EP2504646B1 - Method and apparatus for cryogenically separating a mixture of nitrogen and carbon monoxide - Google Patents

Method and apparatus for cryogenically separating a mixture of nitrogen and carbon monoxide Download PDF

Info

Publication number
EP2504646B1
EP2504646B1 EP10792965.5A EP10792965A EP2504646B1 EP 2504646 B1 EP2504646 B1 EP 2504646B1 EP 10792965 A EP10792965 A EP 10792965A EP 2504646 B1 EP2504646 B1 EP 2504646B1
Authority
EP
European Patent Office
Prior art keywords
liquid
column
carbon monoxide
gas
phase separator
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.)
Active
Application number
EP10792965.5A
Other languages
German (de)
French (fr)
Other versions
EP2504646A2 (en
Inventor
Antoine Hernandez
Arthur Darde
Bernard Saulnier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
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 EP2504646A2 publication Critical patent/EP2504646A2/en
Application granted granted Critical
Publication of EP2504646B1 publication Critical patent/EP2504646B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204Processes 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 characterised by the feed stream
    • F25J3/0223H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes 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 characterised by the separated product stream
    • F25J3/0252Processes 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 characterised by the separated product stream separation of hydrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes 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 characterised by the separated product stream
    • F25J3/0257Processes 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 characterised by the separated product stream separation of nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes 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 characterised by the separated product stream
    • F25J3/0261Processes 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 characterised by the separated product stream separation of carbon monoxide
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/40Features relating to the provision of boil-up in the bottom of a column
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/74Refluxing the column with at least a part of the partially condensed overhead gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/02Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/42Nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/02Internal refrigeration with liquid vaporising loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/04Internal refrigeration with work-producing gas expansion loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/24Quasi-closed internal or closed external carbon monoxide refrigeration cycle
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/90External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34Details about subcooling of liquids
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/80Retrofitting, revamping or debottlenecking of existing plant

Definitions

  • the present invention relates to a method and apparatus for cryogenic separation of a mixture of nitrogen and carbon monoxide, according to the preambles of claims 1 and 4 respectively and known from the document DE-A-2,147,465 .
  • the most common cryogenic process is methane scrubbing
  • the residual methane content in the synthesis gas is compatible with the methane washing process.
  • a methane scrubbing scheme with a CO / N 2 column is described in FR-A-2910603 .
  • the synthesis gas produced is treated in a cold box by partial condensation without a cycle, the inert content (CH 4 , Ar and N 2 ) being very low and compatible with the purity of the product. CO.
  • a partial condensation scheme with a CO / N 2 column is described in US-A-4478621 .
  • the reboiling of the column CO / N 2 is provided by a direct supply of CO at medium pressure in the bottom of the column coming from the compressor CO.
  • the apparatus according to the invention is a partial condensation apparatus including a CO / N 2 column with a common integrated cycle for the cooling of the synthesis gas and for the separation energy CO / N 2 .
  • At least a portion of the reboiling energy of the CO / N 2 column is provided by an external reboiler where the feed gas of the CO / N 2 column is condensed totally or partially. This makes it possible to reduce the MPCO flow rate of the cycle compressor and thus reduce the energy of the compressor by about 15%.
  • the process scheme may include a CO / N 2 distillation column alone or a CO / N 2 column with a CO / CH 4 column.
  • This invention can also be applied when it is desired to invest a CO / N 2 separation column treating impure CO coming from a cold box which does not comprise a CO / N 2 column. As the nitrogen content in CO increases over time, it then becomes necessary to add a CO / N 2 separation step. The new column is then installed in a dedicated cold box that must be supplied with frigories and reboiling energy.
  • DE-A-4228784 and DE-A-2147465 describe processes comprising the features of the preamble of claim 1 and similar to that of Figure 1 .
  • a flow of nitrogen and carbon monoxide 1 is cooled in an exchanger 3. It is condensed at least partially in a reboiler 5 fed by the liquid column of the column 15. The vaporized liquid is returned to the column.
  • the at least partially condensed flow rate is expanded in a valve 7 and sent to a phase separator 9. the liquid 11 of the phase separator and the gas 13 of the phase separator 9 are sent to the column at different heights or not.
  • the bottom liquid of the column is expanded in a valve 19 and sent to the head condenser 23 forming part of the column.
  • a nitrogen flow is removed as a purge and heats up in the exchanger 3.
  • the vaporized carbon monoxide 27 also heats up in the exchanger 3 and is compressed in the first stage 29 of a compressor. It is cooled in a cooler 31 by water and then divided in two. The flow 33 cools to an intermediate temperature in the exchanger 3 to form the flow 45 which is sent to the bottom of the column 15. The flow 41 is cooled very partially in the exchanger 3, expanded in a turbine 43 and The remainder of the carbon monoxide is compressed at the product pressure by the compressor stage 37 and cooled by the cooler 31A to form the product flow 39.
  • the stage 29 is all the more small part of the reboil is provided by flow 1.
  • a flow of nitrogen, hydrogen and carbon monoxide 1 is cooled in an exchanger 3 and then in a heat exchanger 3A.
  • the flow 1 is sent to a first phase separator 51 where it separates into a flow rate 53 rich in hydrogen and a liquid flow 57.
  • the flow 53 is heated in the exchangers 3,3A and the flow 57 is expanded in a valve 55 and then sent to a second phase separator 61.
  • the gas of the second separator of phases is heated in the heat exchangers 3,3A to form the flow 77.
  • the liquid 63 is separated in two.
  • a portion 67 is expanded in a valve 69, sent to a phase separator 71 and then the flow rates 73,75 are sent to the distillation column 15.
  • the remainder 65 of the liquid of the separator 61 is heated in the exchanger 3A to forming the flow 65 which serves to heat the reboiler 5 fed by the tank liquid 17 of the column 15. Having served to reboil the column, the flow 65 is expanded in the valve 7, sent to the separator 9 and then to the column of the same way as for the Figure 1 .
  • a nitrogen flow is removed as a purge and heats up in the exchanger 3.
  • the vaporized carbon monoxide 27 also heats up in the exchanger 3 and is compressed in the first stage 29 of a compressor. It is cooled in a cooler 31 by water and then divided in two.
  • the flow 33 cools to an intermediate temperature in the exchanger 3 and is divided in two to form the flow 133.
  • This flow 133 is cooled in the exchanger 135 against liquid nitrogen 137.
  • the liquid nitrogen 137 vaporizes and heats in the exchanger 3.
  • the flow 133 is expanded and mixed with the flow 21 downstream of the valve 19.
  • the flow 45 is sent to the bottom of the column 5 after cooling in the exchanger 3A.
  • the liquid carbon monoxide 79 is withdrawn from the condenser 23, expanded in the valve 81, sent to the phase separator 83 to produce a liquid portion and a gas portion.
  • the liquid portion 85 vaporizes in the exchange line 3A and the gas 87 is mixed with the flow rate of carbon monoxide 27 for the compressor 29.
  • a flow of nitrogen, hydrogen and carbon monoxide 1 is cooled in an exchanger 3 and then in a heat exchanger 3A.
  • the flow 1 is sent to a first phase separator 51 where it separates into a gaseous flow 53 rich in hydrogen and a liquid flow 57.
  • the flow 53 is heated in the exchangers 3,3A and the flow 57 is expanded in a valve 55 and then sent to a second phase separator 61.
  • the gas of the second phase separator heats up in the exchangers 3,3A to form the flow 77.
  • the liquid 63 is separated in two.
  • a portion 67 is expanded in a valve 69, sent to a phase separator 71 and then the flow rates 73,75 are sent to the distillation column 5.
  • the remainder 65 of the liquid of the separator 61 is heated in the exchanger 3A to forming the flow 65 which serves to heat the reboiler 5 fed by the tank liquid 17 of the column 5. Having served to reboil the column the flow 65 is expanded in the valve 7, sent to the separator 9 and then to the column of the same way as for the Figure 1 .
  • a nitrogen flow is removed as a purge and is heated in the exchanger 3.
  • the vaporized carbon monoxide enriched flow 27 also warms up in the exchanger 3 and is compressed in the first stage 29 of a compressor. It is cooled in a cooler 31 by water and then divided in two.
  • the flow 33 cools to an intermediate temperature in the exchanger 3 and is divided in two to form the flow 93.
  • This flow 93 is expanded in the turbine 91 to form the expanded flow 93 which is mixed with the flow 27 for to heat up in the exchanger 3.
  • the flow 45 from the stage 29 is sent to the bottom of the column 5 after cooling in the exchanger 3A.
  • the liquid carbon monoxide 79 is withdrawn from the condenser 23, expanded in the valve 81, sent to the phase separator 83 to produce a liquid portion and a gas portion.
  • the liquid portion 85 vaporizes in the exchange line 3A and the gas 87 is mixed with the flow rate of carbon monoxide 27 for the compressor 29.

