JP5933120B2 - 空気の精製 - Google Patents
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- JP5933120B2 JP5933120B2 JP2015514363A JP2015514363A JP5933120B2 JP 5933120 B2 JP5933120 B2 JP 5933120B2 JP 2015514363 A JP2015514363 A JP 2015514363A JP 2015514363 A JP2015514363 A JP 2015514363A JP 5933120 B2 JP5933120 B2 JP 5933120B2
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- 238000004887 air purification Methods 0.000 title 1
- 239000003463 adsorbent Substances 0.000 claims description 177
- 230000008929 regeneration Effects 0.000 claims description 99
- 238000011069 regeneration method Methods 0.000 claims description 99
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 66
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 60
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 51
- 238000001179 sorption measurement Methods 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229910001868 water Inorganic materials 0.000 claims description 41
- 239000010457 zeolite Substances 0.000 claims description 40
- 229910021536 Zeolite Inorganic materials 0.000 claims description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 37
- 239000001569 carbon dioxide Substances 0.000 claims description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 35
- 239000001272 nitrous oxide Substances 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 2
- 239000003570 air Substances 0.000 description 95
- 239000007789 gas Substances 0.000 description 81
- 239000010410 layer Substances 0.000 description 23
- 229930195733 hydrocarbon Natural products 0.000 description 21
- 150000002430 hydrocarbons Chemical class 0.000 description 21
- 238000011144 upstream manufacturing Methods 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012080 ambient air Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 ethylene, propylene, acetylene Chemical group 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 101100261173 Arabidopsis thaliana TPS7 gene Proteins 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- GLQOALGKMKUSBF-UHFFFAOYSA-N [amino(diphenyl)silyl]benzene Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(N)C1=CC=CC=C1 GLQOALGKMKUSBF-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 210000004534 cecum Anatomy 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000003584 silencer Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- F25J3/04—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 for air
- F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
- F25J3/04157—Afterstage cooling and so-called "pre-cooling" of the feed air upstream the air purification unit and main heat exchange line
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
- F25J3/04—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 for air
- F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
- F25J3/04163—Hot end purification of the feed air
- F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
- F25J3/04—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 for air
