GB2587072A - Large-scale preparation method for highly stable cesium removal adsorbent, product thereof and use thereof - Google Patents
Large-scale preparation method for highly stable cesium removal adsorbent, product thereof and use thereof Download PDFInfo
- Publication number
- GB2587072A GB2587072A GB2009144.3A GB202009144A GB2587072A GB 2587072 A GB2587072 A GB 2587072A GB 202009144 A GB202009144 A GB 202009144A GB 2587072 A GB2587072 A GB 2587072A
- Authority
- GB
- United Kingdom
- Prior art keywords
- adsorbent
- ferrocyanide
- activated carbon
- transition metal
- particulate
- 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.)
- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 240
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052792 caesium Inorganic materials 0.000 title abstract description 40
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 36
- 150000002500 ions Chemical class 0.000 claims abstract description 21
- 229910001417 caesium ion Inorganic materials 0.000 claims abstract description 20
- 229910001419 rubidium ion Inorganic materials 0.000 claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 230000007704 transition Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 238000000034 method Methods 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 36
- 229910052723 transition metal Inorganic materials 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 239000002861 polymer material Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 150000003624 transition metals Chemical class 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- -1 transition metal salt Chemical class 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 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 8
- 239000005720 sucrose Substances 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
- 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
- 229920001661 Chitosan Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 230000002285 radioactive effect Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 44
- 238000003756 stirring Methods 0.000 description 26
- 239000007791 liquid phase Substances 0.000 description 24
- 238000005191 phase separation Methods 0.000 description 24
- 239000002699 waste material Substances 0.000 description 20
- 239000008188 pellet Substances 0.000 description 18
- 238000005202 decontamination Methods 0.000 description 15
- 230000003588 decontaminative effect Effects 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 238000011282 treatment Methods 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 230000002829 reductive effect Effects 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000011068 loading method Methods 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base 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
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000000276 potassium ferrocyanide Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- 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
- 230000002328 demineralizing effect Effects 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000264 sodium ferrocyanide Substances 0.000 description 4
- 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 4
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- DYPHJEMAXTWPFB-UHFFFAOYSA-N [K].[Fe] Chemical compound [K].[Fe] DYPHJEMAXTWPFB-UHFFFAOYSA-N 0.000 description 3
- FJAAKDGALOFQSO-UHFFFAOYSA-N [K].[Ni] Chemical compound [K].[Ni] FJAAKDGALOFQSO-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000011161 development Methods 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 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
- NCCSSGKUIKYAJD-UHFFFAOYSA-N rubidium(1+) Chemical compound [Rb+] NCCSSGKUIKYAJD-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- VDNXILQBKLFION-UHFFFAOYSA-N [K].[Cu] Chemical compound [K].[Cu] VDNXILQBKLFION-UHFFFAOYSA-N 0.000 description 2
- NFVZIERLAZUYBQ-UHFFFAOYSA-N [K].[Zn] Chemical compound [K].[Zn] NFVZIERLAZUYBQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- MIAJZAAHRXPODB-UHFFFAOYSA-N cobalt potassium Chemical compound [K].[Co] MIAJZAAHRXPODB-UHFFFAOYSA-N 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 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
- 239000007790 solid phase Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 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
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013208 measuring procedure Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture 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
- 238000011056 performance test Methods 0.000 description 1
- DTEMQJHXKZCSMQ-UHFFFAOYSA-J phosphonato phosphate;zirconium(4+) Chemical compound [Zr+4].[O-]P([O-])(=O)OP([O-])([O-])=O DTEMQJHXKZCSMQ-UHFFFAOYSA-J 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
- 238000000746 purification Methods 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/0225—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
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- 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
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Abstract
The present invention relates to a large-scale preparation method for highly stable cesium removal adsorbent, a product thereof and use thereof. In particular, the present invention 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 covering the inorganic oxide or activated carbon support; and a polymeric material layer covering the transition metal-stabilized ferrocyanide layer. The adsorbent has high crushing strength and low ion leaching rate. The present invention further relates to a preparation method for the adsorbent and use of same for removing radioactive isotope Cs ions and removing stable isotope Cs ions, and use of same for removing radioactive isotope Rb ions and removing stable isotope Rb ions.
Description
LARGE-SCALE PREPARATION PROCESS OF HIGHLY STABLE ADSORBENT FOR REMOVING CESIUM, THE RESULTING ADSORBENT AND USE THEREOF
S
TECHNICAL FIELD
100011 The invention refers to the field of inorganic materials, in particular to a large-scale preparation process of highly stable adsorbent for removing cesium, the resulting adsorbent and use thereof. The adsorbent also has good adsorption performance for 10 rubidium
BACKGROUND
100021 According to the Medium-and Long-term Development Plan of Nuclear Power (2005-2020) in China, the nuclear power capacity in Mainland China will increase to 58 GW in operation and 30 OW under construction by 2020; and China will comprehensively realize a goal of building a nuclear powerful nation in 2030. Facing the new situation and new challenges in the development of nuclear energy, China urgently needs to develop vigorously in radioactive waste treatment, nuclear emergency technology, radioactive effluent discharge standards, and the like.
100031 Efficient and timely treatment of radioactive liquids is one of the important issues to be solved in the establishment of a defense-in-depth system for nuclear safety. Therefore, it is urgent to carry out research, development, and reserve of new technologies, new devices, and new materials for emergency treatment of waste liquid, and to establish multi-level technical support for waste liquid treatment and disposal in nuclear power plants. The first level is the actual elimination of radionuclides during normal operation of nuclear power plants. This technology is mainly aimed at the removal of radioactive waste during the normal operation of nuclear power plants, and achieves the reduced amount of wastes while ensuring the stability and effectiveness of the treatment process. The second level is the timely on-site emergency treatment of waste liquid comprising a wide range of nuclides with various forms when some problems such as fuel damage occur in a power plant. This technology could achieve the removal of contaminants in a timely, rapid and efficient manner and prevent the leakage of radioactive materials. The third level is the last defense line in the defense-in-depth system. That is, in the extreme case of an accident that exceeds design standards, the off-site nuclear emergency treatment is quickly initiated to minimize the environmental impact of the nuclear accident.
