WO2010079177A2 - Procédé et appareil pour éliminer les contaminants gazeux d'un courant de gaz comprenant des contaminants gazeux - Google Patents

Procédé et appareil pour éliminer les contaminants gazeux d'un courant de gaz comprenant des contaminants gazeux Download PDF

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Publication number
WO2010079177A2
WO2010079177A2 PCT/EP2010/050070 EP2010050070W WO2010079177A2 WO 2010079177 A2 WO2010079177 A2 WO 2010079177A2 EP 2010050070 W EP2010050070 W EP 2010050070W WO 2010079177 A2 WO2010079177 A2 WO 2010079177A2
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Prior art keywords
separation device
stream
gas stream
liquid phase
contaminant
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/EP2010/050070
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English (en)
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WO2010079177A3 (fr
Inventor
Helmar Van Santen
Cornelius Johannes Schellekens
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to BRPI1006067A priority Critical patent/BRPI1006067A2/pt
Priority to AU2010204311A priority patent/AU2010204311A1/en
Priority to RU2011133062/06A priority patent/RU2011133062A/ru
Priority to US13/143,474 priority patent/US20120031143A1/en
Publication of WO2010079177A2 publication Critical patent/WO2010079177A2/fr
Anticipated expiration legal-status Critical
Publication of WO2010079177A3 publication Critical patent/WO2010079177A3/fr
Ceased legal-status Critical Current

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/0605Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
    • F25J3/061Natural gas or substitute natural gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/002Separation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 absorption
    • B01D53/1431Pretreatment by other processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 absorption
    • B01D53/1456Removing acid components
    • B01D53/1462Removing mixtures of hydrogen sulfide and carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/26Drying gases or vapours
    • B01D53/261Drying gases or vapours by adsorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/26Drying gases or vapours
    • B01D53/263Drying gases or vapours by absorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/26Drying gases or vapours
    • B01D53/265Drying gases or vapours by refrigeration (condensation)
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75Multi-step processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10Working-up natural gas or synthetic natural gas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10Working-up natural gas or synthetic natural gas
    • C10L3/101Removal of contaminants
    • C10L3/102Removal of contaminants of acid contaminants
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/0605Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
    • F25J3/0625H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0635Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/067Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of carbon dioxide
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0675Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of H2/CO mixtures, i.e. of synthesis gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/24Hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/304Hydrogen sulfide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702Hydrocarbons
    • B01D2257/7022Aliphatic hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/06Polluted air
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/20Processes or apparatus using other separation and/or other processing means using solidification of components
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/70Flue or combustion exhaust gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/04Recovery of liquid products
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/64Separating heavy hydrocarbons, e.g. NGL, LPG, C4+ hydrocarbons or heavy condensates in general
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/66Separating acid gases, e.g. CO2, SO2, H2S or RSH
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F25J2220/82Separating low boiling, i.e. more volatile components, e.g. He, H2, CO, Air gases, CH4
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00Processes or apparatus involving steps for expanding of process streams
    • F25J2240/40Expansion without extracting work, i.e. isenthalpic throttling, e.g. JT valve, regulating valve or venturi, or isentropic nozzle, e.g. Laval
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00Processes or apparatus involving steps for expanding of process streams
    • F25J2240/60Expansion by ejector or injector, e.g. "Gasstrahlpumpe", "venturi mixing", "jet pumps"
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02Recycle of a stream in general, e.g. a by-pass stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/12External refrigeration with liquid vaporising loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/60Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/66Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/42Modularity, pre-fabrication of modules, assembling and erection, horizontal layout, i.e. plot plan, and vertical arrangement of parts of the cryogenic unit, e.g. of the cold box
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention concerns a process for removing gaseous contaminants, especially carbon dioxide and/or hydrogen sulphide, from a feed gas stream comprising methane and gaseous contaminants.
  • the invention further comprises a cryogenic separation device to carry out the process, as well as products made in the process .
  • WO 03/062725 a process is described for the removal of freezable species from a natural gas stream by cooling a natural gas stream to form a slurry of solid acidic contaminants in compressed liquefied natural gas.
  • the solids are separated from the liquid by means of a cyclone. It will be clear that a complete separation of the liquid from the solids is not easily achieved.
  • WO 2004/070297 a process for removing contaminants from a natural gas stream has been described.
