EP3252406B1 - Method for liquefying carbon dioxide from a natural gas stream - Google Patents

Method for liquefying carbon dioxide from a natural gas stream Download PDF

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Publication number
EP3252406B1
EP3252406B1 EP17171766.3A EP17171766A EP3252406B1 EP 3252406 B1 EP3252406 B1 EP 3252406B1 EP 17171766 A EP17171766 A EP 17171766A EP 3252406 B1 EP3252406 B1 EP 3252406B1
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EP
European Patent Office
Prior art keywords
natural gas
unit
liquefaction
current
stream
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EP17171766.3A
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German (de)
French (fr)
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EP3252406A1 (en
Inventor
Pierre COSTA DE BEAUREGARD
Michele MURINO
Delphine PICHOT
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/005—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0022—Hydrocarbons, e.g. natural gas
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0027—Oxides of carbon, e.g. CO2
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    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
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    • F25J1/0204—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a single flow SCR cycle
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    • F25J1/0211—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle
    • F25J1/0212—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle as a single flow MCR cycle
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    • F25J1/0236—Heat exchange integration providing refrigeration for different processes treating not the same feed stream
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    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • F25J1/0237—Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
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    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0285—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings
    • F25J1/0288—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings using work extraction by mechanical coupling of compression and expansion of the refrigerant, so-called companders
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    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/50—Processes or apparatus using other separation and/or other processing means using absorption, i.e. with selective solvents or lean oil, heavier CnHm and including generally a regeneration step for the solvent or lean oil
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
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    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/60—Natural gas or synthetic natural gas [SNG]
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    • F25J2260/80—Integration in an installation using carbon dioxide, e.g. for EOR, sequestration, refrigeration etc.

