EP4249837A1 - Method for replacing first apparatus for separating mixture of carbon monoxide, methane and hydrogen - Google Patents

Method for replacing first apparatus for separating mixture of carbon monoxide, methane and hydrogen Download PDF

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Publication number
EP4249837A1
EP4249837A1 EP23156991.4A EP23156991A EP4249837A1 EP 4249837 A1 EP4249837 A1 EP 4249837A1 EP 23156991 A EP23156991 A EP 23156991A EP 4249837 A1 EP4249837 A1 EP 4249837A1
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EP
European Patent Office
Prior art keywords
column
carbon monoxide
methane
compressor
tank
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23156991.4A
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German (de)
French (fr)
Inventor
Michele MURINO
Anais Konieczny
Roxane GIAMETTA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP4249837A1 publication Critical patent/EP4249837A1/en
Pending legal-status Critical Current

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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
    • 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
    • F25J3/0261—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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/40—Features relating to the provision of boil-up in the bottom of a column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—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
    • F25J2200/76—Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/24—Quasi-closed internal or closed external carbon monoxide refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/80—Retrofitting, revamping or debottlenecking of existing plant

Definitions

  • the present invention relates to a process for replacing a first apparatus for separating a mixture of carbon monoxide, methane and hydrogen.
  • a process for replacing a separation apparatus by cryogenic distillation of such a mixture is particularly relevant.
  • An object of the invention is to provide a solution to the above challenges.
  • the insufficient liquid reflux is supplemented by increasing the flow of liquefied cycle CO in the exchange line against the previously mentioned vaporized impure CO.
  • a further optimization is to heat the column with carbon monoxide at medium pressure, which increases the reboiling energy and thus further reduces the overheating of the vaporized bottom liquid coming from the stripping column. This will have the advantage of reducing the sensitivity of the column to instabilities of the heat exchange line.
  • the invention applies to any case where a CO cycle compressor has excess medium pressure carbon monoxide production and/or insufficient high pressure carbon monoxide production for the process in which it is to be incorporated.
  • FIG. 1 represents a process according to the invention.
  • the apparatus used includes a K1 exhaustion column and a CO/CH 4 K2 separation column as well as a separation system S upstream of the column. of exhaustion.
  • This system S operates at a cryogenic temperature and makes it possible to separate a flow 1 containing carbon monoxide, methane and hydrogen and possibly nitrogen by partial condensation and/or distillation and/or washing in order to produce at least a mixture 3 in liquid form containing carbon monoxide, methane and hydrogen.
  • the system S uses for example produced by at least one partial condensation step to produce the mixture.
  • the mixture may be the liquid produced by at least one partial condensation step, for example.
  • the mixture is sent to the top of an exhaustion column which at least partially eliminates the hydrogen which forms the head gas 5 of the column.
  • the gas 5 is heated in an indirect contact heat exchanger E, for example a plate and fin exchanger, where the flow 1 cools to bring it to a cryogenic temperature.
  • Part of the liquid from tank 7 of column K1 is vaporized in a reboiler R1 and sent to the tank of column K1. All the rest of the liquid 11 is expanded in a valve V3, vaporized in the exchanger E and sent at an intermediate temperature of the exchanger E to feed the separation column K2 at an intermediate level thereof, being entirely in the form gaseous.
  • the separation column K2 separates the gas formed by vaporizing the liquid 11 to form an overhead gas 17 enriched in carbon monoxide and a liquid rich in methane.
  • a part 13 of the tank liquid is vaporized in a reboiler R2 and the rest of the liquid 15 is reheated in the exchanger E to form a product or fuel for an additional process.
  • the gas enriched in carbon monoxide 17 is reheated in the heat exchanger E in a compressor comprising at least two stages C1, C2.
  • a part 19 of the compressed gas for example only in the first stage and being at an intermediate pressure of the compressor, is cooled in the heat exchanger E.
  • a part 24 of the gas is withdrawn from the exchanger at an intermediate temperature thereof. this and is used to heat the reboiler R1 and/or the reboiler R2.
  • the two reboilers are heated by two flow rates 26, 28 formed by dividing part 24 in two to heat the reboilers R1, R2 in series.
  • the liquids formed are expanded in the valves V1, V2 respectively, then mixed to form a flow 30 which is subcooled in the exchanger E to form a liquid which feeds the head of the separation column K2.
  • a part 23 of the gas 19 cools to the cold end of the exchanger E, condensing there, subcooling there, is expanded in a valve V4 and is also sent to the head of the separation column K2.
  • the K2 column does not include an overhead condenser.
  • the main product of the process is the gas enriched in CO 21 compressed in the last stage C2 of the compressor.
  • a C1 compressor from an existing process can be incorporated into this new process.
  • the fact that the existing compressor is sized to produce a flow rate greater than flow rate 21 poses no problem since stage C1 must precisely compress flow rates 19, 21, while stage 21 only compresses flow rate 21.
  • the frigories of the process are provided by a turbine (not shown) which expands CO from the cryogenic cycle and/or by a supply of cold liquid coming from an external source.
  • the first device is replaced by a second device as described above and illustrated in the figure comprising a separation system by partial condensation and a, possibly the pre-existing, separation column as well as the pre-existing compressor, the compressor being connected to the separation column for compressing a gas enriched in carbon monoxide having a flow rate D up to the pressure P, being connected to another compressor which compresses a first part of the flow rate D up to a pressure P', greater than P and at a CO cycle where a second part of the flow D circulates.
  • a separation system by partial condensation and a, possibly the pre-existing, separation column as well as the pre-existing compressor the compressor being connected to the separation column for compressing a gas enriched in carbon monoxide having a flow rate D up to the pressure P, being connected to another compressor which compresses a first part of the flow rate D up to a pressure P', greater than P and at a CO cycle where a second part of the flow D circulates.

