CN101460233A - 由合成气制备二氧化碳和氢气的方法 - Google Patents

由合成气制备二氧化碳和氢气的方法 Download PDF

Info

Publication number
CN101460233A
CN101460233A CNA2007800206680A CN200780020668A CN101460233A CN 101460233 A CN101460233 A CN 101460233A CN A2007800206680 A CNA2007800206680 A CN A2007800206680A CN 200780020668 A CN200780020668 A CN 200780020668A CN 101460233 A CN101460233 A CN 101460233A
Authority
CN
China
Prior art keywords
carbon dioxide
synthesis gas
gas stream
logistics
hydrogen
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.)
Pending
Application number
CNA2007800206680A
Other languages
English (en)
Inventor
H·E·霍沃德
M·M·沙
J·F·比林厄姆
R·库马
B·T·诺伊
D·P·博纳奎斯特
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.)
Praxair Technology Inc
Original Assignee
Praxair Technology Inc
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 Praxair Technology Inc filed Critical Praxair Technology Inc
Publication of CN101460233A publication Critical patent/CN101460233A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—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
    • 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
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0476—Vacuum pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • 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
    • F25J3/0204—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 feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis 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
    • 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
    • F25J3/0252—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 hydrogen
    • 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
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40058—Number of sequence steps, including sub-steps, per cycle
    • B01D2259/40069—Eight
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40058—Number of sequence steps, including sub-steps, per cycle
    • B01D2259/40071—Nine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40058—Number of sequence steps, including sub-steps, per cycle
    • B01D2259/40073—Ten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/406—Further details for adsorption processes and devices using more than four beds
    • B01D2259/4062—Further details for adsorption processes and devices using more than four beds using six beds
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/86—Carbon dioxide sequestration
    • 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
    • F25J2200/70—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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes 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
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes 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
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/82—Processes or apparatus using other separation and/or other processing means using a reactor with combustion or catalytic reaction
    • 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
    • F25J2210/04—Mixing or blending of fluids with the feed stream
    • 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
    • F25J2215/80—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
    • 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
    • F25J2230/30—Compression of the feed stream
    • 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
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/40—Expansion without extracting work, i.e. isenthalpic throttling, e.g. JT valve, regulating valve or venturi, or isentropic nozzle, e.g. Laval
    • 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • 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
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/80—Integration in an installation using carbon dioxide, e.g. for EOR, sequestration, refrigeration etc.
    • 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
    • F25J2270/02—Internal refrigeration with liquid vaporising loop
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

本发明涉及从氢气设备(1)中形成的合成气物流(18)生产二氧化碳产物物流(756)的方法，所述氢气设备(1)具有合成气反应器(10)、位于合成气反应器下游用以形成合成气物流(12)的水煤气变换反应器(14)，和用以产生从所述合成气物流回收的氢气产物(22)的氢气变压吸附单元(20)。根据本发明，在真空变压吸附系统(80)中从所述合成气物流中分离二氧化碳，以产生氢气富集的合成气物流(76)和粗二氧化碳物流(82)，并随后通过低于环境温度蒸馏过程纯化所述粗二氧化碳物流，从而产生二氧化碳产物(756)。对氢气变压吸附单元的氢气合成气进料物流(78)至少部分由所述氢气富集的物流形成。

