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EP1623171B1 - Cryogenic distillation method and system for air separation - Google Patents

Cryogenic distillation method and system for air separation Download PDF

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Publication number
EP1623171B1
EP1623171B1 EP04722884A EP04722884A EP1623171B1 EP 1623171 B1 EP1623171 B1 EP 1623171B1 EP 04722884 A EP04722884 A EP 04722884A EP 04722884 A EP04722884 A EP 04722884A EP 1623171 B1 EP1623171 B1 EP 1623171B1
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EP
European Patent Office
Prior art keywords
air
booster
turbines
column
pressure
Prior art date
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EP04722884A
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German (de)
French (fr)
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EP1623171A1 (en
Inventor
Patrick Le Bot
Olivier De Cayeux
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
    • F25J3/04163—Hot end purification of the feed air
    • F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
    • F25J3/04175—Hot end purification of the feed air by adsorption of the impurities at a pressure of substantially more than the highest 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
    • F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04048—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams
    • F25J3/04054—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams of air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • F25J3/04296—Claude expansion, i.e. expanded into the main or 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
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04375—Details relating to the work expansion, e.g. process parameter etc.
    • F25J3/04381—Details relating to the work expansion, e.g. process parameter etc. using work extraction by mechanical coupling of compression and expansion so-called companders
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04375—Details relating to the work expansion, e.g. process parameter etc.
    • F25J3/04393—Details relating to the work expansion, e.g. process parameter etc. using multiple or multistage gas work expansion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04406—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
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • F25J2240/04—Multiple expansion turbines in parallel

Definitions

  • the present invention relates to a method and an installation for air separation by cryogenic distillation, according to the preamble of claims 1 and 14. Such a method and such an installation are known from FIG. US Patent 5475980 .
  • the whole turbine coupled to the cold booster is associated with a system of energy dissipation (oil brake), integrated on the axis of the machines and technologically limited to small powers (of the order of 70 KW ).
  • oil brake system of energy dissipation
  • An object of the invention is to provide an alternative that allows for cold booster method diagrams without energy dissipation system integrated into the turbine blower axis, and therefore to consider using this scheme for almost near all sizes of air separation units.
  • the two boosters are connected in series or in parallel and the turbines are connected in parallel.
  • the suction temperature of the second booster is greater than the inlet temperature of the turbines.
  • “Close in terms of pressure” means that the pressures differ by not more than 5 bar, preferably not more than 2 bar.
  • “Close in terms of temperature” means that the temperatures differ by not more than 15 ° C, preferably not more than 10 ° C.
  • a booster is a single-stage compressor.
  • condensation includes pseudo condensation.
  • vaporization includes pseudo vaporization.
  • This invention differs from US-A-5,475,980 in that in Figure 4 (optional turbine 9), the two turbines 8, 32 aspire at very different pressures, the difference being at least 14 bars and in Figure 5, the pressure difference is about 13 bars and a turbine escapes the low pressure, which is penalizing for pure oxygen.
  • Another portion 2 of the air at 15 bars constituting the remainder of the air is cooled in the exchange line to an intermediate temperature greater than the suction temperature of the turbines 17, 19 compressed in a second booster 23 up to About 30 bars and introduced into the exchange line 9 at a higher temperature in order to continue cooling.
  • the air 37 to 30 bar is liquefied in the exchange line and liquid oxygen 25 vaporizes in the exchange line, the vaporization temperature of the liquid being close to the suction temperature of the second booster 23.
  • the liquefied air leaves the exchange line and is sent to the column system.
  • a flow of residual nitrogen 27 is heated in the exchange line 9.
  • the first booster 5 is coupled with one of the turbines 17, 19 and the second booster 23 is coupled with the other of the turbines 19, 17.
  • the column system of an air separation apparatus is constituted by a medium pressure column 100 thermally connected with a low pressure column 200.
  • the medium pressure column operates at a pressure of 5.5 bar but can operate at a higher pressure.
  • the gaseous air 21 from the two turbines 17, 19 is the flow rate sent to the bottom of the medium pressure column 100.
  • the liquefied air 37 is expanded in the valve 39 and divided in two, a part being sent to the medium pressure column 100 and the rest to the low pressure column 200.
  • Rich liquid 51, lower lean liquid 53 and upper lean liquid 55 are fed from medium pressure column 100 to low pressure column 200 after expansion stages in valves and subcooling.
  • Liquid oxygen 57 and liquid nitrogen 59 are withdrawn as final products of the double column.
  • Liquid oxygen is pressurized by the pump 500 and sent as pressurized liquid 25 to the exchange line 9.
  • Other liquids, pressurized or not, can vaporize in the exchange line.
  • Nitrogen gas is optionally withdrawn from the medium pressure column and is also cooled in the exchange line 9.
  • Nitrogen 33 is withdrawn at the top of the low pressure column and warms up (line 29) in the exchange line, after having served to sub-cool the reflux liquids.
  • Residual nitrogen 27 is withdrawn from a lower level of the low pressure column and heats up in the exchange line, after having been used to sub-cool the reflux liquids.
  • the column may optionally produce argon by treating a flow rate withdrawn in low pressure column 200.
  • a flow of air at atmospheric pressure is compressed to 15 bar in a main compressor 1.
  • the air is then optionally cooled and purified to remove impurities and cooled.
  • a first portion of the purified air is supercharged in the first booster 5 to a pressure of about 17 bar before being cooled by a water cooler 7.
  • the air 11 is supercharged in the second booster 23 to about 30 bars after having been cooled to an intermediate temperature of the exchange line 9, close to the vaporization temperature of the liquid oxygen.
  • the air at 30 bar is then reintroduced into the exchanger 9 at a higher temperature and cools down through the exchange line and is liquefied.
  • the air 33 is divided in two, relaxed and sent to two columns 100,200.
  • the second part 2 of the air at 15 bar is cooled in the exchange line at a temperature below the suction temperature of the booster 23, leaves the exchange line and is divided in two. Each portion of the air is expanded in a turbine 17,19 before being sent to the medium pressure column 100.
  • the hot booster 5 is coupled to the turbine 17 and the cold booster 23 is coupled to the turbine 19.
  • the hot booster 5 is removed. All air 1 is sent to the exchange line at a single pressure greater than 5 to 10 bars at medium pressure. This air is withdrawn from the exchange line at an intermediate temperature and all the air is supercharged at a temperature below ambient to a pressure of 18 bar in the cold booster 23. Then the supercharged air is divided in two Part 33 continues cooling to the cold end of the exchange line, liquefies and is expanded to be sent into at least one column of the column system 100, 200.
  • the combined flow of air expanded in the turbines 17, 19 is sent to the medium pressure column and is the only gaseous air inlet in the double column.
  • the cold booster 23 is coupled to the turbine 19 and the turbine 17 is coupled to an electric generator 61 which can be replaced by an oil brake.