Definitions

  • the present invention relates to a process for liquefying a stream of hydrocarbons such as natural gas in particular in a process for the production of liquefied natural gas and liquid CO 2 .
  • refrigerant streams are used to produce cold at different levels of a main heat exchanger by vaporizing against the stream of hydrocarbons to be liquefied (typically natural gas).
  • the present invention relates in particular to a thermal integration process between a natural gas liquefaction unit and a CO 2 purification / liquefaction unit.
  • natural gas can be stored and transported over long distances more easily in the liquid state than in gaseous form, because it occupies a smaller volume for a given mass and does not need to be stored at high pressure.
  • natural gas typically contains hydrocarbons and CO 2 (approximately 0.5% to 5% mol). To avoid freezing of the latter during the liquefaction of natural gas, it should be removed.
  • One way of removing CO 2 from the natural gas stream is, for example, an amine wash located upstream of a liquefaction cycle.
  • Amine washing separates the CO 2 from the feed gas by washing the natural gas stream with an amine solution in an absorption column.
  • the amine solution enriched in CO 2 is recovered in the tank of this absorption column and is regenerated at low pressure in a column for regenerating the amine distillation (or stripping in English).
  • This purification is carried out using a dedicated CO 2 purification unit requiring the installation of a dedicated refrigeration cycle (typically a refrigeration system operating with ammonia for example).
  • a dedicated refrigeration cycle typically a refrigeration system operating with ammonia for example.
  • the function of the so-called “cold group” refrigeration cycle consists in providing the cold necessary for the CO 2 purification / liquefaction process.
  • the condenser of the distillation column used in step 3 represents approximately 50% of the total cold requirements. This cold can be brought in via a dedicated refrigeration cycle (typically with ammonia or propane) possibly coupled with a water cooling system.
  • Document US2011 / 126451 A1 shows a process according to the preamble of claim 1.
  • the refrigeration production system represents a significant cost of the unit for purifying and liquefying CO 2 and adds complexity of implementation on the site of implementation of the process which represents a constraint.
  • An existing solution consists in dissociating the two units (liquefaction of natural gas and purification of CO 2 ) which requires the installation of two systems of production of frigories, one for the liquefaction unit of natural gas and one for the CO 2 purification unit.
  • the inventors of the present invention then developed a solution which makes it possible to solve the problem raised above, namely to minimize the investment in a system for producing frigories in the CO 2 purification / liquefaction unit and therefore d '' optimize investment costs while maintaining optimal efficiency for liquefying natural gas in the liquefaction unit.
  • thermal coupling is meant pooling of the means for producing frigories to ensure the thermal balance of the two units, typically a refrigeration cycle compressor, and possibly a turbine / blower system in the case of nitrogen cycle.
  • turbine / booster system is meant a turbine mechanically coupled (via a common shaft) to a single-stage compressor. The power generated through the turbine is directly transmitted to the single-stage compressor.
  • This thermal integration is materialized by the pooling of any column, heat exchanger, unit or other suitable arrangement (typically a heat exchanger) where currents related to the natural gas liquefaction process and currents related to the CO purification / liquefaction process 2 heat exchange.
  • the process which is the subject of the present invention makes it possible to dispense with the cold group initially necessary for liquefying the CO 2 and to extract the cold directly from the natural gas liquefier.
  • This thermal integration thus makes it possible to dispense with equipment in the CO 2 purification unit.
  • the proposed integration makes it possible to supply cold at the three necessary temperature levels.
  • the present invention also relates to a device for producing liquefied natural gas and liquefied CO 2 comprising a unit for treating a feed gas, producing at least one gas stream enriched in CO 2 and a stream of depleted natural gas. in CO 2 , and a natural gas liquefaction unit, said natural gas liquefaction unit comprising at least one main heat exchanger and a frigory production system characterized in that the frigory production system is capable of and designed for liquefying both the stream enriched in CO 2 from the processing unit and the stream of natural gas depleted in CO 2 flowing in the natural gas liquefaction unit, said natural gas liquefaction unit comprising at least one refrigeration cycle supplied by a refrigerant stream from the main exchanger.
  • the refrigeration requirement of a natural gas liquefaction unit is generally greater than the refrigeration requirement of a CO 2 purification / liquefaction unit, it is relevant to take advantage of the available capacity of the machines (compressors and / or turbine / boosters) of the natural gas liquefaction unit to fully or at least partially meet the refrigeration requirement of the CO 2 purification / liquefaction unit and in particular limit the investment in machinery of the purification / liquefaction unit of CO 2 .
  • the incremental investment to increase the liquefaction capacity of a hydrocarbon liquefier is much lower than the incremental investment to increase the liquid production capacity of a CO 2 purification / liquefaction unit.
  • the stream of hydrocarbons to be liquefied is generally a stream of natural gas obtained from natural gas fields, oil reservoirs or a domestic gas network distributed via pipelines.
  • the flow of natural gas is made up mostly of methane.
  • the feed stream comprises at least 80 mol% of methane.
  • natural gas contains quantities of heavier hydrocarbons than methane, such as for example ethane, propane, butane and pentane as well as certain aromatic hydrocarbons.
  • the natural gas stream also contains non-hydrocarbon products such as H 2 O, N 2 , CO 2 , H 2 S and other sulfur compounds, mercury and others.
  • the feed stream containing natural gas is therefore pretreated before being introduced into the heat exchanger.
  • This pretreatment includes the reduction and / or elimination of undesirable components such as CO 2 and H 2 S, or other steps such as pre-cooling and / or pressurization. Since these measures are well known to those skilled in the art, they are not further detailed here.
  • natural gas as used in the present application relates to any composition containing hydrocarbons including at least methane.
  • the heat exchanger can be any heat exchanger, any unit or other arrangement adapted to allow the passage of a certain number of flows, and thus allow a direct or indirect heat exchange between one or more lines of refrigerant, and a or more feed streams.
  • a natural gas feed stream 1 (considered flow rate 500,000 tonnes per year or approximately 60 tonnes per hour) containing CO 2 is introduced into a treatment unit 2 in which said stream 1 is separated into at least two gas streams 3 and 4.
  • the natural gas feed stream 1 contains for example from 0.1 to 5 mol% of CO 2 .
  • the first stream 3 is a stream of natural gas depleted in CO 2 .
  • the second stream 4 is a stream enriched in CO 2 .
  • the processing unit 2 is a unit which separates the CO 2 from the natural gas stream, for example a chemical absorption unit, in particular an amine washing unit (type MDEA, MEA, etc.) which makes it possible to produce CO 2 pure (or concentrated) at low pressure (typically slightly higher than pressure atmospheric).
  • a chemical absorption unit in particular an amine washing unit (type MDEA, MEA, etc.) which makes it possible to produce CO 2 pure (or concentrated) at low pressure (typically slightly higher than pressure atmospheric).
  • amine washing unit type MDEA, MEA, etc.
  • pure CO 2 is meant a stream containing more than 95 mol% of CO 2 on a dry basis.
  • the stream of natural gas 3 depleted in CO 2 is introduced into l main exchanger 8 of a natural gas liquefaction unit 5 in order to be liquefied.
  • the pressure of this gas stream is for example between 25 and 60 bar absolute.
  • the gas stream 3 contains between 30 ppm by volume and 500 ppm by volume of benzene, usually less than 100 ppm by volume.
  • the gas stream 3 is cooled by heat exchange in the heat exchanger 8 in contact with a refrigerant.
  • the heat exchanger 8 is supplied with at least one stream of refrigerant 8.
  • this stream may be composed of a stream of mixed refrigerant or nitrogen which provides the cold necessary for liquefying the stream of natural gas.
  • the refrigerant stream is sent to the high pressure exchanger (typically from 30 to 60 bar) and returned to low pressure (from 1 to 10 bar).
  • the recompression energy necessary for the operation of the refrigeration cycle is provided by a cycle compressor (possibly supplemented by a turbine / booster system as part of a nitrogen cycle)
  • the stream of natural gas 3 depleted in CO 2 introduced into the main exchanger 8 of a natural gas liquefaction unit 5 is for example liquefied according to the process described in the following lines.
  • the stream of natural gas cooled to a temperature between -20 ° C and -70 ° C, typically between -35 ° C and -40 ° C at the exchanger outlet 8 is introduced into a unit 11 for separating heavy hydrocarbons natural gas stream, for example a washing column in which the heavy products 10 are separated from natural gas.
  • heavy products is meant hydrocarbons having more than four carbon atoms and aromatic compounds including in particular benzene.
  • a gas stream no longer presenting a risk of freezing due to the presence of heavy hydrocarbons or aromatic derivatives (comprising typically less than 1 ppm by volume of benzene) is recovered to be introduced into a second section of the heat exchanger 8.
  • By heat exchange it is cooled to the desired temperature (typically -160 ° C) to be sent to a means for liquefied natural gas 14.
  • the stream of mixed refrigerant recovered at the outlet of the heat exchanger 8 is introduced into a phase separator pot producing a gas stream containing the light elements of the refrigerant at the top of the pot and a liquid stream 13 containing the heavy elements of the refrigerant in the tank of pot.
  • the refrigerant current circulates in closed cycle in the heat exchanger 8 in order to provide the cold necessary to liquefy said stream 3 of natural gas.
  • the liquefaction cycle 9 uses a refrigerant which can be a mixture of refrigerants typically chosen from nitrogen, methane, ethane, ethylene, propane, butane, pentane. It can be a cycle based on a refrigeration cycle consisting of a refrigerant or a mixture of several refrigerants.
  • a refrigerant stream is introduced into the system 9 for producing frigories from the liquefaction unit 5 via a compressor (and optionally via a compressor / booster system).
  • the second gas stream 4 enriched in CO 2 from the treatment unit 2 is compressed at medium pressure (typically 25 Bar abs), cooled, purified (elimination of all traces of H 2 O Hydrocarbons, sulfur derivatives in particular) then returned to a distillation column (stripping column) which separates the incondensables at the head from the concentrated liquid CO 2 15 recovered in the tank.
  • medium pressure typically 25 Bar abs
  • purified elimination of all traces of H 2 O Hydrocarbons, sulfur derivatives in particular
  • part of the liquid stream 13 containing the heavy elements of the refrigerant is extracted and is sent into circulation between the CO 2 purification / liquefaction unit 6 and the natural gas liquefaction unit 5.
  • a refrigerant cycle dedicated to the CO 2 purification / liquefaction unit 6 is avoided by increasing the power of the cycle dedicated to the liquefaction of natural gas (typically around 5%).

Description

La présente invention concerne un procédé de liquéfaction d'un courant d'hydrocarbures tel que le gaz naturel en particulier dans un procédé pour la production de gaz naturel liquéfié et de CO2 liquide.The present invention relates to a process for liquefying a stream of hydrocarbons such as natural gas in particular in a process for the production of liquefied natural gas and liquid CO 2 .

Sur des usines de liquéfaction de gaz naturel typiques, des courants réfrigérants sont utilisés pour produire le froid à différents niveaux d'un échangeur de chaleur principal en se vaporisant contre le courant d'hydrocarbures à liquéfier (typiquement le gaz naturel).In typical natural gas liquefaction plants, refrigerant streams are used to produce cold at different levels of a main heat exchanger by vaporizing against the stream of hydrocarbons to be liquefied (typically natural gas).

