CN117019109A - Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof - Google Patents
Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof Download PDFInfo
- Publication number
- CN117019109A CN117019109A CN202311059860.8A CN202311059860A CN117019109A CN 117019109 A CN117019109 A CN 117019109A CN 202311059860 A CN202311059860 A CN 202311059860A CN 117019109 A CN117019109 A CN 117019109A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- ferrocyanide
- activated carbon
- transition metal
- inorganic oxide
- 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
- 239000003463 adsorbent Substances 0.000 title claims abstract description 240
- 229910052792 caesium Inorganic materials 0.000 title abstract description 42
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 46
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 36
- 150000003624 transition metals Chemical class 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 150000002500 ions Chemical class 0.000 claims abstract description 22
- 229910001417 caesium ion Inorganic materials 0.000 claims abstract description 15
- 229910001419 rubidium ion Inorganic materials 0.000 claims abstract description 13
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 239000002861 polymer material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 50
- 239000002245 particle Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 20
- -1 transition metal salt Chemical class 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 9
- 239000005720 sucrose Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 7
- 229920001661 Chitosan Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 229940005550 sodium alginate Drugs 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims 2
- 230000002285 radioactive effect Effects 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 description 65
- 238000001179 sorption measurement Methods 0.000 description 49
- 238000004140 cleaning Methods 0.000 description 33
- 238000003756 stirring Methods 0.000 description 25
- 238000001035 drying Methods 0.000 description 19
- 239000008188 pellet Substances 0.000 description 18
- 239000002699 waste material Substances 0.000 description 18
- 239000007791 liquid phase Substances 0.000 description 17
- 239000000276 potassium ferrocyanide Substances 0.000 description 16
- 238000005191 phase separation Methods 0.000 description 14
- 238000005202 decontamination Methods 0.000 description 13
- 230000003588 decontaminative effect Effects 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000008213 purified water Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 239000012085 test solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002901 radioactive waste Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000264 sodium ferrocyanide Substances 0.000 description 6
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 6
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- NFVZIERLAZUYBQ-UHFFFAOYSA-N [K].[Zn] Chemical compound [K].[Zn] NFVZIERLAZUYBQ-UHFFFAOYSA-N 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000007123 defense Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 229910001410 inorganic ion Inorganic materials 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002354 radioactive wastewater Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- VDNXILQBKLFION-UHFFFAOYSA-N [K].[Cu] Chemical compound [K].[Cu] VDNXILQBKLFION-UHFFFAOYSA-N 0.000 description 1
- DYPHJEMAXTWPFB-UHFFFAOYSA-N [K].[Fe] Chemical compound [K].[Fe] DYPHJEMAXTWPFB-UHFFFAOYSA-N 0.000 description 1
- FJAAKDGALOFQSO-UHFFFAOYSA-N [K].[Ni] Chemical compound [K].[Ni] FJAAKDGALOFQSO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- MIAJZAAHRXPODB-UHFFFAOYSA-N cobalt potassium Chemical compound [K].[Co] MIAJZAAHRXPODB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001236 detergent effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003758 nuclear fuel Substances 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
- 239000012071 phase Substances 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- LDQICAMJIICDLF-UHFFFAOYSA-N potassium;iron(2+);iron(3+);hexacyanide Chemical compound [K+].[Fe+2].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LDQICAMJIICDLF-UHFFFAOYSA-N 0.000 description 1
- AYIHRPXHCCRGMZ-UHFFFAOYSA-N potassium;nickel(2+) Chemical compound [K+].[Ni+2] AYIHRPXHCCRGMZ-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application relates to a large-scale preparation method of a high-stability cesium removal adsorbent, a product and application thereof. In particular, the application relates to a particulate inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent comprising: a particulate inorganic oxide support or a particulate activated carbon support; a transition metal stabilized ferrocyanide layer coating the inorganic oxide or activated carbon support; and a polymer material layer coating the transition metal stabilized ferrocyanide layer. The adsorbent has high crush strength and low ion leaching rate. The application also relates to a preparation method of the adsorbent and application thereof in removing radioactive isotope Cs ions and stable isotope Cs ions, and application in removing radioactive isotope Rb ions and stable isotope Rb ions.
Description
The application relates to a large-scale preparation method of a high-stability cesium-removing adsorbent, and a product and application thereof, which are classified application of patent application of the application, wherein the application date is 2018, 01 and 04, and the application number is 201810008565.2.
Technical Field
The invention relates to the field of inorganic materials, in particular to a large-scale preparation method of a cesium removal adsorbent with high stability, a product and application thereof, and the adsorbent has good adsorption performance on rubidium.
Background
According to the medium-long term development planning target of the Chinese nuclear power, the installed capacity of the running nuclear power reaches 5800 kilowatts by 2020, and about 3000 kilowatts is built; the aim of building nuclear power to strengthen China is comprehensively achieved by 2030. Facing new challenges in the development of new situations in the nuclear power industry, china is in urgent need of great development in the aspects of radioactive waste treatment, nuclear emergency technology, radioactive effluent emission standards and the like.
The efficient and timely treatment of radioactive liquid is one of the important problems to be solved in the urgent need of establishing a nuclear safety deep defense system, so that development of new technology, new equipment and research and development and storage of new materials for emergency treatment of waste liquid are urgently needed, and multi-level technical guarantee for waste liquid treatment and disposal is established in a nuclear power station. The first level is the actual elimination of radionuclides during normal operation of the nuclear power plant. The technology is mainly aimed at removing radioactive wastes in the normal operation process of the nuclear power station, and realizes the waste minimization while guaranteeing the stability and effectiveness of the treatment process. The second level is that when the problems such as fuel damage occur in the power station, the emergency treatment of the waste liquid in the field is carried out in time under the conditions of wide nuclide range and various forms in the waste liquid. The technology can remove pollution in time, quickly and efficiently, and prevent radioactive substances from leaking out. The third level is the last defense line of the deep defense system, namely, under the extreme condition of over-design reference accidents, the off-site nuclear emergency treatment is rapidly started, and the influence of nuclear accidents on the environment is limited to the greatest extent.
Compared with ion exchange resin, the inorganic ion adsorbent has high selectivity to main trace nuclides Cs, sr, co, ag, I and the like, can efficiently remove target nuclide ions from high-salt radioactive wastewater, can rapidly and greatly reduce the radioactivity of the wastewater, and is little influenced by coexisting non-radioactive ions, so that the inorganic ion adsorbent has long service life and generates a small amount of solid waste. Furthermore, the large amount of radioactive elements is enriched in a small volume of solid inorganic ion exchanger, making radiation protection relatively easy. Compared with waste resin produced by adsorption, the radioactive waste produced by the inorganic adsorption technology has good thermal stability and chemical stability, strong irradiation resistance, difficult radiation decomposition or biological decomposition, convenient post treatment and disposal, and long-term safety in the long-term storage process of an underground disposal field. Further, the waste liquid deep purification device based on the inorganic adsorption technology is simple in structure, has the technical characteristics of effectiveness, strong selectivity, miniaturization, modularization and strong mobility, has low requirements on site service conditions, and is very suitable for special requirements that the components of radioactive waste liquid of a nuclear power plant are complex and the site arrangement space is limited.
