EP2279385B1 - Apparatus and method for separating air by cryogenic distillation - Google Patents

Apparatus and method for separating air by cryogenic distillation Download PDF

Info

Publication number
EP2279385B1
EP2279385B1 EP09742279A EP09742279A EP2279385B1 EP 2279385 B1 EP2279385 B1 EP 2279385B1 EP 09742279 A EP09742279 A EP 09742279A EP 09742279 A EP09742279 A EP 09742279A EP 2279385 B1 EP2279385 B1 EP 2279385B1
Authority
EP
European Patent Office
Prior art keywords
pressure column
level
liquid
low pressure
oxygen
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.)
Not-in-force
Application number
EP09742279A
Other languages
German (de)
French (fr)
Other versions
EP2279385A2 (en
Inventor
Alain Briglia
Bernard Saulnier
Laurent Samy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP2279385A2 publication Critical patent/EP2279385A2/en
Application granted granted Critical
Publication of EP2279385B1 publication Critical patent/EP2279385B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • F25J3/04642—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
    • 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
    • F25J3/04406—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
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/02—Mixing or blending of fluids to yield a certain product
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
    • F25J2250/40—One fluid being 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
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
    • F25J2250/52—One fluid being oxygen enriched compared to air, e.g. "crude oxygen"

Definitions

  • the present invention applies to an apparatus and a method for producing krypton and xenon by air separation by cryogenic distillation and in particular to a method of separating gases from the air with internal compression (in which oxygen gaseous is produced by vaporization under pressure in the exchange line) where a krypton / xenon mixture is extracted.
  • an air separation unit comprising a double column and wherein the oxygen gas is produced by pressurized vaporization in the exchange line (internal compression apparatus) in which it is intended to extract a krypton mixture xenon
  • the yield of this extraction decreases significantly because the pumped oxygen extracted from the low pressure distillation column leads with it a significant part of the compounds to be valued such as krypton and xenon.
  • the low pressure column is fed by the purge rich in krypton and xenon produced by concentration.
  • the krypton and xenon-rich purge produced above will supply the low pressure column with a distillation stage lower than the withdrawal of the liquid oxygen to be pumped and then vaporized in the main exchanger.
  • the final mixture rich in krypton and xenon is extracted from the bottom of the low pressure column for further processing.
  • this return is injected at the suction of the pump to minimize the withdrawal OL of the column, and thus increase the extraction yield of krypton and xenon
  • Such a method makes it possible to extract about 90% of the xenon present in the air, where a conventional method only allows a yield of about 70% at best. As for the extraction yield of krypton, it reaches about 75% while the performance of a conventional apparatus does not allow the better than a yield of the order of 60%.
  • a medium pressure air flow 1 is sent to the medium pressure column 20 of a double air separation column.
  • the double column also comprises a low pressure column 21 thermally coupled with the medium pressure column 20 by means of a vaporizer 24, which vaporizes the bottom liquid of the low pressure column by heat exchange with the nitrogen gas at the top of the middle column pressure.
  • a flow of high pressure liquid air is expanded in a valve and then divided into two.
  • the flow 3 thus formed is sent to the medium pressure column 20 a few theoretical trays above the entry point of the flow 1.
  • the rest of the liquid air 4 is cooled in the subcooler 26, expanded and sent to the column low pressure 21.
  • a lower rich liquid flow rate enriched in oxygen, krypton and xenon is withdrawn in the vat of the medium pressure column 20, cooled in the subcooler 26, then expanded and sent to a vaporizer 22 where it is partially vaporized by exchange of heat with gaseous air enriched with nitrogen 8 from the medium pressure column 20.
  • the gaseous air is condensed to form a flow 9 which is then sent to the low pressure column 21.
  • the vaporized rich liquid 16 is expanded as intermediate gas and sent to the low pressure column while the remaining intermediate liquid 7 is sent to the low pressure column 21 a few trays above the tank.
  • An upper rich liquid flow 6 is withdrawn between the inlet of the air 1 and the air inlet 3 and / or the withdrawal of the flow 8.
  • This flow 6 is cooled in the subcooler 26, mixed with the rich liquid vaporized 16 and sent to the low pressure column 21. Poor liquid enriched in nitrogen 15 is withdrawn at the top of the medium pressure column 20 and sent to the top of the low pressure column 21 after cooling and expansion.
  • Liquid oxygen 10 is withdrawn from the low pressure column 21 a few trays above the tank and preferably above the arrival of the liquid 7. This liquid is pumped by the pump 23 to serve as a product rich in water. oxygen.
  • Liquid oxygen 11 enriched in krypton and xenon is withdrawn in the bottom of the low pressure column 21 and is subsequently purified to produce a mixture of krypton and xenon.
  • Low pressure nitrogen 13 is withdrawn at the top of the low pressure column 21, heated in the subcooler and heated against the air flows 1.2 (heating not shown).