  • water is removed from the feed gas stream. This is especially done by cooling the feed gas stream resulting in methane hydrate formation, followed by removal of the hydrates. Further cooling results in the formation of solid acidic contaminants.
  • a cleaned natural gas stream is obtained. It is preferred to convert the solid contaminant into a liquid by heating the solids.
  • WO 2004/070297 is the removal of the contaminants in a reliable way from the separation vessel, as well as the removal of a pure liquid only, free from solid particles.
  • the continuous stream of solid particles in the described process will occasionally result in the formation of a thick layer of solid material on top of the heat exchanger.
  • a layer of solid material may built up on the bottom of the vessel since solid CO2 has a high density compared to the liquid stream. In addition, this could result in uneven distribution of the heat input required for melting and could result in hot gas plumes forming from the liquid decreasing the clean natural gas stream quality.
  • Object of the present invention is to provide an improved cryogenic separation process which attractively deals with the above-indicated problems.
  • the present invention relates to a process for removing gaseous contaminants from a feed gas stream which comprises methane and gaseous contaminants, the process comprising: 1) providing the feed gas stream; 2) cooling the feed gas stream to a temperature at which a slurry is formed which comprises solid contaminant, liquid phase contaminant and a methane enriched gaseous phase;
  • step 2) introducing the slurry as obtained in step 2) into the top part or intermediate part of a cryogenic separation device;
  • a pump preferably an eductor, a stream comprising liquid phase contaminant, which pump is situated below the heat exchanger and arranged outside or inside the separation device or partly inside or outside the separation device;
  • step 9) separating the stream of liquid phase contaminant obtained in step 8) into a liquid product stream and a recirculation stream which is used as a motive fluid in the eductor in the case that an eductor is used; and 10) introducing into the separation device as described above in step 5) at least part of the stream as removed in step 7) and at least part of the recirculation stream as obtained in step 9) .
  • the present invention uses a recirculation loop of a liquid or slurry stream over the separation device.
  • a liquid or slurry stream is withdrawn downstream of the internal heat exchanger by means of a pump, preferably an eductor, and at least part of the obtained stream is recirculated to the zone above the heat exchanger.
  • a pump preferably an eductor
  • a continuously moving slurry phase is obtained, minimizing any blockages in the separation vessel.
  • a fully liquid stream is withdrawn, especially from the slurry zone above the heat exchanger.
  • liquid phase contaminant as described in step 7) above, as well as the liquid phase contaminant as described in step 9) above may contain some vapor and/or flash gas, e.g. up till 10 wt%, especially up till 5 wt%, more especially up till 2 wt%, of the total liquid phase contaminant.
  • the feed gas stream to be used in accordance with the present invention is a natural gas stream in which the gaseous contaminants are carbon dioxide and/or hydrogen sulphide and/or C2+-hydrocarbons .
  • the amount of the hydrocarbon fraction in the feed gas stream is suitably from 10 to 85 mol% of the gas stream, preferably from 25 to 80 mol%.
  • the hydrocarbon fraction of the natural gas stream comprises especially at least 75 mol% of methane, preferably 90 mol%.
  • the hydrocarbon fraction in the natural gas stream may suitably contain from 0 to 20 mol%, suitably from 0.1 to 10 mol%, of C2 ⁇ Cg compounds.
  • the gas stream may also comprise up to 20 mol%, suitably from 0.1 to 10 mol% of nitrogen, based on the total gas stream.
  • the amount of carbon dioxide in the gas stream is suitably from 10 to 90 vol%, preferably from 20 to 75 vol%, and/or the amount of hydrogen sulphide in the gas stream is suitably from 5 to 40 vol% of the gas stream, preferably from 20 to 35 vol%. Basis for these amounts is the total volume of hydrocarbons, hydrogen sulphide and carbon dioxide. It is observed that the present process is especially suitable for gas streams comprising large amounts of sour contaminants, e.g. 10 vol% or more, suitably from 15 to 90 vol%, and is especially suitable for gas streams comprising carbon dioxide as contaminant.
  • the feed gas stream in step 1) has suitably a temperature between -20 and 15O 0 C, preferably between -10 and 7O 0 C, and a pressure between 10 and 250 bara, preferably between 80 and 120 bara.
