CN104528824B - A kind of produce Zirconium powder and the method for ammonium salt and product simultaneously - Google Patents
A kind of produce Zirconium powder and the method for ammonium salt and product simultaneously Download PDFInfo
- Publication number
- CN104528824B CN104528824B CN201510004777.XA CN201510004777A CN104528824B CN 104528824 B CN104528824 B CN 104528824B CN 201510004777 A CN201510004777 A CN 201510004777A CN 104528824 B CN104528824 B CN 104528824B
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- Prior art keywords
- zirconium
- solid
- solution
- equal
- powder
- Prior art date
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 231
- 238000000034 method Methods 0.000 title claims abstract description 64
- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 136
- 239000007787 solid Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 238000000926 separation method Methods 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 230000033228 biological regulation Effects 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000000376 reactant Substances 0.000 claims abstract description 26
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 17
- 229910016287 MxOy Inorganic materials 0.000 claims abstract description 12
- 239000006193 liquid solution Substances 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000001354 calcination Methods 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 33
- 230000000694 effects Effects 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 15
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 zirconium cation Chemical class 0.000 claims description 13
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 235000013877 carbamide Nutrition 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 210000002700 urine Anatomy 0.000 claims description 4
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 3
- 241000030614 Urania Species 0.000 claims description 3
- SHZGCJCMOBCMKK-KGJVWPDLSA-N beta-L-fucose Chemical compound C[C@@H]1O[C@H](O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-KGJVWPDLSA-N 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 claims description 3
- 229910052699 polonium Inorganic materials 0.000 claims description 3
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 3
- 229910052705 radium Inorganic materials 0.000 claims description 2
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 2
- 229910003452 thorium oxide Inorganic materials 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 238000005406 washing Methods 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 239000000047 product Substances 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011027 product recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 61
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 30
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 25
- 229910001928 zirconium oxide Inorganic materials 0.000 description 25
- 239000012071 phase Substances 0.000 description 22
- 238000005516 engineering process Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 17
- 235000019270 ammonium chloride Nutrition 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 230000007170 pathology Effects 0.000 description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 239000012745 toughening agent Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PLEZGBHMSVTPPQ-UHFFFAOYSA-N [O-2].[Ra+2] Chemical compound [O-2].[Ra+2] PLEZGBHMSVTPPQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003462 bioceramic Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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Abstract
The invention discloses a kind of production Zirconium powder simultaneously and the method for ammonium salt and product.Said method comprising the steps of: zirconium precursor liquid solution, heating are prepared the reactant mixture Han zirconium by (1)；(2) will contain zirconium reactant mixture, regulation pH is less than or equal to 2.0, and solid-liquid separation obtains containing zirconium solid and solution A；(3) zirconium solid will be contained to be configured to containing zirconium serosity, and add metal-oxide MxOyPresoma；(4) will contain zirconium serosity, regulation pH value is more than or equal to 6.0, and solid-liquid separation obtains main component precursor solid and solution B；(5) main component precursor is dried and calcines, after washing pelletize, i.e. prepare Zirconium powder；(6) solution A and solution B being merged, use mineral acid or inorganic base regulation pH between 5.0 to 8.0, transpiring moisture separates out ammonium salt.The method that the present invention provides, by-product recovery rate is high, and economic benefit is obvious, environmental friendliness, and the product purity that it is prepared is high.
Description
Technical field
The invention belongs to technical field of biological material, produce Zirconium powder more particularly, to one simultaneously
Method and product with ammonium salt.
Background technology
Solid solution have the zirconia ceramics of the metal-oxide additives such as yittrium oxide because of have excellent mechanics,
Calorifics, optics, electrical properties and chemical stability, and it is widely used in high-temperature structural material, height
The fields such as temperature optical element, oxygen sensitive element, high-temperature oxide membrane cell, biological structure material.