- F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
- F25J3/04163—Hot end purification of the feed air
- F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
- F25J3/04181—Regenerating the adsorbents
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- 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
- B01D2253/104—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
- B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/402—Dinitrogen oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D2259/40077—Direction of flow
- B01D2259/40081—Counter-current
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/414—Further details for adsorption processes and devices using different types of adsorbents
- B01D2259/4141—Further details for adsorption processes and devices using different types of adsorbents within a single bed
- B01D2259/4145—Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged in series
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
- F25J2205/64—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 by pressure-swing adsorption [PSA] at the hot end
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
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- F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation gas
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- 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
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Of Gases By Adsorption (AREA)
- Separation By Low-Temperature Treatments (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Drying Of Gases (AREA)
Description
a)前記供給空気流を、供給方向において或るフィード温度及び或るフィード圧力で、30℃で測定されるCO2/N2Oのヘンリーの法則の選択性が少なくとも12.5である第1吸着剤、続いて30℃で測定されるCO2の吸着についてのヘンリーの法則の定数が1020mmol/g/気圧よりも小さく、かつ30℃で測定されるCO2/N2Oのヘンリーの法則の選択性が最大5である第2吸着剤に通す工程、
b)第1の期間の後、前記供給空気流を前記第1及び第2吸着剤に通すことを停止する工程、
c)前記第1及び第2吸着剤と接触しているガスを前記フィード圧力よりも低い第2の圧力まで減圧する工程、
d)加熱した再生用ガスを、少なくとも前記第2吸着剤に、前記第2の圧力及び20℃〜80℃の温度で第2の期間、前記供給方向と反対の方向に送り、続いて第2の再生用ガスを、前記第1及び第2吸着剤に、前記第2の圧力及び前記加熱した再生用ガスの温度よりも低い温度で第3の期間、前記供給方向と反対の方向に送る工程、
e)再生用ガスを前記第1及び第2吸着剤に送ることを停止する工程、
f)前記第1及び第2吸着剤と接触しているガスを前記フィード圧力まで再加圧する工程、並びに
g)工程a)〜f)を繰り返す工程
を含み、前記第2吸着剤が、前記第1及び第2吸着剤の合計体積の25〜40体積%を占め、かつ前記加熱した再生用ガスの温度が、前記フィード温度と前記第2の再生用ガスの温度のうちいずれか高い方よりも10〜60℃高い方法を提供する。
単一の直径2.5cm(1インチ)、長さ183cm(6フィート)のカラムを使用して、水で飽和させ、400ppmのCO2及び3ppmのN2Oを含有する空気を、50ppbのCO2の時間平均CO2破過レベルまで精製(CO2除去99.988%)するための圧力スイング吸着プロセスの性能を測定した。パージガスを、ボンベ中の純粋N2によってフィード温度で供給した。サイクルの工程は、供給、減圧、パージ、及び再加圧であった。様々な床敷設スキームを検討し、供給空気流からのN2O除去の割合を、PSA流出物中の50ppbのCO2の時間平均破過レベルで求めた。このPSA操作条件を下記の表3に示す。
CO2及びN2Oの破過試験を、例1で述べたカラムで実施した。試験は、供給空気中に400ppmのCO2及び0.3ppmのN2Oを含有する飽和空気を用いて7バール(700kPa)のフィード圧力及び22℃のフィード温度で行った。床に、床の供給(上流)端には活性アルミナ(Alcan AA−300)を装填し、また床の生成(下流)端には13Xゼオライト(Zeochem Z10−02)を装填した。カラム中のアルミナ対13Xの比を変えて、50ppbのCO2時間平均破過レベルにおけるN2O除去のレベルに及ぼす13X床長の影響を求めた。13Xが占める床の割合は100%(すなわちアルミナなし)、80%、及び60%であった。実験の前にカラムを、流通N2中で200℃において8時間再生した。これらの実験における供給時間は、8〜10時間の範囲にわたった。これらの再生温度及び供給時間は、TSAシステムの代表的なものである。
13Xを使用するTSA法において吸着床からのN2Oの破過を防止するために実行できる方法は、13X層が周囲のすべてのN2Oを吸着することができるようにCO2の破過をはるかに下回る吸着系を稼働させることである。
