CN111362229A - Method for preparing hydrogen for fuel cell from yellow phosphorus tail gas - Google Patents
Method for preparing hydrogen for fuel cell from yellow phosphorus tail gas Download PDFInfo
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- CN111362229A CN111362229A CN202010333204.2A CN202010333204A CN111362229A CN 111362229 A CN111362229 A CN 111362229A CN 202010333204 A CN202010333204 A CN 202010333204A CN 111362229 A CN111362229 A CN 111362229A
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- hydrogen
- unit
- yellow phosphorus
- conversion
- tail gas
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- 239000007789 gas Substances 0.000 title claims abstract description 131
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000001257 hydrogen Substances 0.000 title claims abstract description 105
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 103
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000000446 fuel Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims abstract description 119
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000746 purification Methods 0.000 claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003568 thioethers Chemical class 0.000 claims abstract 3
- 238000010521 absorption reaction Methods 0.000 claims description 43
- 230000008929 regeneration Effects 0.000 claims description 41
- 238000011069 regeneration method Methods 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 31
- 239000003463 adsorbent Substances 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000012629 purifying agent Substances 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 43
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 42
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 22
- 239000012535 impurity Substances 0.000 abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 13
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000002440 industrial waste Substances 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 13
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 229910052785 arsenic Inorganic materials 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 8
- 150000004763 sulfides Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- -1 hydrogen Chemical class 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LQEQXNYQQIBNEM-UHFFFAOYSA-N ethynylphosphane Chemical compound PC#C LQEQXNYQQIBNEM-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
-
- 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
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- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0253—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
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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
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
- B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
- B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B2203/0415—Purification by absorption in liquids
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- 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
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- 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
- C01B2203/0435—Catalytic purification
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- 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
- C01B2203/0435—Catalytic purification
- C01B2203/044—Selective oxidation of carbon monoxide
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- 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
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- 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
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the field of hydrogen extraction, and particularly relates to a method for preparing hydrogen from industrial waste gas, which is characterized by comprising the following steps: yellow phosphorus tail gasRemoving hydrogen sulfide and part of organic sulfides by a PDS unit, removing phosphine, arsine, hydrogen sulfide and organic sulfides by a conversion adsorption unit, reacting carbon monoxide in the yellow phosphorus tail gas with water vapor by a conversion unit under the action of a catalyst to generate hydrogen and carbon dioxide, PSA/H2The hydrogen is obtained by the pressure swing adsorption hydrogen purification unit, and oxygen and trace hydrogen sulfide in the hydrogen are removed by the hydrogen through the catalytic purification unit, so that the oxygen content in the obtained hydrogen is lower than 5ppm, the sulfide content is lower than 0.004ppm, the carbon dioxide content is lower than 2ppm, the water content is lower than 5ppm, the nitrogen content is lower than 100ppm, the hydrogen content and the impurity content reach the GB/T37244-2018 standard, and the requirements of the hydrogen for the fuel cell are met.
Description
Technical Field
The invention belongs to the technical field of hydrogen extraction, and particularly relates to a method for preparing hydrogen for a fuel cell from yellow phosphorus tail gas.
Background
The yellow phosphorus tail gas is the tail gas of a boiler for producing yellow phosphorus, is caused by incomplete combustion and pollutes the atmosphere. The yellow phosphorus tail gas contains 80-90% of carbon monoxide, 5-10% of hydrogen, sulfur, phosphorus, arsenic and other impurities. China is a big yellow phosphorus production country, the production scale is over 60 million tons, and each ton of yellow phosphorus generates 2500-3000 Nm3 yellow phosphorus tail gas. At present, in the treatment of the yellow phosphorus tail gas, a mode of air-release combustion or low-quality fuel is mostly adopted, and a small amount of carbon monoxide obtained by purifying the yellow phosphorus tail gas is used as a raw material of formic acid and methanol. The amount of the yellow phosphorus tail gas of the conventional yellow phosphorus plant is thousands of cubic meters to tens of thousands of cubic meters per hour, and the economic scale of the production of chemical products such as methanol and the like cannot be reached, so the application of the yellow phosphorus tail gas is limited, and the waste of carbon monoxide and hydrogen resources in the yellow phosphorus tail gas is also caused.
Hydrogen is an important resource in novel energy and petrochemical industry and coal chemical industry, and is mainly obtained by separating coal, petroleum and natural gas serving as raw materials through a chemical process at present.
A hydrogen fuel cell is a power generation device that directly converts chemical energy of hydrogen and oxygen into electrical energy. The hydrogen used by the hydrogen fuel cell can be used only when the purity of the hydrogen meets a certain standard, otherwise, the content of impurities such as sulfur, carbon, ammonia and the like in the hydrogen has serious influence on the service life of a proton exchange membrane and a catalyst of the fuel cell, and the cell has the problems of attenuation and the like. The hydrogen concentration is required to be more than 99.99%, preferably 99.9999%, and the CO concentration is required to be less than 50 ppm.