Description

La présente invention est relative à un procédé et à un appareil de séparation cryogénique d'un mélange d'azote et de monoxyde de carbone, conformément aux préambules des revendications 1 et 4 respectivement et connu du document DE-A-2 147 465 .The present invention relates to a method and apparatus for cryogenic separation of a mixture of nitrogen and carbon monoxide, according to the preambles of claims 1 and 4 respectively and known from the document DE-A-2,147,465 .

Les unités de production de monoxyde de carbone et d'hydrogène peuvent être séparées en deux parties :

  • génération du gaz de synthèse (mélange contenant H2, CO, CH4, CO2, Ar et N2 essentiellement). Parmi les diverses voies industrielles de production de gaz de synthèse, celle à base de gazéification de charbon semble se développer de plus en plus notamment dans les pays riches en dépôts de charbon comme la Chine. Le procédé d'oxydation partielle du gaz naturel peut s'avérer également intéressant pour la production de CO seul ou avec des rapports de production H2/CO faible. Une autre voie est le reformage à la vapeur.
  • purification du gaz de synthèse. On retrouve :
  • une unité de lavage avec un solvant liquide pour éliminer la plus grande partie des gaz acides contenus dans le gaz de synthèse
  • une unité d'épuration sur lit d'adsorbants.
  • une unité de séparation par voie cryogénique dite boite froide pour la production de CO.
The production units for carbon monoxide and hydrogen can be separated into two parts:
  • generation of the synthesis gas (mixture containing H 2 , CO, CH 4 , CO 2 , Ar and N 2 essentially). Among the various synthetic gas production industries, the one based on coal gasification seems to develop more and more particularly in countries rich in coal deposits such as China. The partial oxidation process of natural gas can also be interesting for the production of CO alone or with low H 2 / CO production ratios. Another way is steam reforming.
  • purification of the synthesis gas . We find :
  • a washing unit with a liquid solvent to remove most of the acid gases contained in the synthesis gas
  • an adsorbent bed purification unit.
  • cryogenic separation unit called cold box for the production of CO.

Dans le cas d'un gaz de synthèse issu d'un four de reformage à la vapeur, pour la production de CO et d'hydrogène sous pression, le procédé cryogénique le plus fréquent est le lavage au méthane, la teneur résiduelle en méthane dans le gaz de synthèse étant compatible avec le procédé lavage au méthane. Dans certains cas il est nécessaire d'inclure une colonne de séparation CO/N2 dans la boite froide notamment quand la teneur en azote dans le gaz naturel n'est pas compatible avec la pureté du produit CO sans cette colonne CO/N2.In the case of synthesis gas from a steam reforming furnace, for the production of CO and hydrogen under pressure, the most common cryogenic process is methane scrubbing, the residual methane content in the synthesis gas is compatible with the methane washing process. In some cases it is necessary to include a CO / N 2 separation column in the cold box, especially when the nitrogen content in the natural gas is not compatible with the purity of the CO product without this CO / N 2 column.

Un schéma lavage au méthane avec colonne CO/N2 est décrit dans FR-A-2910603 .A methane scrubbing scheme with a CO / N 2 column is described in FR-A-2910603 .

Dans le cas de certains procédé de gazéification de charbon, le gaz de synthèse produit est traité dans une boite froide par condensation partielle sans cycle, la teneur en inertes (CH4, Ar et N2) étant très faible et compatible avec la pureté du CO.In the case of some coal gasification process, the synthesis gas produced is treated in a cold box by partial condensation without a cycle, the inert content (CH 4 , Ar and N 2 ) being very low and compatible with the purity of the product. CO.

