EP2856050B1 - Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and optionally nitrogen - Google Patents

Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and optionally nitrogen Download PDF

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Publication number
EP2856050B1
EP2856050B1 EP13727260.5A EP13727260A EP2856050B1 EP 2856050 B1 EP2856050 B1 EP 2856050B1 EP 13727260 A EP13727260 A EP 13727260A EP 2856050 B1 EP2856050 B1 EP 2856050B1
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EP
European Patent Office
Prior art keywords
column
methane
liquid
carbon monoxide
mixture
Prior art date
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EP13727260.5A
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German (de)
French (fr)
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EP2856050A2 (en
Inventor
Pascal Marty
Jean-Jacques Talbot
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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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Priority to PL13727260T priority Critical patent/PL2856050T3/en
Publication of EP2856050A2 publication Critical patent/EP2856050A2/en
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—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
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    • 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
    • F25J3/0233—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 CnHm with 1 carbon atom or more
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    • 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
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    • 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
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    • 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
    • F25J3/0276—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 H2/N2 mixtures, i.e. of ammonia synthesis gas
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    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/30—Processes or apparatus using separation by rectification using a side column in a single pressure column system
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    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
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    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/76—Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
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    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
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    • 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
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    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
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    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
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    • 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
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
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    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/02—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams using a pump in general or hydrostatic pressure increase
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    • F25J2245/42—Processes or apparatus involving steps for recycling of process streams the recycled stream being nitrogen
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    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/02—Integration in an installation for exchanging heat, e.g. for waste heat recovery
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    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
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    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/40—Vertical layout or arrangement of cold equipments within in the cold box, e.g. columns, condensers, heat exchangers etc.
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    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/42—Modularity, pre-fabrication of modules, assembling and erection, horizontal layout, i.e. plot plan, and vertical arrangement of parts of the cryogenic unit, e.g. of the cold box

Definitions

  • the present invention relates to an apparatus and method for cryogenic separation of a mixture of carbon monoxide, methane and hydrogen and optionally nitrogen.
  • An object of the invention is to make more compact an apparatus for cryogenic separation of a mixture of carbon monoxide, hydrogen and methane when the methane is to be produced under pressure.
  • Another aim of the invention is, in certain cases, to reduce the maximum height of an apparatus for cryogenic separation of a mixture of carbon monoxide, hydrogen and methane. This makes it possible to reduce the cost of the apparatus as well as the transport costs.
  • the liquid methane withdrawn from the bottom of the CO / CH 4 column can be pressurized in a pump to then be stored and / or sent to a customer or to be sent to the head of the methane washing column, if necessary.
  • the Figure 1 represents a methane washing process according to the prior art
  • the Figures 2 and 3 represent methane washing processes according to the invention
  • the Figure 4 represents a partial condensation process according to the prior art
  • the Figure 5 represents a partial condensation process according to the invention
  • the Figure 6 represents a carbon monoxide washing process according to the prior art
  • the Figure 7 represents a carbon monoxide washing process according to the invention
  • the Figure 8 shows a nitrogen washing process according to the prior art
  • the Figure 9 represents a nitrogen washing process according to the invention.
  • a mixture of hydrogen, carbon monoxide and methane 1 is purified in unit 3 to remove water and carbon dioxide.
  • the purified mixture 5 cools in the main cryogenic exchanger 9 to be sent to a phase separator 7, where it is separated to form a gas 11 enriched in hydrogen and a liquid 13 enriched in methane.
  • the gas 11 separates in a methane washing column 17 fed at the top with a washing liquid 41 rich in methane.
  • the bottom liquid of column 17 is mixed with liquid 13 to form liquid 18 rich in CO and CH 4 and also containing nitrogen sent to the top of a stripping column 19 (in English "flash column") having a bottom reboiler 22.
  • the gas 21 withdrawn from the top of the column 19 is enriched in hydrogen and is heated in the exchanger 9 for upgrading as purge gas to a fuel network in general.
  • the bottom liquid 23 of column 19 mainly contains carbon monoxide (and nitrogen) and methane and is expanded in valve 25 and then sent for separation in CO / CH 4 column 27.
  • a gas 44 enriched in carbon monoxide is formed at the top of the column and a liquid enriched in methane 33 is formed at the bottom of the column.
  • the liquid 33 is divided into two, a part 37 being heated (or not) in the main cryogenic exchanger 9 for upgrading as purge gas (or in liquid form by bypassing the exchanger 9) at the pressure of the CO / column.
  • CH 4 (a few bars) and the other part 35 being pressurized by a pump 36 to supply the head of the washing column with methane 17 and for possible upgrading under pressure (fluid 38) in gaseous form via the main cryogenic exchanger 9 (or directly in liquid form by short-circuiting exchanger 9).
  • a carbon monoxide cycle keeps the device cold.
  • the carbon monoxide coming from the top of the column 27 is heated in the exchanger 9, sent as flow 45 to a compressor 51.
  • Part of the carbon monoxide is produced as gas 53 under pressure at the outlet of the compressor.
  • Another part 57 cools in the exchanger 9 and is divided into two.
  • a part 59 at an intermediate temperature of the exchanger 9 is expanded in a turbine 61 and sent by a valve 63 via line 65 to the compressor 51.
  • Another part 67 continues to cool in the exchanger 9.
  • a fraction 69 of the cooled carbon monoxide is used to heat the tank reboiler 22 of the tank. exhaustion column 19 and is condensed.
  • Another fraction 71 is used to heat the bottom reboiler 31 of the CO / CH 4 column 27 and is mixed with the condensed fraction 69.
  • the entire flow 73 is expanded in a valve 73 and sent to the top condenser 29 of the CO column. / CH 4 where it vaporizes to form the flow of carbon monoxide 43 which mixes with the overhead gas from the CO / CH 4 column.
  • phase separator 79 Part of the liquid 77 from the overhead condenser 29 is sent to a phase separator 79. From the phase separator 79 a liquid 81 is withdrawn which is sent to the exchanger 21 which cools the intermediate withdrawals from the methane washing column, the liquid 81 vaporizes therein and the gas is returned to the phase separator 79. The gas 83 from the phase separator 79 is sent to the inlet of the compressor 51 with the gas 43.
  • the three columns 17, 27, 19 are all placed on the ground, which increases the grip (the size) on the ground.
  • the column 27 is raised to a sufficient height.
  • the CO / CH 4 column 27 is placed above the exhaustion column 19, the two columns having the same main axis.
  • the liquid enriched in methane 33 from the bottom of the column 27 passes through a height H to reach the pump 36 and is at a higher pressure because of the hydrostatic pressure. Part of the liquid at the elevated pressure can be taken to serve as a product downstream or upstream of the pump 36.
  • the footprint of the columns of the cold box is thus reduced.
  • the sum of the heights of the two columns 27 and 19 is less than the height of the column 17, the length of the package of the columns of the cold box is not modified.
  • the stripping column comprises a few additional trays at the top of the column, constituting an auxiliary column 20 of reduced diameter compared to column 19.
  • the gas phase is washed with countercurrent with liquid methane 39 to extract the still dissolved carbon monoxide.
  • the liquid / vapor traffic in this section 20 is quite low: all the other gas flows entering the stripping column 19 are located below the section 20.
  • it is therefore justified to reduce the diameter in the upper section 20 of the exhaustion column: it then takes the name of “auxiliary column” (minaret).
  • the auxiliary column 20 is integrated for approximately one meter in the exhaustion column 19.
  • a mixture of hydrogen, carbon monoxide and methane 1 is purified in unit 3 to remove water and carbon dioxide.
  • the purified mixture 5 cools in a main cryogenic exchanger 9 to be sent to a phase separator 7, where it is separated to form a gas 11 enriched in hydrogen and a liquid 13 enriched in methane.
  • the liquid 13 is sent to the top of a stripping column 19 having a bottom reboiler 22.
  • the gas 21 withdrawn from the top of the column 19 is enriched in hydrogen and is heated in the exchanger 9 for upgrading as gas. purge to a fuel network in general.
  • the bottom liquid 23 of column 19 mainly contains carbon monoxide and methane and is sent to separate in the CO / CH 4 column 27.
  • a gas enriched in carbon monoxide is formed at the top of the column and an enriched liquid.
  • methane 33 is formed at the bottom of the column.
  • the liquid 35 is heated in the exchanger to serve as fuel.
  • the liquid 33 is divided into two, a part 37 being heated (or not) in the exchanger main cryogenic 9 for recovery as purge gas (or in liquid form by short-circuiting the exchanger 9) at the pressure of the CO / CH 4 column (a few bars) and the other part 35 being pressurized by a pump 36 for possible recovery under pressure (fluid 38) in gaseous form via the main cryogenic exchanger 9 (or directly in liquid form by bypassing the exchanger 9).
  • a carbon monoxide cycle keeps the device cold.
  • the carbon monoxide coming from the top of the column 27 is heated in the exchanger 9, sent as flow 45 to a compressor 51.
  • Part of the carbon monoxide is produced as gas 53 under pressure at the outlet of the compressor.
  • Another part 57 cools in the exchanger 9 and is divided into two.
  • a part 59 at an intermediate temperature of the exchanger 9 is expanded in a turbine 61 and sent by a valve 63 via the line 65 to the compressor 51.
  • Another part continues its cooling in the exchanger 9.
  • a fraction 69 of the monoxide of cooled carbon serves to heat the bottom reboiler 22 of column 19 and is condensed.
  • Another fraction 71 is used to heat the bottom reboiler 31 of the CO / CH 4 column 27 and is mixed with the condensed fraction 69.
  • the entire flow 73 is expanded in a valve and sent to the top condenser 29 of the CO / column. CH 4 where it vaporizes to form the flow of carbon monoxide 43 which will feed the compressor 51 after passing through the exchanger 9.
  • column 27 is positioned above column 19, which is itself positioned above phase separator 7. It is also possible to place phase separator 7 next to two columns 19, 27.
  • a mixture of hydrogen, carbon monoxide, nitrogen and methane 1 is purified in unit 3 to remove water and carbon dioxide.
  • the purified mixture 5 cools in an exchanger 9 to be sent to a phase separator 7, where it is separated to form a gas 11 enriched in hydrogen and a liquid 13 enriched in methane.
  • Gas 11 separates in a carbon monoxide washing column 601 fed at the top with a washing liquid 623 rich in carbon monoxide.
  • the bottom liquid of the column 601 is mixed with the liquid 13 to form the liquid 18 and the liquid formed is sent to the top of a stripping column 19 (in English “flash column”) having a bottom reboiler 22.
  • the gas 21 withdrawn from the top of column 19 is enriched in hydrogen and is heated in exchanger 9 for upgrading as purge gas to a fuel network in general ....
  • the bottom liquid 23 of column 19 mainly contains carbon monoxide and methane and is sent to separate in the CO / CH 4 column 27.
  • a gas enriched in carbon monoxide 43 is formed at the top of the column and a liquid.
  • enriched in methane 33 is formed at the bottom of the column.
  • the liquid 33 is divided into two, a part 37 being heated (or not) in the main cryogenic exchanger 9 for upgrading as purge gas (or in liquid form by short-circuiting the exchanger 9) at the pressure of the column CO / CH 4 27 (a few bars) and the other part 35 being pressurized by a pump 36 for possible recovery under pressure (fluid 38), in gaseous form via the main cryogenic exchanger 9 (or directly in liquid form in short- circuiting the exchanger 9).
  • a carbon monoxide cycle keeps the device cold.
  • the carbon monoxide coming from the top of the column 27 is heated in the exchanger 9, sent as flow 45 to a compressor 51.
  • Part of the carbon monoxide is produced as gas 53 under pressure at the outlet of the compressor.
  • Another part 57 cools in the exchanger 9 and is divided into two.
  • a part 59 is expanded in a valve 63 then sent through line 65 to the compressor 51.
  • Another part is divided into two fractions.
  • a fraction 69 of the cooled carbon monoxide serves to heat the bottom reboiler 22 of the stripping column 19 and is condensed.
  • Another fraction 71 is used to heat the bottom reboiler 631 of the CO / CH 4 column 27 and is mixed with the condensed fraction 71.
  • the entire flow 73 is expanded in a valve and sent to the overhead condenser 619 of the CO / column. CH 4 where it vaporizes to form the carbon monoxide fluid 43.
  • a carbon monoxide bath 29 at the top of column 27 supplies condenser 619 with gas to be condensed.
  • the overhead gas 635 from the column 27 is sent to the denitrogenation column 603 having an overhead condenser 615.
  • the bottom liquid 613 from the denitrogenation column 603 is sent to the denitrogenation column 603.
  • the overhead gas enriched in nitrogen 617 is heated in the exchanger 9 and directed to a network fuel.
  • the carbon monoxide necessary for washing in column 603 is provided by the fluids 609 and 611 withdrawn from the discharge of the compressor 51. A portion of these fluids is sent as flow 623 to the head of the washing column 601.
  • the installation of A denitrogenation column can be applicable in all the cases mentioned above when the nitrogen must be partially or totally removed from the gas produced.
  • the CO / CH 4 column 27 is positioned above the stripping column 19 so that the flow rate rich in liquid methane 35 is hydrostatically pressurized upstream of the pump 36.
  • the Figure 8 shows a nitrogen washing process in which a mixture of hydrogen, carbon monoxide, nitrogen and methane 1 leaves a unit of the Rectisol ® 804 type and is purified in a purification unit 3 for remove the water, the methanol and the CO 2 (adsorbing the methanol or any other solvent used in an upstream wash may also be required in all the cases mentioned above).
  • the purified mixture 5 is cooled in the exchanger 9 and then sent to a phase separator 7.
  • the gas from the phase separator 7 is mixed with an uncooled part 6 of the gas 5 to form the flow 11. Part of the flow 11 is used to reheat the bottom reboiler 851 of an N 2 / CH 4 850 column, being partially condensed.
  • the partially condensed flow is sent to a phase separator 809.
  • the liquid 819 from the separator 809 is rich in methane and is sent to the pump 36.
  • the gas 827 from the separator 809 joins gas 821 from separator 7, is cooled in exchanger 9, then separated in a phase separator 807 and the product gas 814 feeds the washing column with nitrogen 811 to be separated.
  • Column 811 is fed at the top with a flow of liquid 833 produced by the liquefaction of a flow 831 of gaseous nitrogen in exchanger 9. Another part 835 of the condensed nitrogen is mixed with the heated top gas 829.
  • the bottom liquid 847 of the nitrogen washing column 811 is expanded, then sent to a phase separator 845.
  • the product gas 853 is heated in the exchanger 9 as purge gas.
  • the fluid 849 feeds the column N 2 / CH 4 850 852 to form a gas flow depleted in methane and enriched in nitrogen and a liquid stream enriched in methane.
  • the liquid flow enriched in methane 35 is sent to the pump 36, then feeds a phase separator 821.
  • the gas 825 is sent to the exchanger 9 to produce a gas phase rich in methane.
  • the liquid 823 can either also be sent to the exchanger 9 to produce a phase rich in gaseous methane under pressure, or bypass the exchanger 9 to produce liquid methane under pressure as a final product. It is also possible to produce a phase rich in gaseous or liquid methane at low pressure by vaporizing liquid taken upstream of the pump 36.

