EP3049741B1 - Verfahren und vorrichtung zur kryogenen trennung einer mischung mit mindestens kohlenstoffmonoxid, wasserstoff und stickstoff - Google Patents

Verfahren und vorrichtung zur kryogenen trennung einer mischung mit mindestens kohlenstoffmonoxid, wasserstoff und stickstoff Download PDF

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EP3049741B1
EP3049741B1 EP14796181.7A EP14796181A EP3049741B1 EP 3049741 B1 EP3049741 B1 EP 3049741B1 EP 14796181 A EP14796181 A EP 14796181A EP 3049741 B1 EP3049741 B1 EP 3049741B1
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Prior art keywords
column
gas
hydrogen
enriched
nitrogen
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English (en)
French (fr)
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EP3049741A2 (de
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Angela FERNANDEZ
Pascal Marty
Bhadri PRASAD
Marie-Pascal Victor
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0655—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation 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
    • F25J3/0204—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
    • F25J3/0233—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
    • 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
    • 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
    • F25J3/0295—Start-up or control of the process; Details of the apparatus used, e.g. sieve plates, packings
    • 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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0635—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • 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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/066—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation 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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0665—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation 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
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • 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
    • F25J2200/72—Refluxing the column with at least a part of the totally 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • 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
    • 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
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/60—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being (a mixture of) hydrocarbons
    • 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • 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
    • F25J2280/00—Control of the process or apparatus
    • F25J2280/02—Control in general, load changes, different modes ("runs"), measurements