Based on the application characteristics of high efficiency, high speed and high selectivity of the inorganic adsorbent, the inorganic adsorption technology plays a key role in the treatment of the accident waste liquid of the nuclear power station. In the most typical case of treatment of an accident waste liquid, from the establishment of an initial radioactive waste water treatment system to the gradual perfection in the subsequent operation process, the process route of coupling of inorganic adsorption and membrane technology is always kept, the inorganic adsorption technology is adopted to selectively remove the main nuclides Cs-134 and Cs-137, the radioactivity level of the waste water is greatly reduced, the radiation protection requirement of the subsequent technology is reduced, and the membrane technology is further adopted to remove the radionuclides in the water in a broad spectrum. According to the water quality monitoring result provided by the method, after being processed by the Cs adsorption and reverse osmosis process flow, the radioactivity level of the water sample is 10 from the initial 7 -10 8 The Bq/L level (which is higher than the initial level after the accident) was reduced to 10 3 -10 4 Bq/L. Inorganic adsorbents have also found many applications in nuclear power plant normal operating conditions, such as: the cesium removal adsorbent is adopted by Loviii sa and Hungary Paks power stations in Finland to further reduce the volume of the evaporator waste liquid of the nuclear power station; the Scotland lightning station adopts inorganic adsorbent to selectively remove Cs-134 and Cs-137 from 1500 tons of Na cooling pile waste liquid and 57 tons of Na/K cooling pile high salt content waste liquid; inorganic adsorbents are adopted to treat the acidic dissolution liquid of the fuel element fragments in the retirement process of nuclear facilities of the Bradwell Magnox power station in England; removing Pu/Cs/Sr in concentrated nitric acid dissolution waste liquid by adopting an inorganic adsorbent; and the Savanneah River and Calway Nuclear Power plant in the United states, the Sellafield, england, and the Olkiuoto Nuclear Power plant in Finland all use inorganic adsorbents to treat spent fuel storage pool effluent.
During the last few decades, inorganic adsorbents for cesium removal have not been studied too much, mainly including, for example, zirconyl pyrophosphate (chinese patent of invention CN106342077B of the national institute of atomic energy); inorganic composite adsorbent (Chinese patent No. CN103691393B of Beijing geology institute of nuclear industry) compounded by corresponding treatment of nonmetallic minerals; magnetic cesium selective adsorbents (chinese invention patent CN104054136 of japan Jieshen intelligent corporation and chinese invention patent CN1129922C of chinese atomic energy science institute); and ferrocyanide series cesium-removing inorganic adsorbents developed successfully by the subject group have good performance on the treatment of nuclear power station emergency radioactive wastewater and obtain the authority of various Chinese national patents, such as CN100469435C, CN101279249B, CN102836693B and the like.
Inorganic adsorbents are designed in the AP1000 reactor being built in China to selectively remove Cs-134 and Cs-137 in the process water. The process water mainly comprises reactor core cooling water, nuclear fuel storage pool cooling water and the like under the normal running condition of the nuclear power station, most of the nuclear power stations in China adopt a nuclear grade water filter and ion exchange desalination bed process for removal, filters with different filtering precision are respectively arranged at the front and the rear of the desalination bed, the front filter is used for removing particles in waste liquid, the operation of the desalination bed is protected, the rear filter is mainly used for removing waste resin particles generated by the desalination bed, and the cleanliness of effluent is guaranteed. The operation of the power station has very high requirements on the water quality of the process water, such as extremely low conductivity and ion concentration of the process water to inhibit metal corrosion and ensure the safe operation of the reactor, and extremely low turbidity of the process water to ensure that the filter is not easy to be blocked in the process of processing the process water, prolong the service life of the filter and reduce the solid waste amount. In the process water treatment design of the AP1000, colloid in the waste liquid is removed by adopting a flocculation combined active carbon filtration technology, then main nuclides Cs-134 and Cs-137 are removed by adopting an inorganic adsorbent, and further other nuclides are removed by adopting ion exchange resin. Such removal processes are designed with the objective of improving the nuclide treatment effect and reducing the amount of radioactive waste resin produced. At present, the inorganic adsorbent adopted by the AP1000 design is zeolite, and the phenomena of low adsorption speed and easy pulverization in use cause the rise of turbidity and conductivity of water quality exist.
In view of the above, providing a high-strength and high-stability inorganic adsorbent capable of efficiently removing cesium ions from process water under normal operation conditions of a nuclear power plant is still one of the problems to be solved.
Disclosure of Invention
One object of the present invention is to: the granular cesium removal adsorbent with high strength and high stability is provided, and the Cs-134 and Cs-137 can be efficiently removed from process water under the normal operation condition of a nuclear power station.
The inventors of the present invention have unexpectedly found, through a large number of experiments, that after the surface of a particulate inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent is bound with loose solid phase particles and soluble ions in the adsorbent, a cesium removal adsorbent having mechanical stability and low ion leaching rate can be obtained by coating a polymer material layer thereon.
In one aspect, the present invention provides a particulate inorganic oxide or particulate activated carbon supported transition metal stabilized ferrocyanide adsorbent comprising: inorganic oxide in particle form or activated carbon in particle form is used as a carrier; a transition metal stabilized ferrocyanide layer coating the inorganic oxide or activated carbon support; and a polymer material layer coating the transition metal stabilized ferrocyanide layer.
Preferably, the polymer material comprises sodium alginate, chitosan, polyethylene glycol with a number average molecular weight between 2000 and 6000, polyvinyl alcohol, sucrose or any combination thereof.
Preferably, the adsorbents according to the present invention have a crush strength of 2-100N/particle.
Preferably, the adsorbent according to the invention has such an ion leaching characteristic that after soaking the adsorbent at a liquid-to-solid ratio of 10 for 24 hours, the resulting leachate has a turbidity of less than 10mg/L.
Preferably, the adsorbent according to the invention has such an ion leaching characteristic that after soaking the adsorbent at a liquid-to-solid ratio of 10 for 24 hours, the resulting leachate has a conductivity of less than 15mg/L.
The adsorbent obtained by the method can efficiently remove Cs-134 and Cs-137 from the process water under the normal operation condition of the nuclear power station. The adsorbent can be applied to not only AP1000 type reactors but also various domestic and foreign pressurized water reactor nuclear power stations, so as to reduce the emission of the main nuclides Cs-134 and Cs-137, reduce the dosage of ion exchange resin and realize the aim of waste minimization. Furthermore, the adsorbent obtained by the method has good adsorption performance on the homologous nuclides Rb-88 and Rb-89 existing in the radioactive waste liquid.
On the other hand, the invention also relates to a preparation method of the granular inorganic oxide or granular activated carbon supported transition metal stabilized ferrocyanide adsorbent, which comprises the following steps:
1) Providing a primary adsorbent;
2) Washing the primary adsorbent of step 1) with deionized water until the washing liquid has a conductivity of 25.0 mu s/cm or less and a turbidity of 30mg/L or less; and
3) Coating the washed primary adsorbent with a polymeric material, preferably in the presence of an acid or a base, to obtain a coated primary adsorbent; and
4) Optionally washing the coated primary adsorbent of step 3) with deionized water until the washing liquid has a conductivity of 20.0 mu s/cm or less and a turbidity of 20mg/L or less,
thus obtaining the ferrocyanide adsorbent stabilized by the granular inorganic oxide or granular activated carbon supported transition metal.
Preferably, according to one embodiment of the present invention, the step of providing the primary adsorbent comprises immersing the particulate inorganic oxide or the particulate activated carbon support in an aqueous solution of ferrocyanide for 2 to 48 hours, thereby obtaining a precursor a loaded with ferrocyanide, and then mixing the precursor a with an aqueous solution of a transition metal salt, and reacting for 2 to 24 hours at a temperature of 100 to 150 ℃ in a sealed reaction vessel.
Preferably, according to one embodiment of the present invention, the step of providing the primary adsorbent comprises immersing the particulate inorganic oxide or the particulate activated carbon support in an aqueous solution of a transition metal salt for 2 to 48 hours, thereby obtaining a precursor B loaded with the transition metal salt, and then mixing the precursor B with an aqueous solution of ferrocyanide and reacting at a temperature of 100 to 150 ℃ for 2 to 24 hours in a sealed reaction vessel.
