CN117654461A - Regeneration method of carbon dioxide adsorbent - Google Patents
Regeneration method of carbon dioxide adsorbent Download PDFInfo
- Publication number
- CN117654461A CN117654461A CN202211118239.XA CN202211118239A CN117654461A CN 117654461 A CN117654461 A CN 117654461A CN 202211118239 A CN202211118239 A CN 202211118239A CN 117654461 A CN117654461 A CN 117654461A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- gas
- desorption
- regeneration
- carbon dioxide
- 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
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000003463 adsorbent Substances 0.000 title claims abstract description 118
- 238000011069 regeneration method Methods 0.000 title claims abstract description 88
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 59
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 59
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 77
- 230000008929 regeneration Effects 0.000 claims abstract description 73
- 238000003795 desorption Methods 0.000 claims abstract description 62
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 15
- 239000006096 absorbing agent Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 pure ammonia Chemical compound 0.000 description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- 239000004277 Ferrous carbonate Substances 0.000 description 4
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 4
- 235000019268 ferrous carbonate Nutrition 0.000 description 4
- 229960004652 ferrous carbonate Drugs 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 4
- 239000011656 manganese carbonate Substances 0.000 description 4
- 235000006748 manganese carbonate Nutrition 0.000 description 4
- 229940093474 manganese carbonate Drugs 0.000 description 4
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
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- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- CDUFCUKTJFSWPL-UHFFFAOYSA-L manganese(II) sulfate tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O CDUFCUKTJFSWPL-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
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- 235000011152 sodium sulphate Nutrition 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- ZMMDPCMYTCRWFF-UHFFFAOYSA-J dicopper;carbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[O-]C([O-])=O ZMMDPCMYTCRWFF-UHFFFAOYSA-J 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
Abstract
A regeneration method of carbon dioxide adsorbent belongs to the field of atmospheric pollution control and environmental protection, and is characterized in that the regeneration method comprises two processes of adsorbent desorption and mixed gas treatment after desorption, wherein the desorption adopts ammonia, mixed gas of ammonia and inert gas or mixed gas of ammonia and water as desorption gas to carry out desorption regeneration on the adsorbent after adsorption saturation, the mixed gas containing carbon dioxide after desorption is subjected to cooling and aqueous solution absorption treatment processes to obtain ammonium carbonate or ammonium bicarbonate byproducts, and the adsorbent after desorption is recycled after regeneration activation.
Description
Technical Field
The invention relates to a regeneration method of a carbon dioxide adsorbent, belonging to the field of air pollution control and environmental protection.
Background
Carbon dioxide generated by burning fossil fuel is a main source of greenhouse gases discharged by human activities, besides thermal power plants using coal as main fuel, industrial processes such as cement, glass building materials, ferrous metallurgy and the like also discharge a considerable amount of carbon dioxide, and excessive carbon dioxide discharge has an important influence on global climate environment. For this reason, international convention and governments have made specific action plans and emission reduction measures for controlling and reducing carbon dioxide emissions.
The present inventors developed a method of treating carbon dioxide in a gas stream by adsorption using a solid adsorbent (application No. 2018102129104), and proposed that the adsorbent after adsorption of carbon dioxide can be desorbed and regenerated at a certain temperature, regeneration can be performed in an inert gas such as nitrogen, air or negative pressure, the regeneration temperature is usually 150 ℃ or higher, preferably 450 ℃ to 950 ℃, and the released carbon dioxide can be recovered after further treatment, and the adsorbent can be recycled. Further studies have found that at temperatures below about 650 c, the use of ammonia as a regeneration gas is quite different from the use of an inert gas such as nitrogen, which is the only regeneration medium gas, has no effect on desorption of carbon dioxide, while the presence of ammonia promotes desorption of adsorbed carbon dioxide. The invention provides a regeneration method of the carbon dioxide solid adsorbent on the basis, so as to recover the adsorbed carbon dioxide gas.