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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)
  • Processing Of Solid Wastes (AREA)

Abstract

Methods and apparatus for air separation by cryogenic distillation in a double or triple air separation column. The column in the system with the highest operating pressure is said to be operating at medium pressure. All the air to be distilled is pressurized to a high pressure, which is about 5 bar greater than the medium pressure. The air is purified at this high pressure, and a portion of the purified air is cooled in a heat exchange line, while another portion is expanded in a turbine. Part of the cooled air is drawn from the exchange line with a cold booster, which is mechanically coupled to at least one turbine. An energy dissipation device is also provided which is coupled to the turbine not coupled to the cold booster. The energy dissipation device is either another booster, an oil break system, or an electrical generator.

Description

La présente invention est relative à un procédé et à une installation de séparation d'air par distillation cryogénique, selon le préambule des revendications 1 et 14. Un tel procédé et une telle installation sont connus de la Figure 4 de US-A-5475980 .The present invention relates to a method and an installation for air separation by cryogenic distillation, according to the preamble of claims 1 and 14. Such a method and such an installation are known from FIG. US Patent 5475980 .

Il est connu de produire un gaz de l'air sous pression par vaporisation de liquide pressurisé dans une ligne d'échange d'un appareil de séparation d'air par échange de chaleur avec un gaz comprimé à partir d'une température cryogénique. Des appareils de ce type sont connus de FR-A-2688052 , EP-A-0644388 , EP-A-1014020 et de FR-A-2851330 .It is known to produce pressurized air gas by vaporizing pressurized liquid in an exchange line of an air separation apparatus by exchanging heat with a compressed gas from a cryogenic temperature. Devices of this type are known to FR-A 2688052 , EP-A-0644388 , EP-A-1014020 and of FR-A-2851330 .

L'efficacité énergétique des appareils connus n'est pas excellente car il faut évacuer les entrées thermiques liées à la compression cryogénique.The energy efficiency of known devices is not excellent because it is necessary to evacuate the thermal inputs related to cryogenic compression.

De plus, pour les schémas tels que celui de la Figure 7 de US-A-5475980 , l'ensemble de la turbine couplée au surpresseur froid est associé à un système de dissipation d'énergie (frein d'huile), intégré sur l'axe des machines et technologiquement limité à de petites puissances (de l'ordre de 70 KW).In addition, for schemes such as that in Figure 7 of US Patent 5475980 , the whole turbine coupled to the cold booster is associated with a system of energy dissipation (oil brake), integrated on the axis of the machines and technologically limited to small powers (of the order of 70 KW ).

Néanmoins, ce type de procédé paraît avoir un intérêt économique, en particulier lorsque l'énergie est peu valorisée ou disponible à faible coût. Il est donc potentiellement intéressant de pouvoir s'affranchir de la limite technologique du frein d'huile intégré à l'axe de l'ensemble turbine/booster.Nevertheless, this type of process seems to have an economic interest, in particular when the energy is little valorized or available at low cost. It is therefore potentially interesting to be able to overcome the technological limit of the oil brake integrated in the axis of the turbine / booster assembly.