Description

由合成气制备二氧化碳和氢气的方法
技术领域
[0001]本发明涉及从在氢气设备中形成的合成气物流中生产二氧化碳产物物流的方法，所述氢气设备具有合成气反应器、水煤气变换反应器以形成所述合成气流、以及氢气变压吸附单元以形成氢气产物。更具体地，本发明涉及从合成气物流中回收二氧化碳的方法，其中所述回收通过序贯地真空变压吸附过程和低于环境温度(sub-ambient)的蒸馏过程从合成气流中分离二氧化碳而进行。更具体地，本发明涉及具有如下应用的方法：将所述二氧化碳产物物流用于强化采油或封存。
背景技术
[0002]含一氧化碳和氢气的合成气可进一步纯化以生产氢气和一氧化碳产物，或者可在这种下游化学过程(例如，包括生产甲醇)或者通过费-托方法用于合成燃料的公知气-液体方法中进一步反应。
[0003]通过向位于蒸汽甲烷重整器的辐射段内的蒸汽甲烷重整器管中引入含碳氢化合物的进料(典型地是天然气)，在蒸汽甲烷重整器内产生合成气。所述重整器管填充有用于促进蒸汽甲烷重整反应的催化剂。蒸汽甲烷重整反应是吸热的，因此通过供热入蒸汽甲烷重整器的辐射段的燃烧器来向重整器管供热，以支持所述反应。还可以通过在部分氧化反应器中通过碳氢化合物与氧化剂(如氧气)之间的反应，或者在自热重整器中通过碳氢化合物、氧化剂和蒸汽之间的反应来产生合成气。
[0004]当合成气物流冷却后，合成气的蒸汽和一氧化碳组分可在水煤气变换反应器中进一步反应，以提高合成气的氢气含量。
[0005]集成的蒸汽发生系统位于所述合成气设备内，以产生用于蒸汽甲烷重整反应、用于水煤气变换反应以及用于输出的蒸汽。输出的蒸汽本身可构成有用的产物，该产物可影响氢气设备的经济生存能力。蒸汽甲烷重整器通常具有与辐射段连接的对流热交换段。为了上述目的，给辐射段供热的燃烧器产生的热烟道气通过所述对流段，以产生蒸汽以及使蒸汽过热。所述蒸汽发生系统还利用水煤气变换反应器上游和下游的热交换器。在这方面，蒸汽甲烷重整器中产生的合成气物流必须降温至适于水煤气变换反应器的水平，因此位于水煤气变换反应器上游的热交换器既冷却合成气物流又产生部分蒸汽。由于水煤气变换反应器是放热过程，所以变换后物流中所含的热量通常在位于水煤气变换反应器下游的热交换器中用于产生额外的蒸汽。所有这些蒸汽均导引至蒸汽汇集器，并随后在蒸汽甲烷重整器的对流段进行过热。
[0006]蒸汽甲烷重整反应产生的合成气具有二氧化碳含量。在水煤气变换反应器后，由于蒸汽与一氧化碳的反应，合成气的二氧化碳含量进一步提高。为了合成气的下游处理例如生产甲醇，通常必须从合成气中分离二氧化碳。此外，二氧化碳本身是有价值的产品。例如，强化采油过程利用二氧化碳，其中在注入井中将二氧化碳注入井下以将油驱入生产井。在强化采油过程中，在储油层中注入二氧化碳降低了油的粘度，使得油更容易流动，从而提高了从储层回收的油量。然而，应当指出，当二氧化碳用于这类用途时，其必须非常纯净，因此并不容易从蒸汽甲烷重整设备获得。此外，源自使用碳氢化合物排放的二氧化碳关系到全球变暖。为了解决这一问题，已经建议从工业来源俘获二氧化碳，并注入地下盐水层(brine aquifer)或深海中，以永久地俘获二氧化碳，从而稳定大气二氧化碳水平。
[0007]然而，已经将各种二氧化碳去除系统与蒸汽甲烷重整设备集成起来，最低限度用以从合成气分离二氧化碳，并且回收该二氧化碳用于封存(sequestration)目的，或者用作价值增加的产品。
[0008]U.S.5,000,925描述了从采用蒸汽甲烷重整器的氢气设备回收氢气和二氧化碳的方法。在该方法中，水煤气变换反应器产生的合成气物流被引入氢气变压吸附单元，以产生产物氢气物流和尾气物流。该尾气压缩，并随后用二氧化碳变压吸附单元进行分离，以产生氢气-富集的物流和二氧化碳-富集的物流。将该二氧化碳-富集的物流压缩，并在深冷单元中进一步纯化，以产生液态二氧化碳。所述氢气-富集的物流再循环回蒸汽甲烷重整器。
[0009]U.S.6,551,380公开了一种方法，其中在氢气设备中的水煤气变换反应器产生的合成气物流常规引入氢气变化吸附单元中，以回收氢气并从而产生尾气物流。将该尾气物流压缩，并随后在吸附单元中处理以回收二氧化碳。来自吸附单元的二氧化碳被送至液化器，以产生纯化的液态二氧化碳产物，来自吸附单元的废气被送至第二氢气变压吸附单元以产生氢气。
[0010]由于均使用尾气流作为蒸汽甲烷重整器的一部分燃料，实际上采用任一上述专利中所述方法均存在问题。燃料的任何中断导致蒸汽甲烷重整器系统停机，致使需进行高成本的重新启动，其中蒸汽甲烷重整器的主要燃料(通常为天然气)必须用来使重整器返回到其操作温度。使用尾气的另一问题是，在可以在真空变压吸附过程中对粗二氧化碳物流进行分离之前，必须对尾气进行压缩。压缩步骤导致额外的能量消耗和固定投资。
[0011]如以下将论述的，本发明不从尾气中提取二氧化碳，从而避免了上述问题。此外，本发明通过将二氧化碳回收设置在氢气设备内，相对于现有技术还有其他优点。
发明内容
[0012]本发明提供了从氢气设备生产二氧化碳产物物流的方法。所述氢气设备采用合成气反应器、位于合成气反应器下游的水煤气变换反应器和氢气变压吸附单元来产生氢气产物。
[0013]根据所述方法，通过在真空变压吸附过程中从合成气物流的至少一部分中分离二氧化碳来从水煤气变换反应器制备的合成气物流的至少一部分回收二氧化碳。这种分离产生了氢气富集的合成气物流和粗二氧化碳物流。该粗二氧化塔物流通过低于环境温度的蒸馏过程来纯化，从而产生蒸气形式的二氧化塔产物。氢气合成气进料物流至少部分由所述氢气富集的物流形成，并且引入所述氢气变压吸附单元，从而产生氢气产物。
[0014]如上述描述所证明的，二氧化碳取自所述合成气物流而非尾气物流。此外，由于在氢气变压吸附过程之前去除了二氧化碳，所以有益地改善氢气的回收。
[0015]优选地，所述低于环境温度的蒸馏过程包括压缩和干燥所述粗二氧化碳物流。随后将该粗二氧化碳物流冷却至所述低于环境温度的温度，并在汽提塔中汽提，以从液体塔底物产生液态二氧化碳产物并产生塔顶馏出物。使液态二氧化碳产物物流在至少一个压力膨胀以致冷，并随后蒸发以产生至少一股二氧化碳产物物流作为所述二氧化碳产物。
[0016]粗二氧化碳物流可以在具有经过变温吸附过程的吸附剂的干燥单元中干燥，其中通过使用热再生气流从吸附剂中解吸水分。所述低于环境温度蒸馏过程还可包括对包含塔顶馏出物的塔顶馏出物物流进行精炼，以产生二氧化碳富集的蒸气物流和二氧化碳消耗的蒸气物流。将所述二氧化碳富集的蒸气物流用作再生气流，并随后再循环回用于压缩所述粗二氧化碳物流的压缩器。所述二氧化碳消耗的蒸气物流再循环至，并与所述合成气物流一起进料给所述真空变压吸附过程。次优选的替代方案是将所述二氧化碳消耗的蒸气物流与所述氢气富集的合成气流合并，以形成氢气合成气进料物流。如即将论述的，干燥器单元不必须按以上所述的方式使用。在这种情况下，所述二氧化碳富集的蒸气物流仍可再循环回用于压缩粗二氧化碳物流的压缩器。
[0017]在任何实施方案中，可在压缩器之前或之后从粗二氧化碳物流中催化去除氧气。氧气可通过泄漏进真空变压吸附过程的空气的途径进入粗二氧化碳物流。
[0018]在所述真空变压吸附过程的上游的至少部分所述合成气物流可以在具有经过变温吸附过程的吸附剂的干燥单元中干燥，其中通过使用热再生气体物流从吸附剂中解吸水分。在这种情况下，所述低于环境温度蒸馏过程包括对包含塔顶馏出物的塔顶馏出物物流进行精炼，以产生二氧化碳富集的蒸气物流和二氧化碳消耗的蒸气物流。所述二氧化碳富集的蒸气物流再循环回用于压缩所述粗二氧化碳物流的压缩机，而所述二氧化碳消耗的蒸气物流再循环至，并与所述合成气物流的至少一部分一起进料给所述真空变压吸附过程。可对所述氢气富集的物流进行加热，并用于形成所述热再生气体物流。当所述合成气反应器是蒸汽甲烷重整器时，所述进一步加热的再生气体物流由氢气变压吸附过程产生的尾气物流构成。此后，将该尾气物流用作位于蒸汽甲烷重整器的辐射换热段内的燃烧器的燃料的一部分。可选择地，所述进一步加热的再生气体物流可由含碳氢化合物的进料物流构成，其随后在位于蒸汽甲烷重整器的辐射换热段内的催化剂填充反应管内反应。
[0019]在本发明的另一实施方案中，可以在真空变压吸附过程之前从所述合成气物流的至少一部分中去除水分，并可以从处于低于环境温度蒸馏过程中的粗合成气物流中去除水分。所述水分中的一部分是通过将所述合成气物流的至少一部分冷却以冷凝其中所含的部分水分，并在分离罐中从所述至少部分合成气物流中去除所得冷凝物，而从所述至少部分合成气物流中去除的。
[0020]在本发明任一实施方案中，可对二氧化碳产物进行压缩。此外，所述合成气物流可具有介于约12％到约25％的二氧化碳含量。所述粗二氧化碳物流可以具有介于约70％到约98％之间的二氧化碳含量以及介于0-5000ppm之间的氧气含量。所述二氧化碳产物的纯度可以为约98％到99.9999％的二氧化碳和低于100ppm的氧气。所述二氧化碳产物可压缩至介于约1200psia和约2500psia之间的压力，并随后引入强化采油过程中，或引入二氧化碳储存点用于封存(sequestration)。
附图说明
[0021]虽然申请文件通过权利要求书明确指出了申请人视为其发明的主题，但是申请人相信当结合附图时可以更好地理解所述发明，其中：
[0022]图1是用于实施本发明方法的蒸汽甲烷重整器和二氧化碳回收系统(虚线内显示的)的方法流程图的示意图；
[0023]图2是与图1中采用的二氧化碳回收系统结合使用的真空变压吸附过程的示意图；
[0024]图3是用于实施图2所示方法的真空变压吸附单元的示意图；
[0025]图4是图3所示单元的阀开启图；
[0026]图5是用于实施图1所示二氧化碳回收系统中使用的低于环境温度蒸馏过程的设备的示意图；