La présente invention concerne en particulier un procédé d'intégration thermique entre une unité de liquéfaction de gaz naturel et unité de purification/liquéfaction de CO2.The present invention relates in particular to a thermal integration process between a natural gas liquefaction unit and a CO 2 purification / liquefaction unit.

Il est souhaitable de liquéfier le gaz naturel pour un certain nombre de raisons. A titre d'exemple, le gaz naturel peut être stocké et transporté sur de longues distances plus facilement à l'état liquide que sous forme gazeuse, car il occupe un volume plus petit pour une masse donnée et n'a pas besoin d'être stocké à une pression élevée.It is desirable to liquefy natural gas for a number of reasons. For example, natural gas can be stored and transported over long distances more easily in the liquid state than in gaseous form, because it occupies a smaller volume for a given mass and does not need to be stored at high pressure.

Typiquement, le gaz naturel contient des hydrocarbures et du CO2 (0,5% à 5% mol environ). Afin d'éviter le gel de ce dernier au cours de la liquéfaction du gaz naturel, il convient de le retirer. Un moyen permettant de retirer le CO2 du courant de gaz naturel est par exemple un lavage aux amines situé en amont d'un cycle de liquéfaction.Typically, natural gas contains hydrocarbons and CO 2 (approximately 0.5% to 5% mol). To avoid freezing of the latter during the liquefaction of natural gas, it should be removed. One way of removing CO 2 from the natural gas stream is, for example, an amine wash located upstream of a liquefaction cycle.

Le lavage aux amines sépare le CO2 du gaz d'alimentation par un lavage du courant de gaz naturel par une solution d'amines dans une colonne d'absorption. La solution d'amines enrichie en CO2 est récupérée en cuve de cette colonne d'absorption et est régénérée à basse pression dans une colonne de régénération de l'amine distillation (ou stripping en anglais).Amine washing separates the CO 2 from the feed gas by washing the natural gas stream with an amine solution in an absorption column. The amine solution enriched in CO 2 is recovered in the tank of this absorption column and is regenerated at low pressure in a column for regenerating the amine distillation (or stripping in English).

En tête de cette colonne de distillation, un gaz acide riche en CO2 est rejeté. Ainsi le traitement du courant de gaz naturel par un lavage aux aminés. Ainsi le courant de gaz naturel par un lavage aux amines rejette un flux concentré en CO2 « gaz acide », le plus souvent directement émis à l'atmosphère.At the head of this distillation column, an acid gas rich in CO 2 is rejected. Thus the treatment of the natural gas stream by washing with amines. Thus the stream of natural gas by washing with amines rejects a concentrated flow of CO 2 "acid gas", most often directly emitted to the atmosphere.

Sur des liquéfacteurs de gaz naturel (50,000 tonnes par an à 10 millions de tonnes par an), la quantité de CO2 émis est suffisante (quantité de CO2 émis pouvant aller jusqu'à 200 tonnes par jour) et il est possible de purifier ce « gaz acide» riche en CO2 en CO2 alimentaire.On natural gas liquefiers (50,000 tonnes per year to 10 million tonnes per year), the quantity of CO 2 emitted is sufficient (quantity of CO 2 emitted up to 200 tonnes per day) and it is possible to purify this "acid gas" rich in CO 2 in food CO 2 .

En effet, dans le domaine alimentaire, conformément à la législation en rigueur, pour pouvoir être commercialisé, le CO2 produit doit répondre à des spécifications strictes en termes de qualité et de pureté. Ainsi, par exemple, toute trace d'hydrocarbures ou de dérivés soufrés doit être éliminée (typiquement teneur inférieure au ppm volumique).In fact, in the food sector, in accordance with the legislation in force, to be able to be marketed, the CO 2 produced must meet strict specifications in terms of quality and purity. Thus, for example, any trace of hydrocarbons or sulfur derivatives must be eliminated (typically content less than ppm by volume).

Cette purification est effectuée grâce à une unité dédiée de purification de CO2 nécessitant l'installation d'un cycle frigorifique dédié (typiquement un système de réfrigération fonctionnant à l'ammoniac par exemple).This purification is carried out using a dedicated CO 2 purification unit requiring the installation of a dedicated refrigeration cycle (typically a refrigeration system operating with ammonia for example).

La fonction du cycle frigorifique dit « groupe de froid » consiste à apporter le froid nécessaire au procédé de purification/liquéfaction du CO2.The function of the so-called “cold group” refrigeration cycle consists in providing the cold necessary for the CO 2 purification / liquefaction process.

Typiquement une unité standard de CO2 contient les étapes suivantes :

  • Etape 1 : Compression du CO2 impur jusqu'à une pression comprise entre 15 et 50 bar abs.
  • Etape 2 : Purification du CO2 par exemple par des procédés mettant en œuvre des adsorbants régénératifs, des absorbants ou de catalyseur pour éliminer toute présence d'eau, de mercure, d'hydrocarbures et de dérivés soufrés (liste d'impuretés non exhaustive).
  • Etape 3 : Distillation des incondensables pour séparer en particulier l'oxygène et l'azote du CO2 produit.
Typically a standard CO 2 unit contains the following steps:
  • Step 1: Compression of impure CO 2 up to a pressure between 15 and 50 bar abs.
  • Step 2: Purification of CO 2, for example by processes using regenerative adsorbents, absorbents or catalysts to eliminate any presence of water, mercury, hydrocarbons and sulfur derivatives (non-exhaustive list of impurities) .
  • Step 3: Distillation of the incondensables to separate in particular the oxygen and nitrogen from the CO 2 produced.

Ainsi, classiquement dans une unité de purification/liquéfaction de CO2, il est nécessaire d'apporter du froid à trois niveaux de température :

  1. 1. Froid vers -20°C/-30°C utilisé pour l'étape 3 décrite au paragraphe précédent.
  2. 2. Froid vers 5°C utilisé pour l'étape 2.
  3. 3. Froid à température ambiante pour refroidir le CO2 impur en étape 1.
Thus, conventionally in a CO 2 purification / liquefaction unit, it is necessary to provide cold at three temperature levels:
  1. 1. Cold to -20 ° C / -30 ° C used for step 3 described in the previous paragraph.
  2. 2. Cold around 5 ° C used for step 2.
  3. 3. Cold at room temperature to cool the impure CO 2 in step 1.

