EP2059476A2 - Verfahren zur trennung eines synthesegases, das wasserstoff und kohlenmonoxid, aber auch mindestens kohlendioxid und wasserdampf enthält - Google Patents

Verfahren zur trennung eines synthesegases, das wasserstoff und kohlenmonoxid, aber auch mindestens kohlendioxid und wasserdampf enthält

Info

Publication number
EP2059476A2
EP2059476A2 EP07823687A EP07823687A EP2059476A2 EP 2059476 A2 EP2059476 A2 EP 2059476A2 EP 07823687 A EP07823687 A EP 07823687A EP 07823687 A EP07823687 A EP 07823687A EP 2059476 A2 EP2059476 A2 EP 2059476A2
Authority
EP
European Patent Office
Prior art keywords
flow
gas
separation
pressure
gas mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP07823687A
Other languages
English (en)
French (fr)
Inventor
Pascal Marty
Bernd Polster
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP2059476A2 publication Critical patent/EP2059476A2/de
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01D53/22Separation 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 diffusion
    • 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
    • B01D53/02Separation 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 adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation 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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047Pressure swing adsorption
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/56Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • F25J3/02Processes 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
    • F25J3/0204Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223H2/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
    • F25J3/02Processes 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
    • F25J3/0228Processes 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
    • F25J3/0252Processes 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 hydrogen
    • 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
    • F25J3/02Processes 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
    • F25J3/0228Processes 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
    • F25J3/0257Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of nitrogen
    • 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
    • F25J3/02Processes 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
    • F25J3/0228Processes 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
    • F25J3/0266Processes 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/102Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/104Alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/16Hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/10Single element gases other than halogens
    • B01D2257/108Hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/504Carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/80Water
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/40Further details for adsorption processes and devices
    • B01D2259/40001Methods relating to additional, e.g. intermediate, treatment of process 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
    • B01D53/26Drying gases or vapours
    • B01D53/261Drying gases or vapours by adsorption
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042Purification by adsorption on solids
    • C01B2203/043Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/047Composition of the impurity the impurity being carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0475Composition of the impurity the impurity being carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0495Composition of the impurity the impurity being water
    • 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
    • F25J2205/40Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • 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
    • F25J2205/60Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • 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
    • F25J2205/80Processes or apparatus using other separation and/or other processing means using membrane, i.e. including a permeation step
    • 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
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/151Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a process for the separation of a gaseous mixture in a separation unit of the type in which the gaseous mixture is derived from a reaction unit and comprises, as main constituents of hydrogen (H 2 ) and / or carbon monoxide (CO).
  • gaseous mixtures which in addition to CO and H 2 generally also contain other constituents, in particular carbon dioxide (CO 2 ), methane and water as well as nitrogen and others. impurities.
  • CO 2 carbon dioxide
  • Such mixtures constitute syngas for various productions. They are indeed used as raw material for the production of fluids, for example hydrogen, carbon monoxide, carbon dioxide, or H 2 / CO mixture in a predetermined ratio for various chemical syntheses, particularly the synthesis of methanol, acetic acid or the synthesis of reducing atmospheres for surface treatments, for metallurgical operations, etc.