The Chinese patent CN201510585328.9 specification describes a comprehensive utilization method of yellow phosphorus tail gas, which is characterized in that the yellow phosphorus tail gas is washed by water and alkali, then is subjected to desulfurization, phosphorus, arsenic, fluorine, chlorine, HCN, carbonyl metal and deoxidation deep purification to remove H2S, COS, CS2, PH3, AsH3, HF, HCN, HCl, carbonyl metal and O2 in the yellow phosphorus tail gas, then a part of the yellow phosphorus tail gas after deep purification is subjected to pressure swing adsorption to separate CO, and the other part of the yellow phosphorus tail gas is subjected to conversion to prepare high-concentration H2, wherein the volume ratio of the yellow phosphorus tail gas for pressure swing adsorption to separate CO and the yellow phosphorus tail gas for conversion synthesis of H2 is 1: 1-1: 3. The prepared pure CO and pure H2 can be used as raw material gas for producing glycol. The method is based on the characteristic that the components of the yellow phosphorus tail gas are complex, and the yellow phosphorus tail gas is utilized, so that the environmental pollution is reduced, and the cyclic economic utilization of resources is realized. However, hydrogen gas does not meet the required standard of the hydrogen fuel cell, and has influence on the use of the hydrogen fuel cell.
The yellow phosphorus tail gas contains a large amount of carbon monoxide and also contains high-content impurities such as hydrogen sulfide, phosphine, arsine and the like, and in a common purification process, the high-content hydrogen sulfide in the yellow phosphorus tail gas can influence the removal of the impurities such as the phosphine, the arsine and the like. It is required at present how to remove carbon monoxide and remove high content of impurities such as hydrogen sulfide, phosphine, arsine and the like in yellow phosphorus tail gas and deeply remove trace hydrogen sulfide in hydrogen to make hydrogen so as to achieve proton membrane fuel cell hydrogen.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing hydrogen for a fuel cell from yellow phosphorus tail gas, which directly obtains hydrogen meeting the standard of the hydrogen fuel cell from industrial exhaust gas such as the yellow phosphorus tail gas and the like, overcomes the bottleneck problem that the prior art for preparing the hydrogen needs to consume primary energy raw materials such as coal, petroleum, natural gas and the like, and enriches the source of the hydrogen for the fuel cell; and the utilization of the yellow phosphorus tail gas is improved, the waste and the environmental pollution are reduced, and the comprehensive utilization efficiency of resources is improved.
The invention solves the technical problem and provides a method for preparing hydrogen for a fuel cell from yellow phosphorus tail gas, which is characterized by comprising the following steps: the yellow phosphorus tail gas sequentially passes through a PDS unit, a conversion adsorption unit, a conversion unit and a PSA/H unit2And a pressure swing adsorption hydrogen purification unit and a catalytic purification unit.
The method has a definite sequence for purifying impurities, and the yellow phosphorus tail gas enters the PDS desulfurization unit after being pressurized. The yellow phosphorus tail gas contains a large amount of CO and also contains high-content impurities such as hydrogen sulfide, phosphine, arsine and the like, and the hydrogen sulfide, the phosphine, the arsine and the CO are removed2The order and method of impurities such as CO are critical to obtaining hydrogen gas for hydrogen fuel cells.
The method specifically comprises the following steps:
(1) removing hydrogen sulfide and part of organic sulfides from the yellow phosphorus tail gas through a PDS unit;
hydrogen sulfide in the yellow phosphorus tail gas is removed to 0.1-10 ppm through the PDS unit, and the influence of high-content hydrogen sulfide on a subsequent purification unit is avoided.
(2) Removing phosphine, arsine, hydrogen sulfide and organic sulfide through a conversion adsorption unit;
and (2) enabling the yellow phosphorus tail gas without hydrogen sulfide to enter a conversion adsorption unit, enabling phosphine, arsine and residual hydrogen sulfide to be in contact with an active carbon conversion adsorbent containing metal oxides in the conversion adsorption unit, oxidizing the phosphine into elemental phosphorus or phosphorus oxides, oxidizing the arsine into arsenic or arsenic oxides, oxidizing the hydrogen sulfide into elemental sulfur or sulfur oxides, and adsorbing the elemental sulfur or sulfur oxides on the conversion adsorbent, wherein the conversion adsorbent has dual functions of catalytic oxidation and adsorption.
(3) The CO in the yellow phosphorus tail gas reacts with the water vapor to generate H under the action of a shift catalyst through a shift unit (water vapor shift)2And CO2；
(4) Via PSA/H2Pressure swing adsorption hydrogen purification unit for removing N in hydrogen2Methane and trace amountsCO and sulfides and phosphides of (ii);
(5) removing H by a catalytic purification unit by using a catalyst of metal palladium and platinum highly dispersed on the surface of a carrier2And (5) neutralizing oxygen and trace hydrogen sulfide to obtain the catalyst.
