CN116371348B - Preparation method and application of cesium fixation material - Google Patents
Preparation method and application of cesium fixation material Download PDFInfo
- Publication number
- CN116371348B CN116371348B CN202310440388.6A CN202310440388A CN116371348B CN 116371348 B CN116371348 B CN 116371348B CN 202310440388 A CN202310440388 A CN 202310440388A CN 116371348 B CN116371348 B CN 116371348B
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- China
- Prior art keywords
- cesium
- mass
- fixing material
- deionized water
- metal
- Prior art date
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- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 109
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 150000002926 oxygen Chemical class 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 239000007787 solid Substances 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 46
- 229910021641 deionized water Inorganic materials 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000002351 wastewater Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 31
- 238000001179 sorption measurement Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910018557 Si O Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910018516 Al—O Inorganic materials 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910017299 Mo—O Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 230000002285 radioactive effect Effects 0.000 abstract description 6
- 239000002901 radioactive waste Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000003463 adsorbent Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940083037 simethicone Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
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- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- 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
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- 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
- G21F9/16—Processing by fixation in stable solid media
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- 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
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- 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
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- 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
Abstract
The present application relates to the field of radioactive waste treatment, and more particularly, to a method for preparing and applying a highly selective solidification material for radioactive cesium in a liquid phase. The cesium-fixing material is completely composed of inorganic components, wherein the inorganic components comprise metal-nonmetal oxygen clusters, metal oxides, nonmetal oxides and alkali; the cesium fixing material comprises the following chemical components in percentage by mass: metal-non-metal oxygen clusters: metal oxide and non-metal oxide, alkali= (0.1-1.3), 0.18-0.3, 0.6-0.72 and 0.05-0.1. The preparation and application methods of the cesium-fixing material with high selectivity aim to solve the problems that the prior art cannot adapt to complex environments in nuclear accident emergency treatment, engineering application is difficult and ion mobility is high.
Description
Technical Field
The application relates to the technical field of radioactive waste treatment, in particular to a preparation method and application of a cesium-fixing material.
Background
Compared with fossil energy, nuclear energy belongs to clean and sustainable new energy; compared with other new energy sources such as photovoltaic power generation, hydropower, wind power and the like, the nuclear power production process is more controllable, grid connection is more stable, and industrial operation is more mature. Radioactive cesium has similar properties to Na and K widely existing in natural water, and is extremely easy to rapidly diffuse in a medium and be absorbed by organisms. The nervous system is damaged when the human body is irradiated to 0.25Gy, and when the human body is irradiated to more than 6Gy, canceration or gene mutation of cells can be induced, and even deformity is caused. Therefore, the radioactive cesium in the liquid phase is efficiently removed and fixed to avoid migration into the environment, and the method has great significance for nuclear accident emergency treatment.
Radioactive cesium is usually expressed as Cs in water + There are four main types of processing methods: chemical precipitation, solvent extraction, membrane separation, and adsorption. The adsorption method utilizes the action between the adsorbent and the adsorbate to enrich the target nuclide in the water on the surface of the solid adsorbent, thereby achieving the purpose of removing the target nuclide from the water. When the nuclear power station normally operates, the adsorbent used in the nuclide purification system is ion exchange resin, the adsorbent is in millimeter-level particles, and the adsorbent can be filled in a high-speed adsorption column to ensure the water quality requirement of the effluent of the purification system. However, as an organic adsorption material, the ion exchange resin is enriched in radioactive cesium by virtue of a charged functional group on an organic skeleton, and does not have specific recognition capability for cesium. Thus, a large amount of Na is contained in natural water + 、K + 、Ca 2+ The ion exchange resin cannot achieve effective enrichment of cesium under the interference of the co-existing ions.
In order to realize specific recognition of cesium by the adsorbent, inorganic and inorganic-organic hybrid adsorbents are commonly used in the prior art, and comprise mica, zirconium phosphate, titanium silicon compound, metal ferrocyanide, inorganic modified ion exchange resin and the like. However, these materials all have different application drawbacks, in particular: 1) When physical and chemical conditions such as ambient temperature, pH and the like are changed, the recognition capability of the material to cesium is reduced, the cesium removal rate is reduced, the treatment time is prolonged, and the stability of organic components of the material is poor under a complex treatment environment; 2) In order to utilize the surface recognition sites, the inorganic material is usually nano-powder and cannot be applied to a high-speed adsorption column; 3) The organic components in the material cause the material to remain diffuse after cesium removal and difficult to cure to avoid migration of cesium into the environment. Therefore, these materials cannot meet accident emergency requirements from the standpoint of complex environmental adaptability, engineering applicability, and ion mobility; there is a need to develop materials that can highly selectively enrich the radioactive cesium in the aqueous phase and efficiently limit cesium migration.
Disclosure of Invention
The disclosure provides a preparation method and application of a cesium-fixing material, and aims to provide a high-selectivity cesium-fixing material so as to solve the problems that the prior art cannot adapt to complex environments in nuclear accident emergency treatment, engineering application is difficult and ion mobility is high.
In a first aspect, the present disclosure provides a cesium-fixing material consisting entirely of an inorganic composition comprising metal-nonmetal oxygen clusters, metal oxides, nonmetal oxides, and bases;
the cesium fixing material comprises the following chemical components in percentage by mass: metal-nonmetal oxygen cluster metal oxide nonmetal oxide base= (0.1-1.3): (0.18-0.3): (0.6-0.72): (0.05-0.1).