  • reaction units treating such reaction media include steam reforming units of liquid or gaseous hydrocarbons, auto-thermal reforming, carbon dioxide reforming, reforming or cracking. methanol, or partial oxidation of gaseous, liquid or solid compounds containing carbon and hydrogen.
  • PSA product at least one relatively pure gas known as "PSA product" is obtained.
  • PSA waste at low pressure.
  • a permeation separation is carried out through a membrane, a part of the molecules crosses the membrane, forming a gaseous flow at low pressure called “permeate”, while others, retained by the membrane, constitute the "residue Gas stream available at high pressure.
  • a known solution to this problem is to provide stainless steel equipment, especially for compression steps of said low pressure fluid so that they are protected against acid attacks, or to provide a step of prior drying of the gas stream when must be separated cryogenically, an expensive step because applied to a low pressure stream.
  • the object of the present invention is to provide a less expensive solution to this problem by proposing a separation process of the above type in wherein the risks associated with the presence of water during subsequent treatments during the use of these low pressure fluids resulting from the separation are eliminated by eliminating the water molecules upstream of the low pressure flow generation steps.
  • the invention consists in a process for separating a gas mixture containing essentially hydrogen and carbon monoxide, but also at least carbon dioxide and water vapor, comprising at least the steps of: a) separating S from the gas mixture at a pressure PO into at least two streams I and II in which the stream I is a gas stream at a low pressure P1 containing all the compounds contained in the gas mixture to be separated, in variable proportions, and the flow II is a gaseous flow at a so-called high PII pressure, greater than P1, containing all the compounds contained in the gas mixture to be separated, in variable proportions and different from those of the flow I b) use of the high pressure stream II, c) use of the low pressure stream I, for at least partial upgrading of said stream I, characterized in that prior to step a), the gas mixture to be separated is subjected to a step from: a 0 ) drying the gas mixture containing the water vapor for the removal of the water molecules and obtaining a dry mixture.
  • low pressure is meant a low pressure conventionally obtained at the exit of separation steps, it is a function of the separation mode chosen to perform this step S.
  • the pressure P1 is thus preferably between 1 .1 and 5 bara. for a PSA type process. It is between PO / 100 to PO / 2 for a permeation separation process.
  • the high pressure PII is a high pressure conventionally obtained at the outlet of separation steps, it corresponds to the supply pressure reduced by the pressure losses related to the separation process.
  • the flow I is a dry low pressure stream that can therefore be used without prejudice to the presence of water molecules, whether compressed, directly sent into a cryogenic separation, upgraded by a combination of the two, or directly sent in a network.
  • the separation step S is a permeation separation step with production of at least one permeate I at the pressure P1 and a residue II at the high pressure PII.
  • the product of the separation is found here in the permeate.
  • it In the case of hydrogen, it is generally obtained at a purity of the order of 95%. Given the relatively large percentage of impurities in the permeate, it contains CO 2 , as well as water vapor (when the product to be separated contains). This joint presence of water vapor and CO 2 in the product is harmful since the product obtained at a low pressure will have to be compressed for its external use (additional purification, export via a network or other).
  • the process of the invention makes it possible here, by drying the mixture feeding the permeation step, to solve this problem without the use of stainless steel equipment parts or the step of drying a low pressure fluid (which would require larger dimensions and therefore more expensive).
  • this waste is it also frequently used to provide a product or products, and to do this, given its low pressure, it should generally be compressed, and / or treated by cryogenics, and / or washing.
  • the process of the invention makes it possible, by drying the mixture feeding the permeation step, to solve the problem of the presence of vapor liable to condense, without the use of a piece of stainless steel equipment and without step of drying a low pressure fluid.
  • the step of using the stream I comprises a step of compressing said stream I to obtain a flow at the pressure PIII greater than P1.
  • This compression step can then be performed in a machine whose the elements in contact with said gas stream I are made of steel called "carbon steel" less expensive than the stainless steel elements.
  • the step of using the stream I comprises a cryogenic separation step, subsequent to the compression step when it exists, to obtain at least one purified product.
  • This step is intended to separate and purify a type of molecule contained in said stream I.
  • This molecule may for example be carbon dioxide.