In order to meet the requirement that the hydrogen sulfide content of the hydrogen for the hydrogen fuel cell is lower than 0.004ppm, pure hydrogen enters a catalytic purification unit, and oxygen and trace hydrogen sulfide in the hydrogen are removed in the catalytic purification unit by using a catalyst of metal palladium or platinum highly dispersed on the surface of a carrier, so that the oxygen content in the obtained hydrogen is lower than 5ppm, and the hydrogen sulfide content is lower than 0.004 ppm.
In an optimized scheme, the PSA/H2PSA/R-CO is also arranged between the pressure swing adsorption hydrogen purification unit and the transformation unit2And a pressure swing adsorption carbon dioxide removal unit. PSA/H2PSA/R-CO is also arranged in front of the pressure swing adsorption hydrogen purification unit2Pressure swing adsorption carbon dioxide removal unit for PSA/H reduction2Pressure swing adsorption of the load of the hydrogen purification unit.
Increase of PSA/R-CO2The pressure swing adsorption removes the carbon dioxide unit, divide the pressure swing adsorption purification hydrogen unit into 2 sections of pressure swing adsorption, wherein the first section is PSA/R-CO2The (pressure swing adsorption decarbonization) unit removes carbon dioxide in the conversion gas, and the second stage is PSA/H2The pressure swing adsorption hydrogen purification unit removes nitrogen, methane and trace carbon monoxide, sulfide and phosphide in the hydrogen to obtain the hydrogen with the content of 99.9-99.99%. In a further optimization scheme, the yellow phosphorus tail gas is low-quality fuel or yellow phosphorus tail gas discharged by burning of an emptying torch, and the yellow phosphorus tail gas discharged by burning of the emptying torch is extracted from the bottom of the emptying torch of a yellow phosphorus device by a water ring vacuum pump to obtain the yellow phosphorus tail gas.
In a further optimization scheme, the PSA purification hydrogen unit is connected with the conversion adsorption unit, the conversion adsorption unit is connected with the cooler or the gas-liquid separator, desorbed gas of the PSA purification hydrogen unit returns to the conversion adsorption unit to serve as regenerated gas of the conversion adsorption unit, the conversion adsorption unit is connected with the cooler and the gas-liquid separator, and regenerated waste gas is sent out after being cooled and separated from gas-liquid; the units are connected by pipes.
The PDS unit comprises an absorption tower and an oxidation regeneration tower, wherein the absorption tower and the oxidation regeneration tower are connected in series; and absorption liquid is arranged in the absorption tower, flows through the absorption tower from top to bottom, and enters the oxidation regeneration tower after absorbing the sulfides.
The absorption liquid is an aqueous solution which takes sodium carbonate as an alkali source and is also added with a PDS catalyst and an auxiliary agent.
In the absorption tower, the yellow phosphorus tail gas passes through the absorption tower filled with filler from bottom to top, absorption liquid containing PDS catalyst flows through the absorption tower from top to bottom, the yellow phosphorus tail gas is contacted with the absorption liquid, and hydrogen sulfide and part of organic sulfur compounds in the yellow phosphorus tail gas are absorbed by the absorption liquid. The absorption process can be represented by the following chemical reaction:
H2s (gas) ═ H2S (liquid)
H2S (liquid) + Na2CO3＝NaHS+NaHCO3
NaHS+(X-1)S+NaHCO3＝Na 2SX+CO2+H2O，
Removing part of organic sulfur:
RSH+Na2CO3＝RSNa+NaHCO3
COS+2Na2CO3+H2O＝NaCO2S+2NaHCO3
CS2+2Na2CO3+H2O＝Na2COS2+2NaHCO3。
the absorption liquid after absorbing the sulfide is called rich liquid, the rich liquid enters an oxidation regeneration tower, air is blown into the rich liquid through bubbling gas in the oxidation regeneration tower, the sulfide absorbed in the rich liquid is oxidized into elemental sulfur by oxygen in the air under the action of a PDS catalyst, the elemental sulfur is separated from the solution through a filter, the sulfur is obtained through recovery, and meanwhile, the absorption liquid is regenerated.
Oxidative regeneration process
2NaHS+O2＝2NaOH+2S
2Na2SX+O2+2H2O＝4NaOH+2SX
4RSNa+O2+2H2O+2RSSR+4NaOH
2NaOH+CO2＝Na2CO3+H2O
Na 2COS2+O2＝Na2CO3+2S
The PDS catalyst is a binuclear cobalt phthalocyanine compound catalyst, takes sodium carbonate as an alkali source in desulfurization reaction, and reacts H under the aerobic condition2The compound generated by S and sodium carbonate is catalyzed and oxidized into elemental sulfur, and the sodium carbonate solution can be recycled.