空気からの微量不純物の除去に関して二床のサイクル作動実験を直径0.2mの容器中で行った。全吸着床の長さは2mであった。供給条件で供給空気を水で飽和させ、また380ppmのCO2及び0.3ppmのN2Oを含ませた。すべてのケースにおいて吸着床の供給端は活性アルミナ(Alcan AA−300)を含有した。存在する場合、床の生成端は13Xゼオライト(Zeochem Z10−02、Si/Al=1.15)を含有した。試験された循環過程を下記の表6に示す。
ゼオライトの種類の影響を例4で述べた実験ユニットで調べた。13Xゼオライトの代わりにCaXゼオライト(Ceca G586)及び5Aゼオライト(UOP KEG410)が使用された。CaXゼオライトは、86%Ca交換Xゼオライトであり、また5Aゼオライトは、74%Ca交換Aゼオライトである。活性アルミナ(Alcan AA−300)75%及びゼオライト25%の床充填との比較実験を行った。
例4で述べた実験ユニットを、下記の表8に示した実験条件で使用した。これらの2つの実験において体積アルミナ/13Xの敷設をアルミナ75%/ゼオライト25%に保ち、使用された13Xゼオライトは両ケースにおいてZeochem Z10−02であった。一方のケースでは非含浸アルミナ(Alcan AA−300)を使用し、他方では含浸アルミナ(5重量%のK2CO3を含むAlcan AA−320)を使用した。これらの試験の間の時間平均CO2破過レベルは20ppbであった。
様々な吸着剤上でのCO2及びN2Oの吸着を、200℃での最初の熱再生後に標準的な体積吸着ユニットにおいて測定した。1回の吸着及び真空再生のサイクル後の直線に低圧吸着データの線形の部分を合わせることによって、対応するヘンリーの法則の定数を求めた。続いてそれら2つの値の比によってヘンリーの法則の選択性を求めた。表9は、様々な吸着剤の30℃におけるCO2/N2O選択性を示す。
例4で述べた装置を、表10に示した条件下で使用した。
例6で述べた方法を使用し、Alcan AA−320(75体積%)及びZeochem Z10−02(25体積%)を含有する床について吸着床を出る温度を測定した。可動している時間の間に床を出る最高温度は62℃であった。床を出る平均温度は54℃であった。したがって床を出る最高温度は、供給温度より12℃高かった。この低い温度上昇は、50℃などの高い供給温度が使用される場合、深冷蒸留における下流部門の機械的問題を防ぐために特に重要である。アルミナは再加圧の間に有意な量の酸素及び窒素を吸着しないので、この低温の増大が、この方法の低再生温度及び吸着床中に存在する高比率のアルミナによって生じたものと本発明者等は見なしている。
Claims (12)
- 深冷蒸留の前に供給空気流中の水、二酸化炭素、及び亜酸化窒素のレベルを低減するための方法であって、
a)前記供給空気流を、供給方向において或るフィード温度及び或るフィード圧力で、アルミナ又は含浸アルミナから選択される第1吸着剤、続いて30℃で測定されるCO2の吸着についてのヘンリーの法則の定数が1020mmol/g/気圧よりも小さく、かつ30℃で測定されるCO2/N2Oのヘンリーの法則の選択性が最大5である第2吸着剤に通す工程、
b)第1の期間の後、前記供給空気流を前記第1及び第2吸着剤に通すことを停止する工程、
c)前記第1及び第2吸着剤と接触しているガスを前記フィード圧力よりも低い第2の圧力まで減圧する工程、
d)加熱した再生用ガスを、少なくとも前記第2吸着剤に、前記第2の圧力及び20℃〜80℃の温度で第2の期間、前記供給方向と反対の方向に送り、続いて再生用ガスを、前記第1及び第2吸着剤に、前記第2の圧力及び前記加熱した再生用ガスの温度よりも低い第2の温度で第3の期間、前記供給方向と反対の方向に送る工程、
e)再生用ガスを前記第1及び第2吸着剤に送ることを停止する工程、
f)前記第1及び第2吸着剤と接触しているガスを前記フィード圧力まで再加圧する工程、並びに
g)工程a)〜f)を繰り返す工程
を含み、前記第2吸着剤が、前記第1及び第2吸着剤の合計体積の25〜40体積%を占め、前記加熱した再生用ガスの温度が、前記フィード温度と前記再生用ガスの第2の温度のうちいずれか高い方よりも10〜60℃高く、前記第1の期間が30〜60分である、方法。 - 前記第2の期間が2〜30分である、請求項1に記載の方法。
- 前記加熱した再生用ガスの温度が30〜70℃である、請求項1又は2に記載の方法。
- 前記第3の期間が10〜40分である、請求項1〜3のいずれか1項に記載の方法。
- 前記再生用ガスの第2の温度が前記フィード温度よりも最大で5℃高い、請求項1〜4のいずれか1項に記載の方法。
- 前記第2吸着剤が、前記第1及び第2吸着剤によって占められる合計体積の28〜35体積%を占める、請求項1〜5のいずれか1項に記載の方法。
- 前記第2吸着剤が、1.15以上のSi/Al比を有するNaXゼオライト、及び5Aゼオライトから選択される、請求項1〜6のいずれか1項に記載の方法。
- 前記第2吸着剤の下流の亜酸化窒素レベルが、前記供給空気中の初期レベルの18%以下である、請求項1〜7のいずれか1項に記載の方法。
- [工程d)の間に供給される加熱された再生用ガス及び第2の温度の再生用ガス]/[工程a)の間に供給される供給空気]のモル比が1未満である、請求項1〜8のいずれか1項に記載の方法。
- 前記第2の圧力が、0.5バール(50kPa)〜2バール(200kPa)である、請求項1〜9のいずれか1項に記載の方法。
- 前記フィード圧力が、2バール(200kPa)〜50バール(5000kPa)である、請求項1〜10のいずれか1項に記載の方法。
- 吸着床中に、
アルミナ又は含浸アルミナから選択される第1吸着剤の層と、
30℃で測定されるCO2の吸着についてのヘンリーの法則の定数が1020mmol/g/気圧よりも小さく、かつ30℃で測定されるCO2/N2Oのヘンリーの法則の選択性が最大5である第2吸着剤の層
とを含み、
前記第2吸着剤が前記第1及び第2吸着剤の合計体積の25〜40体積%を占める、
装置の、
プロセス中の、フィード圧力で供給空気流中の水、二酸化炭素、及び亜酸化窒素のレベルを低減させるための、
使用であって、
少なくとも前記第2吸着剤が、加熱した再生用ガスを前記フィード圧力よりも低い第2の圧力で通すことによって再生され、
前記第1吸着剤の少なくとも一部が、前記第2の圧力でかつ前記加熱した再生用ガスの温度よりも低い第2の温度を有する再生用ガスを通すことによって再生され、
前記加熱した再生用ガスが20℃〜80℃であり、かつ前記供給空気流の温度と前記再生用ガスの第2の温度のうちいずれか高い方よりも10〜60℃高い温度を有する、
使用。
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