Disclosure of Invention
The technical scheme adopted by the invention is as follows: a method for regenerating carbon dioxide adsorbent includes such steps as desorbing the adsorbent, and treating the mixed gas after desorbing, which is the gas containing ammonia, including pure ammonia, the mixed gas of ammonia and inertial gas, or the mixed gas of ammonia and water, as the desorbed gas, desorbing the saturated adsorbent at a certain temp for regenerating it, cooling, absorbing by aqueous solution, and so on.
The main principle of the desorption of the adsorbent is that the gaseous ammonia is found and utilized to replace the carbon dioxide adsorbed in the adsorbent, namely the adsorption capacity of ammonia and the adsorbent is larger than the adsorption capacity of carbon dioxide and the adsorbent under certain conditions, so that the carbon dioxide adsorbed in the adsorbent is replaced, and the desorption of the adsorbent is realized.
A process for regenerating the carbon dioxide adsorbent by using ammonia gas or ammonia water as the desorbing gas includes such steps as introducing the adsorbent to be regenerated into a regenerating reactor, vacuumizing to remove or replace the gas in the reactor, introducing ammonia gas or the mixture of ammonia gas and water vapour to replace the carbon dioxide gas adsorbed by adsorbent, cooling, water absorbing to obtain ammonium carbonate or ammonium hydrogen carbonate solution, removing carbon dioxide gas, mixing the residual gas containing ammonia with fresh regenerating gas, and cyclic use. When ammonia or aqueous ammonia is used as the desorption gas, the desorption temperature is generally 100 ℃ or higher and 650 ℃ or lower, preferably 200 to 400 ℃, and may be different depending on the regeneration gas and the adsorbent component, and may be generally the same as the operating temperature of the adsorbent or slightly higher. When the mixed gas of ammonia and water vapor is used as desorption regeneration gas, the proportion of each component in the gas flow can be adjusted at will, the ammonia concentration is not required to be more than 0.5%, and the ammonia concentration can be determined by experiments according to the property of a specific adsorbent and the carbon dioxide adsorption and desorption amount. Ammonia is often used instead of pure ammonia from the standpoint of storage and safety in use. The ammonia water and the ammonia gas can be replaced by high-temperature decomposition of organic amine such as urea, methylamine and ethylamine or inorganic ammonium salt, and the effect is equivalent.
The adsorbent after removing carbon dioxide is vacuumized, or in the air or in the presence of oxygen, and is properly heated to remove ammonia gas adsorbed by the adsorbent, and finally the regeneration and activation of the adsorbent are completed. The regeneration activation temperature is generally about 20 to 50 ℃ and above higher than the desorption temperature.
The regeneration reactor can adopt a fixed bed, a moving bed (including rotary type), a boiling bed, a fluidized bed, a circulating fluidized bed and other gas-solid contact reactors which are commonly used in chemical unit operation, can adopt various forms such as concurrent flow, countercurrent flow, cross flow and the like, can be vertically or horizontally or obliquely placed, has a substantially equivalent effect, and the specific reactor structure can refer to related chemical equipment manuals.
According to the regeneration process of carbon dioxide, a certain proportion of inert gas comprising nitrogen, argon or helium and other gases which do not react with carbon dioxide can be added into the regeneration gas flow, the content of the inert gas can be adjusted according to the needs, the special requirements are avoided, the inert gas is generally 1-99%, and the added inert gas has no influence on the basic desorption process of the adsorbent.
In the desorption regeneration process of the carbon dioxide adsorbent, the water absorption device can adopt common equipment such as a bubbling tower, a sieve plate tower, a spray tower, a fluidized bed and the like for chemical gas-liquid reaction absorption, and can be arranged in one or more stages so as to ensure that ammonia and carbon dioxide are completely reacted and absorbed. The cooling temperature of the desorbed mixed gas is generally below 80 ℃ so as to be beneficial to the reaction of ammonia and carbon dioxide and the subsequent water absorption.