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Description

La présente invention est relative à un appareil et procédé de séparation cryogénique d'un mélange de monoxyde de carbone, de méthane et d'hydrogène et éventuellement de l'azote.The present invention relates to an apparatus and method for cryogenic separation of a mixture of carbon monoxide, methane and hydrogen and optionally nitrogen.

Les mélanges peuvent être constitués par :

  • du monoxyde de carbone, d'hydrogène, avec les impuretés méthane et d'azote (boite froide H2/CO).
  • de l'azote avec les impuretés hydrogène, monoxyde de carbone et méthane (boite froide lavage à l'azote).
The mixtures can be made up of:
  • carbon monoxide, hydrogen, with methane and nitrogen impurities (H 2 / CO cold box).
  • nitrogen with the impurities hydrogen, carbon monoxide and methane (cold box washing with nitrogen).

Il est connu d'effectuer une première séparation par voie cryogénique d'un mélange de monoxyde de carbone, d'hydrogène et de méthane pour produire un gaz riche en hydrogène et un mélange liquide contenant principalement du CO, du CH4 (et l'azote). Ce deuxième mélange est typiquement séparé dans une colonne CO/CH4 pour produire un gaz enrichi en monoxyde de carbone (et contenant l'azote) et un liquide enrichi en méthane.It is known to carry out a first separation by cryogenic route of a mixture of carbon monoxide, hydrogen and methane to produce a gas rich in hydrogen and a liquid mixture mainly containing CO, CH 4 (and nitrogen). This second mixture is typically separated in a CO / CH 4 column to produce a gas enriched in carbon monoxide (and containing nitrogen) and a liquid enriched in methane.

On peut dénombrer plusieurs méthodes pour effectuer la première séparation.There are several methods of performing the first separation.

