EP2504646A2 - Method for cryogenically separating a mixture of nitrogen and carbon monoxide - Google Patents

Method for cryogenically separating a mixture of nitrogen and carbon monoxide

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Publication number
EP2504646A2
EP2504646A2 EP10792965A EP10792965A EP2504646A2 EP 2504646 A2 EP2504646 A2 EP 2504646A2 EP 10792965 A EP10792965 A EP 10792965A EP 10792965 A EP10792965 A EP 10792965A EP 2504646 A2 EP2504646 A2 EP 2504646A2
Authority
EP
European Patent Office
Prior art keywords
liquid
gas
column
carbon monoxide
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.)
Granted
Application number
EP10792965A
Other languages
German (de)
French (fr)
Other versions
EP2504646B1 (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
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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

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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
    • F25J3/0204—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 characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • 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
    • F25J3/0228—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 characterised by the separated product stream
    • F25J3/0252—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 characterised by the separated product stream separation of hydrogen
    • 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
    • F25J3/0228—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 characterised by the separated product stream
    • F25J3/0257—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 characterised by the separated product stream separation of nitrogen
    • 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
    • F25J3/0228—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 characterised by the separated product stream
    • F25J3/0261—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 characterised by the separated product stream separation of carbon monoxide
    • 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
    • F25J2200/40—Features relating to the provision of boil-up in the bottom of a 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
    • F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes 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
    • 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising loop
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/24—Quasi-closed internal or closed external carbon monoxide refrigeration cycle
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904—External 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34—Details about subcooling of liquids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/80—Retrofitting, 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.
  • the production units for carbon monoxide and hydrogen can be separated into two parts:
  • cryogenic separation unit called cold box for the production of CO.
  • 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 washing 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, Ar and N 2 ) being very low and compatible with the purity of the 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 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 disclose methods comprising the features of the preamble of claim 1 and similar to that of FIG. 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:
  • the feed gas is cooled in a heat exchanger (3) ii) at least a portion of the feed gas or at least a portion of a gas derived from the feed gas is supplied to a bottom reboiler of the distillation column in order to condense it at least partially by producing a liquid and optionally a gas
  • 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.
  • the at least part of the liquid of the second phase separator is vaporized in the heat exchanger.
  • an apparatus for separating a feed gas containing as main components nitrogen and carbon monoxide and optionally hydrogen comprising: i) a distillation column having a bottom reboiler and optionally a top condenser
  • v) means for sending at least a portion of the feed gas or at least a portion of a gas derived from the feed gas to the reboiler to at least partially condense it by producing a liquid and optionally a gas
  • 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.
  • the apparatus comprises:
  • the heat exchanger is connected to the column and to the second phase separator in order to vaporize at least a portion of the liquid of the second separator in order to divert the heating gas from the reboiler the distillation column comprises a top condenser.
  • a flow rate of nitrogen and carbon monoxide 1 is cooled in a heat exchanger 3. It condenses at least partially in a loop, which is then fed to the tank 15 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 1 1 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 with water and then divided in half. 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, expands in a turbine 43 and remixed with the flow 27. The rest of the carbon monoxide is compressed to the product pressure by the stage 37 of the compressor and cooled by the cooler 31 A to form the product flow 39.
  • the stage 29 is located as much smaller than some of the reboiling is provided by the 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 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 fed to the distillation column 5.
  • the remainder 65 of the liquid of the separator 61 is heated in the exchanger 3A to form the flow 65 which serves to heat the reboiler 5 fed by the liquid tank 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 in the same way as in Figure 1.
  • a nitrogen flow rate is removed as a temperature and is heated in the exchanger 3.
  • the vaporized carbon monoxide 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 with 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 1 against liquid nitrogen 137.
  • the liquid nitrogen 137 is vaporized and heated in the exchanger 3.
  • the flow 133 is expanded and mixed with the flow 21 downstream of the valve 19.
  • the flow 45 which is sent to the bottom of the column 5 after cooling in the exchanger 3A.
  • the carbon monoxide liquefied 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 part 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 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 fed to the distillation column 5.
  • the remainder 65 of the liquid of the separator 61 is heated in the exchanger 3A to form the flow 65 which serves to heat the reboiler 5 fed by the liquid tank 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 in the same way as for Figure 1.
  • a nitrogen flow is removed as a purge and is heated in the exchanger 3.
  • the enriched flow rate of vaporized carbon monoxide 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 with water and then diverted in half.
  • the flow 33 is cooled 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 to heat up in the exchanger 3.
  • the flow 45 from the shelf 29 is sent to the tank 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 part vaporizes in the exchange line 3A and the gas 87 is mixed with the flow rate of carbon monoxide 27 for the compressor 29.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

