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EP1552230A1 - Method and installation for production of noble gases and oxygen by means of cryogenic air distillation - Google Patents

Method and installation for production of noble gases and oxygen by means of cryogenic air distillation

Info

Publication number
EP1552230A1
EP1552230A1 EP03758191A EP03758191A EP1552230A1 EP 1552230 A1 EP1552230 A1 EP 1552230A1 EP 03758191 A EP03758191 A EP 03758191A EP 03758191 A EP03758191 A EP 03758191A EP 1552230 A1 EP1552230 A1 EP 1552230A1
Authority
EP
European Patent Office
Prior art keywords
column
flow
oxygen
enriched
pressure column
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03758191A
Other languages
German (de)
French (fr)
Inventor
Lasad Jaouani
Frédéric Judas
Bernard Saulnier
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.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
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 LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Publication of EP1552230A1 publication Critical patent/EP1552230A1/en
Withdrawn legal-status Critical Current

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
    • F25J3/04078—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
    • F25J3/04303—Lachmann expansion, i.e. expanded into oxygen producing or low pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
    • F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04642—Recovering noble gases from air
    • F25J3/04648—Recovering noble gases from air argon
    • F25J3/04654—Producing crude argon in a crude argon column
    • F25J3/04666—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04642—Recovering noble gases from air
    • F25J3/04745—Krypton and/or Xenon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/32—Processes or apparatus using separation by rectification using a side column fed by a stream from the high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
    • F25J2200/54—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column in the low pressure column of a double pressure main column system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/90—Details relating to column internals, e.g. structured packing, gas or liquid distribution
    • F25J2200/94—Details relating to the withdrawal point
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/12—Particular process parameters like pressure, temperature, ratios

Definitions

  • the present invention relates to a process and installation for the production of oxygen and rare gases by air distillation.
  • the production of a weak mixture of krypton and xenon is conventionally carried out from a purge at the level of the main vaporizer of a double column of air separation (see 'Tieftemperaturtechriik' by Hausen and Linde, edition of 1985, pp. 337-340 and 'Separation of Gases' by Isalski, 1989 edition, pp. 96-98).
  • the oxygen production is then withdrawn from the low pressure column a few trays above the vaporizer. In the case where the oxygen is drawn off in the gaseous form, this arrangement makes it possible to recover a large fraction of the krypton present in the air and all of the xenon.
  • DE-A-2605305 describes an air separation device in which a fluid containing krypton and xenon is produced in a purification column supplied by. two flow rates of rich liquid coming from the medium pressure column, the reboiling of the purification column being ensured by a vaporizer supplied with the overhead gas from an argon column.
  • An object of the present invention is to propose systems making it possible to increase the krypton and xenon yield of devices producing gaseous oxygen by pumping and vaporizing liquid oxygen (or more generally with high draw-off of liquid oxygen in the bottom of the column low pressure) and preferably also producing argon.
  • Another object of the present invention is to find a main vaporizer with a high oxygen content that is massively purged and thus to greatly limit the concentration of hydrocarbons / impurities (advantage of pump oxygen), which is not the case with the diagram. classic producing a weak mixture of krypton and xenon. According to an object of the invention,.
  • a process for producing oxygen and rare gases by distillation in a column system comprising at least one medium pressure column, a low pressure column and an auxiliary column in which: i) at least one flow of cooled and purified air at the medium pressure column where it separates, ii) at least a first nitrogen-enriched flow is withdrawn from the medium pressure column and at least part of this flow is sent directly or indirectly to the low pressure column, iii) an intermediate flow is withdrawn from an intermediate level of the medium pressure column, iv) a flow, enriched in oxygen with respect to the intermediate flow, is withdrawn from the medium pressure column and it is sent to the bottom of the auxiliary column , v) a flow rich in nitrogen is drawn off from the head of the low pressure column, vi) a liquid flow rich in oxygen is drawn off from the low pressure column as a product, possibly after s a vaporization step to form a gaseous product, vii) an oxygen-enriched flow rate, also enriched in krypton and xenon, is drawn
  • the liquid flow rate sent as reflux to the auxiliary column is liquefied air and / or liquid enriched in nitrogen compared to a flow rate of liquefied air sent to the medium pressure column.
  • the tank of the auxiliary column is heated by an overhead gas from an argon column.
  • the liquefied air and / or the liquid enriched in nitrogen with respect to the air is produced by heat exchange with the liquid flow rich in oxygen coming from the tank of the low pressure column, possibly after a pressurization step.
  • the liquid enriched in nitrogen contains at least 80% mol. nitrogen.
  • an installation for producing oxygen and rare gases by distillation in a column system comprising at least one medium pressure column, a low pressure column and an auxiliary column comprising: i) means for sending at least one flow of cooled and purified air to the medium pressure column where it separates, ii " ) means for withdrawing at least a first flow enriched in nitrogen from the medium pressure column and means for sending to the at least part of this flow directly or indirectly to the low pressure column, iii) means for withdrawing a nitrogen-rich flow from the head of the low pressure column, iv) means for withdrawing an intermediate flow of an intermediate level of the medium pressure column, v) means for sending a flow, richer in oxygen than the intermediate flow, from the tank of the medium pressure column to the tank of the
  • the installation comprises: a purification column, means for sending the third oxygen-enriched flow at the head of the purification column and means for withdrawing at least some theoretical plates lower in the column, a fourth flow enriched in oxygen constituting a mixture enriched in krypton and xenon.
  • a double air separation column comprises a medium pressure column K01 and a low pressure column K02, thermally connected to each other by means of a main vaporizer E02 which is used to condense at least part nitrogen gas at the top of the column
  • An argon column K10 is supplied with a fluid enriched in argon 7 coming from the low pressure column K02 and a liquid enriched in argon 9 is returned from the argon column K10 to the low pressure column K02.
  • a flow rich in ARGON argon is withdrawn at the head of column K10.
  • the other part of the medium pressure air AIR P is cooled in the main exchange line and sent to the medium pressure column tank K01.
  • the principle of the present invention is to concentrate the krypton and the xenon in a rich liquid LR2 which will then be treated at the level of an auxiliary column K05.
  • Two rich liquids LR1 and LR2 are therefore drawn off from the medium pressure column K01: a “classic” rich liquid drawn off at an intermediate level a few trays above the column tank and containing a small amount of krypton and xenon LR1 and a liquid rich in vats, concentrated in krypton and xenon LR2.
  • This "classic" LR1 rich liquid can then be sent to column K02 after being sub-cooled.
  • the rich tank liquid LR2 is sent to the condenser E10 of the argon mixture K10 after sub-cooling (not shown). Trays are installed above this equipment to concentrate krypton and xenon at the argon mixture condenser.
  • This set constitutes column K05.
  • Part of the reflux of this column is provided by part 5 of the AIR LIQ liquid air which does not supply the column K01, and this after having sub-cooled it.
  • the other part of the reflux is provided by a part 15 of the lean liquid 11 conventionally sent in column K02 via line 13 and containing at least 80% mol. nitrogen.
  • a gas 16 is drawn off at the intermediate level of the column K05, below the reflux injection points and constitutes the rich vaporized liquid. It is then recycled in column K02.
  • the overhead gas WN2 'from column K05 constitutes part of the waste gas WN2 leaving the cold box.
  • the PURGE purge of the mixture condenser E10 contains most of the krypton and xenon present in the air and having been treated by columns K01 and K05. This flow feeds a device allowing the concentration of rare gases. For example, it can be sent to the weak mixture column krypton-xenon (K90). The tank in this column contains the product to be recovered. Steam 17 from column K90 is returned to the column tank K05.
  • Liquid oxygen OL is preferably pressurized by a pump and then vaporized in the exchange line or in a dedicated vaporizer, by heat exchange with the pressurized air. Alternatively a nitrogen cycle can be used to vaporize the liquid oxygen OL.
  • all of the AIR LIQ liquid air present at the outlet of the exchange line can be withdrawn from column K01 (preferably at the level of introduction of liquid air) and then distributed between column K02 and K05 after being sub-cooled as seen in Figure 4.
  • the waste gas WN2 'from column K05 is returned to column K02 below the point of injection of the lean liquid 13.
  • the flow rate 16 is eliminated and replaced by a sending of residual nitrogen WN2 'from the head of the auxiliary column K05 at an intermediate point of the low pressure column.
  • the blown air is sent to the column tank K05 in order to recover the krypton and the xenon it contains.
  • diagrams described in Figures 1 to 9 can also include distillation units such as an Etienne column for example (column operating at an intermediate pressure between medium and low pressures and supplied with rich liquid).
  • distillation units such as an Etienne column for example (column operating at an intermediate pressure between medium and low pressures and supplied with rich liquid).