Un but de l'invention est de proposer une alternative qui permette de réaliser des schémas de procédé à surpresseur froid sans système de dissipation d'énergie intégré à l'axe turbine surpresseur, et donc d'envisager d'utiliser ce schéma pour à peu près toutes les tailles d'appareils de séparation d'air.An object of the invention is to provide an alternative that allows for cold booster method diagrams without energy dissipation system integrated into the turbine blower axis, and therefore to consider using this scheme for almost near all sizes of air separation units.

Selon la présente invention, il est prévu un procédé selon la revendication 1.According to the present invention there is provided a method according to claim 1.

Selon d'autres aspects facultatifs de l'invention :

  • les conditions d'admission et de refoulement des deux turbines sont proches ou identiques en termes de pression et de température ;
  • l'air envoyé aux turbines est à la haute pression (Figure 2) ;
  • l'air envoyé aux turbines est à une pression supérieure à la haute pression et provient du surpresseur froid et/ou du surpresseur constituant le dispositif de dissipation ou faisant partie de celui-ci (Figures 1 et 3) ;
  • tout l'air envoyé aux turbines provient du surpresseur constituant le dispositif de dissipation ou faisant partie de celui-ci et l'air surpressé dans le surpresseur froid poursuit son refroidissement dans la ligne d'échange, est détendu, liquéfié et envoyé à au moins une colonne de la double colonne ou la triple colonne (Figure 1) ;
  • une partie de l'air surpressée dans le surpresseur froid est envoyée aux turbines et le reste poursuit son refroidissement dans la ligne d'échange, est détendu, liquéfié et envoyé à au moins une colonne de la double colonne ou la triple colonne (Figure 3) ;
  • au moins une partie de l'air à la haute pression est surpressée dans le surpresseur froid ;
  • l'air à haute pression est divisé en au moins deux parties, une partie étant surpressée dans le surpresseur froid et une autre partie (le reste) dans le surpresseur constituant le dispositif de dissipation ou faisant partie de celui-ci (Figure 1) ;
  • au moins une partie de l'air provenant du surpresseur constituant le dispositif de dissipation ou faisant partie de celui-ci est envoyée au surpresseur froid (Figure 2) ;
  • au moins une partie de l'air surpressé dans le surpresseur constituant le dispositif de dissipation ou faisant partie de celui-ci est envoyée aux turbines ;
  • une partie de l'air provenant du surpresseur constituant le dispositif de dissipation ou faisant partie de celui-ci se refroidit contre au moins un liquide qui se vaporise dans la ligne d'échange, est détendu, liquéfié et envoyé à une colonne de la double ou triple colonne ;
  • on produit au moins un produit final sous forme liquide ;
  • tout l'air gazeux destiné aux colonnes de la double ou triple colonne provient des turbines de détente d'air.
According to other optional aspects of the invention:
  • the inlet and outlet conditions of the two turbines are close or identical in terms of pressure and temperature;
  • the air sent to the turbines is at high pressure ( Figure 2 );
  • the air sent to the turbines is at a pressure higher than the high pressure and comes from the cold booster and / or the booster constituting the dissipation device or part of it ( Figures 1 and 3 );
  • all the air sent to the turbines comes from the booster constituting the dissipation device or part of it and the supercharged air in the cold booster continues cooling in the exchange line, is relaxed, liquefied and sent to at least one column of the double column or the triple column ( Figure 1 );
  • a portion of the air blown into the cold booster is sent to the turbines and the remainder continues cooling in the exchange line, is expanded, liquefied and sent to at least one column of the double column or the triple column ( Figure 3 );
  • at least some of the air at high pressure is overpressed in the cold booster;
  • the high-pressure air is divided into at least two parts, one part being overpressed in the cold booster and another part (the rest) in the booster constituting the dissipation device or forming part thereof ( Figure 1 );
  • at least a part of the air coming from the booster forming the dissipation device or part of it is sent to the cold booster ( Figure 2 );
  • at least a portion of the supercharged air in the blower constituting the dissipation device or part of it is sent to the turbines;
  • a part of the air coming from the booster forming the dissipation device or part of it is cooled against at least one liquid which vaporizes in the exchange line, is expanded, liquefied and sent to a double column or triple column;
  • at least one final product is produced in liquid form;
  • all the gaseous air intended for the columns of the double or triple column comes from the air expansion turbines.

Selon un autre aspect de l'invention, il est prévu une installation selon la revendication 14.According to another aspect of the invention, there is provided an installation according to claim 14.

