EP2673582A2 - 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

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Publication number
EP2673582A2
EP2673582A2 EP12707884.8A EP12707884A EP2673582A2 EP 2673582 A2 EP2673582 A2 EP 2673582A2 EP 12707884 A EP12707884 A EP 12707884A EP 2673582 A2 EP2673582 A2 EP 2673582A2
Authority
EP
European Patent Office
Prior art keywords
nitrogen
flow
rich
methane
feed rate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12707884.8A
Other languages
German (de)
French (fr)
Other versions
EP2673582B1 (en
Inventor
Golo Zick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP2673582A2 publication Critical patent/EP2673582A2/en
Application granted granted Critical
Publication of EP2673582B1 publication Critical patent/EP2673582B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0209—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 rate.
  • 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 CO2 and CH 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 presents several disadvantages such as low efficiency, many wear parts or adsorbent bottles and very large buffer capacities.
  • 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 CO2 and other impurities mentioned above.
  • a nitrogen enrichment is carried out by adding a nitrogen-rich flow rate to the distillation column. It is important to inject the nitrogen into the lower part of the column to avoid the flammability zone throughout the column.
  • the distillation column is withdrawn from a tank flow, the tank flow being enriched in methane with respect to the feed rate
  • the feed rate contains between 3 and 35% oxygen.
  • 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 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 re-reboiler condenser to the column and the vaporized gas is mixed with the nitrogen-rich flow; a nitrogen-rich liquid flow is vaporized by heat exchange with the feed rate to produce the nitrogen-rich gas flow;
  • an apparatus for cryogenic separation of a feed flow rich in methane containing oxygen and nitrogen comprising:
  • iv) means for withdrawing from the distillation column a liquid enriched in methane with respect to the feed rate and for sending it to the condenser-reboiler,
  • v) means for extracting from the condenser-reboiler a liquid rich in methane and for sending it to the exchanger
  • viii) means for sending a nitrogen-rich liquid to vaporize in the exchanger and means for sending the nitrogen-rich gas stream thus formed to a lower portion of the column mixed with the methane-rich gas to participate in the distillation.
  • the apparatus may comprise a storage of the nitrogen-rich liquid connected to the means for sending the liquid to vaporize in the exchanger.
  • FIG. 2 shows a simplified diagram of the method according to the invention.
  • a flow of feed gas 1 which may be a biogas comprises between 30 and 50% of methane, with a CH / CO2 ratio of 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 for removing 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 processing unit 2 is cooled in a heat exchanger 3 of the plate and fin type at a pressure of between 6 and 15 bars.
  • the gas 4 is sent to a tank condenser-reboiler 5 of a simple distillation column 6.
  • the gas is cooled in the condenser-reboiler 5 and is at least partially condensed, while heating the vessel of the column 6
  • the fluid produced 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 1 1.
  • the bottom 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. If not nitrogen liquid 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)

Abstract

In a process for the cryogenic separation of a methane-rich feed stream containing between 3 and 35% of oxygen and also nitrogen, the feed stream is cooled in order to produce a cooled stream, at least one portion of the cooled stream is sent to a distillation column, a bottom stream is withdrawn from the distillation column, the bottom stream being enriched in methane compared to the feed stream, a stream enriched in oxygen compared to the feed stream is withdrawn from the distillation column, and a nitrogen-rich stream is sent to the column.

