US20170350648A1 - Process for liquefying carbon dioxide resulting from a natural gas stream - Google Patents

Process for liquefying carbon dioxide resulting from a natural gas stream Download PDF

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Publication number
US20170350648A1
US20170350648A1 US15/611,505 US201715611505A US2017350648A1 US 20170350648 A1 US20170350648 A1 US 20170350648A1 US 201715611505 A US201715611505 A US 201715611505A US 2017350648 A1 US2017350648 A1 US 2017350648A1
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United States
Prior art keywords
natural gas
liquefaction
stream
gas stream
unit
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US15/611,505
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English (en)
Inventor
Pierre COSTA DE BEAUREGARD
Michele MURINO
Delphine PICHOT
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Marvell Semiconductor Inc
Original Assignee
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Marvell Semiconductor Inc
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Application filed by LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude, Marvell Semiconductor Inc filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Assigned to MARVELL SEMICONDUCTOR, INC. reassignment MARVELL SEMICONDUCTOR, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: QI, YIHONG, ZHENG, XIAYU
Assigned to L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude reassignment L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COSTA DE BEAUREGARD, Pierre, MURINO, Michele, PICHOT, Delphine
Publication of US20170350648A1 publication Critical patent/US20170350648A1/en
Abandoned legal-status Critical Current