The main components of the carbon dioxide adsorbent comprise at least one element of iron, manganese, cobalt, copper, zinc or aluminum of component A, at least one element of sodium, potassium, lithium, cesium, calcium, barium or magnesium of component B, and at least one solid compound or mixed compound of sulfate radical, chlorine or carbonate radical of component C, wherein the mass percent of each component is 4-96% of component A, 1-75% of component B and 1-75% of component C. The preparation method comprises the steps of mixing a product obtained by the reaction of a material U, a material V and water, drying and activating the product to obtain a solid product, wherein the material U is at least one of sulfate, chloride and carbonate of an L component (iron, manganese, cobalt and copper), the material V is at least one of hydroxide or carbonate of a B component (sodium, potassium and lithium) and oxide, hydroxide or carbonate of an F component (calcium, barium and magnesium); the preparation method of the purifying agent comprises the following steps: (1) Mixing a material U, a material V and water in a mixing reactor, wherein the molar addition ratio of the material U to the material V is 1:0.1-1:10, the molar addition of the water is 1-20 times of the total amount of the materials, and when the materials are provided with crystal water, no water or little water is added; (2) The product obtained by the mixing reaction is formed into particles, or formed into a ball, plate or honeycomb ceramic shape, or loaded on a general catalyst carrier; (3) Drying the molded product at a drying temperature of 40 ℃ or higher; (4) And (3) activating the dried product, wherein the activation temperature is more than 100 ℃. Specific preparation methods, adsorption processes, operation parameters and the like are described in detail in the aforementioned reference invention documents. The adsorbent generally has an adsorption purification temperature of 60 ℃ or higher for carbon dioxide, the highest purification temperature is the same as the highest activation temperature of the adsorbent, and the preferred temperature range is 150 ℃ to 450 ℃, so that the purification temperature of the adsorbent containing iron or cobalt is higher, and the purification temperature of the adsorbent containing manganese and copper is lower. The adsorbent also comprises one or any two or more of oxides of metal iron, cobalt, manganese, copper, cerium or zirconium as active components, and can adopt aluminum oxide, kaolin and the like as matrixes and calcium oxide, barium oxide, sulfate or chloride as an auxiliary agent. The preparation method is generally that the nitrate solution of the metal oxide and related matrix and auxiliary agent (taking alumina and calcium oxide as examples) are mixed according to a certain proportion, and then the granular adsorbent is prepared through dehydration, granulation, drying (about 60-95 ℃) and activation (about 500-700 ℃). The content of the active ingredient metal oxide is generally not higher than 90%, and the content of the matrix and the auxiliary agent is generally more than 10%.
The adsorbent is used for simulating the carbon dioxide adsorption experiment of the combustion flue gas of the boiler, the adsorption quantity of the carbon dioxide is about 0.2-1% of the mass of the adsorbent, and the regeneration effect of the similar adsorbent is approximately equivalent. The desorption regeneration temperature of the carbon dioxide adsorbent varies according to the composition of the adsorbent, and generally the desorption regeneration temperature of the adsorbent mainly comprising iron and cobalt may be higher and the desorption regeneration temperature of the adsorbent mainly comprising manganese and copper may be lower.
The carbon dioxide adsorbent is used for adsorbing carbon dioxide in various air flows, wherein the air flows comprise combustion tail gas of various industrial processes, such as combustion tail gas of various internal combustion engines (including mobile sources of vehicles, ships and the like), related air flows generated by other industrial processes, and air flows containing carbon dioxide generated by fossil fuel combustion or other processes, such as thermal power generation, building materials, smelting and the like.
Compared with the prior art, the invention has the advantages that: the ammonia gas or the ammonia water vapor mixed gas is used as the regeneration gas of the carbon dioxide adsorbent, so that the desorption regeneration of the adsorbent is realized at a lower temperature, the energy utilization efficiency is improved, and meanwhile, related byproducts can be obtained, so that the effective utilization of resources is realized.
Drawings
FIG. 1 is a schematic diagram of a regeneration reactor for a fixed bed carbon dioxide adsorbent used in an embodiment of the present invention.
FIG. 2 is a schematic diagram of a desorption regeneration process for a carbon dioxide adsorbent according to an embodiment of the present invention.