Definitions

  • the present invention relates to a process and apparatus for cryogenic separation of a mixture containing at least carbon monoxide, hydrogen and nitrogen.
  • the nitrogen content is fluctuating
  • the condensers at the top of the columns CO / N 2 are of type "bath vaporizer”.
  • the condenser installed has de facto an excess of heat exchange surface leading to condense all of the mixture CO / N 2 bottom tank, which no longer allows to maintain the operating pressure of the column. It is no longer possible to maintain the purity of the CO to be produced and the risk of stopping the unit follows.
  • FR-A-2895067 and WO-2008/099124 describe solutions using an addition of nitrogen in case of drop of nitrogen content in the mixture.
  • an apparatus for the cryogenic separation of a mixture of carbon monoxide, hydrogen, and nitrogen and optionally methane comprising a depletion column, a denitrogenation column and optionally a separation column having an overhead condenser, a conduit for supplying the mixture, in liquid form at the top of the depletion column, a conduit for removing a hydrogen-depleted liquid connected to the depletion column, a conduit for removing a hydrogen-enriched gas from the depletion column, means for sending the depleted liquid to hydrogen or a fluid derived from this liquid at the denitrogenation column, a pipe for withdrawing a carbon monoxide enriched liquid from the denitrogenation column and a pipe for withdrawing a nitrogen-enriched gas from the head of the denitrogenation column, characterized in that it comprises means for sending at least a portion of the hydrogen enriched gas or fluid derived therefrom to the denitrogenation column.
  • the apparatus may include a separation column having an overhead condenser and wherein the means for supplying fluid derived from the hydrogen-enriched gas to the denitrogenation column comprises a conduit for supplying at least a portion of the hydrogen-enriched gas to an hydrogen-depleted liquid separation column, the conduit being connected to an intermediate point of the separation column and a conduit for supplying gas from the overhead condenser which has not condensed thereon to the denitrogenation column.
  • the apparatus may include a separation column having an overhead condenser, the conduit for removing the hydrogen depleted liquid from the depletion column being connected to the separation column, the conduit for removing a hydrogen enriched gas being connected to the separation column and comprising a carbon monoxide enriched gas outlet line at the top of the separation column and a pipe for sending a non-condensed gas from the head condenser (6) of the separation column to the denitrogenation column .
  • the apparatus may include means for detecting the nitrogen content of the mixture and / or nitrogen enriched gas and / or carbon monoxide enriched gas and means for controlling the flow rate of the at least a portion of the enriched gas. hydrogen or fluid derived from this gas sent to the denitrogenation column.
  • the apparatus may comprise means for sending at least a portion of the hydrogen-enriched gas to the separation column at an intermediate point of the separation column or to the denitrogenation column by a detector of the nitrogen content of the mixture and / or gas enriched with carbon monoxide and / or nitrogen enriched gas and / or a flow detector of the mixture and / or carbon monoxide enriched gas and / or nitrogen enriched gas.
  • the innovation of the present invention is to compensate for nitrogen reduction by importing a portion of the overhead gas from the column from exhaustion upstream of the CO / N 2 column to the CO / N 2 column: the overhead gas of the depletion column contains hydrogen, which makes it possible to increase the flow rate of incondensables directed towards the CO / N column 2 .
  • flow control means (FIC)
  • a mixture of carbon monoxide, nitrogen and hydrogen is cooled in an exchanger 9 and sent to a distillation column 1 (or separator pot).
  • a hydrogen-enriched overhead gas 12 exits at the top of the column 1 and heats up in the exchanger 9.
  • the tank liquid 13 is expanded and then sent to the top of a depletion column 2 heated in the tank by a reboiler 8.
  • the hydrogen enriched overhead gas 14 is heated in the exchanger 9 and then burned.
  • the tank liquid containing mainly nitrogen and carbon monoxide is expanded and sent to the middle of a denitrogenation column 4.
  • the tank liquor enriched in carbon monoxide is sent to the exchanger 18 where it is used to condensing the overhead gas from the denitrogenation column.
  • a nitrogen-enriched gas exits the column head.
  • valve of the pipe 26 opens and hydrogen-enriched gas is sent from the top of the depletion column to the denitrogenation column 4, preferably by mixing it with the gas formed by expanding the liquid of line 16 in a valve.
  • the mixture to be separated comprises nitrogen, hydrogen, methane and carbon monoxide.
  • the incondensables (H 2 -N 2 ) of the CO / CH 4 column are not recovered: they are sent directly to the flare or to a fuel network
  • the innovation consists in offsetting the reduction of nitrogen by an import of overhead gas (which contains hydrogen) from the exhaustion column upstream of the CO / CH 4 column, to the CO / CH 4 column. then an import of incondensables from the CO / CH 4 column to the CO / N 2 column.
  • the flows of each of the new lines are controlled by a FIC.
  • the impure CO flow rate is controlled by a PIC added to the CO / CH 4 column in order to decouple the two operating pressures of the columns.
  • the incondensables at the head of column CO / N 2 are then directed to the fuel network via the purge line N 2 which passes through the exchange line.
  • a mixture of carbon monoxide, nitrogen, hydrogen and methane is cooled in an exchanger 9 and sent to a methane feed column 1 fed at the top with liquid methane 11 or to a separator pot.
  • a hydrogen-enriched overhead gas 12 leaves at the top of column 1 and heats up in exchanger 9.
  • the tank liquid 13 is expanded and sent to the top of a depletion column 2 heated in the tank by a reboiler 8.
  • the hydrogen enriched overhead gas 14 is heated in the exchanger 9 and then burned.
  • the vessel liquid containing mainly methane and carbon monoxide is expanded and sent to the middle of a distillation column 3 having a vessel reboiler 7 and a head condenser 6.
  • An incondensable gas flow 22 has come out of this condenser 6.
  • a carbon monoxide enriched overhead gas 16 exits the column 3 and is sent to the denitrogenation column 4.
  • the tank liquid enriched in methane is pumped by the pump 5, divided in two.
  • a portion 20 vaporizes in the exchanger 9 and the remainder feeds the washing column 1 as flow 11.
  • a nitrogen-enriched gas 21 leaves the head of the column and a liquid 22 exits the carbon monoxide enriched tank.
  • the carbon monoxide vaporizes in the head condenser 18 which is a bath vaporizer.
  • the flow rates of each of the new lines 24, 26 are controlled by a detector of minimum nitrogen purity of the nitrogen purge 21 coming from the head of the column CO / N 2 4 in general after passing through the exchange lines. .
  • the impure CO flow 16 is controlled by a pressure controller added to the CO / CH 4 column in order to decouple the two operating pressures of the columns.
  • Condensable, including hydrogen, columnar head CO / N 2 are then directed to a fuel network via the nitrogen purge line 21 which passes through the heat exchange line.