[0027]图6是与图5所示的低于环境温度蒸馏过程结合使用的干燥器单元的示意图；
[0028]图7是图1的替代性实施方案；
[0029]图8是图1的替代性实施方案；
[0030]图9是图1的替代性实施方案；
[0031]图10是图1的替代性实施方案；
[0032]图11是图1的替代性实施方案；以及
[0033]图12是图1的替代性实施方案。
[0034]为了避免在附图解释中的重复，在各附图中，相同的附图标记用于在图中具有共同描述的部件。
具体实施方式
[0035]参见图1，显示了氢气设备1，其具有用于产生粗合成气物流12的蒸汽甲烷重整器10、下游水煤气变换反应器14、以及用于从合成气物流18中回收二氧化碳的二氧化碳回收系统16，所述合成气物流中的氢气含量已经通过水煤气变换反应器14提高了。
[0036]在氢气设备1中，提供了变压吸附单元20来以公知方式将所述氢气纯化为氢气产物物流22。例如，氢气吸附单元20可具有多个异相操作的吸附剂床，从而当一个床吸附非氢气组分并产生纯化的氢气产物作为塔顶馏出物(overhead)时，另一床在比当前在线用以产生氢气产物的床更低的压力下再生。用于这种目的的吸附剂的例子包括氧化铝活化的碳和沸石化合物的层。合成气物流18在变压吸附单元20内的纯化产生了尾气物流24，其含有氢气、二氧化碳、一氧化碳、氮气、甲烷和其他碳氢化合物。
[0037]尾气物流24可与天然气物流30或其他含碳氢化合物的燃料合并，以形成燃料物流32。将燃料物流32与含氧气的物流36(如空气)一起引入位于蒸汽甲烷重整器10的辐射换热段34内的燃烧器内，以支持燃料物流32的燃烧。含碳氢化合物的物流38也可以是天然气，将其与过热的蒸汽物流40合并以产生反应物流42，并引入诸如位于蒸汽甲烷重整器10的辐射段34内的重整器管44的重整器管内。在蒸汽甲烷重整器10中，碳氢化合物与蒸汽在公知的蒸汽甲烷重整反应中反应，该反应的本质为吸热的。通过燃料物流32的燃烧来供应热量，以支持这类蒸汽甲烷重整器。这种燃烧产生的烟道气通过具有过程气体换热器48以及构成蒸汽再生系统一部分的蒸汽过热器50的蒸汽甲烷重整器10的对流段46。烟道气从烟囱作为烟道气排放成为烟道气物流52。
[0038]在过程气体沸腾器(boiler)54中对粗合成气物流12进行冷却，所述沸腾器与蒸汽过热器50一起形成了蒸汽再生系统的一部分。过程气体沸腾器54用以将粗合成气物流12冷却至适合于水煤气变换反应器14内的水煤气变换反应的温度，在水煤气变换反应器中通过将粗合成气物流12中的蒸汽组分与一氧化碳反应来上调氢气含量。所得合成气物流18(本领域也称为变换的物流)可通过进料加热器(未示出，但本领域也公知该加热器用于加热含碳氢化合物的进料38)。在加热后，含碳氢化合物的进料38通过加氢处理器，其将硫物种转化为硫化氢，并随后进入基于锌的吸附剂床，以从进料中去除硫化氢。所述加氢处理器和吸附剂床并未示出，不过是本领域公知地。
[0039]合成气物流18通过沸腾进料水加热器56，其同样构成所述蒸汽发生系统的一部分。在沸腾进料水加热器56中产生的蒸汽和过程气体沸腾器54中得到蒸汽物流一起引入蒸汽汇集器。从蒸汽汇集器取出蒸汽作为蒸气物流58，并部分形成在形成反应物流42时所用的蒸汽物流40。过热的蒸汽物流58的另一部分用于形成输出蒸汽物流60。
[0040]随后合成气物流18通过翅扇式冷却器66，并随后在进入变压吸附系统20之前通过水冷式冷却器68。合成气物流18具有介于约200psia到约500psia之间的压力，介于约60℉到约150℉之间，优选介于约90℉到约110℉之间的温度，以及介于约60摩尔％到约80摩尔％之间的氢气、约12摩尔％到约25摩尔％之间的二氧化碳、约0.1摩尔％到约5摩尔％之间的一氧化碳、约3摩尔％到约7摩尔％之间的甲烷、至多约5摩尔％的氮气的组成并被水饱和。
[0041]通过控制阀70、72和74来控制合成气物流18相对于二氧化碳去除系统16的流动。当控制阀72和74处于关闭位置时，控制阀70处于开启位置。如上所述，完全由合成气物流18形成的氢气合成气进料物流78通过变压吸附单元20。当控制阀70处于关闭位置，而控制阀72和74设定为开启位置时，合成气物流18作为物流18a通过二氧化碳回收系统16，随后返回作为氢气富集的气体物流76，其由已经去除二氧化碳从而相比合成气物流18具有更低二氧化碳含量的合成气物流18构成。在这种情况下，完全由氢气富集气体物流76构成的氢气合成气进料物流78，其被引导至变压吸附系统20用于生产氢气。如本领域技术人员可以理解的，控制阀72和74处于关闭位置的设定使得能够在包含于二氧化碳分离系统16内的设备上进行维护活动。阀70和72的部分开启能够使得可从合成气物流18的一部分中回收二氧化碳，并且这样物流18a由一部分合成气物流18构成。氢气富集的气体物流76通过阀74返回，并与合成气物流18的剩余部分混合形成氢气合成气进料物流78，其继续流动至氢气变压吸附单元20。由于从合成气物流18中去除了二氧化碳，因而减少了氢气变压吸附单元20上的负荷。氢气回收率可以提高多至0.5％。
[0042]为了在二氧化碳回收单元16内回收二氧化碳，将物流18a引入单元80内进行的真空变压吸附过程中。这产生了氢气富集的合成气物流76和粗二氧化碳物流82。在待论述的低于环境的蒸馏过程中对粗二氧化碳物流82进行进一步纯化。
[0043]参见图2，单元80可结合包括十个步骤的过程，以及包括6个床(A1-A6)的设备(如图3所示)。所述6个床(A1-A6)中每一个都含有吸附水分的氧化铝吸附剂层和吸附二氧化碳的硅胶吸附剂。设备10中用以实现图2所述方法的阀位置如图4所示。为了本领域公知的目的，应用采用阀定位器(valve positioner)的阀来控制流动。应当理解，所示的压力和步骤持续时间仅用于说明目的。过程步骤通常包括：
[0044]1.进料步骤：处于高压(如约375psia)并由水煤气变换反应器14产生的物流18a转移至单元80。在氢气变压吸附单元20中，对单独的氢气富集气体物流76或其与剩余合成气物流18的结合做进一步处理。在预定时间后或在二氧化碳突破(breakthrough)处于物流18a的床后，进料步骤终止。
[0045]2.并流(CoC)减压1(DP1)：将现在处于高进料压力(如100-500psia)的已完成进料步骤的二氧化碳真空变压吸附(“VPSA”)床沿与进料物流相同(如图2所示)或相反(图2中未显示)的方向减压至中等压力(如80-400psia)。
[0046]3.并流(CoC)减压2(DP2)：将现在处于中等压力(如80-400psia)的二氧化碳VPSA床沿与进料物流相同(如图2所示)或相反(图2中未显示)的方向进一步减压至更低压力(如60-300psia)。
[0047]4.并流(CoC)减压3(DP3)：将现在处于某中等压力(如60-300psia)的二氧化碳VPSA床沿与进料物流相同(如图2所示)或相反(图2中未显示)的方向进一步减压至更低压力(如50-200psia)。
[0048]5.最终减压(DPf)：将现在处于低于步骤4开始时的压力(约50-200psia)的二氧化碳VPSA床沿与进料物流相同(如图2所示)和/或相反(图2中未显示)的方向进一步减压至接近环境压力的压力(约20psia)，以产生图8所示的二氧化碳产物610。该物流可构成粗二氧化碳物流82的一部分。
[0049]6.排空：通过真空泵609将现在接近环境压力(约20psia)的二氧化碳VPSA床沿与进料物流相同(图2中未显示)或相反(图2中所示)的方向排空至预定的低压，低于环境压力的压力(约1-12psia)。来自处于排空步骤的床的气体(图3中的物流608)构成了粗二氧化碳物流82的一部分。任意地，可在进入产物罐612之前，用鼓风机(未示出)对物流608进行进一步压缩。
[0050]7.逆流(CcC)压力补偿3(PE3)：排空的床现在沿与进料物流相同(图2中未显示)或相反(图2中所示)的方向压力补偿至步骤4(DP3)产生的气体的压力范围(即至约50-200psia)。该步骤通过将来自步骤4的CO2保持在VPSA系统内提高了CO2的回收率。这样通过消除将CO2送至废物物流的需求而使CO2的损失最小化。
[0051]8.逆流(CcC)压力补偿2(PE2)：步骤7中经压力补偿的床现在沿与进料物流相同(图2中未显示)或相反(图2中所示)的方向压力补偿至步骤3(DP2)中产生的气体的压力范围(即至约60-300psia)。该步骤通过将来自步骤3的CO2保持在单元80内提高了CO2的回收率。这样通过消除将CO2送至废物物流的需求而使CO2的损失最小化。
[0052]9.逆流(CcC)压力补偿1(PE1)：步骤8中经压力补偿的床沿与进料物流相同(图2中未显示)或相反(图2中所示)的方向进一步压力补偿至步骤2(DP1)产生的气体的压力范围(即至约80-400psia)。该步骤通过将来自步骤2的CO2保持在单元80内进一步提高了CO2的回收率。这样通过消除将CO2送至废物物流的需求而使CO2的损失最小化。
[0053]10.再加压(FeRP)：通过进料气体或者通过处于步骤1的另一床产生的流出物(即进料物流出物)的一部分将压力补偿后的床再次加压至进料压力(100-500psia)。再加压至进料压力后，该床现在准备好返回至步骤1了。