Le condenseur de la colonne de distillation mise en œuvre à l'étape 3 représente environ 50% du total des besoins en froid. Ce froid peut être apporté via un cycle frigorifique dédié (typiquement à l'ammoniac ou au propane) couplé éventuellement d'un système de refroidissement à l'eau. Document US2011/126451 A1 montre un procédé selon la préambule de la revendication 1. Le système de production de frigories représente un coût important de l'unité de purification et de liquéfaction du CO2 et ajoute de la complexité de mise en œuvre sur le site de mise en œuvre du procédé ce qui représente une contrainte.The condenser of the distillation column used in step 3 represents approximately 50% of the total cold requirements. This cold can be brought in via a dedicated refrigeration cycle (typically with ammonia or propane) possibly coupled with a water cooling system. Document US2011 / 126451 A1 shows a process according to the preamble of claim 1. The refrigeration production system represents a significant cost of the unit for purifying and liquefying CO 2 and adds complexity of implementation on the site of implementation of the process which represents a constraint.

Une solution existante consiste à dissocier les deux unités (liquéfaction de gaz naturel et purification de CO2) ce qui nécessite la mise en place de deux systèmes de production de frigories, un pour l'unité de liquéfaction de gaz naturel et un pour l'unité de purification de CO2.An existing solution consists in dissociating the two units (liquefaction of natural gas and purification of CO 2 ) which requires the installation of two systems of production of frigories, one for the liquefaction unit of natural gas and one for the CO 2 purification unit.

Les inventeurs de la présente invention ont alors mis au point une solution permettant de résoudre le problème soulevé ci-dessus, à savoir minimiser l'investissement dans un système de production de frigories dans l'unité de purification/liquéfaction de CO2 et donc d'optimiser les dépenses d'investissement tout en gardant une efficacité optimale pour la liquéfaction du gaz naturel dans l'unité de liquéfaction.The inventors of the present invention then developed a solution which makes it possible to solve the problem raised above, namely to minimize the investment in a system for producing frigories in the CO 2 purification / liquefaction unit and therefore d '' optimize investment costs while maintaining optimal efficiency for liquefying natural gas in the liquefaction unit.

La présente invention a pour objet un procédé de production de gaz naturel liquéfié et de dioxyde de carbone (CO2) liquide selon la revendication 1 comprenant au moins les étapes suivantes :

  • Etape a) : séparation d'un gaz d'alimentation de gaz naturel, contenant des hydrocarbures et du dioxyde de carbone dans une unité de traitement, en un courant gazeux enrichi en CO2 et un courant de gaz naturel appauvri en CO2 ;
  • Etape b) : liquéfaction du courant de gaz naturel appauvri en CO2 issu de l'étape a) dans une unité de liquéfaction de gaz naturel comprenant au moins un échangeur de chaleur principal et un système de production de frigories, ladite unité de liquéfaction de gaz naturel comprenant au moins un cycle de réfrigération alimenté par un courant réfrigérant ;
  • Etape c) : liquéfaction simultanée du courant gazeux enrichi en CO2 issu de l'étape a) dans une unité de liquéfaction de CO2;
    caractérisé en ce que le froid nécessaire à la liquéfaction du courant gazeux enrichi en CO2 et à la liquéfaction du gaz naturel est fourni par ledit système de production de frigories de l'unité de liquéfaction de gaz naturel et en ce que tout ou partie du froid nécessaire à la liquéfaction du courant gazeux enrichi en CO2 provient d'une partie dudit courant réfrigérant alimentant le cycle de réfrigération de ladite unité de liquéfaction de gaz naturel. De préférence tout le froid nécessaire à la liquéfaction du courant gazeux enrichi en CO2 provient d'une partie dudit courant réfrigérant alimentant le cycle de réfrigération de ladite unité de liquéfaction de gaz naturel.L'objet de la présente invention est de coupler thermiquement une unité de liquéfaction d'un gaz riche en hydrocarbures, typiquement du gaz naturel, avec une unité de purification/liquéfaction de CO2.
The subject of the present invention is a process for producing liquefied natural gas and liquid carbon dioxide (CO 2 ) according to claim 1 comprising at least the following steps:
  • Step a): separation of a natural gas feed gas, containing hydrocarbons and carbon dioxide in a treatment unit, into a gas stream enriched in CO 2 and a stream of natural gas depleted in CO 2 ;
  • Step b): liquefaction of the CO 2 depleted natural gas stream from step a) in a natural gas liquefaction unit comprising at least one main heat exchanger and a frigory production system, said liquefaction unit natural gas comprising at least one refrigeration cycle supplied by a refrigerant stream;
  • Step c): simultaneous liquefaction of the gas stream enriched in CO 2 from step a) in a CO 2 liquefaction unit;
    characterized in that the cold necessary for the liquefaction of the gas stream enriched in CO 2 and for the liquefaction of natural gas is supplied by said frigory production system of the natural gas liquefaction unit and in that all or part of the cold necessary for the liquefaction of the gas stream enriched in CO 2 comes from a portion of said refrigerant stream supplying the refrigeration cycle of said natural gas liquefaction unit. Preferably all the cold necessary for the liquefaction of the gas stream enriched in CO 2 comes from a portion of said refrigerant stream supplying the refrigeration cycle of said unit of The object of the present invention is to thermally couple a liquefaction unit of a gas rich in hydrocarbons, typically natural gas, with a CO 2 purification / liquefaction unit.

Par couplage thermique, on entend mise en commun des moyens de production de frigories pour assurer le bilan thermique des deux unités, typiquement compresseur de cycle de réfrigération, et éventuellement un système turbine/surpresseur dans le cas de cycle azote.By thermal coupling is meant pooling of the means for producing frigories to ensure the thermal balance of the two units, typically a refrigeration cycle compressor, and possibly a turbine / blower system in the case of nitrogen cycle.

Par système turbine/surpresseur on entend une turbine mécaniquement couplée (via un arbre commun) à un compresseur mono-étagé. La puissance générée à travers la turbine étant directement transmise au compresseur mono-étagé.By turbine / booster system is meant a turbine mechanically coupled (via a common shaft) to a single-stage compressor. The power generated through the turbine is directly transmitted to the single-stage compressor.

Cette intégration thermique se matérialise par la mise en commun toute colonne, échangeur thermique, unité ou autre agencement adapté (typiquement un échangeur thermique) où des courants liés au procédé de liquéfaction de gaz naturel et des courants liés au procédé de purification/liquéfaction du CO2 échangent thermiquement.This thermal integration is materialized by the pooling of any column, heat exchanger, unit or other suitable arrangement (typically a heat exchanger) where currents related to the natural gas liquefaction process and currents related to the CO purification / liquefaction process 2 heat exchange.