Abstract

Dans un procédé de remplacement d'un premier appareil de séparation d'un mélange de monoxyde de carbone, de méthane et d'hydrogène utilisant une colonne de lavage au méthane, une colonne de séparation de monoxyde de carbone et de méthane et un compresseur de monoxyde de carbone (C1) relié à la colonne de séparation conçu pour comprimer un débit D jusqu'à une pression P, P étant la pression de production du produit de l'appareil, le premier appareil est remplacé par un deuxième appareil de séparation d'un mélange de monoxyde de carbone, de méthane et d'hydrogène comprenant une colonne d'épuisement (K1), une colonne de séparation (K2), des moyens pour envoyer le mélange (3) sous forme liquide en tête de la colonne d'épuisement, des moyens pour soutirer un gaz enrichi en hydrogène (5) en tête de la colonne d'épuisement et des moyens pour soutirer un liquide de cuve (7) appauvri en hydrogène en cuve de la colonne d'épuisement, des moyens pour vaporiser complètement une première partie (11) du liquide de cuve pour envoyer le débit gazeux formé à une colonne de séparation, des moyens (R1) pour vaporiser le reste (9) du liquide de cuve et de le renvoyer à la colonne d'épuisement, des moyens pour soutirer un débit gazeux enrichi en monoxyde de carbone (17) en tête de la colonne et des moyens pour soutirer un débit liquide enrichi en méthane (15) en cuve de la colonne, un compresseur (C1, C2) qui est le compresseur du premier appareil et des moyens pour y envoyer le débit gazeux enrichi en monoxyde de carbone (23) pour s'y comprimer.In a process for replacing a first apparatus for separating a mixture of carbon monoxide, methane and hydrogen using a methane washing column, a carbon monoxide and methane separation column and a compressor. carbon monoxide (C1) connected to the separation column designed to compress a flow rate D to a pressure P, P being the production pressure of the product of the device, the first device is replaced by a second separation device d a mixture of carbon monoxide, methane and hydrogen comprising an exhaustion column (K1), a separation column (K2), means for sending the mixture (3) in liquid form to the top of the column exhaustion, means for withdrawing a gas enriched in hydrogen (5) at the head of the exhaustion column and means for withdrawing a tank liquid (7) depleted in hydrogen in the tank of the exhaustion column, means for completely vaporize a first part (11) of the tank liquid to send the gas flow formed to a separation column, means (R1) for vaporizing the remainder (9) of the tank liquid and returning it to the exhaustion column , means for withdrawing a gas flow enriched in carbon monoxide (17) at the top of the column and means for withdrawing a liquid flow enriched in methane (15) in the tank of the column, a compressor (C1, C2) which is the compressor of the first device and means for sending the gas flow enriched with carbon monoxide (23) there to be compressed there.