Landscapes

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

Abstract

The invention relates to a method and installation for the production of noble gases and oxygen by means of cryogenic air distillation. The method of producing noble gases and oxygen by means of distillation in a column system comprising at least one medium-pressure column (K01), one low-pressure column (K02) and one auxiliary column (K05) consists in: drawing off an intermediary flow discharge (LR1) at an intermediary level of the medium-pressure column and transferring same to the low-pressure column; drawing off a flow discharge (LR2) from the medium-pressure column, which is enriched in oxygen in relation to the intermediary flow discharge, and transferring same to the tank of the auxiliary column; drawing off a nitrogen-rich flow discharge (WN2) from the head of the low-pressure column; drawing off an oxygen-rich liquid flow discharge (CL) from the tank of the low-pressure column by way of a product, optionally after a vaporisation step in order to form a gaseous product; and drawing off an oxygen-enriched flow discharge (PURGE) from the auxiliary column, which is also enriched in krypton and xenon in relation to the second oxygen-enriched flow discharge and transferring a liquid flow discharge (5, 15) containing at least 78 % mol. of nitrogen as a reflux to the auxiliary column.

Description

Procédé et installation de production d'oxygène et de gaz rares par distillation cryogénique d'air Method and installation for producing oxygen and rare gases by cryogenic air distillation
La présente invention est relative à un procédé et installation de production d'oxygène et de gaz rares par distillation d'air. La production de mixture faible de krypton et de xénon est classiquement réalisée à partir d'une purge au niveau du vaporiseur principal d'une double colonne de séparation d'air (voir 'Tieftemperaturtechriik' de Hausen et Linde, édition de 1985, pp.337-340 et 'Séparation of Gases' d' Isalski, édition de 1989, pp.96-98). La production d'oxygène est alors soutirée de la colonne basse pression quelques plateaux au-dessus du vaporiseur. Dans le cas où le soutirage de l'oxygène est fait sous forme gazeuse, cet arrangement permet de récupérer une fraction importante du krypton présent dans l'air et la totalité du xénon.The present invention relates to a process and installation for the production of oxygen and rare gases by air distillation. The production of a weak mixture of krypton and xenon is conventionally carried out from a purge at the level of the main vaporizer of a double column of air separation (see 'Tieftemperaturtechriik' by Hausen and Linde, edition of 1985, pp. 337-340 and 'Separation of Gases' by Isalski, 1989 edition, pp. 96-98). The oxygen production is then withdrawn from the low pressure column a few trays above the vaporizer. In the case where the oxygen is drawn off in the gaseous form, this arrangement makes it possible to recover a large fraction of the krypton present in the air and all of the xenon.
Cependant, dans le cas d'un appareil produisant de l'oxygène par procédés dits « à pompe », environ 30 % du krypton et du xénon présents dans l'air sont « perdus » dans l'oxygène liquide soutiré de la colonne basse pression.However, in the case of an apparatus producing oxygen by so-called “pump” processes, approximately 30% of the krypton and xenon present in the air are “lost” in the liquid oxygen withdrawn from the low pressure column. .
DE-A-2605305 décrit un appareil de séparation d'air dans lequel un fluide contenant de krypton et xénon est produit dans une colonne d'épuration alimentée par. deux débits de liquide riche provenant de la colonne moyenne pression, le rebouillage de la colonne d'épuration étant assurée par un vaporiseur alimenté par le gaz de tête d'une colonne argon.DE-A-2605305 describes an air separation device in which a fluid containing krypton and xenon is produced in a purification column supplied by. two flow rates of rich liquid coming from the medium pressure column, the reboiling of the purification column being ensured by a vaporizer supplied with the overhead gas from an argon column.
Un but de la présente invention est de proposer des systèmes permettant d'augmenter le rendement krypton et xénon des appareils produisant de l'oxygène gazeux par pompage et vaporisation d'oxygène liquide (ou plus généralement à fort soutirage oxygène liquide en cuve de la colonne basse pression ) et, de préférence, produisant également de l'argon.An object of the present invention is to propose systems making it possible to increase the krypton and xenon yield of devices producing gaseous oxygen by pumping and vaporizing liquid oxygen (or more generally with high draw-off of liquid oxygen in the bottom of the column low pressure) and preferably also producing argon.
Un autre but de la présente invention est de retrouver un vaporiseur principal à haute teneur en oxygène massivement purgé et ainsi limiter fortement en concentration hydrocarbures/impuretés (avantage de l'oxytonne à pompe), ce qui n'est pas le cas avec le schéma classique produisant une mixture faible de krypton et de xénon. Selon un objet de l'invention, . il est prévu un procédé de production d'oxygène et de gaz rares par distillation dans un système de colonnes comprenant au moins une colonne moyenne pression, une colonne basse pression et une colonne auxiliaire dans lequel : i) on envoie au moins un débit d'air refroidi et épuré à la colonne moyenne pression où il se sépare, ii) on soutire au moins un premier débit enrichi en azote de la colonne moyenne pression et on envoie au moins une partie de ce débit directement ou indirectement à la colonne basse pression, iii) on soutire un débit intermédiaire d'un niveau intermédiaire de la colonne moyenne pression, iv) on soutire un débit, enrichi en oxygène par rapport au débit intermédiaire, de la colonne moyenne pression et on l'envoie en cuve de la colonne auxiliaire, v) on soutire un débit riche en azote de la tête de la colonne basse pression, vi) on soutire un débit liquide