Le procédé objet de la présente invention permet de se passer du groupe de froid initialement nécessaire pour liquéfier le CO2 et de soutirer le froid directement du liquéfacteur de gaz naturel. Cette intégration thermique permet ainsi de se passer d'un équipement dans l'unité de purification de CO2.The process which is the subject of the present invention makes it possible to dispense with the cold group initially necessary for liquefying the CO 2 and to extract the cold directly from the natural gas liquefier. This thermal integration thus makes it possible to dispense with equipment in the CO 2 purification unit.

L'intégration proposée permet de fournir du froid aux trois niveaux de température nécessaires.The proposed integration makes it possible to supply cold at the three necessary temperature levels.

Selon d'autres modes de réalisation, l'invention a aussi pour objet :

  • Un procédé tel que défini précédemment, caractérisé en ce que le gaz d'alimentation comprend de 0,1% molaire à 5% molaire de CO2
  • Un procédé tel que défini précédemment, caractérisé en ce que le courant gazeux enrichi en CO2 issu de l'étape a) comprend au moins 95% molaire de CO2.
  • Un procédé tel que défini précédemment, caractérisé en ce que préalablement à l'étape b), le courant de gaz naturel issu de l'étape a) est prétraité dans une unité de prétraitement.
  • Un procédé tel que défini précédemment, caractérisé en ce que ladite unité de traitement mise en œuvre à l'étape a) est une unité de lavage aux aminés.
  • Un procédé tel que défini précédemment, caractérisé en ce que le courant gazeux enrichi en CO2 issu de l'étape a) est purifié préalablement à l'étape c), le froid nécessaire à cette purification étant fourni par ledit système de production de frigories de l'unité de liquéfaction de gaz naturel.
  • Un procédé tel que défini précédemment, caractérisé en ce que le courant enrichi en CO2 ainsi purifié comprend au moins 99,5% molaire de CO2.
  • Un procédé tel que défini précédemment, caractérisé en ce que ledit système de production de frigories comprend au moins un compresseur et éventuellement un système turbine-surpresseur.
  • Un procédé tel que défini précédemment, caractérisé en ce que le courant réfrigérant alimentant ledit au moins un cycle de réfrigération de ladite unité de liquéfaction de gaz naturel contient au moins un des constituants choisis parmi l'azote, le méthane, l'éthylène, l'éthane, le propane, l'ammoniac, le butane et le pentane.
According to other embodiments, the subject of the invention is also:
  • A process as defined above, characterized in that the feed gas comprises from 0.1 mol% to 5 mol% CO 2
  • A process as defined above, characterized in that the gas stream enriched in CO 2 from step a) comprises at least 95 mol% of CO 2 .
  • A method as defined above, characterized in that prior to step b), the stream of natural gas from step a) is pretreated in a pretreatment unit.
  • A method as defined above, characterized in that said processing unit implemented in step a) is an amine washing unit.
  • A process as defined above, characterized in that the gas stream enriched in CO 2 from step a) is purified before step c), the cold necessary for this purification being supplied by said system of production of frigories of the natural gas liquefaction unit.
  • A process as defined above, characterized in that the stream enriched in CO 2 thus purified comprises at least 99.5 mol% of CO 2 .
  • A method as defined above, characterized in that said frigory production system comprises at least one compressor and possibly a turbine-booster system.
  • A process as defined above, characterized in that the refrigerant stream supplying said at least one refrigeration cycle of said natural gas liquefaction unit contains at least one of the constituents chosen from nitrogen, methane, ethylene, l ethane, propane, ammonia, butane and pentane.

La présente invention a aussi pour objet un dispositif de production de gaz naturel liquéfié et de CO2 liquéfié comprenant une unité de traitement d'un gaz d'alimentation, produisant au moins un courant gazeux enrichi en CO2 et un courant de gaz naturel appauvri en CO2, et une unité de liquéfaction de gaz naturel, ladite unité de liquéfaction de gaz naturel comprenant au moins un échangeur de chaleur principal et un système de production de frigories caractérisé en ce que le système de production de frigories est apte à et conçu pour liquéfier à la fois le courant enrichi en CO2 issu de l'unité de traitement et le courant de gaz naturel appauvri en CO2 circulant dans l'unité de liquéfaction de gaz naturel, ladite unité de liquéfaction de gaz naturel comprenant au moins un cycle de réfrigération alimenté par un courant réfrigérant issu de l'échangeur principal.The present invention also relates to a device for producing liquefied natural gas and liquefied CO 2 comprising a unit for treating a feed gas, producing at least one gas stream enriched in CO 2 and a stream of depleted natural gas. in CO 2 , and a natural gas liquefaction unit, said natural gas liquefaction unit comprising at least one main heat exchanger and a frigory production system characterized in that the frigory production system is capable of and designed for liquefying both the stream enriched in CO 2 from the processing unit and the stream of natural gas depleted in CO 2 flowing in the natural gas liquefaction unit, said natural gas liquefaction unit comprising at least one refrigeration cycle supplied by a refrigerant stream from the main exchanger.

Selon d'autres modes de réalisations la présente invention a également pour objet :

  • Un dispositif tel que défini précédemment, caractérisé en ce que ledit système de production de frigories comprend un cycle frigorifique, comportant un compresseur entraîné par un moteur thermique, un circuit de circulation d'un fluide réfrigérant.
  • Un dispositif tel que défini précédemment, caractérisé en ce qu'il comprend une unité de purification et de liquéfaction de gaz enrichi en CO2 comprenant au moins un moyen de compression, un moyen de purification et au moins une colonne de distillation, caractérisé en ce que ledit dispositif est conçu tel que le froid nécessaire pour la mise en œuvre de l'unité de purification et de liquéfaction de gaz enrichi en CO2 provient du courant réfrigérant alimentant le cycle de réfrigération de la dite unité de liquéfaction de gaz naturel.
According to other embodiments, the subject of the present invention is also:
  • A device as defined above, characterized in that said frigory production system comprises a refrigeration cycle, comprising a compressor driven by a heat engine, a circuit for circulating a coolant.
  • A device as defined above, characterized in that it comprises a unit for purifying and liquefying gas enriched in CO 2 comprising at least one compression means, a purification means and at least one distillation column, characterized in that that said device is designed such that the cold necessary for the implementation of the purification and liquefaction unit of gas enriched in CO 2 comes from the refrigerant current supplying the refrigeration cycle of said natural gas liquefaction unit.