Il est connu d'effectuer la première séparation du mélange de monoxyde de carbone, d'hydrogène et de méthane pour éliminer l'hydrogène par condensation partielle suivie d'une deuxième séparation du deuxième mélange contenant principalement du monoxyde de carbone (et azote) et du méthane dans une colonne CO/CH4.It is known to perform the first separation of the mixture of carbon monoxide, hydrogen and methane to remove hydrogen by partial condensation followed by a second separation of the second mixture mainly containing carbon monoxide (and nitrogen) and methane in a CO / CH 4 column.

Il est également connu d'effectuer une première séparation du mélange dans une colonne de lavage au monoxyde de carbone ou au méthane ou à l'azote pour produire le deuxième mélange de monoxyde de carbone et de méthane. Ce deuxième mélange est ensuite séparé dans une colonne CO/CH4.It is also known practice to carry out a first separation of the mixture in a washing column with carbon monoxide or with methane or with nitrogen to produce the second mixture of carbon monoxide and methane. This second mixture is then separated in a CO / CH 4 column.

Un but de l'invention est de rendre plus compact un appareil de séparation cryogénique d'un mélange de monoxyde de carbone, d'hydrogène et de méthane lorsque le méthane doit être produit sous pression.An object of the invention is to make more compact an apparatus for cryogenic separation of a mixture of carbon monoxide, hydrogen and methane when the methane is to be produced under pressure.

Un autre but de l'invention est, dans certains cas, de diminuer la hauteur maximale d'un appareil de séparation cryogénique d'un mélange de monoxyde de carbone, d'hydrogène et de méthane. Ceci permet de réduire le coût de l'appareil ainsi que les coûts de transport.Another aim of the invention is, in certain cases, to reduce the maximum height of an apparatus for cryogenic separation of a mixture of carbon monoxide, hydrogen and methane. This makes it possible to reduce the cost of the apparatus as well as the transport costs.

Le méthane liquide soutiré de la cuve de la colonne CO/CH4 peut être pressurisé dans une pompe pour être ensuite stocké et/ou envoyé à un client ou pour être envoyé en tête de la colonne de lavage au méthane, le cas échéant.The liquid methane withdrawn from the bottom of the CO / CH 4 column can be pressurized in a pump to then be stored and / or sent to a customer or to be sent to the head of the methane washing column, if necessary.

Il est un autre but de la présente invention d'alimenter la pompe de méthane liquide par un liquide pressurisé par pression hydrostatique en surélevant la cuve de la colonne CO/CH4.It is another object of the present invention to supply the pump with liquid methane with a liquid pressurized by hydrostatic pressure by raising the bottom of the CO / CH 4 column.

Les caractéristiques du préambule de la revendication 1 sont connues de US6098424 A ou US 2010/043489 A1 . D'autres appareils similaires sont connus de EP-A-1080765 et Walter Bals « H2-CO-Anlage BASF Ludwigshafen », 1980, Linde Berichte aus Technik und Wissenschaft.The features of the preamble of claim 1 are known from US6098424 A or US 2010/043489 A1 . Other similar devices are known from EP-A-1080765 and Walter Bals "H2-CO-Anlage BASF Ludwigshafen", 1980, Linde Berichte aus Technik und Wissenschaft.

Selon un objet de l'invention, il est prévu un appareil selon la revendication 1. Selon d'autres aspects facultatifs, l'appareil comprend :

  • une pompe reliée à la troisième conduite, disposée plus près du sol que la cuve de la deuxième colonne.
  • une colonne auxiliaire dont la tête est éventuellement reliée à la pompe et dont la cuve est reliée à la tête de la première colonne par des moyens pour envoyer du gaz de la tête de la première colonne à la cuve de la colonne auxiliaire et par des moyens pour envoyer du liquide de la cuve de la colonne auxiliaire vers la tête de la première colonne, la colonne auxiliaire étant disposée à côté de la première colonne.
  • la colonne auxiliaire est disposée de sorte que sa cuve est plus loin du sol que la tête de la première colonne.
  • la colonne auxiliaire est fixée à la deuxième colonne.
  • la première unité comprend une colonne de prétraitement, une conduite pour amener le mélange de la colonne de prétraitement à la première colonne, la colonne auxiliaire étant fixée à la colonne de pré-traitement.
  • l'appareil comprend une colonne de post-traitement en aval de la deuxième colonne, la colonne auxiliaire étant fixée à la colonne de post-traitement.
  • la première unité comprend une colonne de lavage au méthane, cette colonne étant reliée à la première colonne pour l'alimenter avec le mélange qui est un liquide de cuve de la colonne de lavage au méthane, la tête de la colonne de lavage au méthane étant reliée à la pompe.
  • la première unité comprend un séparateur de phases et des moyens pour amener du liquide du séparateur de phases comme le mélange qui alimente la première colonne.
  • la première unité comprend une colonne de lavage et la première colonne, le liquide de lavage étant riche en monoxyde de carbone, ainsi que des moyens pour envoyer le liquide de cuve de la colonne de lavage à la première colonne.
  • la première unité comprend une colonne de lavage, le liquide de lavage étant riche en azote, la colonne de lavage constituant la première colonne.
  • des moyens pour produire du méthane liquide comme produit final.
  • la première unité comprend une colonne de lavage à l'azote, le deuxième liquide contient du méthane et de l'azote et la deuxième colonne produit un gaz enrichi en azote.
According to an object of the invention, there is provided an apparatus according to claim 1. According to other optional aspects, the apparatus comprises:
  • a pump connected to the third pipe, placed closer to the ground than the bottom of the second column.
  • an auxiliary column, the head of which is optionally connected to the pump and the vessel of which is connected to the head of the first column by means for sending gas from the head of the first column to the vessel of the auxiliary column and by means to send liquid from the bottom of the auxiliary column to the head of the first column, the auxiliary column being arranged next to the first column.
  • the auxiliary column is arranged so that its tank is further from the ground than the head of the first column.
  • the auxiliary column is attached to the second column.
  • the first unit comprises a pre-treatment column, a line for supplying the mixture from the pre-treatment column to the first column, the auxiliary column being attached to the pre-treatment column.
  • the apparatus comprises a post-treatment column downstream of the second column, the auxiliary column being attached to the post-treatment column.
  • the first unit comprises a methane washing column, this column being connected to the first column to supply it with the mixture which is a bottom liquid of the methane washing column, the head of the methane washing column being connected to the pump.
  • the first unit comprises a phase separator and means for supplying liquid from the phase separator as the mixture which feeds the first column.
  • the first unit comprises a washing column and the first column, the washing liquid being rich in carbon monoxide, as well as means for sending the bottom liquid from the washing column to the first column.
  • the first unit comprises a washing column, the washing liquid being rich in nitrogen, the washing column constituting the first column.
  • means for producing liquid methane as a final product.
  • the first unit includes a nitrogen wash column, the second liquid contains methane and nitrogen, and the second column produces nitrogen enriched gas.

Selon un autre objet de l'invention, il est prévu un procédé selon la revendication 10.According to another object of the invention, there is provided a method according to claim 10.

Selon d'autres aspects facultatifs de l'invention :

  • le rebouilleur de cuve est chauffé par un gaz de cycle qui est le monoxyde de carbone.
  • un gaz de tête de la première colonne se réchauffe dans un échangeur où se refroidit le mélange.
  • tout le gaz de tête de la première colonne se réchauffe dans l'échangeur.
  • le liquide enrichi en méthane est pressurisé en partie par une pompe disposée plus près du sol que la cuve de la deuxième colonne.
  • la pompe est au sol.
  • on envoie un gaz de tête de la première colonne à la cuve d'une colonne auxiliaire et du liquide enrichi en méthane à la tête de la colonne, la colonne auxiliaire étant disposée à côté de la première colonne.
  • la première unité comprend une colonne de prétraitement, une conduite pour amener le mélange de la colonne de prétraitement à la première colonne, la colonne auxiliaire étant fixée à la colonne de pré-traitement.
  • l'appareil comprend une colonne de post-traitement en aval de la deuxième colonne, la colonne auxiliaire étant fixée à la colonne de post-traitement.
  • la première unité comprend une colonne de lavage au méthane, le liquide de cuve de la colonne de lavage étant envoyé à la première colonne comme le mélange et du liquide enrichi en méthane pressurisé étant envoyé à la colonne de lavage.
  • la première unité comprend une colonne de lavage, alimentée par un liquide de lavage étant riche en monoxyde de carbone ou en azote, le liquide de cuve de la colonne de lavage étant envoyé à la première colonne.
  • le procédé produit du méthane liquide comme produit final provenant de la cuve de la deuxième colonne.
  • la première unité comprend une colonne de lavage à l'azote, le deuxième liquide contient du méthane et de l'azote et la deuxième colonne produit un gaz enrichi en azote.
According to other optional aspects of the invention:
  • the vessel reboiler is heated by a cycle gas which is carbon monoxide.
  • an overhead gas from the first column is heated in an exchanger where the mixture cools.
  • all the overhead gas from the first column is heated in the exchanger.
  • the liquid enriched in methane is pressurized in part by a pump placed closer to the ground than the bottom of the second column.
  • the pump is on the ground.
  • an overhead gas from the first column is sent to the bottom of an auxiliary column and a liquid enriched in methane to the head of the column, the auxiliary column being arranged next to the first column.
  • the first unit comprises a pre-treatment column, a line for supplying the mixture from the pre-treatment column to the first column, the auxiliary column being attached to the pre-treatment column.
  • the apparatus comprises a post-treatment column downstream of the second column, the auxiliary column being attached to the post-treatment column.
  • the first unit comprises a methane wash column, the bottom liquid of the wash column being sent to the first column as the mixture and pressurized methane enriched liquid being sent to the wash column.
  • the first unit comprises a washing column, supplied with a washing liquid being rich in carbon monoxide or nitrogen, the bottom liquid of the washing column being sent to the first column.
  • the process produces liquid methane as a final product from the bottom of the second column.
  • the first unit includes a nitrogen wash column, the second liquid contains methane and nitrogen, and the second column produces nitrogen-enriched gas.