100041 As compared with ion exchange resin, inorganic ion adsorbent has high selectivity to main nuclides with trace amount including Cs, Sr, Co, Ag, I, and the like, and has effectiveness on removing target nuclide ions from high-salt radioactive wastewater, significant decrease on radioactivity of waste liquids, and less influence by coexisting non-radioactive ions. Thus, inorganic ion adsorbent has many advantages including long service life and small production of solid waste. In addition, a large amount of radionuclides are enriched in a small volume of solid inorganic ion exchanger, resulting in relatively easy radiation protection. As compared with waste resin obtained by adsorption, inorganic adsorption technology produces radioactive waste having good thermal stability and chemical stability, strong radiation resistance, and being difficult to be decomposed by radiation or biodegraded, being convenient for subsequent treatment and disposal, and more safety for long-term storage in underground disposal sites. Further, the advanced waste liquid purification device based on the inorganic adsorption technology has advantages including simple structure, high effectiveness and selectiveness, miniaturization, modularization, and portability, meanwhile low requirements for on-site service conditions. Thus this device is very suitable for a nuclear power plant which usually produces radioactive waste liquid with complicated components and has special requirements such as very limited on-site space [0005] Based on the characteristics of high efficiency, rapidity and high selectivity of inorganic adsorbents, inorganic adsorption technology plays a key role in treatment of waste liquid from nuclear power plant accident. Taking the treatment of waste liquid generated from Fukushima nuclear accident in Japan as the most typical case, from the establishment of the initial radioactive wastewater treatment system to the gradual improvement in the later operation process, a coupled process route of inorganic adsorption + membrane technology has been maintained, wherein the inorganic adsorption process is used to selectively remove the main nuclides Cs-134 and Cs-137, greatly reduce the radioactivity level of the wastewater, reduce the requirements on radiation protection in the subsequent processes, and the membrane process is further utilized to broadly remove radionuclides in water. According to the water quality monitoring results provided by Fukushima, after Cs adsorption and reverse osmosis processes, the radioactivity level of the water sample was reduced from the initial level of IC-108 Bq/L (the initial level after the accident was higher than this level) to a level of 103-101 Bq/L. Inorganic adsorbents have also been used in nuclear power plants under normal operating conditions.
For example, adsorbents for removing cesium are used in the Loviisa power plant in Finland and the Paks power plant in Hungary, to further reduce the volume of the nuclear power plant evaporator waste liquid. Inorganic adsorbents are used in the Dundee power plant in Scotland to selectively remove Cs-134 and Cs-137 from 1500 tons of waste liquid generated from Na-cooled reactor and 57 tons of high salinity waste liquid generated from Na/IC-cooled reactor. An inorganic adsorbent is used in the Bradvvell Magnox power plant in the United Kingdom to treat the acidic solution of fuel element debris during the decommissioning of the nuclear facility. The Japan Atomic Energy Research Institute (JAERI) uses inorganic adsorbents to remove Pu/Cs/Sr in waste liquid dissolved in concentrated nitric acid. The Savannah River and Callaway nuclear power plants in the United States, the Sellafield nuclear power plant in the United Kingdom, and the Olkiluoto nuclear power plant in Finland all use inorganic adsorbents to treat waste liquid in spent fuel storage pool 100061 k the past few decades, there have been only a small amount of studies on inorganic adsorbents for removing caesium, including, for example, zirconium pyrophosphate (Chinese invention patent publication CN106342077B from China Institute of Atomic Energy); inorganic composite adsorbent composed of non-metallic minerals treated by corresponding treatments (Chinese invention patent publication CN103691393B of Beijing Research Institute of Uranium Geology); magnetic caesium-selective adsorbent (Chinese invention patent publication CN104054136 of Japan INC Corp, and Chinese invention patent publication CN1129922C of China Institute of Atomic Energy); and the ferrocyanide series of inorganic adsorbent for removing caesium as developed by our research group, wherein these series have good performance in the treatment of emergency radioactive wastewater from nuclear power plants, and have obtained many patents in China, such as CN100469435C, CN 101279249B, CN102836693B, etc. 10007] The AP1000 reactors under construction in China are designed to remove Cs- 134 and Cs-137 in process water by inorganic adsorbent. The process water mainly includes core cooling water in the normal operation of nuclear power plants, cooling water in nuclear fuel storage pools, etc. In most of the nuclear power plants in operation in China, a nuclear-grade water filter and an ion-exchange demineralizing bed are used for removing, wherein filters with different filtration precisions are provided before and after the demineralizing bed with filters. The front filter is used to remove particulate matters from the waste liquid to protection the demineralizing bed in operation, whereas the later filter is mainly used to remove the waste resin particles generated by the demineralizing bed to ensure the cleanliness of the effluent. Operation of a power plant requires very high water quality for the process water. For example, the process water requires extremely low electrical conductivity and ion concentration to inhibit metal corrosion and ensure safe operation of reactor, and requires very low turbidity to avoid the filter from being blocked during treatment with process water, thereby prolonging the service life of the filter and reducing the amount of solid waste. In the design of process water treatment in AP1000, flocculation combined with activated carbon filtration technology is used to remove the colloid in waste liquid, followed by inorganic adsorbent to remove the main nuclides Cs- 134 and Cs-137, and subsequent ion exchange resin to remove other nuclides. Such a removing process is designed to improve the handling of radionuclides and to reduce the amount of radioactive waste resin produced. At present, the inorganic adsorbent designed and used in the A P1000 is zeolite. However, during the application, there is a phenomenon that the inorganic adsorbent exhibits a low adsorption speed and is prone to powdering which causes the increased turbidity and conductivity of water.
100081 In view of the above, it is still an urgent problem to be solved to provide a high-strength, high-stability inorganic adsorbent capable of efficiently removing cesium ions from process water under normal operating conditions of a nuclear power plant.
SUMMARY
100091 It is an object of the present invention to provide a high-strength, high-stability particulate adsorbent for removing cesium and achieving efficient removal of Cs-134 and Cs-137 from process water under normal operating conditions of a nuclear power plant.
100101 After extensive experiments, the present inventors have surprisingly found that an adsorbent for removing cesium with good mechanical stability and low ion leaching rate is obtained by washing and removing solid phase particles loosely coupled on surface of the transition metal stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or activated carbon as well as soluble ions in the adsorbent, and coating the adsorbent with a polymer material layer.
100111 k one aspect, the present disclosure provides a transition metal stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon, comprising: a particulate inorganic oxide support or a particulate activated carbon support; a transition metal-stabilized ferrocyanide layer for coating the inorganic oxide support or the activated carbon support; and a polymer material layer for coating the transition metal-stabilized ferrocyanide layer.
100121 Preferably, the polymer material comprises sodium alginate, chitosan, polyethylene glycol having a number average molecular weight of between 2000 and 6000, polyvinyl alcohol, sucrose or any combination thereof 100131 Preferably, the adsorbent according to the invention has a crushing strength of 2-100 N/particle.
100141 Preferably, the adsorbent according to the invention has an ion leaching property so that after immersing the adsorbent for 24 hours at a liquid-solid ratio of 10, the obtained leach solution has a turbidity of lower than 10 mg/L.
100151 Preferably, the adsorbent according to the invention has an ion leaching property so that after immersing the adsorbent for 24 hours at a liquid-solid ratio of 10, the obtained leach solution has an electric conductivity of lower than 15 nS/cm.