Selon d'autres aspects facultatifs, l'installation comprend

  • des moyens pour envoyer de l'air aux turbines depuis le surpresseur froid et/ou le surpresseur constituant le moyen de dissipation d'énergie ou faisant partie de celui-ci ;
  • des moyens pour envoyer au moins une partie de l'air à distiller au surpresseur constituant le moyen de dissipation d'énergie ou faisant partie de celui-ci.
According to other optional aspects, the installation includes
  • means for supplying air to the turbines from the cold booster and / or the booster constituting the energy dissipating means or part thereof;
  • means for sending at least a portion of the air to be distilled to the booster constituting the energy dissipating means or forming part of it.

De préférence les deux surpresseurs sont connectés en série ou en parallèle et les turbines sont connectées en parallèle.Preferably the two boosters are connected in series or in parallel and the turbines are connected in parallel.

De préférence la température d'aspiration du deuxième surpresseur est supérieure à la température d'entrée des turbines.Preferably the suction temperature of the second booster is greater than the inlet temperature of the turbines.

On utilisera une turbine complémentaire, fonctionnant en parallèle de la turbine du premier ensemble turbine surpresseur, et équipée de son propre système de dissipation d'énergie. Favorablement, ce système sera un surpresseur suivi d'un réfrigérant à eau installé en partie chaude.It will use a complementary turbine, operating in parallel with the turbine of the first blower assembly booster, and equipped with its own energy dissipation system. Favorably, this system will be a booster followed by a water cooler installed in the hot part.

« Proches en termes de pression » veut dire que les pressions diffèrent d'au plus 5 bars, de préférence d'au plus 2 bars. « Proches en termes de température » veut dire que les températures diffèrent d'au plus de 15°C, de préférence au plus 10°C."Close in terms of pressure" means that the pressures differ by not more than 5 bar, preferably not more than 2 bar. "Close in terms of temperature" means that the temperatures differ by not more than 15 ° C, preferably not more than 10 ° C.

Un surpresseur est un compresseur à un seul étage.A booster is a single-stage compressor.

Toutes les pressions mentionnées sont des pressions absolues.All pressures mentioned are absolute pressures.

Le terme « condensation » comprend la pseudo condensation. Le terme « vaporisation » comprend la pseudo vaporisation.The term "condensation" includes pseudo condensation. The term "vaporization" includes pseudo vaporization.

Cette invention se distingue de US-A- 5 475 980 en ce sens que dans la Figure 4 (turbine 9 optionnelle), les deux turbines 8, 32 aspirent à des pressions très différenciées, la différence étant d'au moins 14 bars et dans la Figure 5, la différence de pressions est d'environ 13 bars et une turbine échappe à la basse pression, ce qui est pénalisant pour de l'oxygène pur.This invention differs from US-A-5,475,980 in that in Figure 4 (optional turbine 9), the two turbines 8, 32 aspire at very different pressures, the difference being at least 14 bars and in Figure 5, the pressure difference is about 13 bars and a turbine escapes the low pressure, which is penalizing for pure oxygen.

L'invention sera décrite en plus de détails en se référant aux figures dans lesquelles :

  • Les Figures 1, 2 et 3 représentent un appareil de séparation d'air selon l'invention.
  • Dans la Figure 1, un débit d'air à la pression atmosphérique est comprimé à environ 15 bars dans un compresseur principal (non-illustré). L'air est ensuite éventuellement refroidi, avant d'être épuré pour enlever les impuretés (non-illustré). L'air épuré est divisé en deux. Une partie de l'air 3 est envoyée à un surpresseur 5 jusqu'à une pression d'entre 17 et 20 bars et ensuite l'air surpressé est refroidi par un réfrigérant à l'eau 7 avant d'être envoyé au bout chaud de la ligne d'échange pincipal 9 de l'appareil de séparation d'air. L'air surpressé 11 se refroidit jusqu'à une température intermédiaire avant de sortir de la ligne d'échange et d'être divisé en deux fractions. Une fraction 13 est envoyée dans une turbine 17 et le reste, une fraction 15 est envoyée dans une turbine 19. Les deux turbines ont la même température et pression d'aspiration et la même température et pression de sortie mals il est évidemment possible que ces températures et pression soient proches les unes des autres au lieu d'être identiques. Les deux débits turbines sont mélangés pour former un débit 21 d'air gazeux qui est envoyé vers le système de colonnes comme il sera décrit vis-à-vis de la Figure 2. En variante, la turbine 19 peut être une turbine d'insufflation débouchant à la pression de la colonne basse pression.
The invention will be described in more detail with reference to the figures in which:
  • The Figures 1 , 2 and 3 represent an air separation apparatus according to the invention.
  • In the Figure 1 an air flow at atmospheric pressure is compressed to about 15 bar in a main compressor (not shown). The air is then optionally cooled, before being purified to remove impurities (not shown). The clean air is divided in two. Part of the air 3 is sent to a booster 5 up to a pressure of between 17 and 20 bar and then the supercharged air is cooled by a water cooler 7 before being sent to the hot end of the main exchange line 9 of the air separation apparatus. The pressurized air 11 cools to an intermediate temperature before exiting the exchange line and being divided into two fractions. A fraction 13 is sent into a turbine 17 and the remainder, a fraction 15 is sent into a turbine 19. The two turbines have the same temperature and suction pressure and the same temperature and outlet pressure mals it is obviously possible that these temperatures and pressure are close to each other instead of being identical. The two turbine flows are mixed to form a flow rate of gaseous air which is sent to the column system as will be described with respect to Figure 2 . Alternatively, the turbine 19 may be an insufflation turbine opening to the pressure of the low pressure column.

