230B corresponds to 1.08% of the total air flow. It is expanded in the valve 1 16A 65 bar abs to about 10.2 bar abs and introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107A.
  • 230C corresponds to 0.84% of the total air flow. It is expanded in the valve 1 16B 65 bar abs to about 18.9 bar abs and introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107B.
  • the fraction of air 107C recycled between the third stage 230C and the fourth stage 230D corresponds to 22.08% of the total air flow rate. It is expanded in the valve 1 16C from 65 bar abs to about 35.1 bar abs and introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107C.
  • These three air fractions represent a total recycle air flow rate of 24% of the total air flow rate, which means that the fluid 505 corresponds to a flow rate of 50.5% of the total air flow, and that the flow rate through the valve 231 is 26.5%.
  • the vaporization of the three air fractions 107A, 107B and 107C takes place in the heat exchanger 5 respectively at temperatures of about -166 ° C, -155 ° C and -142 ° C, as can be seen on Figure 4, which is less than the vaporization temperature of oxygen, which is about -125 ° C.
  • a phase separator should be added if the expanded flow is a two-phase fluid, the liquid phase being introduced into the heat exchanger 5 and the vapor phase being mixed with the flow 107.
  • condensation covers the condensation of a form vapor to a liquid or partially liquid form. It also covers the pseudo-condensation of a supercritical fluid when it is cooled from a temperature above the supercritical temperature to a temperature below the supercritical temperature.
  • Figure 4 shows the exchange diagram corresponding to the process of Figure 3.
  • a less optimized variant of FIG. 3 should involve the subdivision of the flow rate 107 into one or two fractions and the recycling of these fractions, after vaporization, with return to the compressor 230.
  • valves 231, 16A, 16B and 16C could be replaced by liquid turbines, that is, an expansion system producing work in order to reduce the irreversibility associated with the isenthalpic expansion. These liquid turbines could be installed in parallel or in series.
  • the compressor 230 in the basic case, is considered to be a machine driven by a motor, but could also be driven by a steam turbine or a gas turbine (the same as that for the Main Air Compressor 6) .
  • any one of the four compressor stages 230A, 230B, 230C and 230D could be driven by an expansion machine of any of the fluids of this cryogenic air separation process, preferably at a low temperature. temperature.
  • any one of the four compressor stages 230A, 230B, 230C and 230D could have a suction temperature lower than the ambient temperature, preferably slightly higher than the vaporization temperature of the oxygen, at about -125. ° C.
  • specific energy kWh / Nm3 of O2
  • the specific energy required for the production of oxygen at 40 bar abs according to the invention is 92.9%. that is to say a gain of 7.1%.
  • the fractions 107A, 107B, 107C could be separated from the air passing through 231 and extracted from the heat exchanger 5 at a temperature higher than the temperature of the cold end of the heat exchanger 5.
  • the process may be modified to vaporize the pumped liquid nitrogen, as an additional flow rate or as a flow rate to replace the pumped oxygen flow rate.
  • the compressor 230 should be supplied with at least a portion of the high pressure nitrogen gas 40.
  • liquid buffers 131, 152 are added to the storage unit, and release cryogenic liquids to decorrelate oxygen production by the ASU from consumer consumption. In addition, it reduces power consumption during peak hours without reducing the flow of oxygen to the end user, and increasing the consumption of hydrogen at off-peak times, without increasing the flow rate. oxygen to the end user.
  • the feed air is compressed in the compressor 6 and purified in the purification unit 7 and subdivided into two.
  • a flow 505 is compressed in a compressor 230 and is sent to the heat exchanger, where it undergoes a partial condensation, or "pseudo-condensation", because it is beyond the critical pressure.
  • the compressor 230 is a four-stage centrifugal compressor 230A, 230B, 230C and 230D, for example of the integrated speed-multiplier type, cooled by intermediate water coolers 232A, 232B, 232C and a 232D final cooler.
  • the suction pressure of the compressor is 5.5 bar abs
  • the intermediate pressures are 10.2 bar abs, 18.9 bar abs and 35.1 bar abs
  • final pressure 65 bar abs The suction flow rate is 23% of the total air flow rate when no cryogenic liquid is stored or destocked.
  • the flow 505 is divided into a first secondary flow 505A, which goes directly to the heat exchanger 5, and a second secondary flow, which goes to the refrigeration unit 102 to be cooled to -5 ° C and introduced into the heat exchanger 5.
  • a first fraction of the high-pressure air is withdrawn and sent to the two-phase expansion device 1 16D, reintroduced into the heat exchanger 5 to be heated and recycled to 35.1 bar abs in the compressor 230 at the level of stage 230D as flow 107D.
  • This first fraction has a flow rate of 18.4% of the total air flow.
  • a second fraction is cooled to -192.2 ° C by complete passage through the heat exchanger 5 and is expanded in the valve 231 to be sent to the liquid air storage unit 131 (LAIR) as a flow 234.
  • the flow rate of this second fraction is only 23% of the total air flow from the main air compressor 6.
  • a fraction 107 is withdrawn from the cold end of the heat exchanger 5 and subdivided into three.
  • the fraction of air 107A recycled between the first stage 230A and the second stage 230B corresponds to 1.1% of the total air flow. It is expanded in the valve 1 16A 65 bar abs to about 10.2 bar abs and introduced into the heat exchanger 5, where it is evaporated, heated after vaporization to give a recirculation air 107A.
  • the air fraction 107B recycled between the second stage 230B and the third stage 230C corresponds to 3.15% of the total air flow rate. It is expanded in the valve 1 16B 65 bar abs to about 18.9 bar abs and is introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107B.
  • the air fraction 107C is expanded in the valve 1 16C from 65 bar abs to about 1.2 bar abs and is introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107C which can be used to regenerate air purifiers if the ASU 101 is not running. It represents 4.45% of the total air flow.
  • a liquid oxygen storage tank 152 powered by ASU 101 provides oxygen 151 to the system.
  • a liquid oxygen pump 37 pressurizes the oxygen to the required pressure level before introduction into the heat exchanger 5, where it undergoes vaporization or pseudo-vaporization.
  • the ASU 101 is powered by air 510 from the same compressor 6 (MAC) and liquid air 235 which is used to compensate for the production of liquid oxygen 150.
  • MAC compressor 6
  • the flow 510 is cooled in a heat exchanger independent of the heat exchanger 5 by heat exchange with nitrogen gas from the air separation unit (not shown). It is possible to cool the cold flow 510 in the heat exchanger 5, but this would make the system less flexible.
  • compressor systems supplying air to the ASU and the cold recovery system when both units are in the same location, if it is considered more convenient and / or more efficient. This is particularly the case when the two units do not operate simultaneously at the same capacity.
  • a single compressor would require accurate measurement dynamics and lose efficiency at low capacity. With different compressor systems, it is possible to optimize the measurement dynamics on each machine.
  • valves 231, 16A, 16B and 16C could be replaced by liquid-displacing turbines, ie a work-producing expansion system, in order to reduce the irreversibility associated with isenthalpic expansion. .
  • liquid-displacing turbines ie a work-producing expansion system, in order to reduce the irreversibility associated with isenthalpic expansion.
  • These liquid-displacing turbines could be installed in parallel and / or in series.
  • the air separation unit operates such that the amount of liquid oxygen stored in the storage tank 152 increases.
  • the amount of liquid oxygen vaporized in the heat exchanger 5 is less than the liquid oxygen produced by the air separation unit. No air is sent to the valve 1 16C, and the purification unit 7 is regenerated using a nitrogen flow from the air separation unit 101.
  • the air flows 510 are sent to the air separation unit via a heat exchanger independent of the heat exchanger 5, and an air flow 235 is sent to the air unit. separation of air from the storage tank 131, and the liquid oxygen 150 is sent to the storage tank 152. However, the amount of liquid air sent to the tank 131 exceeds the amount of air which is withdrawn, and the amount of liquid oxygen sent to the tank 152 exceeds the amount of liquid oxygen that is withdrawn.
  • the air separation unit will not operate, or operate at a low capacity, usually 50% or less of maximum capacity, even if the total oxygen produced is well above 50% of the maximum capacity. No air is sent to the air separation unit through flow rates 510 and 235.
  • the liquid oxygen stored in the vessel 152 is vaporized to give the oxygen gas flow rate.
  • the regeneration of the purification unit 7 is carried out using the flow 107C.
  • the liquid air produced by the vaporization of the liquid oxygen is stored in the storage tank 131 during the peak periods, and no gaseous or liquid air is sent to the air separation unit 101.
  • the process may be modified to vaporize the pumped liquid nitrogen as an additional flow rate, or as a flow rate to replace the pumped oxygen flow rate.
  • a nitrogen cycle (rather than an air cycle), as shown in FIG. 6.
  • the compressor 230 is powered by at least a portion of the In this case, it is necessary to have an available nitrogen source, coming from the air separation unit 101 operating at reduced capacity, or other separation units of air, optionally via a nitrogen line. This is why air is the preferred fluid for such an application because it is available independently of any air separation unit.
  • the compressed nitrogen is cooled and condensed in the heat exchanger 5.
  • the compressed nitrogen is then subdivided into at least two portions, three portions being presented here, expanded to at least two different pressures, and vaporized in the heat exchanger 5.
  • valves 1 16A and 1 16B are returned to intermediate positions of nitrogen compressor 230, and the vaporized nitrogen from valve 1 16C can be used to regenerate the purification unit if the air separation does not work.
  • the produced liquid nitrogen 234 is expanded in the valve 231 and stored in the storage unit 131 for use.
  • the liquid oxygen can be vaporized against the nitrogen in the periods during which the air separation unit does not operate, for example the periods during which the electricity is particularly expensive.

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Abstract

A method for separating air by cryogenic distillation in a system of columns comprising a first column (8) and a second column (9) operating at a lower pressure than the first column, comprising the steps of compressing all of the feed air in a first compressor (6) to a first output pressure of at least 1 bar greater than the pressure of the first column, sending a first portion of the air under the first output pressure to the second compressor (230), and compressing the air to a second output pressure, cooling and condensing at least a portion of the air under the second output pressure in a heat exchanger (5), withdrawal of a liquid (OL) from a column of the system of columns, pressurising the liquid (37) and evaporating the liquid by heat exchange in the heat exchanger (5), and pressure reduction of a portion of the compressed air to a second output pressure, at least partially evaporating said air (107) in the heat exchanger, optionally additional heating of said air in the heat exchanger, and sending at least a portion of this air to the second compressor (108).