riche en oxygène de la colonne basse pression en tant que produit, éventuellement après une étape de vaporisation pour former un produit gazeux, vii) on soutire de la colonne auxiliaire un débit enrichi en oxygène, également enrichi en krypton et en xénon par rapport au deuxième débit enrichi en oxygène, caractérisé en ce que l'on envoie le débit intermédiaire à la colonne basse pression et on envoie un débit liquide contenant au moins 78 % mol. d'azote comme reflux à la colonne auxiliaire.Another object of the present invention is to find a main vaporizer with a high oxygen content that is massively purged and thus to greatly limit the concentration of hydrocarbons / impurities (advantage of pump oxygen), which is not the case with the diagram. classic producing a weak mixture of krypton and xenon. According to an object of the invention,. there is provided a process for producing oxygen and rare gases by distillation in a column system comprising at least one medium pressure column, a low pressure column and an auxiliary column in which: i) at least one flow of cooled and purified air at the medium pressure column where it separates, ii) at least a first nitrogen-enriched flow is withdrawn from the medium pressure column and at least part of this flow is sent directly or indirectly to the low pressure column, iii) an intermediate flow is withdrawn from an intermediate level of the medium pressure column, iv) a flow, enriched in oxygen with respect to the intermediate flow, is withdrawn from the medium pressure column and it is sent to the bottom of the auxiliary column , v) a flow rich in nitrogen is drawn off from the head of the low pressure column, vi) a liquid flow rich in oxygen is drawn off from the low pressure column as a product, possibly after s a vaporization step to form a gaseous product, vii) an oxygen-enriched flow rate, also enriched in krypton and xenon, is drawn off from the auxiliary column, characterized in that the intermediate flow to the low pressure column and a liquid flow containing at least 78% mol is sent. nitrogen as reflux to the auxiliary column.
De préférence le débit liquide envoyé comme reflux à la colonne auxiliaire est de l'air liquéfié et/ou du liquide enrichi en azote par rapport à un débit d'air liquéfié envoyé à la colonne moyenne pression. Selon des aspects facultatifs : - la cuve de la colonne auxiliaire est chauffée par un gaz de tête d'une colonne argon. l'air liquéfié et/ou le liquide enrichi en azote par rapport à l'air est produit par échange de chaleur avec le débit liquide riche en oxygène provenant de la cuve de la colonne basse pression, éventuellement après une étape de pressurisation. - le liquide enrichi en azote contient au moins 80 % mol. d'azote. l'air liquéfié ne provient pas de la colonne moyenne pression, le débit liquide envoyé en tête de la colonne auxiliaire est plus riche en azote que le débit intermédiaire ; au moins 10% de l'oxygène produit est soutiré sous forme liquide de la colonne basse pression. Selon un autre objet de l'invention, il est prévu une installation de production d'oxygène et de gaz rares par distillation dans un système de colonnes comprenant au moins une colonne moyenne pression , une colonne basse pression et une colonne auxiliaire comprenant : i) des moyens pour envoyer au moins un débit d'air refroidi et épuré à la colonne moyenne pression où il se sépare, ii") des moyens pour soutirer au moins un premier débit enrichi en azote de la colonne moyenne pression et des moyens pour envoyer au moins une partie de ce débit directement ou indirectement à la colonne basse pression, iii) des moyens pour soutirer un débit riche en azote de la tête de la colonne basse pression, iv) des moyens pour soutirer un débit intermédiaire d'un niveau intermédiaire de la colonne moyenne pression, v) des moyens pour envoyer un débit, plus riche en oxygène que le débit intermédiaire, de la cuve de la colonne moyenne pression en cuve de la colonne auxiliaire, vi) des moyens pour envoyer un débit liquide comme reflux à la colonne auxiliaire, vii) des moyens pour soutirer un débit liquide riche en oxygène (OL) de la cuve de la colonne basse pression en tant que produit, éventuellement après une étape de vaporisation pour former un produit gazeux, et viii) des moyens pour soutirer de la colonne auxiliaire un troisième débit enrichi en oxygène (PURGE), également enrichi en krypton et en xénon par rapport au deuxième débit enrichi en oxygène, caractérisée en ce qu'elle comprend des moyens pour envoyer comme débit de reflux à la colonne auxiliaire de l'air liquéfié ou un débit liquide enrichi en azote par rapport à un débit d'air liquide envoyé à la colonne moyenne pression . Selon d'autres aspects facultatifs, l'installation comprend : une colonne d'épuration, des moyens pour envoyer le troisième débit enrichi en oxygène en tête de la colonne d'épuration et des moyens pour soutirer au moins quelques plateaux théoriques plus bas dans la colonne, un quatrième débit enrichi en oxygène constituant un mélange enrichi en krypton et xénon. une ligne d'échange dans laquelle l'air liquéfié et/ou le liquide enrichi en azote par rapport à l'air est produit par échange de chaleur avec le débit liquide riche en oxygène provenant de la cuve de la colonne basse pression, éventuellement après une étape de pressurisation.Preferably the liquid flow rate sent as reflux to the auxiliary column is liquefied air and / or liquid enriched in nitrogen compared to a flow rate of liquefied air sent to the medium pressure column. According to optional aspects: - the tank of the auxiliary column is heated by an overhead gas from an argon column. the liquefied air and / or the liquid enriched in nitrogen with respect to the air is produced by heat exchange with the liquid flow rich in oxygen coming from the tank of the low pressure column, possibly after a pressurization step. - the liquid enriched in nitrogen contains at least 80% mol. nitrogen. the liquefied air does not come from the medium pressure column, the liquid flow sent to the head of the auxiliary column is richer in