Le besoin frigorifique d'une unité de liquéfaction de gaz naturel étant généralement plus important que le besoin frigorifique d'une unité de purification/liquéfaction de CO2, il est pertinent de profiter de la capacité disponible des machines (compresseurs et/ou turbine/surpresseurs) de l'unité de liquéfaction de gaz naturel pour assurer en totalité ou au moins partiellement le besoin frigorifique de l'unité de purification/liquéfaction de CO2 et notamment limiter l'investissement en machinerie de l'unité de purification/liquéfaction de CO2.As the refrigeration requirement of a natural gas liquefaction unit is generally greater than the refrigeration requirement of a CO 2 purification / liquefaction unit, it is relevant to take advantage of the available capacity of the machines (compressors and / or turbine / boosters) of the natural gas liquefaction unit to fully or at least partially meet the refrigeration requirement of the CO 2 purification / liquefaction unit and in particular limit the investment in machinery of the purification / liquefaction unit of CO 2 .

En particulier, l'investissement incrémental pour augmenter la capacité de liquéfaction d'un liquéfacteur d'hydrocarbures est bien inférieur à l'investissement incrémental pour augmenter la capacité de production liquide d'une unité de purification/liquéfaction de CO2.In particular, the incremental investment to increase the liquefaction capacity of a hydrocarbon liquefier is much lower than the incremental investment to increase the liquid production capacity of a CO 2 purification / liquefaction unit.

En outre, d'autres étapes de traitement intermédiaires entre la séparation courant hydrocarbures/CO2 et la liquéfaction des hydrocarbures peuvent être réalisées. Le courant d'hydrocarbures à liquéfier est généralement un flux de gaz naturel obtenu à partir de champs de gaz naturel, des réservoirs de pétrole ou d'un réseau de gaz domestique distribué via des pipelines.In addition, other intermediate processing steps between the separation of the hydrocarbon / CO 2 stream and the liquefaction of the hydrocarbons can be carried out. The stream of hydrocarbons to be liquefied is generally a stream of natural gas obtained from natural gas fields, oil reservoirs or a domestic gas network distributed via pipelines.

Habituellement, le flux de gaz naturel est composé essentiellement de méthane. De préférence, le courant d'alimentation comprend au moins 80% mol de méthane. En fonction de la source, le gaz naturel contient des quantités d'hydrocarbures plus lourds que le méthane, tels que par exemple l'éthane, le propane, le butane et le pentane ainsi que certains hydrocarbures aromatiques. Le flux de gaz naturel contient également des produits non-hydrocarbures tels que H2O, N2, CO2, H2S et d'autres composés soufrés, le mercure et autres.Usually the flow of natural gas is made up mostly of methane. Preferably, the feed stream comprises at least 80 mol% of methane. Depending on the source, natural gas contains quantities of heavier hydrocarbons than methane, such as for example ethane, propane, butane and pentane as well as certain aromatic hydrocarbons. The natural gas stream also contains non-hydrocarbon products such as H 2 O, N 2 , CO 2 , H 2 S and other sulfur compounds, mercury and others.

Le flux d'alimentation contenant le gaz naturel est donc prétraité avant d'être l'introduit dans l'échangeur de chaleur.The feed stream containing natural gas is therefore pretreated before being introduced into the heat exchanger.

Ce prétraitement comprend la réduction et/ou l'élimination des composants indésirables tels que le CO2 et le H2S, ou d'autres étapes telles que le pré-refroidissement et/ou la mise sous pression. Etant donné que ces mesures sont bien connues de l'homme de l'art, elles ne sont pas davantage détaillées ici.This pretreatment includes the reduction and / or elimination of undesirable components such as CO 2 and H 2 S, or other steps such as pre-cooling and / or pressurization. Since these measures are well known to those skilled in the art, they are not further detailed here.

Dans le procédé objet de la présente invention, il est essentiel de prétraiter le courant de gaz naturel afin d'extraire un courant enrichi en CO2 qui sera lui-même liquéfié grâce au système de production de frigories de l'unité de liquéfaction du gaz naturel.In the process which is the subject of the present invention, it is essential to pretreat the stream of natural gas in order to extract a stream enriched in CO 2 which will itself be liquefied by means of the frigory production system of the gas liquefaction unit natural.

L'expression "gaz naturel" telle qu'utilisée dans la présente demande se rapporte à toute composition contenant des hydrocarbures dont au moins du méthane. Cela comprend une composition « brute » (préalablement à tout traitement ou lavage), ainsi que toute composition ayant été partiellement, substantiellement ou entièrement traitée pour la réduction et/ou élimination d'un ou plusieurs composés, y compris, mais sans s'y limiter, le soufre, le dioxyde de carbone, l'eau, le mercure et certains hydrocarbures lourds et aromatiques.The expression "natural gas" as used in the present application relates to any composition containing hydrocarbons including at least methane. This includes a "crude" composition (prior to any treatment or washing), as well as any composition that has been partially, substantially or entirely treated for the reduction and / or elimination of one or more compounds, including, but not limited to limit, sulfur, carbon dioxide, water, mercury and some heavy and aromatic hydrocarbons.

L'échangeur de chaleur peut être tout échangeur thermique, toute unité ou autre agencement adapté pour permettre le passage d'un certain nombre de flux, et ainsi permettre un échange de chaleur direct ou indirect entre une ou plusieurs lignes de fluide réfrigérant, et un ou plusieurs flux d'alimentation.The heat exchanger can be any heat exchanger, any unit or other arrangement adapted to allow the passage of a certain number of flows, and thus allow a direct or indirect heat exchange between one or more lines of refrigerant, and a or more feed streams.

L'invention sera décrite de manière plus détaillée en se référant à la figure qui illustre le schéma d'un mode de réalisation particulier d'une mise en œuvre d'un procédé selon l'invention.The invention will be described in more detail with reference to the figure which illustrates the diagram of a particular embodiment of an implementation of a method according to the invention.

Sur la figure, un flux d'alimentation de gaz naturel 1 (débit considéré 500,000 tonnes par an soit environ 60 tonnes par heures) contenant du CO2 est introduit dans une unité de traitement 2 dans laquelle ledit flux 1 est séparé en au moins deux courants gazeux 3 et 4. Le flux d'alimentation de gaz naturel 1 contient par exemple de 0,1 à 5% molaire de CO2.In the figure, a natural gas feed stream 1 (considered flow rate 500,000 tonnes per year or approximately 60 tonnes per hour) containing CO 2 is introduced into a treatment unit 2 in which said stream 1 is separated into at least two gas streams 3 and 4. The natural gas feed stream 1 contains for example from 0.1 to 5 mol% of CO 2 .

Le premier courant 3 est un courant de gaz naturel appauvri en CO2. Le deuxième courant 4 est un courant enrichi en CO2.The first stream 3 is a stream of natural gas depleted in CO 2 . The second stream 4 is a stream enriched in CO 2 .