Un schéma condensation partielle sans colonne de séparation est décrit dans EP-A-1729077 et dans FR-A-2930332 .A partial condensation scheme without a separation column is described in EP-A-1729077 and in FR-A-2930332 .

Un schéma de condensation partielle avec une colonne CO/N2 est décrit dans US-A- 4478621 . Le rebouillage de la colonne CO/N2 étant apporté par une alimentation directe de CO à moyenne pression en cuve de colonne venant du compresseur CO.A partial condensation scheme with a CO / N 2 column is described in US-A-4478621 . The reboiling of the column CO / N 2 is provided by a direct supply of CO at medium pressure in the bottom of the column coming from the compressor CO.

Dans le cas où la teneur en méthane dans le gaz de synthèse ne permet pas un procédé de lavage au méthane dans la production combinée de CO et d'hydrogène et où la teneur en azote dans le gaz de synthèse n'est pas compatible avec la pureté de CO sans séparation CO/N2, l'appareil selon l'invention est un appareil de condensation partielle incluant une colonne CO/N2 avec cycle intégré commun pour le refroidissement du gaz de synthèse et pour l'énergie de séparation CO/N2.In the case where the methane content in the synthesis gas does not allow a methane scrubbing process in the combined production of CO and hydrogen and where the nitrogen content in the synthesis gas is not compatible with the CO purity without CO / N 2 separation, the apparatus according to the invention is a partial condensation apparatus including a CO / N 2 column with a common integrated cycle for the cooling of the synthesis gas and for the separation energy CO / N 2 .

Au moins une partie de l'énergie de rebouillage de la colonne CO/N2 est apportée par un rebouilleur externe où le gaz d'alimentation de la colonne CO/N2 est condensé totalement ou partiellement. Cela permet de réduire le débit MPCO du compresseur de cycle et ainsi réduire l'énergie du compresseur de l'ordre de 15%.At least a portion of the reboiling energy of the CO / N 2 column is provided by an external reboiler where the feed gas of the CO / N 2 column is condensed totally or partially. This makes it possible to reduce the MPCO flow rate of the cycle compressor and thus reduce the energy of the compressor by about 15%.

Le schéma de procédé peut inclure une colonne de distillation CO/N2 seule ou bien une colonne CO/N2 avec une colonne CO/CH4.The process scheme may include a CO / N 2 distillation column alone or a CO / N 2 column with a CO / CH 4 column.

Cette invention peut s'appliquer également lorsque l'on souhaite investir une colonne de séparation CO/N2 traitant du CO impur venant d'une boite froide qui ne comprend pas de colonne CO/N2. La teneur d'azote dans le CO augmentant dans le temps, il devient alors nécessaire de rajouter une étape de séparation CO/N2. La nouvelle colonne est alors installée dans une boite froide dédiée qu'il faut alimenter en frigories et en énergie de rebouillage.This invention can also be applied when it is desired to invest a CO / N 2 separation column treating impure CO coming from a cold box which does not comprise a CO / N 2 column. As the nitrogen content in CO increases over time, it then becomes necessary to add a CO / N 2 separation step. The new column is then installed in a dedicated cold box that must be supplied with frigories and reboiling energy.

DE-A-4228784 et DE-A-2147465 décrivent des procédés comprenant les caractéristiques du préambule de la revendication 1 et similaires à celui de la Figure 1. DE-A-4228784 and DE-A-2147465 describe processes comprising the features of the preamble of claim 1 and similar to that of Figure 1 .

Selon un objet de l'invention, il est prévu un procédé de séparation d'un gaz d'alimentation contenant comme composants principaux de l'azote et du monoxyde de carbone et éventuellement de l'hydrogène dans une colonne de distillation dans lequel :

  1. i) on refroidit le gaz d'alimentation dans un échangeur de chaleur (3)
  2. ii) on envoie au moins une partie d'un gaz dérivé du gaz d'alimentation à un rebouilleur de cuve de la colonne de distillation afin de la condenser au moins partiellement en produisant un liquide et éventuellement un gaz
  3. iii) on envoie au moins une partie du liquide et éventuellement au moins une partie du gaz à la colonne
  4. iv) on soutire un débit enrichi en azote gazeux de la colonne
  5. v) on soutire un débit enrichi en monoxyde de carbone de la colonne, on le réchauffe dans l'échangeur de chaleur caractérisé en ce que l'on comprime le débit enrichi en monoxyde de carbone pour fournir un produit enrichi en monoxyde de carbone à une pression de production, on envoie le gaz d'alimentation après refroidissement dans un premier séparateur de phases, on détend le liquide du premier séparateur de phases , on envoie le liquide détendu dans un deuxième séparateur de phases et on vaporise au moins une partie du liquide du deuxième séparateur de phases pour dériver le gaz à envoyer au rebouilleur.
According to one object of the invention, there is provided a method for separating a feed gas containing, as main components, nitrogen and carbon monoxide and optionally hydrogen in a distillation column in which:
  1. i) the feed gas is cooled in a heat exchanger (3)
  2. ii) at least a portion of a gas derived from the feed gas is sent to a bottom reboiler of the distillation column in order to condense it at least partially by producing a liquid and optionally a gas
  3. iii) at least a portion of the liquid and at least a portion of the gas is sent to the column
  4. iv) a flow enriched in nitrogen gas from the column is withdrawn
  5. v) a carbon monoxide enriched flow is withdrawn from the column, it is heated in the heat exchanger characterized in that the carbon monoxide enriched flow is compressed to provide a product enriched in carbon monoxide at a rate of production pressure, the feed gas is sent after cooling in a first phase separator, the liquid is depressurized from the first phase separator, the expanded liquid is sent to a second phase separator and at least a portion of the liquid is vaporized the second phase separator for diverting the gas to be sent to the reboiler.