Preferably, the metal-nonmetal oxygen cluster is one or more of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid, the metal oxide is amorphous activated alumina, the nonmetal oxide is amorphous activated silica, and the alkali is one or more of sodium hydroxide or potassium hydroxide.
Preferably, the metal-nonmetal oxygen clusters in the structure in the cesium immobilization material are composed of 1 central tetrahedron and 4 groups of trimetallic clusters.
Preferably, the microstructure of the cesium-immobilization material comprises a host and a guest, the host being bonded to the guest;
the network polymerization structure formed by connecting Al-O tetrahedron and Si-O tetrahedron through O is taken as a host, the oxygen cluster structure formed by connecting W-O or Mo-O octahedron and P-O or Si-O tetrahedron through O is taken as an object, and the host and the object can be connected through O by the W-O or Mo-O octahedron and the Al-O tetrahedron or the Si-O tetrahedron.
The cesium ion source has the capability of efficiently selecting cesium and fixing the cesium ion source on a material in a complex water environment with multiple cations simultaneously existing and a severe pH value change. This advantage derives from:
1) The guest has cesium recognition sites, and is specifically bound to cesium directly by tungsten or molybdenum;
2) The hosts are connected in the form of oxygen tetrahedra through oxygen atoms, and electronegativity of the surfaces of the host network polymeric structures can reduce competitive occupation of alkali metal ions on the guests in a low pH range.
Cesium has a specific effect on tungsten or molybdenum in metal oxygen clusters, so that cesium can be fixed on a material with high selectivity under the interference of coexisting ions, and the material is endowed with high selectivity on cesium. Solves the problems that the cesium is difficult to be removed efficiently by utilizing ion exchange and electrostatic action in the prior art, and particularly, the cesium cannot be specifically identified and fixed in the strong acid wastewater.
Preferably, the ratio of the metal oxide to the non-metal oxide is 1:0.8-4.
Preferably, the guest structure is a nanocrystal, the average particle size is 50nm-100nm, the host structure is amorphous, the macroscopic surface is rough, and the specific surface area is about 5-20m 2 /g。
Preferably, the cesium-fixation material presents a spheroid-like appearance, and the particle size of the cesium-fixation material is 10-1500 μm.
Preferably, the particle size of the cesium-immobilization material is 600-800 μm.
The high-selectivity cesium-fixing material with the particle size close to millimeter level can be obtained, can be directly filled into a high-speed adsorption column, can obtain higher flow velocity under reasonable head loss, and improves the treatment efficiency.
In a second aspect, the present disclosure provides a method for preparing a cesium-fixing material, comprising the steps of:
a, synthesizing an object:
a1: dissolving 1-10 parts by mass of nonmetallic acid salt in deionized water, heating to 80-100 ℃ after the nonmetallic acid salt is completely dissolved, and adjusting the pH value to be 5.0-6.5 by hydrochloric acid;
a2: dissolving 8-60 parts by mass of metal acid salt in deionized water, adding the solution prepared by the A1, heating to 90-100 ℃, adjusting the pH value to 1.0-2.5 by hydrochloric acid, carrying out vigorous stirring reaction for 1-4 hours, and cooling to room temperature;
a3: extracting metal-nonmetal oxygen clusters in the solution prepared by the A2 by using an organic solvent, and recrystallizing after drying to obtain a solid substance which is a guest;
and B, synthesizing a main body:
b1: adding 1 part by mass of the alkali into 1.5-3.5 parts by mass of deionized water, and stirring until the alkali is completely dissolved;
b2: taking the mass ratio of the metal oxide to the nonmetal oxide of 1:2-2:1, mixing the prepared mixture with the solution prepared in the B1, wherein the mass ratio of the prepared mixture to the solution prepared in the B1 is 2-4:1, stirring for 3-10 min to completely mix the mixture into slurry, and dripping the slurry into the slurry with the viscosity of 500mm at the speed of 0.5-2.0 mL/s 2 /s-1500mm 2 In an organic medium of/s, regulating the rotating speed to 500-800 rpm, continuously stirring for 20-30 min, and separating out solid components;
b3: adding the solid component prepared in the step B2 into deionized water, preserving heat at 50-80 ℃, separating out the solid component, heating, naturally standing, cooling to room temperature, and cleaning to obtain a main body;
c, host-guest domain-limited combination:
c1: adding 0.1-3 parts by mass of the object and 1 part by mass of the main body into 150 parts by mass of deionized water, uniformly mixing by shaking by a vortex mixer, placing in a constant-temperature oscillator, and oscillating for 12-24 hours at the rotation speed of 100-200 rpm at the temperature of 25-65 ℃;
c2: separating out solid components in the mixed system prepared by the C1, and washing with deionized water until the cleaning liquid is free of impurities, thereby obtaining the solid cesium material.
The preparation method can combine the guest domain with the host, and maintain the structure stable in a wider pH range. When the pH value is in the range of 3-10 due to the stable structure of the cesium fixing material, the loss rate of metal-nonmetal oxygen clusters is less than 0.1%, and higher cesium removal rate can be obtained. Solves the problems of poor stability and small applicable pH range of the composite material in cesium removal in the prior art.
The preparation method can obtain a nanoscale object structure, and can be uniformly dispersed on a host without agglomeration, so that cesium recognition sites of the object are fully exposed, and the material has high enrichment capacity and high reaction speed on cesium. Solves the problems of low cesium removal performance, long time and large secondary waste amount of the adsorbent in complex environment.