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

An apparatus and to a method for producing krypton and xenon by separating air by cryogenic distillation and in particular to a method for separating gasses from air using internal compression (in which the gaseous oxygen is produced by vaporization under pressure in the exchange line) where a krypton/xenon mixture is extracted is provided.

Description

La présente invention s'applique à un appareil et à un procédé de production de krypton et xénon par séparation d'air par distillation cryogénique et en particulier à un procédé de séparation des gaz de l'air à compression interne (dans lequel l'oxygène gazeux est produit par vaporisation sous pression dans la ligne d'échange) où l'on extrait un mélange krypton/xénon.The present invention applies to an apparatus and a method for producing krypton and xenon by air separation by cryogenic distillation and in particular to a method of separating gases from the air with internal compression (in which oxygen gaseous is produced by vaporization under pressure in the exchange line) where a krypton / xenon mixture is extracted.

Le document US 6 220 054 qui est considéré comme étant l'état de la technique le plus proche de l'objet de la revendication 1 décrit dans la figure 1 un procédé de séparation d'air par distillation cryogénique dans une double colonne comprenant une colonne moyenne pression et une colonne basse pression dans lequel:

  • i) on envoie de l'air gazeux comprimé, refroidi et épuré à un premier niveau de la colonne moyenne pression
  • ii) on envoie de l'air liquide comprimé, refroidi et épuré à un deuxième niveau de la colonne moyenne pression au-dessus du premier
  • iii) on soutire un liquide enrichi en oxygène, en krypton et en xénon de la cuve de la colonne moyenne pression
  • v) on vaporise partiellement le liquide enrichi en oxygène, en krypton et en xénon pour former un gaz intermédiaire et un liquide intermédiaire
  • vi) on soutire un premier débit riche en oxygène à un troisième niveau de la colonne basse pression
  • vii) on envoie le liquide intermédiaire du vaporiseur à la colonne basse pression à la colonne basse pression
  • viii) on soutire un deuxième débit liquide riche en oxygène de la colonne basse pression à un quatrième niveau inférieur au troisième niveau.
The document US 6,220,054 which is considered to be the state of the art closest to the subject of claim 1 described in figure 1 a process for separating air by cryogenic distillation in a double column comprising a medium pressure column and a low pressure column in which:
  • i) compressed, cooled and purified air gas is sent to a first level of the medium pressure column
  • ii) compressed, cooled and purified liquid air is supplied to a second level of the medium pressure column above the first
  • iii) a liquid enriched with oxygen, krypton and xenon is withdrawn from the vessel of the medium pressure column
  • v) partially vaporizing the oxygen-enriched liquid, krypton and xenon to form an intermediate gas and an intermediate liquid
  • vi) a first oxygen rich flow is withdrawn at a third level of the low pressure column
  • vii) the intermediate liquid of the vaporizer is sent to the low pressure column at the low pressure column
  • viii) a second oxygen rich liquid flow is withdrawn from the low pressure column at a fourth level below the third level.

Dans une unité de séparation des gaz de l'air comprenant une double colonne et où l'oxygène gazeux est produit par vaporisation sous pression dans la ligne d'échange (appareil à compression interne) dans lequel il est prévu d'extraire un mélange krypton/xénon, il est constaté que le rendement de cette extraction décroît de façon significative du fait que l'oxygène pompé extrait de la colonne de distillation basse pression entraîne avec lui un partie non négligeable des composés à valoriser tel que le krypton et le xénon.In an air separation unit comprising a double column and wherein the oxygen gas is produced by pressurized vaporization in the exchange line (internal compression apparatus) in which it is intended to extract a krypton mixture xenon, it is found that the yield of this extraction decreases significantly because the pumped oxygen extracted from the low pressure distillation column leads with it a significant part of the compounds to be valued such as krypton and xenon.