After adsorption and regeneration are carried out on an adsorption tower in the conversion adsorption unit, reducing the temperature of the adsorption tower to be below 80 ℃ by using nitrogen or carbon dioxide gas, and preparing for next adsorption and purification; wherein the adsorption temperature is 10-80 ℃, the regeneration temperature is 120-200 ℃, and the regeneration is reverse regeneration of superheated steam.
The conversion adsorption unit comprises at least 2 conversion adsorbers, program control valves and pipelines, conversion adsorbents are arranged in the conversion adsorbers, at least one conversion adsorber is in an adsorption step, the yellow phosphorus tail gas enters the conversion adsorber in the adsorption step from bottom to top, phosphine in the yellow phosphorus tail gas is contacted with the conversion adsorbents and oxidized into phosphorus or oxides of phosphorus and phosphorus are adsorbed on the conversion adsorbents, arsine in the yellow phosphorus tail gas is contacted with the conversion adsorbents and oxidized into arsenic or oxides of arsenic are adsorbed on the conversion adsorbents, hydrogen sulfide in the yellow phosphorus tail gas is contacted with the conversion adsorbents and oxidized into sulfur or oxides of sulfur and sulfur are adsorbed on the conversion adsorbents, and other adsorbers are in a regeneration step. In the regeneration step, firstly, superheated steam with the temperature of 120-200 ℃ is introduced into the adsorber from top to bottom, sulfur and sulfide, phosphorus and sulfide, arsenic and arsenide adsorbed on the conversion adsorbent are desorbed out of the adsorber, the conversion adsorbent is regenerated to obtain catalytic conversion and adsorption activity again, and then, gases such as nitrogen or carbon dioxide are introduced to reduce the temperature of the adsorber to 30-80 ℃.
The conversion adsorbent is activated carbon with a metal oxide-containing surface and rich micro-and mesoporous structures, and the specific surface area of the conversion adsorbent is 600-1500 m2(ii)/g, the metal oxide content is greater than 3g/100 g; the metal oxide is calcium,A magnesium metal oxide.
The catalytic purifying agent used in the catalytic purifying unit is active alumina or active carbon loaded with 0.02-2% of metal palladium or 0.01-0.2 of metal platinum, and aims to remove trace oxygen in hydrogen to below 1ppm and remove trace hydrogen sulfide in hydrogen to below 4 ppb.
And a compression unit is arranged between the PDS unit and the conversion adsorption unit and is a compressor, and the primarily purified yellow phosphorus tail gas is pressurized to 1.0-3.0 Mpa.
The hydrogen content of the pure hydrogen gas is 99.9-99.999%, the hydrogen gas has the oxygen content of less than 5ppm, the sulfide content of less than 4ppb, the carbon dioxide content of less than 2ppm, the water content of less than 5ppm, the nitrogen content of less than 100ppm and the impurity content of GB/T37244-2018, meets the requirements of the hydrogen for the fuel cell and the hydrogen for the fuel cell.
Drawings
The invention will be described in further detail with reference to the following drawings and detailed description:
FIG. 1 is a schematic view of the process of the present invention
FIGS. 2 and 3 are schematic views of the structure of the apparatus of the present invention
Wherein the specific labels in the figures are:
1. the system comprises a water ring supercharger, a PDS desulfurization unit, a conversion adsorption unit, a compressor, a steam conversion unit, a PSA purification hydrogen unit, a catalytic purification unit, a PSA decarburization unit, a hydrogen purification unit
Detailed Description
The invention will be further described with reference to specific embodiments using conventional equipment and instruments, wherein the equipment such as the water ring booster, the compressor, the vacuum pump, the vapor conversion unit, etc. are conventional general equipment in the art, and are commercially available, and the steps are performed according to the corresponding requirements of the equipment:
example 1
The method for preparing hydrogen for fuel cells from yellow phosphorus tail gas comprises the steps of sequentially passing the yellow phosphorus tail gas through a PDS unit, a conversion adsorption unit, a transformation unit, a pressure swing adsorption decarbonization unit, a PSA/H2 pressure swing adsorption hydrogen purification unit and a catalytic purification unit.
The method comprises the following steps:
(1) removing hydrogen sulfide and part of organic sulfides from the yellow phosphorus tail gas through a PDS unit;
the yellow phosphorus tail gas is low-quality fuel or yellow phosphorus tail gas discharged by the combustion of an emptying torch.