In the figure: 1 a regeneration gas inlet; 2 an air flow distributor; 3 an adsorbent; 4, a regeneration gas outlet; 5 an adsorbent inlet; 6 an adsorbent discharge port; 7, an overhaul port; 101 regenerating the reactor; 102 a condenser; 103 absorber one; 104 absorber two.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples.
A regeneration reactor and desorption regeneration process of carbon dioxide adsorbent are shown in fig. 1 and 2, respectively. The regeneration reactor (101) is provided with a regeneration gas inlet (1), a gas flow distributor (2), a regeneration gas outlet (4), an adsorbent adding port (5), an adsorbent discharging port (6) and an overhaul port (7). The absorbent (3) to be regenerated is placed above the gas flow distributor (2). The mixed gas treatment system after desorption consists of a condenser (102), an absorber I (103) and an absorber II (103), wherein the condenser (102) is provided with a refrigerant inlet and a refrigerant outlet, and the absorber is provided with a clear water inlet and an absorption liquid outlet.
The treatment process is that an adsorbent (3) needing to be regenerated is added above an air flow distributor (2) in a regeneration reactor (101) through an adsorbent adding port (5), after the gas in the reactor is pumped out, desorption regeneration gas is introduced through a regeneration gas inlet (1), so that the desorption regeneration gas contacts with the filled adsorbent (3) through the air flow distributor (2), and carbon dioxide gas adsorbed by the adsorbent is replaced and carried out, and is discharged through a regeneration gas outlet (4) and then enters a mixed gas treatment system after desorption regeneration. The mixed gas containing water vapor, ammonia and carbon dioxide discharged from the regeneration gas outlet (4) sequentially passes through the condenser (102) for cooling, then enters an absorption system, ammonia and carbon dioxide in the air flow are subjected to chemical reaction and are respectively absorbed by the added clean water in the absorber I (103) and the absorber II (104), the ammonium carbonate or ammonium bicarbonate solution obtained after absorption is discharged from the solution discharge port of the absorber, and the tail gas containing ammonia for removing the carbon dioxide is returned and mixed with the new desorption gas to be used as desorption gas, so that one cycle is completed.
The embodiment of the invention adopts the granular adsorbent particle size of about 3-5 mm, and the adsorbent saturated by carbon dioxide adsorption in the simulated boiler combustion flue gas is regenerated, and the adsorption quantity of the carbon dioxide is about 0.5-0.8% of the mass of the adsorbent. The preparation and the operating parameters of the adsorption process and the like can be seen in the specification and examples of the related invention application.
Example 1: a regeneration reactor of a fixed bed carbon dioxide adsorbent is shown in figure 1, and a desorption regeneration process is shown in figure 2. The size of the regeneration reactor is phi 300mm multiplied by 600mm, the external heat preservation and the heating can be carried out, the reactor is made of carbon steel, the condenser is a coiled glass condenser with phi 150mm, the cooling water temperature of the condenser is about 35-40 ℃, the temperature of the regenerated air flow at the outlet of the condenser is about 50-80 ℃, the absorbers are all filled absorption towers with phi 150mm multiplied by 1500mm, and the spraying amount of the absorption liquid is about 15L/min. The primary main components of the adsorbent to be regenerated are ferrous sulfate and calcium oxide (about 1:2, molar ratio, the same applies hereinafter) in proportion according to the relevant preparation process, the granular adsorbent is prepared by drying and activating (about 600-750 ℃) the specific preparation process can be referred to the description of the relevant invention, the same applies hereinafter, and the primary main components are manganese sulfate tetrahydrate and potassium hydroxide (about 1:2) for regeneration of the adsorbent according to the relevant preparation process. The adsorption operating temperature of the adsorbent is about 400 c,
the treatment process comprises adding carbon dioxide adsorbent about 25kg to be regenerated above the gas flow distributor (2) in the regeneration reactor (101) via the adsorbent inlet (5), pumping gas in the regeneration reactor, and introducing mixed regeneration gas of ammonia and water vapor into the reactor via the regeneration gas inlet (3), wherein H 2 O about 80%, NH3 about 20% (volume), gas flow rate about 2L/min, maintaining the temperature in the regeneration reactor at 100, 150, 250, 350, 450 and 550 deg.C, discharging the regenerated gas through the regeneration gas outlet (4) at the upper part of the regeneration reactor (101), and sequentially passing through the condenser, the absorber I and the absorber II, and tail gasAnd returning to the gas inlet of the regeneration reactor to be mixed with the new make-up gas. When the temperatures in the regeneration reactors are 100, 150, 250, 350, 450 and 550 ℃, respectively, the time for complete desorption of the two adsorbents (carbon dioxide removal rate is about not less than 98% and the same applies hereinafter) at the above temperatures is about: the adsorbents with the primary main components of ferrous sulfate and calcium oxide are respectively 360, 240, 120, 75, 50 and 40min, and the adsorbents with the primary main components of manganese sulfate tetrahydrate and potassium hydroxide are respectively 300, 200, 90, 60, 40 and 35min. The adsorbent after desorption is activated for about 60 minutes in the atmosphere with the air flow rate of about 2L/min and the temperature of 550 ℃ and the regeneration process is completed.