Description

La présente invention est relative à un procédé de remplacement d'un premier appareil de séparation d'un mélange de monoxyde de carbone, de méthane et d'hydrogène. En particulier elle concerne un procédé de remplacement d'un appareil de séparation par distillation cryogénique d'un tel mélange.The present invention relates to a process for replacing a first apparatus for separating a mixture of carbon monoxide, methane and hydrogen. In particular it relates to a process for replacing a separation apparatus by cryogenic distillation of such a mixture.

Il est parfois nécessaire de changer de technologie pour une séparation d'un mélange d'hydrogène et de monoxyde de carbone.It is sometimes necessary to change technology for the separation of a mixture of hydrogen and carbon monoxide.

Parmi les technologies de pointe actuelles pour la séparation cryogénique d'un gaz de synthèse comprenant de l'hydrogène et du monoxyde de carbone, on peut citer : 1. Lavage au solvant de gaz de synthèse (avec azote ou méthane comme liquide de lavage)Current state-of-the-art technologies for cryogenic separation of syngas including hydrogen and carbon monoxide include: 1. Solvent washing of syngas (with nitrogen or methane as washing liquid)

2. Condensation partielle2. Partial condensation

Alors que la première technique convient mieux à une composition de gaz de synthèse riche en H2, la deuxième fonctionne mieux pour une composition de gaz de synthèse riche en CO.While the first technique is best suited for an H2-rich syngas composition, the second works best for a CO-rich syngas composition.

Il est courant dans l'industrie de modifier périodiquement le rapport de gaz de synthèse CO / H2 pour mieux suivre les besoins des consommateurs.It is common in the industry to periodically change the CO/H2 syngas ratio to better keep up with consumer needs.

Dans le cas où cela se produit dans le sens d'une augmentation de la concentration de CO dans le gaz de synthèse, associée à une augmentation de la production, l'installation de séparation cryogénique du gaz de synthèse ne pourra plus traiter le nouveau fluide parce que :

  1. i) sa capacité sera insuffisante pour traiter l'augmentation de la production
  2. ii) le processus de lavage au solvant n'est plus le meilleur schéma de processus disponible.
In the event that this occurs in the direction of an increase in the concentration of CO in the syngas, associated with an increase in production, the cryogenic syngas separation installation will no longer be able to process the new fluid because :
  1. i) its capacity will be insufficient to handle the increase in production
  2. ii) the solvent wash process is no longer the best process flowsheet available.

Il sera alors nécessaire de remplacer l'installation par une nouvelle, fonctionnant par exemple avec un procédé de condensation partielle.It will then be necessary to replace the installation with a new one, operating for example with a partial condensation process.

Dans cette situation, on pourrait être intéressé à conserver le compresseur de cycle CO de l'ancien appareil, car ce type de machine est très coûteux.In this situation, one might be interested in keeping the CO cycle compressor from the old unit, as this type of machine is very expensive.

Cela présente deux défis:

  1. i) adapter le nouveau cycle à la capacité existante du compresseur
  2. ii) concevoir la colonne de séparation CO / CH4 pour disposer d'un équipement facile à réguler.
This presents two challenges:
  1. i) adapt the new cycle to the existing compressor capacity
  2. ii) design the CO / CH 4 separation column to have equipment that is easy to regulate.

L'adaptation du cycle est un défi en raison de

  • la capacité du compresseur relativement faible par rapport à la nouvelle taille de l'appareil
  • le fait que la production de CO moyenne pression est excédentaire, alors que la production de CO haute pression n'est pas suffisante pour alimenter le rebouilleur de la colonne CO / CH4.
Cycle adaptation is a challenge due to
  • the relatively low compressor capacity compared to the new size of the device
  • the fact that the production of medium pressure CO is excess, while the production of high pressure CO is not sufficient to supply the reboiler of the CO / CH 4 column.

