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US20150047390A1 - Process and apparatus for separating a carbon dioxide-rich gas by distillation - Google Patents

Process and apparatus for separating a carbon dioxide-rich gas by distillation Download PDF

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Publication number
US20150047390A1
US20150047390A1 US14/356,206 US201214356206A US2015047390A1 US 20150047390 A1 US20150047390 A1 US 20150047390A1 US 201214356206 A US201214356206 A US 201214356206A US 2015047390 A1 US2015047390 A1 US 2015047390A1
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Prior art keywords
gas
pressure
column
carbon dioxide
compressor
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US14/356,206
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Authur Darde
Xavier Traversac
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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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: TRAVERSAC, XAVIER, DARDE, ARTHUR
Publication of US20150047390A1 publication Critical patent/US20150047390A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • 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
    • F25J1/0027—Oxides of carbon, e.g. CO2
    • 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
    • F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • F25J2200/40—Features relating to the provision of boil-up in the bottom of a column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/70—Flue or combustion exhaust 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F25J2220/82—Separating low boiling, i.e. more volatile components, e.g. He, H2, CO, Air gases, CH4
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/04—Compressor cooling arrangement, e.g. inter- or after-stage cooling or condensate removal
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/80—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being carbon dioxide
    • 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
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/80—Quasi-closed internal or closed external carbon dioxide refrigeration cycle
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • This invention relates to a process and apparatus for separating a carbon dioxide-rich gas by distillation.
  • a carbon dioxide-rich gas can contain at least 50% of carbon dioxide, or even at least 70% of carbon dioxide, and sometimes at least 90% of carbon dioxide. All percentages in this document related to purities are percentages by volumes on a dry basis.
  • the remainder of the gas can include at least one gas among nitrogen, oxygen, argon, hydrogen, carbon monoxide and methane.
  • the mixture may originate from an oxy-combustion process wherein a mixture of oxygen and fuel burns in a boiler to produce a residual gas, at least partly composed of the gas to be separated according to the invention, produced after purification.
  • a CO 2 distillation column is necessary if high purity CO 2 (>90% v, preferably >95% v and more specifically >99% v) production is required.
  • the liquid (or two-phase) CO 2 partially purified by drying and partial condensation is distilled against pure gaseous CO 2 .
  • This pure CO 2 introduced into the column sump to purify the liquid can originate from the purified CO 2 compressor of the unit.
  • CO 2 is necessary at a higher pressure or at the same pressure as the column (the column pressure being between 6 and 70 bars, and more particularly between 10 and 16 bars). All pressures given in this document are absolute pressures.
  • EP-A-2381198 describes a process according to the preamble to claim 1.
  • EP 1953486 and EP 2002190 disclose the concept of reboiling of the distillation column by the use of part of the heat introduced by the feed gas.
  • FR-A-2934170 discloses the use of the carbon dioxide enriched gas produced, to reboil the column.
  • This invention consists of drawing off the CO 2 necessary for reboiling the column from CO 2 production on the downstream side of the cold box. Steam injected into the distillation column sump directly will then be derived from the final compression or the CO 2 cycle or any other purified CO 2 compressor. Different methods can then be envisaged. CO 2 gas can be drawn off before it reaches its final pressure, in other words between compressor stages, for example in the case of a multi-stage compressor. This CO 2 can be sent directly into the column.
  • the CO 2 pressure at the outlet from the compressor can be chosen so that CO 2 at the highest pressure is available, so that a greater pressure reduction can be obtained.
  • the CO 2 pressure reduction can add frigories, particularly in a turbine.