  • the drying step of the invention must be distinguished from a water separation step conventionally present during the treatment of synthesis gas which aims to remove the water present in liquid form in the cooled synthesis gas. .
  • This water separation step delivers a gas stream at its dew point, under pressure and temperature conditions existing locally, which will be subjected to the separation process according to the invention.
  • dry gases are obtained, which is particularly advantageous in the presence of carbon dioxide.
  • Dry gas according to the invention means a gas whose water content is sufficiently low to avoid condensing water in the subsequent steps; it may contain less than 1000 ppm of water, and more particularly less than 100 ppm of water.
  • the drying step according to the invention is carried out upstream of the separation S, ie on a gas stream available under pressure (generally from 15 to 100 bars), which makes it possible to limit the size of the driers.
  • the separation of the gaseous mixture into at least two streams may be carried out by permeation or by pressure modulation adsorption or by combination of these separation modes, in parallel or in series.
  • this relates to an installation for the separation of a gas mixture containing essentially hydrogen and carbon monoxide, but also at least carbon dioxide and water, as well as possibly methane, nitrogen and other impurities, said plant comprising a source of the mixture of the gas to be separated, a separation unit for separating the gas mixture into at least two streams I and II in which the flow I is a gaseous flow at a low pressure Pl, containing all the compounds contained in the gas mixture to be separated, in proportions variables and the flow II is a gaseous flow at a high pressure PII, containing all the compounds contained in the gas mixture to be separated, in variable proportions and different from those of the flow I, a flow utilization module II high pressure, a low-pressure flow I-use module for at least partial upgrading of said flow I, as well as ducts connecting the separation unit to the use module of the gas flow I and the separation unit to the module use of the gas stream II, characterized in that it further comprises a drying unit of the gas mixture to be
  • this compression is advantageously carried out using compressor (s). ) carbon steel less expensive than compressors whose elements of certain stages in contact with the flow at risk of formation of carbonic acid should be provided in stainless steel.
  • the installation comprises a cryogenic separation unit, intended for the treatment of the flow of low pressure gas from the separation unit, where appropriate after compression.
  • FIG. 1 is a diagram of a plant for producing hydrogen from a hydrocarbon vapor reforming unit with purification of hydrogen in a PSA and production of CO 2 from the PSA waste.
  • FIG. 1 The installation shown for illustrative purposes in FIG. 1 essentially comprises a feed module 1 made of a wet gas mixture, a drying unit 2, a PSA type separation unit 3 which produces two gas streams I and II, a means of compression 4 for compressing the flow of gas I, a cryogenic unit or cold box 5 for the production of carbon dioxide.
  • the installation works as follows: -
  • the feed module 1 typically comprises a reformer which, fed with a light hydrocarbon feedstock produces a reforming gas or synthesis gas, which contains predominantly hydrogen and CO, substantial amounts methane, water and CO 2 , as well as nitrogen; this gas is cooled, then the condensed water is removed in a condensate separation flask, the gas from the separator constituting the gaseous mixture 6 containing water vapor to be separated,
  • Unit 3 is a PSA unit that produces the two gas streams I and II.
  • the gas stream II, referenced 8, provides hydrogen produced by the installation.
  • the gas stream I, referenced 9 is the waste gas of the PSA. It contains CO, CO 2 , methane and nitrogen present in the gas supplying the purification unit 3 as well as hydrogen molecules. It is generally obtained at very low pressure of the order of a few hundred millibars.
  • the stream 9 is then treated in the cryogenic unit 5 to supply carbon dioxide 10. For this, the stream 9 is first compressed in the compressor 4, then treated in the cryogenic unit 5 for separation and purification carbon dioxide molecules.
  • the cryogenic unit 5 supplies in addition to pure liquid carbon dioxide 10, hydrogen 1 1, a gaseous stream 12 containing methane, hydrogen, carbon monoxide which will be recycled as fuel, and a purge of nitrogen 13.
  • the process is for the production of hydrogen as well as carbon dioxide.
  • the process conventionally provides, at the end of the cooling step of the synthesis gas, a decarbonation step which aims to eliminate most of the CO 2 molecules. present in the synthesis gas.
  • the drying step according to the invention is then subsequent to this decarbonation step.
  • two adsorbents are combined in the dryers: one (Al 2 O 3 for example) has its function is to eliminate water, while the second (activated carbon for example) has the function of removing residual CO 2 .

