EP3207320B1 - Verfahren und vorrichtung zur variablen gewinnung von argon durch tieftemperaturzerlegung - Google Patents

Verfahren und vorrichtung zur variablen gewinnung von argon durch tieftemperaturzerlegung Download PDF

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Publication number
EP3207320B1
EP3207320B1 EP15771022.9A EP15771022A EP3207320B1 EP 3207320 B1 EP3207320 B1 EP 3207320B1 EP 15771022 A EP15771022 A EP 15771022A EP 3207320 B1 EP3207320 B1 EP 3207320B1
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Prior art keywords
argon
column
gaseous
return flow
pure
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EP15771022.9A
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German (de)
English (en)
French (fr)
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EP3207320A1 (de
Inventor
Stefan Lochner
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Linde GmbH
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Linde GmbH
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04642Recovering noble gases from air
    • F25J3/04648Recovering noble gases from air argon
    • F25J3/04654Producing crude argon in a crude argon column
    • F25J3/04666Producing 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
    • F25J3/04672Producing 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
    • F25J3/04678Producing 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04006Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04078Providing 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
    • F25J3/0409Providing 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04406Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
    • F25J3/04412Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04642Recovering noble gases from air
    • F25J3/04648Recovering noble gases from air argon
    • F25J3/04654Producing crude argon in a crude argon column
    • F25J3/04666Producing 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
    • F25J3/04672Producing 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
    • F25J3/04703Producing 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 being arranged in more than one vessel
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04642Recovering noble gases from air
    • F25J3/04648Recovering noble gases from air argon
    • F25J3/04721Producing pure argon, e.g. recovered from a crude argon column
    • F25J3/04727Producing pure argon, e.g. recovered from a crude argon column using an auxiliary pure argon column for nitrogen rejection
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04763Start-up or control of the process; Details of the apparatus used
    • F25J3/04769Operation, control and regulation of the process; Instrumentation within the process
    • F25J3/04812Different modes, i.e. "runs" of operation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/58Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being argon or crude argon
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00Processes or apparatus involving steps for recycling of process streams
    • F25J2245/50Processes or apparatus involving steps for recycling of process streams the recycled stream being oxygen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00Processes or apparatus involving steps for recycling of process streams
    • F25J2245/58Processes or apparatus involving steps for recycling of process streams the recycled stream being argon or crude argon