Pour ce type d'appareil à compression interne, dans le cas de la production de krypton/xénon associé à une production d'argon plusieurs procédés permettant de remédier à cette problématique ont été imaginés.For this type of internal compression device, in the case of the production of krypton / xenon associated with argon production, several processes to overcome this problem have been devised.

L'invention se résume en deux étapes essentielles :

  1. 1. Appauvrissement de l'air gazeux entrant dans la colonne de séparation en composés à valoriser (krypton, xénon) par transfert de matière avec une portion réduite du liquide riche. Cette étape donne un liquide riche inférieur riche en krypton et xénon, de préférence 100 % du xénon contenu ainsi dans l'alimentation d'air gazeux étant extrait ainsi que plus de 80 % du krypton.
  2. 2. Concentration du liquide riche inférieur riche en krypton et en xénon, par vaporisation partielle dans un vaporiseur/condenseur. La source de chaleur utilisée pour vaporiser le liquide riche inférieur est de préférence un fluide de la colonne d'où provient le dit liquide riche inférieur, fluide provenant d'étage de distillation supérieure qui, en cédant sa chaleur, se condense dans le vaporiseur/condenseur. Le liquide ainsi produit alimente à un étage de distillation approprié la colonne basse pression. Le liquide riche inférieur produit, quant à lui, une phase vaporisée qui alimente la colonne basse pression à un étage de distillation approprié, et une purge où de préférence quasiment 100 % du xénon contenu dans l'alimentation y est extraite, par contre seulement 50 % environ du krypton y est présent
The invention is summarized in two essential steps:
  1. 1. Depletion of the gaseous air entering the separation column into compounds to be upgraded (krypton, xenon) by transfer of material with a reduced portion of the rich liquid. This step gives a rich lower liquid rich in krypton and xenon, preferably 100% of the xenon thus contained in the gaseous air supply being extracted as well as more than 80% of the krypton.
  2. 2. Concentration of the rich lower liquid rich in krypton and xenon, by partial vaporization in a vaporizer / condenser. The heat source used to vaporize the lower rich liquid is preferably a fluid from the column from which the said lower rich liquid comes from, a fluid coming from an upper distillation stage which, by yielding its heat, condenses in the vaporizer / condenser. The liquid thus produced feeds the low pressure column to a suitable distillation stage. The lower rich liquid produces, for its part, a vaporized phase which feeds the low pressure column to a suitable distillation stage, and a purge where preferably almost 100% of the xenon contained in the diet is extracted, however only about 50% of the krypton is present

La colonne basse pression est alimentée par la purge riche en krypton et en xénon produite par concentration. La purge riche en krypton et en xénon produite ci-dessus va alimenter la colonne basse pression, à un étage de distillation inférieur au soutirage de l'oxygène liquide destiné à être pompé pour être ensuite vaporisé dans l'échangeur principal. Le mélange final riche en krypton et en xénon est extraite du fond de la colonne basse pression afin d'y être traité ultérieurement.The low pressure column is fed by the purge rich in krypton and xenon produced by concentration. The krypton and xenon-rich purge produced above will supply the low pressure column with a distillation stage lower than the withdrawal of the liquid oxygen to be pumped and then vaporized in the main exchanger. The final mixture rich in krypton and xenon is extracted from the bottom of the low pressure column for further processing.

Optionnellement, dans le cas où le mélange krypton xénon est sous forme liquide, ce retour est injecté à l'aspiration de la pompe pour minimiser le soutirage OL de la colonne, et ainsi augmenter le rendement d'extraction du krypton et xénonOptionally, in the case where the krypton xenon mixture is in liquid form, this return is injected at the suction of the pump to minimize the withdrawal OL of the column, and thus increase the extraction yield of krypton and xenon

Un tel procédé permet d'extraire de l'ordre de 90 % du xénon présent dans l'air où un procédé conventionnel ne permet qu'un rendement de l'ordre 70 % au mieux. Quant au rendement d'extraction du krypton, celui-ci atteint environ 75 % alors que le rendement d'un appareil conventionnel ne permet au mieux qu'un rendement de l'ordre de 60 %.Such a method makes it possible to extract about 90% of the xenon present in the air, where a conventional method only allows a yield of about 70% at best. As for the extraction yield of krypton, it reaches about 75% while the performance of a conventional apparatus does not allow the better than a yield of the order of 60%.