In one embodiment of the invention, the adsorbent according to the invention is prepared by steps comprising:
(1) Load of ferrocyanide: firstly, adding pure water into a No. 1 reaction kettle, heating to 80-100 ℃, and adding soluble ferrocyanide into the reaction kettle to dissolve the ferrocyanide; secondly, adding a granular inorganic oxide carrier or a granular active carbon carrier into a reaction kettle, dipping for 2-48 hours, then carrying out solid-liquid phase separation and drying to obtain a precursor A loaded with ferrocyanide;
(2) Preparing a transition metal stabilized ferrocyanide adsorbent: firstly, adding pure water into a No. 2 reaction kettle, heating to 80-100 ℃, and adding soluble transition metal salt into the reaction kettle to dissolve the soluble transition metal salt; secondly, adding the precursor A loaded with ferrocyanide obtained in the step (1) into a reaction kettle, uniformly stirring, sealing the reaction kettle, setting the reaction temperature at 100-150 ℃ for 2-24h, and carrying out solid-liquid phase separation after the reaction is finished to obtain a primary cesium removal adsorbent B;
(3) Cleaning the adsorbent: washing the primary cesium removal adsorbent B obtained in step (2) with deionized water, preferably for 10 hours or more, until the electrical conductivity of the washing liquid is 25.0 μs/cm or less and the turbidity is 30.0mg/L or less, and then drying the obtained adsorbent, preferably with a constant temperature oven or a vacuum oven at a drying temperature of 60-120 ℃, denoted as secondary adsorbent C;
(4) Coating an adsorbent: coating a high polymer material layer on the surface of the secondary adsorbent C obtained in the step (3): dissolving a polymer material with a bonding effect in pure water to prepare a solution with a certain concentration; adding the secondary adsorbent C into the solution system; according to different polymer materials, dropwise adding acid or alkali solution in the stirring process; after stirring the mixture for 1-10 hours, solid-liquid phase separation was performed, thereby obtaining a three-stage adsorbent D.
(5) Cleaning the adsorbent: the three-stage cesium removal adsorbent D obtained in step (4) is washed with deionized water, preferably for 10 hours or more until the electrical conductivity of the washing liquid is 20.0 μs/cm or less and the turbidity is 20mg/L or less, followed by solid-liquid phase separation, and the adsorbent is dried, preferably with a constant temperature oven or vacuum oven at a drying temperature of 60 to 120 ℃, to obtain the final cesium removal adsorbent E.
Further, according to the present invention, ferrocyanide employed is soluble and includes potassium ferrocyanide and sodium ferrocyanide. Preferably, the concentration of the aqueous solution of soluble ferrocyanide is 10 to 50wt%.
Further, according to the present invention, the particulate inorganic oxide support includes silica gel pellets, alumina pellets, titania pellets, zirconia pellets, and molecular sieve pellets. Preferably, the pellets have a particle size of 0.5 to 5mm and a crush strength of 2 to 150N/particle.
Further, according to the present invention, the granular activated carbon carrier may be coal-based carbon, or coconut shell carbon, fruit shell carbon, or the like. Preferably, the activated carbon particles have a particle size of about 0.5 to 5mm and a crush strength of 2 to 150N/particle.
Further in accordance with the present invention, the transition metal salt is soluble and includes copper sulfate, copper nitrate, copper chloride, ferrous sulfate, ferric nitrate, nickel sulfate, zinc chloride, zinc sulfate, zinc acetate, cobalt nitrate, cobalt chloride, zirconium oxychloride, manganese sulfate, or any combination thereof. Preferably, the concentration of the aqueous solution of the above soluble salt is 10 to 60wt%.
Further, according to the present invention, the polymer material used includes sodium alginate, chitosan, polyethylene glycol (2000-6000), polyvinyl alcohol, sucrose or a combination thereof. Preferably, the polymer material is formulated as an aqueous solution having a concentration of 1 to 20 wt%.
Further, according to the present invention, the acid added dropwise is hydrochloric acid, sulfuric acid, acetic acid or any combination thereof. Preferably, the concentration of the acid is 0.01 to 1mol/L.
Further, according to the present invention, the base added dropwise is sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water or any combination thereof. Preferably, the concentration of the alkali is 0.01 to 1mol/L;
the series of particle-supported ferrocyanide adsorbents prepared by the preparation method are also within the protection scope of the invention.
The inventors of the present invention have surprisingly found that the particulate inorganic oxide or particulate activated carbon supported transition metal stabilized ferrocyanide adsorbent according to the present invention has the characteristics of stable structure and high adsorption performance. The adsorbent can adsorb radioactive and/or stable isotope Cs ions and also can adsorb radioactive and/or stable isotope Rb ions, so that the adsorbent has wide application prospect. For example, the separation and/or removal or extraction of radioactive or stable isotope Cs ions may be achieved by adsorption, and the use of radioactive or stable isotope Rb ions may also be achieved by separation and/or removal or extraction. Therefore, the application of the granular inorganic oxide or granular activated carbon supported transition metal stabilized ferrocyanide adsorbent in removing the radioactive isotope Cs ions and the stable isotope Cs ions and the application in removing the radioactive isotope Rb ions and the stable isotope Rb ions are also within the protection scope of the invention.
The inventors of the present invention have recognized that by subjecting a primary adsorbent using an inorganic oxide or activated carbon as a carrier and having a series of transition metal stabilized ferrocyanide layers on the surface of the carrier (achieved by two-step reactions of impregnation and hydrothermal treatment) to a water washing process, a portion of solid phase particles loosely bound to the surface of the primary adsorbent can be removed and soluble ions in the primary adsorbent can be sufficiently released, resulting in a washed primary adsorbent having good mechanical strength and low ion leaching characteristics. Further, the mechanical strength of the adsorbent can be further improved by coating the surface of the washed primary adsorbent with a polymer layer, thereby obtaining an adsorbent preferably having a crush strength of 2 to 100N/particle and extremely low ion leaching characteristics.
Detailed Description
The invention is further illustrated in the following in connection with the specific embodiments, but the invention is not limited to the following examples. The methods are conventional unless otherwise indicated, and the starting materials and standard chemical reagents for detection are commercially available from the public sources unless otherwise indicated.
In the following examples, the adsorbent was tested for performance in static adsorption and fixed bed adsorption reaction columns, respectively, and Cs before and after adsorption + Ion concentration was determined by plasma mass spectrometry (ICP-MS) and adsorbent performance was determined by partition coefficient K d And a decontamination factor DF.
In static adsorption measurement, a certain amount of adsorbent is added into a 50mL centrifuge tube, and the centrifuge tube is placed on a constant temperature shaking table to shake for 48-72 h, and Cs before and after adsorption is measured + Ion concentration, adsorbent performance adopts partition coefficient K d And a decontamination factor DF. Adsorption partition coefficient K d (mL/g) is represented by formula 1 below, wherein C 0 And C t The initial concentration of the adsorbed ions and the concentration after the adsorption equilibrium are reached, and F is the ratio of the volume (mL) of the solution to be treated to the mass (mg) of the adsorbent. Decontamination factors such asThe ratio of the water inlet concentration of the adsorbed ions to the water outlet concentration after the adsorption equilibrium is reached is shown in the following formula 2. The general adsorption distribution coefficient describes the characteristics of the adsorption material itself, K d A value of 10 5 The above description shows that the adsorbent has good performance; the magnitude of the decontamination factor is related not only to the adsorption characteristics of the material itself, but also to the amount of adsorbent, with a greater value indicating cleaner removal of contaminants.
K d ＝(C o –C t )×F×1000/C t (1)
The dynamic adsorption performance is carried out by adopting a fixed bed adsorption reaction column, the height of the test column is 10cm, the diameter is 1.5cm, and the water flow rate is 20BV/h. Using the decontamination factor DF to represent the column versus Cs + Is a detergent effect of (a).