In a third aspect, the present disclosure provides an application of cesium-fixing material, comprising the steps of:
(1) 1000-3000 parts by mass of cesium-containing wastewater is injected into a batch reactor;
(2) 1 part by mass of the prepared cesium-fixing material is put into the cesium-containing wastewater, and cesium in the wastewater migrates and is fixed on the cesium-fixing material;
(3) Collecting the effluent of the batch reactor.
Preferably, the application of the cesium fixing material comprises the following steps:
(1) Filling the prepared cesium-fixing material into a high-speed adsorption column, and forming a cesium-fixing material layer in the adsorption column;
(2) Regulating a water inlet valve of the high-speed adsorption column to enable cesium-containing wastewater to continuously flow through the high-speed adsorption column at a flow rate of 10-20 parts by volume/h, wherein the volume ratio of the cesium-containing wastewater to the cesium-fixing material is 10-20:1, and cesium in the wastewater migrates and is fixed on the cesium-fixing material;
(3) Collecting high-speed adsorption column effluent;
wherein, cs in the cesium-containing wastewater + =1 mg/L to 50mg/L, initial ph=3 to 10;
the cesium-containing wastewater can also contain one or more coexisting ions;
the coexisting ions and concentrations may be: cu (Cu) 2+ ＝0-10mg/L，Cr 3+ ＝0-10mg/L，Cd 2+ ＝0-10mg/L，Ni 2+ ＝0-10mg/L，Co 2+ ＝0-10mg/L，Pb 2+ ＝0-10mg/L，Na + ＝0-6000mg/L，K + ＝0-1000mg/L。
Preferably, the method comprises the following steps:
s1, mixing 0.3-1 part by mass of metal oxide, 1-2.4 parts by mass of nonmetal oxide, 1-2 parts by mass of water and 1-1.5 parts by mass of alkali;
s2, adding 1 part by mass of cesium-fixing material after completing cesium-containing wastewater treatment into the mixture of the S1;
s3, fully and uniformly stirring the S2 mixture, and standing for 1d-7d to obtain a dried cesium-fixing block;
the mass ratio of the metal oxide to the nonmetal oxide in the S1 is 1:0.8-4;
in the step S3, after the mixture of the S2 is fully and uniformly stirred, the mixture of the S2 can be respectively injected into a container to form a plurality of cesium fixing blocks.
The application can further cure the used high-selectivity cesium-fixing material by using the same raw materials to form a block with smaller dispersion and migration risks. This is because cesium-fixing materials have good compatibility with homologous metal oxides and non-metal oxides, and the aluminum and silicon components in the system can be chemically bonded with Al-O tetrahedra and Si-O tetrahedra in the host, thereby forming an integrated block. Furthermore, tungsten or molybdenum in the guest reacts directly with cesium rather than solely with oxygen atoms, and the mineral component of the block contains a zeolite phase, so cesium is firmly fixed within the crystal lattice. Solves the problems of unstable organic components and difficult safe post-treatment in the secondary waste in the prior art.
In summary, the application has the following beneficial effects:
1. the advantage of the application is derived from the ability to efficiently select cesium and fix it on materials in complex aqueous environments where multiple cations are present at the same time and the pH varies strongly: 1) The guest has cesium recognition sites, and is specifically bound to cesium directly by tungsten or molybdenum; 2) The hosts are connected in an oxygen tetrahedral form through oxygen atoms, and electronegativity of the surfaces of the host reticular polymeric structures can weaken competitive occupation of alkali metal ions on the guests in a low pH range; cesium has a specific action with tungsten in metal oxygen clusters, so that cesium can be fixed on a material with high selectivity under the interference of coexisting ions, and the material is endowed with high selectivity to cesium. Solves the problems that the cesium is difficult to be removed efficiently by utilizing ion exchange and electrostatic action in the prior art, and particularly, the cesium cannot be specifically identified and fixed in strong acid wastewater;
2. the preparation method can obtain the nanoscale object structure, and can be uniformly dispersed on a host without agglomeration, so that cesium recognition sites of the object are fully exposed, the enrichment capacity of the material for cesium is high, the reaction speed is high, and the problems of low cesium removal performance, long time and large secondary waste amount of the adsorbent in a complex environment are solved;
3. the application can further solidify the used high-selectivity cesium-fixing material with the same raw material to form a block with smaller dispersion and migration risks, because the cesium-fixing material has good compatibility with homologous metal oxide and nonmetal oxide, aluminum and silicon components in the system can be chemically bonded with Al-O tetrahedron and Si-O tetrahedron in a main body to form an integrated block, in addition, tungsten or molybdenum in a guest directly acts with cesium instead of simply by oxygen atoms, and the mineral component of the block contains zeolite phase, so that cesium is firmly fixed in a crystal lattice, and the problems of unstable organic components and difficult safe aftertreatment in secondary waste in the prior art are solved.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the scope of the disclosure.
Drawings
1. FIG. 1 is an SEM image of cesium fixing material of example 1 of the present application;
2. FIG. 2 is an XRD analysis of cesium-fixing material in example 1 of the present application;
3. FIG. 3 is a TEM image of an object according to example 1 of the present application;
4. FIG. 4 is an FT-IR diagram of cesium-immobilization material in example 2 of the application;
5. FIG. 5 shows XPS analysis of cesium immobilized on a subject in application example 2 of the present application;
5. FIG. 6 is a photograph showing sedimentation of cesium-fixing material in application example 4 of the present application;
6. FIG. 7 is a photograph of cesium fixation blocks in application example 3 of the present application.
Detailed Description
The application is further described in detail below with reference to the following examples, which are specifically described: the following examples, in which no specific conditions are noted, are conducted under conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the following examples are commercially available from ordinary sources except for the specific descriptions.