Eventuellement :

  • on comprime une partie du monoxyde de carbone à une pression inférieure ou égale à la pression de production, on la refroidit dans l'échangeur de chaleur et on l'envoie en cuve de la colonne de distillation.
  • on vaporise l'au moins une partie du liquide du deuxième séparateur de phases dans l'échangeur de chaleur.
Eventually :
  • a portion of the carbon monoxide is compressed at a pressure less than or equal to the production pressure, cooled in the heat exchanger and sent to the bottom of the distillation column.
  • the at least a portion of the liquid of the second phase separator is vaporized in the heat exchanger.

Selon un autre aspect de l'invention, il est prévu un appareil de séparation d'un gaz d'alimentation contenant comme composants principaux de l'azote et du monoxyde de carbone et éventuellement de l'hydrogène comprenant :

  1. i) une colonne de distillation ayant un rebouilleur de cuve et éventuellement un condenseur de tête
  2. ii) un échangeur de chaleur
  3. iii) un compresseur
  4. iv) des moyens pour envoyer le gaz d'alimentation dans l'échangeur de chaleur
  5. v) des moyens pour envoyer au moins une partie d'un gaz dérivé du gaz d'alimentation au rebouilleur afin de la condenser au moins partiellement en produisant un liquide et éventuellement un gaz
  6. vi) au moins des moyens pour envoyer au moins une partie du liquide et éventuellement au moins une partie du gaz à la colonne
  7. vii) des moyens pour soutirer un débit enrichi en azote gazeux de la colonne
  8. viii)des moyens pour soutirer un débit enrichi en monoxyde de carbone de la colonne et pour l'envoyer à l'échangeur de chaleur caractérisé en ce qu'il comprend des moyens pour envoyer le débit enrichi en monoxyde de carbone au compresseur pour fournir un produit enrichi en monoxyde de carbone à une pression de production, un premier séparateur de phases (51), un deuxième séparateur de phases, des moyens pour envoyer le gaz d'alimentation refroidi dans le premier séparateur de phases, une vanne de détente pour détendre le liquide du premier séparateur de phases, des moyens pour envoyer le liquide détendu dans le deuxième séparateur de phases et des moyens pour vaporiser au moins une partie du liquide du deuxième séparateur de phases pour dériver le gaz à envoyer au rebouilleur .
According to another aspect of the invention, there is provided an apparatus for separating a feed gas containing as main components nitrogen and carbon monoxide and optionally hydrogen comprising:
  1. i) a distillation column having a bottom reboiler and optionally a top condenser
  2. ii) a heat exchanger
  3. iii) a compressor
  4. iv) means for sending the feed gas into the heat exchanger
  5. v) means for sending at least a portion of a gas derived from the feed gas to the reboiler in order to condense it at least partially by producing a liquid and optionally a gas
  6. vi) at least means for sending at least a portion of the liquid and optionally at least a portion of the gas to the column
  7. vii) means for withdrawing a flow enriched in gaseous nitrogen from the column
  8. viii) means for withdrawing a carbon monoxide enriched flow from the column and for sending it to the heat exchanger, characterized in that it comprises means for sending the flow enriched in carbon monoxide to the compressor to provide a product enriched in carbon monoxide at a production pressure, a first phase separator (51), a second phase separator, means for sending the cooled feed gas into the first phase separator, an expansion valve to relax the liquid of the first phase separator, means for sending the expanded liquid to the second phase separator and means for vaporizing at least a portion of the liquid of the second phase separator to divert the gas to be sent to the reboiler.

Optionnellement, l'appareil comprend :

  • des moyens pour envoyer une partie du débit enrichi en monoxyde de carbone à une pression inférieure ou égale à la pression de production à l'échangeur de chaleur et ensuite en cuve de la colonne de distillation .
  • l'échangeur de chaleur est relié à la colonne et au deuxième séparateur de phases afin de vaporiser au moins une partie du liquide du deuxième séparateur pour dériver le gaz de chauffage du rebouilleur de cuve
  • la colonne de distillation comprend un condenseur de tête.
  • des moyens pour envoyer le liquide de cuve de la colonne au condenseur de tête.
  • des moyens pour envoyer le liquide de cuve vaporisé au compresseur.
Optionally, the apparatus comprises:
  • means for sending a portion of the carbon monoxide enriched flow at a pressure less than or equal to the production pressure to the heat exchanger and then in the distillation column.
  • the heat exchanger is connected to the column and the second phase separator to vaporize at least a portion of the liquid of the second separator to divert the heating gas from the reboiler
  • the distillation column comprises a top condenser.
  • means for sending the tank liquid from the column to the overhead condenser.
  • means for sending the vaporized tank liquid to the compressor.

L'invention sera décrite en plus de détails en se référant aux figures qui représentent un appareil de séparation substantiellement selon l'art antérieur d'un gaz ayant comme composants principaux de l'azote et du monoxyde de carbone pour la Figure 1 et un appareil de séparation selon l'invention d'un gaz ayant comme composants principaux de l'azote, de l'hydrogène et du monoxyde de carbone pour les Figures 2 et 3.The invention will be described in more detail with reference to the figures which show a substantially prior art separation apparatus of a gas having as main components nitrogen and carbon monoxide for the Figure 1 and a separation apparatus according to the invention of a gas having as main components nitrogen, hydrogen and carbon monoxide for Figures 2 and 3 .