  • the feed gas stream may be pre-treated for partial or complete removal of water and optionally some heavy hydrocarbons. This can for instance be done by means of a pre-cooling cycle, against an external cooling loop, a cold internal process stream, or a cold LNG stream. Water may also be removed by means of pre-treatment with molecular sieves, e.g. zeolites, aluminium oxide or silica gel or other drying agents. Water may also be removed by means washing with glycol, MEG, DEG or TEG, or glycerol. Other processes for forming methane hydrates or for drying natural gas are also possible. The amount of water in the gas feed stream is suitably less than 1 vol%, preferably less than 0.1 vol%, more preferably less than 0.01 vol%. Water may also be removed by hydrate formation in the way as described in WO2004/070297.
  • water is removed until the amount of water in the natural gas stream comprises at most 50 ppmw, preferably at most 20 ppmw, more preferably at most 1 ppmw of water, based on the total feed gas stream.
  • the cooling in step 2) of the present process can suitably be done by isenthalpic expansion, preferably isenthalpic expansion over an orifice or a valve, especially a Joule-Thomson valve, or in which the cooling is done by nearly isentropic expansion, especially by means of an expander, preferably a turbo expander or a laval nozzle.
  • a valve is in particular preferred.
  • step 2) the feed gas stream is suitably cooled to a temperature between -40 and -100 0 C, preferably between -50 and -8O 0 C.
  • the feed gas stream is pre-cooled to a temperature between 15 and -45 0 C, preferably between 5 and -25 0 C, before expansion.
  • a pre-cooling of the feed gas stream is done by heat exchange against a cold fluidum, especially an external refrigerant, e.g. a propane cycle, an ethane/propane cascade or a mixed refrigerant cycle, or an internal process loop, suitably a carbon dioxide of hydrogen sulphide stream, or a cold methane stream.
  • a cold fluidum especially an external refrigerant, e.g. a propane cycle, an ethane/propane cascade or a mixed refrigerant cycle, or an internal process loop, suitably a carbon dioxide of hydrogen sulphide stream, or a cold methane stream.
  • the present process is carried out in such a way that substantially all the solid contaminant present in the diluted slurry of contaminants is melted into liquid phase contaminant in step 6) .
  • substantially is meant that at least 95% of the solid contaminant present in the diluted slurry is melted, especially at least 98%. More preferably, all the solid contaminant present in the diluted slurry of contaminants is melted in step 6) .
  • between 0 and 90 vol% of the liquid phase contaminant which is removed from the separation device in step 7) is introduced in the separation device as described in step 5), preferably between 5 and 80 vol% of the liquid phase contaminant as removed in step 7) . It is also possible to introduce all liquid phase contaminant removed in step 7) in the separation device as described in step 5) .
  • the stream comprising liquid phase contaminant is suitably removed from the separation device at a position above the heat exchanger.
  • solid contaminant will mainly comprise carbon dioxide, whereas liquid phase contaminant will usually comprise both carbon dioxide and hydrogen sulphide.
  • a small amount of hydrocarbons may be present .
  • the pump is arranged outside the separation device and the pump communicates with the separation device.
  • the pump is an eductor.
  • Eductors also referred to as siphons, exhausters, ejectors or jet pumps
  • siphons exhausters, ejectors or jet pumps
  • Reference herein to an eductor is to a device to pump produced solid and liquid C02 slurry from the separator to the heat exchanger.
  • the eductor is suitably designed for use in operations in which the head pumped against is low and is less than the head of the fluid used for pumping.
  • suitable eductors also referred to as eductors or jet pumps
  • any type of eductor can be used.
  • the eductor is preferably a liquid jet solid pump.
  • the eductor is arranged inside the separation device or partly inside and outside the separation device.
  • a housing can be positioned around the eductor, enabling the eductor to be removed from the separation device.
  • a housing can, for instance, be a vessel like containment, e.g. a pipe, that can be isolated from the process through valves.
  • the eductor is arranged outside the separation device.
  • the eductor can be of such a size that it fits completely in the separation device or it may cover the entire diameter of the separation device, usually a vessel. However, it may also extend at two locations through the internal wall of the separation device. More preferably, the eductor is arranged below the central bottom part of the separation device.
  • step 10 between 25 and 95 vol% of the stream of liquid phase contaminant removed from the separation device in step 9) is used as a motive fluid in the eductor, preferably between 30 and 85 vol% of the stream of liquid phase contaminant removed from the separation device in step 9) .