Description

Procédé et appareil pour la séparation de l'air par distillation cryogénique  Process and apparatus for the separation of air by cryogenic distillation
La présente invention concerne un procédé et un appareil pour la séparation de l'air par distillation cryogénique. Elle concerne en particulier des procédés et un appareil pour produire de l'oxygène et/ou de l'azote sous une pression élevée. The present invention relates to a method and an apparatus for the separation of air by cryogenic distillation. In particular, it relates to methods and apparatus for producing oxygen and / or nitrogen under high pressure.
L'oxygène gazeux produit par les unités de séparation de l'air est habituellement à une pression élevée d'environ 20 à 50 bar. Le schéma de distillation de base est habituellement un procédé à double colonne produisant de l'oxygène au fond de la deuxième colonne, exploitée sous une pression de 1 à 4 bar. L'oxygène doit être comprimé à une pression plus élevée, grâce à un compresseur d'oxygène ou grâce au procédé de pompage de liquide. Du fait des problèmes de sécurité associés aux compresseurs d'oxygène, les unités de production d'oxygène les plus récentes utilisent le procédé de pompage de liquide. Pour vaporiser l'oxygène liquide sous une pression élevée, on a besoin d'un surpresseur additionnel pour élever une partie de l'air ou de l'azote d'alimentation à une pression plus élevée, comprise dans la plage de 40 à 80 bar. Par essence, le surpresseur remplace le compresseur d'oxygène. L'un des buts du développement de nouveaux cycles de procédé est de diminuer la consommation d'énergie d'une unité de production d'oxygène.  The gaseous oxygen produced by the air separation units is usually at a high pressure of about 20 to 50 bar. The basic distillation scheme is usually a double column process producing oxygen at the bottom of the second column operated at a pressure of 1 to 4 bar. Oxygen must be compressed at a higher pressure, thanks to an oxygen compressor or the liquid pumping process. Because of the safety issues associated with oxygen compressors, the newer oxygen production units use the liquid pumping process. To vaporize liquid oxygen under high pressure, an additional booster is required to elevate a portion of the air or feed nitrogen to a higher pressure in the range of 40 to 80 bar. . In essence, the booster replaces the oxygen compressor. One of the goals of developing new process cycles is to reduce the energy consumption of an oxygen generating unit.
Dans un effort de réduction de cette consommation d'énergie, il est souhaitable d'introduire tous les débits d'air d'alimentation dans les colonnes à une température proche de la température de la colonne, au point où le débit est introduit, pour réduire l'irréversibilité thermodynamique du système. Malheureusement, on ne peut y arriver avec un cycle de pompage "classique".  In an effort to reduce this energy consumption, it is desirable to introduce all feed air flows into the columns at a temperature close to the temperature of the column, at the point where the flow is introduced, for reduce the thermodynamic irreversibility of the system. Unfortunately, you can not do it with a "classic" pumping cycle.
Cet art antérieur est illustré sur la Figure 1 . Sur la Figure 1 , telle que décrite dans FR-A-2 777 641 , on utilise dans une unité de séparation d'air 1 une double colonne 2, comprenant une première colonne 8 et une deuxième colonne 9 opérant à une plus basse pression que la première colonne, thermiquement reliées par un rebouilleur/condenseur 10. La totalité de l'air d'alimentation est comprimée dans un compresseur 6 à la pression de la première colonne 8, purifiée dans l'unité de purification 7, et subdivisée en trois.  This prior art is illustrated in FIG. In FIG. 1, as described in FR-A-2 777 641, a double column 2 is used in an air separation unit 1, comprising a first column 8 and a second column 9 operating at a lower pressure than the first column, thermally connected by a reboiler / condenser 10. The entire supply air is compressed in a compressor 6 at the pressure of the first column 8, purified in the purification unit 7, and subdivided into three .
Un débit 502 est envoyé à un surpresseur 503, refroidi dans un refroidisseur d'eau (non représenté), et encore plus refroidi dans l'échangeur de chaleur 5, puis détendu dans une turbine 501 couplée au surpresseur 503. L'air détendu 502 est envoyé à la deuxième colonne. A flow 502 is sent to a booster 503, cooled in a water cooler (not shown), and further cooled in the heat exchanger 5, then expanded in a turbine 501 coupled to the booster 503. The expanded air 502 is sent to the second column.
Une autre partie de l'air est envoyée à l'échangeur de chaleur 5 sensiblement sous la même pression que la première colonne 8.  Another part of the air is sent to the heat exchanger 5 substantially under the same pressure as the first column 8.
Le troisième débit est comprimé dans un compresseur 230 et envoyé dans l'échangeur de chaleur, où il se condense. L'air liquéfié est subdivisé entre la première colonne 8 et la deuxième colonne 9.  The third flow is compressed in a compressor 230 and sent to the heat exchanger, where it condenses. The liquefied air is subdivided between the first column 8 and the second column 9.
Un débit de liquide enrichi en oxygène LR est détendu et envoyé de la première colonne à la deuxième colonne. Le débit de liquide enrichi en azote LP est détendu et envoyé de la première colonne à la deuxième colonne. De l'azote liquide pur NLMP est produit par la première colonne, puis refroidi de nouveau dans l'échangeur de chaleur 24 et détendu dans la vanne 143 et envoyé à un stockage 144. L'azote gazeux haute pression 39 est soutiré en tête de la première colonne et chauffé dans l'échangeur de chaleur pour former un débit de produit 40. L'oxygène liquide OL est soutiré du fond de la deuxième colonne 9, pressurisé par une pompe 37 et envoyé en partie sous forme d'un débit 38 à l'échangeur de chaleur 5, où il se vaporise par échange de chaleur avec l'air pressurisé pour former un oxygène gazeux pressurisé. Le reste de l'oxygène liquide 52 est soutiré sous forme d'un produit liquide. Un débit gazeux de tête enrichi en azote NR est soutiré de la deuxième colonne 9, chauffé dans l'échangeur de chaleur 5 sous forme d'un débit 33.  An oxygen enriched liquid flow LR is expanded and sent from the first column to the second column. The nitrogen-enriched liquid flow LP is relaxed and sent from the first column to the second column. Pure liquid nitrogen NLMP is produced by the first column, then cooled again in the heat exchanger 24 and expanded in the valve 143 and sent to a storage 144. The high pressure nitrogen gas 39 is withdrawn at the top of the the first column and heated in the heat exchanger to form a product flow 40. The liquid oxygen OL is withdrawn from the bottom of the second column 9, pressurized by a pump 37 and sent partly in the form of a flow rate 38 to the heat exchanger 5, where it vaporizes by heat exchange with the pressurized air to form a pressurized oxygen gas. The remainder of the liquid oxygen 52 is withdrawn as a liquid product. A nitrogen-enriched head gas stream NR is withdrawn from the second column 9, heated in the heat exchanger 5 in the form of a flow rate 33.
De l'argon est produit par utilisation d'une colonne d'argon impur 3 et d'argon pur 4. La colonne d'argon impur est alimentée par un débit 16 provenant de la deuxième colonne 9. Un débit de liquide 17 est envoyé de la base de la colonne d'argon impur 3 à la deuxième colonne 9. Un liquide riche est envoyé au condenseur de tête 12 de la colonne 3 par la vanne 26 et est évaporé pour former un débit 27 qui est renvoyé à la deuxième colonne. Un débit de produit 19 est envoyé au condenseur 20 et de là forme le débit 19. Le débit 19 est condensé dans l'échangeur de chaleur 20 et subdivisé en le débit 48 qui est envoyé au débit de déchets 33 au point d'intersection 50, et un autre débit. L'autre débit est envoyé par la vanne 21 à la colonne 4.  Argon is produced using a column of impure argon 3 and pure argon 4. The impure argon column is fed with a flow 16 from the second column 9. A flow of liquid 17 is sent from the bottom of the impure argon column 3 to the second column 9. A rich liquid is sent to the top condenser 12 of the column 3 through the valve 26 and is evaporated to form a flow 27 which is returned to the second column . A product flow 19 is sent to the condenser 20 and hence the flow 19. The flow 19 is condensed in the heat exchanger 20 and subdivided into the flow 48 which is sent to the waste flow 33 at the point of intersection 50 , and another flow. The other flow is sent by the valve 21 to the column 4.
La colonne d'argon pur 4 produit un débit de produit 45. Le condenseur de tête The pure argon column 4 produces a product flow 45. The head condenser
13 de la colonne d'argon pur 4 est alimenté par le liquide riche en azote LP provenant de la première colonne par la vanne 34, et l'azote vaporisé est soutiré par la vanne 35 sous forme d'un débit 33 et refroidi dans le sous-refroidisseur 24. Le rebouilleur de fond 14 de la colonne d'argon pur est chauffé par utilisation d'air, et l'air liquéfié 23 est envoyé à la première colonne. 13 of the pure argon column 4 is fed by the nitrogen-rich liquid LP from the first column by the valve 34, and the vaporized nitrogen is withdrawn by the valve 35 in the form of a flow 33 and cooled in the subcooler 24. The bottom reboiler 14 of the pure argon column is heated using air, and the liquefied air 23 is sent to the first column.
Un débit de purge 46 est lui aussi soutiré.  A purge flow 46 is also withdrawn.
Le condenseur 20 est alimenté par le liquide riche en azote LP par la vanne 31 , et le liquide vaporisé est envoyé par la vanne 32 au débit de déchets 33.  The condenser 20 is fed by the nitrogen-rich liquid LP through the valve 31, and the vaporized liquid is sent by the valve 32 to the waste flow 33.
La Figure 2 montre les relations entre l'échange de chaleur en kcal/h et la température pour les fluides se refroidissant et se réchauffant dans l'échangeur 5.  Figure 2 shows the relationship between heat exchange in kcal / h and temperature for fluids cooling and heating in exchanger 5.
Certaines versions différentes du procédé de compression à froid sont aussi décrites dans la technique antérieure, comme dans US-A-5 379 598, US-A-5 475 980, US-A-5 596 885, US-A-5 901 576 et US-A-6 626 008.  Some different versions of the cold pressing process are also described in the prior art, such as in US-A-5,379,598, US-A-5,475,980, US-A-5,596,885, US-A-5,901,576. and US-A-6,626,008.