Selon un objet de l'invention, il est prévu un procédé selon la revendication 1.According to one object of the invention, there is provided a method according to claim 1.

Selon des caractéristiques facultatives :

  • on envoie le gaz intermédiaire du vaporiseur à la colonne basse pression à un niveau supérieur au niveau intermédiaire ;
  • on vaporise le liquide enrichi en oxygène, en krypton et en xénon par échange de chaleur avec un gaz soutiré de la colonne moyenne pression ;
  • le gaz soutiré de la colonne moyenne pression est soutiré au-dessus du premier niveau ;
  • le liquide intermédiaire est envoyé du vaporiseur à un niveau intermédiaire de la colonne basse pression inférieur au troisième niveau ;
  • on soutire le deuxième débit liquide riche en oxygène (11) de la colonne basse pression à un quatrième niveau inférieur au niveau intermédiaire ;
  • le liquide intermédiaire est mélangé à un deuxième débit liquide riche en oxygène.
According to optional features:
  • the intermediate gas of the vaporizer is sent to the low pressure column at a level higher than the intermediate level;
  • the enriched oxygen, krypton and xenon-enriched liquid is vaporized by heat exchange with a gas withdrawn from the medium-pressure column;
  • the gas withdrawn from the medium pressure column is withdrawn above the first level;
  • the intermediate liquid is sent from the vaporizer to an intermediate level of the low pressure column below the third level;
  • withdrawing the second oxygen-rich liquid flow (11) from the low pressure column to a fourth level below the intermediate level;
  • the intermediate liquid is mixed with a second oxygen-rich liquid flow.

Selon un autre objet de l'invention, il est prévu un appareil selon la revendication 8.According to another object of the invention, there is provided an apparatus according to claim 8.

Eventuellement, l'appareil comprend :

  • des moyens pour envoyer le gaz intermédiaire du vaporiseur à la colonne basse pression à un niveau supérieur au niveau intermédiaire
  • des moyens pour envoyer un gaz soutiré de la colonne moyenne pression au vaporiseur
  • des moyens pour soutirer le gaz de la colonne moyenne pression est soutiré au-dessus du premier niveau
  • des moyens pour pressuriser et vaporiser le premier débit riche en oxygène, de préférence par échange de chaleur avec l'air à distiller
  • des moyens pour envoyer le liquide intermédiaire du vaporiseur à un niveau intermédiaire de la colonne basse pression inférieur au troisième niveau
  • des moyens pour soutirer le deuxième débit liquide riche en oxygène de la colonne basse pression à un quatrième niveau inférieur au niveau intermédiaire
  • des moyens pour mélanger le liquide intermédiaire à un deuxième débit liquide riche en oxygène
Optionally, the apparatus comprises:
  • means for sending the intermediate gas from the vaporizer to the low pressure column at a level above the intermediate level
  • means for sending a gas withdrawn from the medium pressure column to the vaporizer
  • means for withdrawing the gas from the medium pressure column is withdrawn above the first level
  • means for pressurizing and vaporizing the first flow rich in oxygen, preferably by heat exchange with the air to be distilled
  • means for sending the intermediate liquid of the vaporizer to an intermediate level of the low pressure column lower than the third level
  • means for withdrawing the second oxygen-rich liquid flow from the low pressure column to a fourth level below the intermediate level
  • means for mixing the intermediate liquid with a second oxygen-rich liquid flow

L'invention sera décrite en plus de détail en se référant à la figure.The invention will be described in more detail with reference to the figure.

Un débit d'air gazeux moyenne pression 1 est envoyé à la colonne moyenne pression 20 d'une double colonne de séparation d'air. La double colonne comprend aussi une colonne basse pression 21 couplée thermiquement avec la colonne moyenne pression 20 au moyen d'un vaporiseur 24, qui vaporise le liquide de cuve de la colonne basse pression par échange de chaleur avec l'azote gazeux de tête de la colonne moyenne pression.A medium pressure air flow 1 is sent to the medium pressure column 20 of a double air separation column. The double column also comprises a low pressure column 21 thermally coupled with the medium pressure column 20 by means of a vaporizer 24, which vaporizes the bottom liquid of the low pressure column by heat exchange with the nitrogen gas at the top of the middle column pressure.