Selon la Figure 1, un débit d'azote et de monoxyde de carbone 1 est refroidi dans un échangeur 3. Il se condense au moins partiellement dans un rebouilleur 5 alimenté par le liquide de cuve de la colonne 15. Le liquide vaporisé est renvoyé à la colonne. Le débit au moins partiellement condensé est détendu dans une vanne 7 et envoyé à un séparateur de phases 9. le liquide 11 du séparateur de phases et le gaz 13 du séparateur de phases 9 sont envoyés à la colonne à des hauteurs différentes ou pas. Le liquide de cuve de la colonne est détendu dans une vanne 19 et envoyé au condenseur de tête 23 faisant partie de la colonne. Un débit d'azote est enlevé comme purge 25 et se réchauffe dans l'échangeur 3. Le monoxyde de carbone vaporisé 27 se réchauffe également dans l'échangeur 3 et est comprimé dans la première étage 29 d'un compresseur. Il est refroidi dans un refroidisseur 31 par de l'eau et ensuite divisé en deux. Le débit 33 se refroidit jusqu'à une température intermédiaire dans l'échangeur 3 pour former le débit 45 qui est envoyé en cuve de la colonne 15. Le débit 41 est refroidi très partiellement dans l'échangeur 3, détendu dans une turbine 43 et remélangé avec le débit 27. Le reste 35 du monoxyde de carbone est comprimé à la pression de produit par l'étage 37 du compresseur et refroidi par le refroidisseur 31A pour former le débit produit 39. L'étage 29 se trouve d'autant plus petite qu'une partie du rebouillage est fournie par le débit 1.According to Figure 1 a flow of nitrogen and carbon monoxide 1 is cooled in an exchanger 3. It is condensed at least partially in a reboiler 5 fed by the liquid column of the column 15. The vaporized liquid is returned to the column. The at least partially condensed flow rate is expanded in a valve 7 and sent to a phase separator 9. the liquid 11 of the phase separator and the gas 13 of the phase separator 9 are sent to the column at different heights or not. The bottom liquid of the column is expanded in a valve 19 and sent to the head condenser 23 forming part of the column. A nitrogen flow is removed as a purge and heats up in the exchanger 3. The vaporized carbon monoxide 27 also heats up in the exchanger 3 and is compressed in the first stage 29 of a compressor. It is cooled in a cooler 31 by water and then divided in two. The flow 33 cools to an intermediate temperature in the exchanger 3 to form the flow 45 which is sent to the bottom of the column 15. The flow 41 is cooled very partially in the exchanger 3, expanded in a turbine 43 and The remainder of the carbon monoxide is compressed at the product pressure by the compressor stage 37 and cooled by the cooler 31A to form the product flow 39. The stage 29 is all the more small part of the reboil is provided by flow 1.

Selon la Figure 2, un débit d'azote, d'hydrogène et de monoxyde de carbone 1 se refroidit dans un échangeur 3 et ensuite dans un échangeur 3A. Le débit 1 est envoyé à un premier séparateur de phases 51 où il se sépare en un débit gazeux 53 riche en hydrogène et un débit liquide 57. Le débit 53 se réchauffe dans les échangeurs 3,3A et le débit 57 est détendu dans une vanne 55 et ensuite envoyé à un deuxième séparateur de phases 61. Le gaz du deuxième séparateur de phases se réchauffe dans les échangeurs 3,3A pour former le débit 77. Le liquide 63 est séparé en deux. Une partie 67 est détendue dans une vanne 69, envoyée à un séparateur de phases 71 et ensuite les débits formés 73,75 sont envoyés à la colonne de distillation 15. Le reste 65 du liquide du séparateur 61 est réchauffé dans l'échangeur 3A pour former le débit 65 qui sert à chauffer le rebouilleur 5 alimenté par le liquide de cuve 17 de la colonne 15. Ayant servi à rebouillir la colonne, le débit 65 est détendu dans la vanne 7, envoyé au séparateur 9 et ensuite à la colonne de la même manière que pour la Figure 1.According to Figure 2 a flow of nitrogen, hydrogen and carbon monoxide 1 is cooled in an exchanger 3 and then in a heat exchanger 3A. The flow 1 is sent to a first phase separator 51 where it separates into a flow rate 53 rich in hydrogen and a liquid flow 57. The flow 53 is heated in the exchangers 3,3A and the flow 57 is expanded in a valve 55 and then sent to a second phase separator 61. The gas of the second separator of phases is heated in the heat exchangers 3,3A to form the flow 77. The liquid 63 is separated in two. A portion 67 is expanded in a valve 69, sent to a phase separator 71 and then the flow rates 73,75 are sent to the distillation column 15. The remainder 65 of the liquid of the separator 61 is heated in the exchanger 3A to forming the flow 65 which serves to heat the reboiler 5 fed by the tank liquid 17 of the column 15. Having served to reboil the column, the flow 65 is expanded in the valve 7, sent to the separator 9 and then to the column of the same way as for the Figure 1 .

Un débit d'azote est enlevé comme purge 25 et se réchauffe dans l'échangeur 3. Le monoxyde de carbone vaporisé 27 se réchauffe également dans l'échangeur 3 et est comprimé dans la première étage 29 d'un compresseur. Il est refroidi dans un refroidisseur 31 par de l'eau et ensuite divisé en deux. Le débit 33 se refroidit jusqu'à une température intermédiaire dans l'échangeur 3 et est divisé en deux pour former le débit 133. Ce débit 133 se refroidit dans l'échangeur 135 contre de l'azote liquide 137. L'azote liquide 137 se vaporise et se réchauffe dans l'échangeur 3. Le débit 133 est détendu et mélangé avec le débit 21 en aval de la vanne 19. Le débit 45 est envoyé en cuve de la colonne 5 après refroidissement dans l'échangeur 3A.A nitrogen flow is removed as a purge and heats up in the exchanger 3. The vaporized carbon monoxide 27 also heats up in the exchanger 3 and is compressed in the first stage 29 of a compressor. It is cooled in a cooler 31 by water and then divided in two. The flow 33 cools to an intermediate temperature in the exchanger 3 and is divided in two to form the flow 133. This flow 133 is cooled in the exchanger 135 against liquid nitrogen 137. The liquid nitrogen 137 vaporizes and heats in the exchanger 3. The flow 133 is expanded and mixed with the flow 21 downstream of the valve 19. The flow 45 is sent to the bottom of the column 5 after cooling in the exchanger 3A.

Le monoxyde de carbone liquide 79 est soutiré du condenseur 23, détendu dans la vanne 81, envoyé au séparateur de phases 83 pour produire une partie liquide et une partie gazeuse. La partie liquide 85 se vaporise dans la ligne d'échange 3A et le gaz 87 est mélangé au débit de monoxyde de carbone 27 destiné au compresseur 29.The liquid carbon monoxide 79 is withdrawn from the condenser 23, expanded in the valve 81, sent to the phase separator 83 to produce a liquid portion and a gas portion. The liquid portion 85 vaporizes in the exchange line 3A and the gas 87 is mixed with the flow rate of carbon monoxide 27 for the compressor 29.