Dans US-A-5 379 598 une fraction de l'air d'alimentation est recomprimée par un surpresseur, suivi d'un compresseur à froid, pour donner un débit pressurisé nécessaire à la vaporisation de l'oxygène. Cette approche possède encore au moins deux compresseurs, et l'unité de purification fonctionne encore sous une basse pression.  In US-A-5,379,598 a fraction of the feed air is recompressed by a booster, followed by a cold compressor, to provide a pressurized flow necessary for the vaporization of oxygen. This approach still has at least two compressors, and the purification unit still operates under a low pressure.
Un procédé de compression à froid, tel que décrit dans US-A-5 475 980, fournit une technique pour commander une unité de production d'oxygène avec un compresseur d'air unique. Dans ce procédé, de l'air à distiller est refroidi dans l'échangeur de chaleur, puis est de nouveau comprimé par un surpresseur commandé par une machine de détente dont l'effluent est envoyé dans la première colonne d'un procédé à double colonne, celle qui opère à la pression la plus élevée.  A cold compression process, as described in US-A-5,475,980, provides a technique for controlling an oxygen generating unit with a single air compressor. In this process, the air to be distilled is cooled in the heat exchanger, and is then compressed again by a booster controlled by an expansion machine whose effluent is sent to the first column of a double column process. which operates at the highest pressure.
Ce faisant, la pression de refoulement du compresseur d'air est de l'ordre de 15 bar, ce qui est de même très avantageux pour l'unité de purification. Un inconvénient de cette approche réside dans l'augmentation de la taille de l'échangeur de chaleur en raison du recyclage supplémentaire de l'écoulement, qui est représentatif d'une unité de compression à froid. Il est possible de réduire la taille de l'échangeur en ouvrant les approches de température de l'échangeur. Cependant, cela conduirait à une utilisation inefficace de l'énergie, et à une pression de refoulement plus élevée du compresseur, ce qui augmenterait le coût.  In doing so, the discharge pressure of the air compressor is of the order of 15 bar, which is likewise very advantageous for the purification unit. A disadvantage of this approach is the increased size of the heat exchanger due to the additional recycling of the flow, which is representative of a cold pressing unit. It is possible to reduce the size of the exchanger by opening the temperature approaches of the exchanger. However, this would lead to inefficient use of energy, and higher compressor discharge pressure, which would increase the cost.
Dans US-A-5 596 885, une partie de l'air d'alimentation est soumise à une compression plus poussée dans un surpresseur à chaud, pendant qu'au moins une partie de l'air est encore comprimée dans un surpresseur à froid. L'air provenant des deux surpresseurs est liquéfié, et une partie de l'air comprimé à froid est détendue dans une turbine Claude. US-A-5 901 576 décrit différents arrangements de schémas de compression à froid utilisant la détente d'un liquide riche vaporisé du fond de la première colonne, ou la détente de l'azote haute pression pour entraîner le compresseur à froid. Dans certains cas, on a aussi utilisé des compresseurs à froid entraînés par un moteur. Ces procédés fonctionnent aussi avec de l'air d'alimentation approximativement à la pression de la première colonne et, dans la plupart des cas, on a aussi besoin d'un surpresseur. In US-A-5,596,885, a portion of the feed air is further compressed in a hot booster, while at least a portion of the air is still compressed in a cold booster. . The air from both boosters is liquefied, and some of the cold compressed air is expanded in a Claude turbine. US-A-5,901,576 discloses various arrangements of cold compression schemes using the expansion of a vaporized rich liquid from the bottom of the first column, or the expansion of the high pressure nitrogen to drive the compressor cold. In some cases, motor-driven cold compressors have also been used. These processes also operate with feed air at approximately the pressure of the first column and, in most cases, a booster is also required.
US-A-6 626 008 décrit un cycle de pompe à chaleur utilisant un compresseur à froid pour améliorer le processus de distillation pour la production d'oxygène de faible pureté pour un procédé de production d'oxygène à double vaporiseur. Une faible pression d'air, et un surpresseur, sont aussi représentatifs de ce type de procédé.  US-A-6,626,008 discloses a heat pump cycle using a cold compressor to improve the distillation process for the production of low purity oxygen for a double vaporizer oxygen production process. Low air pressure, and a booster, are also representative of this type of process.
EP-A-1 972 872 décrit des moyens pour améliorer les procédés ci-dessus faisant appel à un compresseur à froid, en particulier par introduction de la totalité des débits d'air d'alimentation dans les colonnes à une température proche de la température de la colonne en le point où le débit est introduit, dans le but de réduire l'irréversibilité thermodynamique du système. Mais elle exige l'addition d'au moins un étage additionnel de compression.  EP-A-1 972 872 discloses means for improving the above processes using a cold compressor, in particular by introducing all the feed air flows into the columns at a temperature close to the temperature. of the column at the point where the flow is introduced, in order to reduce the thermodynamic irreversibility of the system. But it requires the addition of at least one additional compression stage.
La présente invention vise donc à résoudre les inconvénients de ces procédés, en particulier par introduction de tous les débits d'air d'alimentation dans les colonnes à une température proche de la température de la colonne en le point où le débit est introduit, dans le but de réduire l'irréversibilité thermodynamique du système sans ajouter un étage additionnel de compression. Le coût global des produits d'une unité de production d'oxygène peut donc être réduit. L'amélioration principale est due à l'utilisation d'un surpresseur d'air (Booster Air Compressor (BAC)) pour recycler l'air une fois qu'il a été utilisé pour récupérer la chaleur produite par la vaporisation d'un liquide haute pression dans l'échangeur de chaleur principal.  The present invention therefore aims at solving the disadvantages of these processes, in particular by introducing all the feed air flow rates into the columns at a temperature close to the temperature of the column at the point where the flow is introduced, in the goal of reducing the thermodynamic irreversibility of the system without adding an additional compression stage. The overall cost of the products of an oxygen production unit can therefore be reduced. The main improvement is due to the use of an air booster (Booster Air Compressor (BAC)) to recycle air once it has been used to recover the heat produced by the vaporization of a liquid high pressure in the main heat exchanger.
Tous les pourcentages mentionnés sont des pourcentages en moles.  All percentages mentioned are percentages in moles.
Un procédé selon le préambule de la revendication 1 est connu de US6336345. A process according to the preamble of claim 1 is known from US6336345.
Selon la présente invention, il est prévu un procédé pour séparer l'air par distillation cryogénique dans un système de colonnes comprenant une première colonne et une deuxième colonne opérant à une plus basse pression que la première colonne, comprenant les étapes de : According to the present invention there is provided a method for separating air by cryogenic distillation in a column system comprising a first column and a second column operating at a lower pressure than the first column, comprising the steps of:
i) compression de la totalité de l'air d'alimentation dans un premier compresseur jusqu'à une première pression de sortie d'au plus un bar supérieur à la pression de la première colonne, de préférence sensiblement égale à la pression de la première colonne, i) compressing all of the feed air in a first compressor to a first outlet pressure of at most one bar greater than the pressure of the first column, preferably substantially equal to the pressure of the first column,
ii) envoi d'une première partie de l'air sous la première pression de sortie à un deuxième compresseur, et compression de l'air à une deuxième pression de sortie, iii) refroidissement et condensation d'au moins une partie de l'air sous la deuxième pression de sortie dans un échangeur de chaleur,  ii) sending a first portion of the air under the first output pressure to a second compressor, and compressing the air to a second output pressure, iii) cooling and condensing at least a portion of the air under the second outlet pressure in a heat exchanger,
iv) prélèvement du liquide d'une colonne du système de colonnes, pressurisation du liquide et vaporisation du liquide par échange de chaleur dans l'échangeur de chaleur,  iv) removal of the liquid from a column of the column system, pressurization of the liquid and vaporization of the liquid by heat exchange in the heat exchanger,
v) détente d'au moins une fraction de l'air refroidi et condensé sous la deuxième pression de sortie jusqu'à une pression intermédiaire comprise entre la première pression de sortie et la deuxième pression de sortie, au moins vaporisation partielle dudit air dans l'échangeur de chaleur, éventuellement chauffage dudit air dans l'échangeur de chaleur caractérisé en ce qu'au moins une partie de cet air est envoyée au deuxième compresseur pour être comprimée jusqu'à la deuxième pression de sortie.  v) expanding at least a fraction of the air cooled and condensed under the second outlet pressure to an intermediate pressure between the first outlet pressure and the second outlet pressure, at least partially vaporizing said air in the heat exchanger, optionally heating said air in the heat exchanger characterized in that at least a portion of this air is sent to the second compressor to be compressed to the second outlet pressure.
De l'air épuré et refroidi est envoyé du premier compresseur au système de colonnes pour s'y séparer.  Clean, cooled air is sent from the first compressor to the column system to separate.
Selon d'autres aspects facultatifs de l'invention qui peuvent être combinés entre eux :  According to other optional aspects of the invention which can be combined with each other:
la détente est réalisée dans au moins une vanne.  the expansion is performed in at least one valve.
la détente est réalisée dans au moins une turbine et produit du travail. la température de l'au moins une fraction avant détente est inférieure à la somme de la température de la vaporisation du liquide et l'approche de température minimale dans l'échangeur de chaleur.  the expansion is performed in at least one turbine and produces work. the temperature of the at least one fraction before expansion is less than the sum of the temperature of the vaporization of the liquid and the minimum temperature approach in the heat exchanger.
le deuxième compresseur est un compresseur multi-étages.  the second compressor is a multi-stage compressor.
ladite au moins une troisième pression est au moins la pression d'entrée de l'un des étages du deuxième compresseur.  said at least one third pressure is at least the inlet pressure of one of the stages of the second compressor.
un étage du deuxième compresseur est entraîné par une machine de détente d'un fluide du procédé.  a stage of the second compressor is driven by a machine for expanding a process fluid.
la température d'entrée de la machine de détente est inférieure à la température ambiante.  the inlet temperature of the expansion machine is lower than the ambient temperature.
au moins un étage du deuxième compresseur a une température d'aspiration inférieure à la température ambiante. la température d'aspiration est supérieure à la température de vaporisation du liquide, mais en est proche. at least one stage of the second compressor has a suction temperature lower than the ambient temperature. the suction temperature is higher than the vaporization temperature of the liquid, but is close to it.
le liquide est un débit enrichi en oxygène,  the liquid is a flow enriched in oxygen,
le liquide est un débit enrichi en azote.  the liquid is a flow enriched in nitrogen.