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
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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
    • 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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    • 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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    • F25J1/0212—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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    • F25J1/0237—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
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    • 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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    • 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 producing liquefied natural gas and liquid CO 2 .
  • refrigerant streams are used to produce the refrigeration at various levels of a main heat exchanger by vaporizing against the stream of hydrocarbons to be liquefied (typically natural gas).
  • natural gas may be stored and transported over long distances more easily in the liquid state than in the gas form, since it occupies a much smaller volume for a given mass and does not need to be stored at a high pressure.
  • natural gas typically contains hydrocarbons and CO 2 (0.5 mol % to 5 mol % approximately).
  • CO 2 0.5 mol % to 5 mol % approximately.
  • One means for removing the CO 2 from the natural gas stream is for example amine scrubbing upstream of a liquefaction cycle.
  • Amine scrubbing separates the CO 2 from the feed gas by scrubbing the natural gas stream with a solution of amines in an absorption column.
  • the CO 2 -enriched amine solution is recovered at the bottom of this absorption column and is regenerated at low pressure in a distillation (or stripping) column for regenerating the amine.
  • the CO 2 produced in order to be able to be sold, the CO 2 produced must meet strict specifications in terms of quality and purity.
  • any trace of hydrocarbons or of sulphur derivatives must be eliminated (content typically less than 1 ppm by volume).
  • This purification is carried out by means of 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 operation of the “refrigeration unit” refrigeration cycle consists in providing the refrigeration necessary for the CO 2 purification/liquefaction process.
  • a standard CO 2 unit contains the following steps:
  • Step 1 Compression of the impure CO 2 to a pressure between 15 and 50 bar abs.
  • Step 2 Purification of the CO 2 for example by processes that use regenerative adsorbents, absorbents or catalyst to eliminate any presence of water, mercury, hydrocarbons and sulphur derivatives (non-exhaustive list of impurities).
  • Step 3 Distillation of the noncondensable gases in order to separate in particular oxygen and nitrogen from the CO 2 produced.
  • the condenser of the distillation column used in step 3 represents around 50% of the total of the refrigeration requirements.
  • This refrigeration may be provided via a dedicated refrigeration cycle (typically an ammonia or propane refrigeration cycle) optionally coupled with a water cooling system.
  • the system for producing frigories represents a high cost of the CO 2 purification and liquefaction unit and adds complexity of implementation to the site for implementing the process which represents a constraint.
  • One existing solution consists in separating the two (natural gas liquefaction and CO 2 purification) units which requires the installation of two systems for producing frigories, one for the natural gas liquefaction unit and one for the CO 2 purification unit.
  • the present invention relates in particular to a process of thermal integration between a natural gas liquefaction unit and CO 2 purification/liquefaction unit.
  • the inventors of the present invention have then developed a solution that 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 to optimize the investment expenditure while retaining an optimal efficiency for the liquefaction of the natural gas in the liquefaction unit.
  • the subject of the present invention is a process for producing liquefied natural gas and liquid carbon dioxide (CO 2 ) comprising at least the following steps:
  • Thermal coupling is understood to mean sharing the means for producing frigories in order to ensure the thermal balance of the two units, typically refrigeration cycle compressor, and optionally a turbine/booster system in the case of a nitrogen cycle.
  • a turbine/booster system is understood to mean 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 realized by the sharing of any column, heat exchanger, unit or other suitable arrangement (typically a heat exchanger) where streams linked to the natural gas liquefaction process and streams linked to the CO 2 purification/liquefaction process exchange thermally.
  • the process that is the subject of the present invention makes it possible to do without the refrigeration unit initially necessary for liquefying the CO 2 and to extract the refrigeration directly from the natural gas liquefier.
  • This thermal integration thus makes it possible to do without one piece of equipment in the CO 2 purification unit.
  • the proposed integration makes it possible to provide refrigeration at the three temperature levels needed.
  • the invention also relates to:
  • Another subject of the present invention is a device for producing liquefied natural gas and liquefied CO 2 comprising a feed gas treatment unit, producing at least a CO 2 -enriched gas stream and a CO 2 -depleted natural gas stream, and a natural gas liquefaction unit, said natural gas liquefaction unit comprising at least a main heat exchanger and a system for producing frigories, characterized in that the system for producing frigories is capable of and designed for liquefying both the CO 2 -enriched stream resulting from the treatment unit and the CO 2 -depleted natural gas stream circulating in the natural gas liquefaction unit, said natural gas liquefaction unit comprising at least one refrigeration cycle supplied by a refrigerant stream resulting from the main exchanger.
  • the present invention also relates to:
  • 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 benefit from the available capacity of the machines (compressors and/or turbine/boosters) of the natural gas liquefaction unit in order to provide, fully or at least partially, the refrigeration requirement of the CO 2 purification/liquefaction unit and in particular to limit the investment in machinery of the CO 2 purification/liquefaction unit.
  • the incremental investment for increasing the liquefaction capacity of a hydrocarbon liquefier is much lower than the incremental investment for increasing 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 natural gas stream is essentially composed of methane.
  • the feed stream comprises at least 80 mol % of methane.
  • the natural gas contains quantities of hydrocarbons heavier than methane, such as for example ethane, propane, butane and pentane and also 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 sulphur-containing compounds, mercury and others.
  • the feed stream containing the natural gas is therefore pretreated before being introduced into the heat exchanger.
  • This pretreatment comprises the reduction and/or the elimination of the undesirable components such as the CO 2 and the H 2 S, or other steps such as precooling and/or pressurization. Given that these measures are well known to a person skilled in the art, they are not described in further detail here.
  • natural gas as used in the present application relates to any composition containing hydrocarbons including at least methane.
  • the heat exchanger may be any heat exchanger, any unit or other arrangement suitable for allowing the passage of a certain number of streams, and thus enabling a direct or indirect heat exchange between one or more refrigerant fluid lines, and one or more feed streams.
  • FIG. 1 illustrates a schematic representation of one embodiment of the present invention.
  • a natural gas feed stream 1 (flow rate considered: 500 000 tonnes per year, i.e. around 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 mol % to 5 mol % of CO 2 .
  • the first stream 3 is a CO 2 -depleted natural gas stream.
  • the second stream 4 is a CO 2 -enriched stream.
  • the treatment unit 2 is a unit that separates the CO 2 from the natural gas stream, for example a chemical absorption unit, in particular an amine (of MDEA, MEA, etc. type) scrubbing unit that makes it possible to produce pure (or concentrated) CO 2 at low pressure (typically slightly greater than atmospheric pressure).
  • Pure CO 2 is understood to mean a stream containing more than 95 mol % of CO 2 on a dry basis.
  • the CO 2 -depleted natural gas stream 3 is introduced into the 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 by at least one refrigerant stream 8 .
  • this stream may be composed of a nitrogen or mixed refrigerant stream that provides the refrigeration necessary for the liquefaction of the natural gas stream.
  • the refrigerant stream is sent into the exchanger at high pressure (typically from 30 to 60 bar) and sent back at low pressure (from 1 to 10 bar).
  • the recompression energy necessary for the operation of the refrigeration cycle is provided by a cycle compressor (optionally supplemented by a turbine/booster system within the context of a nitrogen cycle).
  • the CO 2 -depleted natural gas stream 3 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 natural gas stream cooled to a temperature between ⁇ 20° C. and ⁇ 70° C., typically between ⁇ 35° C. and ⁇ 40° C. at the outlet of the exchanger 8 is introduced into a unit 11 for separating the heavy hydrocarbons from the natural gas stream, for example a scrubbing column in which the heavy products 10 are separated from the natural gas.
  • Heavy products are understood to mean hydrocarbons having more than four carbon atoms and aromatic compounds including in particular benzene.
  • a gas stream that no longer presents a risk of freezing due to the presence of heavy hydrocarbons or aromatic derivatives (typically comprising less than 1 ppm by volume of benzene) is recovered in order to be introduced into a second section of the heat exchanger 8 .
  • a heat exchange Via heat exchange, it is cooled to the desired temperature (typically ⁇ 160° C.) in order to be sent to a liquefied natural gas storage means 14.
  • the mixed refrigerant stream recovered at the outlet of the heat exchanger 8 is introduced into a phase separator vessel that produces a gas stream containing the light elements of the refrigerant at the top of the vessel and a liquid stream 13 containing the heavy elements of the refrigerant at the bottom of the vessel.
  • the refrigerant stream circulates in a closed cycle in the heat exchanger 8 in order to provide the refrigeration necessary for liquefying said natural gas stream 3 .
  • the liquefaction cycle 9 uses a refrigerant that may be a mixture of refrigerants typically selected from nitrogen, methane, ethane, ethylene, propane, butane and pentane. It may 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 9 rigories-producing system 9 of the liquefaction unit 5 via a compressor (and optionally via a compressor/booster system).
  • the second CO 2 -enriched gas stream 4 resulting from the treatment unit 2 is compressed to medium pressure (typically 25 bar abs), cooled, purified (elimination of any trace of H 2 O, hydrocarbons, sulphur derivatives in particular) then sent back to a distillation column (stripping column) that separates the noncondensable gases at the top from the concentrated liquid CO 2 15 recovered at the bottom.
  • medium pressure typically 25 bar abs
  • purified separation of any trace of H 2 O, hydrocarbons, sulphur derivatives in particular