L'unité de traitement 2 est une unité qui sépare le CO2 du courant de gaz naturel par exemple une unité d'absorption chimique, en particulier une unité de lavage aux amines (type MDEA, MEA, ...) qui permet de produire du CO2 pur (ou concentré) à basse pression (typiquement légèrement supérieur à la pression atmosphérique). Par CO2 pur on entend un courant contenant plus de 95% molaire de CO2 sur une base sèche.The processing unit 2 is a unit which separates the CO 2 from the natural gas stream, for example a chemical absorption unit, in particular an amine washing unit (type MDEA, MEA, etc.) which makes it possible to produce CO 2 pure (or concentrated) at low pressure (typically slightly higher than pressure atmospheric). By pure CO 2 is meant a stream containing more than 95 mol% of CO 2 on a dry basis.

Après d'éventuelles étapes de pré-traitement pour éliminer toutes traces de mercure, d'eau ou de dérivés soufrés par exemple(pré-traitement dans l'unité 7), le courant de gaz naturel 3 appauvri en CO2 est introduit dans l'échangeur principal 8 d'une unité de liquéfaction de gaz naturel 5 afin d'être liquéfié.After possible pre-treatment steps to remove all traces of mercury, water or sulfur derivatives for example (pre-treatment in unit 7), the stream of natural gas 3 depleted in CO 2 is introduced into l main exchanger 8 of a natural gas liquefaction unit 5 in order to be liquefied.

La pression de ce courant gazeux est par exemple comprise entre 25 et 60 bar absolus. Typiquement, le courant gazeux 3 contient entre 30 ppm en volume et 500 ppm en volume de benzène, usuellement moins de 100 ppm en volume. Le courant gazeux 3 est refroidi par échange thermique dans l'échangeur de chaleur 8 au contact d'un réfrigérant. L'échangeur de chaleur 8 est alimenté par au moins un courant de réfrigérant 8.The pressure of this gas stream is for example between 25 and 60 bar absolute. Typically, the gas stream 3 contains between 30 ppm by volume and 500 ppm by volume of benzene, usually less than 100 ppm by volume. The gas stream 3 is cooled by heat exchange in the heat exchanger 8 in contact with a refrigerant. The heat exchanger 8 is supplied with at least one stream of refrigerant 8.

Par exemple, ce courant peut être composé d'un courant de réfrigérant mixte ou d'azote qui fournit le froid nécessaire à la liquéfaction du courant de gaz naturel. Le courant de réfrigérant est envoyé dans l'échangeur à haute pression (typiquement de 30 à 60 bars) et renvoyé à basse pression (de 1 à 10 bar). L'énergie de recompression nécessaire au fonctionnement du cycle frigorifique est assurée par un compresseur de cycle (éventuellement complété par un système turbine/surpresseur dans le cadre d'un cycle azote)For example, this stream may be composed of a stream of mixed refrigerant or nitrogen which provides the cold necessary for liquefying the stream of natural gas. The refrigerant stream is sent to the high pressure exchanger (typically from 30 to 60 bar) and returned to low pressure (from 1 to 10 bar). The recompression energy necessary for the operation of the refrigeration cycle is provided by a cycle compressor (possibly supplemented by a turbine / booster system as part of a nitrogen cycle)

Le courant de gaz naturel 3 appauvri en CO2 introduit dans l'échangeur principal 8 d'une unité de liquéfaction de gaz naturel 5 est par exemple liquéfié selon le procédé décrit dans les lignes suivantes.The stream of natural gas 3 depleted in CO 2 introduced into the main exchanger 8 of a natural gas liquefaction unit 5 is for example liquefied according to the process described in the following lines.

Le courant de gaz naturel refroidi à une température comprise entre - 20°C et -70°C, typiquement comprise entre -35°C et -40°C en sortie d'échangeur 8 est introduit dans une unité 11 de séparation des hydrocarbures lourds du courant de gaz naturel, par exemple une colonne de lavage dans laquelle les produits lourds 10 sont séparés du gaz naturel. Par produits lourds on entend les hydrocarbures ayant plus de quatre atomes de carbone et les composés aromatiques dont notamment le benzène.The stream of natural gas cooled to a temperature between -20 ° C and -70 ° C, typically between -35 ° C and -40 ° C at the exchanger outlet 8 is introduced into a unit 11 for separating heavy hydrocarbons natural gas stream, for example a washing column in which the heavy products 10 are separated from natural gas. By heavy products is meant hydrocarbons having more than four carbon atoms and aromatic compounds including in particular benzene.

Un courant liquide 10 contenant tous les hydrocarbures que l'on souhaite extraire du courant de gaz naturel, tel que le benzène, (du courant gazeux initial 1 est évacué en cuve de colonne lavage.A liquid stream 10 containing all the hydrocarbons that it is desired to extract from the stream of natural gas, such as benzene, (from the initial gaseous stream 1 is discharged into the washing column tank.

En tête de colonne, un courant gazeux ne présentant plus de risque de gel dû à la présence d'hydrocarbures lourds ou de dérivés aromatiques (comprenant typiquement moins de 1 ppm en volume de benzène) est récupéré pour être introduit dans une deuxième section de l'échangeur de chaleur 8. Par échange thermique il est refroidi à la température souhaitée (typiquement -160°C) pour être envoyé vers un moyen de stockage de gaz naturel liquéfié 14.At the top of the column, a gas stream no longer presenting a risk of freezing due to the presence of heavy hydrocarbons or aromatic derivatives (comprising typically less than 1 ppm by volume of benzene) is recovered to be introduced into a second section of the heat exchanger 8. By heat exchange it is cooled to the desired temperature (typically -160 ° C) to be sent to a means for liquefied natural gas 14.

Le courant de réfrigérant mixte récupéré en sortie de l'échangeur de chaleur 8 est introduit dans un pot séparateur de phases produisant un courant gazeux contenant les éléments légers du réfrigérant en tête de pot et un courant liquide 13 contenant les éléments lourds du réfrigérant en cuve de pot. Le courant réfrigérant circule en cycle fermé dans l'échangeur de chaleur 8 afin d'apporter le froid nécessaire pour liquéfier ledit courant 3 de gaz naturel.The stream of mixed refrigerant recovered at the outlet of the heat exchanger 8 is introduced into a phase separator pot producing a gas stream containing the light elements of the refrigerant at the top of the pot and a liquid stream 13 containing the heavy elements of the refrigerant in the tank of pot. The refrigerant current circulates in closed cycle in the heat exchanger 8 in order to provide the cold necessary to liquefy said stream 3 of natural gas.