Une autre partie 2 de l'air à 15 bars constituant le reste de Pair est refroidie dans la ligne d'échange à une température intermédiaire supérieure à la température d'aspiration des turbines 17, 19. comprimée dans un deuxième surpresseur 23 jusqu'à 30 bars environ et introduite dans la ligne d'échange 9 à une température plus élevée afin de poursuivre son refroidissement.Another portion 2 of the air at 15 bars constituting the remainder of the air is cooled in the exchange line to an intermediate temperature greater than the suction temperature of the turbines 17, 19 compressed in a second booster 23 up to About 30 bars and introduced into the exchange line 9 at a higher temperature in order to continue cooling.

Ainsi, l'air 37 à 30 bars se liquéfie dans la ligne d'échange et de l'oxygène liquide 25 se vaporise dans la ligne d'échange, la température de vaporisation du liquide étant proche de la température d'aspiration du deuxième surpresseur 23. L'air liquéfié sort de la ligne d'échange et est envoyé vers le système de colonnes.Thus, the air 37 to 30 bar is liquefied in the exchange line and liquid oxygen 25 vaporizes in the exchange line, the vaporization temperature of the liquid being close to the suction temperature of the second booster 23. The liquefied air leaves the exchange line and is sent to the column system.

Un débit d'azote résiduaire 27 se réchauffe dans la ligne d'échange 9.A flow of residual nitrogen 27 is heated in the exchange line 9.

Le premier surpresseur 5 est couplé avec l'une des turbines 17, 19 et le deuxième surpresseur 23 est couplé avec l'autre des turbines 19, 17.The first booster 5 is coupled with one of the turbines 17, 19 and the second booster 23 is coupled with the other of the turbines 19, 17.

Le système de colonnes d'un appareil de séparation d'air est constitué par une colonne moyenne pression 100 thermiquement reliée avec une colonne basse pression 200.The column system of an air separation apparatus is constituted by a medium pressure column 100 thermally connected with a low pressure column 200.

La colonne moyenne pression opère à une pression de 5,5 bars mais peut opérer à une pression plus élevée.The medium pressure column operates at a pressure of 5.5 bar but can operate at a higher pressure.

L'air gazeux 21 provenant des deux turbines 17, 19 est le débit envoyé en cuve de la colonne moyenne pression 100.The gaseous air 21 from the two turbines 17, 19 is the flow rate sent to the bottom of the medium pressure column 100.

l'air liquéfié 37 est détendu dans la vanne 39 et divisé en deux, une partie étant envoyée à la colonne moyenne pression 100 et le reste à la colonne basse pression 200.the liquefied air 37 is expanded in the valve 39 and divided in two, a part being sent to the medium pressure column 100 and the rest to the low pressure column 200.

Du liquide riche 51, du liquide pauvre inférieur 53 et du liquide pauvre supérieur 55 sont envoyés depuis la colonne moyenne pression 100 vers ta colonne basse pression 200 après des étapes de détente dans des vannes et de sous-refroidissement.Rich liquid 51, lower lean liquid 53 and upper lean liquid 55 are fed from medium pressure column 100 to low pressure column 200 after expansion stages in valves and subcooling.

De l'oxygène liquide 57 et de l'azote liquide 59 sont soutirés comme produits finaux de la double colonne.Liquid oxygen 57 and liquid nitrogen 59 are withdrawn as final products of the double column.

De l'oxygène liquide est pressurisé par la pompe 500 et envoyé comme liquide pressurisé 25 vers la ligne d'échange 9. D'autres liquides, pressurisés ou non, peuvent se vaporiser dans la ligne d'échange.Liquid oxygen is pressurized by the pump 500 and sent as pressurized liquid 25 to the exchange line 9. Other liquids, pressurized or not, can vaporize in the exchange line.

De l'azote gazeux est optionnellement soutiré de la colonne moyenne pression et se refroidit également dans la ligne d'échange 9.Nitrogen gas is optionally withdrawn from the medium pressure column and is also cooled in the exchange line 9.

De l'azote 33 est soutiré en tête de la colonne basse pression et se réchauffe (conduite 29) dans la ligne d'échange, après avoir servi à sous-refroidir les liquides de reflux.Nitrogen 33 is withdrawn at the top of the low pressure column and warms up (line 29) in the exchange line, after having served to sub-cool the reflux liquids.