The standard basis is national standard GB14569.1-2011, the performance requirement of low-level horizontal radioactive waste curing body-cement curing body;
the nonmetallic acid salts include: potassium phosphate, sodium phosphate, ammonium phosphate, dipotassium phosphate, disodium phosphate, diammonium phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate; potassium silicate, sodium silicate, ammonium silicate;
the metal acid salts include: tungstate or molybdate;
the organic solvent extraction solvent includes: chloroform, n-octanol and diethyl ether;
the organic medium includes: simethicone, polyethylene glycol or triglyceride oil.
Examples
Example 1
The preparation method of the cesium-fixing material specifically comprises the following steps:
(1) Synthesizing an object:
1) Taking 4g of Na 2 HPO 4 ·12H 2 O is dissolved in 150g of deionized water, after all the O is dissolved, the solution is stirred and heated to 80 ℃ and then the aqueous solution of hydrochloric acid (V) is added dropwise Water and its preparation method :V HCl =1:1), the pH was adjusted to 6.0 and maintained at 80 ℃;
2) 40g of Na 2 WO 4 ·2H 2 O is dissolved in 100g deionized water, added into the 1) solution and heated to 90 ℃, the pH is regulated to 2.0 by the hydrochloric acid aqueous solution, and the mixture is reacted for 2 hours under vigorous stirring and cooled to room temperature;
3) Adding 100g diethyl ether into the solution 2), shaking until the solution is layered, and separating the lowest layer to obtain H 3 PW 12 O 40 Drying in air, and recrystallizing to obtain white powder to obtain guest H 3 PW 12 O 40 。
(2) A synthesis main body:
1) Adding 1g of NaOH into 2.5g of deionized water, and stirring until the NaOH is completely dissolved;
2) Mixing 2g of amorphous mixture of activated alumina and activated silica (1:1) with 1g of NaOH solution, stirring for 10min to obtain slurry, and dripping the slurry into a slurry with a viscosity of 1000mm at a rate of 1.0mL/s 2 In/s silicone oil, regulating the rotating speed to 600rpm, continuously stirring for 20min, and separating out solid components;
3) Adding 1g of solid component into deionized water, continuously preserving heat at 55 ℃ for 6 hours, separating out the solid component, putting the solid component into an oven, continuously preserving heat at 50 ℃ for 24 hours, taking out the solid component, putting the solid component into a muffle furnace, heating to 500 ℃ and preserving heat for 7 hours, naturally standing and cooling to room temperature, and washing the solid component with deionized water until the cleaning liquid is free of impurities to obtain a main body.
(3) Host-guest domain binding:
1) Adding 2g of object and 1g of main body into 150g of deionized water, oscillating for 30s by a vortex mixer, uniformly mixing, then placing into a constant-temperature oscillator, and oscillating for 24h at 25 ℃ at a rotating speed of 180 rpm;
2) Separating out the solid components in the mixed system of 1), and washing with deionized water until the cleaning liquid is free of impurities, thereby obtaining the cesium-solid material.
The cesium-fixing material obtained in example 1 has the appearance of a pellet with a particle size of about 110 micrometers, a rough surface, a microscopic morphology shown in fig. 1, an xrd analysis shown in fig. 2, and diffraction lines or characteristic peaks from top to bottom respectively as a host, the cesium-fixing material and a guest. It can be seen that H 3 PW 12 O 40 Uniformly distributed in each part of the three-dimensional network structure of the main body, and no H is present 3 PW 12 O 40 The obvious characteristic peak of (2) and the main characteristic peak intensity is obviously weakened, which indicates H 3 PW 12 O 40 Uniformly dispersed and not agglomerated.
The average particle size of the commercial phosphotungstic acid powder 12067-99-1 was about 600nm, and the object obtained in example 1 had an average particle size of about 100nm, and was found in FIG. 3 to be only 1/6 of the commercial product.
Example 2
The preparation method of the cesium-fixing material specifically comprises the following steps:
(1) Synthesizing an object:
1) Taking 6g of Na 2 HPO 4 ·12H 2 O is dissolved in 150g of deionized water, after all the O is dissolved, the solution is stirred and heated to 80 ℃ and then the aqueous solution of hydrochloric acid (V) is added dropwise Water and its preparation method :V HCl =1:1), the pH was adjusted to 5.5 and maintained at 80 ℃;
2) 50g of Na 2 WO 4 ·2H 2 O is dissolved in 100g deionized water, added into the 1) solution and heated to 90 ℃, the pH is regulated to 1.5 by the hydrochloric acid aqueous solution, and the mixture is reacted for 3 hours under vigorous stirring and cooled to room temperature;
3) Adding 100g diethyl ether into the solution 2), shaking until the solution is layered, and separating the lowest layer to obtain H 3 PW 12 O 40 Drying in air, and recrystallizing to obtain white powder to obtain guest H 3 PW 12 O 40 。
(2) A synthesis main body:
1) Adding 1g of NaOH into 2.5g of deionized water, and stirring until the NaOH is completely dissolved;
2) Mixing 2g of amorphous mixture of activated alumina and activated silica (1:3) with 1g of NaOH solution, stirring for 10min to obtain slurry, and dripping the slurry into 600mm viscosity at a rate of 2.0mL/s 2 In/s silicone oil, regulating the rotating speed to 500rpm, continuously stirring for 25min, and separating out solid components;
3) Adding 1g of solid component into deionized water, continuously preserving heat at 55 ℃ for 6 hours, separating out the solid component, putting the solid component into an oven, continuously preserving heat at 50 ℃ for 24 hours, taking out the solid component, putting the solid component into a muffle furnace, heating to 500 ℃ and preserving heat for 7 hours, naturally standing and cooling to room temperature, and washing the solid component with deionized water until the cleaning liquid is free of impurities to obtain a main body.