Selon la Figure 3, un débit d'azote, d'hydrogène et de monoxyde de carbone 1 se refroidit dans un échangeur 3 et ensuite dans un échangeur 3A. Le débit 1 est envoyé à un premier séparateur de phases 51 où il se sépare en un débit gazeux 53 riche en hydrogène et un débit liquide 57. Le débit 53 se réchauffe dans les échangeurs 3,3A et le débit 57 est détendu dans une vanne 55 et ensuite envoyé à un deuxième séparateur de phases 61. Le gaz du deuxième séparateur de phases se réchauffe dans les échangeurs 3,3A pour former le débit 77. Le liquide 63 est séparé en deux. Une partie 67 est détendue dans une vanne 69, envoyée à un séparateur de phases 71 et ensuite les débits formés 73,75 sont envoyés à la colonne de distillation 5. Le reste 65 du liquide du séparateur 61 est réchauffé dans l'échangeur 3A pour former le débit 65 qui sert à chauffer le rebouilleur 5 alimenté par le liquide de cuve 17 de la colonne 5. Ayant servi à rebouillir la colonne le débit 65 est détendu dans la vanne 7, envoyé au séparateur 9 et ensuite à la colonne de la même manière que pour la Figure 1.According to Figure 3 a flow of nitrogen, hydrogen and carbon monoxide 1 is cooled in an exchanger 3 and then in a heat exchanger 3A. The flow 1 is sent to a first phase separator 51 where it separates into a gaseous flow 53 rich in hydrogen and a liquid flow 57. The flow 53 is heated in the exchangers 3,3A and the flow 57 is expanded in a valve 55 and then sent to a second phase separator 61. The gas of the second phase separator heats up in the exchangers 3,3A to form the flow 77. The liquid 63 is separated in two. A portion 67 is expanded in a valve 69, sent to a phase separator 71 and then the flow rates 73,75 are sent to the distillation column 5. The remainder 65 of the liquid of the separator 61 is heated in the exchanger 3A to forming the flow 65 which serves to heat the reboiler 5 fed by the tank liquid 17 of the column 5. Having served to reboil the column the flow 65 is expanded in the valve 7, sent to the separator 9 and then to the column of the same way as for the Figure 1 .

Un débit d'azote est enlevé comme purge 25 et se réchauffe dans l'échangeur 3. Le débit enrichi en monoxyde de carbone vaporisé 27 se réchauffe également dans l'échangeur 3 et est comprimé dans la première étage 29 d'un compresseur. Il est refroidi dans un refroidisseur 31 par de l'eau et ensuite divisé en deux. Le débit 33 se refroidit jusqu'à une température intermédiaire dans l'échangeur 3 et est divisé en deux pour former le débit 93. Ce débit 93 se détendu dans la turbine 91 pour former le débit détendu 93 qui est mélangé avec le débit 27 pour se réchauffer dans l'échangeur 3. Le débit 45 provenant de l'étage 29 est envoyé en cuve de la colonne 5 après refroidissement dans l'échangeur 3A.A nitrogen flow is removed as a purge and is heated in the exchanger 3. The vaporized carbon monoxide enriched flow 27 also warms up in the exchanger 3 and is compressed in the first stage 29 of a compressor. It is cooled in a cooler 31 by water and then divided in two. The flow 33 cools to an intermediate temperature in the exchanger 3 and is divided in two to form the flow 93. This flow 93 is expanded in the turbine 91 to form the expanded flow 93 which is mixed with the flow 27 for to heat up in the exchanger 3. The flow 45 from the stage 29 is sent to the bottom of the column 5 after cooling in the exchanger 3A.

Le monoxyde de carbone liquide 79 est soutiré du condenseur 23, détendu dans la vanne 81, envoyé au séparateur de phases 83 pour produire une partie liquide et une partie gazeuse. La partie liquide 85 se vaporise dans la ligne d'échange 3A et le gaz 87 est mélangé au débit de monoxyde de carbone 27 destiné au compresseur 29.The liquid carbon monoxide 79 is withdrawn from the condenser 23, expanded in the valve 81, sent to the phase separator 83 to produce a liquid portion and a gas portion. The liquid portion 85 vaporizes in the exchange line 3A and the gas 87 is mixed with the flow rate of carbon monoxide 27 for the compressor 29.

Claims (9)

  1. Method for separating a feed gas containing, as the main components, nitrogen and carbon monoxide and optionally hydrogen in a distillation column (15) wherein:
    i) the feed gas is cooled in a heat exchanger (3)
    ii) at least part of a gas derived from the feed gas is sent to a vessel reboiler (5) of the distillation column in order to at least partially condense it, producing a liquid and optionally a gas
    iii) at least part of the liquid and optionally at least part of the gas is sent to the column
    iv) a flow enriched with gaseous nitrogen is drawn off from the column
    v) a flow enriched with carbon monoxide is drawn off from the column and is heated in the heat exchanger, characterised in that the flow enriched with carbon monoxide is compressed in order to supply a product enriched with carbon monoxide at a production pressure, the feed gas is sent after cooling into a first phase separator (51), the liquid from the first phase separator (61) is expanded, the expanded liquid is sent into a second phase separator and at least part of the liquid from the second phase separator is vaporised in order to derive the gas to be sent to the vessel reboiler.
  2. Method according to claim 1, wherein part of the carbon monoxide is compressed at a pressure less than or equal to the production pressure, is cooled in the heat exchanger (3) and is sent to the vessel of the distillation column (15).
  3. Method according to claim 1, wherein at least part of the liquid from the second phase separator (61) is vaporised in the heat exchanger (33).
  4. Apparatus for separating a feed gas containing, as the main components, nitrogen and carbon monoxide and optionally hydrogen, comprising:
    a. a distillation column (15) having a vessel reboiler (5) and optionally a head condenser (23)
    b. a heat exchanger (3)
    c. a compressor (29, 37)
    d. means for sending the feed gas into the heat exchanger
    e. means for sending at least part of a gas derived from the feed gas to the reboiler in order to at least partially condense it, producing a liquid and optionally a gas
    f. at least means for sending at least part of the liquid and optionally at least part of the gas to the column
    g. means for drawing off a flow enriched with gaseous nitrogen from the column
    h. means for drawing off a flow enriched with carbon monoxide from the column and sending it to the heat exchanger, characterised in that it comprises means for sending the flow enriched with carbon monoxide to the compressor in order to supply a product enriched with carbon monoxide at a production pressure, a first phase separator (51), a second phase separator (61), means for sending the cooled feed gas into the first phase separator, an expansion valve (55) for expanding the liquid from the first phase separator, means for sending the expanded liquid into the second phase separator and means (3) for vaporising at least part of the liquid from the second phase separator in order to derive the gas to be sent to the vessel reboiler (5).
  5. Apparatus according to claim 4, comprising means for sending part of the flow enriched with carbon monoxide at a pressure less than or equal to the production pressure to the heat exchanger (3) and next to the vessel of the distillation column (15).
  6. Apparatus according to claim 4, wherein the heat exchanger (3) is connected to the column (15) and to the second phase separator (61) in order to vaporise at least part of the liquid from the second separator in order to derive the heating gas for the vessel reboiler (5).
  7. Apparatus according to claim 4, wherein the distillation column comprises a head condenser.
  8. Apparatus according to claim 7, comprising means for sending the vessel liquid from the column to the head condenser.
  9. Apparatus according to claim 8, comprising means for sending the vaporised vessel liquid to the compressor.
EP10792965.5A 2009-11-24 2010-11-04 Method and apparatus for cryogenically separating a mixture of nitrogen and carbon monoxide Active EP2504646B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0958305A FR2953004B1 (en) 2009-11-24 2009-11-24 PROCESS FOR CRYOGENIC SEPARATION OF A NITROGEN MIXTURE AND CARBON MONOXIDE
PCT/FR2010/052368 WO2011067492A2 (en) 2009-11-24 2010-11-04 Method for cryogenically separating a mixture of nitrogen and carbon monoxide