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FR1654996A FR3052240B1 (fr) 2016-06-02 2016-06-02 Procede de liquefaction de dioxyde de carbone issu d'un courant de gaz naturel
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FR3141758A1 (fr) 2022-11-04 2024-05-10 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Appareil et procédé de production de gaz naturel refroidi et de CO2 liquide
FR3138196A3 (fr) 2022-11-04 2024-01-26 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Appareil et procédé de production de gaz naturel refroidi et de CO2 liquide

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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
US20130008204A1 (en) * 2010-03-25 2013-01-10 University Of Manchester Refrigeration process
US20150210936A1 (en) * 2014-01-28 2015-07-30 Kenneth L. Burgers Method and system for treating a flow back fluid exiting a well site

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CA2317539C (fr) * 1998-01-08 2003-08-19 Satish Reddy Separation du dioxyde de carbone par autorefrigeration
JP4138399B2 (ja) * 2002-08-21 2008-08-27 三菱重工業株式会社 液化天然ガスの製造方法
RU2011106108A (ru) * 2008-07-18 2012-08-27 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) Двухстадийный способ производства очищенного газа
WO2011153087A1 (fr) * 2010-06-03 2011-12-08 Ortloff Engineers, Ltd Traitement d'hydrocarbures gazeux
DE102014005936A1 (de) * 2014-04-24 2015-10-29 Linde Aktiengesellschaft Verfahren zum Verflüssigen einer Kohlenwasserstoff-reichen Fraktion

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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
US20130008204A1 (en) * 2010-03-25 2013-01-10 University Of Manchester Refrigeration process
US20150210936A1 (en) * 2014-01-28 2015-07-30 Kenneth L. Burgers Method and system for treating a flow back fluid exiting a well site

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