Definitions

  • the invention relates to a method according to the preamble of claim 1 and a device according to the preamble of claim 9.
  • a method and such a device are from the documents EP1482266 A1 , US2012 / 0125045 A1 and FR2943773 A1 known.
  • a known type of argon extraction is, for example, in EP 2600090 A1 described.
  • argon and oxygen are separated in a crude argon column (which is in two parts here) and, in a further step, the pure argon column, argon and nitrogen.
  • the raw argon from the raw argon column is fed into the pure argon column in gaseous form.
  • Argon-enriched is used here to denote a stream which has a higher argon concentration than air.
  • the raw argon column can be made in one or more parts. It has a top condenser which is cooled with a liquid from the air separation process in the narrower sense, in particular with bottom liquid from the high-pressure column.
  • the entire liquid pure argon product stream is withdrawn from the bottom of the pure argon column as the end product.
  • the end product is obtained, for example, directly as a liquid product and introduced into a liquid tank. Alternatively, it is taken in liquid form from the pure argon column or from the tank, pressurized in liquid form, heated in the main heat exchanger and fed directly to a consumer as a pressurized gas product.
  • argon is sold as a liquid product.
  • the invention is based on the object of increasing the efficiency of the oxygen production in a method mentioned at the beginning when the argon requirement fluctuates relative to the main product requirement.
  • Effective of the oxygen separation is understood here as meaning the oxygen yield, in particular the energy expenditure per Nm 3 of oxygen generated, with the purity of the oxygen product remaining the same.
  • the efficiency of the oxygen generation depends on the quality of the argon separation. Therefore, even if the argon product is not needed or is not needed in full, the invention tries to keep the argon yield as high as possible. If you - as in the prior art - reduce the conversion of the argon columns, you only gain the liquefaction capacity for the argon that is not required, but the oxygen separation loses its efficiency.
  • the gaseous argon return flow has an argon content which is at least twice as high as that of the argon-enriched flow from the low-pressure column (measured in molar amounts).
  • the cold contained in it is recovered in the main heat exchanger by heating the gaseous argon return flow without mixing with another flow in a separate passage of the main heat exchanger.
  • the crude argon column or a part of it can be driven or with a constant throughput with variable argon production the nominal or maximum throughput for which the process is designed.
  • the oxygen yield and the oxygen purity thus remain consistently high.
  • the entire amount of pure argon product is discharged as the end product.
  • the “second operating mode” can then be formed by any operating mode in which the end product quantity is smaller than in the first operating mode.
  • the excess part of the amount of pure argon product is then drawn off as a gaseous argon backflow before the pure argon column or from the pure argon column before it reaches the bottom of the pure argon column. In extreme cases, no argon end product is produced at all and the pure argon column only emits residual gas at the top.
  • the pure products of the low-pressure column are not contaminated and the argon product can be used to regenerate adsorbers or in an evaporative cooler.
  • the absolute total amount of argon that is taken from the crude argon column and the pure argon column is kept essentially constant.
  • Essentially constant is understood here to mean a deviation of less than 5 mol%, in particular of less than 2.5%.
  • this total amount of argon is made up of the amount of argon product and the amount of argon contained in the residual gas from the top of the pure argon column. If, for example, no argon product at all is obtained in the second operating mode, the argon contained in the argon return flow (s) and the amount of argon contained in the residual gas from the top of the pure argon column add to the total amount of argon.
  • Atmospheric air is sucked in through a filter 2 by an air compressor 3.
  • the compressed air 4 from the air compressor 3 is cooled in a pre-cooling device 5 and cleaned in a cleaning device 6.
  • the cleaned air 7 is fed to a main heat exchanger 8.
  • a first cold air stream 9 is introduced into the high-pressure column 10 in essentially gaseous form.
  • the high-pressure column 10 is part of a double column which also has a low-pressure column 11 and a main condenser 12. These apparatus are part of a distillation column system.
  • a portion 16 of this liquid is immediately withdrawn again, cooled in a subcooling countercurrent 17 and introduced into the low-pressure column 11 via line 18.
  • An oxygen-enriched fraction 19 from the bottom of the high pressure column 10 is cooled in the subcooling countercurrent 17.
  • the cooled, oxygen-enriched fraction 20 is passed to a first part 21 through the sump heater 91 of the pure argon column 83 and further into the evaporation chamber of the crude argon column top condenser 90.
  • a second part 22 flows directly into the evaporation chamber of the pure argon column top condenser 91.
  • the remaining liquid and the gaseous components from the top condensers are combined in pairs and fed into the low-pressure column 11 via lines 23 and 24. Alternatively, these streams can each be fed separately into the low-pressure column.
  • a part of the top nitrogen 25 of the high pressure column 10 is condensed in the main condenser 12 and a first part 26 is applied to the high pressure column.
  • a second part 27 of the liquid nitrogen flows through the subcooling countercurrent 17 and through line 28 to the top of the low pressure column.
  • gaseous oxygen from the bottom of the low-pressure column 11 can be fed into the residual gas line 33 via the line X.
  • An argon-enriched stream 80 from the low-pressure column 11 is introduced into a crude argon column, which in the example is designed as a split crude argon column with two sections 81, 82.
  • first operating mode the top steam 70 of the first section 81 is introduced completely into the second section 82 via line 70a.
  • Return liquid is generated in the top condenser 90.
  • the liquid 87 arriving in the sump of the second section 82 is applied to the top of the first section 81 by means of a pump 88 via line 89.
  • the liquid 84 that collects in the sump of the first section 81 is also pumped and returned to the low-pressure column 11 via line 6.
  • a gaseous crude argon fraction 71 is removed and fed in gaseous form into the pure argon column 83 in its entirety.
  • a liquid pure argon product stream 72 is withdrawn from the bottom of the pure argon column 83.
  • a residual gas stream 73 is drawn off from the top condenser 91 of the pure argon column and blown off into the atmosphere (ATM).
  • the gaseous argon return flow or part of it is formed by part of the overhead vapor 70 of the first section 81 of the crude argon column. It is passed through the separate passage 108 of the main heat exchanger with the aid of lines 101, 102a, 105, 106, 107. A portion 102b may be introduced into the impure nitrogen 32 downstream of the subcooling countercurrent 17; alternatively, the introduction can be carried out upstream of the subcooling countercurrent 17.
  • the gaseous argon return flow is formed by part of the crude argon fraction 71 or by the entire crude argon fraction 71 and passed through the lines 103, 104, 106 into the separate passage 108 of the main heat exchanger. A part of it can be introduced into the gaseous nitrogen product stream 30 downstream of the subcooling countercurrent 17 (lines 103, 104, 105); alternatively, the introduction can be carried out upstream of the subcooling countercurrent 17.
  • the argon return flow is passed through a separate passage 108 of the main heat exchanger 8.
  • Passage is understood here to mean a plurality of passages of the main heat exchanger 8 through which the same stream flows.
  • the various withdrawals 101, 103 of the argon return flow can each be combined with any type of routing through the main heat exchanger 8.
  • the line 101 is opened and 0 to 3.5% of the top vapor 70 or the rising vapor in the crude argon column 81, 82 is fed into the main heat exchanger 8.
  • the operator only needs 70% of the maximum possible amount of argon as a product.
  • the "second pure argon product quantity" is thus 70% of the maximum argon product.
  • the argon return flow 101 then comprises, for example, 1% of the overhead vapor 70.
  • the remainder of the overhead vapor 70 of FIG Crude argon column continues to be introduced into second section 82 of the crude argon column via line 70a.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Separation By Low-Temperature Treatments (AREA)
EP15771022.9A 2014-10-16 2015-09-23 Verfahren und vorrichtung zur variablen gewinnung von argon durch tieftemperaturzerlegung Active EP3207320B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15771022T PL3207320T3 (pl) 2014-10-16 2015-09-23 Sposób i urządzenie do zmiennego pozyskiwania argonu przez rozkład niskotemperaturowy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14003544 2014-10-16
PCT/EP2015/001886 WO2016058666A1 (de) 2014-10-16 2015-09-23 Verfahren und vorrichtung zur variablen gewinnung von argon durch tieftemperaturzerlegung