[0054]如图2中进一步显示的，粗二氧化碳物流82由来自物流608(步骤7)和610(步骤6)的二氧化碳构成，并由产物罐612排放。预期粗二氧化碳物流82具有约80摩尔％或更高的二氧化碳纯度水平。所述的十步过程是针对CO2 VPSA单元中的一个床的一个循环。上述十个步骤是以循环方式进行的，从而步骤1的进料-输入和进料-流出是连续的。此外，排空步骤(序号6)设计为连续的。这确保了真空泵609连续操作，并且对至单元80或至氢气变压吸附单元20的进料-输入没有间断。应当指出，所示的压力和步骤持续时间仅为说明目的，并且本领域技术人员可以理解可采用压力和步骤的其他组合。在所述单元80中，最终减压过程中产生的气体与来自步骤序号6的排空的气体混合。因此，单元80的氢气损失极小或没有。
[0055]在单元80之后，粗二氧化碳物流82包含介于约70体积％至约98体积％的二氧化碳。粗二氧化碳物流82的剩余部分为氢气、一氧化碳、甲烷和氮气，如果有的话。在低于环境温度的蒸馏过程中对粗二氧化碳物流82做进一步纯化，该蒸馏过程通过在压缩机700中将粗二氧化碳物流84压缩至介于约100psia到约1000psia之间，更优选介于约300psia到约800psia之间的压力而开始。最佳的压力取决于二氧化碳的收缩(contraction)。例如，当粗二氧化碳物流82中的二氧化碳浓度为约95％时，优选介于约300psia到约500psia之间的压力。在浓度约80％时，优选介于约500psia到约800psia之间的压力。
[0056]压缩后，在冷却器702中对粗二氧化碳物流82进行冷却以除去压缩热，从而冷凝粗二氧化碳物流82中的水分。通过将二氧化碳物流引入分离罐704中来去除所得冷凝物，脱离的水分作为水流706排放。随后，在干燥单元708(以下将具体描述)中对粗二氧化碳物流82进行进一步干燥，并随后引入低温箱(cold box)710。
[0057]进一步参见图5，在低温箱710内，粗二氧化碳物流82被引入主换热器720中，在其中其部分冷却并随后引入再沸器722中，该再沸器用以在汽提塔724内部产生煮沸(boil up)或引发上升的蒸气相。随后，再次将粗二氧化碳物流82引入主换热器720内，其中其完全冷却以至少部分液化粗二氧化碳物流82。随后，将粗二氧化碳物流82引入膨胀阀726进入汽提塔724，以在该塔内引发下降的液相。
[0058]如本领域公知地，汽提塔724优选具有规整填料以使朝上流过填料的上升蒸气相与液相的降液膜接触。也可使用其他本领域公知的蒸气-液体接触元件，如筛板。作为接触的结果，下降的液相变为越来越富集二氧化碳(挥发性较弱的组分)，而上升的蒸气相变为越来越富集杂质，该杂质相比二氧化碳具有更高的挥发性。源自合成气物流18的粗二氧化碳物流82含有二氧化碳和诸如氢气、一氧化碳和甲烷的杂质。由于所有这类杂质相比二氧化碳挥发性更高，其将从降液中汽提出来，以产生二氧化碳消耗的塔顶馏出物，和二氧化碳富集的液体塔底料。
[0059]可从汽提塔724提取塔顶馏出物物流728，其由二氧化碳消耗的塔顶馏出物构成，并进一步精炼。这可通过将塔顶馏出物物流728引入辅助换热器730从而二氧化碳塔顶馏出物物流728为至少部分液化来实现。随后，将二氧化碳塔顶馏出物物流730引入相分离器732，以产生二氧化碳消耗的蒸气物流734和二氧化碳富集的液体物流736。二氧化碳富集的液体物流736在膨胀阀738中膨胀，并随后与二氧化碳消耗的蒸气物流734一起流入辅助换热器730。膨胀阀738提供了用于二氧化碳塔顶馏出物物流728部分液化的致冷。随后，二氧化碳富集的液体物流736在主换热器720中汽化，以形成二氧化碳富集的蒸气物流737，而二氧化碳消耗的蒸气物流734在主换热器720中进一步升温。
[0060]将二氧化碳富集的蒸气物流737用于再生换热器单元708，并随后再循环至压缩机700的压缩的适当阶段，使得该物流可含有约98体积％的二氧化碳。在这方面，二氧化碳富集的蒸气物流737可具有介于约50psia到约150psia之间的压力，并且可含有粗二氧化碳物流82中的二氧化碳的约10％到约15％。根据计算，这种物流的再循环能将从粗二氧化碳物流的二氧化碳回收率提高至高于约99％。优选将二氧化碳消耗的蒸气物流734再循环回单元80，因为其二氧化碳浓度高于合成气物流18并可以含有介于约20摩尔％到约30摩尔％之间的二氧化碳。
[0061]可从汽提塔724中以液体形式提取二氧化碳产物物流742，其由二氧化碳富集的液体塔底料构成。为了产生致冷，二氧化碳产物物流742可划分成辅助物流746和748，且通过使用膨胀750将辅助物流746膨胀至更低的压力，并通过使用膨胀阀752将辅助物流748膨胀至更高的压力。随后，将辅助物流746和748在主换热器720中气化。将所得更低压的辅助物流746引入产物压缩机754的入口。将更高压的辅助物流748引入产物压缩机754的中间段。如可以理解地，可在单一压力对二氧化碳产物物流742进行膨胀。然而，如可以理解地，这不会具有象所述实施方案一样的能量效率。
[0062]所得压缩产物物流756可引入管线中，以将其输送至油田用于强化采油过程，其中将压缩产物物流引入注入井以将油田内的油驱动至生产井。可选择地，可将二氧化碳送至封存地点，用于永久贮存所述二氧化碳。这类过程通常需要压力介于约1200psia到约2500psia之间的二氧化碳。在这方面，通常合成气物流18具有介于约12％到约25％之间的二氧化碳含量。上述发明能够经操作以使粗二氧化碳物流具有介于约70％到约98％之间的二氧化碳含量，介于0-5000ppm的氧气含量。此外，尤其在强化采油的情况下，二氧化碳产物应当具有介于约98％到99.9999％之间的二氧化碳纯度，和低于100ppm的氧气，优选低于10ppm的氧气。
[0063]参见图6，显示了干燥器单元708的实施方案。干燥器单元708具有两个含有氧化铝吸附剂的床800和802。当床800在线从粗二氧化碳物流82吸附水分时，阀806和808开启。阀810和812关闭。在这时，对床802进行再生，为了该目的，对床802进行减压、加热以解吸之前吸附的水分，冷却并随后再加压以使床802返回线上和吸附。
[0064]在减压过程中，将干燥器旁通阀814设为开启位置，用于再生的二氧化碳富集的蒸气物流737绕过床802，并在冷却器819中冷却后流至压缩机700。阀816设为开启位置使得床802能减压。在床802减压后，阀814关闭而阀816、817和818开启，使得二氧化碳富集的蒸气物流737能通过加热器820，以将二氧化碳富集的蒸气物流737加热至介于约300℉到600℉的温度，通过床802并通过冷却器819后排放到压缩机700。这使得水分从床802内的吸附剂解吸。随后，通过开启加热器旁通阀826并关闭再生阀818对床802进行冷却。冷却后，加热器旁通阀826和阀816及817关闭，而干燥器旁通阀814开启。此时，阀828裂开，使粗二氧化碳物流82中所含的部分粗二氧化碳进入床802用于再加压目的。一旦再加压，将阀806和808设定在关闭位置，而阀828和830设定在开放位置，使得床802可以回到线上，而床800以与床802相同的方式并使用阀810和812进行再生。该过程为连续的，从而允许连续流动。
[0065]应当指出，虽然上述低于环境温度蒸馏过程是优选的，本领域公知的其他类型的蒸馏过程也是可能的。例如，使用多个连续塔来进一步精炼塔顶馏出物物流728。同样，尽管干燥器单元708是优选地，如本领域公知的，在本发明范围内其他类型的干燥器单元也是可能的。实际上，可使用公知的逆流换热器，尽管消耗更高而效率更低。
[0066]参见图7，显示了图1的替代实施方案，其中二氧化碳消耗的蒸气物流734与氢气富集的合成气物流76合并，以形成氢气进料物流78。
[0067]参见图8，显示了图1的替代实施方案，其中通过含有公知催化床的类型的脱氧单元758来去除粗二氧化碳物流84中的氧气。虽然，所示脱氧单元758直接位于压缩机700的下游，其也可位于压缩机700的上游。脱氧单元758也可位于低温箱710的下游，以从二氧化碳消耗的蒸气物流734中去除氧气。尽管另一替代方案是将脱氧单元758置于氢气PSA单元20的上游，以从氢气富集的物流78中去除氧气。在排空步骤中，真空变压吸附单元80可将氧气引入所述系统中，所述系统可能具有安全和纯度问题。脱氧单元758通过去除这些氧气缓解了这种问题。
[0068]参见图9、10和11，与干燥器单元708同类型的干燥器760可置于真空变压吸附单元80的上游。在这些图所示的实施方案中，合成气物流18的全部或部分用作待干燥的物流，以替代粗二氧化碳物流82。在图9中，再生物流是氢气富集的气体物流76。在图10中，再生物流是尾气体物流24，且在图10中再生物流是含碳氢化合物的物流36，其在蒸汽甲烷重整器11中反应。应当想到在干燥器单元708的情况下，再生物流是二氧化碳富集的蒸气物流737。如图12所示，另一选择是在冷却单元762中冷却物流18a，以冷凝其水分。随后，将物流18a引入分离罐764中，以从合成气物流中分离冷凝物。在该实施方案中保留了干燥器单元708。在图9-11所示的实施方案中，完全去除水分防止了二氧化碳和水冷凝物形成腐蚀性的碳酸的任何可能性，从而可在设备中使用更廉价的材料，这类设备如粗二氧化碳压缩机、真空变压单元部件(如容器、阀和二氧化碳鼓风机)和连接这些单元的管路。通常用在多级式粗二氧化碳压缩机各级之间的水分离罐也可取消。图12所示的实施方案通过去除足量水分将粗二氧化碳物流82保持在高于露点防止了任何冷凝，从而提供了部分与上述相同的优点。
实施例1.
[0069]以下计算的实施例描述了各种物流的细节。图2所示的实施方案用于报导表1所示的结果。数值基于二氧化碳真空变压吸附单元80和氢气变压吸附单元20的试验数据。
[0070]基于合成气物流18中二氧化碳量，上述实施例中的总二氧化碳回收率为约85％。如果根据图1所示的实施方案将二氧化碳消耗的蒸气物流734再循环并与合成气物流18混合，那么二氧化碳的总回收率可提高到约95％。
表1.
 