100161 The resulting adsorbent is capable of efficiently removing Cs-134 and Cs-137 from process water under normal operating conditions of a nuclear power plant. The adsorbent is suitable for use not only in the API 000 reactor, but also in various types of pressurized water reactor nuclear power plants in China and abroad to reduce the emissions of the main nuclides Cs-134 and Cs-137 and reduce the amount of ion exchange resin, thereby achieving the goal of the reduced amount of waste. Moreover, the resulting adsorbent also has good adsorption properties to the nuclides of the same group such as Rb-88 and Rb-89 present in the radioactive waste liquid.
100171 k another aspect, the present disclosure also relates to a process for the preparation of the transition metal stabilized ferrocyanide adsorbents supported by a particulate inorganic oxide or a particulate activated carbon as described above, comprising the steps of: 10018] 1) providing a primary adsorbent; 100191 2) washing the primary adsorbent from step 1) with deionized water until the washing liquid has an electric conductivity of 25.0!AS/cm or lower and a turbidity of 30 mg/L or lower; and 100201 3) coating the primary adsorbent with a polymer material, preferably in the presence of an acid or a base, to obtain the coated primary adsorbent; and 100211 4) optionally, washing the coated primary adsorbent from step 3) with deionized water until the resulting washing liquid has an electric conductivity of 20.0 p.S/cm or lower and a turbidity of 20 mg/L or lower, 100221 thereby obtaining the transition metal stabilized ferrocyanide adsorbents supported by a particulate inorganic oxide or a particulate activated carbon.
100231 Preferably, according to an embodiment of the present invention, the step of providing a primary adsorbent comprises: immersing the particulate inorganic oxide or particulate activated carbon support in an aqueous solution of ferrocyanide for 2 to 48 hours, thereby obtaining a precursor A loaded with ferrocyanide, then mixing the precursor A with an aqueous solution of a transition metal salt and reacting at a temperature of 100 to 150 °C for 2 to 24 hours.
100241 Preferably, according to an embodiment of the present invention, the step of providing a primary adsorbent comprises: immersing the particulate inorganic oxide or 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 transition metal salt, then mixing the precursor B with an aqueous solution of ferrocyanide and reacting at a temperature of 100 to 150 °C for 2 to 24 hours.
100251 In a particular embodiment of the invention, the adsorbent according to the invention is prepared by the following steps: 100261 (1) loading of ferrocyanide: firstly adding pure water in reaction vessel No. 1 and heating to 80-100 °C, and adding soluble ferrocyanide to dissolve it, secondly, adding a particulate inorganic oxide support or a particulate activated carbon support to the reaction vessel, and immersing for 2 to 48 hours, followed by performing a solid-liquid phase separation and drying, to obtain a precursor A loaded with ferrocyanide; 100271 (2) preparation of transition metal stabilized ferrocyanide adsorbent: first adding pure water in reaction vessel No. 2 and heating to 80-100 °C, and adding soluble transition metal salt to dissolve it; secondly, adding the precursor A loaded with ferrocyanide obtained in step (1) to the reaction vessel, and after stirring uniformly, sealing the reaction vessel, and reacting at a reaction temperature of 100-150 °C for 2 to 24 hours; and after the completion of the reaction, performing a solid-liquid phase separation, thereby obtaining a primary adsorbent B for removing cesium; 100281 (3) cleaning the adsorbent: cleaning the primary adsorbent B for removing cesium obtained in step (2) with deionized water, preferably for 10 hours or longer, until the washing liquid has an electric conductivity of 25.0 MS/cm or lower and a turbidity of 30.0 mg/L or lower; then drying the obtained adsorbent, preferably in constant temperature oven or vacuum oven at a dry temperature of 60-120 °C, thereby obtaining secondary adsorbent C; 100291 (4) coating the adsorbent: coating the surface of the secondary adsorbent C obtained from step (3) with polymer material by the following procedure: dissolving the polymer material having a binding effect in pure water to prepare a solution having a certain concentration; adding the secondary adsorbent C into solution system; adding an acidic or alkali solution dropwise under stirring, depending on the polymer material; after stirring the mixture for 1 to 10 hours, performing a solid-liquid phase separation to obtain a tertiary adsorbent D; 100301 (5) washing the adsorbent: washing the tertiary adsorbent D for removing cesium obtained in step (4) with deionized water, preferably for 10 hours or longer, until the resulting washing liquid has an electric conductivity of 20.0 ftS/cm or lower and a turbidity of 20 mg/L or lower, followed by performing a solid-liquid phase separation, and drying the adsorbent, preferably using a constant temperature oven or a vacuum oven at a drying temperature of 60 to 120 °C, thereby obtaining the final adsorbent E for removing cesium.
100311 Further, according to the disclosure, the ferrocyanide used is soluble, including potassium ferrocyanide and sodium ferrocyanide. Preferably, the soluble ferrocyanide has a concentration of 10 to 50 wt.% in aqueous solution.
100321 Further, according to the disclosure, the particulate inorganic oxide support comprises silica gel pellets, alumina pellets, titanium oxide pellets, zirconia pellets, and molecular sieve pellets. Preferably, the pellets have a particle size of 0.5 to 5 mm and a crush strength of 2 to 150 N/particle.
[0033] Further, according to the disclosure, the particulate activated carbon support may be coal-based carbon, or coconut shell carbon, shell carbon or the like. Preferably, the activated carbon particles have a particle size of 0.5 to 5 mm, and a crushing strength of 2 to 150 N/particle.
[0034] Further, according to the disclosure, the transition metal salt is soluble, including copper sulfate, copper nitrate, copper chloride, ferrous sulfate, iron nitrate, nickel 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 from 10 to 60 wt.%.
[0035] Further, according to the disclosure, the polymer material comprises sodium alginate, chitosan, polyethylene glycol (2000-6000), polyvinyl alcohol, sucrose, or any combination thereof Preferably, the polymer material is formulated into an aqueous solution having a concentration of from 1 to 20 wt.%.
[0036] Further, according to the disclosure, 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 1 mol/L.
[0037] Further, according to the disclosure, the base added dropwise is sodium hydroxide, sodium carbonate, sodium bicarbonate, aqueous ammonia or any combination thereof Preferably, the concentration of the base is 0.01 to 1 mol/L.
[0038] The series of particulate supported ferrocyanide adsorbents prepared by the above preparation methods are also within the scope of the present invention.
[0039] The present inventors have surprisingly found that the transition metal stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or activated carbon according to the present invention has the characteristics of stable structure and high adsorption performance. The adsorbent has a broad application prospect because it can adsorb not only radioactive and/or stable isotope Cs ions, but also radioactive and/or stable isotope Rb ions. For example, through adsorption, the adsorbent can be used for the separation and/or removal or extraction of radioactive or stable isotope Cs ions, as well as for the separation and/or removal or extraction of radioactive or stable isotope Rb ions.