The existing production technology of the zirconia ceramics of the metal oxide stabilities such as yittrium oxide typically uses chemistry
Method, electric smelting method, coprecipitation etc..These methods are all not involved with how processing and produce at zirconium oxide
During the by-product that generates, be also not involved with water in production process recycles problem.If
By-product in production process is directly discharged in environment, natural water and composition of the soil can be changed,
Cause environmental pollution.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides one and produce oxygen simultaneously
Change zirconium powder body and the method for ammonium salt and product, its object is to by twice solid-liquid separation and reclaim separation
After liquid phase carry out post processing, thus solve existing Zirconium powder production method and cannot reclaim by-product
The cyclic utilization rate of thing, chemical reagent and pure water is low and by-product causes the technology of environmental pollution to ask
Topic.
For achieving the above object, according to one aspect of the present invention, it is provided that one produces oxidation simultaneously
Zirconium powder body and the method for ammonium salt, comprise the following steps:
(1) by zirconium precursor liquid solution, there is chemical reaction in heating so that zirconium is cation ic-converted to be become to aoxidize
Zirconium, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion more than or equal to 90%, prepare
Containing zirconium reactant mixture；Described zirconium precursor liquid solution, its zirconium cation concn is less than or equal to 5.0
mol/L；
(2) by step (1) prepare containing zirconium reactant mixture, with mineral acid, inorganic base or urine
Element regulation pH, less than or equal to 2.0, then carries out solid-liquid separation process, obtains containing zirconium solid and solution
A；
(3) the solid pure water containing zirconium prepared in step (2) is configured to mass concentration 5% to 70%
Between containing zirconium serosity, and according to required stoichiometric proportion to described containing in zirconium serosity add burning
Thing MxOyPresoma so that M in productxOyAccount for key component ZrO2Molar percentage less than or
Equal to one in yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements of 15 moles of %, M or
Multiple；
(4) by step (3) prepares containing zirconium serosity, regulate with mineral acid, inorganic base or carbamide
PH value be more than or equal to 6.0, then carry out solid-liquid separation process, obtain main component precursor solid and
Solution B；
(5) the main component precursor solid prepared in step (4) is dried and calcines, wash pelletize
After i.e. prepare described Zirconium powder.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use
Mineral acid or inorganic base regulation pH are between 5.0 to 8.0, and transpiring moisture separates out ammonium salt.
Preferably, described method, its step (2), step (4) and/or step (6) are described inorganic
Acid conventional example hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid etc..
Preferably, described method, its step (2), step (4) and/or step (6) are described inorganic
Alkali is conventional such as ammonium hydroxide.
Preferably, described method, its step (2), step (4) and/or step (6) use nitrogenous
Mineral acid or inorganic base regulation pH value.
Preferably, described method, its step (1) described zirconium precursor body be basic zirconium chloride, zirconium chloride,
The combination of one or more in zirconium nitrate, Disulfatozirconic acid., zirconium carbonate and zirconium phosphate.
Preferably, described method, its described step (1) reaction temperature between 40 DEG C to 400 DEG C,
Pressure is between 0.1MPa to 3.25MPa；Preferable temperature is between 50 DEG C to 250 DEG C, and pressure exists
Between 0.1MPa to 1.2MPa；More preferably temperature is between 80 DEG C to 150 DEG C, and pressure is at 0.1MPa
Between 0.5MPa.
Preferably, described method, its described step (5) calcining heat between 800 DEG C to 1100 DEG C,
Heating rate, between 200 DEG C/h to 1200 DEG C/h, maintains calcining maximum temperature 0.5 hour to 5 hours.
It is another aspect of this invention to provide that provide a kind of Zirconium powder, provide according to the present invention
Prepared by the method simultaneously producing Zirconium powder and ammonium salt.
Preferably, described Zirconium powder, its key component is ZrO2+HfO2+MxOy, wherein MxOy
For metal-oxide, its content less than or equal to 15 moles of %, M selected from yttrium, calcium, magnesium, cerium, praseodymium,
One or more in vanadium, molybdenum and titanium elements, described main component accounts for the percent mass of Zirconium powder
Ratio more than 90%, other metal-oxides every kind account for the mass fraction of described Zirconium powder less than or
Equal to 0.01%.
Preferably, described Zirconium powder, its other metal-oxides described are silicon dioxide, oxidation
Ferrum, aluminium oxide, Cs2O, cobalt oxide, strontium oxide, oxidation polonium, radium oxide, urania, oxidation
Thorium, plutonium oxide, fracium oxide.