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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)

Claims (13)

  1. Verfahren zur kryogenen Trennung einer Mischung, enthaltend mindestens Kohlenmonoxid, Wasserstoff und Stickstoff, wobei: die Mischung (13) in flüssiger Form an den Kopf einer Abstreifsäule (2) geschickt wird, wo sie sich trennt, um eine Flüssigkeit, abgereichert an Wasserstoff (15, 16) und ein Gas, angereichert mit Wasserstoff (14), zu bilden, die Flüssigkeit (16), abgereichert an Wasserstoff oder ein Fluid (16), abgeleitet von dieser Flüssigkeit, an eine Säule zum Entfernen von Stickstoff (4) geschickt wird, wo sie sich trennt, um eine Flüssigkeit, angereichert mit Kohlenmonoxid (22) und ein Gas, angereichert mit Stickstoff (21), zu bilden, umfassend den Hauptteil des Stickstoffs, der in der Mischung enthalten ist,
    dadurch gekennzeichnet, dass:
    - wenn der Gehalt an Stickstoff der Mischung und/oder des Gases, angereichert mit Stickstoff und/oder für die Variante ii) eines Gases, angereichert mit Kohlenmonoxid (16), geringer als ein Schwellenwert ist,
    i) mindestens ein Teil des Gases, angereichert mit Wasserstoff (26), der von der Abstreifsäule stammt, an einen Zwischenpunkt der Säule zum Entfernen von Stickstoff geschickt wird, oder
    ii) wenn das Fluid von der Flüssigkeit, abgereichert an Wasserstoff, durch Destillation in einer Trennsäule (3) abgeleitet ist, mindestens ein Teil (26) des Gases, angereichert mit Wasserstoff (14), der von der Abstreifsäule stammt, an einen Zwischenpunkt der Trennsäule geschickt wird, das Gas, angereichert mit Kohlenmonoxid am Kopf der Trennsäule entfernt wird, und ein nicht kondensiertes Gas (24) eines Kopfkondensators (6) der Trennsäule an die Säule zum Entfernen von Stickstoff geschickt wird.
  2. Verfahren nach Anspruch 1, wobei gemäß Variante ii) die Mischung Methan enthält und die Flüssigkeit, abgereichert an Wasserstoff (15), in die Trennsäule (3) geschickt wird, wobei diese einen Kopfkondensator aufweist, wobei eine Flüssigkeit, angereichert mit Methan (19), im Sumpf erzeugt wird, und ein Gas (16), angereichert mit Kohlenmonoxid, am Kopf der Säule entnommen wird.
  3. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Schicken des Gases, angereichert mit Wasserstoff (26), an die Trennsäule (3) oder an die Säule zum Entfernen von Stickstoff (4) durch einen Detektor des Durchsatzes des Gases, angereichert mit Stickstoff (21), ausgelöst wird.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei für die Variante ii) das Schicken von nicht kondensiertem Gas (24) im Kondensator (6) hin zur Säule zum Entfernen von Stickstoff durch einen Detektor des Durchsatzes, angereichert mit Stickstoff am Kopf der Säule zum Entfernen von Stickstoff ausgelöst wird.
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei für die Variante ii), wo die Trennsäule (3) mit Druck von der Säule zum Entfernen von Stickstoff (4) durch einen Druckdetektor (PIC) auf dem Gas, angereichert mit Kohlenmonoxid (16), am Kopf der Trennsäule entkoppelt wird.
  6. Verfahren nach einem der vorhergehenden Ansprüche für die Variante ii), wobei das nicht kondensierte Gas (24) im Kondensator mit dem Gas (16), angereichert mit Kohlenmonoxid, gemischt wird.
  7. Verfahren nach einem der vorhergehenden Ansprüche für die Variante ii), wobei nur dann, wenn der Gehalt an Stickstoff der Mischung und/oder des Gases, angereichert mit Kohlenmonoxid und/oder des Gases, angereichert mit Stickstoff, geringer als ein Schwellenwert ist, mindestens ein Teil des Gases, angereichert mit Wasserstoff (26), an die Trennsäule (3) an einen Zwischenpunkt der Trennsäule geschickt wird, und ein Gas (24), das vom Kopfkondensator stammt, das dort nicht kondensiert wurde, an die Säule zum Entfernen von Stickstoff (4) geschickt wird.
  8. Verfahren nach einem der vorhergehenden Ansprüche, wobei für die Variante ii) die Mischung eine Sumpfflüssigkeit (13) einer Methanwaschsäule (1) ist, wobei die Waschflüssigkeit (11) vom Sumpf der Trennsäule (3) stammt.