The crush strength of the adsorbents according to the present invention is determined as follows. The crushing strength of the adsorbent is measured by a domestic crushing strength instrument, and the model of the instrument is as follows: YHKC-2A particle strength tester. In the measurement, 60-100 adsorbent particles are randomly selected, the particles are placed at the center position right below the pressing hammer one by one in the measurement, the handle is rotated to enable the pressing hammer to fall down, the pressing hammer slowly rotates when approaching the particles, the pressing hammer is enabled to slowly contact, and when the sound of particle breakage is heard, the force of the crushing moment loaded on the particles is given on the instrument. The ion leaching characteristics of the adsorbents according to the present invention are determined by: firstly, the adsorbent is soaked in 10 times of pure water, and is stirred by a stirrer or is rocked by a cradle, and after a certain period of time, the turbidity and the conductivity of the soaked liquid are measured by a turbidity meter HACH 2100N and a conductivity meter DDSJ-308A respectively. The turbidity meter used was 0.001mg/L in precision and the conductivity meter used was 0.01. Mu.s/cm in precision.
Example 1: preparation and cesium removal performance of silica gel supported adsorbent
Silica gel Si-1 with high mechanical strength and granularity of 0.5-2.0mm is preferably prepared, and the steps are as follows:
(1) Copper salt loading: firstly, adding pure water into a No. 1 reaction kettle, heating to 80-100 ℃, and adding copper sulfate into the reaction kettle to dissolve the copper sulfate to form a solution with the concentration of 10-50%; secondly, adding silica gel particles Si-1 serving as a carrier into a reaction kettle, soaking for 2-48 hours, then carrying out solid-liquid phase separation and drying to obtain a precursor Si-1-A loaded with copper sulfate.
(2) Preparing a transition metal stabilized ferrocyanide adsorbent: firstly, adding pure water into a No. 2 reaction kettle, heating to 80-100 ℃, and adding sodium ferrocyanide into the reaction kettle to dissolve the sodium ferrocyanide and form a solution with the concentration of 10-50%; and (2) adding the precursor Si-1-A loaded with the copper sulfate obtained in the step (1) into a reaction kettle, uniformly stirring, sealing the reaction kettle, setting the reaction temperature at 100 ℃ for reaction for 24 hours, and carrying out solid-liquid phase separation after the reaction is finished to obtain the primary cesium removal adsorbent Si-1-B.
(3) Cleaning the adsorbent: and (3) cleaning the primary cesium removal adsorbent Si-1-B obtained in the step (2) by purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the conductivity in the washing liquid after continuous stirring for 24 hours is 22.8 mu s/cm and the turbidity is reduced to 17.8mg/L, and drying the obtained adsorbent to obtain the secondary adsorbent Si-1-C.
(4) Coating an adsorbent: the method for coating the surface of the secondary adsorbent Si-1-C obtained in the step (3) with the polymer layer comprises the steps of adopting chitosan as a binder, firstly dissolving chitosan in pure water to prepare a solution with the concentration of 2-10wt%, adding the secondary adsorbent Si-1-C into a solution system, gradually adding 1.0M sodium hydroxide solution into the system after stirring for 1h until the pH value in the solution reaches 10-11, continuing stirring and reacting for 5-10h, and separating solid from liquid to obtain the tertiary adsorbent Si-1-D.
(5) Cleaning the adsorbent: and (3) cleaning the three-stage cesium removal adsorbent Si-1-D obtained in the step (4) by adopting purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the turbidity of the washing liquid after continuous stirring for 24 hours is less than 20mg/L and the conductivity is less than 20 mu s/cm, then separating solid from liquid, and drying the adsorbent in vacuum to obtain the final silica gel supported copper potassium ferrocyanide cesium removal adsorbent.
The determination shows that the crushing strength of the adsorbent is 12-14N/particle, the turbidity in the liquid is 6mg/L, the conductivity is 11 mu s/cm, and the COD concentration in the solution is 1.5mg/L after soaking for 24 hours under the condition of 10 liquid-solid ratio. In the adsorption performance measured by adopting a static adsorption method, the initial concentration of Cs ions in the solution is 10mg/L, the coexisting concentration of boric acid is 500mg/L in terms of boron, the volume of the test solution is 50mL, and the decontamination coefficient DF value of Cs is 26.2 under the condition that the mass of the adsorbent is 10mg, which is equivalent to the removal rate of Cs being more than 95%.
Example 2: preparation of alumina-supported adsorbent and cesium removal performance
Alumina pellets Al-1 with high mechanical strength and granularity of 0.5-2.0mm are preferably prepared, and the zinc potassium ferrocyanide adsorbent is prepared by the following steps:
(1) Load of ferrocyanide: firstly, adding pure water into a No. 1 reaction kettle, heating to 80-100 ℃, and adding potassium ferrocyanide into the reaction kettle to dissolve the potassium ferrocyanide to form a solution with the concentration of 10-50%; secondly, adding alumina pellets Al-1 serving as a carrier into a reaction kettle, soaking for 2-48 hours, then carrying out solid-liquid phase separation, and drying in a constant-temperature oven to obtain a precursor Al-1-A loaded with ferrocyanide.
(2) Preparing a transition metal stabilized ferrocyanide adsorbent: firstly, adding pure water into a No. 2 reaction kettle, heating to 80-100 ℃, and adding zinc acetate into the reaction kettle to dissolve the zinc acetate and form a solution with the concentration of 10-50%; and (2) adding the precursor Al-1-A loaded with ferrocyanide obtained in the step (1) into a reaction kettle, uniformly stirring, sealing the reaction kettle, setting the reaction temperature at 100 ℃ for reaction for 8-16h, and carrying out solid-liquid phase separation after the reaction is finished to obtain the primary cesium removal adsorbent Al-1-B.
(3) Cleaning the adsorbent: and (3) cleaning the primary cesium removal adsorbent Al-1-B obtained in the step (2) by purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the conductivity in the washing liquid after continuous stirring for 24 hours is 18.2 mu s/cm and the turbidity is reduced to 21.3mg/L, and drying the obtained adsorbent to obtain the secondary adsorbent Al-1-C.
(4) Coating an adsorbent: the surface of the secondary adsorbent Al-1-C obtained in the step (3) is coated with a high polymer layer, the method is that polyvinyl alcohol and polyethylene glycol (6000) are respectively adopted as binders, firstly, the polyvinyl alcohol and the polyethylene glycol are respectively dissolved in pure water to prepare a solution, the concentration of the polyvinyl alcohol solution is 1-10wt%, and the concentration of the polyethylene glycol (6000) is 5-30%. Adding a secondary adsorbent Al-1-C into the solution system, wherein the liquid-solid ratio is 10:1; and (3) continuing stirring and reacting for 2-10h, and then separating solid and liquid phases to obtain the tertiary adsorbent Al-1-D.
(5) Cleaning the adsorbent: and (3) cleaning the three-stage cesium removal adsorbent Al-1-D obtained in the step (4) by adopting purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the turbidity of the washing liquid after continuous stirring for 24 hours is less than 20mg/L and the conductivity is less than 20 mu s/cm, then separating solid from liquid, and drying the adsorbent in vacuum to obtain the final aluminum oxide supported zinc potassium ferrocyanide cesium removal adsorbent.
The determination shows that the crushing strength of the adsorbent is 3-9N/particle, the turbidity in the liquid is 3mg/L, the conductivity is 7 mu s/cm and the COD concentration in the solution is 2.7mg/L after soaking for 24 hours under the condition of 10 liquid-solid ratio. In the adsorption performance measured by adopting a static adsorption method, the initial concentration of Cs ions in the solution is 10mg/L, the coexisting concentration of boric acid is 500mg/L in terms of boron, the volume of the test solution is 50mL, and the decontamination coefficient DF value of Cs is 23.2 under the condition that the mass of the adsorbent is 10mg, which is equivalent to the removal rate of Cs being more than 95%.