In a method for separating a feed gas, containing nitrogen and carbon monoxide as main components, in a distillation column (15): the feed gas is cooled in a heat exchanger (3); at least a portion of the feed gas, or at least a portion of a gas derived from the feed gas, is sent to a reboiler (5) of the distillation column so as to condense the gas while producing a liquid, and optionally a gas; at least a portion of the liquid is sent to the column; a nitrogen gas-rich flow is extracted from the column; a carbon monoxide-rich flow is extracted from the column, heated in the heat exchanger, and compressed so as to provide a carbon monoxide-rich material at production pressure; the feed gas is sent, after cooling, into a first phase separator (51); the liquid is released from the first phase separator (51); the released liquid is sent into a second phase separator; and at least a portion of the liquid from the second phase separator is vaporized so as to obtain the gas to be sent to the tank reboiler.

Description

Procédé de séparation cryogénique d'un mélange d'azote et de monoxyde de carbone  Process for the cryogenic separation of a mixture of nitrogen and carbon monoxide
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. The present invention relates to a method and apparatus for cryogenic separation of a mixture of nitrogen and carbon monoxide.
Les unités de production de monoxyde de carbone et d'hydrogène peuvent être séparées en deux parties :  The production units for carbon monoxide and hydrogen can be separated into two parts:
- génération du paz de synthèse (mélange contenant H2, CO, CH4,generation of the synthesis paz (mixture containing H 2 , CO, CH 4 ,
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. 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 du paz de synthèse. On retrouve :  purification of the synthetic paz. We find :
- une unité de lavage avec un solvant liquide pour éliminer la plus grande partie des gaz acides contenus dans le gaz de synthèse  a washing unit with a liquid solvent to eliminate most of the acid gases contained in the synthesis gas
- une unité d'épuration sur lit d'adsorbants.  an adsorbent bed purification unit.
- une unité de séparation par voie cryogénique dite boite froide pour la production de CO.  - A 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. 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 (CH , Ar et N2) étant très faible et compatible avec la pureté du CO. A methane washing scheme with a CO / N 2 column is described in FR-A-2910603. In the case of certain coal gasification processes, the synthesis gas produced is treated in a cold box by partial condensation without a cycle, the inert content (CH, Ar and N 2 ) being very low and compatible with the purity of the CO .
Un schéma condensation partielle sans colonne de séparation est décrit dans EP-A-1729077 et dans FR-A-2930332.  A partial condensation diagram 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/CH . The process scheme may include a CO / N 2 distillation column alone or a CO / N 2 column with a CO / CH 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 . 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 : DE-A-4228784 and DE-A-2147465 disclose methods comprising the features of the preamble of claim 1 and similar to that of FIG. 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:
i) on refroidit le gaz d'alimentation dans un échangeur de chaleur (3) ii) on envoie au moins une partie du gaz d'alimentation ou 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  i) the feed gas is cooled in a heat exchanger (3) ii) at least a portion of the feed gas or at least a portion of a gas derived from the feed gas is supplied to a bottom reboiler of the distillation column in order to condense it at least partially by producing a liquid and optionally a gas
iii) on envoie au moins une partie du liquide et éventuellement au moins une partie du gaz à la colonne  iii) at least a portion of the liquid and at least a portion of the gas is sent to the column
iv) on soutire un débit enrichi en azote gazeux de la colonne  iv) a flow enriched in nitrogen gas from the column is withdrawn
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.  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 :  Eventually :
- 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.  - Part 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.
- on vaporise l'au moins une partie du liquide du deuxième séparateur de phases dans l'échangeur de chaleur.  the at least part 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 d u monoxyd e d e ca rbon e et éventu el l em ent d e l ' hydrogène comprenant : i) une colonne de distillation ayant un rebouilleur de cuve et éventuellement un condenseur de tête 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: i) a distillation column having a bottom reboiler and optionally a top condenser
ii) un échangeur de chaleur  ii) a heat exchanger
iii) un compresseur  iii) a compressor
iv) des moyens pour envoyer le gaz d'alimentation dans l'échangeur de chaleur  iv) means for sending the feed gas into the heat exchanger
v) des moyens pour envoyer au moins une partie du gaz d'alimentation ou 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  v) means for sending at least a portion of the feed gas or at least a portion of a gas derived from the feed gas to the reboiler to at least partially condense it by producing a liquid and optionally a gas
vi) au moins des moyens pour envoyer au moins une partie du liquide et éventuellement au moins une partie du gaz à la colonne  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