  9. Verfahren nach Anspruch 1, wobei gemäß Variante i) das Fluid, abgeleitet von der Flüssigkeit, abgereichert an Wasserstoff, hergestellt wird, indem die Flüssigkeit (16) in einem Ventil expandiert wird.
  10. Vorrichtung zur kryogenen Trennung einer Mischung aus Kohlenmonoxid, Wasserstoff und Stickstoff und eventuell Methan, umfassend eine Abstreifsäule (2), eine Säule zum Entfernen von Stickstoff (4) und eventuell eine Trennsäule (3) mit einem Kopfkondensator (6), eine Leitung, um die Mischung (13) in Form einer Flüssigkeit am Kopf der Abstreifsäule zu schicken, eine Leitung zum Entfernen einer Flüssigkeit, abgereichert an Wasserstoff (15, 16), die mit der Abstreifsäule verbunden ist, eine Leitung zum Entfernen eines Gases, angereichert mit Wasserstoff (14) der Abstreifsäule, Mittel zum Schicken der Flüssigkeit, abgereichert an Wasserstoff (16), oder eines Fluid, abgeleitet von dieser Flüssigkeit, an die Säule zum Entfernen von Stickstoff, eine Leitung, um Flüssigkeit (22), angereichert mit Kohlenmonoxid, von der Säule zum Entfernen von Stickstoff zu entnehmen und eine Leitung, um Gas (21), angereichert mit Stickstoff, des Kopfes der Säule zum Entfernen von Stickstoff zu entnehmen, dadurch gekennzeichnet, dass sie Mittel umfasst, um mindestens einen Teil des Gases, angereichert mit Wasserstoff, oder ein Fluid, abgeleitet von diesem Gas, an die Säule zum Entfernen von Stickstoff zu schicken.
  11. Vorrichtung nach Anspruch 10, umfassend eine Trennsäule (3) mit einem Kopfkondensator (6), wobei die Leitung zum Entfernen der Flüssigkeit, abgereichert an Wasserstoff (14), der Abstreifsäule mit der Trennsäule verbunden ist, wobei die Leitung zum Entfernen eines Gases, angereichert mit Wasserstoff, mit der Trennsäule verbunden ist und eine Leitung umfasst, um Gas, angereichert mit Kohlenmonoxid (16), am Kopf der Trennsäule zu holen, und eine Leitung, um ein nicht kondensiertes Gas (24) des Kopfkondensators (6) der Trennsäule an die Säule zum Entfernen von Stickstoff zu schicken.
  12. Vorrichtung nach einem der Ansprüche 10 oder 11, umfassend Mittel zum Nachweis des Gehalts an Stickstoff der Mischung und/oder des Gases, angereichert mit Stickstoff, und/oder des Gases, angereichert mit Kohlenmonoxid (16), sowie Mittel, um den Durchsatz des mindestens einen Teils des Gases, angereichert mit Wasserstoff, zu regulieren, oder Fluid, abgeleitet von diesem Gas, geschickt an die Säule zum Entfernen von Stickstoff.
  13. Vorrichtung nach Anspruch 10, 11 oder 12, umfassend Mittel, um mindestens einen Teil des Gases, angereichert mit Wasserstoff, an die Trennsäule zu schicken, an einen Zwischenpunkt der Trennsäule, oder an die Säule zum Entfernen von Stickstoff durch einen Detektor des Gehalts an Stickstoff der Mischung und/oder des Gases, angereichert mit Kohlenmonoxid und/oder des Gases, angereichert mit Stickstoff, und/oder eines Detektors des Durchsatzes der Mischung und/oder des Gases, angereichert mit Kohlenmonoxid und/oder des Gases, angereichert mit Stickstoff.
EP14796181.7A 2013-09-24 2014-09-23 Verfahren und vorrichtung zur kryogenen trennung einer mischung mit mindestens kohlenstoffmonoxid, wasserstoff und stickstoff Active EP3049741B1 (de)

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PCT/FR2014/052368 WO2015044575A2 (fr) 2013-09-24 2014-09-23 Procede et appareil de separation cryogenique d'un melange contenant au moins du monoxyde de carbone, de l'hydrogene et de l'azote

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US4805414A (en) * 1987-12-15 1989-02-21 Union Carbide Corporation Process to recover hydrogen-free higher boiling synthesis gas component
FR2754541B1 (fr) * 1996-10-15 1998-12-24 Air Liquide Procede et installation pour la separation d'un melange d'hydrogene et/ou d'au moins un hydrocarbure et/ou d'azote et/ou d'oxyde de carbone
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FR3011069A1 (fr) 2015-03-27
US10539365B2 (en) 2020-01-21
US20160245583A1 (en) 2016-08-25
WO2015044575A2 (fr) 2015-04-02
WO2015044575A3 (fr) 2015-09-17
EP3049741A2 (de) 2016-08-03
CN105745506B (zh) 2019-07-02
FR3011069B1 (fr) 2015-09-11

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