- le débit de production du ou des produits liquides n'est pas supérieur à 10% de l'air d'alimentation, de préférence n'est pas supérieur à 5% de l'air d'alimentation.  - The production rate of the liquid product or products is not greater than 10% of the supply air, preferably not more than 5% of the supply air.
Selon un autre aspect de l'invention, il est prévu un appareil pour séparer l'air par distillation cryogénique dans un système de colonnes comprenant une première colonne et une deuxième colonne opérant à une plus basse pression que la première colonne, comprenant en outre :  According to another aspect of the invention there is provided an apparatus for separating air by cryogenic distillation in a column system comprising a first column and a second column operating at a lower pressure than the first column, further comprising:
i) un premier compresseur pour comprimer l'air d'alimentation jusqu'à une première pression de sortie d'au moins un bar supérieur à la pression de la première colonne, de préférence sensiblement égale à la pression de la première colonne, ii) un deuxième compresseur et un moyen pour envoyer une première partie de l'air sous la première pression de sortie au deuxième compresseur pour comprimer l'air jusqu'à une deuxième pression de sortie,  i) a first compressor for compressing the supply air to a first outlet pressure of at least one bar greater than the pressure of the first column, preferably substantially equal to the pressure of the first column, ii) a second compressor and means for sending a first portion of the air under the first output pressure to the second compressor to compress the air to a second output pressure,
iii) un échangeur de chaleur, dans lequel au moins une partie de l'air sous la deuxième pression de sortie est refroidie et condensée,  iii) a heat exchanger, wherein at least a portion of the air under the second outlet pressure is cooled and condensed,
iv) un moyen pour soutirer le liquide d'une colonne du système de colonnes, un moyen pour pressuriser le liquide, un moyen pour envoyer le liquide pressurisé à l'échangeur de chaleur, et un moyen pour soutirer le liquide vaporisé de l'échangeur de chaleur,  iv) means for withdrawing the liquid from a column of the column system, means for pressurizing the liquid, means for supplying the pressurized liquid to the heat exchanger, and means for withdrawing the vaporized liquid from the exchanger heat,
v) un moyen pour détendre une fraction de l'air refroidi et condensé sous la deuxième pression de sortie, un moyen pour envoyer ledit fluide d'air à l'échangeur de chaleur, un moyen pour envoyer au moins une partie dudit air ayant été vaporisée dans l'échangeur de chaleur sous au moins une troisième pression, intermédiaire entre les première et deuxième pressions de sorties, au deuxième compresseur pour être comprimé jusqu'à la deuxième pression de sortie et  v) means for expanding a fraction of the cooled and condensed air under the second outlet pressure, means for supplying said air fluid to the heat exchanger, means for sending at least a portion of said air having been vaporized in the heat exchanger under at least a third pressure, intermediate between the first and second outlet pressures, at the second compressor to be compressed to the second outlet pressure and
vi) des moyens pour envoyer de l'air épuré et refroidi au système de colonnes pour s'y séparer.  vi) means for sending purified and cooled air to the column system for separation therefrom.
Selon d'autres aspects facultatifs de l'invention :  According to other optional aspects of the invention:
le premier stockage et éventuellement le deuxième stockage est indépendant du système de colonnes. l'appareil comprend une turbine de détente de la fraction de débit auxiliaire comprimé dans le deuxième compresseur. the first storage and possibly the second storage is independent of the column system. the apparatus comprises an expansion turbine of the auxiliary flow rate fraction compressed in the second compressor.
L'invention va être maintenant décrite plus en détail par référence aux Figures 3, 5 et 6, qui sont des schémas de circulation des fluides représentant des procédés de séparation cryogénique d'air selon l'invention, et la Figure 4, qui est un diagramme d'échange de chaleur pour l'échangeur 5 de la Figure 3.  The invention will now be described in more detail with reference to FIGS. 3, 5 and 6, which are fluid flow schemes showing cryogenic air separation methods according to the invention, and FIG. heat exchange diagram for the exchanger 5 of FIG. 3.
Dans la forme de réalisation de la Figure 3, dans une unité de séparation d'air 1 , on utilise une double colonne 2, comprenant une première colonne 8 et une deuxième colonne 9 mis à disposition, reliées thermiquement par un rebouilleur/condenseur 10. La totalité de l'air d'alimentation est comprimée dans le compresseur 6 à une pression d'au moins un bar supérieur à la pression de la première colonne 8, de préférence sensiblement égale à la pression de la première colonne 8, en permettant une perte de charge dans les conduites intermédiaires, purifiée dans l'unité de purification 7 et subdivisée en trois.  In the embodiment of FIG. 3, in an air separation unit 1, a double column 2 is used, comprising a first column 8 and a second column 9 made available, thermally connected by a reboiler / condenser 10. The entire supply air is compressed in the compressor 6 at a pressure of at least one bar greater than the pressure of the first column 8, preferably substantially equal to the pressure of the first column 8, allowing a pressure drop in the intermediate pipes, purified in the purification unit 7 and subdivided into three.
Un débit 502 est envoyé à un surpresseur 503, refroidi dans un refroidisseur d'eau (non représenté), puis encore refroidi dans l'échangeur de chaleur 5, puis détendu dans une turbine 501 , couplée au surpresseur 503. L'air détendu 502 est envoyé à la deuxième colonne.  A flow 502 is sent to a booster 503, cooled in a water cooler (not shown), then further cooled in the heat exchanger 5, then expanded in a turbine 501, coupled to the booster 503. The air relaxed 502 is sent to the second column.
Une autre partie 507 de l'air est envoyée à l'échangeur de chaleur 5 sous une pression sensiblement égale à celle de la première colonne 8.  Another part 507 of the air is sent to the heat exchanger 5 under a pressure substantially equal to that of the first column 8.
Le troisième débit 505 est comprimé dans un compresseur 230 et envoyé à l'échangeur de chaleur, où il se condense. Dans ce cas, on considère que le compresseur 230 est un compresseur centrifuge à quatre étages 230A, 230B, 230C et 230D, par exemple du type à multiplication de vitesse intégrée refroidi par des refroidisseurs intermédiaires d'eau 232A, 232B, 232C et un refroidisseur final 232D. La pression d'aspiration du compresseur est de 5,5 bar abs, les pressions intermédiaires sont de 10,2 bar abs, 18,9 bar abs et 35,1 bar abs, et la pression finale de sortie est de 65 bar abs. Le débit d'aspiration est de 26,5% du débit total de l'air. L'air liquéfié est subdivisé entre la première colonne 8, la deuxième colonne 9, et les fractions à détendre dans les vannes 1 16A, 1 16B et 1 16C.  The third flow 505 is compressed in a compressor 230 and sent to the heat exchanger, where it condenses. In this case, it is considered that the compressor 230 is a four-stage centrifugal compressor 230A, 230B, 230C and 230D, for example of the integrated speed-multiplication type cooled by intermediate water coolers 232A, 232B, 232C and a cooler. final 232D. The compressor suction pressure is 5.5 bar abs, the intermediate pressures are 10.2 bar abs, 18.9 bar abs and 35.1 bar abs, and the final outlet pressure is 65 bar abs. The suction flow rate is 26.5% of the total air flow. The liquefied air is subdivided between the first column 8, the second column 9, and the fractions to be expanded in the valves 1 16A, 1 16B and 1 16C.
Un débit de liquide enrichi en oxygène LR est détendu et envoyé de la première colonne à la deuxième colonne. Un débit de liquide enrichi en azote LP est détendu et envoyé de la première colonne à la deuxième colonne. De l'azote liquide pur NLMP est produit par la première colonne 8, de nouveau refroidi dans l'échangeur de chaleur 24 et détendu dans la vanne 143 et envoyé au stockage 144. L'azote gazeux haute pression 39 est soutiré en tête de la première colonne et chauffé dans l'échangeur de chaleur pour former un débit de produit 40. L'oxygène liquide OL est soutiré du fond de la deuxième colonne 9, pressurisé par une pompe 37 et envoyé en partie sous forme d'un débit 38 à l'échangeur de chaleur 5, où il se vaporise par échange de chaleur avec l'air pressurisé pour former de l'oxygène gazeux pressurisé. Le reste de l'oxygène liquide 52 est soutiré sous forme d'un produit liquide. Un débit gazeux NR de tête, enrichi en azote, est soutiré de la deuxième colonne 9, chauffé dans l'échangeur de chaleur 5 sous forme d'un débit 33. An oxygen enriched liquid flow LR is expanded and sent from the first column to the second column. An LP-enriched liquid flow rate is expanded and fed from the first column to the second column. NLMP pure liquid nitrogen is produced by the first column 8, cooled again in the heat exchanger 24 and expanded in the valve 143 and sent to the storage 144. The high pressure nitrogen gas 39 is withdrawn at the top of the first column and heated in the heat exchanger to form a product flow 40. The liquid oxygen OL is withdrawn from the bottom of the second column 9, pressurized by a pump 37 and sent partly as a flow 38 to the heat exchanger 5, where it vaporizes by heat exchange with the pressurized air to form pressurized gaseous oxygen. The remainder of the liquid oxygen 52 is withdrawn as a liquid product. A nitrogen-enriched top-stream gas stream NR is withdrawn from the second column 9, heated in the heat exchanger 5 in the form of a flow 33.