物流 18 82 干燥器单元708后的82 734 737 76
流率，MMscfd 75 14.2 15.6 3.9 1.6 64.7
压力，psia 380 18 700 447 135 375
温度℉ 100 100 95 55 55 97
组成(摩尔份数)
H2 0.7570 0.1199 0.1098 0.4384 0.0052 0.8777
CO2 0.1605 0.7925 0.8202 0.2938 0.9640 0.0297
CO 0.0249 0.0184 0.0172 0.0673 0.0041 0.0289
CH4 0.0539 0.0546 0.0525 0.1995 0.0267 0.0625
N2 0.0010 0.0003 0.0003 0.0011 0.0001 0.0012
H2O 0.0027 0.0143 0.0000 0.0000 0.0000 0.0000
物流 22 24 *746 *748 756
流率，MMscfd 50.2 14.4 5.1 5.1 10.2
压力，psia 370 20 176 330 2000
温度℉ 97 95 58 58 100
组成(摩尔份数)
H2 0.99996 0.4522 0 0 0
CO2 0 0.1333 0.9999 0.9999 0.9999
CO 0.68ppm 0.1294 0 0 0
CH4 0.05ppm 0.2799 0.0001 0.0001 0.0001
N2 0.00004 0.0052 0 0 0
H2O 0 0.0000 0 0 0
*从主换热器720的的热端排出之后。
[0071]虽然参照优选实施方案对本发明进行了描述，但本领域技术人员可以理解，在不脱离所附权利要求定义的本发明精神和范围的情况下可做出各种改变、增加和省略。