Publications (2)

Publication Number Publication Date
EP2504646A2 EP2504646A2 (en) 2012-10-03
EP2504646B1 true EP2504646B1 (en) 2019-01-02

Family

ID=42364047

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10792965.5A Active EP2504646B1 (en) 2009-11-24 2010-11-04 Method and apparatus for cryogenically separating a mixture of nitrogen and carbon monoxide

Country Status (6)

Country Link
US (1) US9625209B2 (en)
EP (1) EP2504646B1 (en)
JP (1) JP2013511697A (en)
CN (1) CN102893110B (en)
FR (1) FR2953004B1 (en)
WO (1) WO2011067492A2 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2982168B1 (en) * 2011-11-04 2015-05-01 Air Liquide PROCESS AND APPARATUS FOR SEPARATING CARBON DIOXIDE-RICH GAS BY DISTILLATION
FR3011069B1 (en) * 2013-09-24 2015-09-11 Air Liquide METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A MIXTURE CONTAINING AT LEAST CARBON MONOXIDE, HYDROGEN AND NITROGEN
FR3013107A1 (en) * 2013-11-14 2015-05-15 Air Liquide METHOD AND APPARATUS FOR DEAZATING A FLUID RICH IN CARBON MONOXIDE
FR3084453B1 (en) * 2018-07-25 2020-11-27 Air Liquide METHOD AND APPARATUS FOR THE CRYOGENIC SEPARATION OF A MIXTURE OF CARBON MONOXIDE, HYDROGEN AND METHANE FOR THE PRODUCTION OF CH4
DE102020130946B4 (en) * 2020-11-23 2023-02-02 Xenon Holding Gmbh Cryogenic process for recovering valuable substances from a hydrogen-rich feed gas
FR3118144A3 (en) * 2020-12-22 2022-06-24 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude METHOD AND APPARATUS FOR THE CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN, METHANE, NITROGEN AND CARBON MONOXIDE

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3000188A (en) * 1956-11-15 1961-09-19 Kellogg M W Co Gas separation
DE1619724A1 (en) * 1967-06-22 1971-03-25 Messer Griesheim Gmbh Process for reducing the compression work in a rectification circuit
DE2147465C3 (en) * 1971-09-23 1975-06-12 Linde Ag, 6200 Wiesbaden Process for the decomposition of a gas mixture by rectification at low temperature
US4217759A (en) * 1979-03-28 1980-08-19 Union Carbide Corporation Cryogenic process for separating synthesis gas
DE3215829A1 (en) 1982-04-28 1983-11-03 Linde Ag, 6200 Wiesbaden METHOD FOR PRODUCING CARBON MONOXIDE
DE3736354A1 (en) * 1987-10-27 1989-05-11 Linde Ag PROCESS FOR H (DOWN ARROW) 2 (DOWN ARROW) / CO-DISASSEMBLY BY PARTIAL CONDENSATION AT DEEP TEMPERATURE
DE3822175A1 (en) * 1988-06-30 1990-01-04 Linde Ag Process for removing nitrogen from nitrogen-containing natural gas
FR2664263B1 (en) * 1990-07-04 1992-09-18 Air Liquide PROCESS AND PLANT FOR THE SIMULTANEOUS PRODUCTION OF METHANE AND CARBON MONOXIDE.
DE4210637A1 (en) * 1992-03-31 1993-10-07 Linde Ag Process for the production of high-purity hydrogen and high-purity carbon monoxide
DE4228784A1 (en) * 1992-08-28 1994-03-03 Linde Ag Process to separate constituents of a gas mixt. with a single-stage rectifier at low temp. - needs no expansion chamber or compressor
US6161397A (en) * 1998-08-12 2000-12-19 Air Products And Chemicals, Inc. Integrated cryogenic and non-cryogenic gas mixture separation
DE60018083T2 (en) * 2000-12-18 2005-12-29 Air Products And Chemicals, Inc. Process and apparatus for separating carbon monoxide and hydrogen from a gas mixture
US6568206B2 (en) * 2001-07-18 2003-05-27 Air Products And Chemicals, Inc. Cryogenic hydrogen and carbon monoxide production with membrane permeate expander
US6578377B1 (en) * 2002-03-11 2003-06-17 Air Products And Chemicals, Inc. Recovery of hydrogen and carbon monoxide from mixtures including methane and hydrocarbons heavier than methane
ES2364242T3 (en) * 2003-05-19 2011-08-29 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude PROCEDURES AND INSTALLATION TO PROVIDE GAS CARBON MONOXIDE AND / OR A MIXTURE CONTAINING CARBON MONOXIDE.
FR2843447B1 (en) * 2003-09-30 2009-02-06 Air Liquide PROCESS AND PLANT FOR PRODUCING CARBON MONOXIDE BY CRYOGENIC DISTILLATION
AU2005224612A1 (en) * 2004-03-11 2005-09-29 Advanced Extraction Technologies, Inc. Use of cryogenic temperatures in processing gases containing light components with physical solvents
DE102005025651A1 (en) 2005-06-03 2006-12-07 Linde Ag Process and apparatus for recovering products from synthesis gas
FR2903766A1 (en) * 2006-12-05 2008-01-18 Air Liquide Producing carbon monoxide and hydrogen from a mixture of methane and nitrogen by cryogenic distillation, comprises washing an initial gas mixture with a liquid methane in a first column to provide gaseous hydrogen and a washing liquid
FR2910603B1 (en) 2006-12-21 2009-03-06 Air Liquide PROCESS FOR SEPARATING A MIXTURE OF CARBON MONOXIDE, METHANE, HYDROGEN AND, POSSIBLY, NITROGEN BY CRYOGENETIC DISTILLATION
FR2930332A1 (en) 2008-04-18 2009-10-23 Air Liquide METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN AND CARBON MONOXIDE
US20100251765A1 (en) * 2009-04-01 2010-10-07 Air Products And Chemicals, Inc. Cryogenic Separation of Synthesis Gas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2504646A2 (en) 2012-10-03
FR2953004B1 (en) 2013-12-20
FR2953004A1 (en) 2011-05-27
CN102893110A (en) 2013-01-23
CN102893110B (en) 2014-11-26
US20120279254A1 (en) 2012-11-08
US9625209B2 (en) 2017-04-18
JP2013511697A (en) 2013-04-04
WO2011067492A2 (en) 2011-06-09
WO2011067492A3 (en) 2014-03-20