Further, a fixed bed small adsorption column is adopted for dynamic measurement, the height of the adsorption column is 10cm, the diameter of the adsorption column is 1.5cm, the whole adsorption column is filled with the adsorbent, the flow rate of the treated water is 20BV/h, and the initial concentration of Cs is 10mg/L. The measurement result shows that the decontamination coefficient of Cs can also reach 330 when the treated water amount reaches 3870 BV.
Example 3: preparation and performance of titanium oxide supported adsorbent
Titanium oxide pellets Ti-1 with high mechanical strength and granularity of 0.5-2.0mm are preferably prepared, and the cobalt potassium ferrocyanide adsorbent is prepared by the following steps:
(1) Load of ferrocyanide: firstly, adding pure water into a No. 1 reaction kettle, heating to 80-100 ℃, and adding potassium ferrocyanide into the reaction kettle to dissolve the potassium ferrocyanide to form a solution with the concentration of 10-50%; secondly, adding titanium oxide pellets Ti-1 serving as a carrier into a reaction kettle, soaking for 2-48 hours, then carrying out solid-liquid phase separation, and drying in a constant-temperature oven to obtain a precursor Ti-1-A loaded with ferrocyanide.
(2) Preparing a transition metal stabilized ferrocyanide adsorbent: firstly, adding pure water into a No. 2 reaction kettle, heating to 80-100 ℃, and adding cobalt nitrate into the reaction kettle to dissolve the cobalt nitrate and form a solution with the concentration of 10-50%; and (2) adding the precursor Ti-1-A loaded with ferrocyanide obtained in the step (1) into a reaction kettle, uniformly stirring, sealing the reaction kettle, setting the reaction temperature at 100 ℃ for 4-12h, and carrying out solid-liquid phase separation after the reaction is finished to obtain the primary cesium removal adsorbent Ti-1-B.
(3) Cleaning the adsorbent: and (3) cleaning the primary cesium removal adsorbent Ti-1-B obtained in the step (2) by purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the conductivity in the washing liquid after continuous stirring for 24 hours is 22.4 mu s/cm and the turbidity is reduced to 15.8mg/L, and drying the obtained adsorbent to obtain the secondary adsorbent Ti-1-C.
(4) Coating an adsorbent: coating a high polymer layer on the surface of the secondary adsorbent Al-1-C obtained in the step (3), wherein polyvinyl alcohol, sucrose and polyethylene glycol, sucrose (6000) are respectively adopted as binders, and firstly, polyvinyl alcohol and polyethylene glycol are respectively dissolved in pure water to prepare a solution, wherein the concentration of the polyvinyl alcohol solution is 1-10wt%, and the concentration of the polyethylene glycol (6000) is 5-30%; and then adding sucrose into the solution to dissolve, and controlling the concentration of the sucrose and polyvinyl alcohol or polyethylene glycol to be 1-4 times. Adding a secondary adsorbent Ti-1-C into a solution system, wherein the liquid-solid ratio is 10:1; and (3) continuing stirring and reacting for 2-10h, and then separating solid and liquid phases to obtain the three-stage adsorbent Ti-1-D.
(5) Cleaning the adsorbent: and (3) cleaning the three-stage cesium removal adsorbent Al-1-D obtained in the step (4) by adopting purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the turbidity of the washing liquid after continuous stirring for 24 hours is less than 20mg/L and the conductivity is less than 20 mu s/cm, then separating solid from liquid, and drying the adsorbent in vacuum to obtain the final aluminum oxide supported zinc potassium ferrocyanide cesium removal adsorbent.
The determination shows that the crushing strength of the adsorbent is 3-9N/particle, the turbidity in the liquid is 2mg/L, the conductivity is 6 mu s/cm and the COD concentration in the solution is 1.6mg/L after soaking for 24 hours under the condition of 10 liquid-solid ratio. In the adsorption performance measured by adopting a static adsorption method, the initial concentration of Cs ions in the solution is 10mg/L, the coexisting concentration of boric acid is 500mg/L in terms of boron, the volume of the test solution is 50mL, and the decontamination coefficient DF value of Cs is 26.7 under the condition that the mass of the adsorbent is 10mg, which is equivalent to the removal rate of Cs being more than 95%.
Further, a fixed bed small adsorption column is adopted for dynamic measurement, the height of the adsorption column is 10cm, the diameter of the adsorption column is 1.5cm, the whole adsorption column is filled with the adsorbent, the flow rate of the treated water is 20BV/h, and the initial concentration of Cs is 10mg/L. The measurement result shows that the decontamination coefficient of the adsorbent to Cs can also reach 310 when the treated water amount reaches 4213 BV.
Example 4: preparation of zirconia supported adsorbent and adsorption performance of rubidium and cesium
Zirconia pellets Zr-1 having a monoclinic phase, preferably having a pellet size of 0.5 to 2.0mm and a very high mechanical strength, crush strength greater than 30N/particle, are preferred as the adsorbent carrier, on which the iron (III) potassium ferrocyanide adsorbent is prepared by the steps of:
(1) Load of ferrocyanide: firstly, adding pure water into a No. 1 reaction kettle, heating to 80-100 ℃, and adding sodium ferrocyanide into the reaction kettle to dissolve the sodium ferrocyanide to form a solution with the concentration of 10-50%; secondly, adding zirconia pellets Zr-1 serving as a carrier into a reaction kettle, soaking for 10-48 hours, then carrying out solid-liquid phase separation, and drying in a constant-temperature oven to obtain a precursor Zr-1-A loaded with ferrocyanide.
(2) Preparing a transition metal stabilized ferrocyanide adsorbent: firstly, adding pure water into a No. 2 reaction kettle, heating to 80-100 ℃, and adding ferric nitrate into the reaction kettle to dissolve the pure water and form a solution with the concentration of 10-50%; secondly, adding the precursor Zr-1-A loaded with ferrocyanide obtained in the step (1) into a reaction kettle, uniformly stirring, sealing the reaction kettle, setting the reaction temperature at 120 ℃ for reaction for 10-24 hours, and carrying out solid-liquid phase separation after the reaction is finished to obtain the primary cesium removal adsorbent Zr-1-B.
(3) Cleaning the adsorbent: and (3) cleaning the primary cesium removal adsorbent Zr-1-B obtained in the step (2) by purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the conductivity in the washing liquid after continuous stirring for 24 hours is 15.6 mu s/cm and the turbidity is reduced to 25.8mg/L, and drying the obtained adsorbent to obtain the secondary adsorbent Zr-1-C.
(4) Coating an adsorbent: the surface of the secondary adsorbent Zr-1-C obtained in the step (3) is coated with a polymer layer, the method is that sodium alginate is adopted as a binder, and firstly sodium alginate is dissolved in pure water to prepare a solution, and the concentration is 1-10wt%. Adding a secondary adsorbent Zr-1-C into the solution system, wherein the liquid-solid ratio is 10:1; stirring for 1h, then dripping 1M hydrochloric acid solution until the pH value is 4-5, continuing stirring and reacting for 2-10h, and then separating solid from liquid to obtain the three-stage adsorbent Zr-1-D.
(5) Cleaning the adsorbent: and (3) cleaning the three-stage cesium removal adsorbent Zr-1-D obtained in the step (4) by adopting purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the turbidity of the washing liquid after continuous stirring for 24 hours is less than 20mg/L and the conductivity is less than 20 mu s/cm, then separating solid from liquid, and drying the adsorbent in vacuum to obtain the final zirconium oxide supported iron potassium ferrocyanide (Prussian blue) cesium removal adsorbent.
The crushing strength of the adsorbent is measured to be 41N/particle, after the adsorbent is soaked for 24 hours under the condition of a liquid-solid ratio of 10, the turbidity in the liquid is 7mg/L, the conductivity is 12 mu s/cm, and the COD concentration in the solution is 1.9mg/L.