Un débit d'air liquide à haute pression est détendu dans une vanne puis divisé en deux. Le débit 3 ainsi formé est envoyé à la colonne moyenne pression 20 quelques plateaux théoriques au dessus du point d'entrée du débit 1. Le reste de l'air liquide 4 est refroidi dans le sous-refroidisseur 26, détendu puis envoyé à la colonne basse pression 21.A flow of high pressure liquid air is expanded in a valve and then divided into two. The flow 3 thus formed is sent to the medium pressure column 20 a few theoretical trays above the entry point of the flow 1. The rest of the liquid air 4 is cooled in the subcooler 26, expanded and sent to the column low pressure 21.

Un débit de liquide riche inférieur 5 enrichi en oxygène, en krypton et en xénon est soutiré en cuve de la colonne moyenne pression 20, refroidi dans le sous-refroidisseur 26, puis détendu et envoyé à un vaporiseur 22 où il se vaporise partiellement par échange de chaleur avec de l'air gazeux enrichi en azote 8 provenant de la colonne moyenne pression 20. L'air gazeux est condensé pour former un débit 9 qui est ensuite envoyé à la colonne basse pression 21. Le liquide riche vaporisé 16 est détendu comme gaz intermédiaire et envoyé à la colonne basse pression alors que le liquide intermédiaire restant 7 est envoyé à la colonne basse pression 21 quelques plateaux au-dessus de la cuve. Un débit de liquide riche supérieur 6 est soutiré entre l'arrivée de l'air 1 et l'arrivée d'air 3 et/ou le soutirage du débit 8. Ce débit 6 est refroidi dans le sous-refroidisseur 26, mélangé avec le liquide riche vaporisé 16 et envoyé à la colonne basse pression 21. Du liquide pauvre enrichi en azote 15 est soutiré en tête de la colonne moyenne pression 20 et envoyé en tête de la colonne basse pression 21 après refroidissement et détente.A lower rich liquid flow rate enriched in oxygen, krypton and xenon is withdrawn in the vat of the medium pressure column 20, cooled in the subcooler 26, then expanded and sent to a vaporizer 22 where it is partially vaporized by exchange of heat with gaseous air enriched with nitrogen 8 from the medium pressure column 20. The gaseous air is condensed to form a flow 9 which is then sent to the low pressure column 21. The vaporized rich liquid 16 is expanded as intermediate gas and sent to the low pressure column while the remaining intermediate liquid 7 is sent to the low pressure column 21 a few trays above the tank. An upper rich liquid flow 6 is withdrawn between the inlet of the air 1 and the air inlet 3 and / or the withdrawal of the flow 8. This flow 6 is cooled in the subcooler 26, mixed with the rich liquid vaporized 16 and sent to the low pressure column 21. Poor liquid enriched in nitrogen 15 is withdrawn at the top of the medium pressure column 20 and sent to the top of the low pressure column 21 after cooling and expansion.

De l'oxygène liquide 10 est soutiré de la colonne basse pression 21 quelques plateaux au-dessus de la cuve et de préférence au-dessus de l'arrivée du liquide 7. Ce liquide est pompé par la pompe 23 pour servir de produit riche en oxygène.Liquid oxygen 10 is withdrawn from the low pressure column 21 a few trays above the tank and preferably above the arrival of the liquid 7. This liquid is pumped by the pump 23 to serve as a product rich in water. oxygen.

De l'oxygène liquide 11 enrichi en krypton et xénon est soutiré en cuve de la colonne basse pression 21 et est épuré ultérieurement pour produire un mélange de krypton et xénon.Liquid oxygen 11 enriched in krypton and xenon is withdrawn in the bottom of the low pressure column 21 and is subsequently purified to produce a mixture of krypton and xenon.

De l'azote basse pression 13 est soutiré en tête de la colonne basse pression 21, chauffé dans le sous-refroidisseur et chauffé contre les débits d'air 1,2 (chauffage non-illustré).Low pressure nitrogen 13 is withdrawn at the top of the low pressure column 21, heated in the subcooler and heated against the air flows 1.2 (heating not shown).