Claims (12)

1.从氢气设备中形成的合成气物流生产二氧化碳产物物流的方法，所述氢气设备具有合成气反应器、位于合成气反应器下游用以形成合成气物流的水煤气变换反应器、和用以产生从所述合成气物流回收的氢气产物的氢气变压吸附单元，所述方法包括：
通过在真空变压吸附系统中从所述合成气物流的至少一部分中分离二氧化碳，来从所述合成气物流的所述至少一部分中回收二氧化碳，从而产生氢气富集的合成气物流和粗二氧化碳物流，并通过低于环境温度蒸馏过程对所述粗二氧化碳物流进行纯化，从而产生蒸气形式的二氧化碳产物；以及
至少部分由所述氢气富集的物流形成氢气合成气进料物流，并将所述氢气合成气物流引入所述氢气变压吸附单元，从而产生所述氢气产物。
2.根据权利要求1所述的方法，其中所述低于环境温度蒸馏过程包括压缩并干燥所述粗二氧化碳物流，将所述粗二氧化碳物流冷却至低于所述环境温度，在汽提塔中对所述粗二氧化碳物流进行汽提，以从液塔底部产生液态二氧化碳产物并产生塔顶馏出物，在至少一个压力对液态二氧化碳产物物流进行膨胀以产生致冷，蒸发所述液体二氧化碳产物物流以产生至少一股二氧化碳产物物流作为所述二氧化碳产物。
3.根据权利要求2所述的方法，其中：
在具有经受了变温吸附过程的吸附剂的干燥单元中对所述粗二氧化碳物流进行干燥，在所述变温吸附过程中用热再生气体物流从所述吸附剂中解吸水分；
所述低于环境温度蒸馏过程包括进一步精炼由塔顶馏出物构成的塔顶馏出物物流，以产生二氧化碳富集的蒸气物流和二氧化碳消耗的蒸气物流；
所述二氧化碳富集的蒸气物流用作所述再生气体物流，且之后循环回在压缩所述粗二氧化碳物流中使用的压缩机；和
所述二氧化碳消耗的蒸气物流循环回并与所述合成气物流一起进料给所述真空变压吸附过程。
4.根据权利要求2所述的方法，其中：
在具有经受了变温吸附过程的吸附剂的干燥单元中对所述粗二氧化碳物流进行干燥，在所述变温吸附过程中用热再生气体物流从所述吸附剂中解吸水分；
所述低于环境温度蒸馏过程包括进一步精炼由塔顶馏出物构成的塔顶馏出物物流，以产生二氧化碳富集的蒸气物流和二氧化碳消耗的蒸气物流；
所述二氧化碳富集的蒸气物流用作所述再生气体物流，且之后循环回在压缩所述粗二氧化碳物流中使用的压缩机；
所述二氧化碳消耗的蒸气物流与所述氢气富集的合成气物流合并，以形成所述氢气合成气进料物流。
5.根据权利要求3或4所述的方法，还包括在所述压缩机之前或之后，从所述粗二氧化碳物流中催化去除氧气。
6.根据权利要求2所述的方法，其中：
所述低于环境温度蒸馏过程包括进一步精炼由塔顶馏出物构成的塔顶馏出物物流，以产生二氧化碳富集的蒸气物流和二氧化碳消耗的蒸气物流；
所述二氧化碳富集的蒸气物流循环回在压缩所述粗二氧化碳物流中使用的压缩机；以及
所述二氧化碳消耗的蒸气物流循环回并与所述合成气物流的至少一部分一起进料给所述真空变压吸附过程。
7.根据权利要求6的方法，其中：
将在所述真空变压吸附过程的上游的所述合成气物流的所述至少一部分在具有经过变温吸附过程的吸附剂的干燥单元中干燥，其中在所述变温吸附过程中使用热再生气体物流从所述吸附剂中解吸水分；以及
加热所述氢气富集的物流并用于形成所述热再生气体物流。
8.根据权利要求6所述的方法，其中：
所述合成气反应器是蒸汽甲烷重整器；以及
将在所述真空变压吸附过程的上游的所述合成气物流的所述至少一部分在具有经过变温吸附过程的吸附剂的干燥单元中干燥，其中在所述变温吸附过程中使用热再生气体物流从所述吸附剂中解吸水分；以及
所述进一步加热的再生气体物流由所述氢气变压吸附过程产生的尾气物流构成，之后所述尾气物流用作燃烧器燃料的一部分，该燃烧器位于所述蒸汽甲烷重整器的辐射换热段中。
9.根据权利要求6所述的方法，其中：
所述合成气反应器是蒸汽甲烷重整器；以及
将在所述真空变压吸附过程的上游的所述合成气物流的所述至少一部分在具有经过变温吸附过程的吸附剂的干燥单元中干燥，其中在所述变温吸附过程中使用热再生气体物流从所述吸附剂中解吸水分；以及
所述进一步加热的再生气体物流由所述含碳氢化合物的进料物流构成，之后该含碳氢化合物的进料物流在催化剂填充的反应管内反应，该反应管位于所述蒸汽甲烷重整器的辐射换热段中。
10.根据权利要求3或4所述的方法，其中：
在所述真空变压吸附过程之前从所述合成气物流的所述至少一部分中去除水分，并在所述低于环境温度蒸馏过程中从所述粗合成气物流中去除水分；以及
通过将所述合成气物流的所述至少一部分冷却以冷凝其中所含水分的至少一部分，并在分离罐中从所述合成气物流的所述至少一部分中去除所得冷凝物，以从所述合成气体物流的所述至少一部分中去除所述部分的水分。
11.根据权利要求1所述的方法，还包括压缩所述二氧化碳产物。
12.根据权利要求11所述的方法，还包括：
所述合成气物流的二氧化碳含量介于约12％到约25％之间；
所述粗二氧化碳物流具有约70％到约98％之间的二氧化碳含量，和介于0-5000ppm之间的氧气含量；
所述二氧化碳产物的纯度为约98-99.9999％的二氧化碳，和低于100ppm的氧气；
所述二氧化碳产物压缩至约1200psia到约2500psia之间的压力；以及
将所述至少一股二氧化碳物流引入强化采油过程，或者引入二氧化碳贮存点用于封存。
CNA2007800206680A 2006-04-03 2007-03-28 由合成气制备二氧化碳和氢气的方法 Pending CN101460233A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/395,137 2006-04-03
US11/395,137 US7871457B2 (en) 2006-04-03 2006-04-03 Carbon dioxide production method

Publications (1)

Publication Number Publication Date
CN101460233A true CN101460233A (zh) 2009-06-17

Family

ID=38432840

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2007800206680A Pending CN101460233A (zh) 2006-04-03 2007-03-28 由合成气制备二氧化碳和氢气的方法

Country Status (8)

Country Link
US (1) US7871457B2 (zh)
EP (1) EP2004307A1 (zh)
KR (1) KR20090015041A (zh)
CN (1) CN101460233A (zh)
BR (1) BRPI0709807A2 (zh)
CA (1) CA2647909C (zh)
MX (1) MX2008012826A (zh)
WO (1) WO2007123673A1 (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408111A (zh) * 2010-07-13 2012-04-11 气体产品与化学公司 酸性合成气物流的分离
CN102656112A (zh) * 2009-12-16 2012-09-05 鲁奇有限责任公司 用于操作重整炉的方法和重整设备
CN102667057A (zh) * 2009-10-19 2012-09-12 格雷特波因特能源公司 整合的强化采油方法
CN102659103A (zh) * 2012-04-15 2012-09-12 山东省舜天化工集团有限公司 一种尿素用co2原料气的制备方法
CN103537163A (zh) * 2012-07-09 2014-01-29 通用电气公司 用于气体处理的系统及方法
CN110877897A (zh) * 2018-09-06 2020-03-13 气体产品与化学公司 具有co调节的双产物h2和co制备
CN112638849A (zh) * 2018-09-04 2021-04-09 巴斯夫欧洲公司 在没有二氧化碳排放下由合成气制备甲醇的方法