Cela conduit traditionnellement à concevoir une colonne CO / CH4 difficile à réguler et très sensible aux changements de conditions de procédé car:

  • l'énergie de rebouillage manquante de la colonne CO / CH4 est fournie via un flux surchauffé de CO vaporisé impur
  • le débit de liquide de cuve soutiré de la colonne d'épuisement (en anglais « stripping column ») et amené à la colonne CO/CH4 sous forme liquide est faible par rapport au le débit de liquide de cuve vaporisé.
This traditionally leads to designing a CO/CH 4 column that is difficult to regulate and very sensitive to changes in process conditions because:
  • the missing reboiling energy from the CO/CH 4 column is supplied via a superheated stream of impure vaporized CO
  • the flow rate of tank liquid withdrawn from the stripping column and brought to the CO/CH 4 column in liquid form is low compared to the flow rate of vaporized tank liquid.

Par conséquent, de petites instabilités dans la température de la ligne d'échange ou dans le flux de répartition du liquide de cuve soutiré de la colonne d'épuisement ont un impact important sur le profil de température de la colonne.Therefore, small instabilities in the exchange line temperature or in the distribution flow of the bottom liquid withdrawn from the stripping column have a large impact on the column temperature profile.

Un objet de l'invention est d'apporter une solution aux défis ci-dessus.An object of the invention is to provide a solution to the above challenges.

Selon un aspect de l'invention, il est prévu un procédé de remplacement d'un premier appareil de séparation d'un mélange de monoxyde de carbone, de méthane et d'hydrogène utilisant une colonne de lavage au méthane, une colonne de séparation de monoxyde de carbone et de méthane et un compresseur de monoxyde de carbone relié à la colonne de séparation conçu pour comprimer un débit D jusqu'à une pression P, P étant la pression de production du produit de l'appareil, le premier appareil étant remplacé par un deuxième appareil tel que décrit ci-dessus comprenant un système de séparation par condensation partielle et une, éventuellement la, colonne de séparation ainsi que le compresseur, le compresseur étant relié à la colonne de séparation pour comprimer un gaz enrichi en monoxyde de carbone ayant un débit D jusqu'à la pression P, étant relié à un autre compresseur qui comprime une première partie du débit D jusqu'à une pression P', supérieure à P et à un cycle de CO où circule une deuxième partie du débit D. Selon d'autres aspects facultatifs :

  • le deuxième appareil comprend un rebouilleur de cuve de la colonne de séparation et des moyens pour sortir un débit enrichi en monoxyde de carbone du compresseur reliés au rebouilleur de cuve de la colonne de séparation pour y amener du gaz comprimé pour chauffer le rebouilleur de cuve de la colonne de séparation.
  • le deuxième appareil comprend un rebouilleur de cuve de la colonne d'épuisement et des moyens pour sortir un débit enrichi en monoxyde de carbone du compresseur reliés au rebouilleur de cuve de la colonne d'épuisement pour y amener du gaz comprimé pour chauffer le rebouilleur de cuve de la colonne d'épuisement.
According to one aspect of the invention, there is provided a method of replacing a first apparatus for separating a mixture of carbon monoxide, methane and hydrogen using a methane washing column, a methane separation column, carbon monoxide and methane and a carbon monoxide compressor connected to the separation column adapted to compress a flow rate D to a pressure P, P being the product production pressure of the apparatus, the first apparatus being replaced by a second device as described above comprising a separation system by partial condensation and one, optionally the, separation column as well as the compressor, the compressor being connected to the separation column to compress a gas enriched in carbon monoxide having a flow D up to the pressure P, being connected to another compressor which compresses a first part of the flow D up to a pressure P', greater than P and to a CO cycle where a second part of the flow D circulates According to other optional aspects:
  • the second apparatus comprises a tank reboiler of the separation column and means for outputting a flow enriched in carbon monoxide from the compressor connected to the tank reboiler of the separation column to supply compressed gas to heat the tank reboiler of the separation column the separation column.
  • the second apparatus comprises a bottom reboiler of the stripping column and means for outputting a flow enriched in carbon monoxide from the compressor connected to the bottom reboiler of the stripping column to supply compressed gas therein to heat the reboiler tank of the exhaustion column.

Selon l'invention, il est mieux de vaporiser tout le liquide de cuve soutiré de la colonne d'épuisement (CO impur) destiné à la colonne CO/CH4 avant de l'envoyer à la colonne CO/CH4 entièrement sous forme gazeuse. Ceci élimine les problèmes dus aux instabilités et permet également de réduire le surchauffage du monoxyde de carbone, ce qui améliore l'efficacité exégétique du procédé.According to the invention, it is better to vaporize all the tank liquid withdrawn from the exhaustion column (impure CO) intended for the CO/CH 4 column before sending it to the CO/CH 4 column entirely in gaseous form . This eliminates problems due to instabilities and also reduces overheating of carbon monoxide, which improves the exegetical efficiency of the process.

Le reflux liquide insuffisant est complété en augmentant le débit de CO de cycle liquéfié dans la ligne d'échange contre le CO impur vaporisé mentionné auparavant. Une optimisation supplémentaire est de chauffer la colonne avec du monoxyde de carbone à la moyenne pression, ce qui augmenter l'énergie de rebouillage et ainsi de réduire encore le surchauffage du liquide de cuve vaporisé provenant de la colonne d'épuisement. Ceci aura pour avantage de réduire la sensibilité de la colonne aux instabilités de la ligne d'échange thermique.The insufficient liquid reflux is supplemented by increasing the flow of liquefied cycle CO in the exchange line against the previously mentioned vaporized impure CO. A further optimization is to heat the column with carbon monoxide at medium pressure, which increases the reboiling energy and thus further reduces the overheating of the vaporized bottom liquid coming from the stripping column. This will have the advantage of reducing the sensitivity of the column to instabilities of the heat exchange line.

Ainsi il devient possible d'exploiter le compresseur de cycle existant qui aurait sinon, comme déjà mentionné, une production de monoxyde de carbone moyenne pression excédentaire et une production de monoxyde de carbone haute pression insuffisante.Thus it becomes possible to operate the existing cycle compressor which would otherwise, as already mentioned, have excess medium pressure carbon monoxide production and insufficient high pressure carbon monoxide production.

L'invention s'applique à tout cas où un compresseur de cycle CO a une production de monoxyde de carbone moyenne pression excédentaire et/ou une production de monoxyde de carbone haute pression insuffisante pour le procédé dans lequel il doit être incorporé.The invention applies to any case where a CO cycle compressor has excess medium pressure carbon monoxide production and/or insufficient high pressure carbon monoxide production for the process in which it is to be incorporated.

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

[FIG. 1] représente un procédé selon l'invention.[ FIG. 1 ] represents a process according to the invention.

L'appareil utilisé comprend une colonne d'épuisement K1 et une colonne de séparation CO/CH4 K2 ainsi qu'un système de séparation S en amont de la colonne de l'épuisement. Ce système S opère à une température cryogénique et permet de séparer un débit 1 contenant du monoxyde de carbone, du méthane et de l'hydrogène et éventuellement de l'azote par condensation partielle et/ou distillation et/ou lavage afin de produire au moins un mélange 3 sous forme liquide contenant du monoxyde de carbone, du méthane et de l'hydrogène. Le système S emploie par exemple produit par au moins une étape de condensation partielle pour produire le mélange. Le mélange peut être le liquide produit par au moins une étape de condensation partielle, par exemple. Le mélange est envoyé en tête d'une colonne d'épuisement qui en élimine au moins partiellement l'hydrogène qui forme le gaz de tête 5 de la colonne. Le gaz 5 se réchauffe dans un échangeur de chaleur par contact indirect E, par exemple un échangeur à plaques et à ailettes, où se refroidit le débit 1 pour l'amener à une température cryogénique.The apparatus used includes a K1 exhaustion column and a CO/CH 4 K2 separation column as well as a separation system S upstream of the column. of exhaustion. This system S operates at a cryogenic temperature and makes it possible to separate a flow 1 containing carbon monoxide, methane and hydrogen and possibly nitrogen by partial condensation and/or distillation and/or washing in order to produce at least a mixture 3 in liquid form containing carbon monoxide, methane and hydrogen. The system S uses for example produced by at least one partial condensation step to produce the mixture. The mixture may be the liquid produced by at least one partial condensation step, for example. The mixture is sent to the top of an exhaustion column which at least partially eliminates the hydrogen which forms the head gas 5 of the column. The gas 5 is heated in an indirect contact heat exchanger E, for example a plate and fin exchanger, where the flow 1 cools to bring it to a cryogenic temperature.

Une partie du liquide de cuve 7 de la colonne K1 est vaporisé dans un rebouilleur R1 et envoyé en cuve de la colonne K1. Tout le reste du liquide 11 est détendu dans une vanne V3, vaporisé dans l'échangeur E et envoyé à une température intermédiaire de l'échanger E alimenter la colonne de séparation K2 à un niveau intermédiaire de celle-ci, se trouvant entièrement sous forme gazeuse.Part of the liquid from tank 7 of column K1 is vaporized in a reboiler R1 and sent to the tank of column K1. All the rest of the liquid 11 is expanded in a valve V3, vaporized in the exchanger E and sent at an intermediate temperature of the exchanger E to feed the separation column K2 at an intermediate level thereof, being entirely in the form gaseous.

La colonne de séparation K2 séparer le gaz formé en vaporisant le liquide 11 pour former un gaz de tête 17 enrichi en monoxyde de carbone et un liquide riche en méthane. Une partie 13 du liquide de cuve est vaporisée dans un rebouilleur R2 et le reste du liquide 15 est réchauffé dans l'échangeur E pour former un produit ou du carburant pour un procédé annexe.The separation column K2 separates the gas formed by vaporizing the liquid 11 to form an overhead gas 17 enriched in carbon monoxide and a liquid rich in methane. A part 13 of the tank liquid is vaporized in a reboiler R2 and the rest of the liquid 15 is reheated in the exchanger E to form a product or fuel for an additional process.

Le gaz enrichi en monoxyde de carbone 17 est réchauffé dans l'échangeur de chaleur E dans un compresseur comprenant au moins deux étages C1, C2. Une partie 19 du gaz comprimé par exemple uniquement dans le premier étage et se trouvant à une pression intermédiaire du compresseur est refroidie dans l'échangeur de chaleur E. Une partie 24 du gaz est soutirée de l'échangeur à une température intermédiaire de celui-ci et sert à réchauffer le rebouilleur R1 et/ou le rebouilleur R2. Ici les deux rebouilleurs sont chauffés par deux débits 26, 28 formés en séparant en deux la partie 24 pour chauffer les rebouilleurs R1, R2 en série. Les liquides formés sont détendus dans les vannes V1, V2 respectivement, puis mélangés pour former un débit 30 qui est sousrefroidi dans l'échangeur E pour former un liquide qui alimente la tête de la colonne de séparation K2. Optionnellement une partie 23 du gaz 19 se refroidit jusqu'au bout froid de l'échangeur E, s'y condensant, s'y sous refroidit, est détendue dans une vanne V4 et est envoyée également en tête de la colonne de séparation K2.The gas enriched in carbon monoxide 17 is reheated in the heat exchanger E in a compressor comprising at least two stages C1, C2. A part 19 of the compressed gas, for example only in the first stage and being at an intermediate pressure of the compressor, is cooled in the heat exchanger E. A part 24 of the gas is withdrawn from the exchanger at an intermediate temperature thereof. this and is used to heat the reboiler R1 and/or the reboiler R2. Here the two reboilers are heated by two flow rates 26, 28 formed by dividing part 24 in two to heat the reboilers R1, R2 in series. The liquids formed are expanded in the valves V1, V2 respectively, then mixed to form a flow 30 which is subcooled in the exchanger E to form a liquid which feeds the head of the separation column K2. Optionally a part 23 of the gas 19 cools to the cold end of the exchanger E, condensing there, subcooling there, is expanded in a valve V4 and is also sent to the head of the separation column K2.

La colonne K2 ne comprend pas de condenseur de tête. Le produit principal du procédé est le gaz enrichi en CO 21 comprimé dans le dernier étage C2 du compresseur.The K2 column does not include an overhead condenser. The main product of the process is the gas enriched in CO 21 compressed in the last stage C2 of the compressor.

En cas de restructuration d'un appareil de séparation d'un mélange de monoxyde de carbone, d'hydrogène et de méthane, un compresseur C1 d'un procédé existant peut être incorporé dans ce nouveau procédé. Le fait que le compresseur existant soit dimensionné pour produire un débit plus grand que le débit 21 ne pose aucun problème puisque l'étage C1 doit justement comprimer les débits 19, 21, alors que l'étage 21 ne comprime que le débit 21.In the event of restructuring an apparatus for separating a mixture of carbon monoxide, hydrogen and methane, a C1 compressor from an existing process can be incorporated into this new process. The fact that the existing compressor is sized to produce a flow rate greater than flow rate 21 poses no problem since stage C1 must precisely compress flow rates 19, 21, while stage 21 only compresses flow rate 21.

Les frigories du procédé sont fournies par une turbine (non-illustrée) qui détend du CO du cycle cryogénique et / ou par un apport de liquide froid provenant d'une source extérieure.The frigories of the process are provided by a turbine (not shown) which expands CO from the cryogenic cycle and/or by a supply of cold liquid coming from an external source.

Ainsi on peut remplacer un premier appareil de séparation d'un mélange de monoxyde de carbone, de méthane et d'hydrogène utilisant une colonne de lavage au méthane ou une colonne de lavage au monoxyde de carbone, une colonne de séparation de monoxyde de carbone et de méthane et un compresseur de monoxyde de carbone relié à la colonne de séparation conçu pour comprimer un débit D jusqu'à une pression P, P étant la pression de production du produit de l'appareil. Le premier appareil est remplacé par un deuxième appareil tel que décrit ci-dessus et illustré dans la figure comprenant un système de séparation par condensation partielle et une, éventuellement la préexistante, colonne de séparation ainsi que le compresseur préexistant, le compresseur étant relié à la colonne de séparation pour comprimer un gaz enrichi en monoxyde de carbone ayant un débit D jusqu'à la pression P, étant relié à un autre compresseur qui comprime une première partie du débit D jusqu'à une pression P', supérieure à P et à un cycle de CO où circule une deuxième partie du débit D.Thus it is possible to replace a first apparatus for separating a mixture of carbon monoxide, methane and hydrogen using a methane washing column or a carbon monoxide washing column, a carbon monoxide separation column and of methane and a carbon monoxide compressor connected to the separation column designed to compress a flow rate D to a pressure P, P being the product production pressure of the device. The first device is replaced by a second device as described above and illustrated in the figure comprising a separation system by partial condensation and a, possibly the pre-existing, separation column as well as the pre-existing compressor, the compressor being connected to the separation column for compressing a gas enriched in carbon monoxide having a flow rate D up to the pressure P, being connected to another compressor which compresses a first part of the flow rate D up to a pressure P', greater than P and at a CO cycle where a second part of the flow D circulates.

Claims (3)