De l'argon est produit par utilisation de la colonne d'argon impur 3 et d'argon pur 4. La colonne d'argon impur est alimentée par le débit 16 provenant de la deuxième colonne 9. Un débit de liquide 17 est envoyé de la base de la colonne d'argon impur 3 à la deuxième colonne 9. Le liquide enrichi en oxygène est envoyé au condenseur de tête 12 de la colonne 3 par la vanne 26 et évaporé pour former le débit 27, qui est renvoyé à la deuxième colonne. Un débit de produit 19 est envoyé au condenseur 20, et, de là, forme le débit 19. Le débit 19 est condensé dans l'échangeur de chaleur 20 et subdivisé en un débit 48 qui est envoyé au débit de déchets 33 au point d'intersection 50, et un autre débit. L'autre débit est envoyé par la vanne 21 à la colonne 4.  Argon is produced by using the column of impure argon 3 and pure argon 4. The impure argon column is fed by the flow 16 from the second column 9. A flow of liquid 17 is sent from the base of the impure argon column 3 to the second column 9. The oxygen enriched liquid is sent to the top condenser 12 of the column 3 by the valve 26 and evaporated to form the flow 27, which is returned to the second column. A product flow 19 is sent to the condenser 20, and from there, forms the flow 19. The flow 19 is condensed in the heat exchanger 20 and subdivided into a flow 48 which is sent to the waste flow 33 at the point d intersection 50, and another flow. The other flow is sent by the valve 21 to the column 4.
La colonne d'argon pur 4 produit un débit de produit 45. Le condenseur de tête 13 de la colonne d'argon pur 4 est alimenté par le liquide LP riche en azote provenant de la première colonne par l'intermédiaire de la vanne 34, et l'azote vaporisé est soutiré par la vanne 35 sous forme d'un débit 33 et refroidi dans le sous-refroidisseur 24. Le rebouilleur de fond 14 de la colonne d'argon pur est chauffé par utilisation d'air, et l'air liquéfié 23 est envoyé à la première colonne.  The pure argon column 4 produces a product flow 45. The overhead condenser 13 of the pure argon column 4 is fed by the nitrogen-rich LP liquid from the first column via the valve 34, and the vaporized nitrogen is withdrawn by the valve 35 in the form of a flow 33 and cooled in the subcooler 24. The bottom reboiler 14 of the pure argon column is heated by using air, and the liquefied air 23 is sent to the first column.
Un débit de purge 46 est de même soutiré.  A purge flow 46 is likewise withdrawn.
Le liquide 43 riche en azote est recueilli par l'intermédiaire de la vanne 143 dans le stockage 144.  Nitrogen-rich liquid 43 is collected via valve 143 into storage 144.
Le condenseur 20 est alimenté par le liquide LP riche en azote par l'intermédiaire de la vanne 31 , et le liquide vaporisé est envoyé par la vanne 32 au débit de déchets 33. Après refroidissement et condensation dans l'échangeur de chaleur 5 vers l'extrémité froide de l'échangeur de chaleur, le débit d'air 505 sous 65 bar est subdivisé en deux. Une partie de l'air est détendue dans la vanne 231 et envoyée aux colonnes 8 et 9 sous forme liquide. The condenser 20 is fed with the LP liquid rich in nitrogen through the valve 31, and the vaporized liquid is sent by the valve 32 to the waste flow 33. After cooling and condensation in the heat exchanger 5 towards the cold end of the heat exchanger, the air flow 505 at 65 bar is subdivided into two. Part of the air is expanded in the valve 231 and sent to the columns 8 and 9 in liquid form.
Le reste de l'air 107 est subdivisé en trois fractions 107A, 107B, 107C. La fraction d'air 107A recyclée entre le premier étage 230A et le deuxième étage 230B correspond à 1 ,08% du débit d'air total. Elle est détendue dans la vanne 1 16A de 65 bar abs à environ 10,2 bar abs et introduite dans l'échangeur de chaleur 5, où elle est vaporisée, chauffée après vaporisation pour donner un air de recyclage 107A.  The remainder of the air 107 is subdivided into three fractions 107A, 107B, 107C. The fraction of air 107A recycled between the first stage 230A and the second stage 230B corresponds to 1.08% of the total air flow. It is expanded in the valve 1 16A 65 bar abs to about 10.2 bar abs and introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107A.
La fraction d'air 107B recyclée entre le deuxième étage 230B et le troisième étage The air fraction 107B recycled between the second stage 230B and the third stage
230C correspond à 0,84% du débit d'air total. Elle est détendue dans la vanne 1 16B de 65 bar abs à environ 18,9 bar abs et introduite dans l'échangeur de chaleur 5, où elle est vaporisée, chauffée après vaporisation pour donner un air de recyclage 107B. 230C corresponds to 0.84% of the total air flow. It is expanded in the valve 1 16B 65 bar abs to about 18.9 bar abs and introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107B.
La fraction d'air 107C recyclée entre le troisième étage 230C et le quatrième étage 230D correspond à 22,08% du débit d'air total. Elle est détendue dans la vanne 1 16C de 65 bar abs à environ 35,1 bar abs et introduite dans l'échangeur de chaleur 5, où elle est vaporisée, chauffée après vaporisation pour donner un air de recyclage 107C.  The fraction of air 107C recycled between the third stage 230C and the fourth stage 230D corresponds to 22.08% of the total air flow rate. It is expanded in the valve 1 16C from 65 bar abs to about 35.1 bar abs and introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107C.
Ces trois fractions d'air représentent un débit total d'air de recyclage de 24% du débit d'air total, ce qui signifie que le fluide 505 correspond à un débit de 50,5% du débit d'air total, et que le débit par la vanne 231 est de 26,5%. La vaporisation des trois fractions d'air 107A, 107B et 107C a lieu dans l'échangeur de chaleur 5 respectivement à des températures d'environ -166°C, -155°C et -142°C, comme on peut le voir sur la Figure 4, ce qui est inférieur à la température de vaporisation de l'oxygène, qui est d'environ -125°C. Un séparateur de phase devrait être ajouté si le débit détendu est un fluide diphasique, la phase liquide étant introduite dans l'échangeur de chaleur 5 et la phase vapeur étant mélangée au débit 107. Le terme "condensation" recouvre la condensation d'une forme vapeur à une forme liquide ou partiellement liquide. Il recouvre aussi la pseudo-condensation d'un fluide supercritique quand il est refroidi d'une température supérieure à la température supercritique à une température inférieure à la température supercritique.  These three air fractions represent a total recycle air flow rate of 24% of the total air flow rate, which means that the fluid 505 corresponds to a flow rate of 50.5% of the total air flow, and that the flow rate through the valve 231 is 26.5%. The vaporization of the three air fractions 107A, 107B and 107C takes place in the heat exchanger 5 respectively at temperatures of about -166 ° C, -155 ° C and -142 ° C, as can be seen on Figure 4, which is less than the vaporization temperature of oxygen, which is about -125 ° C. A phase separator should be added if the expanded flow is a two-phase fluid, the liquid phase being introduced into the heat exchanger 5 and the vapor phase being mixed with the flow 107. The term "condensation" covers the condensation of a form vapor to a liquid or partially liquid form. It also covers the pseudo-condensation of a supercritical fluid when it is cooled from a temperature above the supercritical temperature to a temperature below the supercritical temperature.
La Figure 4 présente le diagramme d'échange correspondant au procédé de la Figure 3. Une variante moins optimisée de la Figure 3 devrait impliquer la subdivision du débit 107 en une ou deux fractions et le recyclage de ces fractions, après vaporisation, avec retour au compresseur 230. Figure 4 shows the exchange diagram corresponding to the process of Figure 3. A less optimized variant of FIG. 3 should involve the subdivision of the flow rate 107 into one or two fractions and the recycling of these fractions, after vaporization, with return to the compressor 230.
Pour simplifier le procédé décrit ci-dessus, considérant les faibles débits de 107A et de 107B, il est possible de conserver une fraction d'air recyclé unique 107C.  To simplify the process described above, considering the low flow rates of 107A and 107B, it is possible to maintain a single recycled air fraction 107C.
Les vannes, 231 , 1 16A, 1 16B et 1 16C pourraient être remplacées par des turbines à liquide, c'est-à-dire un système de détente produisant du travail dans le but de diminuer l'irréversibilité associée à la détente isenthalpique. Ces turbines à liquide pourraient installées en parallèle ou en série.  The valves 231, 16A, 16B and 16C could be replaced by liquid turbines, that is, an expansion system producing work in order to reduce the irreversibility associated with the isenthalpic expansion. These liquid turbines could be installed in parallel or in series.
Le compresseur 230, dans le cas de base, est considéré comme étant une machine entraînée par un moteur, mais pourrait aussi être entraîné par une turbine à vapeur ou une turbine à gaz (le même que celui pour le Compresseur d'Air Principal 6). En tant que variante, l'un quelconque des quatre étages de compresseur 230A, 230B, 230C et 230D pourrait être entraîné par une machine de détente de l'un quelconque des fluides de ce procédé de séparation cryogénique d'air, de préférence à basse température. En outre, l'un quelconque des quatre étages de compresseur 230A, 230B, 230C et 230D pourrait avoir une température d'aspiration inférieure à la température ambiante, de préférence légèrement supérieure à la température de vaporisation de l'oxygène, à environ -125°C. En termes d'énergie spécifique (kWh/Nm3 d'O2), si la technique antérieure correspond à 100, l'énergie spécifique nécessaire à la production d'oxygène sous 40 bar abs selon l'invention est de 92,9, c'est-à-dire un gain de 7,1 %.  The compressor 230, in the basic case, is considered to be a machine driven by a motor, but could also be driven by a steam turbine or a gas turbine (the same as that for the Main Air Compressor 6) . Alternatively, any one of the four compressor stages 230A, 230B, 230C and 230D could be driven by an expansion machine of any of the fluids of this cryogenic air separation process, preferably at a low temperature. temperature. In addition, any one of the four compressor stages 230A, 230B, 230C and 230D could have a suction temperature lower than the ambient temperature, preferably slightly higher than the vaporization temperature of the oxygen, at about -125. ° C. In terms of specific energy (kWh / Nm3 of O2), if the prior art corresponds to 100, the specific energy required for the production of oxygen at 40 bar abs according to the invention is 92.9%. that is to say a gain of 7.1%.
Les fractions 107A, 107B, 107C pourraient être séparées de la partir de l'air passant par 231 et extraites de l'échangeur de chaleur 5 à une température supérieure à la température de l'extrémité froide de l'échangeur de chaleur 5.  The fractions 107A, 107B, 107C could be separated from the air passing through 231 and extracted from the heat exchanger 5 at a temperature higher than the temperature of the cold end of the heat exchanger 5.
Le procédé peut être modifié pour vaporiser l'azote liquide pompé, en tant que débit additionnel ou en tant que débit remplaçant le débit d'oxygène pompé.  The process may be modified to vaporize the pumped liquid nitrogen, as an additional flow rate or as a flow rate to replace the pumped oxygen flow rate.