(3) Host-guest domain binding:
1) Adding 3g of object and 1g of main body into 150g of deionized water, oscillating for 30s by a vortex mixer, uniformly mixing, then placing into a constant-temperature oscillator, and oscillating for 24h at 45 ℃ and 200 rpm;
2) Separating out the solid components in the 1) mixed system, and washing the solid components with deionized water until the cleaning liquid is free of impurities, thereby obtaining the solid cesium material with the average particle size of about 800 mu m.
The FT-IR analysis of the cesium-immobilization material obtained in example 2, which is shown in FIG. 4, illustrates the formation of AlPW 12 O 40 。
Example 3
The preparation method of the cesium-fixing material specifically comprises the following steps:
(1) Synthesizing an object:
1) Taking 2g of Na 2 PO 3 Dissolving in 150g of deionized water, stirring and heating to 80 ℃ after all the solution is dissolved, dropwise adding 12M hydrochloric acid aqueous solution, adjusting the pH to 6.0, and keeping the temperature at 80 ℃;
2) Will 30gNa 2 MoO 4 ·2H 2 O is dissolved in 100g deionized water, added into the 1) solution and heated to 90 ℃, the pH value is regulated to 1.0 by the hydrochloric acid aqueous solution, and the mixture is reacted for 2 hours under vigorous stirring and cooled to room temperature;
3) Adding 100g diethyl ether into the solution 2), shaking until the solution is layered, and separating the lowest layer to obtain H 3 PMo 12 O 40 Drying in air, and recrystallizing to obtain white powder to obtain guest H 3 PMo 12 O 40 。
(2) A synthesis main body:
1) Adding 1g of NaOH into 2.5g of deionized water, and stirring until the NaOH is completely dissolved;
2) Mixing 2g of amorphous mixture of activated alumina and activated silica (1:2) with 1g of NaOH solution, stirring for 10min to obtain slurry, and dripping the slurry into a slurry with a viscosity of 1000mm at a rate of 1.0mL/s 2 In/s silicone oil, regulating the rotating speed to 600rpm, continuously stirring for 30min, and separating out solid components;
3) Adding 1g of solid component into deionized water, continuously preserving heat at 55 ℃ for 6 hours, separating out the solid component, putting the solid component into an oven, continuously preserving heat at 50 ℃ for 24 hours, taking out the solid component, putting the solid component into a muffle furnace, heating to 500 ℃ and preserving heat for 7 hours, naturally standing and cooling to room temperature, and washing the solid component with deionized water until the cleaning liquid is free of impurities to obtain a main body.
(3) Host-guest domain binding:
1) Adding 2g of object and 1g of main body into 150g of deionized water, oscillating for 30s by a vortex mixer, uniformly mixing, then placing into a constant-temperature oscillator, and oscillating for 24h at 25 ℃ at a rotating speed of 180 rpm;
2) Separating out the solid components in the mixed system of 1), and washing with deionized water until the cleaning liquid is free of impurities, thereby obtaining the cesium-solid material.
Example 4
The preparation method of the cesium-fixing material specifically comprises the following steps:
(1) Synthesizing an object:
1) Taking 2g of Na 2 SiO 3 ·9H 2 O is dissolved in 150g of deionized water, after all the O is dissolved, the solution is stirred and heated to 80 ℃ and then the aqueous solution of hydrochloric acid (V) is added dropwise Water and its preparation method ：V HCl =1:1), the pH was adjusted to 6.3 and maintained at 80 ℃;
2) Will 60g Na 2 WO 4 ·2H 2 O is dissolved in 100g deionized water, added into the 1) solution and heated to 90 ℃, the pH is regulated to 2.5 by the hydrochloric acid aqueous solution, and the mixture is reacted for 4 hours under vigorous stirring and cooled to room temperature;
3) Adding 100g diethyl ether into the solution 2), shaking until the solution is layered, and separating the lowest layer to obtain H 4 SiW 12 O 40 Drying in air, and recrystallizing to obtain white powder to obtain guest H 4 SiW 12 O 40 。
(2) A synthesis main body:
1) Adding 1g of NaOH into 1.5g of deionized water, and stirring until the NaOH is completely dissolved;
2) 3g of a mixture of amorphous activated alumina and activated silica (1:1) was mixed with 1g of NaOH solution and stirred for 10min to completely mix into a slurry, and the slurry was dropped into a slurry having a viscosity of 500mm at a rate of 0.5mL/s 2 In/s silicone oil, regulating the rotating speed to 750rpm, continuously stirring for 30min, and separating out solid components;
3) Adding 1g of solid component into deionized water, continuously preserving heat at 65 ℃ for 6 hours, separating out the solid component, putting the solid component into an oven, continuously preserving heat at 65 ℃ for 24 hours, taking out the solid component, putting the solid component into a muffle furnace, heating to 500 ℃ and preserving heat for 6 hours, naturally standing and cooling to room temperature, and washing the solid component with deionized water until the cleaning liquid is free of impurities to obtain a main body.