Procédé de remplacement d'un premier appareil de séparation d'un mélange de monoxyde de carbone, de méthane et d'hydrogène utilisant une colonne de lavage au méthane, une colonne de séparation de monoxyde de carbone et de méthane et un compresseur de monoxyde de carbone (C1) relié à la colonne de séparation conçu pour comprimer un débit D jusqu'à une pression P, P étant la pression de production du produit de l'appareil, le premier appareil étant remplacé par un deuxième appareil de séparation d'un mélange de monoxyde de carbone, de méthane et d'hydrogène comprenant une colonne d'épuisement (K1), une colonne de séparation (K2), des moyens pour envoyer le mélange (3) sous forme liquide en tête de la colonne d'épuisement, des moyens pour soutirer un gaz enrichi en hydrogène (5) en tête de la colonne d'épuisement et des moyens pour soutirer un liquide de cuve (7) appauvri en hydrogène en cuve de la colonne d'épuisement, des moyens pour vaporiser complètement une première partie (11) du liquide de cuve pour envoyer le débit gazeux formé à une colonne de séparation, des moyens (R1) pour vaporiser le reste (9) du liquide de cuve et de le renvoyer à la colonne d'épuisement, des moyens pour soutirer un débit gazeux enrichi en monoxyde de carbone (17) en tête de la colonne et des moyens pour soutirer un débit liquide enrichi en méthane (15) en cuve de la colonne, un compresseur (C1) ayant au moins deux étages qui est le compresseur du premier appareil et des moyens pour y envoyer le débit gazeux enrichi en monoxyde de carbone (23) pour s'y comprimer, le compresseur étant relié à la colonne de séparation pour comprimer un gaz enrichi en monoxyde de carbone ayant un débit D jusqu'à la pression P et étant relié à un autre compresseur (C2) qui comprime une première partie du débit D jusqu'à une pression P', supérieure à P et à un cycle de CO où circule une deuxième partie du débit D.Method for replacing a first apparatus for separating a mixture of carbon monoxide, methane and hydrogen using a methane washing column, a carbon monoxide and methane separation column and a carbon monoxide compressor carbon (C1) connected to the separation column designed to compress a flow rate D to a pressure P, P being the production pressure of the product of the device, the first device being replaced by a second device for separating a mixture of carbon monoxide, methane and hydrogen comprising an exhaustion column (K1), a separation column (K2), means for sending the mixture (3) in liquid form to the head of the exhaustion column , means for withdrawing a gas enriched in hydrogen (5) at the head of the exhaustion column and means for withdrawing a tank liquid (7) depleted in hydrogen in the tank of the exhaustion column, means for completely vaporizing a first part (11) of the tank liquid for sending the gas flow formed to a separation column, means (R1) for vaporizing the remainder (9) of the tank liquid and returning it to the exhaustion column, means for withdrawing a gas flow enriched in carbon monoxide (17) at the top of the column and means for withdrawing a liquid flow enriched in methane (15) in the tank of the column, a compressor (C1) having at least two stages which is the compressor of the first device and means for sending there the gas flow enriched in carbon monoxide (23) to compress there, the compressor being connected to the separation column to compress a gas enriched in carbon monoxide having a flow D up to the pressure P and being connected to another compressor (C2) which compresses a first part of the flow D up to a pressure P', greater than P and to a CO cycle where a second part of the flow D circulates . Procédé selon la revendication 1 dans lequel le deuxième appareil comprend un rebouilleur de cuve (R2) de la colonne de séparation (K2) et des moyens pour sortir un débit enrichi en monoxyde de carbone (24, 26) du compresseur reliés au rebouilleur de cuve de la colonne de séparation pour y amener du gaz comprimé pour chauffer le rebouilleur de cuve de la colonne de séparation.Method according to claim 1 in which the second apparatus comprises a bottom reboiler (R2) of the separation column (K2) and means for outputting a flow enriched in carbon monoxide (24, 26) from the compressor connected to the bottom reboiler of the separation column to supply compressed gas to heat the bottom reboiler of the separation column. Procédé selon la revendication 1 dans lequel le deuxième appareil comprend un rebouilleur de cuve (R1) de la colonne d'épuisement (K1) et des moyens pour sortir un débit enrichi en monoxyde de carbone (24, 26) du compresseur reliés au rebouilleur de cuve de la colonne d'épuisement pour y amener du gaz comprimé pour chauffer le rebouilleur de cuve de la colonne d'épuisement.Method according to claim 1 in which the second apparatus comprises a tank reboiler (R1) of the stripping column (K1) and means for outputting a flow enriched in carbon monoxide (24, 26) from the compressor connected to the reboiler of stripping column tank to supply compressed gas to heat the stripping column tank reboiler.
EP23156991.4A 2022-03-21 2023-02-16 Method for replacing first apparatus for separating mixture of carbon monoxide, methane and hydrogen Pending EP4249837A1 (en)

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