Preferably, described Zirconium powder, wherein chlorine element mass percent is less than or equal to 0.05%.
Preferably, described Zirconium powder, its ratio radiation activity recorded according to ISO 13356:2008
Less than or equal to 100Bq/kg.
Preferably, described Zirconium powder, the four directions of its Zirconium powder and the content of cube crystalline phase are big
In or equal to 90%.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it is possible to
Obtain following beneficial effect:
(1) method that the present invention provides, during chemical method synthesis is zirconic, can be by all
The liquid of solid-liquid separation process collects, and regulates it by adding mineral acid, inorganic base or carbamide
PH so that it is pH is more than or equal to 5.0 less than or equal to 8.0, and then the way by evaporation is permissible
Reclaim ammonium salt, and Water circulation condensation obtained is to zirconium oxide production technology.The most both warp can have been increased
Ji benefit, can reduce again the production technology impact on environment.Thus solve chemical method and produce oxidation
Zirconium technique affects problem to environment.
(2) method that the present invention provides, it is possible to separate the impurity in zirconium oxide preparation, reduce chlorine element
Discharge, thus reduce pollution to environment.Highly purified Zirconium powder can be produced in a large number simultaneously,
Preparation for high purity ceramic.
Accompanying drawing explanation
Fig. 1 is to produce zirconium oxide and the preparation process schematic diagram of ammonium salt while the present invention provides；
Fig. 2 is embodiment 1 and the prepared zirconic X-ray diffracting spectrum of comparative example 11.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing
And embodiment, the present invention is further elaborated.Should be appreciated that described herein specifically
Embodiment only in order to explain the present invention, is not intended to limit the present invention.Additionally, it is disclosed below
Just may be used as long as technical characteristic involved in each embodiment of the present invention does not constitutes conflict each other
To be mutually combined.
The present invention produces Zirconium powder and the method for ammonium salt, as it is shown in figure 1, include while providing
Following steps:
(1) by zirconium precursor liquid solution, there is chemical reaction in heating so that zirconium is cation ic-converted to be become to aoxidize
Zirconium, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion more than or equal to 90%, prepare
Containing zirconium reactant mixture；Described zirconium precursor liquid solution, its zirconium cation concn is less than or equal to 5.0
mol/L；The pH of zirconium precursor liquid solution is regulated and controled with mineral acid, inorganic base or carbamide.
Described zirconium precursor body is basic zirconium chloride, zirconium chloride, zirconium nitrate, Disulfatozirconic acid., zirconium carbonate and phosphoric acid
The combination of one or more of zirconium.The concentration of zirconium precursor liquid solution is less than or equal to 5.0 mol/L, excellent
Be selected between 0.1 mol/L to 2.0 mol/L, more preferably 0.3 mol/L to 1.2 mol/L it
Between.
The pH of reaction solution is less than or equal to 12.0, and preferably pH is less than or equal to 10.0, more preferably pH
Less than or equal to 8.0.
Reaction temperature is between 40 DEG C to 400 DEG C, and pressure is between 0.1MPa to 3.25MPa；Preferably
Temperature is between 50 DEG C to 250 DEG C, and pressure is between 0.1MPa to 1.2MPa；More preferably temperature exists
Between 80 DEG C to 150 DEG C, pressure is between 0.1MPa to 0.5MPa.
Response time is as the criterion with the conversion ratio of zirconium ion in reaction solution, it is to be ensured that the conversion ratio of zirconium ion
More than or equal to 90%, more preferably more than or equal to 95%, optimal it is more than or equal to 98%.
If the conversion ratio of zirconium is less than 90%, then on the one hand, can cause during follow-up solid-liquid separation
The loss of unconverted zirconium ion, thus reduce the utilization ratio of raw material, increase the manufacture of Zirconium powder
Cost；On the other hand, unconverted zirconium ion can enter ammonium salt manufacturing process during solid-liquid separation,
Together separate out with ammonium salt and affect the purity of ammonium salt.
If the pH of solution is more than 2.0, understands the metal cation beyond some zirconium and form precipitation,
Cause solid-liquid separation can not fully remove the metal impurities beyond zirconium, thus cause product zirconia powder
The content overproof or more higher than radiation activity of impurity in body.