Equipements :Facilities:

20 Colonne moyenne pression, 21 Colonne basse pression, 22 Vaporiseur liquide riche inférieur, 23 Pompe oxygène liquide. 20 Medium pressure column, 21 Low pressure column, 22 Lower rich liquid vaporizer, 23 Liquid oxygen pump.

Fluides :Fluids:

1 Air gazeux moyenne pression, 2 Air liquide haute pression, 3 Air liquide détendu alimentant la colonne moyenne pression, 4 Air liquide détendu alimentant la colonne basse pression, 5 Liquide riche inférieur enrichie en krypton xénon, 16 Liquide riche inférieur vaporisé appauvri en krypton xénon, 7 Purge riche en krypton xénon, 8 Air pauvre extrait de la colonne moyenne pression, 9 Air pauvre liquide, 10 Oxygène liquide extrait de la colonne basse pression, 11 Oxygène liquide extrait de la colonne basse pression riche en krypton xénon. 1 Medium pressure gaseous air, 2 High pressure liquid air, 3 Relaxed liquid air supplying the medium pressure column, 4 Relaxed liquid air supplying the low pressure column, 5 Lower rich liquid enriched in krypton xenon, 16 Lower rich vaporized liquid depleted in krypton xenon , 7 Purge rich in krypton xenon, 8 Poor air extracted from the medium pressure column, 9 Poor liquid air, 10 Oxygen liquid extracted from the low pressure column, 11 Liquid oxygen extracted from the low pressure column rich in krypton xenon.

Claims (15)

  1. Process for producing krypton and xenon by separating air by cryogenic distillation in a double column comprising a medium pressure column (20) and a low pressure column (21), wherein:
    i) cooled and purified compressed gaseous air (1) is sent to a first level of the medium pressure column;
    ii) cooled and purified compressed liquid air (3) is sent to a second level of the medium pressure column, above the first level;
    iii) a liquid (5) enriched in oxygen, krypton and xenon is drawn off from the bottom of the medium pressure column;
    iv) a liquid (6) is drawn off from the medium pressure column at a level between the first and second levels and sent to the low pressure column;
    v) the liquid enriched in oxygen, krypton and xenon is partially vaporised to form an intermediate gas (16) and an intermediate liquid (7);
    vi) a first oxygen-rich liquid stream (10) is drawn off at a third level of the low pressure column, pressurised and vaporised;
    vii) the intermediate liquid is sent from the vaporiser to the low pressure column at an intermediate level of the low pressure column, lower than the third level, and
    viii) a second oxygen-rich liquid stream (11) is drawn off from the low pressure column at a fourth level, lower than the third level, and purified to produce a mixture of krypton and xenon.
  2. Process according to claim 1, wherein the vaporised intermediate gas (6) is sent to the low pressure column (21) at a level higher than the intermediate level.
  3. Process according to either claim 1 or claim 2, wherein the liquid enriched in oxygen, krypton and xenon (5) is vaporised by heat exchange with a gas (8) drawn off from the medium pressure column.
  4. Process according to claim 3, wherein the gas (8) drawn off from the medium pressure column is drawn off above the first level.
  5. Process according to any one of the preceding claims, wherein the intermediate liquid is sent from the vaporiser to an intermediate level of the low pressure column, lower than the third level.
  6. Process according to claim 5, wherein the second oxygen-rich liquid stream (11) is drawn off from the low pressure column at a fourth level, lower than the intermediate level.
  7. Process according to any one of claims 1 to 4, wherein the intermediate liquid is mixed with a second oxygen-rich liquid stream.
  8. Apparatus for separating air by cryogenic distillation comprising a double column formed by a medium pressure column (20) and a low pressure column (21) and a vaporiser (22) comprising:
    i) means for sending cooled and purified compressed gaseous air (3) to a first level of the medium pressure column;
    ii) means for sending cooled and purified compressed liquid air to a second level of the medium pressure column, above the first level;
    iii) means for drawing off a liquid (5) enriched in oxygen, krypton and xenon from the bottom of the medium pressure column;
    iv) means for drawing off a liquid from the medium pressure column at a level between the first and second levels and it is sent to the low pressure column;
    v) means for sending at least a portion of the liquid enriched in oxygen, krypton and xenon to the vaporiser, where it is partially vaporised to form an intermediate gas (16) and an intermediate liquid (7);
    vi) means for drawing off a first oxygen-rich liquid stream (10) at a third level of the low pressure column, means (23) for pressurising it and means for vaporising it;
    vii) means for sending the intermediate liquid from the vaporiser to the low pressure column at an intermediate level of the low pressure column and
    viii) means for drawing off a second oxygen-rich liquid stream from the low pressure column at a fourth level, lower than the third level, lower than the intermediate level, and means for purifying it to produce a mixture of krypton and xenon.
  9. Apparatus according to claim 8, comprising means for sending the intermediate gas from the vaporiser (22) to the low pressure column (21) at a level higher than the intermediate level.
  10. Apparatus according to either claim 8 or claim 9, comprising means for sending a gas drawn off from the medium pressure column (20) to the vaporiser (22).
  11. Apparatus according to claim 10, comprising means for drawing off the gas from the medium pressure column (20) above the first level.
  12. Apparatus according to claims 8 to 11, comprising means for pressurising and vaporising the first oxygen-rich stream, preferably by heat exchange with the air to be distilled.
  13. Apparatus according to any one of claims 8 to 12, comprising means for sending the intermediate liquid from the vaporiser to an intermediate level of the low pressure column, lower than the third level.
  14. Apparatus according to claim 13, comprising means for drawing off the second oxygen-rich liquid stream (11) from the low pressure column at a fourth level, lower than the intermediate level.
  15. Apparatus according to any one of claims 8 to 12, comprising means for mixing the intermediate liquid with a second oxygen-rich liquid stream.
EP09742279A 2008-04-23 2009-04-08 Apparatus and method for separating air by cryogenic distillation Not-in-force EP2279385B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0852727A FR2930629B1 (en) 2008-04-23 2008-04-23 APPARATUS AND METHOD FOR AIR SEPARATION BY CRYOGENIC DISTILLATION
PCT/FR2009/050625 WO2009136081A2 (en) 2008-04-23 2009-04-08 Apparatus and method for separating air by cryogenic distillation