Il est de même possible d'utiliser un cycle d'azote (plutôt qu'un cycle d'air) dans une variante qui n'est pas couverte par les revendications. Dans ce cas, le compresseur 230 devrait être alimenté par au moins une partie de l'azote gazeux haute pression 40.  It is also possible to use a nitrogen cycle (rather than an air cycle) in a variant that is not covered by the claims. In this case, the compressor 230 should be supplied with at least a portion of the high pressure nitrogen gas 40.
Il est de même possible d'utiliser l'invention pour réduire la pression de calcul de l'échangeur de chaleur 5, c'est-à-dire la deuxième pression d'air avec une plus faible pénalité d'énergie grâce au recyclage du débit 107. Les procédés illustrés présentent des systèmes à double colonne, mais on comprendra aisément que l'invention s'applique à des systèmes à triple colonne. It is also possible to use the invention to reduce the design pressure of the heat exchanger 5, that is to say the second air pressure with a lower energy penalty through the recycling of the flow 107. The illustrated methods have dual column systems, but it will be readily understood that the invention is applicable to triple column systems.
Ils pourraient aussi être utilisés avec des cycles de procédé produisant de l'oxygène de faible pureté (habituellement, de ΓΟ2 à 95% au lieu d'O2 à 99,5%), tels que les cycles de procédé "à double vaporiseur".  They could also be used with process cycles producing low purity oxygen (usually from à2 to 95% instead of O2 to 99.5%), such as "dual vaporizer" process cycles.
Dans la forme de réalisation de la Figure 5, il est prévu d'exploiter le système de la Figure 3 pour récupérer du froid de l'oxygène liquide d'une manière plus indépendante à partir de l'unité de séparation d'air 101 .  In the embodiment of Figure 5, it is intended to operate the system of Figure 3 to recover cold liquid oxygen in a more independent manner from the air separation unit 101.
En particulier, des tampons liquides 131 , 152 sont ajoutés à l'unité de stockage, et libèrent des liquides cryogéniques pour décorréler la production d'oxygène par l'ASU de la consommation par le client. En outre, il permet de réduire la consommation d'énergie aux heures de pointe sans réduire le débit d'oxygène allant vers l'utilisateur final, et l'augmentation de la consommation d'hydrogène aux heures creuses, sans augmentation du débit d'oxygène vers l'utilisateur final.  In particular, liquid buffers 131, 152 are added to the storage unit, and release cryogenic liquids to decorrelate oxygen production by the ASU from consumer consumption. In addition, it reduces power consumption during peak hours without reducing the flow of oxygen to the end user, and increasing the consumption of hydrogen at off-peak times, without increasing the flow rate. oxygen to the end user.
L'air d'alimentation est comprimé dans le compresseur 6 et purifié dans l'unité de purification 7 et subdivisé en deux.  The feed air is compressed in the compressor 6 and purified in the purification unit 7 and subdivided into two.
Un débit 505 est comprimé dans un compresseur 230 et est envoyé à l'échangeur de chaleur, où il subit une condensation partielle, ou "pseudo-condensation", car il se trouve au-delà de la pression critique. Dans ce cas, on considère que le compresseur 230 est un compresseur centrifuge à quatre étages 230A, 230B, 230C et 230D, par exemple du type à multiplicateur de vitesse intégré, refroidi par des refroid isseurs intermédiaires d'eau 232A, 232B, 232C et un refroidisseur final 232D. La pression d'aspiration du compresseur est de 5,5 bar abs, les pressions intermédiaires sont de 10,2 bar abs, 18,9 bar abs et 35,1 bar abs, pression finale 65 bar abs. Le débit d'aspiration est de 23% du débit d'air total quand aucun liquide cryogénique n'est stocké ou déstocké.  A flow 505 is compressed in a compressor 230 and is sent to the heat exchanger, where it undergoes a partial condensation, or "pseudo-condensation", because it is beyond the critical pressure. In this case, it is considered that the compressor 230 is a four-stage centrifugal compressor 230A, 230B, 230C and 230D, for example of the integrated speed-multiplier type, cooled by intermediate water coolers 232A, 232B, 232C and a 232D final cooler. The suction pressure of the compressor is 5.5 bar abs, the intermediate pressures are 10.2 bar abs, 18.9 bar abs and 35.1 bar abs, final pressure 65 bar abs. The suction flow rate is 23% of the total air flow rate when no cryogenic liquid is stored or destocked.
Le débit 505 est divisé en un premier débit secondaire 505A, qui va directement à l'échangeur de chaleur 5, et un deuxième débit secondaire, qui va à l'unité de réfrigération 102 pour être refroidi à -5°C et introduit dans l'échangeur de chaleur 5.  The flow 505 is divided into a first secondary flow 505A, which goes directly to the heat exchanger 5, and a second secondary flow, which goes to the refrigeration unit 102 to be cooled to -5 ° C and introduced into the heat exchanger 5.
En un point intermédiaire de l'échangeur de chaleur 5, à une température de At an intermediate point of the heat exchanger 5, at a temperature of
-124°C, une première fraction de l'air haute pression est soutirée et envoyée au machine de détente à deux phases 1 16D, réintroduit dans l'échangeur de chaleur 5 pour être chauffé et recyclé à 35,1 bar abs dans le compresseur 230 au niveau de l'étage 230D en tant que débit 107D. Cette première fraction a un débit de 18,4% du débit d'air total. At -124 ° C., a first fraction of the high-pressure air is withdrawn and sent to the two-phase expansion device 1 16D, reintroduced into the heat exchanger 5 to be heated and recycled to 35.1 bar abs in the compressor 230 at the level of stage 230D as flow 107D. This first fraction has a flow rate of 18.4% of the total air flow.
Une deuxième fraction est refroidie à -192,2°C par passage complet à travers l'échangeur de chaleur 5 et est détendue dans la vanne 231 pour être envoyée à l'unité de stockage 131 d'air liquide (LAIR) en tant que débit 234. Le débit de cette deuxième fraction n'est que de 23% du débit d'air total provenant du compresseur d'air principal 6.  A second fraction is cooled to -192.2 ° C by complete passage through the heat exchanger 5 and is expanded in the valve 231 to be sent to the liquid air storage unit 131 (LAIR) as a flow 234. The flow rate of this second fraction is only 23% of the total air flow from the main air compressor 6.
Une fraction 107 est soutirée de l'extrémité froide de l'échangeur de chaleur 5 et subdivisée en trois. La fraction d'air 107A recyclée entre le premier étage 230A et le deuxième étage 230B correspond à 1 ,1 % du débit d'air total. Elle est détendue dans la vanne 1 16A de 65 bar abs à environ 10,2 bar abs et introduite dans l'échangeur de chaleur 5, où elle est évaporée, chauffée après vaporisation pour donner un air de recyclage 107A.  A fraction 107 is withdrawn from the cold end of the heat exchanger 5 and subdivided into three. The fraction of air 107A recycled between the first stage 230A and the second stage 230B corresponds to 1.1% of the total air flow. It is expanded in the valve 1 16A 65 bar abs to about 10.2 bar abs and introduced into the heat exchanger 5, where it is evaporated, heated after vaporization to give a recirculation air 107A.
La fraction d'air 107B recyclée entre le deuxième étage 230B et le troisième étage 230C correspond à 3,15% du débit d'air total. Elle est détendue dans la vanne 1 16B de 65 bar abs à environ 18,9 bar abs et est introduite dans l'échangeur de chaleur 5, où elle est vaporisée, chauffée après vaporisation pour donner un air de recyclage 107B.  The air fraction 107B recycled between the second stage 230B and the third stage 230C corresponds to 3.15% of the total air flow rate. It is expanded in the valve 1 16B 65 bar abs to about 18.9 bar abs and is introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107B.
La fraction d'air 107C est détendue dans la vanne 1 16C de 65 bar abs à environ 1 ,2 bar abs et est introduite dans l'échangeur de chaleur 5, où elle est vaporisée, chauffée après vaporisation pour donner un air de recyclage 107C qui peut être utilisé pour régénérer des purificateur d'air si l'ASU 101 n'est pas en marche. Elle représente 4,45% du débit d'air total.  The air fraction 107C is expanded in the valve 1 16C from 65 bar abs to about 1.2 bar abs and is introduced into the heat exchanger 5, where it is vaporized, heated after vaporization to give a recirculation air 107C which can be used to regenerate air purifiers if the ASU 101 is not running. It represents 4.45% of the total air flow.
Ces trois fractions d'air 107A, 107B, 107C, et la première fraction d'air détendue dans la turbine 1 16D représentent un débit total d'air de recyclage de 27,1 % du débit d'air total provenant du compresseur 230, ce qui signifie que le fluide 505 représente 50,1 % du débit d'air total provenant du compresseur principal 6, et le débit passant par la vanne 231 correspond à 23% du débit d'air total.  These three air fractions 107A, 107B, 107C, and the first fraction of air expanded in the turbine 1 16D represent a total flow of recycling air of 27.1% of the total air flow from the compressor 230, which means that the fluid 505 represents 50.1% of the total air flow from the main compressor 6, and the flow rate through the valve 231 is 23% of the total air flow.
Une cuve de stockage d'oxygène liquide 152 alimentée par l'ASU 101 fournit l'oxygène 151 au système. Une pompe d'oxygène liquide 37 pressurise l'oxygène jusqu'au niveau de pression requis avant introduction dans l'échangeur de chaleur 5, où il subit une vaporisation ou une pseudo-vaporisation. L'ASU 101 est alimentée par un air 510 provenant du même compresseur 6 (MAC) et par l'air liquide 235 qui est utilisé pour compenser la production d'oxygène liquide 150. A liquid oxygen storage tank 152 powered by ASU 101 provides oxygen 151 to the system. A liquid oxygen pump 37 pressurizes the oxygen to the required pressure level before introduction into the heat exchanger 5, where it undergoes vaporization or pseudo-vaporization. The ASU 101 is powered by air 510 from the same compressor 6 (MAC) and liquid air 235 which is used to compensate for the production of liquid oxygen 150.