En particulier, le cycle de liquéfaction 9 met en œuvre un réfrigérant pouvant être un mélange de réfrigérants choisis parmi typiquement l'azote, le méthane, l'éthane, l'éthylène, le propane, le butane, le pentane. Il peut s'agir d'un cycle basé sur un cycle frigorifique constitué d'un réfrigérant ou d'un mélange de plusieurs réfrigérants.In particular, the liquefaction cycle 9 uses a refrigerant which can be a mixture of refrigerants typically chosen from nitrogen, methane, ethane, ethylene, propane, butane, pentane. It can be a cycle based on a refrigeration cycle consisting of a refrigerant or a mixture of several refrigerants.

Un courant de réfrigérant est introduit dans le système 9 de production de frigories de l'unité de liquéfaction 5 via un compresseur (et éventuellement un via système compresseur/surpresseur).A refrigerant stream is introduced into the system 9 for producing frigories from the liquefaction unit 5 via a compressor (and optionally via a compressor / booster system).

Le deuxième courant gazeux 4 enrichi en CO2 issu de l'unité de traitement 2 est comprimé à moyenne pression (typiquement 25 Bar abs), refroidi, purifié (élimination de toute trace d'H2O Hydrocarbures, dérivés soufrés en particulier) puis renvoyé dans une colonne de distillation (colonne de stripping) qui sépare les incondensables en tête du CO2 liquide concentré 15 récupéré en cuve.The second gas stream 4 enriched in CO 2 from the treatment unit 2 is compressed at medium pressure (typically 25 Bar abs), cooled, purified (elimination of all traces of H 2 O Hydrocarbons, sulfur derivatives in particular) then returned to a distillation column (stripping column) which separates the incondensables at the head from the concentrated liquid CO 2 15 recovered in the tank.

Pour assurer le froid nécessaire au bon fonctionnement de l'unité de purification/liquéfaction 6, Une partie du courant liquide 13 contenant les éléments lourds du réfrigérant est extraite et est envoyée en circulation entre l'unité de purification/liquéfaction de CO2 6 et l'unité de liquéfaction de gaz naturel 5. Ainsi grâce à cette intégration thermique, on évite un cycle frigorigène dédié à l'unité 6 de purification/liquéfaction de CO2 en augmentant la puissance du cycle dédié à la liquéfaction du gaz naturel (typiquement de l'ordre de 5%).To ensure the cold necessary for the proper functioning of the purification / liquefaction unit 6, part of the liquid stream 13 containing the heavy elements of the refrigerant is extracted and is sent into circulation between the CO 2 purification / liquefaction unit 6 and the natural gas liquefaction unit 5. Thus thanks to this thermal integration, a refrigerant cycle dedicated to the CO 2 purification / liquefaction unit 6 is avoided by increasing the power of the cycle dedicated to the liquefaction of natural gas (typically around 5%).

Claims (7)

  1. Method for producing liquefied natural gas (14) and liquid (15) carbon dioxide (CO2) comprising at least the following steps:
    - Step a): separating a natural gas supply gas (1), containing hydrocarbons and carbon dioxide in a treatment unit (2), into a CO2-enriched gaseous current (4) and a CO2-depleted natural gas current (3);
    - Step b): liquefying the CO2-depleted natural gas current (3) from step a) in a natural gas liquefaction unit (5) comprising at least one main heat exchanger (8) and one frigorie-producing system (9), said natural gas liquefaction unit (5) comprising at least one refrigeration cycle supplied by a refrigerating current;
    - Step c): simultaneously liquefying the CO2-enriched gaseous current (4) from step a) in a CO2 liquefaction unit (6);
    characterised in that the cold necessary for the liquefaction of the CO2-enriched gaseous current (4) and for the liquefaction of the natural gas is provided by said frigorie-producing system (9) of the natural gas liquefaction unit (5) and in that the cold necessary for the liquefaction of the CO2-enriched gaseous current (4) comes from some (13) of said refrigerating current supplying the refrigeration cycle of said natural gas liquefaction unit (5); characterised in that the supply gas (1) comprises 0.1% molar to 5% molar of CO2; and characterised in that said frigorie-producing system comprises at least one compressor and one turbine-compressor system.
  2. Method according to one of the preceding claims, characterised in that the CO2-enriched gaseous current (4) from step a) comprises at least 95% molar of CO2.
  3. Method according to one of the preceding claims, characterised in that prior to step b), the natural gas current (3) from step a) is pre-treated in a pre-treatment unit (7).
  4. Method according to one of the preceding claims, characterised in that said treatment unit (2) implemented in step a) is an amine-scrubbing unit.
  5. Method according to one of the preceding claims, characterised in that the CO2-enriched gaseous current (4) from step a) is purified prior to step c), the cold necessary for this purification being provided by said frigorie-producing system of the natural gas liquefaction unit (5).
  6. Method according to the preceding claim, characterised in that the CO2-enriched current thus purified comprises at least 99.5% molar of CO2.
  7. Method according to one of the preceding claims, characterised in that the refrigerating current (13) supplying said at least one refrigeration cycle of said natural gas liquefaction unit (5) contains at least one of the components selected from among nitrogen, methane, ethylene, ethane, propane, ammoniac, butane and pentane.
EP17171766.3A 2016-06-02 2017-05-18 Method for liquefying carbon dioxide from a natural gas stream Active EP3252406B1 (en)

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US6301927B1 (en) * 1998-01-08 2001-10-16 Satish Reddy Autorefrigeration separation of carbon dioxide
JP4138399B2 (en) * 2002-08-21 2008-08-27 三菱重工業株式会社 Method for producing liquefied natural gas
BRPI0916778A2 (en) * 2008-07-18 2018-02-14 Shell Internationale Res Maartschappij B V process for producing purified gas from a feed gas stream, and liquefied natural gas
US20110126451A1 (en) * 2009-11-30 2011-06-02 Chevron U.S.A., Inc. Integrated process for converting natural gas from an offshore field site to liquefied natural gas and liquid fuel
CN103415752A (en) * 2010-03-25 2013-11-27 曼彻斯特大学 Refrigeration process
CA2800699C (en) * 2010-06-03 2016-01-19 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US10787615B2 (en) * 2014-01-28 2020-09-29 Praxair Technology, Inc. Method and system for treating a flow back fluid exiting a well site
DE102014005936A1 (en) * 2014-04-24 2015-10-29 Linde Aktiengesellschaft Process for liquefying a hydrocarbon-rich fraction

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