Therefore, uses of the transition metal stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon according to the present invention as described above for removing radioisotope (also referred to as "radioactive isotope") Cs ions and removing stable isotope Cs ions, as well as removing radioisotope Rb ions and removing stable isotope Rb ions are also within the scope of the present invention.
100401 The inventors have recognized that, by using an inorganic oxide or activated carbon as a support and washing the primary adsorbent with water to remove parts of solid phase particles loosely coupled on surface of the primary adsorbent and sufficiently release soluble ions from primary adsorbents, the washed primary adsorbents have good mechanical strength and lower ion leaching property. Furthermore, the mechanical strength of adsorbents can be further improved by coating the surface of the washed primary adsorbents with a polymer material, so that the obtained adsorbents preferably have a crushing strength of 2 to 100 N/particle and an extremely low ion leaching property.
DETAILED DESCRIPTION OF THE INVENTION
100411 The present invention will be further described below in conjunction with specific embodiments, but the invention is not limited to the following examples. Unless otherwise specified, the mentioned methods are conventional methods, and the raw materials and standard chemical reagents used for detection are commercially available by an open commercial route.
100421 In the following examples, the adsorbents are subjected to static adsorption tests and fixed bed adsorption reaction columns performance tests. The concentrations of Cs-I-ion before and after the adsorption are determined by plasma mass spectrometry (ICPMS), and the performances of adsorbents are expressed by partition coefficient Kd and decontamination factor DF.
[0043] In static adsorption test, a certain amount of adsorbents are added to a SO mL centrifuge tube and shaken on a constant temperature shaker for from 48 h to 72 h. The concentrations of Cs ion before and after adsorption are measured. The performances of the adsorbents are expressed by partition coefficient Kd and decontamination factor DF. The adsorption partition coefficient Kd (mL/g) is shown in the below Equation 1, wherein Co and Ct are the initial concentration of the ions to be adsorbed and the concentration of the adsorbed ions after reaching the adsorption equilibrium, respectively, and F is the ratio of the volume of the treated solution (mL) and the mass of the adsorbent (mg). The decontamination factor is the ratio of the influent concentration to the effluent concentration of the adsorbed ions after reaching the adsorption equilibrium, as shown in the below Equation 2. Generally, the adsorption partition coefficient indicates the characteristics of an adsorbent material itself, and the Kd value of 105 or greater indicates good performance of adsorbent. The value of the decontamination factor is related not only to the adsorption characteristics of the material itself, but also to the amount of adsorbent. Larger value of the decontamination factor indicates that the contaminants are removed cleaner.
100441 Kd=(CO -Ct) X F X 1000/C) ( ) 100451 DF - In (2) 100461 is tested using a fixed bed adsorption The dynamic adsorption performance reaction column having a height of 10 cm, a diameter of 1.5 cm, and a water flow rate of 20 BV/h. The decontamination factor DF is used to indicate the decontamination effect of the adsorption column on Cs+.
100471 The crushing strength of the adsorbent according to the present invention is determined as follows: measuring the crushing strength of the adsorbent using a crushing strength tester made in China, Model: YFIKC-2A type Particle Strength Tester. In a measuring procedure, from 60 to 100 adsorbent particles are randomly selected, and the particles are placed one by one directly beneath the center of hammer. The handle is rotated to make the hammer fall. When approaching the particles, the handle is slowly rotated so that the hammer slowly touches particle. When a sound of particle breakage comes out, the tester shows the force loaded on the particles at the moment of crushing, expressed in Newtons. The ion leaching characteristics of the adsorbent according to the invention are determined as follows: first immersing the adsorbent in 10 volumes of pure water, stirring with a stirrer, or shaking with a shaker for a certain period of time, then measuring turbidity and electrical conductivity of the soaking liquid using an HACH 2100 N turbidimeter and a DDSJ-308A conductivity meter, respectively. The turbidimeter has an accuracy of 0.001 mg/L. The conductivity meter has an accuracy of 0.01 RS/cm.
100481 Example 1. Preparation of silica gel supported adsorbent and performance for removing cesium 100491 Silica gel Si-1 having a high mechanical strength and a particle size of 0.5 to 2.0 mm was used. A potassium copper ferrocyanide adsorbent was prepared thereon, by the following steps: 100501 (1) loading of copper salt: firstly adding pure water in reaction vessel No. 1 and heating to 80-100 °C, and adding copper sulfate to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding silica gel particles Si-1 as a support to the reaction vessel, and immersing for 2 to 48 hours, followed by performing a solid-liquid phase separation and drying, to obtain a precursor Si-I-A loaded with copper sulfate; 100511 (2) preparation of transition metal stabilized ferrocyanide adsorbent: first adding pure water in reaction vessel No. 2 and heating to 80-100 °C, and adding sodium ferrocyanide to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding the precursor Si-1 -A loaded with copper sulfate obtained in step (1) to the reaction vessel, and after stirring uniformly, sealing the reaction vessel, and reacting at a reaction temperature of 100 °C for 24 hours; and after the completion of the reaction, performing a solid-liquid phase separation, thereby obtaining a primary adsorbent Si-1-B for removing cesium; 100521 (3) cleaning the adsorbent: cleaning the primary adsorbent for removing cesium obtained in step (2) with deionized water, with the volume ratio of water used for each wash to the adsorbents of 10:1, until the washing liquid after continuous stirring for 24 hours had an electric conductivity of 22.8 uS/cm and a turbidity reduced to 1 7. 8 mg/L; then drying the obtained adsorbent, thereby obtaining secondary adsorbent Si-l-C; [00531 (4) coating the adsorbent: coating the surface of the secondary adsorbent Si-1-C obtained from step (3) with polymer material by the following procedure: dissolving chitosan as a binder in pure water to prepare a solution having a concentration of 2 to 10 wt.%; adding the secondary adsorbent Si-1-C into solution system; after stirring for 1 hour, adding dropwise a 1.0 M sodium hydroxide solution, until the solution had a pH value of 10 to 11; keeping stirring and reacting for 5 to 10 hours; performing a solid-liquid phase separation, thereby obtaining a tertiary adsorbent Si-l-D; 100541 (5) washing the adsorbent: washing the tertiary adsorbent Si-1-D for removing cesium obtained in step (4) with purified water, with the volume ratio of water used for each wash to the adsorbent of 10:1, until the resulting washing liquid after continuous stirring for 24 hours had a turbidity of lower than 20 mg/L and an electric conductivity of lower than 20.0 pS/cm, followed by performing a solid-liquid phase separation, and vacuum drying the adsorbent, thereby obtaining the final potassium copper ferrocyanide adsorbent supported by silica gel for removing cesium.