L'invention sera décrite en plus de détail par rapport aux Figures.The invention will be described in more detail with respect to the Figures.

La Figure 1 représente un procédé de lavage au méthane selon l'art antérieur, les Figures 2 et 3 représentent des procédés de lavage au méthane selon l'invention, la Figure 4 représente un procédé de condensation partielle selon l'art antérieur, la Figure 5 représente un procédé de condensation partielle selon l'invention, la Figure 6 représente un procédé de lavage au monoxyde de carbone selon l'art antérieur, la Figure 7 représente un procédé de lavage au monoxyde de carbone selon l'invention, la Figure 8 représente un procédé de lavage à l'azote selon l'art antérieur et la Figure 9 représente un procédé de lavage à l'azote selon l'invention.The Figure 1 represents a methane washing process according to the prior art, the Figures 2 and 3 represent methane washing processes according to the invention, the Figure 4 represents a partial condensation process according to the prior art, the Figure 5 represents a partial condensation process according to the invention, the Figure 6 represents a carbon monoxide washing process according to the prior art, the Figure 7 represents a carbon monoxide washing process according to the invention, the Figure 8 shows a nitrogen washing process according to the prior art and the Figure 9 represents a nitrogen washing process according to the invention.

Selon la Figure 1, un mélange d'hydrogène, de monoxyde de carbone et de méthane 1 est épuré dans l'unité 3 pour enlever l'eau et le dioxyde de carbone. Le mélange épuré 5 se refroidit dans l'échangeur cryogénique principal 9 pour être envoyé à un séparateur de phases 7, où il est séparé pour former un gaz 11 enrichi en hydrogène et un liquide 13 enrichi en méthane. Le gaz 11 se sépare dans une colonne 17 de lavage au méthane alimentée en tête par un liquide de lavage 41 riche en méthane.According to Figure 1 , a mixture of hydrogen, carbon monoxide and methane 1 is purified in unit 3 to remove water and carbon dioxide. The purified mixture 5 cools in the main cryogenic exchanger 9 to be sent to a phase separator 7, where it is separated to form a gas 11 enriched in hydrogen and a liquid 13 enriched in methane. The gas 11 separates in a methane washing column 17 fed at the top with a washing liquid 41 rich in methane.

Le liquide de cuve de la colonne 17 est mélangé avec le liquide 13 pour former le liquide 18 riche en CO et CH4 et contenant aussi l'azote envoyé en tête d'une colonne d'épuisement 19 (en anglais « flash column ») ayant un rebouilleur de cuve 22. Le gaz 21 soutiré en tête de la colonne 19 est enrichi en hydrogène et se réchauffe dans l'échangeur 9 pour valorisation en tant que gaz de purge vers un réseau de carburant en général.The bottom liquid of column 17 is mixed with liquid 13 to form liquid 18 rich in CO and CH 4 and also containing nitrogen sent to the top of a stripping column 19 (in English "flash column") having a bottom reboiler 22. The gas 21 withdrawn from the top of the column 19 is enriched in hydrogen and is heated in the exchanger 9 for upgrading as purge gas to a fuel network in general.

Le liquide de cuve 23 de la colonne 19 contient principalement du monoxyde de carbone (et azote) et du méthane et est détendu dans la vanne 25 puis envoyé pour séparation dans la colonne CO/CH4 27. Un gaz 44 enrichi en monoxyde de carbone est formé en tête de la colonne et un liquide enrichi en méthane 33 est formé en cuve de la colonne. Le liquide 33 est divisé en deux, une partie 37 étant réchauffée (ou pas) dans l'échangeur cryogénique principal 9 pour valorisation comme gaz de purge (ou sous forme liquide en bipassant l'échangeur 9) à la pression de la colonne CO/CH4 (quelques bars) et l'autre partie 35 étant pressurisée par une pompe 36 pour alimenter la tête de la colonne de lavage au méthane 17 et pour valorisation éventuelle sous pression (fluide 38) sous forme gazeuse via l'échangeur cryogénique principal 9 (ou directement sous forme liquide en court-circuitant l'échangeur 9).The bottom liquid 23 of column 19 mainly contains carbon monoxide (and nitrogen) and methane and is expanded in valve 25 and then sent for separation in CO / CH 4 column 27. A gas 44 enriched in carbon monoxide is formed at the top of the column and a liquid enriched in methane 33 is formed at the bottom of the column. The liquid 33 is divided into two, a part 37 being heated (or not) in the main cryogenic exchanger 9 for upgrading as purge gas (or in liquid form by bypassing the exchanger 9) at the pressure of the CO / column. CH 4 (a few bars) and the other part 35 being pressurized by a pump 36 to supply the head of the washing column with methane 17 and for possible upgrading under pressure (fluid 38) in gaseous form via the main cryogenic exchanger 9 (or directly in liquid form by short-circuiting exchanger 9).

Un cycle de monoxyde de carbone assure le maintien en froid de l'appareil. Le monoxyde de carbone provenant de la tête de la colonne 27 est réchauffé dans l'échangeur 9, envoyé comme débit 45 à un compresseur 51. Une partie du monoxyde de carbone est produit comme gaz 53 sous pression à la sortie du compresseur. Une autre partie 57 se refroidit dans l'échangeur 9 et est divisée en deux. Une partie 59 à une température intermédiaire de l'échangeur 9 est détendue dans une turbine 61 et envoyée par une vanne 63 par la conduite 65 au compresseur 51. Une autre partie 67 poursuit son refroidissement dans l'échangeur 9. Une fraction 69 du monoxyde de carbone refroidi sert à chauffer le rebouilleur de cuve 22 de la colonne d'épuisement 19 et se trouve condensée. Une autre fraction 71 sert à chauffer le rebouilleur de cuve 31 de la colonne CO/CH4 27 et est mélangée avec la fraction condensée 69. Le débit entier 73 est détendu dans une vanne 73 et envoyé au condenseur de tête 29 de la colonne CO/CH4 où il se vaporise pour former le débit de monoxyde de carbone 43 qui se mélange avec le gaz de tête de la colonne CO/CH4.A carbon monoxide cycle keeps the device cold. The carbon monoxide coming from the top of the column 27 is heated in the exchanger 9, sent as flow 45 to a compressor 51. Part of the carbon monoxide is produced as gas 53 under pressure at the outlet of the compressor. Another part 57 cools in the exchanger 9 and is divided into two. A part 59 at an intermediate temperature of the exchanger 9 is expanded in a turbine 61 and sent by a valve 63 via line 65 to the compressor 51. Another part 67 continues to cool in the exchanger 9. A fraction 69 of the cooled carbon monoxide is used to heat the tank reboiler 22 of the tank. exhaustion column 19 and is condensed. Another fraction 71 is used to heat the bottom reboiler 31 of the CO / CH 4 column 27 and is mixed with the condensed fraction 69. The entire flow 73 is expanded in a valve 73 and sent to the top condenser 29 of the CO column. / CH 4 where it vaporizes to form the flow of carbon monoxide 43 which mixes with the overhead gas from the CO / CH 4 column.