Publications (2)

Publication Number Publication Date
EP3207320A1 EP3207320A1 (de) 2017-08-23
EP3207320B1 true EP3207320B1 (de) 2021-06-30

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US (1) US10690408B2 (ja)
EP (1) EP3207320B1 (ja)
JP (1) JP2017536523A (ja)
KR (1) KR20170070172A (ja)
CN (1) CN107076512B (ja)
BR (1) BR112017006788A2 (ja)
CA (1) CA2963023A1 (ja)
CL (1) CL2017000874A1 (ja)
PL (1) PL3207320T3 (ja)
RU (1) RU2700970C2 (ja)
WO (1) WO2016058666A1 (ja)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108731376A (zh) * 2018-04-18 2018-11-02 衢州杭氧气体有限公司 一种氩气生产工艺及其生产线
CN109764638B (zh) * 2018-12-13 2021-11-19 包头钢铁(集团)有限责任公司 一种大型制氧机组氩系统变负荷方法
WO2022174976A1 (de) 2021-02-16 2022-08-25 Linde Gmbh Bereitstellung eines stickstoffprodukts
EP3992560A1 (de) 2021-05-27 2022-05-04 Linde GmbH Verfahren zum auslegen einer tieftemperaturzerlegungsanlage mit argonproduktion

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU658372A1 (ru) * 1976-12-20 1979-04-25 Научно-Исследовательский Институт Технологии Криогенного Машиностроения Установка разделени воздуха
JPS5449978A (en) * 1977-09-28 1979-04-19 Hitachi Ltd Air separation plant
US5133790A (en) * 1991-06-24 1992-07-28 Union Carbide Industrial Gases Technology Corporation Cryogenic rectification method for producing refined argon
CA2142317A1 (en) * 1994-02-24 1995-08-25 Anton Moll Process and apparatus for the recovery of pure argon
JPH1082582A (ja) * 1996-09-06 1998-03-31 Nippon Sanso Kk 空気液化分離装置及びその起動方法
US6269659B1 (en) * 1998-04-21 2001-08-07 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method and installation for air distillation with production of argon
DE10334560A1 (de) * 2003-05-28 2004-12-16 Linde Ag Verfahren und Vorrichtung zur Gewinnung von Krypton und/oder Xenon durch Tieftemperaturzerlegung von Luft
FR2943773B1 (fr) * 2009-03-27 2012-07-20 Air Liquide Procede et appareil de separation d'air par distillation cryogenique
US8899075B2 (en) * 2010-11-18 2014-12-02 Praxair Technology, Inc. Air separation method and apparatus

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Publication number Publication date
PL3207320T3 (pl) 2021-12-13
RU2017116601A3 (ja) 2019-03-28
US20170299262A1 (en) 2017-10-19
EP3207320A1 (de) 2017-08-23
CL2017000874A1 (es) 2017-12-11
US10690408B2 (en) 2020-06-23
CA2963023A1 (en) 2016-04-21
JP2017536523A (ja) 2017-12-07
BR112017006788A2 (pt) 2017-12-26
CN107076512B (zh) 2020-05-19
RU2017116601A (ru) 2018-11-19
KR20170070172A (ko) 2017-06-21
RU2700970C2 (ru) 2019-09-24
CN107076512A (zh) 2017-08-18
WO2016058666A1 (de) 2016-04-21

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