nitrogen than the intermediate flow; at least 10% of the oxygen produced is withdrawn in liquid form from the low pressure column. According to another object of the invention, there is provided an installation for producing oxygen and rare gases by distillation in a column system comprising at least one medium pressure column, a low pressure column and an auxiliary column comprising: i) means for sending at least one flow of cooled and purified air to the medium pressure column where it separates, ii " ) means for withdrawing at least a first flow enriched in nitrogen from the medium pressure column and means for sending to the at least part of this flow directly or indirectly to the low pressure column, iii) means for withdrawing a nitrogen-rich flow from the head of the low pressure column, iv) means for withdrawing an intermediate flow of an intermediate level of the medium pressure column, v) means for sending a flow, richer in oxygen than the intermediate flow, from the tank of the medium pressure column to the tank of the auxiliary column, vi) means for sending a liquid flow as reflux to the auxiliary column, vii) means for withdrawing a liquid flow rich in oxygen (OL) from the tank of the low pressure column as a product, possibly after a vaporization step to form a gaseous product, and viii) means for withdrawing from the auxiliary column a third oxygen-enriched flow (PURGE), also enriched in krypton and xenon with respect to the second oxygen-enriched flow, characterized in that it comprises means for sending as flow of reflux to the auxiliary column of liquefied air or a liquid flow enriched in nitrogen compared to a flow of liquid air sent to the medium pressure column. According to other optional aspects, the installation comprises: a purification column, means for sending the third oxygen-enriched flow at the head of the purification column and means for withdrawing at least some theoretical plates lower in the column, a fourth flow enriched in oxygen constituting a mixture enriched in krypton and xenon. an exchange line in which the liquefied air and / or the liquid enriched in nitrogen with respect to the air is produced by heat exchange with the liquid flow rich in oxygen coming from the tank of the low pressure column, possibly after a pressurization step.
L'invention sera maintenant décrite en se référant aux Figures 1 à 9 qui sont des schémas de principe d'installations selon l'invention.The invention will now be described with reference to Figures 1 to 9 which are block diagrams of installations according to the invention.
Dans l'exemple de la Figure 1 , une double colonne de séparation d'air comprend une colonne moyenne pression K01 et une colonne basse pression K02, thermiquement reliées entre elles au moyen d'un vaporiseur principal E02 qui sert à condenser au moins une partie de l'azote gazeux de tête de la colonneIn the example of Figure 1, a double air separation column comprises a medium pressure column K01 and a low pressure column K02, thermally connected to each other by means of a main vaporizer E02 which is used to condense at least part nitrogen gas at the top of the column
K01 par échange de chaleur avec de l'oxygène en cuve de la colonne K02.K01 by heat exchange with oxygen in the tank of column K02.
Une colonne argon K10 est alimentée par un fluide enrichi en argon 7 provenant de la colonne basse pression K02 et un liquide enrichi en argon 9 est renvoyé de la colonne argon K10 à la colonne basse pression K02. Un débit riche en argon ARGON est soutiré en tête de la colonne K10.An argon column K10 is supplied with a fluid enriched in argon 7 coming from the low pressure column K02 and a liquid enriched in argon 9 is returned from the argon column K10 to the low pressure column K02. A flow rich in ARGON argon is withdrawn at the head of column K10.
Dans le cas des appareils à pompe, une partie de l'air sec et décarbonaté est comprimée dans un surpresseur d'air (non-illustré) jusqu'à la pression suffisante pour permettre la vaporisation de l'oxygène, éventuellement pompé. Elle est alors condensée dans la ligne d'échange principale (non-illustré). Au bout froid de la ligne d'échange principale, ce flux est détendu dans une vanne ou dans une turbine hydraulique. La phase liquide AIR LIQ de ce fluide peut être alors répartie en débits 1 ,3 et 5 entre la colonne moyenne pression K01 , la colonne basse pression K02 et la colonne auxiliaire K05 respectivement. L'air liquide contient 78% mol. d'azote.In the case of pumped appliances, part of the dry, decarbonated air is compressed in an air booster (not shown) until the pressure is sufficient to allow the vaporization of the oxygen, possibly pumped. It is then condensed in the main exchange line (not shown). At the cold end of the main exchange line, this flow is expanded in a valve or in a hydraulic turbine. The AIR LIQ liquid phase of this fluid can be then divided into flow rates 1, 3 and 5 between the medium pressure column K01, the low pressure column K02 and the auxiliary column K05 respectively. Liquid air contains 78 mol%. nitrogen.
L'autre partie de l'air à moyenne pression AIR P est refroidie dans la ligne d'échange principale et envoyée en cuve de colonne moyenne pression K01.The other part of the medium pressure air AIR P is cooled in the main exchange line and sent to the medium pressure column tank K01.
Le principe de la présente invention est de concentrer le krypton et le xénon dans un liquide riche LR2 qui sera ensuite traité au niveau d'une colonne auxiliaire K05. Deux liquides riches LR1 et LR2 sont donc soutirés de la colonne moyenne pression K01 : un liquide riche « classique » soutiré à un niveau intermédaire quelques plateaux au dessus de la cuve de colonne et contenant une faible quantité du krypton et du xénon LR1 et un liquide riche de cuve, concentré en krypton et en xénon LR2. Ce liquide riche « classique » LR1 peut être ensuite envoyé à la colonne K02 après avoir été sous-refroidi.The principle of the present invention is to concentrate the krypton and the xenon in a rich liquid LR2 which will then be treated at the level of an auxiliary column K05. Two rich liquids LR1 and LR2 are therefore drawn off from the medium pressure column K01: a “classic” rich liquid drawn off at an intermediate level a few trays above the column tank and containing a small amount of krypton and xenon LR1 and a liquid rich in vats, concentrated in krypton and xenon LR2. This "classic" LR1 rich liquid can then be sent to column K02 after being sub-cooled.