100551 As measured, the prepared adsorbent had a crushing strength of 12 to 14 N/particle. After immersing for 24 hours at a liquid-solid ratio of 10, the liquid had a turbidity of 6 mg/L, an electric conductivity of 11 p5/cm, and the COD concentration of the solution was 1.5 mg/L. In static adsorption method for testing the adsorption performance, the solution had an initial Cs ion concentration of 10 mg/L, and a coexisting boric acid concentration of 500 mg/L in terms of boron. Under the conditions that the volume of the test solution was 50 mL and the mass of the adsorbent was 10 mg, the decontamination factor DE value was 26.2, corresponding to a Cs-removal rate of greater than 95%.
100561 Example 2: Preparation of alumina supported adsorbent and performance for removing cesium 100571 Alumina pellets A1-1 having a relatively high mechanical strength and a particle size of 0.5 to 2.0 mm were used. A potassium zinc ferrocyanide adsorbent was prepared thereon, by the following steps: 100581 (1) loading of ferrocyanide: firstly adding pure water in reaction vessel No. 1 and heating to 80-100 °C, and adding potassium ferrocyanide to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding alumina pellets Al-1 as a support to the reaction vessel, and immersing for 2 to 48 hours, followed by performing a solid-liquid phase separation and drying in a constant temperature oven, to obtain a precursor AI-1-A loaded with ferrocyanide; [0059] (2) preparation of transition metal stabilized ferrocyanide adsorbent: first adding pure water in reaction vessel No. 2 and heating to 80-100 °C, and adding zinc acetate to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding the precursor A1-1-A loaded with ferrocyanide obtained in step (1) to the reaction vessel, and after stirring uniformly, sealing the reaction vessel, and reacting at a reaction temperature of 100 °C for 8 to 16 hours; and after the completion of the reaction, performing a solid-liquid phase separation, thereby obtaining a primary adsorbent Al-l-B for removing cesium; 100601 (3) cleaning the adsorbent: cleaning the primary adsorbent Al-1 -B for removing cesium obtained in step (2) with deionized water, with the volume ratio of water used for each wash to the adsorbents of 10:1, until the washing liquid after continuous stirring for 24 hours had an electric conductivity of 18.2 RS/cm and a turbidity reduced to 21.3 mg/L; then drying the obtained adsorbent, thereby obtaining secondary adsorbent Al-1-C; 100611 (4) coating the adsorbent: coating the surface of the secondary adsorbent Al-]-C obtained from step (3) with polymer material by the following procedure: dissolving polyvinyl alcohol and polyethylene glycol (6000) as binders in pure water to prepare a solution having a polyvinyl alcohol concentration of 1 to 10 wt.% and a polyethylene glycol (6000) concentration of 5 to 30 wt.%; adding the secondary adsorbent Al-1 -C into solution system at a liquid-solid ratio of 10; keeping stirring and reacting for 2 to 10 hours; performing a solid-liquid phase separation, thereby obtaining a tertiary adsorbent Al-1-D; 100621 (5) washing the adsorbent: washing the tertiary adsorbent A1-1-D for removing cesium obtained in step (4) with purified water, with the volume ratio of water used for each wash to the adsorbent of 10:1, until the resulting washing liquid after continuous stirring for 24 hours had a turbidity of lower than 20 mg/L and an electric conductivity of lower than 20 RS/cm, followed by performing a solid-liquid phase separation, and vacuum drying the adsorbent, thereby obtaining the final potassium zinc ferrocyanide adsorbent supported by alumina for removing cesium.
100631 As measured, the prepared adsorbent had a crashing strength of 3 to 9 N/particle. After immersing for 24 hours at a liquid-solid ratio of 10, the liquid had a turbidity of 3 mg/L, an electric conductivity of 7 RS/cm, and the COD concentration of the solution was 2.7 mg/L. In static adsorption method for testing the adsorption performance, the solution had an initial Cs ion concentration of 10 mg/L, and a coexisting boric acid concentration of 500 mg/L in terms of boron. Under the conditions that the volume of the test solution was 50 mL and the mass of the adsorbent was 10 mg, the decontamination factor DF value was 23.2, corresponding to a Cs-removal rate of greater than 95%.
100641 Furthermore, small adsorption column of fixed bed was used for dynamic measurement. The adsorption column had a height of 10 cm and a diameter of 1.5 cm. The adsorbent filled the entire adsorption column. The treated water flow rate was 20 BV/h. The initial concentration of Cs was 10 mg/L. The measurement results showed that the adsorbent had a decontamination factor on Cs could reach 330 when the amount of the treated water reached 3870 BV.
100651 Example 3: Preparation of titanium oxide supported adsorbent and performance 100661 Titanium oxide pellets Ti-1 having a relatively high mechanical strength and a particle size of 0.5 to 2.0 mm were used. A potassium cobalt ferrocyanide adsorbent was prepared thereon, by the following steps: 100671 (1) loading of ferrocyanide: firstly adding pure water in reaction vessel No. 1 and heating to 80-100 °C, and adding potassium ferrocyanide to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding titanium oxide pellets Ti-1 as a support to the reaction vessel, and immersing for 2 to 48 hours, followed by performing a solid-liquid phase separation and drying in a constant temperature oven, to obtain a precursor Ti-l-A loaded with ferrocyanide; 100681 (2) preparation of transition metal stabilized ferrocyanide adsorbent: first adding pure water in reaction vessel No. 2 and heating to 80-100 °C, and adding cobalt nitrate to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding the precursor Ti-l-A loaded with ferrocyanide obtained in step (1) to the reaction vessel, and after stirring uniformly, sealing the reaction vessel, and reacting at a reaction temperature of 100 °C for 4 to 12 hours; and after the completion of the reaction, performing a solid-liquid phase separation, thereby obtaining a primary adsorbent Ti-1-B for removing cesium; 100691 (3) cleaning the adsorbent: cleaning the primary adsorbent Ti-l-B for removing cesium obtained in step (2) with deionized water, with the volume ratio of water used for each wash to the adsorbents of 10:1, until the washing liquid after continuous stirring for 24 hours had an electric conductivity of 22.4 RS/cm and a turbidity reduced to 15.8 mg/L, then drying the obtained adsorbent, thereby obtaining secondary adsorbent Ti-l-C; [0070] (4) coating the adsorbent: coating the surface of the secondary adsorbent Ti-1-C obtained from step (3) with polymer material by the following procedure: using polyvinyl alcohol+sucrose and polyethylene glycol (6000) as binders, dissolving polyvinyl alcohol and polyethylene glycol in pure water to prepare a solution having a polyvinyl alcohol concentration of 1 to 10 wt.% and a polyethylene glycol (6000) concentration of 5 to 30 wt.%; secondly, adding sucrose in the solution and dissolve it at a controlled rate of sucrose to polyvinyl alcohol or polyethylene glycol of 1:1 to 4:1; adding the secondary adsorbent Ti-1-C into solution system at a liquid-solid ratio of 10:1; keeping stirring and reacting for 2 to 10 hours; performing a solid-liquid phase separation, thereby obtaining a tertiary adsorbent Ti-1-D; 100711 (5) washing the adsorbent: washing the tertiary adsorbent Ti-1 -D for removing cesium obtained in step (4) with purified water, with the volume ratio of water used for each wash to the adsorbent of 10:1, until the resulting washing liquid after continuous stirring for 24 hours had a turbidity of lower than 20 mg/L and an electric conductivity of lower than 20 RS/cm, followed by performing a solid-liquid phase separation, and vacuum drying the adsorbent, thereby obtaining the final potassium cobalt ferrocyanide adsorbent supported by titanium oxide for removing cesium.