vii) des moyens pour soutirer un débit enrichi en azote gazeux de la colonne  vii) means for withdrawing a flow enriched in gaseous nitrogen from the column
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 .  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 :  Optionally, the apparatus comprises:
- 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 .  - Means for sending a portion of the carbon monoxide enriched flow at a pressure less than or equal to the production pressure at the heat exchanger and then in the bottom of the distillation column.
- 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. the heat exchanger is connected to the column and to the second phase separator in order to vaporize at least a portion of the liquid of the second separator in order to divert the heating gas from the reboiler the distillation column comprises a top condenser.
- des moyens pour envoyer le liquide de cuve de la colonne au condenseur de tête.  means for sending the tank liquid from the column to the overhead condenser.
- des moyens pour envoyer le liquide de cuve vaporisé au compresseur. 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 com me com posa nts pri nci paux de l 'azote , de l 'hyd rog ène et d u monoxyde de carbone pour les Figures 2 et 3.  means for sending the vaporized tank liquid to the compressor. 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 Figure 1 and apparatus method of separation according to the invention of a gas having particular com posa nts of nitrogen, hydrogene 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 rebou il leur 5 al imenté par le l iq u ide 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 1 1 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 ensu ite d ivisé 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, détend u dans u ne turbine 43 et remélangé avec le débit 27. Le reste d u monoxyde de carbone est comprimé à la pression de produit par l'étage 37 du compresseur et refroidi par le refroidisseur 31 A 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 FIG. 1, a flow rate of nitrogen and carbon monoxide 1 is cooled in a heat exchanger 3. It condenses at least partially in a loop, which is then fed to the tank 15 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 1 1 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 with water and then divided in half. 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, expands in a turbine 43 and remixed with the flow 27. The rest of the carbon monoxide is compressed to the product pressure by the stage 37 of the compressor and cooled by the cooler 31 A to form the product flow 39. The stage 29 is located as much smaller than some of the reboiling is provided by the 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 ensu ite 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 ensu ite 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 1 7 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 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 fed to the distillation column 5. The remainder 65 of the liquid of the separator 61 is heated in the exchanger 3A to form the flow 65 which serves to heat the reboiler 5 fed by the liquid tank 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 in the same way as in Figure 1.
U n débit d 'azote est enlevé comme pu rge 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 refroid i 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 1 35 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 qui est envoyé en cuve de la colonne 5 après refroidissement dans l'échangeur 3A.  A nitrogen flow rate is removed as a temperature and is heated in the exchanger 3. The vaporized carbon monoxide 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 with 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 1 against liquid nitrogen 137. The liquid nitrogen 137 is vaporized and heated in the exchanger 3. The flow 133 is expanded and mixed with the flow 21 downstream of the valve 19. The flow 45 which is sent to the bottom of the column 5 after cooling in the exchanger 3A.
Le monoxyde de carbone l iq u ide 79 est soutiré du condenseu r 23, détendu dans la vanne 81 , envoyé au séparateur de phases 83 pour produire une partie liquide et une partie gazeuse. La partie liquide 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 carbon monoxide liquefied 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 part 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 ensu ite 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 1 7 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 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 fed to the distillation column 5. The remainder 65 of the liquid of the separator 61 is heated in the exchanger 3A to form the flow 65 which serves to heat the reboiler 5 fed by the liquid tank 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 in the same way as for Figure 1.
Un débit d'azote est enlevé comme purge 25 et se réchauffe dans l 'échangeur 3. Le débit enrich i 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 d ivisé en deux. Le débit 33 se refroid it 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 proven a nt d e l ' étag e 29 est en voyé 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 enriched flow rate of vaporized carbon monoxide 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 with water and then diverted in half. The flow 33 is cooled 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 to heat up in the exchanger 3. The flow 45 from the shelf 29 is sent to the tank 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 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 part 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