  • One purpose of the invention is a process for separation of a feed gas containing at least 50% of carbon dioxide by distillation wherein:
  • Another purpose of the invention relates to apparatus for separation of a feed gas containing at least 50% of carbon dioxide by distillation comprising a heat exchanger, a distillation column, means of transferring the feed gas into the heat exchanger to be at least partially liquefied, means of transferring the at least partially liquefied fluid from the heat exchanger into the column, means of drawing off a carbon dioxide depleted gas from the top of the column, means of drawing off a carbon dioxide enriched liquid from the column sump, a compressor, means of transferring a gas richer in carbon dioxide than the feed gas to the compressor and a pressure reduction means, characterised in that it comprises means of transferring the carbon dioxide enriched gas at a first pressure from the compressor to the pressure reduction means to reduce its pressure to a second pressure, and means of transferring the carbon dioxide enriched gas to the pressure reduction means to the column or a vaporiser in order to vaporise a liquid in the column sump.
  • the pressure reduction means may be a valve or a turbine.
  • CO 2 originating from the column sump is vaporised against CO 2 originating from the final compression or from the CO 2 cycle or any other CO 2 compressor. This CO 2 is then cooled and even condensed as a function of its pressure and its temperature.
  • the advantage of having a dedicated exchanger is that the CO 2 from the process is not mixed with the CO 2 from a chiller, for example in the case of a liquefier.
  • the CO 2 thus cooled can be used cold as a gas or it can be directly liquefied in the reboiler for subsequent use in the same process or in another process.
  • FIG. 1 illustrates one preferred embodiment of the invention.
  • FIG. 2 illustrates another preferred embodiment of the invention.
  • FIG. 3 illustrates another preferred embodiment of the invention.
  • FIG. 1 shows oxy-combustion apparatus 1 (or another source) that produces fumes purified to produce a carbon dioxide-rich gas containing at least 50%, or even at least 70% of carbon dioxide.
  • the gas 2 contains at least one other impurity, for example nitrogen, oxygen, argon, hydrogen, carbon monoxide or methane.
  • the gas 2 is at least partially liquefied in a heat exchanger 3 to produce a fluid 4 that is transferred to the top of a distillation column 5 . It is separated there to form a head gas 6 enriched with at least one compound among nitrogen, oxygen, argon, hydrogen, carbon monoxide and methane.
  • the gas 6 is depleted in carbon dioxide.
  • the sump liquid 7 is depleted in at least one compound among nitrogen, oxygen, argon, hydrogen, carbon monoxide and methane.
  • the carbon dioxide enriched liquid 7 contains at least 60% of carbon dioxide, preferably at least 70% of carbon dioxide and is sent to a storage 9 .
  • the liquid 11 drawn off from storage can be an end product.
  • the liquid 7 is transferred through the conduit 13 to the vaporiser 15 to form a gas.
  • This gas is compressed in a compressor 17 composed of one, or possibly four or even six to eight stages, 17 A, 17 B, 17 C, 17 D, 17 E, 17 F.
  • the gas compressed in all stages is a gas product 19 at a third pressure between 50 bars and 200 bars depending on the application.
  • the pressure of the gas 21 compressed in the first three stages 17 A, 17 B, 17 C is reduced from a first pressure to a second pressure in a valve 23 and is then cooled in the exchanger 3 and injected directly into the sump of the column 5 .
  • the valve 23 can also be downstream from the exchanger 3 .
  • the gas 21 may be cooled in an exchanger that is not the exchanger 3 .
  • the gas can even be transferred into the column at the outlet temperature from the compressor stage.
  • the column 5 functions at between 6 and 70 bars, and more particularly between 10 and 16 bars.
  • FIG. 2 shows that the gas 21 can be the gas 21 A diverted downstream from stage 17 A, the gas 21 B downstream from stage 17 B, the gas 21 C diverted downstream from stage 17 C, diverted downstream from stage 17 D, the gas 21 E diverted downstream from stage 17 E or the gas diverted downstream from stage 17 F.
  • valve 23 may be replaced by a turbine 25 upstream or downstream from cooling before entering into the column. This makes it possible to benefit from the pressure difference by chilling.
  • FIG. 3 is different from FIG. 2 in that the gas at reduced pressure after valve 23 as far as the second column is not transferred into the column but rather to a vaporiser 31 outside the column.