De l'azote résiduaire 27 est soutiré d'un niveau inférieur de la colonne basse pression et se réchauffe dans la ligne d'échange, après avoir servi à sous-refroidir les liquides de reflux.Residual nitrogen 27 is withdrawn from a lower level of the low pressure column and heats up in the exchange line, after having been used to sub-cool the reflux liquids.

La colonne peut éventuellement produire de l'argon en traitant un débit soutiré en colonne basse pression 200.The column may optionally produce argon by treating a flow rate withdrawn in low pressure column 200.

En variante de la Figure 1, seule une partie de l'air surpressé dans le premier surpresseur est envoyée vers les turbines 17, 19. Le reste de l'air 41 se retrouve liquéfié à la sortie de la ligne d'échange. Le liquide est ensuite détendu dans une vanne 43 et mélangé au liquide 30 détendu dans la vanne 39. Le reste de la Figure est identique à celle de la Figure 1.As a variant of the Figure 1 only a portion of the compressed air in the first booster is sent to the turbines 17, 19. The rest of the air 41 is liquefied at the exit of the exchange line. The liquid is then expanded in a valve 43 and mixed with the liquid 30 expanded in the valve 39. The remainder of the Figure is identical to that of the Figure 1 .

Dans la Figure 2, un débit d'air à la pression atmosphérique est comprimé à 15 bars dans un compresseur principal 1. L'air est ensuite éventuellement refroidi et épuré pour enlever les impuretés et refroidi. Une première partie de l'air épuré est surpressée dans le premier surpresseur 5 jusqu'à une pression d'environ 17 bars avant d'être refroidi par un réfrigérant à l'eau 7.In the Figure 2 , a flow of air at atmospheric pressure is compressed to 15 bar in a main compressor 1. The air is then optionally cooled and purified to remove impurities and cooled. A first portion of the purified air is supercharged in the first booster 5 to a pressure of about 17 bar before being cooled by a water cooler 7.

En sortie de réfrigérant 7, l'air 11 est surpressé dans le deuxième surpresseur 23 jusqu'à environ 30 bars après avoir été refroidi jusqu'à une température intermédiaire de la ligne d'échange 9, proche de la température de vaporisation de l'oxygène liquide. L'air à 30 bars est ensuite réintroduit dans l'échangeur 9 à une température plus élevée et se refroidit en traversant la ligne d'échange et se trouve liquéfié. L'air 33 est divisé en deux, détendu et envoyé aux deux colonnes 100,200.At the outlet of the refrigerant 7, the air 11 is supercharged in the second booster 23 to about 30 bars after having been cooled to an intermediate temperature of the exchange line 9, close to the vaporization temperature of the liquid oxygen. The air at 30 bar is then reintroduced into the exchanger 9 at a higher temperature and cools down through the exchange line and is liquefied. The air 33 is divided in two, relaxed and sent to two columns 100,200.

La deuxième partie 2 de l'air à 15 bars est refroidie dans la ligne d'échange à une température inférieure à la température d'aspiration du surpresseur 23, sort de la ligne d'échange et est divisée en deux. Chaque partie de l'air est détendue dans une turbine 17,19 avant d'être envoyée à la colonne moyenne pression 100.The second part 2 of the air at 15 bar is cooled in the exchange line at a temperature below the suction temperature of the booster 23, leaves the exchange line and is divided in two. Each portion of the air is expanded in a turbine 17,19 before being sent to the medium pressure column 100.

Le surpresseur chaud 5 est couplé à la turbine 17 et le surpresseur froid 23 est couplé à la turbine 19.The hot booster 5 is coupled to the turbine 17 and the cold booster 23 is coupled to the turbine 19.

Dans la Figure 2, les deux turbines 17 et 19 sont alimentées non pas avec de l'air provenant du surpresseur chaud mais avec de l'air à la haute pression. Le surpresseur froid 23 surprese tout l'air provenant du surpresseur chaud 5 et cet air est ensuite liquéfié. La pression d'entrée des turbines est donc plus basse que dans la Figure 1. Le reste de la Figure 2 est identique à la Figure 1.In the Figure 2 the two turbines 17 and 19 are fed not with air from the hot booster but with air at high pressure. The cold booster 23 overheats all the air from the hot booster 5 and this air is then liquefied. The inlet pressure of the turbines is therefore lower than in the Figure 1 . The rest of the Figure 2 is identical to the Figure 1 .

Dans la Figure 3, le surpresseur chaud 5 est supprimé. Tout l'air 1 est envoyé à la ligne d'échange à une seule pression supérieure de 5 à 10 bars à la moyenne pression. Cet air est soutiré de la ligne d'échange à une température intermédiaire et tout l'air est surpressé à une température inférieure à l'ambiante jusqu'à une pression de 18 bars dans le surpresseur froid 23. Ensuite l'air surpressé est divisé en deux Une partie 33 poursuit son refroidissement jusqu'au bout froid de la ligne d'échange, se liquéfie et est détendue pour être envoyée dans au moins une colonne du système de colonnes 100, 200.In the Figure 3 , the hot booster 5 is removed. All air 1 is sent to the exchange line at a single pressure greater than 5 to 10 bars at medium pressure. This air is withdrawn from the exchange line at an intermediate temperature and all the air is supercharged at a temperature below ambient to a pressure of 18 bar in the cold booster 23. Then the supercharged air is divided in two Part 33 continues cooling to the cold end of the exchange line, liquefies and is expanded to be sent into at least one column of the column system 100, 200.