REVENDICATIONS
1 . 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 (15) dans lequel : 1. A method of separating a feed gas containing as main components nitrogen and carbon monoxide and optionally hydrogen in a distillation column (15) wherein:
i) on refroidit le gaz d'alimentation dans un échangeur de chaleur (3) ii) on envoie au moins une partie du gaz d'alimentation ou au moins une partie d'un gaz dérivé du gaz d'alimentation à un rebouilleur (5) de cuve de la colonne de distillation afin de la condenser au moins partiellement en produisant un liquide et éventuellement un gaz  i) the feed gas is cooled in a heat exchanger (3) ii) at least a portion of the feed gas or at least a portion of a gas derived from the feed gas is supplied to a reboiler (5); ) of the distillation column to at least partially condense it by producing a liquid and optionally a gas
iii) on envoie au moins une partie du liquide et éventuellement au moins une partie du gaz à la colonne  iii) at least a portion of the liquid and at least a portion of the gas is sent to the column
iv) on soutire un débit enrichi en azote gazeux de la colonne  iv) a flow enriched in nitrogen gas from the column is withdrawn
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 (51 ), on détend le liquide du premier séparateur de phases (61 ), 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 de cuve.  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 fed after cooling into a first phase separator (51), the liquid is depressurized from the first phase separator (61), the expanded liquid is sent to a second phase separator and vaporized at least a portion of the liquid of the second phase separator for diverting the gas to be sent to the bottom reboiler.
2. Procédé selon la revendication 1 dans lequel 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 (3) et on l'envoie en cuve de la colonne de distillation (15). 2. Method according to claim 1 wherein a portion 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 sent to the tank of the distillation column (15).
3. Procédé selon la revendication 1 dans lequel on vaporise l'au moins une partie du liquide du deuxième séparateur de phases (61 ) dans l'échangeur de chaleur (33). 3. Method according to claim 1 wherein the at least a portion of the liquid of the second phase separator (61) is vaporized in the heat exchanger (33).
4. 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 : 4. Apparatus for separating a feed gas containing as main components nitrogen and carbon monoxide and optionally hydrogen comprising:
a. une colonne de distillation (15) ayant un rebouilleur de cuve (5) et éventuellement un condenseur de tête (23)  at. a distillation column (15) having a bottom reboiler (5) and optionally a top condenser (23)
b. un échangeur de chaleur (3)  b. heat exchanger (3)
c. un compresseur (29,37)  vs. a compressor (29,37)
d. des moyens pour envoyer le gaz d'alimentation dans l'échangeur de chaleur  d. means for feeding the feed gas into the heat exchanger
e. des moyens pour envoyer au moins une partie du gaz d'alimentation ou 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  e. means for sending at least a portion of the feed gas or at least a portion of a gas derived from the feed gas to the reboiler to at least partially condense it by producing a liquid and optionally a gas
f. au moins des moyens pour envoyer au moins une partie du liquide et éventuellement au moins une partie du gaz à la colonne  f. at least means for sending at least a portion of the liquid and optionally at least a portion of the gas to the column
g. des moyens pour soutirer un débit enrichi en azote gazeux de la colonne  boy Wut. means for withdrawing a nitrogen gas-enriched flow from the column
h. 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 (61 ), des moyens pour envoyer le gaz d'alimentation refroidi dans le premier séparateur de phases, une vanne de détente (55) 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 (3) pour vaporiser au moins une partie du liquide du deuxième séparateur de phases pour dériver le gaz à envoyer au rebouilleur de cuve (5).  h. means for withdrawing a flow of carbon monoxide enriched from the column and for sending it to the heat exchanger characterized in that it comprises means for sending the carbon monoxide enriched flow to the compressor to provide an enriched product 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 of the first phase separator, means for sending the expanded liquid into the second phase separator and means (3) for vaporising at least a portion of the liquid of the second phase separator to divert the gas to be sent. at the reboiler (5).
5. Appareil selon la revendication 4 comprenant 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 (3) et ensuite en cuve de la colonne de distillation (15). 5. Apparatus according to claim 4 comprising means for sending a portion of the carbon monoxide enriched flow to a pressure less than or equal to the production pressure at the heat exchanger (3) and then in the vat of the distillation column (15).
6. Appareil selon la revendication 4 dans lequel l'échangeur de chaleur (3) est relié à la colonne (15) et au deuxième séparateur de phases (61 ) afin de vaporiser au moins une partie du liquide du deuxième séparateur pour dériver le gaz de chauffage du rebouilleur de cuve (5). 6. Apparatus according to claim 4 wherein the heat exchanger (3) is connected to the column (15) and the second phase separator (61) to vaporize at least a portion of the liquid of the second separator to divert the gas heating the tank reboiler (5).
7. Appareil selon la revendication 4 dans lequel la colonne de distillation comprend un condenseur de tête. The apparatus of claim 4 wherein the distillation column comprises a top condenser.
8. Appareil selon la revendication 8 comprenant des moyens pour envoyer le liquide de cuve de la colonne au condenseur de tête. 8. Apparatus according to claim 8 comprising means for sending the column liquid from the column to the overhead condenser.
9. Appareil selon la revendication 9 comprenant des moyens pour envoyer le liquide de cuve vaporisé au compresseur. 9. Apparatus according to claim 9 including means for sending the vaporized tank 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)

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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

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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
DE60336638D1 (en) * 2003-05-19 2011-05-19 Air Liquide Method and apparatus for obtaining gaseous 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
WO2005090887A1 (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
See references of WO2011067492A2 *

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EP2504646B1 (en) 2019-01-02
US20120279254A1 (en) 2012-11-08
WO2011067492A3 (en) 2014-03-20
FR2953004B1 (en) 2013-12-20
US9625209B2 (en) 2017-04-18
WO2011067492A2 (en) 2011-06-09
JP2013511697A (en) 2013-04-04
CN102893110B (en) 2014-11-26
CN102893110A (en) 2013-01-23

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