Le débit 510 est refroidi dans un échangeur de chaleur indépendant de l'échangeur de chaleur 5 par échange de chaleur avec l'azote gazeux provenant de l'unité de séparation d'air (non représentée). Il est possible de refroidir le débit froid 510 dans l'échangeur de chaleur 5, mais cela rendrait le système moins flexible.  The flow 510 is cooled in a heat exchanger independent of the heat exchanger 5 by heat exchange with nitrogen gas from the air separation unit (not shown). It is possible to cool the cold flow 510 in the heat exchanger 5, but this would make the system less flexible.
Il est de même possible d'avoir l'unité de séparation d'air et ce système de récupération du froid en des emplacements distincts. Dans ce cas, on aurait un système de compresseur fournissant de l'air à l'ASU et un autre système compresseur fournissant de l'air au système de récupération de froid, et le transport de l'air liquide 235 et de l'oxygène liquide 150 peut être réalisé par camion ou canalisation. Les stockages de liquide 152 et 131 doivent aussi être doublés sur chaque site.  It is also possible to have the air separation unit and this cold recovery system in separate locations. In this case, we would have a compressor system supplying air to the ASU and another compressor system supplying air to the cold recovery system, and transporting the liquid air 235 and oxygen liquid 150 can be made by truck or pipe. The liquid stores 152 and 131 must also be doubled at each site.
Il pourrait aussi y avoir des systèmes compresseurs distincts fournissant de l'air à l'ASU et au système de récupération de froid quand les deux unités se trouvent sur le même emplacement, si cela est considéré comme étant plus commode et/ou plus efficace. C'est particulièrement le cas quand les deux unités ne fonctionnent pas simultanément à la même capacité. Un compresseur unique exigerait une dynamique de mesure précise et perdrait son efficacité à faible capacité. Avec des systèmes de compresseurs différents, il est possible d'optimiser la dynamique de mesure sur chaque machine.  There may also be separate compressor systems supplying air to the ASU and the cold recovery system when both units are in the same location, if it is considered more convenient and / or more efficient. This is particularly the case when the two units do not operate simultaneously at the same capacity. A single compressor would require accurate measurement dynamics and lose efficiency at low capacity. With different compressor systems, it is possible to optimize the measurement dynamics on each machine.
Pour simplifier le procédé décrit ci-dessus, considérant les faibles débits de 107A et de 107B, il est possible de maintenir une fraction d'air recyclé unique 107D et de l'air basse pression vers l'unité de purification 107C.  To simplify the process described above, considering the low flow rates of 107A and 107B, it is possible to maintain a single recycled air fraction 107D and low pressure air to the purification unit 107C.
Les vannes 231 , 1 16A, 1 16B et 1 16C pourraient être remplacées par des turbines détendant du liquide, c'est-à-dire un système de détente produisant du travail, dans le but de diminuer l'irréversibilité associée à la détente isenthalpique. Ces turbines détendant du liquide pourraient être installées en parallèle et/ou en série.  The valves 231, 16A, 16B and 16C could be replaced by liquid-displacing turbines, ie a work-producing expansion system, in order to reduce the irreversibility associated with isenthalpic expansion. . These liquid-displacing turbines could be installed in parallel and / or in series.
Pendant les périodes creuses, quand le coût de l'électricité est inférieur à une valeur donnée, l'unité de séparation d'air fonctionne de telle sorte que la quantité d'oxygène liquide stockée dans la cuve de stockage 152 augmente. La quantité d'oxygène liquide vaporisée dans l'échangeur de chaleur 5 est inférieure à l'oxygène liquide produit par l'unité de séparation d'air. Aucun air n'est envoyé à la vanne 1 16C, et l'unité de purification 7 est régénérée par utilisation d'un débit d'azote provenant de l'unité de séparation d'air 101 . During off-peak periods, when the cost of electricity is less than a given value, the air separation unit operates such that the amount of liquid oxygen stored in the storage tank 152 increases. The amount of liquid oxygen vaporized in the heat exchanger 5 is less than the liquid oxygen produced by the air separation unit. No air is sent to the valve 1 16C, and the purification unit 7 is regenerated using a nitrogen flow from the air separation unit 101.
Les débits d'air 510 sont envoyés à l'unité de séparation d'air par l'intermédiaire d'un échangeur de chaleur indépendant de l'échangeur de chaleur 5, et un débit d'air 235 est envoyé à l'unité de séparation d'air à partir de la cuve de stockage 131 , et l'oxygène liquide 150 est envoyé à la cuve de stockage 152. Cependant, la quantité d'air liquide envoyée à la cuve 131 dépasse la quantité d'air qui en est soutirée, et la quantité d'oxygène liquide envoyée à la cuve 152 dépasse la quantité d'oxygène liquide qui en est soutirée.  The air flows 510 are sent to the air separation unit via a heat exchanger independent of the heat exchanger 5, and an air flow 235 is sent to the air unit. separation of air from the storage tank 131, and the liquid oxygen 150 is sent to the storage tank 152. However, the amount of liquid air sent to the tank 131 exceeds the amount of air which is withdrawn, and the amount of liquid oxygen sent to the tank 152 exceeds the amount of liquid oxygen that is withdrawn.
Pendant les périodes de pointe, quand le coût de l'électricité est supérieur à une valeur donnée, l'unité de séparation d'air ne fonctionne pas, ou fonctionne à faible capacité, habituellement de 50% ou moins de la capacité maximale, même si l'oxygène total produit est très supérieur à 50% de la capacité maximale. Aucun air n'est envoyé à l'unité de séparation d'air par les débits 510 et 235. L'oxygène liquide stocké dans la cuve 152 est vaporisé pour donner le débit d'oxygène gazeux. La régénération de l'unité de purification 7 est réalisée par utilisation du débit 107C.  During peak periods, when the cost of electricity is greater than a given value, the air separation unit will not operate, or operate at a low capacity, usually 50% or less of maximum capacity, even if the total oxygen produced is well above 50% of the maximum capacity. No air is sent to the air separation unit through flow rates 510 and 235. The liquid oxygen stored in the vessel 152 is vaporized to give the oxygen gas flow rate. The regeneration of the purification unit 7 is carried out using the flow 107C.
L'air liquide produit par la vaporisation de l'oxygène liquide est stocké dans la cuve de stockage 131 pendant les périodes de pointe, et aucun air gazeux ou liquide n'est envoyé à l'unité de séparation d'air 101 .  The liquid air produced by the vaporization of the liquid oxygen is stored in the storage tank 131 during the peak periods, and no gaseous or liquid air is sent to the air separation unit 101.
Le procédé peut être modifié pour vaporiser l'azote liquide pompé en tant que débit additionnel, ou en tant que débit remplaçant le débit d'oxygène pompé.  The process may be modified to vaporize the pumped liquid nitrogen as an additional flow rate, or as a flow rate to replace the pumped oxygen flow rate.
Il est de même possible d'utiliser un cycle d'azote (plutôt qu'un cycle d'air), comme on le voit sur la Figure 6. Dans ce cas, le compresseur 230 est alimenté par au moins une partie de l'azote gazeux haute pression 40. Mais, dans ce cas, il est nécessaire d'avoir une source d'azote disponible, provenant de l'unité de séparation d'air 101 fonctionnant à capacité réduite, ou d'autres unités de séparation d'air, en option par l'intermédiaire d'une conduite d'azote. C'est la raison pour laquelle c'est l'air qui est le fluide préféré pour une telle application, car il est disponible indépendamment de toute unité de séparation d'air.  It is likewise possible to use a nitrogen cycle (rather than an air cycle), as shown in FIG. 6. In this case, the compressor 230 is powered by at least a portion of the In this case, it is necessary to have an available nitrogen source, coming from the air separation unit 101 operating at reduced capacity, or other separation units of air, optionally via a nitrogen line. This is why air is the preferred fluid for such an application because it is available independently of any air separation unit.
Dans ce cas, la totalité de l'air d'alimentation est comprimée dans le compresseur d'air principal 6 jusqu'à la pression requise pour la séparation d'air dans l'ASU 101 .  In this case, all of the supply air is compressed in the main air compressor 6 to the pressure required for air separation in the ASU 101.
L'azote comprimé est refroidi et condensé dans l'échangeur de chaleur 5. L'azote comprimé est ensuite subdivisé en au moins deux portions, trois portions étant présentées ici, détendu à au moins deux pressions différentes, et vaporisé dans l'échangeur de chaleur 5. The compressed nitrogen is cooled and condensed in the heat exchanger 5. The compressed nitrogen is then subdivided into at least two portions, three portions being presented here, expanded to at least two different pressures, and vaporized in the heat exchanger 5.
L'azote vaporisé provenant des vannes 1 16A et 1 16B est renvoyé à des positions intermédiaires du compresseur d'azote 230, et l'azote vaporisé provenant de la vanne 1 16C peut servir à régénérer l'unité de purification si l'unité de séparation d'air ne fonctionne pas.  The vaporized nitrogen from valves 1 16A and 1 16B is returned to intermediate positions of nitrogen compressor 230, and the vaporized nitrogen from valve 1 16C can be used to regenerate the purification unit if the air separation does not work.
L'azote liquide produit 234 est détendu dans la vanne 231 et stocké dans l'unité de stockage 131 pour utilisation.  The produced liquid nitrogen 234 is expanded in the valve 231 and stored in the storage unit 131 for use.
Ainsi, l'oxygène liquide peut être vaporisé contre l'azote dans les périodes au cours desquelles l'unité de séparation d'air ne fonctionne pas, par exemple les périodes au cours desquelles l'électricité est particulièrement onéreuse.  Thus, the liquid oxygen can be vaporized against the nitrogen in the periods during which the air separation unit does not operate, for example the periods during which the electricity is particularly expensive.
Ces variantes de l'invention pourraient être utilisées pour récupérer le froid d'un système de secours d'oxygène/azote liquide dans le cas d'une indisponibilité planifiée (maintenance) ou non planifiée (incident) de la ou des unités de séparation d'air.  These variants of the invention could be used to recover the cold from an oxygen / liquid nitrogen backup system in the event of a planned (maintenance) or unplanned (incident) unavailability of the separation unit or units. 'air.