  • the methane enriched gaseous phase is removed from the top part of the cryogenic separation device at a high level, preferably at the top of the reactor .
  • the outlet for the methane enriched gaseous phase will usually be above the level at which the stream of liquid phase contaminant obtained from the heat exchanger is introduced into the separation device in step 5) .
  • the cooling process as described in step (2) of the present process is preferably carried out at a close distance, e.g. up to a few meters, preferably at most 1 m, to the separator vessel. It may also be done inside the separation vessel, thus minimizing any problems due to the transport of the solid particles.
  • the separation device is suitably a vessel which comprises a vertical cylindrical housing. The diameter may vary from 1 to 10 - IO ⁇ meter, or even more, the height may vary from 3 to 35 meters or even more. In general, the slurry level in the separation vessel will vary between 30 and 70 % of the height of the vessel.
  • the temperature of the slurry is suitably about 1 to 45 0 C higher than the temperature of the contaminated gas stream on introduction is the separator vessel, preferably 3 to 4O 0 C.
  • the heat exchanger preferably uses a process stream to supply the heat for melting the solid contaminants.
  • a suitable process stream is the methane enriched gaseous phase .
  • a suitable internal structure to remove the stream comprising liquid phase contaminant from the separation device in step 9) is a conical section or a cylindrical section that is closed at the upper end. Also a standpipe may be used with a closed upper end to prevent solids transport with this liquid stream. In addition, filters may be used, suitably equipped with heat tracing to prevent blockage.
  • the content of contaminants in the methane enriched gaseous phase as removed from the separation device in step 4) is suitably less than 10 vol%, preferably less than 5 vol%.
  • the content of methane in the contaminants product stream is suitably less than 2 wt%, preferably less than 1 wt%, based on total weight of the stream.
  • the feed gas stream provided in step 1) of the present process can suitably have been subjected to one or more purification processes in which gaseous contaminants are removed from a feed gas stream, before step 2) of the present process is carried out.
  • Such a purification process can suitably comprise the steps of: a) providing a feed gas stream; b) cooling the feed gas stream to a temperature at which liquid phase contaminant is formed as well as a methane enriched gaseous phase; and c) separating the two phases obtained in step 2) by means of a gas/liquid separator.
  • steps a) and b) can be repeated twice or three times before step 2) in accordance with the present invention is carried out.
  • Such a process has, for instance been described in WO 2006/087332 which is hereby incorporated by reference.
  • the feed gas stream can be subjected to a number of combinations of subsequent cooling and separation steps, before step 2) of the present invention is carried out.
  • step a) the methane enriched gaseous phase can be recompressed in one or more compression steps before step 2) in accordance with the present invention is carried out.
  • the feed gas stream may between steps 1) and 2) be cooled to a temperature at which at least part of the feed gas stream is present in the liquid phase, the cooled feed stream so obtained may be separated by means of a cryogenic distillation into a bottom stream rich in liquid phase contaminant and lean in methane and into a top stream rich in methane and lean in gaseous contaminant, and the feed gas stream so obtained may then be subjected to the remaining steps 2) -10) of the process according to the present invention.
  • the cryogenic distillation section to be used in the cryogenic distillation is as such known in the art.
  • the feed gas stream is cooled to a temperature between -10 and -5O 0 C, preferably between -20 and -4O 0 C before introduction into the cryogenic distillation section.
  • the bottom temperature of the cryogenic distillation section is between -15 and 35 0 C, preferably between -5 and 3O 0 C.
  • a reboiler may be present to supply heat to the column.
  • the top temperature of the cryogenic distillation section is between -70 and -4O 0 C, preferably between -60 and -3O 0 C.
  • a condenser may be present, to introduce cold into the column.
  • the methane enriched gaseous phase obtained in step 4) may further be purified, in an additional cryogenic distillation process using a cryogenic distillation section which is as such known in the art .
  • the bottom temperature of the cryogenic distillation section is between -30 and 1O 0 C, preferably between -10 and 5 0 C.
  • a reboiler may be present to supply heat to the distillation section.
  • the top temperature of the cryogenic distillation section is between -110 and -8O 0 C, preferably between -100 and -9O 0 C.
  • a condenser may be present, to provide reflux and a liquefied (LNG) product.
  • Suitable absorbing liquids may comprise chemical solvents or physical solvents or mixtures thereof.