The competitive adsorption performance of cesium and lithium, sodium, potassium and rubidium is measured by adopting a static adsorption method, the volume of the test solution is 50mL, and the mass of the adsorbent is 10mg. Boric acid concentration in the test solution is 500ppm by boron, and initial concentration of Cs is 10mg/L; the coexisting lithium, sodium, potassium and rubidium ions were used in two concentrations, corresponding to the same molar ratios as 10mg/L Cs, respectively. In the experiment, the change in the adsorption performance of the adsorbent to Cs was measured in a state of competition with coexisting ions. At the position of Cs alone + The decontamination factor of the adsorbent to Cs in the presence of the adsorbent is 23.2, and the adsorbent has the same mole number of Li + 、Na + 、K + 、Rb + The decontamination coefficients for Cs were 21.6, 11.3, 9.2 and 9.4, respectively.
From experimental data, the supported ferrocyanide series adsorbent developed by the invention has certain adsorption characteristics to the ions of the first main group, mainly Na + 、K + 、Rb + And Cs + The method has a certain competition relationship, but has poor adsorption performance on Li, so that the adsorption removal performance of nuclide Cs can not be influenced by LiOH in the process waste liquid of the nuclear power station. In general, the radionuclide Rb is simultaneously present in the nuclear power plant process effluent + Therefore, the load type ferrocyanide series adsorbent developed by the invention can remove Rb-88, rb-89, cs-134 and Cs-137 in the process water at the same time.
Example 4: preparation of activated carbon supported adsorbent and cesium adsorption performance thereof
Preferably, coconut shell activated carbon particles with granularity of 0.5-2.0mm are used as a carrier, the coconut shell activated carbon particles are washed by pure water until the pH value is neutral and the conductivity is less than 20 mu S/cm, and then the activated carbon particles are dried to be used as an adsorbent carrier. The measurement shows that the selected activated carbon particles have higher mechanical strength, the crushing strength is more than 20N/particle, and the nickel (II) potassium ferrocyanide adsorbent is prepared on the activated carbon particles, and the steps are as follows:
(1) Load of ferrocyanide: firstly, adding pure water into a No. 1 reaction kettle, heating to 80-100 ℃, and adding potassium ferrocyanide into the reaction kettle to dissolve the potassium ferrocyanide to form a solution with the concentration of 10-50%; secondly, adding activated carbon particles serving as a carrier into a reaction kettle, soaking for 10-48 hours, then carrying out solid-liquid phase separation, and drying in a constant-temperature oven to obtain a precursor GAC-1-A loaded with ferrocyanide.
(2) Preparing a transition metal stabilized ferrocyanide adsorbent: firstly, adding pure water into a No. 2 reaction kettle, heating to 80-100 ℃, and adding nickel sulfate into the reaction kettle to dissolve the nickel sulfate and form a solution with the concentration of 10-50%; secondly, adding the precursor GAC-1-A loaded with ferrocyanide obtained in the step (1) into a reaction kettle, uniformly stirring, sealing the reaction kettle, setting the reaction temperature at 120 ℃ for reaction for 10-24 hours, and carrying out solid-liquid phase separation after the reaction is finished to obtain the primary cesium removal adsorbent GAC-1-B.
(3) Cleaning the adsorbent: and (3) cleaning the primary cesium removal adsorbent GAC-1-B obtained in the step (2) by purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the conductivity of the cleaning solution after continuous stirring for 24 hours is less than 20 mu s/cm and the turbidity is reduced by less than 20mg/L, and drying the obtained adsorbent and marking the adsorbent as a secondary adsorbent GAC-1-C.
(4) Coating an adsorbent: the surface of the secondary adsorbent GAC-1-C obtained in the step (3) is coated with a high molecular layer, the method is that polyvinyl alcohol is used as a binder, and firstly the polyvinyl alcohol is dissolved in pure water to prepare a solution, and the concentration is 1-10wt%. Adding a secondary adsorbent GAC-1-C into the solution system, wherein the liquid-solid ratio is 10:1; and continuing stirring and reacting for 2-10h, and then separating solid and liquid phases to obtain the tertiary adsorbent GAC-1-D.
(5) Cleaning the adsorbent: and (3) cleaning the three-stage cesium removal adsorbent GAC-1-D obtained in the step (4) by adopting purified water, wherein the volume of water used for each cleaning is 10 times of the volume of the adsorbent until the turbidity of the washing liquid after continuous stirring for 24 hours is less than 20mg/L and the conductivity is less than 20 mu s/cm, then separating solid from liquid, and drying the adsorbent in vacuum to obtain the final granular active carbon-loaded nickel potassium ferrocyanide cesium removal adsorbent.
The crushing strength of the adsorbent is measured to be 32N/particle, after the adsorbent is soaked for 24 hours under the condition of a liquid-solid ratio of 10, the turbidity in the liquid is 12mg/L, the conductivity is 18 mu s/cm, and the COD concentration in the solution is 1.4mg/L.
The cesium adsorption performance was measured by a static adsorption method, the volume of the test solution was 40mL, and the mass of the adsorbent was 10mg. The boric acid concentration in boron in the test solution was 1000ppm, and the initial concentration of Cs was 10mg/L. The decontamination factor of the adsorbent for Cs was determined to be 48.3 in the experiment.
The various aspects of the present invention have been explained above by way of specific examples, but it will be understood by those skilled in the art that: the present invention is not limited to the specific embodiments described above, and equivalents of the various means, materials, process steps, etc., disclosed herein, as well as combinations of the various means, materials, process steps, etc., will be within the scope of the invention.
To further illustrate certain aspects of the invention, the invention also specifically provides some non-limiting embodiments as follows:
1. a particulate inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent comprising: a particulate inorganic oxide support, or a particulate activated carbon support; a transition metal stabilized ferrocyanide layer coating the inorganic oxide or activated carbon support; and a polymer material layer coating the transition metal stabilized ferrocyanide layer.
2. The adsorbent of embodiment 1, wherein the polymeric material layer comprises sodium alginate, chitosan, polyethylene glycol having a number average molecular weight between 2000 and 6000, polyvinyl alcohol, sucrose, or any combination thereof.
3. The adsorbent of embodiment 1 or 2, having a crush strength of 2-100N/particle.
4. The adsorbent according to any one of embodiments 1 to 3, which has such an ion leaching property that the turbidity of the resulting liquid after soaking the adsorbent at a liquid-solid ratio of 10 for 24 hours is 10mg/L or less.
5. The adsorbent according to any one of embodiments 1 to 4, which has such an ion leaching property that the electrical conductivity of the resulting liquid after soaking the adsorbent at a liquid-solid ratio of 10 for 24 hours is 15 μs/cm or less.
6. The adsorbent of any one of embodiments 1 to 5, wherein the transition metal stabilized ferrocyanide layer is formed by: reacting the support loaded with ferrocyanide with an aqueous solution of a transition metal salt in a sealed reaction vessel at a temperature of 100-150 ℃ for 2-24 hours, or reacting the support loaded with a transition metal salt with an aqueous solution of ferrocyanide for 2-24 hours.
7. The sorbent as claimed in claim 6, wherein the transition metal salt comprises copper sulfate, copper nitrate, copper chloride, ferrous sulfate, ferric nitrate, nickel sulfate, zinc chloride, zinc sulfate, zinc acetate, cobalt nitrate, cobalt chloride, zirconium oxychloride, manganese sulfate, or any combination thereof.
8. The adsorbent of any one of claims 1 to 7, wherein the support has a crush strength greater than 20N/particle or greater than 30N/particle.
9. A process for preparing a particulate inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent comprising:
1) Providing a primary adsorbent;
2) Washing the primary adsorbent of step 1) with deionized water until the washing liquid has a conductivity of 25.0 mu s/cm or less and a turbidity of 30mg/L or less;
3) Coating the washed primary adsorbent with a polymeric material, thereby obtaining a coated primary adsorbent; and
4) Optionally washing the coated primary adsorbent of step 3) with deionized water until the washing solution has a conductivity of 20.0 mu s/cm or less and a turbidity of 20mg/L or less,
thus obtaining the ferrocyanide adsorbent stabilized by the granular inorganic oxide or the activated carbon supported transition metal.