Une partie du liquide 77 du condenseur de tête 29 est envoyée à un séparateur de phases 79. Du séparateur de phases 79 on soutire un liquide 81 qui est envoyé à l'échangeur 21 qui refroidit les soutirages intermédiaires de la colonne de lavage au méthane, le liquide 81 s'y vaporise et le gaz est renvoyé au séparateur de phases 79. Le gaz 83 du séparateur de phases 79 est envoyé à l'entrée du compresseur 51 avec le gaz 43.Part of the liquid 77 from the overhead condenser 29 is sent to a phase separator 79. From the phase separator 79 a liquid 81 is withdrawn which is sent to the exchanger 21 which cools the intermediate withdrawals from the methane washing column, the liquid 81 vaporizes therein and the gas is returned to the phase separator 79. The gas 83 from the phase separator 79 is sent to the inlet of the compressor 51 with the gas 43.

On notera que les trois colonnes 17, 27, 19 sont toutes posées au sol, ce qui augmente la prise (l'encombrement) au sol. Pour répondre à une hauteur hydrostatique nécessaire pour alimenter la pompe 36 en liquide riche en CH4 sans risque de cavitation, la colonne 27 est surélevée d'une hauteur suffisante.It will be noted that the three columns 17, 27, 19 are all placed on the ground, which increases the grip (the size) on the ground. To meet a hydrostatic height necessary to supply the pump 36 with liquid rich in CH4 without risk of cavitation, the column 27 is raised to a sufficient height.

Selon l'invention, comme indiqué Figure 2, la colonne CO/CH4 27 est placée au-dessus de la colonne d'épuisement 19, les deux colonnes ayant le même axe principal. Ainsi le liquide enrichi en méthane 33 de la cuve de la colonne 27 traverse une hauteur H pour arriver à la pompe 36 et se trouve à une pression plus élevée à cause de la pression hydrostatique. Une partie du liquide à la pression surélevée peut être prise pour servir de produit en aval ou en amont de la pompe 36. L'encombrement au sol des colonnes de la boite froide s'en trouve ainsi réduit. En outre, si la somme des hauteurs des deux colonnes 27 et 19 est inférieure à la hauteur de la colonne 17, la longueur du paquet des colonnes de la boite froide n'est pas modifiée.According to the invention, as indicated Figure 2 , the CO / CH 4 column 27 is placed above the exhaustion column 19, the two columns having the same main axis. Thus the liquid enriched in methane 33 from the bottom of the column 27 passes through a height H to reach the pump 36 and is at a higher pressure because of the hydrostatic pressure. Part of the liquid at the elevated pressure can be taken to serve as a product downstream or upstream of the pump 36. The footprint of the columns of the cold box is thus reduced. In addition, if the sum of the heights of the two columns 27 and 19 is less than the height of the column 17, the length of the package of the columns of the cold box is not modified.

Dans une boite froide avec lavage au méthane classique comme illustrée à la Figure 1, la phase liquide 18 du fond de cuve de la colonne de lavage 17 est envoyée vers la colonne d'épuisement 19. Celle-ci a pour fonction d'éliminer l'hydrogène résiduel encore dissout dans le monoxyde de carbone.In a cold box with conventional methane washing as illustrated on Figure 1 , the liquid phase 18 of the bottom of the tank of the washing column 17 is sent to the stripping column 19. This has the function of removing the residual hydrogen still dissolved in the carbon monoxide.

A la différence de la Figure 1, pour améliorer la récupération de monoxyde de carbone, la colonne d'épuisement comprend quelques plateaux supplémentaires en tête de colonne, constituant une colonne auxiliaire 20 à diamètre réduit par rapport à la colonne 19. Dans cette section supplémentaire, la phase gazeuse est lavée à contre-courant par du méthane liquide 39 pour en extraire le monoxyde de carbone encore dissout. Le trafic liquide/vapeur dans cette section 20 est assez faible : tous les autres débits de gaz entrant dans la colonne d'épuisement 19 sont situés en dessous de la section 20. Afin d'assurer une bonne distribution liquide/vapeur et un bon contact entre les phases, il est donc justifié de diminuer le diamètre dans la section supérieure 20 de la colonne d'épuisement : elle prend alors le nom de « colonne auxiliaire » (minaret).Unlike the Figure 1 , to improve the recovery of carbon monoxide, the stripping column comprises a few additional trays at the top of the column, constituting an auxiliary column 20 of reduced diameter compared to column 19. In this additional section, the gas phase is washed with countercurrent with liquid methane 39 to extract the still dissolved carbon monoxide. The liquid / vapor traffic in this section 20 is quite low: all the other gas flows entering the stripping column 19 are located below the section 20. In order to ensure a good liquid / vapor distribution and a good contact between the phases, it is therefore justified to reduce the diameter in the upper section 20 of the exhaustion column: it then takes the name of “auxiliary column” (minaret).

La colonne 19 est alimentée par le liquide de lavage 18 en dessous de la colonne auxiliaire. La colonne auxiliaire 20 est alimentée en tête par un liquide 39 riche en méthane provenant de la pompe 36. Le gaz de tête 21 de la colonne auxiliaire est envoyé après réchauffage dans l'échangeur 9 comme gaz de purge.Column 19 is supplied with washing liquid 18 below the auxiliary column. The auxiliary column 20 is fed at the top with a liquid 39 rich in methane coming from the pump 36. The overhead gas 21 from the auxiliary column is sent after reheating to the exchanger 9 as purge gas.

(A) Pour faciliter son support, la colonne auxiliaire 20 s'intègre sur environ un mètre dans la colonne d'épuisement 19.(A) To facilitate its support, the auxiliary column 20 is integrated for approximately one meter in the exhaustion column 19.

D'autre part, la mise en place de la colonne CO/CH4 27 nécessitant une certaine élévation pour pouvoir alimenter la ou les pompes 36 de méthane positionnées en fond de cuve avec une hauteur nette d'aspiration (désignée par NPSH) disponible suffisante, dans la Figure 2, on propose de positionner la colonne CO/CH4 27 au dessus de la colonne d'épuisement 19 (avec ou sans la colonne auxiliaire 20). C'est souvent l'accumulation verticale de ces deux colonnes 19, 27 ou des trois colonnes 19, 20, 27 cumulées qui détermine le dimensionnement en hauteur du paquet des colonnes. La Figure 3 montre alors une autre variante qui permet de réduire la dimension verticale du paquet (« casing » en anglais) des colonnes (ensemble de la colonne d'épuisement 19 et la colonne CO/CH4 27).On the other hand, the installation of the CO / CH 4 column 27 requiring a certain elevation in order to be able to supply the methane pump (s) 36 positioned at the bottom of the tank with a sufficient net suction height (designated NPSH) available , in the Figure 2 , it is proposed to position the CO / CH 4 column 27 above the stripping column 19 (with or without the auxiliary column 20). It is often the vertical accumulation of these two columns 19, 27 or of the three cumulative columns 19, 20, 27 which determines the height dimensioning of the package of columns. The Figure 3 then shows another variant which makes it possible to reduce the vertical dimension of the package (“casing” in English) of the columns (all of the exhaustion column 19 and the CO / CH 4 column 27).

Une innovation de la présente invention consiste à relocaliser la colonne auxiliaire 20 de tête de colonne d'épuisement, par exemple en la fixant sur le côté de la colonne de lavage 17. Cette relocalisation peut être effectuée ailleurs dans la boite froide (sur une autre colonne par exemple, telle que la deuxième colonne 27 ou une colonne de post-traitement telle qu'une colonne de déazotation) pour autant que la colonne auxiliaire 20 reste positionnée en charge sur la partie inférieure de la colonne d'épuisement 19. Cette idée permet de réduire à la fois :

  • la longueur de la virole de la partie inférieure de la colonne d'épuisement 19 pour la raison (A) mentionnée ci-avant
  • l'élévation de la virole de la colonne CO/CH4 27 grâce au repositionnement de la colonne auxiliaire 20 (tout en s'assurant que la nouvelle élévation reste compatible avec le NPSH requis pour la ou les pompes de méthane).
An innovation of the present invention consists in relocating the auxiliary column 20 at the top of the exhaustion column, for example by fixing it to the side of the washing column 17. This relocation can be carried out elsewhere in the cold box (on another column for example, such as the second column 27 or a post-treatment column such as a denitrogenation column) as long as the auxiliary column 20 remains positioned under load on the lower part of the exhaustion column 19. This idea allows to reduce at the same time:
  • the length of the shell of the lower part of the stripping column 19 for reason (A) mentioned above
  • the elevation of the shell of the CO / CH 4 column 27 thanks to the repositioning of the auxiliary column 20 (while ensuring that the new elevation remains compatible with the NPSH required for the methane pump (s)).

Lorsque le paquet « colonnes « est dimensionné en hauteur par l'ensemble « colonne d'épuisement 19 + colonne CO/CH4 27 », cette hauteur s'en trouve donc réduite.When the “columns” package is dimensioned in height by the “exhaustion column 19 + CO / CH 4 column 27” assembly, this height is therefore reduced.