100721 As measured, the prepared adsorbent had a crushing strength of 3 to 9 N/particle. After immersing for 24 hours at a liquid-solid ratio of 10, the liquid had a turbidity of 2 mg/L, an electric conductivity of 6 RS/cm, and the COD concentration of the solution was 1.6 mg/L. In static adsorption method for testing the adsorption performance, the solution had an initial Cs ion concentration of 10 mg/L, and a coexisting boric acid concentration of 500 mg/L in terms of boron. Under the conditions that the volume of the test solution was 50 mL and the mass of the adsorbent was 10 mg, the decontamination factor DF value was 26.7, corresponding to a Cs-removal rate of greater than 95%.
[0073] Furthermore, small adsorption column of fixed bed was used for dynamic measurement. The adsorption column had a height of 10 cm and a diameter of 1.5 cm. The adsorbent filled the entire adsorption column. The treated water flow rate was 20 BV/h. The initial concentration of Cs was 10 mg/L. The measurement results showed that the adsorbent had a decontamination factor on Cs could reach 310 when the amount of the treated water reached 4213 BV.
[0074] Example 4: Preparation of zirconium oxide supported adsorbent and adsorption performance for rubidium and caesium [0075] Zirconium oxide pellets Zr-1 having monoclinic crystalline form were used as a support in adsorbent. The pellets had a very high mechanical strength and a particle size of 0.5 to 2.0 mm and a crushing strength of greater than 30 N/particle. A potassium iron (HI) ferrocyanide adsorbent was prepared thereon, by the following steps: 100761 (1) loading of ferrocyanide: firstly adding pure water in reaction vessel No. 1 and heating to 80-100 °C, and adding sodium ferrocyanide to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding zirconium oxide pellets Zr-1 as a support to the reaction vessel, and immersing for 2 to 48 hours, followed by performing a solid-liquid phase separation and drying in a constant temperature oven, to obtain a precursor Zr-l-A loaded with ferrocyanide; 100771 (2) preparation of transition metal stabilized ferrocyanide adsorbent: first adding pure water in reaction vessel No. 2 and heating to 80-100°C, and adding iron nitrate to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding the precursor Zr-l-A loaded with ferrocyanide obtained in step (1) to the reaction vessel, and after stirring uniformly, sealing the reaction vessel, and reacting at a reaction temperature of 120 °C for 10 to 24 hours; and after the completion of the reaction, performing a solid-liquid phase separation, thereby obtaining a primary adsorbent Zr-1 -B for removing cesium; 100781 (3) cleaning the adsorbent: cleaning the primary adsorbent Zr-l-B for removing cesium obtained in step (2) with deionized water, with the volume ratio of water used for each wash to the adsorbents of 10:1, until the washing liquid after continuous stirring for 24 hours had an electric conductivity of 15.6 RS/cm and a turbidity reduced to 25.8 mg/L; then drying the obtained adsorbent, thereby obtaining secondary adsorbent Zr-1-C; 100791 (4) coating the adsorbent: coating the surface of the secondary adsorbent Zr-1-C obtained from step (3) with polymer material by the following procedure: using sodium alginate as a binder, first dissolving sodium alginate as a binder in pure water to prepare a solution having a concentration of 1 to 10 wt.%; adding the secondary adsorbent Zr-1 -C into solution system at a liquid-solid ratio of 10:1; after stirring for 1 hour, adding dropwise 1 M hydrochloric acid solution, until the solution had a pH value of 4 to 5; keeping stirring and reacting for 2 to 10 hours; performing a solid-liquid phase separation, thereby obtaining a tertiary adsorbent Zr-1-D; 100801 (5) washing the adsorbent: washing the tertiary adsorbent Zr-1-D for removing cesium obtained in step (4) with purified water, with the volume ratio of water used for each wash to the adsorbent of 10:1, until the resulting washing liquid after continuous stirring for 24 hours had a turbidity of lower than 20 mg/L and an electric conductivity of lower than 20.0 RS/cm, followed by performing a solid-liquid phase separation, and vacuum drying the adsorbent, thereby obtaining the final potassium iron ferrocyanide adsorbent supported by zirconium oxide for removing cesium.
100811 As measured, the prepared adsorbent had a crushing strength of 41 N/particle.
After immersing for 24 hours at a liquid-solid ratio of 10, the liquid had a turbidity of 7 mg/L, an electric conductivity of 12 pS/cm, and the COD concentration of the solution was 1.9 mg/L.
100821 Static adsorption method was used for determining the competitive adsorption performance of cerium and lithium, sodium, potassium and rubidium. The volume of the test solution was 50 mL, and the mass of the adsorbent was 10 mg. The test solution had a boric acid concentration of 500 ppm in terms of boron and an initial Cs ion concentration of 10 mg/L. The coexisting lithium, sodium, potassium, and rubidium ions had two concentrations, respectively equivalent to the same molar ratio as 10 mg/L of Cs. In experiments, the adsorption performance of the adsorbent on Cs was measured under the competitive state of coexisting ions. In the presence of Cs-alone, the decontamination factor of the adsorbent to Cs is 23.2. Under the same molar number of Li-, Na-, Kt Rb+, the decontamination factor for Cs are 21.6, 11.3, 9.2 and 9.4.
100831 As can be seen from the experimental results, the series of supported ferrocyanide adsorbents developed in the present invention had certain adsorption for the ions in Group 1 (Group IA in old IUPAC), wherein Nat Kt and Rb+ mainly have a certain competition relationship with Cs+. However, Li has a very poor adsorption performance, so the LiOH present in the process waste liquid of the nuclear power plant will not affect the adsorption and removal performance of the nuclide Cs. Generally, the radionuclide Rb+ is simultaneously present in the process waste liquid of the nuclear power plant. As a result, the series of the supported ferrocyanide adsorbents developed by the invention are capable of simultaneously removing Rb-88, Rb-89 and Cs-134 as well as Cs-137 in the process water.