Families Citing this family (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1020603C2 (nl) * 2002-05-15 2003-11-18 Tno Werkwijze voor het drogen van een product met behulp van een regeneratief adsorbens.
US7666251B2 (en) * 2006-04-03 2010-02-23 Praxair Technology, Inc. Carbon dioxide purification method
US7550030B2 (en) 2006-04-03 2009-06-23 Praxair Technology, Inc. Process and apparatus to recover high purity carbon dioxide
US7763100B2 (en) * 2006-07-06 2010-07-27 Praxair Technology, Inc. Vacuum pressure swing adsorption process and enhanced oxygen recovery
FR2904780B1 (fr) * 2006-08-10 2009-10-09 Air Liquide 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
US8080090B2 (en) * 2007-02-16 2011-12-20 Air Liquide Process & Construction, Inc. Process for feed gas cooling in reboiler during CO2 separation
US7766999B2 (en) * 2007-02-16 2010-08-03 Air Liquide Process & Construction, Inc. Process for vaporizing the product CO2 at two different pressures during CO2 separation
DE102007010875A1 (de) * 2007-03-06 2008-09-11 Linde Ag Verfahren und Vorrichtung zur Wasserstoffabtrennung aus Gasströmen mit Sauerstoffanteil
US7819932B2 (en) * 2008-04-10 2010-10-26 Carbon Blue-Energy, LLC Method and system for generating hydrogen-enriched fuel gas for emissions reduction and carbon dioxide for sequestration
US8084010B2 (en) * 2008-04-14 2011-12-27 Plasma Energy Technologies Inc. Coal/coke/heavy residual oil boiler with sulfur and carbon dioxide capture and recovery
GB0808385D0 (en) 2008-05-08 2008-06-18 Naneum Ltd A condensation apparatus
FR2933313B1 (fr) * 2008-07-03 2011-07-22 Air Liquide Traitement de gaz humide contenant des poussieres
US7909913B2 (en) * 2008-07-17 2011-03-22 Air Products And Chemicals, Inc. Gas purification by adsorption of hydrogen sulfide
US8535417B2 (en) * 2008-07-29 2013-09-17 Praxair Technology, Inc. Recovery of carbon dioxide from flue gas
US7927572B2 (en) * 2008-09-26 2011-04-19 Praxair Technology, Inc. Purifying carbon dioxide and producing acid
US8216344B2 (en) * 2008-09-26 2012-07-10 Praxair Technology, Inc. Purifying carbon dioxide using activated carbon
FR2939785B1 (fr) * 2008-12-11 2012-01-27 Air Liquide Production d'hydrogene a partir de gaz reforme et capture simultanee du co2 coproduit.
US8007761B2 (en) * 2008-12-24 2011-08-30 Praxair Technology, Inc. Carbon dioxide emission reduction method
JP4746111B2 (ja) * 2009-02-27 2011-08-10 三菱重工業株式会社 Ｃｏ２回収装置及びその方法
US8137435B2 (en) 2009-03-31 2012-03-20 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Carbon dioxide recovery from low concentration sources
US8303930B2 (en) * 2009-05-18 2012-11-06 American Air Liquide, Inc. Processes for the recovery of high purity hydrogen and high purity carbon dioxide
US8814961B2 (en) 2009-06-09 2014-08-26 Sundrop Fuels, Inc. Various methods and apparatuses for a radiant-heat driven chemical reactor
US8771387B2 (en) * 2009-06-09 2014-07-08 Sundrop Fuels, Inc. Systems and methods for solar-thermal gasification of biomass
US9663363B2 (en) 2009-06-09 2017-05-30 Sundrop Fuels, Inc. Various methods and apparatuses for multi-stage synthesis gas generation
FR2949553B1 (fr) * 2009-09-02 2013-01-11 Air Liquide Procede de production d'au moins un gaz pauvre en co2 et d'un ou plusieurs fluides riches en co2
KR101164546B1 (ko) 2009-10-07 2012-07-10 한국에너지기술연구원 고효율 수소 생산을 위한 다단 수성가스 분리막 반응장치
US8057773B2 (en) * 2009-12-28 2011-11-15 Institute Francais du Pétrole Reduction of greenhouse gas emission from petroleum refineries
CN102985195B (zh) 2010-06-08 2016-01-27 三照普燃料公司 用于超高热通量化学反应器的各种方法和装置
EP2590898B1 (en) 2010-07-09 2020-12-09 Arnold Keller Carbon dioxide capture and liquefaction
EP2609379B1 (en) * 2010-08-23 2018-10-03 Dresser-Rand Company Process for throttling a compressed gas for evaporative cooling
US8715394B2 (en) * 2010-11-24 2014-05-06 Lehigh University Autothermal cycle for CO2 capture
EP2476477B1 (en) * 2011-01-13 2021-03-17 General Electric Technology GmbH A method for drying a wet co2 rich gas stream from an oxy-combustion process
EP2665678A4 (en) * 2011-01-17 2018-04-04 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process and apparatus for production of ammonia synthesis gas and pure methane by cryogenic separation
US8808425B2 (en) * 2011-08-30 2014-08-19 Air Products And Chemicals, Inc. Process and apparatus for producing hydrogen and carbon monoxide
FR2988167B1 (fr) * 2012-03-13 2018-06-15 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede et appareil de separation d'un melange contenant du dioxyde de carbone par distillation
US9295961B2 (en) 2012-03-26 2016-03-29 Sundrop Fuels, Inc. Various methods and apparatuses for internally heated radiant tubes in a chemical reactor
US9416077B2 (en) 2012-09-14 2016-08-16 Sundrop Fuels, Inc. Renewable carbon content in methanol and other products from gasification of biomass
EP2724766A1 (en) * 2012-10-26 2014-04-30 Alstom Technology Ltd A method of treating a carbon dioxide rich flue gas and a flue gas treatment system
CN103361138B (zh) * 2013-07-24 2015-02-18 开封黄河空分集团有限公司 一种用提氢解析气制取液化天然气和合成氨原料气的方法
EP2845837A1 (en) * 2013-09-09 2015-03-11 Casale SA Process and plant for the production of ammonia make-up gas including production of a hydrogen gas by steam reforming
WO2016086141A1 (en) 2014-11-26 2016-06-02 Sundrop Fuels, Inc. Biomass to transportation fuels using a fischer-tropsch process
EP3216512A1 (en) 2016-03-08 2017-09-13 Casale SA A temperature-swing adsorption process
CN105664667A (zh) * 2016-03-11 2016-06-15 西安华江环保科技股份有限公司 一种lng深冷分离富氢尾气氢气回收装置及工艺
US11261390B2 (en) * 2018-09-10 2022-03-01 Korea Institute Of Science And Technology Apparatus and method of preparing synthetic fuel using natural gas
EP3733264A1 (en) 2019-05-02 2020-11-04 Casale Sa A pressure swing adsorption process for producing hydrogen and carbon dioxide
US11492255B2 (en) 2020-04-03 2022-11-08 Saudi Arabian Oil Company Steam methane reforming with steam regeneration
US11583824B2 (en) 2020-06-18 2023-02-21 Saudi Arabian Oil Company Hydrogen production with membrane reformer
US11999619B2 (en) 2020-06-18 2024-06-04 Saudi Arabian Oil Company Hydrogen production with membrane reactor
US11492254B2 (en) 2020-06-18 2022-11-08 Saudi Arabian Oil Company Hydrogen production with membrane reformer
KR20220043468A (ko) * 2020-09-29 2022-04-05 현대자동차주식회사 압력흡착시스템 및 방법
FR3118717A1 (fr) * 2021-01-14 2022-07-15 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé et appareil de séchage d’un débit riche en dioxyde de carbone
FR3119227B1 (fr) * 2021-01-27 2023-03-10 Air Liquide Procédé et appareil de séparation d’un débit riche en dioxyde de carbone par distillation pour produire du dioxyde de carbone liquide
US11807532B2 (en) * 2021-03-29 2023-11-07 Uop Llc Method of recovering a hydrogen enriched product and CO2 in a hydrogen production unit
US12036505B2 (en) 2021-03-29 2024-07-16 Uop Llc Three-product pressure swing adsorption system
US11772966B2 (en) 2021-03-29 2023-10-03 Uop Llc Integrated hydrogen production and bio-renewable conversion process
US11814287B2 (en) 2021-03-29 2023-11-14 Uop Llc Method of producing a hydrogen-enriched product and recovering CO2 in a hydrogen production process unit
EP4098609A1 (de) * 2021-05-31 2022-12-07 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren und anlage zum herstellen von reinwasserstoff durch dampfreformierung mit reduzierter kohlendioxid-emission
US11718575B2 (en) 2021-08-12 2023-08-08 Saudi Arabian Oil Company Methanol production via dry reforming and methanol synthesis in a vessel
US11787759B2 (en) 2021-08-12 2023-10-17 Saudi Arabian Oil Company Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel
US11578016B1 (en) 2021-08-12 2023-02-14 Saudi Arabian Oil Company Olefin production via dry reforming and olefin synthesis in a vessel
KR102526185B1 (ko) * 2021-09-29 2023-04-28 한국생산기술연구원 유동층 간접 열교환 방식의 메탄 열분해를 통한 수소 및 탄소 생산 시스템
WO2023054754A1 (ko) * 2021-09-29 2023-04-06 한국생산기술연구원 축열방식의 메탄 열분해를 통한 수소 및 탄소 생산 반응기 및 이를 포함하는 조합 반응기
CN114001011A (zh) * 2021-10-29 2022-02-01 重庆建峰化工股份有限公司 一种合成压缩机的真空建立方法
NO346934B1 (no) * 2021-12-08 2023-03-06 Hyper Energy Australia Pty Ltd Anordning for produksjon av hydrogen og co2 fra tilført hydrokarbon og vann
US11617981B1 (en) 2022-01-03 2023-04-04 Saudi Arabian Oil Company Method for capturing CO2 with assisted vapor compression