Selon la Figure 4, un mélange d'hydrogène, de monoxyde de carbone et de méthane 1 est épuré dans l'unité 3 pour enlever l'eau et le dioxyde de carbone. Le mélange épuré 5 se refroidit dans un l'échangeur cryogénique principal 9 pour être envoyé à un séparateur de phases 7, où il est séparé pour former un gaz 11 enrichi en hydrogène et un liquide 13 enrichi en méthane. Le liquide 13 est envoyé en tête d'une colonne d'épuisement 19 ayant un rebouilleur de cuve 22. Le gaz 21 soutiré en tête de la colonne 19 est enrichi en hydrogène et se réchauffe dans l'échangeur 9 pour valorisation en tant que gaz de purge vers un réseau de carburant en général.According to Figure 4 , a mixture of hydrogen, carbon monoxide and methane 1 is purified in unit 3 to remove water and carbon dioxide. The purified mixture 5 cools in a main cryogenic exchanger 9 to be sent to a phase separator 7, where it is separated to form a gas 11 enriched in hydrogen and a liquid 13 enriched in methane. The liquid 13 is sent to the top of a stripping column 19 having a bottom reboiler 22. The gas 21 withdrawn from the top of the column 19 is enriched in hydrogen and is heated in the exchanger 9 for upgrading as gas. purge to a fuel network in general.

Le liquide de cuve 23 de la colonne 19 contient principalement du monoxyde de carbone et du méthane et est envoyé se séparer dans la colonne CO/CH4 27. Un gaz enrichi en monoxyde de carbone est formé en tête de la colonne et un liquide enrichi en méthane 33 est formé en cuve de la colonne. Le liquide 35 est réchauffé dans l'échangeur pour servir de carburant. Le liquide 33 est divisé en deux, une partie 37 étant réchauffée (ou pas) dans l'échangeur cryogénique principal 9 pour valorisation comme gaz de purge (ou sous forme liquide en court-circuitant l'échangeur 9) à la pression de la colonne CO/CH4 (quelques bars) et l'autre partie 35 étant pressurisée par une pompe 36 pour valorisation éventuelle sous pression (fluide 38) sous forme gazeuse via l'échangeur cryogénique principal 9 (ou directement sous forme liquide en bipassant l'échangeur 9).The bottom liquid 23 of column 19 mainly contains carbon monoxide and methane and is sent to separate in the CO / CH 4 column 27. A gas enriched in carbon monoxide is formed at the top of the column and an enriched liquid. methane 33 is formed at the bottom of the column. The liquid 35 is heated in the exchanger to serve as fuel. The liquid 33 is divided into two, a part 37 being heated (or not) in the exchanger main cryogenic 9 for recovery as purge gas (or in liquid form by short-circuiting the exchanger 9) at the pressure of the CO / CH 4 column (a few bars) and the other part 35 being pressurized by a pump 36 for possible recovery under pressure (fluid 38) in gaseous form via the main cryogenic exchanger 9 (or directly in liquid form by bypassing the exchanger 9).

Un cycle de monoxyde de carbone assure le maintien en froid de l'appareil. Le monoxyde de carbone provenant de la tête de la colonne 27 est réchauffé dans l'échangeur 9, envoyé comme débit 45 à un compresseur 51. Une partie du monoxyde de carbone est produite comme gaz 53 sous pression à la sortie du compresseur. Une autre partie 57 se refroidit dans l'échangeur 9 et est divisée en deux. Une partie 59 à une température intermédiaire de l'échangeur 9 est détendue dans une turbine 61 et envoyée par une vanne 63 par la conduite 65 au compresseur 51. Une autre partie poursuit son refroidissement dans l'échangeur 9. Une fraction 69 du monoxyde de carbone refroidi sert à chauffer le rebouilleur de cuve 22 de la colonne 19 et se trouve condensée. Une autre fraction 71 sert à chauffer le rebouilleur de cuve 31 de la colonne CO/CH4 27 et est mélangée avec la fraction condensée 69. Le débit entier 73 est détendu dans une vanne et envoyé au condenseur de tête 29 de la colonne CO/CH4 où il se vaporise pour former le débit de monoxyde de carbone 43 qui va alimenter le compresseur 51 après passage dans l'échangeur 9.A carbon monoxide cycle keeps the device cold. The carbon monoxide coming from the top of the column 27 is heated in the exchanger 9, sent as flow 45 to a compressor 51. Part of the carbon monoxide is produced as gas 53 under pressure at the outlet of the compressor. Another part 57 cools in the exchanger 9 and is divided into two. A part 59 at an intermediate temperature of the exchanger 9 is expanded in a turbine 61 and sent by a valve 63 via the line 65 to the compressor 51. Another part continues its cooling in the exchanger 9. A fraction 69 of the monoxide of cooled carbon serves to heat the bottom reboiler 22 of column 19 and is condensed. Another fraction 71 is used to heat the bottom reboiler 31 of the CO / CH 4 column 27 and is mixed with the condensed fraction 69. The entire flow 73 is expanded in a valve and sent to the top condenser 29 of the CO / column. CH 4 where it vaporizes to form the flow of carbon monoxide 43 which will feed the compressor 51 after passing through the exchanger 9.

On notera que les deux colonnes 19, 27 sont toutes posées au sol.It will be noted that the two columns 19, 27 are all placed on the ground.

Pour l'innovation de la Figure 5, on notera qu'à la différence de la Figure 4, la colonne 27 est positionnée au-dessus la colonne 19, qui est elle-même positionnée au-dessus du séparateur de phases 7. Il est également possible de placer le séparateur de phases 7 à côté des deux colonnes 19, 27.For the innovation of Figure 5 , it will be noted that unlike the Figure 4 , column 27 is positioned above column 19, which is itself positioned above phase separator 7. It is also possible to place phase separator 7 next to two columns 19, 27.

Selon la Figure 6, un mélange d'hydrogène, de monoxyde de carbone, d'azote et de méthane 1 est épuré dans l'unité 3 pour enlever l'eau et le dioxyde de carbone. Le mélange épuré 5 se refroidit dans un échangeur 9 pour être envoyé à un séparateur de phases 7, où il est séparé pour former un gaz 11 enrichi en hydrogène et un liquide 13 enrichi en méthane. Le gaz 11 se sépare dans une colonne 601 de lavage au monoxyde de carbone alimentée en tête par un liquide de lavage 623 riche en monoxyde de carbone.According to Figure 6 , a mixture of hydrogen, carbon monoxide, nitrogen and methane 1 is purified in unit 3 to remove water and carbon dioxide. The purified mixture 5 cools in an exchanger 9 to be sent to a phase separator 7, where it is separated to form a gas 11 enriched in hydrogen and a liquid 13 enriched in methane. Gas 11 separates in a carbon monoxide washing column 601 fed at the top with a washing liquid 623 rich in carbon monoxide.

Le liquide de cuve de la colonne 601 est mélangé avec le liquide 13 pour former le liquide 18 et le liquide formé est envoyé en tête d'une colonne d'épuisement 19 (en anglais « flash column ») ayant un rebouilleur de cuve 22. Le gaz 21 soutiré en tête de la colonne 19 est enrichi en hydrogène et se réchauffe dans l'échangeur 9 pour valorisation en tant que gaz de purge vers un réseau de carburant en général....The bottom liquid of the column 601 is mixed with the liquid 13 to form the liquid 18 and the liquid formed is sent to the top of a stripping column 19 (in English “flash column”) having a bottom reboiler 22. The gas 21 withdrawn from the top of column 19 is enriched in hydrogen and is heated in exchanger 9 for upgrading as purge gas to a fuel network in general ....

Le liquide de cuve 23 de la colonne 19 contient principalement du monoxyde de carbone et du méthane et est envoyé se séparer dans la colonne CO/CH4 27. Un gaz enrichi en monoxyde de carbone 43 est formé en tête de la colonne et un liquide enrichi en méthane 33 est formé en cuve de la colonne. Le liquide 33 est divisé en deux, une partie 37 étant réchauffée (ou pas) dans l'échangeur cryogénique principal 9 pour valorisation comme gaz de purge (ou sous forme liquide en court-circuitant l'échangeur 9) à la pression de la colonne CO/CH4 27 (quelques bars) et l'autre partie 35 étant pressurisée par une pompe 36 pour valorisation éventuelle sous pression (fluide 38), sous forme gazeuse via l'échangeur cryogénique principal 9 (ou directement sous forme liquide en court-circuitant l'échangeur 9).The bottom liquid 23 of column 19 mainly contains carbon monoxide and methane and is sent to separate in the CO / CH 4 column 27. A gas enriched in carbon monoxide 43 is formed at the top of the column and a liquid. enriched in methane 33 is formed at the bottom of the column. The liquid 33 is divided into two, a part 37 being heated (or not) in the main cryogenic exchanger 9 for upgrading as purge gas (or in liquid form by short-circuiting the exchanger 9) at the pressure of the column CO / CH 4 27 (a few bars) and the other part 35 being pressurized by a pump 36 for possible recovery under pressure (fluid 38), in gaseous form via the main cryogenic exchanger 9 (or directly in liquid form in short- circuiting the exchanger 9).