100841 Example 5: Preparation of activated carbon supported adsorbent and adsorption performance for cesium 100851 Coconut shell activated carbon particles having a particle size of 0.5 to 2.0 mm were used as support. The particles were washed with pure water until the pH is neutral and the electric conductivity is lower than 2ORS/cm. After drying, the activated carbon particles were used as adsorbent support. As measured, the used activated carbon particles had a relatively high mechanical strength and a crushing strength of greater than 20N/particle. A potassium nickel (11) ferrocyanide adsorbent was prepared thereon, by the following steps: 100861 (1) loading of ferrocyanide: firstly adding pure water in reaction vessel No. 1 and heating to 80-100 °C, and adding potassium ferrocyanide to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding activated carbon particles as support into the reaction vessel, and immersing for 10 to 48 hours, followed by performing a solid-liquid phase separation and drying in a constant temperature oven, to obtain a precursor GAC-1-A loaded with ferrocyanide; 100871 (2) preparation of transition metal stabilized ferrocyanide adsorbent: first adding pure water in reaction vessel No 2 and heating to 80-100 °C, and adding nickel sulfate to dissolve it and form a solution having a concentration of 10 to 50%; secondly, adding the precursor GAC-1-A loaded with ferrocyanide obtained in step (1) to the reaction vessel, and after stirring uniformly, sealing the reaction vessel, and reacting at a reaction temperature of 120 °C for 10 to 24 hours; and after the completion of the reaction, performing a solid-liquid phase separation, thereby obtaining a primary adsorbent GAC-1-B for removing cesium; 100881 (3) cleaning the adsorbent: cleaning the primary adsorbent GAC-1-B for removing cesium obtained in step (2) with deionized water, with the volume ratio of water used for each wash to the adsorbents of 10:1, until the washing liquid after continuous stirring for 24 hours had an electric conductivity of lower than 20 RS/cm and a turbidity of lower than 20 mg/L; then drying the obtained adsorbent, thereby obtaining secondary adsorbent GAC-1-C; [00891 (4) coating the adsorbent: coating the surface of the secondary adsorbent GAC- 1-C obtained from step (3) with polymer material by the following procedure: using polyvinyl alcohol as a binder, dissolving polyvinyl alcohol in pure water to prepare a solution having a concentration of 1 to 10 wt.%; secondly, adding the secondary adsorbent GAC-1-C into solution system at a liquid-solid ratio of 10:1; keeping stirring and reacting for 2 to 10 hours; performing a solid-liquid phase separation, thereby obtaining a tertiary adsorbent GAC-1-D; 100901 (5) washing the adsorbent: washing the tertiary adsorbent GAC-1-D for removing cesium obtained in step (4) with purified water, with the volume ratio of water used for each wash to the adsorbent of 10:1, until the resulting washing liquid after continuous stirring for 24 hours had a turbidity of lower than 20 mg/L and an electric conductivity of lower than 20 pS/cm, followed by performing a solid-liquid phase separation, and vacuum drying the adsorbent, thereby obtaining the final potassium nickel ferrocyanide adsorbent supported by particulate activated carbon for removing cesium.
100911 As measured, the prepared adsorbent had a crushing strength of 32 N/particle.
After immersing for 24 hours at a liquid-solid ratio of 10, the liquid had a turbidity of 12 mg/L, an electric conductivity of 18 pS/cm, and the COD concentration of the solution was 1.4 mg/L.
100921 Static adsorption method was used for determining the adsorption performance of cerium. The volume of the test solution was 40 mL, and the mass of the adsorbent was 10 mg. The test solution had a boric acid concentration of 1000 ppm in terms of boron and an initial Cs ion concentration of 10 mg/L, after measurement, the decontamination factor of the adsorbent to Cs is 48.3.
100931 While various aspects of the invention have been described hereinbefore with reference to the particular exemplary embodiments, it will be understood by those skilled in the art that the present invention is not limited to the specific embodiments described hereinbefore. Various equivalents to the technical means, raw materials, process steps and the like may be substituted without departing from the scope of the invention. All of these equivalents and the combination thereof are intended to fall within the scope of the invention, [0094] To further illustrate certain aspects of the invention, the invention also specifically provides some non-limiting embodiments as follows: 100951 1. A transition metal stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or activated carbon comprising: a particulate inorganic oxide support or a particulate activated carbon support; a transition metal-stabilized ferrocyanide layer for coating the inorganic oxide support or the activated carbon support; and a polymer material layer for coating the transition metal-stabilized ferrocyanide layer.
[0096] 2. The adsorbent of embodiment 1, wherein the polymer material layer comprises sodium alginate, chitosan, polyethylene glycol having a number average molecular weight of between 2000 and 6000, polyvinyl alcohol, sucrose or any combination thereof 100971 3. The adsorbent of embodiments 1 or 2, having a crushing strength of 2-100 N/particle 100981 4. The adsorbent of embodiments 1 or 2, having an ion leaching property so that after immersing the adsorbent for 24 hours at a liquid-solid ratio of 10, the obtained liquid has a turbidity of 10 mg/L or lower.
100991 5. The adsorbent of embodiments 1 or 2, having an ion leaching property so that after immersing the adsorbent for 24 hours at a liquid-solid ratio of 10, the obtained liquid has an electric conductivity of 15 RS/cm or lower.
1001001 6. A process for the preparation of the transition metal stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon, comprising the steps of 1001011 1) providing primary adsorbent; 1001021 2) washing the primary adsorbent from step 1) with deionized water until the washing liquid has an electric conductivity of 25.0 RS/cm or lower and a turbidity of 30 mg/L or lower; 1001031 3) coating the primary adsorbent with a polymer material, to obtain the coated primary adsorbent; and 1001041 4) optionally, washing the coated primary adsorbent from step 3) with deionized water until the resulting washing liquid has an electric conductivity of 20.0 RS/cm or lower and a turbidity of 20 mg/L or lower, 1001051 thereby obtaining the transition metal stabilized ferrocyanide adsorbents supported by a particulate inorganic oxide or activated carbon 1001061 7. The process according to embodiment 6, wherein the step of providing a primary adsorbent comprises: immersing the particulate inorganic oxide or particulate activated carbon support in an aqueous solution of ferrocyanide for 2 to 48 hours, thereby obtaining a precursor A loaded with ferrocyanide, then mixing the precursor A with an aqueous solution of a transition metal salt, and reacting at a temperature of 100 to 150 °C for 2 to 24 hours.