Les procédés illustrés présentent des systèmes à double colonne, mais on comprendra aisément que l'invention s'applique à des systèmes à triple colonne. Elle pourrait aussi être utilisée avec des cycles de procédé produisant de l'oxygène de faible pureté (habituellement de ΓΟ2 à 95% au lieu d'O2 à 99,5%), tels que des cycles de procédé "à double vaporiseur".  The illustrated methods have dual column systems, but it will be readily understood that the invention is applicable to triple column systems. It could also be used with process cycles producing low purity oxygen (usually from à2 to 95% instead of O2 to 99.5%), such as "dual vaporizer" process cycles.

Claims

Revendications claims
1 . Procédé de séparation d'air par distillation cryogénique dans un système de colonnes comprenant une première colonne et une deuxième colonne opérant à une plus basse pression que la première colonne, comprenant les étapes de : 1. A method of separating air by cryogenic distillation in a column system comprising a first column and a second column operating at a lower pressure than the first column, comprising the steps of:
i) compression de la totalité de l'air d'alimentation dans un premier compresseur (6) jusqu'à une première pression de sortie d'au plus un bar supérieur à et de préférence sensiblement égale à la pression de la première colonne,  i) compressing all of the supply air in a first compressor (6) to a first outlet pressure of at most one bar greater than and preferably substantially equal to the pressure of the first column,
ii) envoi d'une première partie de l'air (505) sous la première pression de sortie à un deuxième compresseur (230), et compression de l'air à une deuxième pression de sortie,  ii) sending a first portion of the air (505) under the first output pressure to a second compressor (230), and compressing the air to a second output pressure,
iii) refroidissement et condensation d'au moins une partie de l'air sous la deuxième pression de sortie dans l'échangeur de chaleur (5),  iii) cooling and condensing at least a portion of the air under the second outlet pressure in the heat exchanger (5),
iv) envoi d'un débit d'air gazeux sous la première pression de sortie au système de colonnes, sans compression plus poussée, et séparation de l'air dans le système de colonnes,  iv) sending a flow of gaseous air under the first exit pressure to the column system, without further compression, and separating the air in the column system,
v) prélèvement du liquide d'une colonne du système de colonnes, pressurisation du liquide et vaporisation du liquide (38) par un échange de chaleur dans l'échangeur de chaleur, et  v) withdrawing the liquid from a column of the column system, pressurizing the liquid and vaporizing the liquid (38) by exchanging heat in the heat exchanger, and
vi) détente d'au moins une fraction de l'air refroidi et condensé, de la deuxième pression de sortie à au moins une troisième pression, vaporisation au moins partielle dudit air (107A, 107B, 107C) dans l'échangeur de chaleur sous l'au moins une troisième pression, la troisième pression étant intermédiaire entre la première pression de sortie et la deuxième pression de sortie, éventuellement chauffage dudit air au moins partiellement vaporisé dans l'échangeur de chaleur caractérisé en ce qu'au moins une partie vaporisée de cet air est envoyé au deuxième compresseur (230) pour être comprimée jusqu'à la deuxième pression de sortie.  vi) expanding at least a fraction of the cooled and condensed air from the second outlet pressure to at least a third pressure, at least partially vaporizing said air (107A, 107B, 107C) in the heat exchanger under the at least one third pressure, the third pressure being intermediate between the first outlet pressure and the second outlet pressure, optionally heating said air at least partially vaporized in the heat exchanger characterized in that at least one vaporized part this air is sent to the second compressor (230) to be compressed to the second output pressure.
2. Procédé selon la revendication 1 , dans lequel la détente est réalisée dans au moins une vanne (1 16A,1 16B,1 16C). 2. The method of claim 1, wherein the expansion is performed in at least one valve (1 16A, 1 16B, 1 16C).
3. Procédé selon la revendication 1 , dans lequel la détente est réalisée dans au moins une turbine et produit du travail. 3. The method of claim 1, wherein the expansion is performed in at least one turbine and produces work.
4. Procédé selon la revendication 1 , dans lequel la température de l'au moins une fraction avant détente est inférieure à la somme de la température de la vaporisation du liquide et l'approche de température minimale dans l'échangeur de chaleur. The method of claim 1, wherein the temperature of the at least one fraction before expansion is less than the sum of the vaporization temperature of the liquid and the minimum temperature approach in the heat exchanger.
5. Procédé selon la revendication 1 , dans lequel le deuxième compresseur est un compresseur multi-étages. The method of claim 1, wherein the second compressor is a multi-stage compressor.
6. Procédé selon la revendication 5, dans lequel ladite au moins une troisième pression est au moins la pression d'entrée de l'un des étages du deuxième compresseur. The method of claim 5 wherein said at least one third pressure is at least the inlet pressure of one of the stages of the second compressor.
7. Procédé selon l'une quelconque des revendications précédentes, dans lequel un étage du deuxième compresseur est entraîné par une machine de détente sur un fluide du procédé. The method of any of the preceding claims, wherein a stage of the second compressor is driven by an expansion machine on a process fluid.
8. Procédé selon la revendication 7, dans lequel la température d'entrée de la machine de détente est inférieure à la température ambiante. The method of claim 7, wherein the inlet temperature of the flashing machine is below room temperature.
9. Procédé selon l'une quelconque des revendications précédentes, dans lequel au moins un étage du deuxième compresseur a une température d'aspiration inférieure à la température ambiante. The method of any of the preceding claims, wherein at least one stage of the second compressor has a suction temperature lower than room temperature.
10. Procédé selon la revendication 9, dans lequel la température d'aspiration est supérieure à la température de vaporisation du liquide, mais en est proche. The method of claim 9, wherein the suction temperature is higher than the vaporization temperature of the liquid, but is close to it.
1 1 . Procédé selon l'une quelconque des revendications précédentes, dans lequel le liquide est un débit enrichi en oxygène. 1 1. A process as claimed in any one of the preceding claims, wherein the liquid is a flow enriched with oxygen.
12. Procédé selon l'une quelconque des revendications précédentes, dans lequel le liquide est un débit enrichi en azote. The process of any one of the preceding claims, wherein the liquid is a nitrogen enriched flow.
13. Procédé selon l'une quelconque des revendications précédentes, dans lequel le débit de production du ou des produits liquides finaux n'est pas supérieur à 10% de l'air d'alimentation, de préférence n'est pas supérieur à 5% de l'air d'alimentation. Process according to any one of the preceding claims, in which the production rate of the final liquid product or products is not greater than 10% of the feed air, preferably not more than 5%. supply air.
14. Appareil pour séparer l'air par distillation cryogénique dans un système de colonnes comprenant une première colonne et une deuxième colonne opérant à une plus basse pression que la première colonne, comprenant en outre : Apparatus for separating air by cryogenic distillation in a column system comprising a first column and a second column operating at a lower pressure than the first column, further comprising:
i) un premier compresseur (6) pour comprimer l'air d'alimentation à une première pression de sortie, d'au plus un bar supérieure à la pression de la première colonne, ii) un deuxième compresseur (230) et un moyen pour envoyer une première partie de l'air sous la première pression de sortie du premier compresseur au deuxième compresseur pour comprimer l'air à une deuxième pression de sortie,  i) a first compressor (6) for compressing the supply air at a first outlet pressure, at most one bar greater than the pressure of the first column, ii) a second compressor (230) and means for send a first portion of the air under the first output pressure of the first compressor to the second compressor to compress the air to a second output pressure,
iii) un échangeur de chaleur (5), dans lequel au moins une partie de l'air sous la deuxième pression de sortie est refroidie et condensée,  iii) a heat exchanger (5), wherein at least a portion of the air under the second outlet pressure is cooled and condensed,
iv) un moyen pour prélever le liquide d'une colonne du système de colonnes, un moyen (37) pour pressuriser le liquide, un moyen pour envoyer le liquide pressurisé à l'échangeur de chaleur, et un moyen pour prélever le liquide vaporisé de l'échangeur de chaleur, et  iv) means for withdrawing the liquid from a column of the column system, means (37) for pressurizing the liquid, means for supplying the pressurized liquid to the heat exchanger, and means for withdrawing the vaporized liquid from the heat exchanger, and
v) un moyen pour détendre une fraction de l'air refroidi et condensé sous la deuxième pression de sortie, un moyen pour envoyer ledit air détendu à l'échangeur de chaleur et un moyen pour envoyer au moins une partie dudit air détendu, ayant été vaporisée dans l'échangeur de chaleur sous au moins une troisième pression, intermédiaire(s) entre les première et deuxième pressions de sorties, de l'échangeur de chaleur au deuxième compresseur, pour le comprimer à la deuxième pression de sortie et  v) means for expanding a fraction of the cooled and condensed air under the second outlet pressure, means for supplying said expanded air to the heat exchanger and means for sending at least a portion of said expanded air, having been vaporized in the heat exchanger under at least a third pressure, intermediate (s) between the first and second outlet pressures, from the heat exchanger to the second compressor, to compress it at the second outlet pressure and
vi) des moyens pour envoyer de l'air épuré et refroidi au système de colonnes pour s'y séparer.  vi) means for sending purified and cooled air to the column system for separation therefrom.
15. Appareil selon la revendication 14 où le moyen pour détendre est une vanne ou une turbine. Apparatus according to claim 14 wherein the means for expanding is a valve or a turbine.
EP18736971.5A 2017-05-24 2018-05-18 Method and apparatus for air separation by cryogenic distillation Active EP3631327B1 (en)

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FR1754624A FR3062197B3 (en) 2017-05-24 2017-05-24 METHOD AND APPARATUS FOR SEPARATING AIR BY CRYOGENIC DISTILLATION
FR1754619A FR3066809B1 (en) 2017-05-24 2017-05-24 METHOD AND APPARATUS FOR AIR SEPARATION BY CRYOGENIC DISTILLATION
PCT/FR2018/051201 WO2018215716A1 (en) 2017-05-24 2018-05-18 Method and apparatus for air separation by cryogenic distillation

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CN110678710B (en) 2021-12-10
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FR3066809B1 (en) 2020-01-31
EP3631327B1 (en) 2021-06-23
US20200132367A1 (en) 2020-04-30
US12025372B2 (en) 2024-07-02
RU2019140617A (en) 2021-06-10
FR3062197A3 (en) 2018-07-27
FR3066809A1 (en) 2018-11-30
FR3062197B3 (en) 2019-05-10
CN110678710A (en) 2020-01-10
WO2018215716A1 (en) 2018-11-29

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