Example 2: the primary main components of the adsorbent are ferrous sulfate, cobalt sulfate, manganese sulfate and copper sulfate, respectively, are mixed with sodium hydroxide and calcium oxide (about 1:1:3) according to the preparation process of the related invention, and are dried and activated (about 500-600 ℃) to prepare the particle adsorbent. The adsorbent operating temperature was 350 ℃. The regeneration reactor temperatures were 150, 250, 350, 450 and 550 ℃, respectively, with the other conditions being the same as in example 1. The time required for complete desorption of the adsorbent was about: ferrous sulfate 200, 150, 100, 80 and 60min; cobalt sulfate 220, 170, 120, 90 and 70min; manganese sulfate for 150, 120, 80, 60 and 50min; copper sulfate 150, 120, 70, 45 and 35min. The adsorbent after desorption is activated at the air flow rate of about 2L/min at 600 ℃ for about 60min, and the regeneration process is completed.
Example 3: the main components of the adsorbent are ferric oxide, cobalt oxide, manganese oxide, copper oxide, cerium oxide or zirconium oxide and calcium oxide respectively according to the molar ratio of about 1:5, and the preparation method comprises the steps of mixing metal nitrate solution (about 50% by mass) of the oxide and calcium oxide powder, dehydrating, granulating, drying (about 60-95 ℃) and activating (about 550-650 ℃) to obtain the particle adsorbent. The regeneration reactor temperatures were about 300, 400, 500 and 650 ℃, respectively, with the other conditions being the same as in example 1. The time required for complete desorption of the adsorbent was about: iron oxide (main component, the same applies below) for 150, 120, 90 and 40min; cobalt oxide 180, 130, 100 and 50min; manganese oxide 130, 100, 70 and 30min; copper oxide 120, 90, 60 and 25min; cerium oxide 150, 120, 90 and 50min; zirconia 130, 110, 60 and 30min. The adsorbent after desorption is activated for 60min at the temperature of 650 ℃ at the air flow rate of about 2L/min, and the regeneration process is completed.
Example 4: the main components of the adsorbent are ferrous hydroxide, ferric hydroxide, manganese hydroxide, cobalt hydroxide, copper hydroxide, cuprous hydroxide, zinc hydroxide and aluminum hydroxide, sodium sulfate, calcium oxide and water according to the proportion of about 1:1:3:6, and the granular adsorbent is prepared by drying (about 60-95 ℃) and activating (about 650 ℃) according to the related preparation process. The regeneration reactor temperatures were about 300, 400 and 500 ℃, respectively, with the other conditions being the same as in example 1. The time required for complete desorption of the adsorbent was about: ferrous hydroxide 120, 90 and 50min; iron hydroxides 130, 100 and 60min; manganese hydroxide for 100, 70 and 50min; cobalt hydroxide 120, 90 and 50min; copper hydroxide for 90, 60 and 40min; cuprous hydroxide for 100, 60 and 40min; the method comprises the steps of carrying out a first treatment on the surface of the Zinc hydroxide 120, 90 and 50min; aluminum hydroxide 120, 90 and 50min. The adsorbent after desorption is activated for 60min at the temperature of 500 ℃ at the air flow rate of about 2L/min, and the regeneration process is completed.