The PDS unit comprises an absorption tower and an oxidation regeneration tower, wherein the absorption tower and the oxidation regeneration tower are connected in series; absorbing liquid in the absorption tower is aqueous solution taking sodium carbonate as an alkali source, and PDS catalyst and other auxiliaries are added, yellow phosphorus tail gas in the absorption tower passes through the absorption tower filled with filler from bottom to top, and the absorbing liquid containing the PDS catalyst flows through the absorption tower from top to bottom; and (3) the absorption liquid after absorbing the sulfide enters an oxidation regeneration tower, air is blown into the absorption liquid through bubbling gas, the sulfide is oxidized into elemental sulfur by oxygen in the air, the elemental sulfur is separated from the solution through a filter, and the absorption liquid is regenerated while the sulfur is recovered. The PDS catalyst is a binuclear cobalt phthalocyanine compound catalyst.
(2) Removing phosphine, arsine, hydrogen sulfide and organic sulfide through a conversion adsorption unit;
adsorbing at 10 deg.C, reversely regenerating the adsorption tower with 120 deg.C water vapor, and reducing the temperature of the adsorption tower to below 80 deg.C with nitrogen or carbon dioxide gas after the hot vapor regeneration, to prepare for next adsorption purification.
The conversion adsorption unit consists of at least 2 conversion adsorbers, program-controlled valves and pipelines, at least one adsorber is in the adsorption step, the yellow phosphorus tail gas enters the adsorber in the adsorption step from bottom to top, sulfur and sulfide, phosphorus and sulfide, arsenic and arsenide are adsorbed on the conversion adsorbent, and other adsorbers are in the regeneration step; in the regeneration step, firstly superheated steam with the temperature of 120 ℃ is introduced into the adsorber from top to bottom, sulfur and sulfide, phosphorus and sulfide, arsenic and arsenide adsorbed on the conversion adsorbent are desorbed from the adsorber, the conversion adsorbent is regenerated to obtain catalytic conversion and adsorption activity again, and then gas such as nitrogen or carbon dioxide is introduced to reduce the temperature of the adsorber to 30 ℃.
The conversion adsorber is internally provided with an adsorbent, the surface of the conversion adsorbent contains metal oxide, and the activated carbon with abundant micropore and mesopore structures has a specific surface area of 600m2The content of metal oxides such as calcium, magnesium and the like is more than 3g/100 g.
The conversion adsorbers in the conversion adsorption unit are connected by pipelines, the program control valves are arranged between the conversion adsorbers and on the pipelines, the process of the conversion adsorption unit comprises an adsorption purification step and a regeneration step, at least one adsorber is in the adsorption step, and other adsorbers are in the regeneration step.
(3) The CO in the yellow phosphorus tail gas reacts with the water vapor to generate H under the action of a catalyst through a conversion unit (water vapor conversion)2And CO2；
(4) Via PSA/H2Pressure swing adsorption hydrogen purification unit for removing N in hydrogen2Methane and trace amounts of CO and sulfides and phosphides;
(5) removing H by a catalytic purification unit by using a catalyst of metal palladium and platinum highly dispersed on the surface of a carrier2And (5) neutralizing oxygen and trace hydrogen sulfide to obtain the catalyst. The catalytic purifying agent adopted by the catalytic purifying unit is a catalyst of active alumina or active carbon loaded with 0.02% of metal palladium or 0.01% of metal platinum.
Example 2
A method for preparing hydrogen for a fuel cell from yellow phosphorus tail gas sequentially comprises the following steps:
(1) removing hydrogen sulfide and part of organic sulfides from the yellow phosphorus tail gas through a PDS unit;
the yellow phosphorus tail gas is low-quality fuel or yellow phosphorus tail gas discharged by the combustion of an emptying torch.
The PDS unit comprises an absorption tower and an oxidation regeneration tower, wherein the absorption tower and the oxidation regeneration tower are connected in series; absorbing liquid in the absorption tower is aqueous solution taking sodium carbonate as an alkali source, and PDS catalyst and other auxiliaries are added, yellow phosphorus tail gas in the absorption tower passes through the absorption tower filled with filler from bottom to top, and the absorbing liquid containing the PDS catalyst flows through the absorption tower from top to bottom; and (3) the absorption liquid after absorbing the sulfide enters an oxidation regeneration tower, air is blown into the absorption liquid through bubbling gas, the sulfide is oxidized into elemental sulfur by oxygen in the air, the elemental sulfur is separated from the solution through a filter, and the absorption liquid is regenerated while the sulfur is recovered. The PDS catalyst is a binuclear cobalt phthalocyanine compound catalyst.
(2) Removing phosphine, arsine, hydrogen sulfide and organic sulfide through a conversion adsorption unit;
adsorbing at 80 deg.C, reversely regenerating the adsorption tower with 150 deg.C or 200 deg.C water vapor, and reducing the temperature of the adsorption tower to below 80 deg.C with nitrogen or carbon dioxide gas after the regeneration of hot vapor, to prepare for next adsorption purification.