  • the vaporiser 31 is also supplied by sump liquid 26 from the column 5 .
  • the vaporised liquid is returned to the column.
  • the gas 21 transferred to the vaporiser is liquefied to form the liquid 29 for subsequent use in the process or in another process.
  • the compressor 17 or some stages of the compressor, can form a cycle compressor in the unit.
  • the compressed gas in the compressor 17 may be a fully or partly vaporised liquid 11 . Otherwise some or all of the gas can originate from an external source, for example a pipe or other equipment.
  • the pressure in the column 5 can vary between 6 bars and 70 bars and may contain structured linings or trays.
  • the gas 21 that is used for reboiling may be at the pressure in the column, in the case of direct injection as shown in FIGS. 1 and 2 . Otherwise, the gas sent to the external reboiler 31 may be at a higher pressure than the pressure in the column (external reboiling and condensation) or at a lower pressure (external reboiling on sensible heat alone).
  • the second pressure can be lower or higher than the pressure in the column, or identical to the pressure in the column. If the second pressure is higher than the pressure in the column, it is at least 1 bar higher than the pressure in the column.
  • the pressure in the column is conventionally the pressure measured at the middle of the column.

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

Abstract

In a process for separating a gas rich in carbon dioxide by distillation, the gas rich in carbon dioxide is cooled in a heat exchanger and is sent to a distillation column, a gas depleted in carbon dioxide is withdrawn from the top of the column and a liquid enriched in carbon dioxide is withdrawn from the bottom of the column, a gas enriched in carbon dioxide is compressed in a compressor down to a first pressure and at least one portion of the gas enriched in carbon dioxide originating from the compressor is expanded from the first pressure to a second pressure lower than the first pressure, for example the pressure of the column, and the expanded gas is used to heat the bottom of the column.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application is a 371 of International Application PCT/FR2012/052417, filed Oct. 23, 2012, which claims priority to French Application No. 1160039, filed Nov. 4, 2011, the entire contents of which are incorporated herein by reference.
    • BACKGROUND
  • This invention relates to a process and apparatus for separating a carbon dioxide-rich gas by distillation.
  • It is known that a mixture containing carbon dioxide as one of its main components can be separated by distillation. A carbon dioxide-rich gas can contain at least 50% of carbon dioxide, or even at least 70% of carbon dioxide, and sometimes at least 90% of carbon dioxide. All percentages in this document related to purities are percentages by volumes on a dry basis. The remainder of the gas can include at least one gas among nitrogen, oxygen, argon, hydrogen, carbon monoxide and methane. The mixture may originate from an oxy-combustion process wherein a mixture of oxygen and fuel burns in a boiler to produce a residual gas, at least partly composed of the gas to be separated according to the invention, produced after purification.
  • A CO2 distillation column is necessary if high purity CO2 (>90% v, preferably >95% v and more specifically >99% v) production is required. The liquid (or two-phase) CO2 partially purified by drying and partial condensation is distilled against pure gaseous CO2. This pure CO2 introduced into the column sump to purify the liquid can originate from the purified CO2 compressor of the unit. In this case, CO2 is necessary at a higher pressure or at the same pressure as the column (the column pressure being between 6 and 70 bars, and more particularly between 10 and 16 bars). All pressures given in this document are absolute pressures.
  • Most processes of this type based on distillation to purify the mixture use a distillation column, the sump of which is heated by the mixture to be distilled.
  • EP-A-2381198 describes a process according to the preamble to claim 1.
  • In the case of U.S. Pat. No. 3,498,067, DE-A-3639779 and JP-A-56077673, the mixture is sent to the column and according to documents FR-A-2934170, EP-A-1953486, US20020059807, U.S. Pat. No. 3,130,026, WO-A-2006054008, WO-A-2007126972, EP-A-0965564, EP-A-0994318, the liquid in the sump vaporises against the mixture in a dedicated exchanger, separated from another larger exchanger that cools the mixture.