Similar Documents

Publication Publication Date Title
EP2268989B1 (en) Method and device for cryogenically separating a mixture of hydrogen and carbon monoxide
EP2504646B1 (en) Method and apparatus for cryogenically separating a mixture of nitrogen and carbon monoxide
EP2122282B1 (en) Method for separating a mixture of carbon monoxide, methane, hydrogen and nitrogen by cryogenic distillation
EP0547946B2 (en) Process for the production of impure oxygen
EP0677483B1 (en) Process and apparatus for the separation of a gaseous mixture
FR2885679A1 (en) METHOD AND INSTALLATION FOR SEPARATING LIQUEFIED NATURAL GAS
EP0968959B1 (en) Process for the production of carbon monoxide
EP2147270B1 (en) Method and device for separating a mixture of hydrogen, methane and carbon monoxide by cryogenic distillation
CA2899564C (en) Separation at sub-ambient temperature of a gaseous mixture containing carbon dioxide and a lighter contaminant
WO2015140460A2 (en) Method and device for cryogenically separating a synthesis gas containing carbon monoxide, methane and hydrogen
EP3724573A1 (en) Method and apparatus for the cryogenic separation of a synthesis gas containing a nitrogen separation step
EP2137474B1 (en) Method and apparatus for producing carbon monoxide by cryogenic distillation
FR2767317A1 (en) PROCESS FOR CONVERTING A FLOW CONTAINING HYDROCARBONS BY PARTIAL OXIDATION
FR2942869A1 (en) Cryogenic separation method for mixture of carbon monoxide, hydrogen and nitrogen, involves constituting nitrogenless flow with final product at range or pressure higher than range set during pressurization in pump or compressor
WO2013135993A2 (en) Method and device for separating a mixture containing carbon dioxide by means of distillation
WO2003042615A1 (en) Method and installation for helium production
EP1682836B1 (en) Method and installation for producing carbon monoxide by cryogenic distillation
EP3599438A1 (en) Method and device for cryogenic separation of a mixture of carbon monoxide, hydrogen and methane for the production of ch4
FR3057942A1 (en) METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A SYNTHESIS GAS BY PARTIAL CONDENSATION
FR3118144A3 (en) METHOD AND APPARATUS FOR THE CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN, METHANE, NITROGEN AND CARBON MONOXIDE
FR3097951A1 (en) METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF SYNTHESIS GAS FOR THE PRODUCTION OF CH4
FR3071827A3 (en) PROCESS FOR THE PRODUCTION OF A RICH CARBON MONOXIDE PRODUCT

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

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL 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 RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
R17D Deferred search report published (corrected)

Effective date: 20140320

17P Request for examination filed

Effective date: 20140922

RBV Designated contracting states (corrected)

Designated state(s): AL 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 RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180821

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL 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 RS SE SI SK SM 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

Ref country code: AT

Ref legal event code: REF

Ref document number: 1084922

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190115

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: 602010056277

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1084922

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190102

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: 20190502

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: 20190102

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: 20190102

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: 20190402

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: 20190102

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: 20190102

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: 20190102

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

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: 20190502

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: 20190402

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: 20190403

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: 20190102

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: 20190102

Ref country code: RS

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: 20190102

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010056277

Country of ref document: DE

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

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: 20190102

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: 20190102

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: 20190102

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: 20190102

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: 20190102

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: 20190102

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: 20190102

Ref country code: AL

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: 20190102

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

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

Ref country code: SM

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: 20190102

26N No opposition filed

Effective date: 20191003

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

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: 20190102

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: 20190102

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: LI

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

Effective date: 20191130

Ref country code: CH

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

Effective date: 20191130

Ref country code: MC

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: 20190102

Ref country code: LU

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

Effective date: 20191104

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

Effective date: 20191104

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: 20191130

Ref country code: IE

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

Effective date: 20191104

Ref country code: GB

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

Effective date: 20191104

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: 20190102

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; INVALID AB INITIO

Effective date: 20101104

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: 20190102

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: 20190102

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

Ref country code: BE

Payment date: 20221118

Year of fee payment: 13

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230523

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

Ref country code: NL

Payment date: 20231120

Year of fee payment: 14

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

Ref country code: DE

Payment date: 20231121

Year of fee payment: 14

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

Ref country code: BE

Payment date: 20231120

Year of fee payment: 14