The conversion adsorption unit consists of at least 2 conversion adsorbers, program-controlled valves and pipelines, at least one adsorber is in the adsorption step, the yellow phosphorus tail gas enters the adsorber in the adsorption step from bottom to top, sulfur and sulfide, phosphorus and sulfide, arsenic and arsenide are adsorbed on the conversion adsorbent, and other adsorbers are in the regeneration step; in the regeneration step, firstly, superheated steam with the temperature of 150 ℃ or 200 ℃ is introduced into the adsorber from top to bottom, sulfur and sulfide, phosphorus and sulfide, arsenic and arsenide adsorbed on the conversion adsorbent are desorbed from the adsorber, the conversion adsorbent is regenerated to obtain catalytic conversion and adsorption activity again, and then gas such as nitrogen or carbon dioxide is introduced to reduce the temperature of the adsorber to 80 ℃.
Active carbon with rich micropore and mesopore structure containing metal oxide on conversion adsorbent surface and with B surface area of 1500m2The content of metal oxides such as calcium, magnesium and the like is more than 3g/100 g.
(3) And (5) a compression step.
(4) The CO in the yellow phosphorus tail gas reacts with the water vapor to generate H under the action of a catalyst through a conversion unit (water vapor conversion)2And CO2；
(5) Decarbonizing by pressure swing adsorption (PSA/CO)2) Unit removal of CO from a shift gas2，PSA/H2Pressure swing adsorption hydrogen purification unit for removing N in hydrogen2Methane and trace amounts of CO and sulfides and phosphides;
(6) removing oxygen and trace hydrogen sulfide in H2 by using a catalyst of metal palladium and platinum highly dispersed on the surface of the carrier through a catalytic purification unit. The catalytic purifying agent adopted by the catalytic purifying unit is a catalyst of 2% of metal palladium or 0.2 of metal platinum loaded on activated alumina or activated carbon.
The yellow phosphorus tail gas purified by the PDS desulfurization unit and the conversion adsorption unit enters a steam conversion unit to convert CO in the yellow phosphorus tail gas into H2And CO2Conversion of CO vapor to H2And CO2Is conventional technology, and can increase the content of residual CO and H in the reaction gas in order to increase the conversion rate of carbon monoxide2The yield of the method is usually realized by adopting a two-section or multi-section shift catalytic reactor connected in series, hydrogen-rich gas from a conversion unit enters a pressure swing adsorption hydrogen purification unit, and the pressure swing adsorption hydrogen purification unit consists of a plurality of adsorption towers connected in parallel, a program control valve and a PLC or DCS automatic control system. The hydrogen-rich gas enters an adsorption tower in the adsorption step, impurities such as carbon dioxide, carbon monoxide, methane, hydrogen sulfide and nitrogen are adsorbed by an adsorbent filled in the adsorption tower, and pure hydrogen gas is obtained from an outlet of the adsorption tower.
In addition, the PSA purification hydrogen unit is connected with the conversion adsorption unit, the conversion adsorption unit is connected with the cooler or the gas-liquid separator, desorbed gas of the PSA purification hydrogen unit returns to the conversion adsorption unit to be used as regenerated gas of the conversion adsorption unit, the conversion adsorption unit is connected with the cooler and the gas-liquid separator, and regenerated waste gas is sent out after being cooled and separated from gas-liquid; the units are connected by pipes.
Example 3
A method for preparing hydrogen for fuel cell from yellow phosphorus tail gas sequentially comprises a PDS absorption desulfurization unit, a conversion adsorption unit, a water vapor conversion unit, a pressure swing adsorption hydrogen purification unit and a catalytic purification unit.
The yellow phosphorus tail gas has the following composition content in the following table 1: (wherein S, P, As, F are g/Nm3)
TABLE 1
| Composition of | H2 | O2 | N2 | CO | CH4 | CO2 | ΣS | ΣP | ΣAs | ΣF | H2O | Σ |
| The content is V% | 10.0 | 0.80 | 4.00 | 80.0 | 1.00 | 2.50 | 30 | 0.08 | 0.02 | 0.12 | Saturation of | 100 |
3000Nm of yellow phosphorus tail gas3The flow rate of the catalyst is 0.05Mpa, the catalyst enters a PDS desulfurization unit consisting of two absorption towers connected in series and an oxidation regeneration tower, hydrogen sulfide in the yellow phosphorus tail gas is removed to 10ppm and then enters a conversion adsorption unit consisting of three conversion adsorbers, and the PH in the feed gas is removed3、As3H、CS2And impurity components such as COS and the like, wherein each adsorber sequentially undergoes the steps of adsorption (A), heating flushing (H), cold blowing (C) and the like at different time, heating regeneration gas comes from superheated steam (250 ℃ to 0.4Mpa) generated by boiler steam through an electric heater, sewage after waste gas condensation is heated and flushed is merged into a yellow phosphorus furnace sewage system, and waste gas is directly sent into a torch combustion pipeline; the cold blowing regeneration gas comes from the desorption gas of the pressure swing adsorption unit and is regenerated once in about 8 hours. The purified gas is pressurized to 0.8Mpa by a compression unit, enters a steam conversion unit consisting of two steam conversion reactors connected in series, carbon monoxide in the yellow phosphorus tail gas reacts with water to generate hydrogen and carbon dioxide in the steam conversion unit, the converted gas enters a PSA hydrogen purification unit consisting of five adsorbers, a W2400 reciprocating vacuum pump (the air pumping quantity is more than 2400l/s) and a series of program control valves after heat exchange and temperature reduction, the carbon dioxide, the carbon monoxide, the nitrogen and other impurity gases in the gas are selectively adsorbed by adsorbents filled in an adsorption tower, pure hydrogen is obtained from the top of the adsorption tower, a pressure swing adsorption unit operates under the flow of 5-2-2/V, desorbed waste gas generated by reverse discharge and evacuation is sent to a conversion adsorption unit to be used as regenerated cold blowing gas of the conversion adsorption unit, the hydrogen obtained from the outlet end of the adsorber enters a catalytic purification unit at the pressure of more than or equal to 0.45Mpa, further removing trace hydrogen sulfide and oxygen contained in the hydrogen to obtain O2The contents are all less than 3 ppm. The hydrogen sulfide is less than 0.004ppm, the requirement of hydrogen for the hydrogen fuel cell is met, and the obtained hydrogen amount is 2200Nm 3/h.