(3) Host-guest domain binding:
1) Adding 3g of object and 1g of main body into 150g of deionized water, oscillating for 40s by a vortex mixer, uniformly mixing, then placing into a constant-temperature oscillator, and oscillating for 18h at 35 ℃ and a rotating speed of 200 rpm;
2) Separating out the solid components in the 1) mixed system, and washing the solid components with deionized water until the cleaning liquid is free of impurities, thereby obtaining the solid cesium material with the average particle size of about 120 mu m.
Application example
Application example 1
The application method of the cesium fixing material specifically comprises the following steps:
1g of the cesium immobilization material obtained in example 1 was taken in a batch reactor. The water inlet of the reactor was opened, 1000g of cesium-containing wastewater was injected into the reactor, the initial pH of the cesium-containing wastewater was 6.5, cs + =10mg/L, simultaneously containing coexisting ions Cu 2+ ＝5mg/L、Cr 3+ ＝10mg/L、Cd 2+ ＝2mg/L、Ni 2+ ＝3mg/L、Co 2+ ＝10mg/L、Pb 2+ ＝1mg/L、Na + =20mg/L and K + =10mg/L. The stirrer switch is turned on, the stirring speed is set to be 350ppm, the adsorption balance is achieved in 100min, the stirring is stopped, and the water outlet of the reactor is opened.
Cs + The concentration of the effluent is 0.85mg/L, and the removal rate reaches 91.5%.
Application example 1 also provides another application method, which specifically comprises the following steps:
1g of the cesium immobilization material obtained in example 1 was taken in a reactor. The water inlet of the reactor was opened, 1000g of cesium-containing wastewater was injected into the reactor, the initial pH of the cesium-containing wastewater was 2, cs + ＝10mg/L，Na + =6g/L. The stirring switch was turned on, the stirring speed was set at 300rpm, and adsorption equilibrium was reached at 100 min. Stopping stirring, and opening the water outlet of the reactor to discharge water.
Cs + The concentration of the effluent is about 0.2mg/L, and the removal rate reaches 98 percent.
Application example 2
The application method of the cesium fixing material specifically comprises the following steps:
1g of the cesium immobilization material obtained in example 2 was taken in a batch reactor. The reactor water inlet was opened and 1000g of cesium-containing wastewater was injected into the reactor, initial ph=3.0-10.0, cs + =10mg/L. The stirring switch is started, the stirring speed is set to 300rpm, the adsorption balance is achieved in 100min, the stirring is stopped, and the water outlet of the reactor is opened. Cs in effluent + The concentration is stabilized at about 0.8mg/L, the removal efficiency can reach more than 91%, and H 3 PW 12 O 40 The loss rate of (2) is less than 0.1%.
The XPS analysis of the cesium-fixing material after application at pH=6.5 is shown in the lower spectral line of FIG. 5 (the upper spectral line is the cesium-fixing material in example 2), which indicates that the high-selectivity cesium-fixing process is mainly Cs and PW in the object 12 O 40 3- W of (c) undergo a specific reaction.
Application example 2 also provides another application method of the cesium-fixing material, which specifically comprises the following steps:
the cesium fixation material 1L obtained in example 2 was taken in a high-speed adsorption column, and the high-speed adsorption column was packed with a cesium fixation material layer. Opening the water inlet of the reactor, continuously injecting cesium-containing wastewater into the reaction column at a flow rate of 10L/h, wherein Na is contained in the wastewater + ＝1000mg/L、K + =1000 mg/L, initial pH was 6.5. Opening a water outlet of the reactor to collect the processed water, wherein Cs + The concentration is stabilized at about 4.62mg/L, and the removal rate reaches 95%.1kg of cesium-fixing material can treat about 1700L of cesium-containing wastewater.
Application example 3
The application method of the cesium fixing material specifically comprises the following steps:
1g of metal oxide, 2.4g of non-metal oxide, 1.7g of water and 1g of alkali are mixed, 2g of cesium fixation material used in application example 2 is added into the mixture, after the mixture is fully stirred, the slurry is injected into a container, and after standing for 3d, the mixture is taken out, and the obtained cesium fixation block is shown in figure 7. After 28d standard curing, the leaching rate and cumulative leaching score of Cs in the block at 42d were on the order of 10 respectively - 4 cm/d and 10 -2 cm, the numerical value meets the requirements of national standard GB14569.1-2011, low and horizontal radioactive waste curing body performance requirement-Cement curing body.
Application example 4
The application method of the cesium fixing material specifically comprises the following steps:
opening a water inlet of a batch reactor, injecting 2000mLL cesium-containing wastewater into the batch reactor, taking 1g of the cesium-containing wastewater obtained in example 4, adding the cesium-containing wastewater into the cesium-containing wastewater, and starting a stirring switch; after the reaction was completed, stirring was stopped, immediately sampling was performed with a sampling bottle and photographing was recorded as stopping stirring for 1s, and photographing was performed at 3s and 5s, respectively, as shown in fig. 6, and it was seen that substantially all cesium fixation material settled to the bottom of the reactor after 5 s.
Comparative application example 1
The method of using cesium-immobilization material of application example 1 was followed, except that 1g of commercially available strong acid type 001X 7 cation exchange resin was used in a batch reactor. The water inlet of the reactor was opened, 1000mL of cesium-containing wastewater was injected into the reactor, the initial pH of the cesium-containing wastewater was 6.5, cs + =10mg/L, simultaneously containing coexisting ions Cu 2+ ＝10mg/L、Cr 3+ ＝10mg/L、Cd 2+ ＝10mg/L、Ni 2+ ＝10mg/L、Co 2+ ＝10mg/L、Pb 2+ ＝10mg/L、Na + =50mg/L and K + =50mg/L. Turning on the switch of the stirrer, setting stirring speed to 350ppm, balancing the reaction at 120min, stopping stirring, and calculating to obtain 001×7 Cs + The adsorption capacity of (C) is about 4.9mg/g, and the removal efficiency is only 49%.