  • EP 1953486 and EP 2002190 disclose the concept of reboiling of the distillation column by the use of part of the heat introduced by the feed gas.
  • FR-A-2934170 discloses the use of the carbon dioxide enriched gas produced, to reboil the column.
    • SUMMARY
  • This invention consists of drawing off the CO2 necessary for reboiling the column from CO2 production on the downstream side of the cold box. Steam injected into the distillation column sump directly will then be derived from the final compression or the CO2 cycle or any other purified CO2 compressor. Different methods can then be envisaged. CO2 gas can be drawn off before it reaches its final pressure, in other words between compressor stages, for example in the case of a multi-stage compressor. This CO2 can be sent directly into the column.
  • The higher the pressure to which CO2 is compressed, the more the expansion cools the gas available to reboil the column. Therefore, the CO2 pressure at the outlet from the compressor can be chosen so that CO2 at the highest pressure is available, so that a greater pressure reduction can be obtained. The CO2 pressure reduction can add frigories, particularly in a turbine.
  • One purpose of the invention is a process for separation of a feed gas containing at least 50% of carbon dioxide by distillation wherein:
    • i) the rich feed gas is cooled in a heat exchanger and is transferred into a distillation column,
    • ii) carbon dioxide depleted gas is drawn off from the top of the column and a carbon dioxide enriched liquid is drawn off from the column sump,
    • iii) a gas richer in carbon dioxide than the feed gas is compressed to a first pressure in a compressor, characterised in that:
    • iv) the pressure of part of the carbon dioxide enriched gas from the compressor is reduced from a first pressure to a second pressure lower than the first pressure, for example the pressure in the column, and the expanded gas is used to heat the column sump.
  • According to other optional aspects:
    • at least part of the carbon dioxide enriched gas is produced by vaporising at least part of the carbon dioxide enriched liquid drawn off from the column.
    • the carbon dioxide enriched gas originates at least partly from an external source.
    • at least part of the expanded gas is transferred into the column.
    • at least part of the expanded gas is transferred into the column to be separated.
    • at least part of the expanded gas is transferred into a vaporiser in the column sump to heat part of the liquid in the column sump.
    • a second part of the carbon dioxide enriched gas is compressed in the compressor to a third pressure higher than the first pressure.
    • at least part of the gas at the third pressure forms an end product of the process.
    • at least part of the gas from the compressor forms a refrigeration cycle gas for the process and is then condensed, cooled, expanded, heated and returned to the compressor.
    • the second pressure is higher than the pressure in the column by at least 1 bar or is lower than the pressure in the column.
    • the third pressure is between 50 and 200 bars.
  • Another purpose of the invention relates to apparatus for separation of a feed gas containing at least 50% of carbon dioxide by distillation comprising a heat exchanger, a distillation column, means of transferring the feed gas into the heat exchanger to be at least partially liquefied, means of transferring the at least partially liquefied fluid from the heat exchanger into the column, means of drawing off a carbon dioxide depleted gas from the top of the column, means of drawing off a carbon dioxide enriched liquid from the column sump, a compressor, means of transferring a gas richer in carbon dioxide than the feed gas to the compressor and a pressure reduction means, characterised in that it comprises means of transferring the carbon dioxide enriched gas at a first pressure from the compressor to the pressure reduction means to reduce its pressure to a second pressure, and means of transferring the carbon dioxide enriched gas to the pressure reduction means to the column or a vaporiser in order to vaporise a liquid in the column sump.
  • The pressure reduction means may be a valve or a turbine.
  • It is also possible to use a dedicated exchanger that will act as a reboiler. CO2 originating from the column sump is vaporised against CO2 originating from the final compression or from the CO2 cycle or any other CO2 compressor. This CO2 is then cooled and even condensed as a function of its pressure and its temperature. The advantage of having a dedicated exchanger is that the CO2 from the process is not mixed with the CO2 from a chiller, for example in the case of a liquefier.