Example 5: the primary main components of the adsorbent are ferrous carbonate, manganese carbonate and basic cupric carbonate which are respectively mixed with calcium hydroxide, sodium sulfate and water according to the proportion of about 1:2:1:6, and the granular adsorbent is prepared by drying (about 60-95 ℃) and activating (about 500-600 ℃) according to the related preparation process. The adsorption working temperature is about 250-300 ℃. The regeneration reactor temperatures were about 150, 250 and 400 ℃, respectively, with the other conditions being the same as in example 1. The time required for complete desorption of the adsorbent was about: ferrous carbonate 150, 120 and 70min; manganese carbonate for 150, 100 and 60min; basic copper carbonate 120, 90 and 45min. The adsorbent after desorption is activated for 60min at the temperature of 300 ℃ at the air flow rate of about 2L/min, and the regeneration process is completed.
Example 6: the primary main components of the adsorbent are ferric chloride, cobalt chloride, manganese chloride and copper chloride, and sodium hydroxide and calcium oxide are respectively prepared according to the proportion of about 1:2:2, and the granular adsorbent is prepared by drying (about 60-95 ℃) and activating (about 450-500 ℃) according to the related preparation process. The adsorption operating temperature was 250 ℃. The regeneration reactor temperatures were about 200, 300 and 400 ℃, respectively, with the other conditions being the same as in example 1. The time required for complete desorption of the adsorbent was about: ferric chloride for 150, 120 and 70min; cobalt chloride for 150, 120 and 80min; manganese chloride 120, 100 and 60min; copper chloride 100, 80 and 50min. The adsorbent after desorption is activated for 60min at the temperature of 350 ℃ at the air flow rate of about 2L/min, and the regeneration process is completed.
Example 7: the primary main components of the adsorbent are ferrous carbonate, manganese carbonate and basic copper carbonate, potassium hydroxide, calcium oxide and water are respectively prepared according to the proportion of about 1:2:2:6, and the granular adsorbent is prepared by drying (about 60-95 ℃) and activating (about 550 ℃) according to the related preparation process. The adsorption working temperature is about 250-300 ℃. The regeneration reactor temperatures were about 150, 250 and 350 c, respectively, using a mixture of ammonia and nitrogen as the regeneration gas, wherein nitrogen was about 90% and ammonia was about 10% by volume, with the other conditions being the same as in example 1. As a result, the time required for the complete desorption of the adsorbent at different temperatures was about: ferrous carbonate 200, 120 and 90min; 180, 100 and 70min of manganese carbonate; basic copper carbonate 150, 90 and 50min. The adsorbent after desorption is activated for 60min at the air flow rate of about 2L/min and the temperature of 250 ℃ and the regeneration process is completed.
Example 8: the absorbent using ferrous sulfate as the main component in example 2 was regenerated with pure ammonia gas at a regeneration reactor temperature of 250℃under the same conditions as in example 1. As a result, the time required for complete desorption of the adsorbent at this temperature was about 100 minutes, respectively.
Example 9: the primary main components of the adsorbent are ferric hydroxide, manganese hydroxide, cobalt tetra-ammine hydroxide, copper tetra-ammine hydroxide and zinc tetra-ammine hydroxide, respectively, and calcium carbonate and water according to the proportion of about 1:3:6, and according to the related preparation process, the granular adsorbent is prepared by drying (about 60-95 ℃) and activating (about 650 ℃). The adsorption working temperature is about 300-400 ℃. The regeneration reactor temperatures were about 350, 500 and 650 ℃, respectively, with the other conditions being the same as in example 1. The time required for complete desorption of the adsorbent was about: ferric hydroxide for 100, 60 and 30min; manganese hydroxide 120, 70 and 30min; cobalt tetra-ammine hydroxide 120, 70 and 40min; copper tetrammine hydroxide 90, 50 and 20min; zinc tetrammine hydroxide for 100, 60 and 40min. The adsorbent after desorption is activated for 60min at 550 ℃ at the air flow rate of about 2L/min, and the regeneration process is completed.