Publications (2)

Publication Number Publication Date
EP2279385A2 EP2279385A2 (en) 2011-02-02
EP2279385B1 true EP2279385B1 (en) 2012-02-22

Family

ID=40042566

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09742279A Not-in-force EP2279385B1 (en) 2008-04-23 2009-04-08 Apparatus and method for separating air by cryogenic distillation

Country Status (8)

Country Link
US (1) US20110041552A1 (en)
EP (1) EP2279385B1 (en)
JP (1) JP2011519010A (en)
CN (1) CN102016470A (en)
AT (1) ATE546701T1 (en)
FR (1) FR2930629B1 (en)
WO (1) WO2009136081A2 (en)
ZA (1) ZA201007374B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6155515B2 (en) * 2014-06-24 2017-07-05 大陽日酸株式会社 Air separation method and air separation device
EP2993432A1 (en) * 2014-09-02 2016-03-09 Linde Aktiengesellschaft Method for the low-temperature decomposition of air and air separation plant
CN109520207B (en) * 2017-09-18 2022-04-08 乔治洛德方法研究和开发液化空气有限公司 Method and unit for separating air by cryogenic distillation
CN108302899A (en) * 2018-03-29 2018-07-20 浙江新锐空分设备有限公司 A kind of space division system and method extracting poor krypton xenon product using liquefied air
CN113465292B (en) * 2021-07-05 2023-02-21 乔治洛德方法研究和开发液化空气有限公司 Method for increasing yield of krypton/xenon in air rectification device

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5956974A (en) * 1998-01-22 1999-09-28 Air Products And Chemicals, Inc. Multiple expander process to produce oxygen
GB9902101D0 (en) * 1999-01-29 1999-03-24 Boc Group Plc Separation of air
FR2795496B1 (en) * 1999-06-22 2001-08-03 Air Liquide APPARATUS AND METHOD FOR SEPARATING AIR BY CRYOGENIC DISTILLATION
FR2807150B1 (en) * 2000-04-04 2002-10-18 Air Liquide PROCESS AND APPARATUS FOR PRODUCING OXYGEN ENRICHED FLUID BY CRYOGENIC DISTILLATION
FR2844039B1 (en) * 2002-09-04 2005-04-29 Air Liquide PROCESS AND PLANT FOR PRODUCING OXYGEN AND RARE GASES BY CRYOGENIC AIR DISTILLATION
US7296437B2 (en) * 2002-10-08 2007-11-20 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for separating air by cryogenic distillation and installation for implementing this process
US6662593B1 (en) * 2002-12-12 2003-12-16 Air Products And Chemicals, Inc. Process and apparatus for the cryogenic separation of air