Description

Procédé et appareil de séparation cryogénique d'un débit riche en méthane 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 rate.
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 regarding the presence of oxygen in natural gas can be found in US-A-2006/0043000. The percentage of oxygen in natural gas does not exceed 0.1% from other sources.
La séparation de CO2 et de CH 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 CO2 and CH 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 presents several disadvantages such as low efficiency, many wear parts or adsorbent bottles and very large buffer capacities.
Une autre solution pour la séparation est la distillation cryogénique tel que décrit dans WO-A-09/004207. Celle-ci 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. It 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 des 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 can be seen from US-A-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 CO2 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 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. 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. 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. 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 the nitrogen into the lower part of the column to avoid the flammability zone throughout the column.
Selon un objet de l'invention, il est prévu un procédé de séparation cryogénique d'un débit d'alimentation riche en méthane contenant de l'oxygène et de l'azote dans lequel :  According to one object of the invention, there is provided a method of cryogenic separation of a feed flow rich in methane containing oxygen and nitrogen in which:
i) on refroidit le débit d'alimentation pour produire un débit refroidi, ii) on envoie au moins une partie du débit refroidi à une colonne de distillation,  i) the feed rate is cooled to produce a cooled flow rate, ii) at least a portion of the cooled flow rate is sent to a distillation column,
iii) on soutire de la colonne de distillation un débit de cuve, le débit de cuve étant enrichi en méthane par rapport au débit d'alimentation,  iii) the distillation column is withdrawn from a tank flow, the tank flow being enriched in methane with respect to the feed rate,
iv) on soutire de la colonne de distillation un débit enrichi en oxygène par rapport au débit d'alimentation, et  iv) a flow enriched in oxygen is withdrawn from the distillation column with respect to the feed rate, and
v) on envoie un débit gazeux riche en azote, provenant d'une source extérieure à une partie inférieure de la colonne de distillation pour participer à la distillation  v) a nitrogen-rich gas stream from an outside source is sent to a lower part of the distillation column to participate in the distillation;
caractérisé en ce que le débit d'alimentation contient entre 3 et 35% d'oxygène.  characterized in that the feed rate contains between 3 and 35% oxygen.
Selon d'autres caractéristiques optionnelles :  According to other optional features:
le débit d'alimentation contient entre 65 et 97% de méthane ;  the feed rate contains between 65 and 97% methane;
le débit d'alimentation contient entre 3 et 35% en total d'azote et d'oxygène ;  the feed rate contains between 3 and 35% in total of nitrogen and oxygen;
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 ;  the feed rate contains between 3 and 35% nitrogen; the nitrogen-rich flow contains at least 90% nitrogen, or even at least 95% nitrogen;
le débit riche en azote est envoyé en cuve de la colonne de distillation ;  the flow rich in nitrogen is sent to the bottom of the distillation column;
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 d u condenseu r-rebouilleur à la colonne et le gaz vaporisé est mélangé avec le débit riche en azote ; on vaporise un débit liquide riche en azote par échange de chaleur avec le débit d'alimentation pour produire le débit gazeux riche en azote ; 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 re-reboiler condenser to the column and the vaporized gas is mixed with the nitrogen-rich flow; a nitrogen-rich liquid flow is vaporized by heat exchange with the feed rate to produce the nitrogen-rich gas flow;