Le liquide riche de cuve LR2 est envoyé au condenseur E10 de mixture argon K10 après sous-refroidissement (non-illustré). Des plateaux sont installés au-dessus de cet équipement pour concentrer le krypton et le xénon au niveau du condenseur de mixture argon. Cet ensemble constitue la colonne K05. Une partie du reflux de cette colonne est assurée par une partie 5 de l'air liquide AIR LIQ n'alimentant pas la colonne K01 , et ce après l'avoir sous-refroidi. L'autre partie du reflux est assurée par une partie 15 du liquide pauvre 11 classiquement envoyée en colonne K02 via la conduite 13 et contenant au moins 80 % mol. d'azote. Un gaz 16 est soutiré au niveau intermédiaire de la colonne K05, en dessous des points d'injection de reflux et constitue le liquide riche vaporisé. Il est alors recyclé dans la colonne K02. Le gaz de tête WN2' de la colonne K05 constitue une partie du gaz résiduaire WN2 quittant la boite froide.The rich tank liquid LR2 is sent to the condenser E10 of the argon mixture K10 after sub-cooling (not shown). Trays are installed above this equipment to concentrate krypton and xenon at the argon mixture condenser. This set constitutes column K05. Part of the reflux of this column is provided by part 5 of the AIR LIQ liquid air which does not supply the column K01, and this after having sub-cooled it. The other part of the reflux is provided by a part 15 of the lean liquid 11 conventionally sent in column K02 via line 13 and containing at least 80% mol. nitrogen. A gas 16 is drawn off at the intermediate level of the column K05, below the reflux injection points and constitutes the rich vaporized liquid. It is then recycled in column K02. The overhead gas WN2 'from column K05 constitutes part of the waste gas WN2 leaving the cold box.
La purge PURGE du condenseur de mixture E10 contient la majeure partie du krypton et du xénon présents dans l'air et ayant été traités par les colonnes K01 et K05. Ce flux alimente un dispositif permettant la concentration des gaz rares. Par exemple, il peut être envoyé dans la colonne de mixture faible krypton-xénon (K90). La cuve de cette colonne contient le produit à valoriser. La vapeur 17 issue de la colonne K90 est renvoyée en cuve de colonne K05.The PURGE purge of the mixture condenser E10 contains most of the krypton and xenon present in the air and having been treated by columns K01 and K05. This flow feeds a device allowing the concentration of rare gases. For example, it can be sent to the weak mixture column krypton-xenon (K90). The tank in this column contains the product to be recovered. Steam 17 from column K90 is returned to the column tank K05.
La colonne K90 est chauffée par un débit d'air formant une fraction de l'AIR MP. L'air liquéfié ainsi formé peut être renvoyé à la colonne moyenne pressions K01 et/ou à la colonne basse pression K02.Column K90 is heated by an air flow forming a fraction of the AIR MP. The liquefied air thus formed can be returned to the medium pressure column K01 and / or to the low pressure column K02.
La production d'oxygène liquide OL est soutirée en cuve de colonne K02, au niveau du vaporiseur principal E02. Contrairement au schéma classique de production de krypton et de xénon, le vaporiseur principal est donc massivement purgé. L'oxygène liquide OL est de préférence pressurisé par une pompe et ensuite vaporisé dans la ligne d'échange ou dans un vaporiseur dédié, par échange de chaleur avec l'air pressurisé. Alternativement un cycle d'azote peut servir à vaporiser l'oxygène liquide OL.The production of liquid oxygen OL is drawn off in the column tank K02, at the level of the main vaporizer E02. Contrary to the classic production scheme for krypton and xenon, the main vaporizer is therefore massively purged. Liquid oxygen OL is preferably pressurized by a pump and then vaporized in the exchange line or in a dedicated vaporizer, by heat exchange with the pressurized air. Alternatively a nitrogen cycle can be used to vaporize the liquid oxygen OL.
Sur les figures suivantes, différentes variantes issues de la figure 1 sont présentées. Les éléments communs avec la Figure 1 ne seront pas décrits une deuxième fois.In the following figures, different variants from Figure 1 are presented. The elements common to Figure 1 will not be described a second time.
Dans le cas de la Figure 2, la totalité de l'air liquide AIR LIQ issue de la ligne d'échange principale est envoyée en colonne K01. Un fluide intermédiaire sous forme liquide l' est soutiré de la colonne K01 (de préférence au niveau d'introduction de l'air liquide ou à un niveau au-dessus de ce niveau). Il est ensuite réparti entre la colonne K02 et K05 après avoir été sous-refroidi en deux débits 3,5. Un débit 11 contenant au moins 80 % mol/ d'azote est envoyé en tête de la colonne K05.In the case of Figure 2, all of the AIR LIQ liquid air from the main exchange line is sent to column K01. An intermediate fluid in liquid form l 'is withdrawn from the column K01 (preferably at the level of introduction of the liquid air or at a level above this level). It is then distributed between column K02 and K05 after being sub-cooled in two flows 3.5. A flow 11 containing at least 80% mol / nitrogen is sent to the head of column K05.
Dans le cas de la Figure 3, sur la base de la figure 1 , le tronçon de tête de la colonne K05 est supprimé. Le reflux de cette colonne est assuré uniquement par de l'air liquide 5 de préférence sous-refroidi. Cet air liquide est produit par la vaporisation de l'oxygène liquide OL pompé et vaporisé dans la ligne d'échange.In the case of FIG. 3, on the basis of FIG. 1, the head section of the column K05 is deleted. The reflux of this column is ensured only by liquid air 5, preferably sub-cooled. This liquid air is produced by the vaporization of the liquid oxygen OL pumped and vaporized in the exchange line.
Tout le liquide pauvre 13 est envoyé à la colonne basse pression K02.All the lean liquid 13 is sent to the low pressure column K02.
De plus, la totalité de l'air liquide AIR LIQ présent en sortie de ligne d'échange peut être soutiré de la colonne K01 (de préférence au niveau d'introduction de l'air liquide) et ensuite réparti entre la colonne K02 et K05 après avoir été sous-refroidi comme on voit à la Figure 4. Dans le cas des figures 5 et 6, sur la base des figures 3 ou 4, le gaz résiduaire WN2' de la colonne K05 est renvoyé dans la colonne K02 en dessous du point d'injection du liquide pauvre 13.In addition, all of the AIR LIQ liquid air present at the outlet of the exchange line can be withdrawn from column K01 (preferably at the level of introduction of liquid air) and then distributed between column K02 and K05 after being sub-cooled as seen in Figure 4. In the case of FIGS. 5 and 6, on the basis of FIGS. 3 or 4, the waste gas WN2 'from column K05 is returned to column K02 below the point of injection of the lean liquid 13.
Dans le cas de la figure 7, sur la base de la Figure 5, le débit 16 est supprimé et remplacé par un envoi d'azote résiduaire WN2' de la tête de la colonne auxiliaire K05 à un point intermédiaire de la colonne basse pression.In the case of FIG. 7, on the basis of FIG. 5, the flow rate 16 is eliminated and replaced by a sending of residual nitrogen WN2 'from the head of the auxiliary column K05 at an intermediate point of the low pressure column.
Sur toutes les figures décrites précédemment (Figure 1 à 7), il est possible de coupler le dispositif avec le schéma classique de production de krypton et de xénon. Pour cela, il est nécessaire d'installer des plateaux d'enrichissement en cuve de colonne K02. L'oxygène liquide OL est produit quelques plateaux au- dessus du vaporiseur principal E02. Une purge 21 est soutirée au niveau du vaporiseur principal E02. Elle contient environ 70 % mol. du krypton et la totalité du xénon présents dans la colonne K02. Elle est envoyée à la colonne K90 pour récupérer les gaz rares. Un exemple est donné sur la figure 8.In all the figures described above (Figure 1 to 7), it is possible to couple the device with the conventional scheme for producing krypton and xenon. For this, it is necessary to install enrichment trays in the K02 column tank. Liquid oxygen OL is produced a few trays above the main vaporizer E02. A purge 21 is drawn off at the main vaporizer E02. It contains approximately 70% mol. krypton and all of the xenon present in column K02. It is sent to column K90 to recover the rare gases. An example is given in figure 8.
Sur toutes les figures précédentes (Figure 1 à 8), la co-production d'argon est mentionnée. Cependant, il est possible d'adapter les dispositifs décrits précédemment à un appareil sans production d'argon. Il suffit, par exemple, d'installer un échangeur permettant de condenser une fraction de gaz 7 soutiré de la colonne K02. Une fois liquéfié, il est renvoyé (9) en colonne K02. Le rebouillage de la colonne K05 est ainsi assuré.In all the previous figures (Figure 1 to 8), the co-production of argon is mentioned. However, it is possible to adapt the devices described above to a device without producing argon. It suffices, for example, to install an exchanger making it possible to condense a fraction of gas 7 withdrawn from column K02. Once liquefied, it is returned (9) to column K02. Reboiling of column K05 is thus ensured.
Un exemple est donné sur la figure 9.An example is given in figure 9.
Dans la cas d'un schéma avec turbine d'insufflation, l'air insufflé est envoyé en cuve de colonne K05 afin de récupérer le krypton et le xénon qu'il contient.In the case of a diagram with an insufflation turbine, the blown air is sent to the column tank K05 in order to recover the krypton and the xenon it contains.
De plus, les schémas décrits sur les figures de 1 à 9 peuvent également inclure des ensembles de distillation tel qu'une colonne Etienne par exemple (colonne opérant à une pression intermédiaire entre les moyenne et basse pressions et alimentée par du liquide riche). Dans ce cas, il est possible de modifier le condenseur de tête d'une colonne Etienne en remplaçant la- colonne argon K10 des Figures 1 à 9 par une colonne Etienne selon le même principe : adjonction de plateaux au-dessus du condenseur pour concentrer les gaz rares. Il est peut-être également intéressant de ne pas envoyer la totalité de l'air liquide en tête de la colonne auxiliaire mais de n'introduire à cette entrée de la colonne que le débit qui permet d'assurer un LJV (rapport du débit liquide tombant sur le débit de gaz montant dans la section de distillation) nécessaire à la concentration du Kr et du Xe en cuve de K05 en limitant la concentration en oxygène dans la cuve de K05. Le reste du débit d'air liquide est alors envoyé en cuve de la colonne auxiliaire avec le liquide riche LR2. In addition, the diagrams described in Figures 1 to 9 can also include distillation units such as an Etienne column for example (column operating at an intermediate pressure between medium and low pressures and supplied with rich liquid). In this case, it is possible to modify the condenser at the head of an Etienne column by replacing the argon column K10 of Figures 1 to 9 with a Etienne column according to the same principle: adding trays above the condenser to concentrate the rare gases. It may also be advantageous not to send all of the liquid air at the head of the auxiliary column but to introduce at this entry of the column only the flow which makes it possible to ensure an LJV (ratio of the liquid flow falling on the rising gas flow in the distillation section) necessary for the concentration of Kr and Xe in tank of K05 by limiting the concentration of oxygen in the tank of K05. The rest of the liquid air flow is then sent to the tank of the auxiliary column with the rich liquid LR2.