  • The CO2 thus cooled can be used cold as a gas or it can be directly liquefied in the reboiler for subsequent use in the same process or in another process.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 illustrates one preferred embodiment of the invention.
  • FIG. 2 illustrates another preferred embodiment of the invention.
  • FIG. 3 illustrates another preferred embodiment of the invention.
    •  DESCRIPTION OF PREFERRED EMBODIMENTS
  • The invention will be described in more detail with reference to the figures that show apparatus according to the invention.
  • FIG. 1 shows oxy-combustion apparatus 1 (or another source) that produces fumes purified to produce a carbon dioxide-rich gas containing at least 50%, or even at least 70% of carbon dioxide. The gas 2 contains at least one other impurity, for example nitrogen, oxygen, argon, hydrogen, carbon monoxide or methane. The gas 2 is at least partially liquefied in a heat exchanger 3 to produce a fluid 4 that is transferred to the top of a distillation column 5. It is separated there to form a head gas 6 enriched with at least one compound among nitrogen, oxygen, argon, hydrogen, carbon monoxide and methane. The gas 6 is depleted in carbon dioxide. The sump liquid 7 is depleted in at least one compound among nitrogen, oxygen, argon, hydrogen, carbon monoxide and methane. The carbon dioxide enriched liquid 7 contains at least 60% of carbon dioxide, preferably at least 70% of carbon dioxide and is sent to a storage 9. The liquid 11 drawn off from storage can be an end product.
  • According to one variant of the invention, as shown in dashed lines, the liquid 7 is transferred through the conduit 13 to the vaporiser 15 to form a gas. This gas is compressed in a compressor 17 composed of one, or possibly four or even six to eight stages, 17A, 17B, 17C, 17D, 17E, 17F. The gas compressed in all stages is a gas product 19 at a third pressure between 50 bars and 200 bars depending on the application.
  • The pressure of the gas 21 compressed in the first three stages 17A, 17B, 17C is reduced from a first pressure to a second pressure in a valve 23 and is then cooled in the exchanger 3 and injected directly into the sump of the column 5. The valve 23 can also be downstream from the exchanger 3.
  • Alternatively, the gas 21 may be cooled in an exchanger that is not the exchanger 3.
  • The gas can even be transferred into the column at the outlet temperature from the compressor stage.
  • The column 5 functions at between 6 and 70 bars, and more particularly between 10 and 16 bars.
  • FIG. 2 shows that the gas 21 can be the gas 21A diverted downstream from stage 17A, the gas 21B downstream from stage 17B, the gas 21C diverted downstream from stage 17C, diverted downstream from stage 17D, the gas 21E diverted downstream from stage 17 E or the gas diverted downstream from stage 17F. Similarly, valve 23 may be replaced by a turbine 25 upstream or downstream from cooling before entering into the column. This makes it possible to benefit from the pressure difference by chilling.
  • FIG. 3 is different from FIG. 2 in that the gas at reduced pressure after valve 23 as far as the second column is not transferred into the column but rather to a vaporiser 31 outside the column. The vaporiser 31 is also supplied by sump liquid 26 from the column 5. The vaporised liquid is returned to the column. The gas 21 transferred to the vaporiser is liquefied to form the liquid 29 for subsequent use in the process or in another process.
  • The compressor 17, or some stages of the compressor, can form a cycle compressor in the unit.
  • The compressed gas in the compressor 17 may be a fully or partly vaporised liquid 11. Otherwise some or all of the gas can originate from an external source, for example a pipe or other equipment.
  • For all examples, the pressure in the column 5 can vary between 6 bars and 70 bars and may contain structured linings or trays. The gas 21 that is used for reboiling may be at the pressure in the column, in the case of direct injection as shown in FIGS. 1 and 2. Otherwise, the gas sent to the external reboiler 31 may be at a higher pressure than the pressure in the column (external reboiling and condensation) or at a lower pressure (external reboiling on sensible heat alone). Thus, the second pressure can be lower or higher than the pressure in the column, or identical to the pressure in the column. If the second pressure is higher than the pressure in the column, it is at least 1 bar higher than the pressure in the column. The pressure in the column is conventionally the pressure measured at the middle of the column.