Conversion adsorptionActivated carbon with abundant micropore and mesopore structure and containing metal oxide on surface of agent, and specific surface area of activated carbon is 1000m2The content of metal oxides such as calcium, magnesium and the like is more than 3g/100 g. The catalytic purifying agent adopted by the catalytic purifying unit is a catalyst of 1% of metal palladium or 0.015 of metal platinum loaded on activated alumina or activated carbon.
TABLE 2 operating schedule of the conversion adsorption unit
TABLE 3 running timing chart of PSA purification hydrogen unit
5-2-2/V
Example 4
A method for preparing hydrogen for fuel cells from yellow phosphorus tail gas sequentially comprises a PDS absorption desulfurization unit, a conversion adsorption unit, a water vapor conversion unit, a pressure swing adsorption carbon dioxide removal unit, a pressure swing adsorption hydrogen purification unit and a catalytic purification unit.
The composition of the yellow phosphorus tail gas is shown in the following table 4:
table 4 composition:
| composition of | H2 | O2 | N2 | CO | CH4 | CO2 | H2S | ΣS | ΣP | ΣAs | Σ |
| The content is V% | 5.0 | 0.2 | 1.2 | 90.7 | 0.1 | 1.2 | 0.5 | 1.0 | 0.04 | 0.04 | 100 |
Yellow phosphorus tail gas 5000Nm3The flow rate of the catalyst is 0.05Mpa, the catalyst enters a PDS desulfurization unit consisting of two absorption towers connected in series and an oxidation regeneration tower to remove hydrogen sulfide in the yellow phosphorus tail gas to 10ppm, and then the hydrogen sulfide enters a conversion adsorption unit consisting of three conversion adsorbers, and the PH in the feed gas is removed3、As3H、CS2And impurity components such as COS, etc., and each adsorber sequentially undergoes the steps of adsorption (A), heating flushing (H), cold blowing (C) and the like at different times to heat the regenerated gasSuperheated steam (300 ℃ and 0.4Mpa) generated by boiler steam through an electric heater is heated, washed, condensed waste gas is merged into a yellow phosphorus furnace sewage system, and the waste gas is directly sent into a torch combustion pipeline; the cold blowing regeneration gas comes from the desorption gas of the pressure swing adsorption unit and is regenerated once in about 6 hours. The purified gas is pressurized to-1.0 Mpa by a compression unit, enters a steam conversion unit consisting of four steam conversion reactors connected in series, carbon monoxide in the yellow phosphorus tail gas reacts with water to generate hydrogen and carbon dioxide in the steam conversion unit, the converted gas enters a PSA carbon dioxide removal unit consisting of eight adsorbers, two W2400 reciprocating vacuum pumps (the air pumping quantity is more than 2400l/s) and a series of program control valves after heat exchange and temperature reduction, the carbon dioxide, hydrogen sulfide and other impurity gases in the gas are selectively adsorbed by adsorbents filled in adsorption towers, hydrogen-rich gas is obtained from the tops of the adsorption towers, the pressure swing adsorption carbon dioxide removal unit adopts a vacuumizing desorption process to operate under 8-3-2/V process, 3 adsorbers are in the adsorption step, and the other 5 adsorption towers are in uniform pressure drop, The operation steps include that a PSA carbon dioxide removal unit operation time sequence table is shown, carbon dioxide desorption waste gas generated by reverse release and evacuation is sent to a conversion adsorption unit to be used as regeneration cold blowing gas of the conversion adsorption unit, hydrogen-rich gas obtained from the outlet end of an adsorber enters a pressure swing adsorption hydrogen purification unit consisting of six adsorbers, impurities such as carbon monoxide, carbon dioxide, methane, nitrogen and the like in the hydrogen-rich gas are selectively adsorbed by adsorbents filled in an adsorption tower, the pressure swing adsorption hydrogen purification unit adopts a sequential release flushing process and operates under a 6-2-2/P process, 2 adsorbers are in an adsorption step, and the other adsorbers are in steps of uniform pressure drop, sequential release, reverse release, flushing, uniform pressure rise, pressure filling and the like, and the operation steps include the PSA hydrogen purification unit operation time sequence table, pure hydrogen obtained from the outlet of the adsorber enters a catalytic purification unit at a pressure of more than or equal to 0.7Mpa, and trace hydrogen sulfide and oxygen contained in the hydrogen are further removed to reach O2The content is less than 1 ppm. The hydrogen sulfide is less than 4ppb, the requirement of hydrogen for the hydrogen fuel cell is met, and the obtained hydrogen amount is 3500Nm 3/h.