le débit d'alimentation contient moins que 10% d'oxygène. Selon un autre objet de l'invention, il est prévu un appareil de séparation cryogénique d'un débit d'alimentation riche en méthane contenant de l'oxygène et de l'azote comprenant :  the feed rate contains less than 10% oxygen. According to another object of the invention, there is provided an apparatus for cryogenic separation of a feed flow rich in methane containing oxygen and nitrogen, comprising:
i) un échangeur de chaleur pour permettre le refroidissement du débit d'alimentation pour produire un débit refroidi,  i) a heat exchanger to allow cooling of the feed rate to produce a cooled flow,
ii) un condenseur-rebouilleur,  ii) a condenser-reboiler,
iii) une colonne de distillation et des moyens pour envoyer au moins une partie du débit refroidi au condenseur-rebouilleur,  iii) a distillation column and means for sending at least a portion of the cooled flow to the condenser-reboiler,
iv) des moyens pour soutirer de la colonne de distillation un liquide enrichi en méthane par rapport au débit d'alimentation et pour l'envoyer au condenseur-rebouilleur,  iv) means for withdrawing from the distillation column a liquid enriched in methane with respect to the feed rate and for sending it to the condenser-reboiler,
v) des moyens pour soutirer du condenseur-rebouilleur un liquide riche en méthane et pour l'envoyer à l'échangeur,  v) means for extracting from the condenser-reboiler a liquid rich in methane and for sending it to the exchanger,
vi) des moyens pour soutirer du condenseur-rebouilleur un gaz riche en méthane et pour le renvoyer en cuve de la colonne, vii) des moyens pour soutirer de la colonne de distillation un débit enrichi en azote et/ou oxygène par rapport au débit d'alimentation, et  vi) means for extracting from the condenser-reboiler a gas rich in methane and for returning it to the vat of the column, vii) means for extracting from the distillation column a flow enriched in nitrogen and / or oxygen with respect to the flow rate of food, and
viii) des moyens pour envoyer un liquide riche en azote se vaporiser dans l'échangeur et des moyens pour envoyer le débit gazeux riche en azote ainsi formé à une partie inférieure de la colonne mélangé avec le gaz riche en méthane pour participer à la distillation.  viii) means for sending a nitrogen-rich liquid to vaporize in the exchanger and means for sending the nitrogen-rich gas stream thus formed to a lower portion of the column mixed with the methane-rich gas to participate in the distillation.
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 of which FIG. 2 shows a simplified diagram of the method 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 CH /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 refroid it dans le condenseur-rebouilleur 5 et est au moins partiel lement 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 may be a biogas comprises between 30 and 50% of methane, with a CH / CO2 ratio of 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 for removing 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 processing unit 2 is cooled in a heat exchanger 3 of the plate and fin type at a pressure of between 6 and 15 bars. The gas 4 is sent to a tank condenser-reboiler 5 of a simple distillation column 6. The gas is cooled in the condenser-reboiler 5 and is at least partially condensed, while heating the vessel of the column 6 The fluid produced 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 1 1 . 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 1 1. The bottom 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. If not nitrogen liquid from an air separation apparatus can vaporize in the exchanger 3 to supply the gas 20.
Le gaz d'alimentation peut contenir jusqu'à 10% d'oxygène ou jusqu'à 5% d'oxygène.  The feed gas can contain up to 10% oxygen or up to 5% oxygen.