Un cycle de monoxyde de carbone assure le maintien en froid de l'appareil. Le monoxyde de carbone provenant de la tête de la colonne 27 est réchauffé dans l'échangeur 9, envoyé comme débit 45 à un compresseur 51. Une partie du monoxyde de carbone est produite comme gaz 53 sous pression à la sortie du compresseur. Une autre partie 57 se refroidit dans l'échangeur 9 et est divisée en deux. Une partie 59 est détendue dans une vanne 63 puis envoyée par la conduite 65 au compresseur 51. Une autre partie est divisée en deux fractions. Une fraction 69 du monoxyde de carbone refroidi sert à chauffer le rebouilleur de cuve 22 de la colonne d'épuisement 19 et se trouve condensée. Une autre fraction 71 sert à chauffer le rebouilleur de cuve 631 de la colonne CO/CH4 27 et est mélangée avec la fraction condensée 71. Le débit entier 73 est détendu dans une vanne et envoyé au condenseur de tête 619 de la colonne CO/CH4 où il se vaporise pour former le fluide 43 de monoxyde de carbone. Un bain de monoxyde de carbone 29 en tête de la colonne 27 alimente le condenseur 619 en gaz à condenser.A carbon monoxide cycle keeps the device cold. The carbon monoxide coming from the top of the column 27 is heated in the exchanger 9, sent as flow 45 to a compressor 51. Part of the carbon monoxide is produced as gas 53 under pressure at the outlet of the compressor. Another part 57 cools in the exchanger 9 and is divided into two. A part 59 is expanded in a valve 63 then sent through line 65 to the compressor 51. Another part is divided into two fractions. A fraction 69 of the cooled carbon monoxide serves to heat the bottom reboiler 22 of the stripping column 19 and is condensed. Another fraction 71 is used to heat the bottom reboiler 631 of the CO / CH 4 column 27 and is mixed with the condensed fraction 71. The entire flow 73 is expanded in a valve and sent to the overhead condenser 619 of the CO / column. CH 4 where it vaporizes to form the carbon monoxide fluid 43. A carbon monoxide bath 29 at the top of column 27 supplies condenser 619 with gas to be condensed.

Dans le cas où le monoxyde de carbone contient trop d'azote, le gaz de tête 635 de la colonne 27 est envoyé à la colonne de déazotation 603 ayant un condenseur de tête 615. Le liquide de cuve 613 de la colonne de déazotation 603 se vaporise dans le condenseur de tête 615 et est mélangé au fluide 43 pour former le fluide 45 qui est envoyé au compresseur 51 via l'échangeur 9. Le gaz de tête enrichi en azote 617 est réchauffé dans l'échangeur 9 et dirigé vers un réseau de carburant. Le monoxyde de carbone nécessaire au lavage dans la colonne 603 est assuré par les fluides 609 et 611 soutirés au refoulement du compresseur 51. Une partie de ces fluides est envoyée comme débit 623 en tête de la colonne de lavage 601. La mise en place d'une colonne de déazotation peut être applicable dans tous les cas de figure précédemment cités lorsque l'azote doit être partiellement ou totalement retiré du gaz produit.In the event that the carbon monoxide contains too much nitrogen, the overhead gas 635 from the column 27 is sent to the denitrogenation column 603 having an overhead condenser 615. The bottom liquid 613 from the denitrogenation column 603 is sent to the denitrogenation column 603. vaporizes in the overhead condenser 615 and is mixed with the fluid 43 to form the fluid 45 which is sent to the compressor 51 via the exchanger 9. The overhead gas enriched in nitrogen 617 is heated in the exchanger 9 and directed to a network fuel. The carbon monoxide necessary for washing in column 603 is provided by the fluids 609 and 611 withdrawn from the discharge of the compressor 51. A portion of these fluids is sent as flow 623 to the head of the washing column 601. The installation of A denitrogenation column can be applicable in all the cases mentioned above when the nitrogen must be partially or totally removed from the gas produced.

On notera que les quatre colonnes 601, 19, 27, 603 sont toutes posées sur le sol, ce qui augmente la prise au sol.It will be noted that the four columns 601, 19, 27, 603 are all placed on the ground, which increases the grip on the ground.

Selon l'innovation de la Figure 7, la colonne CO/CH4 27 est positionnée au-dessus de la colonne d'épuisement 19 pour que le débit riche en méthane liquide 35 soit pressurisé hydrostatiquement en amont de la pompe 36.According to the innovation of the Figure 7 , the CO / CH 4 column 27 is positioned above the stripping column 19 so that the flow rate rich in liquid methane 35 is hydrostatically pressurized upstream of the pump 36.

La Figure 8 montre un procédé de lavage à l'azote dans lequel un mélange d'hydrogène, de monoxyde de carbone, d'azote et de méthane 1 sort d'une unité de type Rectisol ® 804 et est épuré dans une unité d'épuration 3 pour retirer l'eau, le méthanol et le CO2 (adsorber le méthanol ou tout autre solvant utilisé dans un lavage amont peut être également requis dans tous les cas de figure précédemment cités). Le mélange épuré 5 est refroidi dans l'échangeur 9 puis envoyé à un séparateur de phases 7. Le gaz du séparateur de phases 7 est mélangé avec une partie 6 non refroidie du gaz 5 pour former le débit 11. Une partie du débit 11 est utilisé pour réchauffer le rebouilleur de cuve 851 d'une colonne N2/CH4 850, en étant partiellement condensé. Le débit partiellement condensé est envoyé à un séparateur de phases 809. Le liquide 819 du séparateur 809 est riche en méthane et est envoyé à la pompe 36. Le gaz 827 du séparateur 809 rejoint du gaz 821 du séparateur 7, est refroidi dans l'échangeur 9, puis séparé dans un séparateur de phases 807 et le gaz produit 814 alimente la colonne de lavage à l'azote 811 pour être séparé.The Figure 8 shows a nitrogen washing process in which a mixture of hydrogen, carbon monoxide, nitrogen and methane 1 leaves a unit of the Rectisol ® 804 type and is purified in a purification unit 3 for remove the water, the methanol and the CO 2 (adsorbing the methanol or any other solvent used in an upstream wash may also be required in all the cases mentioned above). The purified mixture 5 is cooled in the exchanger 9 and then sent to a phase separator 7. The gas from the phase separator 7 is mixed with an uncooled part 6 of the gas 5 to form the flow 11. Part of the flow 11 is used to reheat the bottom reboiler 851 of an N 2 / CH 4 850 column, being partially condensed. The partially condensed flow is sent to a phase separator 809. The liquid 819 from the separator 809 is rich in methane and is sent to the pump 36. The gas 827 from the separator 809 joins gas 821 from separator 7, is cooled in exchanger 9, then separated in a phase separator 807 and the product gas 814 feeds the washing column with nitrogen 811 to be separated.

La colonne 811 est alimentée en tête par un débit de liquide 833 produit par la liquéfaction d'un débit 831 d'azote gazeux dans l'échangeur 9. Une autre partie 835 de l'azote condensé est mélangée avec le gaz de tête 829 réchauffé de la colonne 811 contenant de l'hydrogène et envoyé à l'unité d'extraction de CO2/H2S (Rectisol ® par exemple) 804 pour échange thermique ; le gaz formé 843 sort de l'appareil.Column 811 is fed at the top with a flow of liquid 833 produced by the liquefaction of a flow 831 of gaseous nitrogen in exchanger 9. Another part 835 of the condensed nitrogen is mixed with the heated top gas 829. column 811 containing hydrogen and sent to the CO 2 / H 2 S extraction unit (Rectisol ® for example) 804 for heat exchange; the gas formed 843 leaves the apparatus.