Also Published As

Publication number Publication date
US20110041552A1 (en) 2011-02-24
FR2930629A1 (en) 2009-10-30
EP2279385A2 (en) 2011-02-02
WO2009136081A2 (en) 2009-11-12
JP2011519010A (en) 2011-06-30
WO2009136081A3 (en) 2010-04-08
FR2930629B1 (en) 2010-05-07
ATE546701T1 (en) 2012-03-15
ZA201007374B (en) 2011-06-29
CN102016470A (en) 2011-04-13

Similar Documents

Publication Publication Date Title
EP2279385B1 (en) Apparatus and method for separating air by cryogenic distillation
FR2685459A1 (en) PROCESS AND PLANT FOR PRODUCING IMPURED OXYGEN
FR2844039A1 (en) PROCESS AND PLANT FOR THE PRODUCTION OF OXYGEN AND RARE GASES BY CRYOGENIC AIR DISTILLATION
CA2830826C (en) Method and device for separating air by cryogenic distillation
EP1189003B1 (en) Process and apparatus for air separation by cryogenic distillation
EP3058297B1 (en) Method and device for separating air by cryogenic distillation
EP0732556B1 (en) Method and apparatus for vaporizing a liquid stream
EP1132700B1 (en) Process and apparatus for air separation by cryogenic distillation
CA2828716C (en) Device and method for separating air by cryogenic distillation
EP1106945B1 (en) Process for air separation by cryogenic distillation
EP1063485B1 (en) Device and process for air separation by cryogenic distillation
FR2787561A1 (en) Cryogenic distillation of air uses double column with air supply to medium pressure column and oxygen rich fluid from bottom of both low pressure and auxiliary columns
FR2787559A1 (en) Air separation using cryogenic distillation has double column receiving compressed, cooled, and expanded air to produce oxygen rich and nitrogen rich fractions
FR3020867A1 (en) METHOD AND APPARATUS FOR AIR SEPARATION BY CRYOGENIC DISTILLATION FOR THE PRODUCTION OF A MIXTURE OF KRYPTON AND XENON
FR3141995A3 (en) Process and apparatus for air separation by cryogenic distillation
FR3110685A1 (en) Method and apparatus for air separation by cryogenic distillation
FR2967244A3 (en) Method for separating air by cryogenic distillation, involves increasing pressure of oxygen enriched liquid downstream from tank of low pressure column and upstream of head of auxiliary column, where enriched liquid constitutes supply air
FR2844864A1 (en) Vaporization of a cryogenic liquid by heat exchange with water in a steam-heated pool involves using a water-cooling circuit having a compressor
FR2854232A1 (en) Air separation procedure to produce argon uses cryogenic distillation with additional liquid flow containing 18-30 mol percent oxygen fed to low pressure column
FR2974890A1 (en) Method for separating air by cryogenic distillation in installation, involves condensing part of nitrogen enriched gas flow before being sent to average pressure column and/or low pressure column, and heating gas flow rich in oxygen
FR2848652A1 (en) Cryogenic distillation procedure for producing argon includes condensation of flow containing at least 70 per cent mol. of nitrogen by indirect heat exchange with argon-rich liquid flow
FR2844863A1 (en) Vaporization of a cryogenic liquid by heat exchange with water in a steam-heated pool involves using a water-cooling circuit having a compressor

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20101123

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA RS

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 546701

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009005500

Country of ref document: DE

Effective date: 20120419

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120222

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20120222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120522

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120622

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120622

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120523

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 546701

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

BERE Be: lapsed

Owner name: L'AIR LIQUIDE S.A. POUR L'ETUDE ET L'EXPLOITATION

Effective date: 20120430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120430

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20121123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009005500

Country of ref document: DE

Effective date: 20121123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120522

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20130418

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20130515

Year of fee payment: 5

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090408

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20140408

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20141231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140430

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20180420

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602009005500

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191101