Conversion adsorbentActivated carbon with abundant micro-and mesoporous structures and containing metal oxides on the surface and having a specific surface area of 1200m2The content of metal oxides such as calcium, magnesium and the like is more than 3g/100 g. The catalytic purifying agent adopted by the catalytic purifying unit is a catalyst of active alumina or active carbon loaded with 1.5 percent of metal palladium or 0.016 percent of metal platinum.
TABLE 5 timing chart of the operation of the conversion adsorption unit
TABLE 6 operating timing chart of PSA carbon dioxide removal unit 8-3-2/V
TABLE 7 operating sequence of PSA Hydrogen purification Unit Table 6-2-2/P
While the foregoing shows and describes the fundamental principles and principal features of the invention, together with the advantages thereof, the foregoing embodiments and description are illustrative only of the principles of the invention, and various changes and modifications can be made therein without departing from the spirit and scope of the invention, which will fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for preparing hydrogen for a fuel cell from yellow phosphorus tail gas is characterized by comprising the following steps: the yellow phosphorus tail gas sequentially passes through a PDS unit, a conversion adsorption unit, a conversion unit and a PSA/H unit2And a pressure swing adsorption hydrogen purification unit and a catalytic purification unit.
2. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 1, wherein: the PSA/H2PSA/R-CO is also arranged between the pressure swing adsorption hydrogen purification unit and the transformation unit2And a pressure swing adsorption carbon dioxide removal unit.
3. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 1 or 2, characterized in that: the yellow phosphorus tail gas is low-quality fuel or yellow phosphorus tail gas discharged by the combustion of an emptying torch.
4. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 1, wherein: the PDS unit comprises an absorption tower and an oxidation regeneration tower, wherein the absorption tower and the oxidation regeneration tower are connected in series; and absorption liquid is arranged in the absorption tower, flows through the absorption tower from top to bottom, and enters the oxidation regeneration tower after absorbing the sulfides.
5. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 4, wherein: the absorption liquid is an aqueous solution which takes sodium carbonate as an alkali source and is also added with a PDS catalyst and an auxiliary agent.
6. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 1, wherein: after adsorption and regeneration are carried out on an adsorption tower in the conversion adsorption unit, reducing the temperature of the adsorption tower to be below 80 ℃ by using nitrogen or carbon dioxide gas, and preparing for next adsorption and purification; wherein the adsorption temperature is 10-80 ℃, the regeneration temperature is 120-200 ℃, and the regeneration is reverse regeneration of superheated steam.
7. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 1 or 6, wherein: the conversion adsorption unit consists of at least 2 conversion adsorbers, a program control valve and a pipeline, wherein conversion adsorbents are arranged in the conversion adsorbers, at least one conversion adsorber is in the adsorption step, and other adsorbers are in the regeneration step; in the regeneration step, firstly, superheated steam with the temperature of 120-200 ℃ is introduced into the adsorber from top to bottom, and then nitrogen or carbon dioxide gas is introduced to reduce the temperature of the adsorber to 30-80 ℃.
8. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 7, wherein: the conversion adsorbent is activated carbon with a metal oxide-containing surface and rich micro-pore and mesoporous structures, and the specific surface area of the activated carbon is 600-1500 m2(ii)/g, the metal oxide content is greater than 3g/100 g; the metal oxide is calcium or magnesium metal oxide.
9. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 1, wherein: the catalytic purifying agent used in the catalytic purifying unit is a catalyst of active alumina or active carbon loaded with 0.02-2% of metal palladium or 0.01-0.2% of metal platinum.
10. The method for preparing hydrogen for fuel cell from yellow phosphorus tail gas as claimed in claim 1, wherein: and a compression unit is arranged between the PDS unit and the conversion adsorption unit.
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