  • It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above.

Claims (12)

1. A process for separating a feed gas comprising at least 50% of carbon dioxide by distillation, comprising:
i) Cooling the feed gas in a heat exchanger and transferring the cooled feed into a distillation column,
ii) withdrawing carbon dioxide depleted gas from the top of the column and withdrawing a carbon dioxide enriched liquid relative to the carbon dioxide-rich gas from the column sump,
iii) compressing a gas richer in carbon dioxide than the feed gas is in a compressor to a first pressure wherein the pressure of at least a part of the carbon dioxide enriched gas from the compressor is reduced from a first pressure to a second pressure lower than the first pressure, and the expanded gas is used to heat the column sump.
2. The process according to claim 1, wherein at least part of the carbon dioxide enriched gas is produced by vaporising at least part of the carbon dioxide enriched liquid drawn off from the column.
3. The process according to claim 1, wherein the carbon enriched dioxide gas originates at least partly from an external source.
4. The process according to claim 1, wherein at least part of the expanded gas is transferred into the column.
5. The process according to claim 1, wherein at least part of the expanded gas is transferred into a vaporiser in the column sump to heat part of the liquid in the column sump.
6. The process according to claim 1, wherein a second part of the carbon dioxide enriched gas is compressed in the compressor to a third pressure higher than the first pressure.
7. The process according to claim 6, wherein at least part of the gas at the third pressure forms an end product of the process.
8. The process according to claim 1, wherein at least part of the gas from the compressor forms a refrigeration cycle gas for the process and is then condensed, cooled, expanded, heated and returned to the compressor.
9. The process according to claim 1, wherein the second pressure is higher than the pressure in the column by at least 1 bar or is lower than the pressure in the column.
10. An apparatus for separating a feed gas containing at least 50% of carbon dioxide by distillation comprising a heat exchanger, a distillation column, means of transferring the feed gas into the heat exchanger to be at least partially liquefied, means of transferring the at least partially liquefied fluid from the heat exchanger into the column, means of drawing off a carbon dioxide depleted gas from the top of the column, means of drawing off a carbon dioxide enriched liquid from the column sump, a compressor, means of transferring a gas richer in carbon dioxide than the feed gas to the compressor and a pressure reduction means, characterized in that it comprises the means of transferring the carbon dioxide enriched gas at a first pressure from the compressor to the pressure reduction means to reduce its pressure to a second pressure and means of transferring the carbon dioxide enriched gas from the pressure reduction means to the column or a vaporiser in order to vaporise a liquid in the column sump.
11. The apparatus according to claim 10 wherein the pressure reduction means is a turbine.
12. The apparatus according to claim 10, comprising a means of sending the carbon dioxide enriched gas from the pressure reduction means to the column.
US14/356,206 2011-11-04 2012-10-23 Process and apparatus for separating a carbon dioxide-rich gas by distillation Abandoned US20150047390A1 (en)

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FR1160039 2011-11-04
FR1160039A FR2982168B1 (en) 2011-11-04 2011-11-04 PROCESS AND APPARATUS FOR SEPARATING CARBON DIOXIDE-RICH GAS BY DISTILLATION
PCT/FR2012/052417 WO2013064765A1 (en) 2011-11-04 2012-10-23 Process and apparatus for separating a gas rich in carbon dioxide by distillation

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CA2852236A1 (en) 2013-05-10
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FR2982168A1 (en) 2013-05-10
WO2013064765A1 (en) 2013-05-10
AU2012330979A1 (en) 2014-06-26
CN103917284B (en) 2016-06-29
EP2773442A1 (en) 2014-09-10

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