1001071 8. The process according to embodiment 6, wherein the step of providing a primary adsorbent comprises: immersing the particulate inorganic oxide or 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 transition metal salt, then mixing the precursor B with an aqueous solution of ferrocyanide and reacting at a temperature of 100 to 150 °C for 2 to 24 hours.
1001081 9. The process according to any one of embodiments 6-8, wherein the polymer material comprises sodium alginate, chitosan, polyethylene glycol (2000-6000), polyvinyl alcohol, sucrose, or any combination thereof, and is preferably formulated into an aqueous solution having a concentration of from Ito 20 wt.%.
[00109] 10. The process according to any one of embodiments 6-8, wherein the step of coating the primary adsorbent with a polymer material is conducted in the presence of an acid or a base.
1001101 11. The process according to embodiment 10, wherein the acid is selected from the group of hydrochloric acid, sulfuric acid, acetic acid or any combination thereof, preferably in a concentration of 0.01 to 1 mol/L; the base is selected from the group of sodium hydroxide, sodium carbonate, sodium bicarbonate, aqueous ammonia or any combination thereof, preferably in a concentration of 0.01 to 1 mol/L.
1001111 12. The process according to any one of embodiments 7-8, wherein the particulate inorganic oxide support comprises silica gel pellets, alumina pellets, titanium oxide pellets, zirconium oxide pellets, molecular sieve pellets or the combination thereof, and preferably has a particle size of 0.5 to 5 mm and/or a crushing strength of 2 to 150 N/particle.
1001121 13. The process according to any one of embodiments 7-8, wherein the particulate activated carbon support comprises coal-based carbon, coconut shell carbon, nut shell carbon or the combination thereof, and preferably has a particle size of 0.5 to 5 mm, and/or a crushing strength of 2 to 150 N/particle.
1001131 14. The process according to any one of embodiments 7-8, wherein the ferrocyanide comprises potassium ferrocyanide, sodium ferrocyanide or the combination thereof, and preferably the ferrocyanide has a concentration of 10 to 50 wt.% in aqueous solution.
1001141 15. The process according to any one of embodiments 7-8, wherein the transition metal salt comprises copper sulfate, copper nitrate, copper chloride, ferrous sulfate, iron nitrate, nickel nitrate, nickel sulfate, zinc chloride, zinc sulfate, zinc acetate, cobalt nitrate, cobalt chloride, zirconium oxychloride, manganese sulfate, or any combination thereof; and preferably, an aqueous solution of a transition metal salt has a concentration of 10 to 60 wt.%.
1001151 16. A metal ion stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon prepared by the process according to any one of embodiments 6-15.
1001161 17. Use of the metal ion stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon according to any one of embodiments 1-5 or according to embodiment 16 for adsorbing radioisotope Cs ions or adsorbing stable isotope Cs ions.
1001171 18. The use of embodiment 17, for removing or separating or extracting radioisotope Cs ions or for removing or separating or extracting stable isotope Cs ions.
1001181 19. Use of the metal ion stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon according to any one of embodiments 1-5 or according to embodiment 16 for adsorbing radioisotope Rb ions or adsorbing stable isotope Rb ions.
1001191 20. the use of embodiment 19, for removing or separating or extracting radioisotope Rb ions or for removing or separating or extracting stable isotope Rb ions.
Claims (1)
- CLAIMSA transition metal stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or activated carbon comprising: a particulate inorganic oxide support, or a particulate activated carbon support; a transition metal-stabilized ferrocyanide layer for coating the inorganic oxide support or the activated carbon support; and a polymer material layer for coating the transition metal-stabilized ferrocyanide layer. The adsorbent of claim 1, wherein the polymer material layer comprises sodium alginate, chitosan, polyethylene glycol having a number average molecular weight of between 2000 and 6000, polyvinyl alcohol, sucrose or any combination thereof The adsorbent of claims 1 or 2, having a crushing strength of 2-100 N/particle.The adsorbent of claims 1 or 2, having an ion leaching property so that after immersing the adsorbent for 24 hours at a liquid-solid ratio of 10, the obtained leach solution has a turbidity of 10 mg/L or lower.The adsorbent of claims 1 or 2, having an ion leaching property so that after immersing the adsorbent for 24 hours at a liquid-solid ratio of 10, the obtained liquid has an electric conductivity of 15 RS/cm or lower.A process for the preparation of the transition metal stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon, comprising the steps of: 1) providing primary adsorbent; 2) washing the primary adsorbent from step 1) with deionized water until the washing liquid has an electric conductivity of 25.0 RS/cm or lower, and a turbidity of 30 mg/L or lower; 3) coating the primary adsorbent with a polymer material, preferably in the presence of an acid or a base, to obtain the coated primary adsorbent; and 4) optionally, washing the coated primary adsorbent from step 3) with deionized water until the resulting washing liquid has an electric conductivity of 20.0 ttS/cm or lower, and a turbidity of 20 mg/L or lower, thereby obtaining the transition metal stabilized ferrocyanide adsorbents supported by a particulate inorganic oxide or activated carbon.7 The process according to claim 6, wherein the step of providing a primary adsorbent comprises: immersing the particulate inorganic oxide or particulate activated carbon 3 8. 9.support in an aqueous solution of ferrocyanide for 2 to 48 hours, thereby obtaining a precursor A loaded with ferrocyanide, then mixing the precursor A with an aqueous solution of a transition metal salt, and reacting at a temperature of 100 to 150 °C for 2 to 24 hours.The process according to claim 6, wherein the step of providing a primary adsorbent comprises: immersing the particulate inorganic oxide or 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 transition metal salt, then mixing the precursor B with an aqueous solution of ferrocyanide and reacting at a temperature of 100 to 150 °C for 2 to 24 hours.A metal ion stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon prepared by the process according to any one of claims 6-8.Use of the metal ion stabilized ferrocyanide adsorbent supported by a particulate inorganic oxide or a particulate activated carbon according to any one of claims 1-5 or according to claim 9 for adsorbing radioisotope Cs ions or adsorbing stable isotope Cs ions, and/or for adsorbing radioisotope Rb ions or adsorbing stable isotope Rb ions.
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| 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 |
| PCT/CN2018/072213 WO2019134183A1 (en) | 2018-01-04 | 2018-01-11 | Large-scale preparation method for highly stable cesium removal adsorbent, product thereof and use thereof |
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| 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 |
| CN117244518A (en) * | 2023-08-29 | 2023-12-19 | 浙江大学 | Composite adsorption material and preparation method and application thereof |
| CN118527123A (en) * | 2024-07-24 | 2024-08-23 | 江苏方天电力技术有限公司 | Metal modified decoloring agent and preparation method and application thereof |
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| WO2019134183A1 (en) | 2019-07-11 |
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| GB202009144D0 (en) | 2020-07-29 |
| GB2587072B (en) | 2022-09-07 |
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