Le liquide de cuve 847 de la colonne de lavage à l'azote 811 est détendu, puis envoyé à un séparateur de phases 845. Le gaz produit 853 se réchauffe dans l'échangeur 9 comme gaz de purge. Le liquide 849 alimente la colonne N2/CH4 850 pour former un débit gazeux 852 appauvri en méthane et enrichi en azote et un débit liquide enrichi en méthane. Le débit liquide enrichi en méthane 35 est envoyé à la pompe 36, puis alimente un séparateur de phases 821. Le gaz 825 est envoyé à l'échangeur 9 pour produire une phase gazeuse riche en méthane. Le liquide 823 peut soit être également envoyé à l'échangeur 9 pour produire une phase riche en méthane gazeuse sous pression, soit court-circuiter l'échangeur 9 pour produire du méthane liquide sous pression comme produit final. Il est également possible de produire une phase riche en méthane gazeuse ou liquide à basse pression en vaporisant du liquide pris en amont de la pompe 36.The bottom liquid 847 of the nitrogen washing column 811 is expanded, then sent to a phase separator 845. The product gas 853 is heated in the exchanger 9 as purge gas. The fluid 849 feeds the column N 2 / CH 4 850 852 to form a gas flow depleted in methane and enriched in nitrogen and a liquid stream enriched in methane. The liquid flow enriched in methane 35 is sent to the pump 36, then feeds a phase separator 821. The gas 825 is sent to the exchanger 9 to produce a gas phase rich in methane. The liquid 823 can either also be sent to the exchanger 9 to produce a phase rich in gaseous methane under pressure, or bypass the exchanger 9 to produce liquid methane under pressure as a final product. It is also possible to produce a phase rich in gaseous or liquid methane at low pressure by vaporizing liquid taken upstream of the pump 36.

Dans l'innovation de la Figure 9, la colonne N2/CH4 850 est disposée au-dessus de la colonne de lavage à l'azote 811.In the innovation of Figure 9 , Column N 2 / CH 4 850 is disposed above the wash column 811 with nitrogen.

Dans une alternative non couverte par la présente invention, on pourrait également envisager de surélever la colonne 27 en la plaçant uniquement au-dessus d'un séparateur de phases, par exemple au-dessus du séparateur 7 pour la Figure 4, du séparateur 7 pour la Figure 6 ou un des séparateurs 7, 807, 809, 845 pour la Figure 8.In an alternative not covered by the present invention, one could also consider raising the column 27 by placing it only above a phase separator, for example above the separator 7 for the separation. Figure 4 , of separator 7 for the Figure 6 or one of the separators 7, 807, 809, 845 for the Figure 8 .

Claims (15)

  1. Apparatus for cryogenically separating a mixture (5) of methane, carbon monoxide and hydrogen and optionally nitrogen comprising a first separation unit comprising at least a first column (19, 811) and optionally a phase separator (7, 807, 809, 821, 845), the first separation unit being supplied by the mixture (5, 814), a first duct for releasing a gas enriched in hydrogen and optionally in nitrogen (21, 829) from the first unit, a second duct for releasing a liquid (23, 847, 849) containing methane and carbon monoxide from the first column or from the phase separator, a second column (27, 850) connected to the second duct, a third duct connected to the bottom of the second column in order to withdraw a methane-enriched liquid (33) and a fourth duct connected to the top of the second column in order to withdraw a gas enriched in carbon monoxide and optionally in nitrogen (43, 852), the second column comprising a bottom reboiler (31), the apparatus not comprising means for sending overhead gas from the first column in order to heat the bottom reboiler of the second column and the second duct being a duct connected to the bottom of the first column, characterized in that the first column is positioned below the second column, the two columns have the same main axis, so that the methane-enriched liquid (33) is produced at a higher pressure than the pressure of the bottom of the second column, and the methane-enriched liquid is produced at the higher pressure at least partly by hydrostatic pressure.
  2. Apparatus according to Claim 1, comprising a pump (36) connected to the third duct, positioned closer to the ground than the bottom of the second column (27, 850) .
  3. Apparatus according to Claim 2, comprising an auxiliary column (20), the top of which is optionally connected to the pump (36) and the bottom of which is connected to the top of the first column (19, 811) by means for sending overhead gas from the first column to the bottom of the auxiliary column and by means for sending bottoms liquid from the auxiliary column to the top of the first column, the auxiliary column being optionally positioned next to the first column.
  4. Apparatus according to Claim 3, wherein the auxiliary column (20) is positioned so that its bottom is further from the ground than the top of the first column (19) .
  5. Apparatus according to Claim 3 or 4, wherein the auxiliary column (20) is attached to the second column (27) or the first unit comprises a pretreatment column (17), a duct for transporting the mixture from the pretreatment column to the first column, the auxiliary column being attached to the pretreatment column or the apparatus comprises a post-treatment column downstream of the second column, the auxiliary column being attached to the post-treatment column.
  6. Apparatus according to one of Claims 2 to 5, wherein the first unit comprises a methane scrubbing column (17), this column being connected to the first column (19) in order to supply it with the mixture which is a bottoms liquid from the methane scrubbing column, the top of the methane scrubbing column being connected to the pump (36).
  7. Apparatus according to one of Claims 1 to 5, wherein the first unit comprises a phase separator (7) and means for transporting liquid from the phase separator such as the mixture that supplies the first column.
  8. Apparatus according to one of Claims 1 to 5, wherein the first unit comprises a scrubbing column (601), the scrubbing liquid being rich in carbon monoxide, and also means for sending the bottoms liquid from the scrubbing column to the first column (19).
  9. Apparatus according to one of the preceding claims, comprising means for producing liquid methane as final product.
  10. Process for cryogenically separating a mixture of methane and carbon monoxide and also hydrogen and optionally nitrogen, wherein a first separation of the mixture is carried out using at least a first column (19, 811), supplied by the mixture, in order to produce a fluid (23, 847, 849) enriched in methane and containing carbon monoxide, and optionally nitrogen, and also a gas enriched in hydrogen (21, 829), the fluid is separated in a second column (27, 850) in order to produce a gas enriched in carbon monoxide (45), and optionally in nitrogen, and a methane-enriched liquid (35, 37), the second column comprising a bottom reboiler (31) which is heated by a gas (71) other than an overhead gas from the first column and the methane-enriched fluid originates from the bottom of the first column, characterized in that the first column is positioned below the second column, the two columns having the same main axis so that the methane-enriched liquid is pressurized at a higher pressure than the pressure of the bottom of the second column at least partly by hydrostatic pressure.
  11. Process according to Claim 10, wherein the bottom reboiler (31) is heated by a cycle gas (71) which is carbon monoxide.
  12. Process according to either of Claims 10 and 11, wherein an overhead gas (21) from the first column (19) is reheated in an exchanger (9) where the mixture is cooled.
  13. Process according to Claim 12, wherein all the overhead gas (21) from the first column is reheated in the exchanger (9).
  14. Process according to one of Claims 10 to 13, wherein the methane-enriched liquid (35) is pressurized partly by a pump (36) positioned closer to the ground than the bottom of the second column (27).
  15. Process according to Claim 14, wherein the pump (36) is on the ground.
EP13727260.5A 2012-05-31 2013-05-06 Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and optionally nitrogen Active EP2856050B1 (en)

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FR1255063A FR2991442B1 (en) 2012-05-31 2012-05-31 APPARATUS AND METHOD FOR CRYOGENIC SEPARATION OF A MIXTURE OF CARBON MONOXIDE AND METHANE AND HYDROGEN AND / OR NITROGEN
PCT/FR2013/051003 WO2013178901A2 (en) 2012-05-31 2013-05-06 Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and/or nitrogen

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FR3052159B1 (en) * 2016-06-06 2018-05-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude PROCESS AND PLANT FOR THE COMBINED PRODUCTION OF A MIXTURE OF HYDROGEN AND NITROGEN AND CARBON MONOXIDE BY CRYOGENIC DISTILLATION AND WASH
US11137204B2 (en) * 2016-08-25 2021-10-05 Praxair Technology, Inc. Process and apparatus for producing carbon monoxide
FR3057942B1 (en) * 2016-10-21 2019-12-27 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A SYNTHESIS GAS BY PARTIAL CONDENSATION
FR3079288B1 (en) * 2018-03-21 2020-05-22 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude METHOD AND APPARATUS FOR SEPARATING SYNTHESIS GAS BY CRYOGENIC DISTILLATION
SG11202008918SA (en) 2018-03-21 2020-10-29 Air Liquide Method and appliance for separating a synthesis gas by cryogenic distillation
CN108332510A (en) * 2018-03-22 2018-07-27 上海华林工业气体有限公司 A kind of system and method improving the HyCO ice chest CO rate of recovery
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EP2856050A2 (en) 2015-04-08
CN104769376B (en) 2016-08-31
FR2991442A1 (en) 2013-12-06
FR2991442B1 (en) 2018-12-07
CN104769376A (en) 2015-07-08
WO2013178901A2 (en) 2013-12-05
PL2856050T3 (en) 2021-10-25

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