Le reste de l'air sort de la ligne d'échange à une température Intermédiaire inférieure à la température d'aspiration du surpresseur froid, est divisé en deux et envoyé à deux turbines 17, 19 ayant les mêmes conditions ou des conditions proches de température et pression à l'entrée et à la sortie. Le débit réuni d'air détendu dans les turbines 17, 19 est envoyé à la colonne moyenne pression et constitue la seule entrée d'air gazeux dans la double colonne.The rest of the air leaves the exchange line at an intermediate temperature lower than the suction temperature of the cold booster, is divided in two and sent to two turbines 17, 19 having the same conditions or conditions close to temperature. and pressure at the entrance and exit. The combined flow of air expanded in the turbines 17, 19 is sent to the medium pressure column and is the only gaseous air inlet in the double column.

Le surpresseur froid 23 est couplé à la turbine 19 et la turbine 17 est couplée à une génératrice électrique 61 qui peut être remplacée par un frein d'huile.The cold booster 23 is coupled to the turbine 19 and the turbine 17 is coupled to an electric generator 61 which can be replaced by an oil brake.

Claims (17)

  1. A process for the separation of air by cryogenic distillation in an installation comprising a double or triple air separation column (100, 200), the column (100) of which, operating at the higher pressure, operates at a pressure called the medium pressure, and an exchange line (9), in which process:
    a) all the air is taken to a high pressure, at least 5 bar higher than the medium pressure, and purified at this high pressure;
    b) a portion of the purified air stream is cooled in the exchange line and is divided into two fractions;
    c) each fraction is expanded in a turbine (17, 19);
    d) the intake pressure of the two turbines is, or the pressures of the two turbines are, at least 5 bar above the medium pressure;
    e) the delivery pressure of at least one of the two turbines is substantially equal to the medium pressure;
    f) at least one portion of the air expanded in at least one of the turbines is sent to the medium-pressure column of the double or triple column;
    g) a cold booster (23) mechanically coupled to one of the expansion turbines draws in air, which has been cooled in the exchange line, and delivers the air at a temperature above the intake temperature, and the fluid thus compressed is reintroduced into the exchange line in which at least a portion of the fluid condenses;
    h) at least one pressurized liquid coming from one of the columns is vaporized in the exchange line at a vaporization temperature; and
    i) the turbine (17) not coupled to the cold booster is provided with an energy dissipation device, which process is characterized in that the device is chosen from:
    I) a booster (5) other than the cold booster and mechanically coupled to said turbine not coupled to the cold booster followed by a cooler;
    II) an oil brake system; and
    III) an electrical generator (61);
    and in that the portion of the purified air stream is divided into two fractions after having been cooled in the exchange line;
    and, optionally:
    j) the intake temperature of the cold booster (23) is close to the liquid vaporization temperature.
  2. Process according to Claim 1, in which the intake and delivery conditions of the two turbines (17, 19) are similar or identical in terms of pressure and temperature.
  3. Process according to Claim 1 or 2, in which the air (2) sent to the turbines (17, 19) is at the high pressure.
  4. Process according to either of Claims 1 and 2, in which the air (13, 15) sent to the turbines is at a pressure higher than the high pressure and comes from the cold booster (23).
  5. Process according to Claim 4, in which all the air sent to the turbines (17, 19) comes from the booster (5) constituting the dissipation device or forming part of the latter, and the air boosted in the cold booster (23) continues to be cooled in the exchange line, is expanded, liquefied and sent to at least one column (100, 200) of the double column or triple column.
  6. Process according to one of Claims 1 to 4, in which a portion (13, 15) of the air boosted in the cold booster (23) is sent to the turbines (17, 19) and the remainder (33) continues to be cooled in the exchange line, is expanded, liquefied and sent to at least one column of the double column or the triple column.
  7. Process according to one of the preceding claims, in which at least one portion of the air at the high pressure is boosted in the cold booster (23).
  8. Process according to one of the preceding claims, in which the air at high pressure is divided into at least two portions, one portion being boosted in the cold booster (23) and another portion or the remainder in the booster (5) constituting the dissipation device or forming part of the latter.
  9. Process according to one of Claims 1 to 7, in which at least one portion of the air coming from the booster (5) constituting the dissipation device or forming part of the latter is sent to the cold booster (23).