Comparative application example 2
The method of using cesium-immobilization material of application example 1 was followed, except that 1g of the object synthesized in example 1 was taken in a batch reactor. The water inlet of the reactor was opened, 1000mL of cesium-containing wastewater was injected into the reactor, the initial pH of the cesium-containing wastewater was 6.5, cs + =10mg/L, simultaneously containing coexisting ions Na + =6g/L. Turning on the switch of the stirrer, setting stirring speed to 350ppm, stopping stirring at 100min, and calculating to obtain Cs + The removal rate of (2) was only 43%.
Comparative application example 3
The method of using cesium-immobilization material of application example 1 was followed, except that 1g of the synthesized body of example 1 was taken in a batch reactor. The water inlet of the reactor was opened, 1000mL of cesium-containing wastewater was injected into the reactor, the initial pH of the cesium-containing wastewater was 6.5, cs + =10mg/L, simultaneously containing coexisting ions Cu 2+ ＝5mg/L、Cr 3+ ＝10mg/L、Cd 2+ ＝2mg/L、Ni 2+ ＝3mg/L、Co 2+ ＝10mg/L、Pb 2+ ＝1mg/L、Na + =20mg/L and K + =10mg/L. Turning on the switch of the stirrer, setting stirring speed to 350ppm, stopping stirring at 100min, and calculating to obtain Cs + The removal rate of (2) was 9%.
Comparative application example 4
The cesium-immobilization material of application example 1 was used in the same manner as in the application example 1, except that 0.5g of the guest synthesized in example 2 and 0.5g of the host synthesized in example 2 were mixed with each other, and the mixture was fed into a batch reactor. The reactor water inlet was opened and 1000mL of cesium-containing wastewater was injected into the reactor at an initial pH of 6.5, cs + =10mg/L. The stirring switch is turned on, the stirring speed is set to 300rpm, the stirring is stopped when the stirring time is 100min, and the water outlet of the reactor is opened. Cs in effluent + The concentration is stabilized at about 5.8mg/L, and Cs is calculated + The removal efficiency of (2) was 42%.
While the present disclosure has been described with respect to exemplary embodiments thereof, it should be understood that the scope of the present disclosure is not limited thereto, but rather, any changes or substitutions that would occur to one skilled in the art within the scope of the present disclosure should be included in the scope of the present disclosure. Therefore, the protection scope of the present disclosure should be subject to the protection scope of the claims.
Claims (6)
1. A cesium-fixing material, characterized in that said cesium-fixing material is entirely composed of inorganic components including metal-nonmetal oxygen clusters, metal oxides, nonmetal oxides, and bases;
the cesium fixing material comprises the following chemical components in percentage by mass: metal-nonmetal oxygen cluster metal oxide nonmetal oxide base= (0.1-1.3): (0.18-0.3): (0.6-0.72): (0.05-0.1);
the metal-nonmetal oxygen cluster is one or more of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid, the metal oxide is amorphous active alumina, the nonmetal oxide is amorphous active silica, and the alkali is one or more of sodium hydroxide or potassium hydroxide;
the metal-nonmetal oxygen cluster in the structure of the cesium fixing material consists of 1 central tetrahedron and 4 groups of trimetallic clusters; the microstructure of the cesium-fixing material comprises a host and a guest, wherein the host is combined with the guest;
the network polymerization structure formed by connecting an Al-O tetrahedron and a Si-O tetrahedron through O is taken as a host, the oxygen cluster structure formed by connecting a W-O or Mo-O octahedron and a P-O or Si-O tetrahedron through O is taken as an object, and the host and the object are connected through O by the W-O or Mo-O octahedron and the Al-O tetrahedron or the Si-O tetrahedron;
the preparation method of the cesium-fixing material comprises the following steps:
a, synthesizing an object:
a1: dissolving 1-10 parts by mass of nonmetallic acid salt in deionized water, heating to 80-100 ℃ after the nonmetallic acid salt is completely dissolved, and adjusting the pH value to be 5.0-6.5 by hydrochloric acid;
a2: dissolving 8-60 parts by mass of metal acid salt in deionized water, adding the solution prepared by the A1, heating to 90-100 ℃, adjusting the pH value to 1.0-2.5 by hydrochloric acid, carrying out vigorous stirring reaction for 1-4 hours, and cooling to room temperature;
a3: extracting metal-nonmetal oxygen clusters in the solution prepared by the A2 by using an organic solvent, and recrystallizing after drying to obtain a solid substance which is a guest;
and B, synthesizing a main body:
b1: adding 1 part by mass of the alkali into 1.5-3.5 parts by mass of deionized water, and stirring until the alkali is completely dissolved;
b2: taking the mass ratio of the metal oxide to the nonmetal oxide of 1:2-1:1, mixing the prepared mixture with the solution prepared in the B1, wherein the mass ratio of the prepared mixture to the solution prepared in the B1 is 2-4:1, stirring for 3-10 min to completely mix the mixture into slurry, and mixing the slurry at a speed of 0.5-2.0 mL/sViscosity of 500mm 2 /s-1500mm 2 In an organic medium of/s, regulating the rotating speed to 500-800 rpm, continuously stirring for 20-30 min, and separating out solid components;
b3: adding the solid component prepared in the step B2 into deionized water, preserving heat at 50-80 ℃, separating out the solid component, heating, naturally standing, cooling to room temperature, and cleaning to obtain a main body;
c, host-guest domain-limited combination:
c1: adding 0.1-3 parts by mass of the object and 1 part by mass of the main body into 150 parts by mass of deionized water, uniformly mixing by shaking by a vortex mixer, placing in a constant-temperature oscillator, and oscillating for 12-24 hours at the rotation speed of 100-200 rpm at the temperature of 25-65 ℃;
c2: separating out solid components in the mixed system prepared by the C1, and washing with deionized water until the cleaning liquid is free of impurities, thereby obtaining the solid cesium material.