Claims

REVENDICATIONS
1 . Procédé de séparation cryogénique d'un débit d'alimentation (4) riche en méthane contenant de l'oxygène et de l'azote dans lequel : 1. Process for the cryogenic separation of a feed flow (4) rich in methane containing oxygen and nitrogen in which:
i) on refroidit le débit d'alimentation pour produire un débit refroidi, ii) on envoie au moins une partie du débit refroidi à une colonne de distillation (6),  i) the feed rate is cooled to produce a cooled flow rate, ii) at least a portion of the cooled flow rate is sent to a distillation column (6),
iii) on soutire de la colonne de distillation un débit de cuve, le débit de cuve étant enrichi en méthane par rapport au débit d'alimentation, iv) on soutire de la colonne de distillation un débit enrichi en oxygène par rapport au débit d'alimentation, et  iii) the distillation column is withdrawn from a tank flow, the tank flow being enriched in methane with respect to the feed rate, iv) a flow enriched in oxygen is withdrawn from the distillation column with respect to the flow rate of food, and
v) on envoie un débit gazeux riche en azote, provenant d'une source extérieure (16) à une partie inférieure de la colonne de distillation pour participer à la distillation  v) a nitrogen-rich gas stream from an outside source (16) is sent to a lower portion of the distillation column to participate in the distillation
caractérisé en ce que le débit d'alimentation contient entre 3 et 35% d'oxygène.  characterized in that the feed rate contains between 3 and 35% oxygen.
2. Procédé selon la revendication 1 , dans lequel le débit d'alimentation (4) contient entre 65 et 97% de méthane. 2. The method of claim 1, wherein the feed rate (4) contains between 65 and 97% methane.
3. Procédé selon l'une des revendications précédentes, dans lequel le débit d'alimentation (4) contient entre 3 et 35% en total d'azote et d'oxygène. 3. Method according to one of the preceding claims, wherein the feed rate (4) contains between 3 and 35% in total of nitrogen and oxygen.
4. Procédé selon l'une des revendications précédentes, dans lequel le débit d'alimentation (4) contient entre 3 et 35% d'azote. 4. Method according to one of the preceding claims, wherein the feed rate (4) contains between 3 and 35% nitrogen.
5. Procédé selon l'une des revendications précédentes, dans lequel le débit riche en azote (20,21 ) contient au moins 90% d'azote, voire au moins 95% d'azote. 5. Method according to one of the preceding claims, wherein the flow rich in nitrogen (20,21) contains at least 90% nitrogen, or at least 95% nitrogen.
6. Procédé selon l'une des revendications précédentes, dans lequel le débit riche en azote (20, 1 ) est envoyé en cuve de la colonne de distillation (6). 6. Method according to one of the preceding claims, wherein the nitrogen-rich flow (20, 1) is sent to the bottom of the distillation column (6).
7. Procédé selon l'une des revendications précédentes, dans lequel le débit d'alimentation est envoyé à un condenseur-rebouilleur (5) 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. 7. Method according to one of the preceding claims, wherein the feed rate is sent to a condenser-reboiler (5) where it partially vaporizes the tank liquid to form a vaporized gas, the feed rate totally or partially liquefied is sent from the condenser-reboiler to the column and the vaporized gas is mixed with the nitrogen-rich flow.
8. Procédé selon l'une des revendications précédentes, dans lequel on vaporise un débit liquide riche en azote par échange de chaleur avec le débit d'alimentation pour produire le débit gazeux riche en azote. 8. Method according to one of the preceding claims, wherein a nitrogen-rich liquid flow is vaporized by heat exchange with the feed rate to produce the nitrogen-rich gas flow.
9. Procédé selon l'une des revendications précédentes dans lequel le débit d'alimentation contient moins que 10% d'oxygène. 9. Method according to one of the preceding claims wherein the feed rate contains less than 10% oxygen.
10. Appareil de séparation cryogénique d'un débit d'alimentation riche en méthane contenant de l'oxygène et de l'azote comprenant : 10. Apparatus for cryogenic separation of a methane-rich feed stream containing oxygen and nitrogen, comprising:
i) un échangeur de chaleur (3) pour permettre le refroidissement du débit d'alimentation pour produire un débit refroidi,  i) a heat exchanger (3) for cooling the feed rate to produce a cooled flow,
ii) un condenseur-rebouilleur (5),  ii) a condenser-reboiler (5),
iii) une colonne de distillation (6) et des moyens pour envoyer au moins une partie du débit refroidi au condenseur-rebouilleur, iv) des moyens (12) pour soutirer de la colonne de distillation un liquide enrichi en méthane par rapport au débit d'alimentation et pour l'envoyer au condenseur-rebouilleur,  iii) a distillation column (6) and means for sending at least a portion of the cooled flow to the condenser-reboiler, iv) means (12) for withdrawing from the distillation column a liquid enriched in methane with respect to the flow rate of power supply and to send it to the condenser-reboiler,
v) des moyens pour soutirer du condenseur-rebouilleur un liquide riche en méthane et pour l'envoyer à l'échangeur,  v) means for extracting from the condenser-reboiler a liquid rich in methane and for sending it to the exchanger,
vi) des moyens pour soutirer du condenseur-rebouilleur un gaz riche en méthane et pour le renvoyer en cuve de la colonne, vii) des moyens pour soutirer de la colonne de distillation un débit (19) enrichi en azote et/ou oxygène par rapport au débit d'alimentation, et vi) means for extracting from the condenser-reboiler a gas rich in methane and for returning it to the bottom of the column, vii) means for withdrawing from the distillation column a flow rate (19) enriched in nitrogen and / or oxygen with respect to the feed rate, and
viii) des moyens pour envoyer un liquide riche en azote se vaporiser dans l'échangeur (3) et des moyens pour envoyer le débit gazeux riche en azote ainsi formé à une partie inférieure de la colonne (6) mél angé avec l e g az rich e en m étha ne pour participer à la distillation.  viii) means for sending a nitrogen-rich liquid to vaporize in the exchanger (3) and means for sending the nitrogen-rich gas stream thus formed to a lower portion of the column (6) melted with nitrogen in m etha not to participate in the distillation.
1 1 . Appareil selon la revendication 10, comprenant un stockage (16) du liquide riche en azote relié aux moyens pour envoyer le liquide se vaporiser dans l'échangeur. 1 1. An apparatus according to claim 10, comprising a storage (16) of the nitrogen-rich liquid connected to the means for sending the vaporizing liquid into 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)

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