Claims

Revendications claims
1. Procédé de production d'oxygène et de gaz rares par distillation dans un système de colonnes comprenant au moins une colonne moyenne pression (K01 ), une colonne basse pression (K02) et une colonne auxiliaire (K05) dans lequel : i) on envoie au moins un débit d'air (1) refroidi et épuré à la colonne moyenne pression où il se sépare, ii) on soutire au moins un premier débit enrichi en azote (11) de la colonne moyenne pression et on envoie au moins une partie de ce débit directement ou indirectement à la colonne basse pression, iii) on soutire un débit intermédiaire (LR1) d'un niveau intermédiaire de la colonne moyenne, pression, iv) on soutire un débit (LR2), enrichi en oxygène par rapport au débit intermédiaire, de la cuve de la colonne moyenne pression et on l'envoie en cuve de la colonne auxiliaire, v) on soutire un débit riche en azote (WN2) de la tête de la colonne basse pression, vi) on soutire un débit liquide riche en oxygène (OL) de la colonne basse pression en tant que produit, éventuellement après une étape de vaporisation pour former un produit gazeux, vii) on soutire de la colonne auxiliaire un débit enrichi en oxygène (PURGE), également enrichi en krypton et en xénon par rapport au deuxième débit enrichi en oxygène, caractérisé en ce que l'on envoie le débit intermédiaire (LR1) à la colonne basse pression et on envoie au moins un débit liquide (5,15) contenant au moins 78 % mol. d'azote comme reflux à la colonne auxiliaire.1. Process for the production of oxygen and rare gases by distillation in a column system comprising at least one medium pressure column (K01), a low pressure column (K02) and an auxiliary column (K05) in which: i) sends at least one flow of cooled and purified air (1) to the medium pressure column where it separates, ii) at least one first nitrogen-enriched flow (11) is withdrawn from the medium pressure column and at least one part of this flow directly or indirectly at the low pressure column, iii) an intermediate flow (LR1) is withdrawn from an intermediate level of the medium column, pressure, iv) a flow is withdrawn (LR2), enriched with oxygen relative at the intermediate flow rate, from the tank of the medium pressure column and it is sent to the tank of the auxiliary column, v) a nitrogen-rich flow rate (WN2) is drawn off from the head of the low pressure column, vi) it is drawn off oxygen-rich liquid flow (OL) from the lower column p ression as a product, possibly after a vaporization step to form a gaseous product, vii) an oxygen-enriched flow (PURGE) is also withdrawn from the auxiliary column, also enriched in krypton and in xenon with respect to the second oxygen-enriched flow , characterized in that the intermediate flow (LR1) is sent to the low pressure column and at least one liquid flow (5.15) containing at least 78 mol% is sent. nitrogen as reflux to the auxiliary column.
2. Procédé selon la revendication 1 dans lequel on envoie le troisième débit enrichi en oxygène (PURGE) en tête d'une colonne d'épuration (K90) et on soutire au moins quelques plateaux théoriques plus bas dans la colonne un quatrième débit enrichi en oxygène (MIXTURE) constituant un mélange enrichi en krypton et xénon.2. Method according to claim 1, in which the third oxygen-enriched flow rate (PURGE) is sent to the head of a purification column (K90) and at least a few theoretical plates are drawn off in column one. fourth flow enriched in oxygen (MIXTURE) constituting a mixture enriched in krypton and xenon.
3. Procédé selon l'une des revendications précédentes dans lequel le débit liquide (5) envoyé comme reflux à la colonne auxiliaire (K05) est de l'air liquéfié et/ou du liquide enrichi en azote par rapport à un débit d'air liquéfié envoyé à la colonne moyenne pression.3. Method according to one of the preceding claims in which the liquid flow (5) sent as reflux to the auxiliary column (K05) is liquefied air and / or liquid enriched in nitrogen with respect to an air flow liquefied sent to the medium pressure column.
4. Procédé selon l'une des revendications précédentes dans lequel la cuve de la colonne auxiliaire est chauffé par une gaz de tête d'une colonne argon (K10). 4. Method according to one of the preceding claims wherein the tank of the auxiliary column is heated by an overhead gas from an argon column (K10).
5. Procédé selon la revendication 3 ou 4 dans lequel l'air liquéfié (5) et/ou le liquide enrichi en azote par rapport à l'air est produit par échange de chaleur avec le débit liquide riche en oxygène (OL) provenant de la cuve de la colonne basse pression, éventuellement après une étape de pressurisation.5. Method according to claim 3 or 4 wherein the liquefied air (5) and / or the liquid enriched in nitrogen with respect to the air is produced by heat exchange with the liquid flow rich in oxygen (OL) coming from the low pressure column tank, possibly after a pressurization step.
6. Procédé selon la revendication 3 dans lequel le liquide enrichi en azote (15) contient au moins 80 % mol. d'azote.6. The method of claim 3 wherein the liquid enriched in nitrogen (15) contains at least 80% mol. nitrogen.
7. Procédé selon la revendication 3 dans lequel l'air liquéfié (5) ne provient pas de la colonne moyenne pression.7. The method of claim 3 wherein the liquefied air (5) does not come from the medium pressure column.
8. Procédé selon l'une des revendications précédentes dans lequel le débit liquide (5,15) envoyé en tête de la colonne auxiliaire est plus riche en azote que le débit intermédiaire.8. Method according to one of the preceding claims in which the liquid flow rate (5.15) sent at the head of the auxiliary column is richer in nitrogen than the intermediate flow rate.