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Drying Of Gases (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Industrial Gases (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Carbon And Carbon Compounds (AREA)
EP07823687A 2006-08-10 2007-08-03 Verfahren zur trennung eines synthesegases, das wasserstoff und kohlenmonoxid, aber auch mindestens kohlendioxid und wasserdampf enthält Ceased EP2059476A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0653338A FR2904780B1 (fr) 2006-08-10 2006-08-10 Procede de separation d'un gaz de synthese contenant de l'hydrogene et du monoxyde de carbone mais aussi au moins du dioxyde de carbone et de la vapeur d'eau
PCT/FR2007/051778 WO2008017783A2 (fr) 2006-08-10 2007-08-03 Procédé de séparation d'un gaz de synthèse contenant de l'hydrogène et du monoxyde de carbone mais aussi au moins du dioxyde de carbone et de la vapeur d'eau

Publications (1)

Publication Number Publication Date
EP2059476A2 true EP2059476A2 (de) 2009-05-20

Family

ID=37801403

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07823687A Ceased EP2059476A2 (de) 2006-08-10 2007-08-03 Verfahren zur trennung eines synthesegases, das wasserstoff und kohlenmonoxid, aber auch mindestens kohlendioxid und wasserdampf enthält

Country Status (6)

Country Link
US (1) US8231709B2 (de)
EP (1) EP2059476A2 (de)
JP (1) JP2010500439A (de)
CN (1) CN101511727A (de)
FR (1) FR2904780B1 (de)
WO (1) WO2008017783A2 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009016625A2 (en) * 2007-07-29 2009-02-05 Baruchi Barry Baruch Kimchi Method and system for the separation of a mixture containing carbon dioxide, hydrocarbon, and hydrogen
US8585802B2 (en) 2010-07-09 2013-11-19 Arnold Keller Carbon dioxide capture and liquefaction
US8168685B2 (en) * 2011-07-01 2012-05-01 Membrane Technology And Research, Inc Process for the production of methanol including one or more membrane separation steps
FR3073835B1 (fr) 2017-11-22 2022-10-21 Air Liquide Procede et appareil pour la production combinee d'hydrogene et de dioxyde de carbone a partir d'un melange d'hydrocarbures
FR3139477A1 (fr) * 2022-09-12 2024-03-15 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé de séparation
FR3166628A1 (fr) 2024-09-24 2026-03-27 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé et appareil de génération d’un gaz combustible riche en hydrogène

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6090312A (en) * 1996-01-31 2000-07-18 Ziaka; Zoe D. Reactor-membrane permeator process for hydrocarbon reforming and water gas-shift reactions
WO2007123673A1 (en) * 2006-04-03 2007-11-01 Praxair Technology, Inc. Carbon dioxide and hydrogen production method from synthesis gas

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4778670A (en) * 1984-03-02 1988-10-18 Imperial Chemical Industries Plc Technical hydrogen
GB8726804D0 (en) * 1987-11-16 1987-12-23 Boc Group Plc Separation of gas mixtures including hydrogen
US4963339A (en) * 1988-05-04 1990-10-16 The Boc Group, Inc. Hydrogen and carbon dioxide coproduction
US5073356A (en) * 1990-09-20 1991-12-17 Air Products And Chemicals, Inc. Integrated processes for the production of carbon monoxide
US5753010A (en) * 1996-10-28 1998-05-19 Air Products And Chemicals, Inc. Hydrogen recovery by pressure swing adsorption integrated with adsorbent membranes
US5897686A (en) * 1997-10-22 1999-04-27 Air Products And Chemicals, Inc. Synthesis gas drying and CO2 removal
AR021966A1 (es) * 1998-12-22 2002-09-04 Texaco Development Corp Utilizacion de membranas y expansores/compresores en gasificacion
FR2841152B1 (fr) * 2002-06-19 2005-02-11 Air Liquide Procede de traitement d'au moins un gaz de charge par adsorption a modulation de pression
US6630011B1 (en) * 2002-09-17 2003-10-07 Membrane Technology And Research, Inc. Nitrogen removal from natural gas using two types of membranes
FR2877939B1 (fr) * 2004-11-16 2007-02-02 Air Liquide Procede et installation pour la production combinee d'hydrogene et de dioxyde de carbone
US7393382B2 (en) * 2004-12-20 2008-07-01 Idatech Llc Temperature-based breakthrough detection and pressure swing adsorption systems and fuel processing systems including the same
EP1858803B1 (de) * 2005-03-14 2016-07-06 Geoffrey Gerald Weedon Verfahren zur herstellung von wasserstoff unter gleichzeitiger herstellung und abfangung von kohlendioxid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6090312A (en) * 1996-01-31 2000-07-18 Ziaka; Zoe D. Reactor-membrane permeator process for hydrocarbon reforming and water gas-shift reactions
WO2007123673A1 (en) * 2006-04-03 2007-11-01 Praxair Technology, Inc. Carbon dioxide and hydrogen production method from synthesis gas