  10. Process according to one of the preceding claims, in which at least one portion of the air boosted in the booster (5) constituting the dissipation device or forming part of the latter is sent to the turbines (17, 19), the pressure of the air vent to the turbines being optionally above the high pressure.
  11. Process according to one of the preceding claims, in which at least one portion of the air coming from the booster (5) constituting the dissipation device or forming part of the latter is cooled against at least one liquid that vaporizes in the exchange line, is expanded, liquefied and sent to a column of the double or triple column.
  12. Process according to one of the preceding claims, in which at least one final product (57, 59) in liquid form is produced.
  13. Process according to one of the preceding claims, in which all the gaseous air (21) intended for the columns of the double or triple column comes from the air expansion turbines.
  14. Air separation installation for separating air by cryogenic distillation, comprising:
    a) a double or triple air separation column (100, 200), the column (100) of which that operates at the higher pressure operates at a pressure called the medium pressure;
    b) an exchange line (9);
    c) means for taking all the air to a high pressure, higher than the medium pressure, and means for purifying it at this high pressure;
    d) means for sending a portion of the purified air stream into the exchange line in order to cool said stream, and means for dividing this air into two fractions;
    e) two turbines (17, 19) and means for sending a fraction of the air to each turbine;
    f) means for sending at least one portion of the air expanded in at least one of the turbines to the medium-pressure column of the double or triple column;
    g) a cold booster (23), means for sending air, withdrawn from the main exchange line, preferably at an intermediate point, to the cold booster and means for sending air boosted in the cold booster into the exchange line at an intermediate point upstream of the withdrawal point;
    h) means (500) for pressurizing at least one liquid coming from one of the columns, means for sending at least one pressurized liquid into the exchange line, and means for extracting a vaporized liquid from the exchange line; and
    i) the cold booster is coupled to one (19) of the turbines, and the turbine (17) not coupled to the cold booster is coupled to an energy dissipation means, characterized in that the dissipation means comprises:
    I) a booster (5) other than the cold booster and coupled mechanically to said turbine not coupled to the cold booster followed by a cooler; or
    II) an oil brake system; or
    III) an electrical generator (61);
    and in that the means for dividing the air into two fractions are downstream from the exchange line.
  15. Installation according to Claim 14, comprising means for sending air to the turbines from the cold booster (23) and/or from the booster (5) constituting the energy dissipation means or forming part of the latter.
  16. Installation according to Claim 14 or 15, comprising means for sending at least one portion of the air to be distilled into the booster (5) constituting the energy dissipation means or forming part of the latter.
  17. Installation according to one of Claims 14 to 16, in which the two boosters (5, 23) are connected in series or in parallel, and the turbines (17, 19) are connected in parallel.
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US5379598A (en) * 1993-08-23 1995-01-10 The Boc Group, Inc. Cryogenic rectification process and apparatus for vaporizing a pumped liquid product
US5475980A (en) * 1993-12-30 1995-12-19 L'air Liquide, Societe Anonyme Pour L'etude L'exploitation Des Procedes Georges Claude Process and installation for production of high pressure gaseous fluid
FR2744795B1 (en) * 1996-02-12 1998-06-05 Grenier Maurice PROCESS AND PLANT FOR THE PRODUCTION OF HIGH-PRESSURE GASEOUS OXYGEN
DE19815885A1 (en) * 1998-04-08 1999-10-14 Linde Ag Air separation method producing gas, or gas and liquid e.g. for steel plant
FR2787560B1 (en) 1998-12-22 2001-02-09 Air Liquide PROCESS FOR CRYOGENIC SEPARATION OF AIR GASES
DE19951521A1 (en) * 1999-10-26 2001-05-03 Linde Ag Recovering pressurized product by low temperature decomposition of air in rectification system comprises cold compressing heat carrier stream before introducing into mixing column
FR2851330B1 (en) 2003-02-13 2006-01-06 Air Liquide PROCESS AND PLANT FOR THE PRODUCTION OF A GASEOUS AND HIGH PRESSURE PRODUCTION OF AT LEAST ONE FLUID SELECTED AMONG OXYGEN, ARGON AND NITROGEN BY CRYOGENIC DISTILLATION OF AIR
FR2854682B1 (en) * 2003-05-05 2005-06-17 Air Liquide METHOD AND INSTALLATION OF AIR SEPARATION BY CRYOGENIC DISTILLATION

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FR2854682B1 (en) 2005-06-17
DE602004027368D1 (en) 2010-07-08
EP1623171A1 (en) 2006-02-08
US20070017251A1 (en) 2007-01-25
US7464568B2 (en) 2008-12-16
JP4417954B2 (en) 2010-02-17
JP2006525486A (en) 2006-11-09
WO2004099690A1 (en) 2004-11-18
CN100378422C (en) 2008-04-02
CN1784580A (en) 2006-06-07
FR2854682A1 (en) 2004-11-12
PL1623171T3 (en) 2010-10-29
ES2350890T3 (en) 2011-01-28
ATE469329T1 (en) 2010-06-15
US20090078001A1 (en) 2009-03-26

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