Example 10: the adsorbent prepared in example 2 with ferrous sulfate as the main raw component was desorbed using a mixture of nitrogen, steam, air, nitrogen and ammonia (about 90% for nitrogen and about 10% for ammonia), respectively. Other conditions were the same as in example 1. Experimental results show that the method adopts nitrogen, water vapor or air to treat CO 2 The desorption effect of (2) is substantially equal, no obvious desorption phenomenon is caused on carbon dioxide under the regeneration temperature of 450 ℃, and the desorption phenomenon is caused on the mixed gas of nitrogen and ammonia (about 90% of nitrogen and about 10% of ammonia) at 100 ℃, so that the desorption can be completely performed after about 120 minutes when the temperature is increased to 350 ℃.
The above embodiments are only for illustrating the technical solutions of the present invention, and modifications, changes, improvements, etc. of the technical solutions described in the embodiments or any equivalent substitution, modification, variation, improvement, etc. of some technical features thereof should be included in the protection scope of the present invention.
Claims (10)
1. A regeneration method of carbon dioxide adsorbent is characterized by comprising two processes of desorption of adsorbent and treatment of mixed gas after desorption, wherein the desorption adopts ammonia gas, mixed gas of ammonia and inert gas or mixed gas of ammonia and water as desorption gas to carry out desorption regeneration on the adsorbent after adsorption saturation at a certain desorption temperature, the mixed gas containing carbon dioxide after desorption is subjected to cooling and aqueous solution absorption treatment processes to obtain ammonium carbonate or ammonium bicarbonate byproducts, the desorption of adsorbent and the recycling of carbon dioxide gas are realized, and the desorbed adsorbent is recycled after regeneration and activation.
2. The regeneration process according to claim 1, characterized in that the desorption temperature is 100 ℃ to 650 ℃.
3. The regeneration method according to claim 1, wherein the inert gas includes nitrogen, air, argon and helium in an amount of 1% to 99%.
4. The regeneration method according to claim 1, wherein the ammonia content in the ammonia-water mixture is 0.5% or more by volume.
5. The regeneration method according to claim 1, wherein the adsorbent to be desorbed and regenerated is introduced into a regeneration reactor, the gas in the reactor is removed by vacuum pumping or replaced by a regeneration gas, then ammonia gas or a mixed gas of ammonia gas and water vapor is introduced into the reactor to replace carbon dioxide gas adsorbed by the adsorbent, and then the desorbed mixed gas is cooled and absorbed by water to form ammonium carbonate or ammonium bicarbonate solution, so that carbon dioxide gas desorbed by the adsorbent is removed, and tail gas containing ammonia is recycled as desorption gas.
6. The regeneration method according to claim 1 or claim 1, wherein the carbon dioxide-removed adsorbent is regenerated and activated at a certain temperature under negative pressure or in nitrogen or air.
7. The regeneration method according to claim 6 or claim 6, wherein the regeneration activation temperature is 120 ℃ or higher.
8. The regeneration method according to claim 1, wherein the main component of the carbon dioxide adsorbent comprises at least one element of iron, manganese, cobalt, copper, zinc or aluminum of component a, at least one element of sodium, potassium, lithium, cesium, calcium, barium or magnesium of component B, and at least one solid compound or mixed compound of sulfate, chloride or carbonate of component C, wherein the mass percentage of each component is 4-96% of component a, 1-75% of component B, and 1-75% of component C.
9. The regeneration method according to claim 1, wherein the carbon dioxide adsorbent comprises an adsorbent containing at least one compound of oxides of metallic iron, cobalt, manganese, copper, cerium or zirconium as an active ingredient.
10. The regeneration method according to claim 9, wherein the adsorbent uses alumina, kaolin, etc. as a matrix, and calcium oxide, barium oxide, sulfate or chloride as an auxiliary agent.
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