9. Procédé selon l'une des revendications précédentes dans lequel au moins 10% de l'oxygène produit est soutiré sous forme liquide de la colonne basse pression.9. Method according to one of the preceding claims wherein at least 10% of the oxygen produced is withdrawn in liquid form from the low pressure column.
10. Installation de production d'oxygène et de gaz rares par distillation dans un système de colonnes comprenant au moins une colonne moyenne pression (K01), une colonne basse pression (K02) et une colonne auxiliaire (K05) comprenant : i) des moyens (1) pour envoyer au moins un débit d'air refroidi et épuré à la colonne moyenne pression où il se sépare, ii) des moyens pour soutirer au moins un premier débit enrichi en azote (11) de la colonne moyenne pression et des moyens pour envoyer au moins une partie de ce débit directement ou indirectement à la colonne basse pression, iii) des moyens pour soutirer un débit riche en azote (WN2) de la tête de la colonne basse pression, iv) des moyens pour soutirer un débit intermédiaire (LR1) d'un niveau intermédiaire de la colonne moyenne pression, v) des moyens pour envoyer un débit, plus riche en oxygène que le débit intermédiaire, de la colonne moyenne pression en cuve de la colonne auxiliaire, vi) des moyens pour envoyer un débit liquide (5,15) comme reflux à la colonne auxiliaire, vii) des moyens pour soutirer un débit liquide riche en oxygène (OL) de la cuve de la colonne basse pression en tant que produit, éventuellement après une étape de vaporisation pour former un produit gazeux, et viii) des moyens pour soutirer de la colonne auxiliaire un troisièn " débit enrichi en oxygène (PURGE), également enrichi en krypton et en xém par rapport au deuxième débit enrichi en oxygène, caractérisée en ce qu'elle comprend des moyens pour envoyer comr débit de reflux à la colonne auxiliaire de l'air liquéfié ou un débit liquide enrichi azote par rapport à un débit d'air liquide envoyé à la colonne moyenne pression .10. Installation for producing oxygen and rare gases by distillation in a column system comprising at least one medium pressure column (K01), a low pressure column (K02) and an auxiliary column (K05) comprising: i) means (1) to send at least one flow of cooled and purified air to the medium pressure column where it separates, ii) means for withdrawing at least a first nitrogen-enriched flow (11) from the medium pressure column and means to send to at least part of this flow directly or indirectly to the low pressure column, iii) means for withdrawing a nitrogen-rich flow (WN2) from the head of the low pressure column, iv) means for withdrawing an intermediate flow (LR1) an intermediate level of the medium pressure column, v) means for sending a flow, richer in oxygen than the intermediate flow, from the medium pressure column in the tank of the auxiliary column, vi) means for sending a liquid flow (5.15) as reflux to the auxiliary column, vii) means for withdrawing a liquid flow rich in oxygen (OL) from the tank of the low pressure column as a product, possibly after a vaporization step to form a product gaseous, and viii) means for withdrawing from the auxiliary column a third " oxygen-enriched flow rate (PURGE), also enriched in krypton and in xem with respect to the second oxygen-enriched flow rate, characterized in that it comprises means for sending as flow of reflux to the auxiliary column of liquefied air or a nitrogen-enriched liquid flow with respect to a flow of liquid air sent to the medium pressure column.
11. Installation selon la revendication 10 comprenant une colonne d'épuration (K90), des moyens pour envoyer le troisième débit enrichi en oxygène (PURGE) en tête de la colonne d'épuration et des moyens (MIXTURE) pour soutirer au moins quelques plateaux théoriques plus bas dans la colonne un quatrième débit enrichi en oxygène constituant un mélange enrichi en krypton et xénon.11. Installation according to claim 10 comprising a purification column (K90), means for sending the third oxygen-enriched flow (PURGE) at the head of the purification column and means (MIXTURE) for withdrawing at least a few trays theoretical below in the column a fourth flow enriched in oxygen constituting a mixture enriched in krypton and xenon.
12. Installation selon la revendication 10 ou 11 comprenant une ligne d'échange dans laquelle l'air liquéfié et/ou le liquide enrichi en azote par rapport à l'air est produit par échange de chaleur avec le débit liquide riche en oxygène provenant de la cuve de la colonne basse pression, éventuellement après une étape de pressurisation. 12. Installation according to claim 10 or 11 comprising an exchange line in which the liquefied air and / or the liquid enriched in nitrogen with respect to the air is produced by heat exchange with the liquid flow rich in oxygen coming from the low pressure column tank, possibly after a pressurization step.
EP03758191A 2002-09-04 2003-07-30 Method and installation for production of noble gases and oxygen by means of cryogenic air distillation Withdrawn EP1552230A1 (en)

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FR0210922A FR2844039B1 (en) 2002-09-04 2002-09-04 PROCESS AND PLANT FOR PRODUCING OXYGEN AND RARE GASES BY CRYOGENIC AIR DISTILLATION
FR0210922 2002-09-04
PCT/FR2003/002420 WO2004023054A1 (en) 2002-09-04 2003-07-30 Method and installation for production of noble gases and oxygen by means of cryogenic air distillation

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RU2319084C2 (en) 2008-03-10
WO2004023054A1 (en) 2004-03-18
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CN1678875A (en) 2005-10-05

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