10. The method according to embodiment 9, wherein the step of providing the primary adsorbent comprises immersing the particulate inorganic oxide or the particulate activated carbon support in an aqueous solution of ferrocyanide for 2 to 48 hours, thereby obtaining a precursor a loaded with ferrocyanide, and then mixing the precursor a with an aqueous solution of a transition metal salt, and reacting at a temperature of 100 to 150 ℃ for 2 to 24 hours in a sealed reaction vessel.
11. The method according to embodiment 9, wherein the step of providing the primary adsorbent comprises immersing the particulate inorganic oxide or the particulate activated carbon support in an aqueous solution of a transition metal salt for 2 to 48 hours, thereby obtaining a precursor B loaded with the transition metal salt, and then mixing the precursor B with an aqueous solution of ferrocyanide and reacting at a temperature of 100 to 150 ℃ for 2 to 24 hours in a sealed reaction vessel.
12. The method of any of embodiments 9-11, wherein the polymeric material comprises sodium alginate, chitosan, polyethylene glycol (2000-6000), polyvinyl alcohol, sucrose, or a combination thereof, preferably formulated as an aqueous solution having a concentration of 1% to 20% by weight.
13. The method of any of embodiments 9-12, wherein the step of coating the washed primary adsorbent with a polymeric material is performed in the presence of an acid or a base.
14. The method of embodiment 13, wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, or a combination thereof, preferably having a concentration of 0.01-1 mol/L; the base is selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, or a combination thereof, preferably having a concentration of 0.01-1 mol/L.
15. The method of any of embodiments 9-14, wherein the particulate inorganic oxide support comprises silica gel pellets, alumina pellets, titania pellets, zirconia pellets, molecular sieve pellets, or a combination thereof, preferably having a particle size of 0.5 to 5mm, and/or a crush strength of 2-150N/particle, preferably a crush strength of greater than 30N/particle.
16. The method of any of embodiments 9-14, wherein the particulate activated carbon support comprises coal-based carbon, coconut shell carbon, fruit shell carbon, or a combination thereof, preferably having a particle size of 0.5 to 5mm, and/or a crush strength of 2-150N/particle, preferably greater than 20N/particle.
17. The method of any of embodiments 9-16, wherein the ferrocyanide comprises potassium ferrocyanide, sodium ferrocyanide, or a combination thereof, preferably the aqueous solution of ferrocyanide has a concentration of 10-50 wt%.
18. The method of any of embodiments 9-17, wherein the transition metal salt comprises copper sulfate, copper nitrate, copper chloride, ferrous sulfate, ferric nitrate, nickel sulfate, zinc chloride, zinc sulfate, zinc acetate, cobalt nitrate, cobalt chloride, zirconium oxychloride, manganese sulfate, or any combination thereof, preferably the aqueous solution of the transition metal salt has a concentration of 10-60 wt%.
19. A particulate inorganic oxide or activated carbon-supported metal ion-stabilized ferrocyanide adsorbent prepared by the method of any one of embodiments 9-18.
20. Use of the particulate inorganic oxide or activated carbon-supported metal ion-stabilized ferrocyanide adsorbent of any one of embodiments 1-8 or embodiment 19 for adsorbing radioisotope Cs ions or adsorbing stable isotope Cs ions.
21. The use of embodiment 20 for removing or separating or extracting radioisotope Cs ions or for removing or separating or extracting stable isotope Cs ions.
22. Use of the particulate inorganic oxide or activated carbon-supported metal ion-stabilized ferrocyanide adsorbent of any one of embodiments 1-8 or embodiment 19 for adsorbing radioisotope Rb ions or adsorbing stable isotope Rb ions.
23. The use of embodiment 22 for removing or separating or extracting radioisotope Rb ions or for removing or separating or extracting stable isotope Rb ions.
Claims (10)
1. A particulate inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent comprising: a particulate inorganic oxide support, or a particulate activated carbon support; a transition metal stabilized ferrocyanide layer coating the inorganic oxide or activated carbon support; and a polymer material layer coating the transition metal stabilized ferrocyanide layer.
2. The adsorbent of claim 1, wherein the polymeric material layer comprises sodium alginate, chitosan, polyethylene glycol having a number average molecular weight between 2000-6000, polyvinyl alcohol, sucrose, or any combination thereof.
3. The adsorbent of claim 1 or 2, having a crush strength of 2-100N/particle.
4. The adsorbent of claim 1 or 2, which has such an ion leaching property that the turbidity of the resulting impregnation liquid after soaking at a liquid-solid ratio of 10 for 24 hours is 10mg/L or less.
5. The adsorbent of claim 1 or 2, having such ion leaching characteristics that the electrical conductivity of the resulting liquid after soaking the adsorbent at a liquid-solid ratio of 10 for 24 hours is 15 μs/cm or less.
6. A process for preparing a particulate inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent comprising:
1) Providing a primary adsorbent;
2) Washing the primary adsorbent of step 1) with deionized water until the washing liquid has a conductivity of 25.0 mu s/cm or less and a turbidity of 30mg/L or less;
3) Coating the washed primary adsorbent with a polymeric material, preferably in the presence of an acid or a base, to obtain a coated primary adsorbent; and
4) Optionally washing the coated primary adsorbent of step 3) with deionized water until the washing solution has a conductivity of 20.0 mu s/cm or less and a turbidity of 20mg/L or less,
thus obtaining the ferrocyanide adsorbent stabilized by the granular inorganic oxide or the activated carbon supported transition metal.
7. The method of claim 6, wherein the step of providing the primary adsorbent comprises immersing the particulate inorganic oxide or the particulate activated carbon support in an aqueous solution of ferrocyanide for 2 to 48 hours to obtain a precursor a loaded with ferrocyanide, and then mixing the precursor a with an aqueous solution of a transition metal salt and reacting at a temperature of 100 to 150 ℃ for 2 to 24 hours.
8. The method of claim 6, wherein the step of providing the primary adsorbent comprises immersing the particulate inorganic oxide or the particulate activated carbon support in an aqueous solution of a transition metal salt for 2 to 48 hours to obtain a precursor B loaded with the transition metal salt, and then mixing the precursor B with an aqueous solution of ferrocyanide and reacting at a temperature of 100 to 150 ℃ for 2 to 24 hours.
9. A particulate inorganic oxide or activated carbon supported metal ion stabilized ferrocyanide adsorbent prepared by the process of any one of claims 6-8.