  • a preferred absorbing liquid comprises a chemical solvent and/or a physical solvent, suitably as an aqueous solution .
  • Suitable chemical solvents are primary, secondary and/or tertiary amines, including sterically hindered amines .
  • a preferred chemical solvent comprises a secondary or tertiary amine, preferably an amine compound derived from ethanolamine, more especially DIPA, DEA, MMEA (monomethyl-ethanolamine) , MDEA (methyldiethanolamine) TEA (triethanolamine) , or DEMEA (diethyl- monoethanolamine) , preferably DIPA or MDEA. It is believed that these chemical solvents react with acidic compounds such as C02 and H2S.
  • Suitable physical solvents include tetramethylene sulphone (sulpholane) and derivatives, amides of aliphatic carboxylic acids, N-alkyl pyrrolidone, in particular N-methyl pyrrolidine, N-alkyl piperidones, in particular N-methyl piperidone, methanol, ethanol, ethylene glycol, polyethylene glycols, mono- or di(Cl- C4)alkyl ethers of ethylene glycol or polyethylene glycols, suitably having a molecular weight from 50 to 800, and mixtures thereof.
  • the preferred physical solvent is sulfolane. It is believed that CO2 and/or H2S are taken up in the physical solvent and thereby removed.
  • Other treatments of the methane enriched gaseous phase may include a further compression, when the purified gas is wanted at a higher pressure. If the amounts of acidic contaminants in the purified gas are undesirably high, the purified gas may be subjected to one or more repetitions of the present process.
  • the present process enables purification of natural gas comprising substantial amounts of acidic contaminants, resulting in purified natural gas comprising low levels of contaminants, especially of sulphur contaminants.
  • the production of LNG from such natural gas which would be very difficult if not impossible by conventional processes, is made possible.
  • the invention also provides LNG obtained from liquefying purified natural gas obtained by the process.
  • the LNG thus-obtained typically has very low concentrations of contaminants other than natural gas.
  • the top part of the separation device will comprise the top quarter length of the device.
  • the bottom part will comprise the lower quarter up till the lower half of the length of the device.
  • the intermediate part will comprise the remaining.
  • the present invention also relates to a cryogenic separation device for carrying out the process according to the present process, which separation device comprises a top part, an intermediate part and a bottom part; means to introduce a slurry which comprises solid contaminant, liquid phase contaminant and a methane enriched gaseous phase into the top or intermediate part of the separation device; means to remove a methane enriched gaseous phase from the top part of the separation device; means for introducing a stream comprising liquid phase contaminant into the top or intermediate part of the separation device to dilute the slurry inside the separation device; a heat exchanger arranged inside the separation device; a pump, preferably an eductor, which is arranged inside or outside the separation device or partly inside and outside the separation device at a level which is below the level at which the heat exchanger is arranged for removing a stream comprising liquid phase contaminant from the separation device; means to remove a stream comprising liquid phase contaminant from the intermediate or bottom part of the separation device; and means to separate liquid phase contamin
  • the slurry pump preferably an eductor
  • the pump preferably an eductor is arranged below the separation device. More preferably, it is arranged below the central bottom part of the separation device.
  • the process is also suitable for the removal in general of carbon dioxide from carbon dioxide comprising streams, especially (partial) oxidation flue gas streams, more especially streams comprising (beside carbon dioxides) hydrogen, carbon monoxide, nitrogen and/or oxygen, for instance boiler flue gas streams (usually comprising mainly carbon dioxide, nitrogen and oxygen) , partial oxidation process streams (usually containing mainly carbon dioxide, carbon monoxide, hydrogen and optionally nitrogen) , steam methane reforming process streams (usually comprising hydrogen, carbon dioxide and carbon monoxide.
  • streams especially (partial) oxidation flue gas streams, more especially streams comprising (beside carbon dioxides) hydrogen, carbon monoxide, nitrogen and/or oxygen, for instance boiler flue gas streams (usually comprising mainly carbon dioxide, nitrogen and oxygen) , partial oxidation process streams (usually containing mainly carbon dioxide, carbon monoxide, hydrogen and optionally nitrogen) , steam methane reforming process streams (usually comprising hydrogen, carbon dioxide and carbon monoxide.
  • the contaminant-rich stream mainly comprises carbon dioxide and is therefore a C02- rich stream
  • CO2-rich stream is further pressurised and injected into a subterranean formation, preferably for use in enhanced oil recovery or for storage into an aquifer reservoir or for storage into an empty oil reservoir.
  • a liquid CO2-rich stream is obtained, as this liquid stream requires less compression equipment to be injected into a subterranean formation.
  • at least 90%, more preferably at least 95% and most preferably at least 98% of the solid acidic contaminants are melted. In this way a liquid stream of contaminants is obtained, which can be easily transported further.
  • the present invention further relates to a purified gas stream obtained by a process according to the present invention .
  • the present invention also relates to a process for liquefying a feed gas stream comprising purifying the feed gas stream in accordance with the present invention, followed by liquefying the feed gas stream by methods known in the art .
  • a natural gas is passed via a conduit 1 through an expansion means 2, especially a Joule Thomson valve, whereby a stream is obtained of a slurry which comprises solid contaminant, liquid phase contaminant and a methane enriched gaseous phase.
  • the stream of the slurry flows via a conduit 3 into cryogenic separation vessel 4.
  • a methane enriched gaseous phase is removed from the separation vessel via a conduit 5.
  • a stream of liquid phase contaminant is introduced into the separation device via a conduit 6 to dilute the slurry inside the separation device, establishing or maintaining a slurry level 7.
  • the diluted slurry passes then towards a heat exchanger 8.
  • a stream comprising liquid phase contaminant is removed from the separation device, whereby part of the stream is recovered as a liquid product via a conduit 10. Another part of the stream is passed via a conduit 11 to an eductor 12 where it is used as motive fluid, after which it is recirculated to the separation device via the conduit 6.

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Abstract

La présente invention concerne un procédé permettant d'éliminer des contaminants gazeux d'un courant de gaz d'alimentation comprenant du méthane et des contaminants gazeux. Ce procédé comporte plusieurs opérations. On refroidit le courant de gaz d'alimentation de façon à obtenir une boue liquide comprenant le contaminant solide, le contaminant en phase liquide, et une phase gazeuse enrichie en méthane. On introduit la boue liquide ainsi obtenue dans un séparateur cryogénique par le haut duquel on prélève la phase gazeuse enrichie en méthane. On dilue la boue liquide contenant le contaminant en phase liquide, et on la fait passer dans un échangeur thermique dans lequel le contaminant solide se transforme, par fusion, en contaminant en phase liquide. On recycle une partie au moins du contaminant en phase liquide de façon à diluer la boue liquide contenue à l'intérieur du séparateur. Au moyen d'une pompe, ou de préférence un éducteur, on prélève un courant comprenant le contaminant en phase liquide en un point du séparateur inférieur au niveau de boue liquide. On récupère sous forme d'un courant résultant une partie au moins du contaminant en phase liquide prélevé. Une partie au moins en est recyclée vers l'éducteur pour servir de fluide d'entraînement dans le cas d'utilisation de l'éducteur, puis elle est introduite dans le séparateur pour y diluer la boue liquide. L'invention concerne également un dispositif permettant la mise en œuvre du procédé de l'invention, le courant de gaz purifié, et un procédé de liquéfaction d'un courant de gaz d'alimentation.
PCT/EP2010/050070 2009-01-08 2010-01-06 Procédé et appareil pour éliminer les contaminants gazeux d'un courant de gaz comprenant des contaminants gazeux Ceased WO2010079177A2 (fr)

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BRPI1006067A BRPI1006067A2 (pt) 2009-01-08 2010-01-06 processo para remover contaminantes gasosos a partir de uma corrente de gás de alimentação, dispositivo de separação criogênica, corrente de gás purificada, e, processo para liquefazer uma corrente de gás de alimentação.
AU2010204311A AU2010204311A1 (en) 2009-01-08 2010-01-06 Process and apparatus for removing gaseous contaminants from gas stream comprising gaseous contaminants
RU2011133062/06A RU2011133062A (ru) 2009-01-08 2010-01-06 Способ удаления газообразных примесей из потока газа, содержащего газообразные примеси, и устройство для его осуществления
US13/143,474 US20120031143A1 (en) 2009-01-08 2010-01-06 Process and appartus for removing gaseous contaminants from gas stream comprising gaseous contaminants

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BRPI1006067A2 (pt) 2016-04-19

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