2. The cesium immobilization material of claim 1 wherein the guest structure is a nanocrystal, the average particle size is 50nm to 100nm, the host structure is amorphous, the macroscopic surface is rough, and the specific surface area is 5 to 20m 2 /g。
3. Cesium-fixing material according to claim 1 or 2, characterized in that it exhibits a spheroid-like appearance with a particle size of 10 μm-1500 μm.
4. A method for preparing the cesium-fixing material of any one of claims 1 to 3, comprising the steps of:
a, synthesizing an object:
a1: dissolving 1-10 parts by mass of nonmetallic acid salt in deionized water, heating to 80-100 ℃ after the nonmetallic acid salt is completely dissolved, and adjusting the pH value to be 5.0-6.5 by hydrochloric acid;
a2: dissolving 8-60 parts by mass of metal acid salt in deionized water, adding the solution prepared by the A1, heating to 90-100 ℃, adjusting the pH value to 1.0-2.5 by hydrochloric acid, carrying out vigorous stirring reaction for 1-4 hours, and cooling to room temperature;
a3: extracting metal-nonmetal oxygen clusters in the solution prepared by the A2 by using an organic solvent, and recrystallizing after drying to obtain a solid substance which is a guest;
and B, synthesizing a main body:
b1: adding 1 part by mass of the alkali into 1.5-3.5 parts by mass of deionized water, and stirring until the alkali is completely dissolved;
b2: taking the mass ratio of the metal oxide to the nonmetal oxide of 1:2-1:1, mixing the prepared mixture with the solution prepared in the B1, wherein the mass ratio of the prepared mixture to the solution prepared in the B1 is 2-4:1, stirring for 3-10 min to completely mix the mixture into slurry, and dripping the slurry into the slurry with the viscosity of 500mm at the speed of 0.5-2.0 mL/s 2 /s-1500mm 2 In an organic medium of/s, regulating the rotating speed to 500-800 rpm, continuously stirring for 20-30 min, and separating out solid components;
b3: adding the solid component prepared in the step B2 into deionized water, preserving heat at 50-80 ℃, separating out the solid component, heating, naturally standing, cooling to room temperature, and cleaning to obtain a main body;
c, host-guest domain-limited combination:
c1: adding 0.1-3 parts by mass of the object and 1 part by mass of the main body into 150 parts by mass of deionized water, uniformly mixing by shaking by a vortex mixer, placing in a constant-temperature oscillator, and oscillating for 12-24 hours at the rotation speed of 100-200 rpm at the temperature of 25-65 ℃;
c2: separating out solid components in the mixed system prepared by the C1, and washing with deionized water until the cleaning liquid is free of impurities, thereby obtaining the solid cesium material.
5. A method of using the cesium immobilization material of claim 1, comprising the steps of:
(1) Filling the prepared cesium-fixing material into a high-speed adsorption column, and forming a cesium-fixing material layer in the adsorption column;
(2) Regulating a water inlet valve of the high-speed adsorption column to enable cesium-containing wastewater to continuously flow through the high-speed adsorption column at a flow rate of 10-20 parts by volume/h, wherein the volume ratio of the cesium-containing wastewater to the cesium-fixing material is 10-20:1, and cesium in the wastewater migrates and is fixed on the cesium-fixing material;
(3) Collecting high-speed adsorption column effluent;
wherein, cs in the cesium-containing wastewater + =1 mg/L to 50mg/L, initial ph=3 to 10;
the cesium-containing wastewater also contains one or more coexisting ions;
the coexisting ions and concentrations are: cu (Cu) 2+ ＝0-10mg/L，Cr 3+ ＝0-10mg/L，Cd 2+ ＝0-10mg/L，Ni 2+ ＝0-10mg/L，Co 2+ ＝0-10mg/L，Pb 2+ ＝0-10mg/L，Na + ＝0-6000mg/L，K + ＝0-1000mg/L。
6. The method for applying cesium fixation material according to claim 5, comprising the steps of:
s1, mixing 0.3 to 1 part by mass of metal oxide, 1 to 2.4 parts by mass of nonmetal oxide, 1 to 2 parts by mass of water and 1 to 1.5 parts by mass of alkali;
s2, adding 1 part of cesium-fixing material which is subjected to cesium-containing wastewater treatment through the adsorption column into the mixture of the S1;
s3, fully and uniformly stirring the S2 mixture, and standing for 1d-7d to obtain a dried cesium-fixing block;
the mass ratio of the metal oxide to the nonmetal oxide in the S1 is 1:2.4;
in the step S3, the S2 mixture is fully and uniformly stirred and then is respectively injected into a container to form a plurality of cesium fixing blocks.
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