Also Published As

Publication number Publication date
WO2008017783A3 (fr) 2008-04-17
FR2904780A1 (fr) 2008-02-15
FR2904780B1 (fr) 2009-10-09
CN101511727A (zh) 2009-08-19
US20100147147A1 (en) 2010-06-17
US8231709B2 (en) 2012-07-31
WO2008017783A2 (fr) 2008-02-14
JP2010500439A (ja) 2010-01-07

Similar Documents

Publication Publication Date Title
EP1890961B1 (de) Verfahren zur simultanen erzeugung von wasserstoff und kohlenmonoxyd
EP3713870B1 (de) Verfahren und vorrichtung zur kombinierten herstellung von wasserstoff und kohlendioxid aus einem kohlenwasserstoffgemisch
CA2587416C (fr) Procede et installation pour la production combinee d'hydrogene et de dioxyde de carbone
FR2992307A1 (fr) Procede et installation pour la production combinee de gaz de synthese d'ammoniac et de dioxyde de carbone
EP2059476A2 (de) Verfahren zur trennung eines synthesegases, das wasserstoff und kohlenmonoxid, aber auch mindestens kohlendioxid und wasserdampf enthält
FR2775276A1 (fr) Procede et installation de production de monoxyde de carbone et d'hydrogene
WO2016174317A1 (fr) Production d'hélium à partir d'un courant gazeux contenant de l'hydrogène
CA2928640A1 (fr) Appareil et procede de compression et/ou refroidissement ainsi que de purification d'un gaz riche en dioxyde de carbone contenant de l'eau
EP0937681A1 (de) Verfahren und Anlage zur kombinierter Herstellung einer Ammoniak-Synthesemischung und Kohlenmonoxyd
FR2838424A1 (fr) Procede et installation de separation d'un melange d'hydrogene et de monoxyde de carbone
FR3034509B1 (fr) Procede de traitement du gaz naturel pour minimiser la perte d'ethane
FR2969136A1 (fr) Procede pour une production de monoxyde de carbone avec alimentation de boite froide stabilisee
FR2975307A1 (fr) Procede de purification par adsorption avec regeneration au moyen d'un gaz comprenant un constituant non desire dans le gaz purifie
EP2964571B1 (de) Verfahren und vorrichtung zur herstellung von kohlendioxid und wasserstoff
EP3756750A1 (de) Anlage zur aufbereitung eines methan- und kohlendioxidstroms mithilfe eines flügelzellenverdichters und einer membranabscheidungseinheit
EP3252408B1 (de) Verfahren zur reinigung von erdgas und zur verflüssigung von kohlendioxid
EP1097903B1 (de) Verfahren und Vorrichtung zur Herstellung von reinem Wasserstoff ausgehend von einem Gas das Helium enthält
FR2847568A1 (fr) Procede et installation de production d'un melange krypton/xenon a partir d'air
FR2969134A1 (fr) Procede de traitement d'un gaz de synthese obtenu par gazeification, avec recyclage de gaz de flash extraits de la boite froide et de l'unite d'extraction des gaz acides
EP3252406A1 (de) Verflüssigungsverfahren von kohlendioxid aus einem erdgasstrom
WO2006042986A1 (fr) Procede de production d'un gaz de synthese presentant un ratio h2/co inferieur a 2,5
FR3153543A1 (fr) Procédé et appareil de séparation d’un gaz comprenant du CO2, de l’azote et au moins un composé toxique et/ou inflammable
WO2018087497A1 (fr) Procédé de liquéfaction de gaz naturel combiné à une production de gaz de synthèse
EP4702106A1 (de) Verfahren und anlage zur behandlung eines gasstroms aus der pyrolyse von kunststoff und/oder der pyrolyse von biomasse zur gewinnung von olefinen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090310

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20140519

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20180416