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4963339A (en) * 1988-05-04 1990-10-16 The Boc Group, Inc. Hydrogen and carbon dioxide coproduction
US5000925A (en) 1988-05-04 1991-03-19 The Boc Group, Inc. Hydrogen and carbon dioxide coproduction apparatus
US4952223A (en) * 1989-08-21 1990-08-28 The Boc Group, Inc. Method and apparatus of producing carbon dioxide in high yields from low concentration carbon dioxide feeds
CA2100811C (en) * 1992-08-19 1999-01-19 Akhilesh Kapoor Hydrogen and carbon monoxide production by partial oxidation of hydrocarbon feed
US6090312A (en) * 1996-01-31 2000-07-18 Ziaka; Zoe D. Reactor-membrane permeator process for hydrocarbon reforming and water gas-shift reactions
US6301927B1 (en) 1998-01-08 2001-10-16 Satish Reddy Autorefrigeration separation of carbon dioxide
CA2350574C (en) 1998-11-10 2004-08-17 Fluor Corporation Recovery of co2 and h2 from psa offgas in an h2 plant
US6224843B1 (en) * 1999-09-13 2001-05-01 Saudi Basic Industries Corporation Carbon dioxide purification in ethylene glycol plants
US6425938B1 (en) * 2000-11-01 2002-07-30 Air Products And Chemicals, Inc. Single bed pressure swing adsorption process
US6500241B2 (en) 2000-12-19 2002-12-31 Fluor Corporation Hydrogen and carbon dioxide coproduction
US6497852B2 (en) * 2000-12-22 2002-12-24 Shrikar Chakravarti Carbon dioxide recovery at high pressure
FR2872890A1 (fr) 2005-08-08 2006-01-13 Air Liquide Procede integre d'adsorption et de separation cryogenique pour la production de co2 et installation pour la mise en oeuvre du procede

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102667057A (zh) * 2009-10-19 2012-09-12 格雷特波因特能源公司 整合的强化采油方法
CN102656112A (zh) * 2009-12-16 2012-09-05 鲁奇有限责任公司 用于操作重整炉的方法和重整设备
CN102656112B (zh) * 2009-12-16 2014-08-27 鲁奇有限责任公司 用于操作重整炉的方法和重整设备
CN102408111A (zh) * 2010-07-13 2012-04-11 气体产品与化学公司 酸性合成气物流的分离
CN102408111B (zh) * 2010-07-13 2013-12-04 气体产品与化学公司 酸性合成气物流的分离
CN102659103A (zh) * 2012-04-15 2012-09-12 山东省舜天化工集团有限公司 一种尿素用co2原料气的制备方法
CN103537163A (zh) * 2012-07-09 2014-01-29 通用电气公司 用于气体处理的系统及方法
CN103537163B (zh) * 2012-07-09 2017-08-15 通用电气公司 用于气体处理的系统及方法
CN112638849A (zh) * 2018-09-04 2021-04-09 巴斯夫欧洲公司 在没有二氧化碳排放下由合成气制备甲醇的方法
CN112638849B (zh) * 2018-09-04 2023-11-24 巴斯夫欧洲公司 在没有二氧化碳排放下由合成气制备甲醇的方法
CN110877897A (zh) * 2018-09-06 2020-03-13 气体产品与化学公司 具有co调节的双产物h2和co制备
CN110877897B (zh) * 2018-09-06 2023-02-17 气体产品与化学公司 具有co调节的双产物h2和co制备

Also Published As

Publication number Publication date
EP2004307A1 (en) 2008-12-24
US20070232706A1 (en) 2007-10-04
US7871457B2 (en) 2011-01-18
WO2007123673A1 (en) 2007-11-01
CA2647909C (en) 2015-03-24
MX2008012826A (es) 2008-12-01
BRPI0709807A2 (pt) 2011-07-26
KR20090015041A (ko) 2009-02-11
CA2647909A1 (en) 2007-11-01

Similar Documents

Publication Publication Date Title
CN101460233A (zh) 由合成气制备二氧化碳和氢气的方法
JP7297775B2 (ja) 水素および二酸化炭素の生成および分離のためのシステムおよび方法
US7632476B2 (en) Method of recovering carbon dioxide from a synthesis gas stream
EP2401052B1 (en) Improved method for the capture and disposal of carbon dioxide in an energy conversion process
US8535417B2 (en) Recovery of carbon dioxide from flue gas
EP2590898B1 (en) Carbon dioxide capture and liquefaction
CN101468790A (zh) 借助于分压摆动循环化学反应分离二氧化碳
JPS6041004B2 (ja) アンモニア合成ガス及びアンモニアの製造法
CN101712897A (zh) 一种补碳返氢工艺实现焦炉煤气甲烷化合成天然气的方法
JP2024515490A (ja) 水素製造プロセスユニットにおける水素富化生成物の製造及びｃｏ２の回収方法
GB2457970A (en) Energy conversion process for sequestration of carbon dioxide
PL217545B1 (pl) Sposób absorpcyjnego usuwania ditlenku węgla z przemysłowych mieszanin gazowych
JP2000233918A (ja) Ｃｏの製造方法
CN111637685A (zh) 一种带氩气循环和氢气循环的单塔低温精馏回收氩气系统及方法
DK2401052T3 (en) Improved method for the collection and disposal of carbon dioxide in a process for the energy conversion
CN115451648A (zh) 使二氧化碳在蒸馏塔外固化的用于分离和液化甲烷和二氧化碳的方法
CN115636393A (zh) 一种低质煤气的转化系统和方法
CN115451650A (zh) 包括预分离和二氧化碳的外部固化的生物气低温纯化
JP2011073909A (ja) Ｃｏ２回収方法及びｃｏ２回収装置

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20090617