10. Use of a ferrocyanide adsorbent stabilized by a particulate inorganic oxide or a particulate activated carbon as claimed in any one of claims 1 to 5 or by a particulate activated carbon-supported metal ion for adsorbing radioisotope Cs ions or adsorption-stabilized isotope Cs ions and/or for adsorbing radioisotope Rb ions or adsorption-stabilized isotope Rb ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311059860.8A CN117019109A (en) | 2018-01-04 | 2018-01-04 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810008565.2A CN108160048B (en) | 2018-01-04 | 2018-01-04 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
| CN202311059860.8A CN117019109A (en) | 2018-01-04 | 2018-01-04 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810008565.2A Division CN108160048B (en) | 2018-01-04 | 2018-01-04 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117019109A true CN117019109A (en) | 2023-11-10 |
Family
ID=62517182
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311059860.8A Pending CN117019109A (en) | 2018-01-04 | 2018-01-04 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
| CN201810008565.2A Active CN108160048B (en) | 2018-01-04 | 2018-01-04 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810008565.2A Active CN108160048B (en) | 2018-01-04 | 2018-01-04 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (2) | CN117019109A (en) |
| GB (1) | GB2587072B (en) |
| WO (1) | WO2019134183A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109865537A (en) * | 2019-01-17 | 2019-06-11 | 中国辐射防护研究院 | A kind of calcium alginate-copper ferrocyanide compound ion exchanger and preparation method thereof |
| CN109908877B (en) * | 2019-04-03 | 2022-05-03 | 陕西省膜分离技术研究院有限公司 | Preparation method of rubidium ion adsorption microspheres |
| CN109865504B (en) * | 2019-04-03 | 2022-05-03 | 陕西省膜分离技术研究院有限公司 | Rubidium ion adsorption microsphere and application thereof |
| KR102287933B1 (en) * | 2019-11-18 | 2021-08-06 | 상명대학교 천안산학협력단 | Method for preparing hybrid adsorbent for removing cationic and anionic contaminants simultaneously and hybrid adsorbent prepared thereby |
| CN111589411A (en) * | 2020-05-19 | 2020-08-28 | 兴核科学研究(福建)有限责任公司 | Preparation method of cesium-strontium adsorbent particles |
| CN111560196A (en) * | 2020-05-19 | 2020-08-21 | 兴核科学研究(福建)有限责任公司 | Strippable film solutions for radionuclide decontamination, methods of making and using |
| CN112742343A (en) * | 2020-11-13 | 2021-05-04 | 烟台大学 | Copper nickel ferrocyanide/montmorillonite composite material, preparation method and adsorption application thereof |
| CN113509910B (en) * | 2020-11-25 | 2022-06-10 | 中国科学院青海盐湖研究所 | Preparation method of metal ferricyanide adsorbent particles for liquid rubidium and cesium resource extraction |
| CN112973635B (en) * | 2021-03-23 | 2023-08-18 | 江苏嘉盛旺环境科技有限公司 | Preparation process of sewage dephosphorization activated carbon |
| CN115703060A (en) * | 2021-08-03 | 2023-02-17 | 中国科学院青海盐湖研究所 | Preparation method and product of magnetic bimetallic MOF rubidium/cesium adsorbent |
| CN114433023A (en) * | 2022-03-25 | 2022-05-06 | 西南科技大学 | Ferrous potassium nickel cyanide adsorbing material grown in situ on surface of activated carbon and preparation method thereof |
| CN114672654B (en) * | 2022-03-29 | 2023-05-05 | 中国科学院过程工程研究所 | Method for recycling rubidium and cesium in salt lake brine by using heteropolyacid salt electrode |
| CN115522068B (en) * | 2022-09-16 | 2023-08-01 | 河北远大中正生物科技有限公司 | Method for separating rubidium and cesium from high-salt mother solution |
| CN115608330A (en) * | 2022-09-29 | 2023-01-17 | 一重集团大连工程技术有限公司 | Composite microsphere adsorbent for removing radioactive cesium and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100469435C (en) * | 2007-03-16 | 2009-03-18 | 清华大学 | Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials |
| CN101279249B (en) * | 2008-05-23 | 2010-04-07 | 清华大学 | Preparation of potassium zirconium hexacyanoferrate using pellet silica-gel as carrier |
| CN102114403B (en) * | 2009-12-31 | 2013-04-10 | 中国科学院生态环境研究中心 | Compound arsenic-removing adsorbent and preparation method thereof |
| CN102698716B (en) * | 2011-03-28 | 2016-04-06 | 清华大学 | A kind of metal oxide particle adsorbent and preparation method thereof |
| CN102836693B (en) * | 2012-09-19 | 2014-05-14 | 清华大学 | Magnetic-nucleus coated type inorganic ion adsorbent used for removing Cs ions in radioactive wastewater, and preparation method of same |
| JP6320781B2 (en) * | 2014-02-06 | 2018-05-09 | 国立研究開発法人日本原子力研究開発機構 | Ferrocyanide particle-polysaccharide complex |
| CN105597660A (en) * | 2015-12-30 | 2016-05-25 | 清华大学 | Preparing method of particle caesium removing inorganic ion adsorbent and product and application |
| CN106552602B (en) * | 2016-11-07 | 2019-05-21 | 北京师范大学 | It is a kind of for adsorbing the preparation method of the composite adsorbing material of rubidium cesium ion |
-
2018
- 2018-01-04 CN CN202311059860.8A patent/CN117019109A/en active Pending
- 2018-01-04 CN CN201810008565.2A patent/CN108160048B/en active Active
- 2018-01-11 WO PCT/CN2018/072213 patent/WO2019134183A1/en active Application Filing
- 2018-01-11 GB GB2009144.3A patent/GB2587072B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| GB202009144D0 (en) | 2020-07-29 |
| WO2019134183A1 (en) | 2019-07-11 |
| CN108160048B (en) | 2023-07-14 |
| GB2587072A (en) | 2021-03-17 |
| GB2587072B (en) | 2022-09-07 |
| CN108160048A (en) | 2018-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108160048B (en) | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof | |
| Weerasekara et al. | Metal oxide enhanced microfiltration for the selective removal of Co and Sr ions from nuclear laundry wastewater | |
| Ye et al. | The rapid removal of iodide from aqueous solutions using a silica-based ion-exchange resin | |
| JP5922193B2 (en) | NOVEL ADSORBENT, METHOD FOR PRODUCING THE SAME AND USE THEREOF | |
| WO2019134437A1 (en) | Particulate sb 2o 5 adsorbent, preparation method therefor and use thereof for removing radioactive 90sr and 100mag | |
| EP3412361A1 (en) | Method for preparing particulate form caesium-removal inorganic ion adsorbent and product and application thereof | |
| WO2015101071A1 (en) | Silicon-based titanate composite adsorbent for removing radioactive strontium and preparation method therefor | |
| CN102626605A (en) | Material for removing radioactive elements from water and preparation and use methods thereof | |
| Wu et al. | Study on adsorption behavior of cesium using ammonium tungstophosphate (AWP)-calcium alginate microcapsules | |
| EP2750137A1 (en) | Method for removing cesium ions from water and device for removing cesium ions from water | |
| Gomaa et al. | Green extraction of uranium (238U) from natural radioactive resources | |
| Dong et al. | Research on the application potential of spent biological activated carbon from BAC process to remove radionuclides Sr 2+ from water | |
| CN105617982B (en) | In a kind of removal radioactive water110mInorganic adsorbent of Ag and preparation method thereof | |
| JP5967748B2 (en) | Mesoporous silica supporting cesium ion adsorbing compound and cesium collector, cesium recovery method, cesium ion collector, cesium ion concentration sensor and cesium removal filter using the same | |
| CN103578594B (en) | A kind of use nanometer Fe3O4-CeO2The method of radionuclide removed by material | |
| CN105107478A (en) | Zirconium-loaded organic hybridizing adsorbent capable of removing radioactive caesium in water as well as preparation and use method of zirconium-loaded organic hybridizing adsorbent | |
| CN105311973A (en) | Preparation and application of iodine removing material | |
| Yoshizuka et al. | Arsenic and boron in geothermal water and their removal | |
| Mimura et al. | Selective separation and recovery of cesium by ammonium tungstophosphate-alginate microcapsules | |
| Krishna et al. | Performance of immobilized moss in the removal of 137 Cs and 90 Sr from actual low-level radioactive waste solutions | |
| Sun et al. | Efficient Co‐Adsorption and Highly Selective Separation of Cs+ and Sr2+ with a K+‐Activated Niobium Germanate by the pH Control | |
| KR102031100B1 (en) | Cesium adsorbent containing cray with magnetic nanoparticles | |
| JP5963230B2 (en) | Mesoporous silica supporting strontium ion adsorbing compound, strontium ion collector, strontium ion concentration sensor, strontium removal filter and strontium recovery method using the same | |
| CN108579660A (en) | Handle the ternary metal oxide material of radionuclide and its application in waste water | |
| CN114669269B (en) | Cs (cell lines) + 、Sr 2+ Co-adsorption-separation dual-function ion exchanger and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |