EP2673582B1 - Process and device for the cryogenic separation of a methane-rich stream - Google Patents

Process and device for the cryogenic separation of a methane-rich stream Download PDF

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Publication number
EP2673582B1
EP2673582B1 EP12707884.8A EP12707884A EP2673582B1 EP 2673582 B1 EP2673582 B1 EP 2673582B1 EP 12707884 A EP12707884 A EP 12707884A EP 2673582 B1 EP2673582 B1 EP 2673582B1
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Prior art keywords
nitrogen
flow
rich
methane
feed flow
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German (de)
French (fr)
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EP2673582A2 (en
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Golo Zick
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
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
    • F25J3/02—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
    • F25J3/0209—Natural gas or substitute natural 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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/0605—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 feed stream
    • F25J3/061—Natural gas or substitute natural 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
    • F25J3/0257—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
    • F25J3/04—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 for air
    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
    • F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
    • 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
    • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
    • 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/40—Air or oxygen enriched air, i.e. generally less than 30mol% of O2
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/66—Landfill or fermentation off-gas, e.g. "Bio-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
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/42—Integration in an installation using nitrogen, e.g. as utility gas, for inerting or purging purposes in IGCC, POX, GTL, PSA, float glass forming, incineration processes, for heat recovery or for enhanced oil recovery
    • F25J2260/44—Integration in an installation using nitrogen, e.g. as utility gas, for inerting or purging purposes in IGCC, POX, GTL, PSA, float glass forming, incineration processes, for heat recovery or for enhanced oil recovery using nitrogen for cooling 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
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2280/00—Control of the process or apparatus
    • F25J2280/10—Control for or during start-up and cooling down of the installation
    • 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
    • F25J2290/90—Details about safety operation of the installation

Definitions

  • the present invention relates to a method and apparatus for cryogenic separation of a methane-rich feed stream.
  • the product contains less than 2% carbon dioxide and less than 2% for the total oxygen and nitrogen content.
  • a flow rich in methane contains at least 30% methane.
  • Biogas for example from a non-hazardous waste storage facility (ISDND), is a mixture of methane, carbon dioxide, nitrogen, oxygen and traces of other impurities such as water and hydrogen sulphide or volatile organic compounds (VOCs).
  • ISDND non-hazardous waste storage facility
  • VOCs volatile organic compounds
  • the separation of CO 2 and CH 4 is preferably by permeation in a membrane system.
  • Membranes do not, however, make it possible to economically separate methane from gases in the air, but sharp purity requirements must be met for the injection of biogas into the natural gas network. It is then necessary to find a complementary means to separate the methane from the gases of the air.
  • adsorption system for this. This solution has several disadvantages such as low efficiency, many wear parts or adsorbent bottles and very bulky buffer capacity.
  • a catalytic deoxygenator could solve this problem but gives rise to other problems such as the addition of an additional element in the process, the creation of water and C n H m or even coal or a potentially lower reliability of the assembly. biogas purification.
  • An object of the present invention is to find a solution in the form of a process which always ensures an operation of the distillation column out of the flammable zone.
  • feed rate denominates the flow entering the cold box, that is to say in the whole of the cryogenic distillation brick; this stream is already purified with CO 2 and other impurities mentioned above.
  • feed composition is set is to enrich the nitrogen composition as it is plotted with the dotted line.
  • a nitrogen enrichment is carried out by adding a nitrogen-rich flow rate to the distillation column. It is important to inject Nitrogen in the lower part of the column to avoid the flammability zone through the entire column.
  • the apparatus may comprise a storage of the nitrogen-rich liquid connected to the means for sending the liquid to vaporize in the exchanger.
  • figure 2 shows a simplified process diagram according to the invention.
  • a flow of feed gas 1 which can be a biogas comprises between 30 and 50% of methane, with a CH 4 / CO 2 ratio between 1 and 2. It also contains air gases with a nitrogen / oxygen ratio. greater than 3.7 and is saturated with water.
  • the gas 1 is purified by drying, by desulfurization and to remove the carbon dioxide it contains by permeation and / or adsorption in a treatment unit 2, so that it contains substantially only methane nitrogen and oxygen.
  • a typical composition of the treated gas 4 could be 68% methane, 31% nitrogen and 3% oxygen.
  • This feed gas 4 produced by the treatment unit 2 is cooled in a plate-and-fin type heat exchanger 3 at a pressure of between 6 and 15 bar.
  • the gas 4 is sent to a tank condenser-reboiler 5 of a simple distillation column 6.
  • the gas cools in the condenser-reboiler 5 and is at least partially condensed, while heating the tank of the column 6.
  • the produced fluid 7 by condensing the gas 4 is expanded in a valve 8 at a pressure between 1.1 and 5 bar abs. then sent to the top of column 6 as liquid 9.
  • the temperature of the liquid 9 must be greater than 90.7K to avoid the risk of solidifying the methane.
  • This liquid then separates in column 6 to form an overhead gas containing 84% nitrogen and 5% oxygen.
  • This gas 10 is heated in the exchanger 3 to form the waste gas 11.
  • the vessel liquid 12 of the column 6 is withdrawn with a composition of less than 100 ppm of oxygen, traces of nitrogen and the remainder being methane .
  • the tank liquid 12 is sent to the tank reboiler 5 where it partially vaporizes.
  • the formed gas is returned to the bottom of the column via line 21.
  • the remaining bottom liquid 13 vaporizes in exchanger 3 to form a pure methane gas product 14.
  • a liquid nitrogen storage 16 is connected to the exchanger 3 by a pipe 17 to vaporize the liquid nitrogen.
  • the vaporized nitrogen 18 is sent through an expansion valve 19 and the pipe 20 to the tank of the column 6, mixed with the vaporized methane 15 from the reboiler 5.
  • the vaporized nitrogen contains at least 90% nitrogen, or even at least 95% nitrogen. Mixing the nitrogen with the vaporized methane makes it possible to better disperse the nitrogen in the column and to avoid the formation of flammable "pockets".
  • the nitrogen may also come from an air separation apparatus producing nitrogen gas or a nitrogen gas network. Otherwise liquid nitrogen from an air separation apparatus can vaporize in the exchanger 3 to supply the gas 20.
  • the feed gas can contain up to 10% oxygen or up to 5% oxygen.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Description

La présente invention concerne un procédé et un appareil de séparation cryogénique d'un débit d'alimentation riche en méthane.The present invention relates to a method and apparatus for cryogenic separation of a methane-rich feed stream.

Afin d'épurer un débit riche en méthane provenant d'une source organique, pour produire un produit épuré, il est nécessaire d'enlever les impuretés, telles que le dioxyde de carbone, l'oxygène et l'azote. Idéalement le produit contient moins de 2% de dioxyde de carbone et moins de 2% pour le contenu total en oxygène et en azote.In order to purify a flow rich in methane from an organic source, to produce a purified product, it is necessary to remove impurities, such as carbon dioxide, oxygen and nitrogen. Ideally the product contains less than 2% carbon dioxide and less than 2% for the total oxygen and nitrogen content.

Dans ce contexte, un débit riche en méthane contient au moins 30% de méthane.In this context, a flow rich in methane contains at least 30% methane.

Tous les pourcentages de composition de ce document sont des pourcentages molaires.All percentages of composition of this document are molar percentages.

Le biogaz, provenant par exemple d'une installation de stockage de déchets non dangereux (ISDND), est un mélange de méthane, de dioxyde de carbone, d'azote, d'oxygène et des traces d'autres impuretés comme l'eau et le sulfure d'hydrogène ou des composants organiques volatils (COV).Biogas, for example from a non-hazardous waste storage facility (ISDND), is a mixture of methane, carbon dioxide, nitrogen, oxygen and traces of other impurities such as water and hydrogen sulphide or volatile organic compounds (VOCs).

Pour une valorisation du méthane comme biocarburant ou pour l'injection dans le réseau de gaz naturel, une purification est nécessaire. Les impuretés présentes en traces peuvent être facilement arrêtées dans des lits d'adsorption ou d'autres procédés connus à l'homme de l'art.For recovery of methane as biofuel or for injection into the natural gas network, purification is necessary. The impurities present in traces can be easily stopped in adsorption beds or other methods known to those skilled in the art.

Quelques remarques concernant la présence d'oxygène dans le gaz naturel se trouvent dans US-A-2006/0043000 . Le pourcentage d'oxygène dans le gaz naturel ne dépasse pas 0,1% d'après d'autres sources.Some remarks concerning the presence of oxygen in natural gas are found in US-2006/0043000 . The percentage of oxygen in natural gas does not exceed 0.1% from other sources.

La séparation de CO2 et de CH4 se fait préférablement par perméation dans un système de membranes. Les membranes ne permettent cependant pas de séparer économiquement le méthane des gaz de l'air, or il faut respecter des exigences de pureté pointues pour l'injection du biogaz dans le réseau de gaz naturel. Il faut alors trouver un moyen complémentaire pour séparer le méthane des gaz de l'air. On trouve aujourd'hui sur le marché des offres utilisant un système d'adsorption pour cela. Cette solution présente plusieurs inconvénients comme un rendement faible, beaucoup des pièces d'usure ou des bouteilles d'adsorbant et des capacités tampon très volumineuses.The separation of CO 2 and CH 4 is preferably by permeation in a membrane system. Membranes do not, however, make it possible to economically separate methane from gases in the air, but sharp purity requirements must be met for the injection of biogas into the natural gas network. It is then necessary to find a complementary means to separate the methane from the gases of the air. There are today on the market offers using an adsorption system for this. This solution has several disadvantages such as low efficiency, many wear parts or adsorbent bottles and very bulky buffer capacity.

Une autre solution pour la séparation est la distillation cryogénique tel que décrit dans WO-A-09/004207 , qui concerne un procédé et un appareil selon les préambules des revendications 1 et 9 respectivement. Ce procédé peut atteindre des rendements très élevés, travaille en continu et ne demande que très peu de maintenance.Another solution for separation is cryogenic distillation as described in WO-A-09/004207 which relates to a method and an apparatus according to the preambles of claims 1 and 9 respectively. This process can achieve very high yields, works continuously and requires very little maintenance.

Or, avec la présence d'oxygène dans le mélange à séparer, le problème d'inflammabilité du binaire méthane - oxygène se pose suite à la surconcentration d'oxygène au milieu de la colonne de distillation. Même de très petites quantités d'oxygène dans une alimentation loin d'être inflammable s'accumulent dans la colonne et peuvent créer une situation dangereuse.However, with the presence of oxygen in the mixture to be separated, the flammability problem of the methane-oxygen binary arises as a result of the oxygen overconcentration in the middle of the distillation column. Even very small amounts of oxygen in a far flammable diet accumulate in the column and can create a dangerous situation.

Ce problème n'a pas été abordé dans l'art antérieur, comme on voit de US-A-2519955 où on va jusqu'à introduire délibérément un gaz contenant de l'oxygène (de l'air) dans une colonne de distillation de gaz naturel dépourvu d'oxygène.This problem has not been addressed in the prior art, as we see from US Patent 2519955 where it will deliberately introduce a gas containing oxygen (air) into a distillation column of natural gas without oxygen.

Un désoxygénateur catalytique pourrait résoudre cette problématique mais engendre d'autres problèmes comme l'ajout d'un élément supplémentaire dans le procédé, la création d'eau et des CnHm voire du charbon ou une fiabilité potentiellement plus faible de l'ensemble de purification de biogaz.A catalytic deoxygenator could solve this problem but gives rise to other problems such as the addition of an additional element in the process, the creation of water and C n H m or even coal or a potentially lower reliability of the assembly. biogas purification.

Un but de la présente invention est de trouver une solution en forme d'un procédé qui assure toujours une opération de la colonne de distillation hors de la zone d'inflammabilité.An object of the present invention is to find a solution in the form of a process which always ensures an operation of the distillation column out of the flammable zone.

Dans ce qui suit le débit d'alimentation dénomme le flux entrant dans la boîte froide, c'est-à-dire dans l'ensemble de la brique de distillation cryogénique ; ce flux est déjà purifié de CO2 et d'autres impuretés citées ci-dessus.In what follows the feed rate denominates the flow entering the cold box, that is to say in the whole of the cryogenic distillation brick; this stream is already purified with CO 2 and other impurities mentioned above.

Dans le diagramme ternaire de la Figure 1, la zone triangulaire d'inflammabilité est hachée. La ligne continue trace la composition de la phase vapeur entre la tête de la colonne en bas à droite du diagramme et en cuve de la colonne où l'on trouve du méthane pur. On s'aperçoit facilement que cette ligne passe dans la zone d'inflammabilité.In the ternary diagram of the Figure 1 , the triangular area of flammability is minced. The solid line traces the composition of the vapor phase between the top of the column at the bottom right of the diagram and in the bottom of the column where pure methane is found. It is easy to see that this line goes into the flammable zone.

Une possibilité d'éviter cette zone si la composition d'alimentation est fixée est un enrichissement de la composition en azote comme c'est tracé avec la ligne en pointillé.One possibility to avoid this area if the feed composition is set is to enrich the nitrogen composition as it is plotted with the dotted line.

Selon l'invention, un enrichissement en azote est réalisé en rajoutant un débit riche en azote dans la colonne de distillation. Il est important d'injecter l'azote dans la partie inférieure de la colonne pour éviter la zone d'inflammabilité à travers toute la colonne.According to the invention, a nitrogen enrichment is carried out by adding a nitrogen-rich flow rate to the distillation column. It is important to inject Nitrogen in the lower part of the column to avoid the flammability zone through the entire column.

Selon un objet de l'invention, il est prévu un procédé selon la revendication 1.According to one object of the invention, there is provided a method according to claim 1.

Selon d'autres caractéristiques optionnelles :

  • le débit d'alimentation contient entre 65 et 97% de méthane ;
  • le débit d'alimentation contient entre 3 et 35% en total d'azote et d'oxygène ;
  • le débit d'alimentation contient entre 3 et 35% d'azote ;
  • le débit riche en azote contient au moins 90% d'azote, voire au moins 95% d'azote ;
  • le débit riche en azote est envoyé en cuve de la colonne de distillation ;
  • le débit d'alimentation est envoyé à un condenseur-rebouilleur où il vaporise partiellement le liquide de cuve pour former un gaz vaporisé, le débit d'alimentation totalement ou partiellement liquéfié est envoyé du condenseur-rebouilleur à la colonne et le gaz vaporisé est mélangé avec le débit riche en azote ;
  • le débit d'alimentation contient moins que 10% d'oxygène.
According to other optional features:
  • the feed rate contains between 65 and 97% methane;
  • the feed rate contains between 3 and 35% in total of nitrogen and oxygen;
  • the feed rate contains between 3 and 35% nitrogen;
  • the nitrogen-rich flow contains at least 90% nitrogen, or even at least 95% nitrogen;
  • the flow rich in nitrogen is sent to the bottom of the distillation column;
  • the feed rate is sent to a condenser-reboiler where it partially vaporizes the vessel liquid to form a vaporized gas, the feed flow totally or partially liquefied is sent from the condenser-reboiler to the column and the vaporized gas is mixed with nitrogen-rich flow;
  • the feed rate contains less than 10% oxygen.

Selon un autre objet de l'invention, il est prévu un appareil selon la revendication 9.According to another object of the invention, there is provided an apparatus according to claim 9.

L'appareil peut comprendre un stockage du liquide riche en azote relié aux moyens pour envoyer le liquide se vaporiser dans l'échangeur.The apparatus may comprise a storage of the nitrogen-rich liquid connected to the means for sending the liquid to vaporize in the exchanger.

L'invention sera décrite en plus de détail en se référant aux figures dont la figure 2 montre un schéma simplifié de procédé selon l'invention.The invention will be described in more detail with reference to the figures figure 2 shows a simplified process diagram according to the invention.

Un débit de gaz d'alimentation 1 pouvant être un biogaz, comprend entre 30 et 50% de méthane, avec un rapport CH4/CO2 entre 1 et 2. Il contient également des gaz de l'air avec un rapport azote/oxygène supérieur à 3,7 et est saturé en eau. Le gaz 1 est épuré par séchage, par désulfurisation et pour éliminer le dioxyde de carbone qu'il contient par perméation et/ou par adsorption dans une unité de traitement 2, de sorte qu'il ne contient substantiellement plus que du méthane, de l'azote et de l'oxygène. Une composition typique du gaz traité 4 pourrait être 68% de méthane, 31% d'azote et 3% d'oxygène. Ce gaz d'alimentation 4 produit par l'unité de traitement 2 est refroidi dans un échangeur de chaleur 3 du type à plaques et à ailettes à une pression d'entre 6 et 15 bars. Le gaz 4 est envoyé à un condenseur-rebouilleur de cuve 5 d'une simple colonne de distillation 6. Le gaz se refroidit dans le condenseur-rebouilleur 5 et est au moins partiellement condensé, tout en chauffant la cuve de la colonne 6. Le fluide produit 7 en condensant le gaz 4 est détendu dans une vanne 8 à une pression entre 1,1 et 5 bars abs. puis envoyé en tête de la colonne 6 comme liquide 9. La température du liquide 9 doit être supérieure à 90,7K pour éviter le risque de solidifier le méthane.A flow of feed gas 1 which can be a biogas comprises between 30 and 50% of methane, with a CH 4 / CO 2 ratio between 1 and 2. It also contains air gases with a nitrogen / oxygen ratio. greater than 3.7 and is saturated with water. The gas 1 is purified by drying, by desulfurization and to remove the carbon dioxide it contains by permeation and / or adsorption in a treatment unit 2, so that it contains substantially only methane nitrogen and oxygen. A typical composition of the treated gas 4 could be 68% methane, 31% nitrogen and 3% oxygen. This feed gas 4 produced by the treatment unit 2 is cooled in a plate-and-fin type heat exchanger 3 at a pressure of between 6 and 15 bar. The gas 4 is sent to a tank condenser-reboiler 5 of a simple distillation column 6. The gas cools in the condenser-reboiler 5 and is at least partially condensed, while heating the tank of the column 6. The produced fluid 7 by condensing the gas 4 is expanded in a valve 8 at a pressure between 1.1 and 5 bar abs. then sent to the top of column 6 as liquid 9. The temperature of the liquid 9 must be greater than 90.7K to avoid the risk of solidifying the methane.

Ce liquide se sépare ensuite dans la colonne 6 pour former un gaz de tête 10 contenant 84% d'azote et 5% d'oxygène. Ce gaz 10 se réchauffe dans l'échangeur 3 pour former le gaz résiduaire 11. Le liquide de cuve 12 de la colonne 6 est soutiré avec une composition de moins de 100ppm d'oxygène, des traces d'azote et le reste étant du méthane. Le liquide de cuve 12 est envoyé au rebouilleur de cuve 5 où il se vaporise partiellement. Le gaz formé 15 est renvoyé à la cuve de la colonne par la conduite 21. Le liquide de cuve restant 13 se vaporise dans l'échangeur 3 pour former un produit de méthane gazeux pur 14.This liquid then separates in column 6 to form an overhead gas containing 84% nitrogen and 5% oxygen. This gas 10 is heated in the exchanger 3 to form the waste gas 11. The vessel liquid 12 of the column 6 is withdrawn with a composition of less than 100 ppm of oxygen, traces of nitrogen and the remainder being methane . The tank liquid 12 is sent to the tank reboiler 5 where it partially vaporizes. The formed gas is returned to the bottom of the column via line 21. The remaining bottom liquid 13 vaporizes in exchanger 3 to form a pure methane gas product 14.

Un stockage d'azote liquide 16 est relié à l'échangeur 3 par une conduite 17 pour vaporiser l'azote liquide. L'azote vaporisé 18 est envoyé par une vanne de détente 19 et la conduite 20 à la cuve de la colonne 6, mélangé avec le méthane vaporisé 15 provenant du rebouilleur 5. L'azote vaporisé contient au moins 90% d'azote, voire au moins 95% d'azote. Le fait de mélanger l'azote avec le méthane vaporisé permet de mieux disperser l'azote dans la colonne et d'éviter la formation de « poches » inflammables.A liquid nitrogen storage 16 is connected to the exchanger 3 by a pipe 17 to vaporize the liquid nitrogen. The vaporized nitrogen 18 is sent through an expansion valve 19 and the pipe 20 to the tank of the column 6, mixed with the vaporized methane 15 from the reboiler 5. The vaporized nitrogen contains at least 90% nitrogen, or even at least 95% nitrogen. Mixing the nitrogen with the vaporized methane makes it possible to better disperse the nitrogen in the column and to avoid the formation of flammable "pockets".

Pour démarrer la colonne 6, le stockage 16 contenant l'azote liquide pour permettre d'inerter la colonne.To start column 6, storage 16 containing liquid nitrogen to allow the column to be inerted.

L'azote 20 peut également provenir d'un appareil de séparation d'air produisant de l'azote gazeux ou d'un réseau d'azote gazeux. Sinon de l'azote liquide d'un appareil de séparation d'air peut se vaporiser dans l'échangeur 3 pour fournir le gaz 20.The nitrogen may also come from an air separation apparatus producing nitrogen gas or a nitrogen gas network. Otherwise liquid nitrogen from an air separation apparatus can vaporize in the exchanger 3 to supply the gas 20.

De préférence, le gaz d'alimentation peut contenir jusqu'à 10% d'oxygène ou jusqu'à 5% d'oxygène.Preferably, the feed gas can contain up to 10% oxygen or up to 5% oxygen.

Claims (10)

  1. Method for the cryogenic separation of a methane-rich feed flow (4) containing nitrogen and between 3% and 35% oxygen, in which:
    i) the feed flow is cooled (3) in order to produce a cooled flow,
    ii) at least part of the cooled flow is sent (9) to a distillation column (6),
    iii) a vessel flow is withdrawn (12) from the distillation column, the vessel flow being enriched with methane compared with the feed flow,
    iv) a flow enriched with oxygen compared with the feed flow is withdrawn (10) from the distillation column, and
    v) a nitrogen-rich liquid flow coming from an external source (16) is vaporised by heat exchange with the feed flow in order to produce a nitrogen-rich gas flow (18),
    characterised in that the nitrogen-rich gas flow is sent (20, 21) to a bottom part of the distillation column order to participate in the distillation.
  2. Method according to claim 1, in which the feed flow (4) contains between 65% and 97% methane.
  3. Method according to either of the preceding claims, in which the feed flow (4) contains between 3% and 35% in total nitrogen and oxygen.
  4. Method according to either claim 1 or claim 2, in which the feed flow (4) contains between 3% and 35% nitrogen.
  5. Method according to any of the preceding claims, in which the nitrogen-rich flow (20, 21) contains at least 90% nitrogen, or even at least 95% nitrogen.
  6. Method according to any of the preceding claims, in which the nitrogen-rich flow (20, 1) is sent to the vessel of the distillation column (6).
  7. Method according to any of the preceding claims, in which the feed flow is sent to a condenser-reboiler (5), where it partially vaporises the vessel liquid in order to form a vaporised gas, the completely or partially liquefied feed flow is sent from the condenser-reboiler to the column and the vaporised gas is mixed with the nitrogen-rich flow.
  8. Method according to any of the preceding claims, in which the feed flow contains less than 10% oxygen.
  9. Apparatus for the cryogenic separation of a methane-rich feed flow containing oxygen and nitrogen, comprising:
    i) a heat exchanger (3) for cooling the feed flow in order to produce a cooled flow,
    ii) a condenser-reboiler (5),
    iii) a distillation column (6) and means for sending at least part of the cooled flow to the condenser-reboiler,
    iv) means (12) for drawing off from the distillation column a liquid enriched with methane compared with the feed flow and for sending it to the condenser-reboiler,
    v) means (13) for drawing off a methane-rich liquid from the condenser-reboiler and sending it to the exchanger,
    vi) means (15) for drawing off a methane-rich gas from the condenser-reboiler and sending it to the column vessel,
    vii) means (10) for drawing off from the distillation column a flow enriched with oxygen and optionally nitrogen compared with the feed flow,
    viii) means (17) for sending a nitrogen-rich liquid to be vaporised in the exchanger in order to form a nitrogen-rich gas flow,
    characterised in that it comprisesmeans (18, 21) for sending the nitrogen-rich gas flow to the column vessel (6) mixed with the methane-rich gas in order to participate in the distillation.
  10. Apparatus according to claim 9, comprising a storage (16) of the nitrogen-rich liquid connected to the means for sending the liquid to be vaporised in the exchanger.
EP12707884.8A 2011-02-09 2012-02-08 Process and device for the cryogenic separation of a methane-rich stream Active EP2673582B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1151013A FR2971332B1 (en) 2011-02-09 2011-02-09 METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF METHANE RICH FLOW
PCT/FR2012/050269 WO2012107688A2 (en) 2011-02-09 2012-02-08 Process and device for the cryogenic separation of a methane-rich stream

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EP2673582B1 true EP2673582B1 (en) 2018-10-10

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FR3051892B1 (en) 2016-05-27 2018-05-25 Waga Energy PROCESS FOR THE CRYOGENIC SEPARATION OF A SUPPLY RATE CONTAINING METHANE AND AIR GASES, INSTALLATION FOR THE PRODUCTION OF BIO METHANE BY PURIFYING BIOGAS FROM NON-HAZARDOUS WASTE STORAGE FACILITIES (ISDND) USING THE SAME THE PROCESS
AU2018321557B2 (en) * 2017-08-24 2021-09-09 Exxonmobil Upstream Research Company Method and system for LNG production using standardized multi-shaft gas turbines, compressors and refrigerant systems
FR3075658B1 (en) * 2017-12-21 2022-01-28 Air Liquide METHOD FOR LIMITING THE CONCENTRATION OF OXYGEN CONTAINED IN A BIOMETHANE STREAM
FR3075660B1 (en) * 2017-12-21 2019-11-15 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude PROCESS FOR DISTILLING A GASEOUS CURRENT CONTAINING OXYGEN

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WO2012107688A2 (en) 2012-08-16
US10132562B2 (en) 2018-11-20
WO2012107688A3 (en) 2014-07-24
FR2971332B1 (en) 2017-06-16
FR2971332A1 (en) 2012-08-10
US20130312457A1 (en) 2013-11-28

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