The conversion ratio of so-called zirconium cation refers to what zirconium precursor body aqueous solution converted during reacting by heating
Zirconium ion amount, divided by the primary quantity before reaction, is the value calculated according to following formula.
Here CiThe concentration of zirconium, C before finger reacting by heatingfThe concentration of zirconium after finger reacting by heating, V refers to reaction
The volume of solution.
(2) by step (1) prepare containing zirconium reactant mixture, with mineral acid, inorganic base or urine
Element regulation pH, less than or equal to 2.0, then carries out solid-liquid separation process, obtains containing zirconium solid and solution
A.Conventional mineral acid example hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid etc.；Conventional inorganic base such as ammonium hydroxide, i.e.
Ammonia；Preferably, nitrogenous mineral acid or inorganic base are used.
This method does not limit the technological means of solid-liquid separation, if can be sufficiently separated containing zirconium solid and
One or the combination of technology such as the technological means of liquid such as centrifugal, filtration, filter pressing, ultrafiltration etc. can be selected
With.
(3) the solid pure water containing zirconium prepared in step (2) is configured to mass concentration 5% to 70%
Between containing zirconium serosity, and according to required stoichiometric proportion to described containing in zirconium serosity add burning
Thing MxOyPresoma so that M in productxOyAccount for key component ZrO2Molar percentage less than or
Equal to 15 moles of %, preferably between 2 moles of % to 8 mole of %, more preferably at 2.5 moles of % to 3.5
Between mole %, M one or many in yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements
Kind.Pure water containing zirconium River Bank Stability is that (U.S. faces for the one-level that specifies according to GB GB 6682-2000
The Type I of bed pathology meeting CAP is suitable) pure water.
Containing zirconium River Bank Stability method, (U.S. faces the one-level that addition specifies according to GB GB 6682-2000
The Type I of bed pathology meeting CAP is suitable) pure water, between mass concentration preferably 20% to 60%, more
Between preferably 35% to 50%.
Metal-oxide MxOyPresoma be that the oxide of respective metal, hydroxide, salt etc. all may be used
To select.Its form added both can be compound itself, it is also possible to be to prepare with this compound
Solution, it is also possible to be the nanometer or this burning of micron size existed with the form such as colloidal sol or gel
The granule of thing.
(4) by step (3) prepares containing zirconium serosity, regulate with mineral acid, inorganic base or carbamide
PH value is more than or equal to 6.0, preferably greater than or equal to 7.0, more preferably equal to or greater than 8.0, then
Carry out solid-liquid separation process, obtain main component precursor solid and solution B.Conventional mineral acid example hydrochloric acid,
Nitric acid, sulphuric acid, phosphoric acid etc.；Conventional inorganic base such as ammonium hydroxide, i.e. ammonia；Preferably, employing contains
The mineral acid of nitrogen or inorganic base.
Regulation pH value so that the metal oxide precursor of interpolation changes into precipitation, it is to avoid follow-up
Run off during solid-liquid separation, thus affect the zirconic structural stability of product.Through fully
After stirring, the serosity of aforementioned regulation and control pH is carried out solid-liquid separation.
The technological means of solid-liquid separation, to be sufficiently separated the technology of solid and liquid, as being centrifuged,
The one of the technology such as filtration, filter pressing, ultrafiltration or combination.
From containing zirconium solid removes the aniones such as chlorine, come from during subsequent calcination can be significantly decreased
The discharge of the poisonous and corrosive gas of anion, thus alleviate the corrosion to process units and to environment
Pollution.
(5) the main component precursor solid prepared in step (4) is dried and calcines, wash pelletize
After i.e. prepare described Zirconium powder.
Described drying steps, as long as the form of solids is not brought the dry technology significantly changed,
As air-dried, oven drying at low temperature, be spray-dried, be vacuum dried, lyophilization, the one of supercritical drying
Or combine and can select.
Described calcining step, the atmosphere to calcining, can be in atmosphere, it is also possible at noble gas atmosphere
Carry out in enclosing.Mode of heating can use electrical heating, chemical combustion heating, microwave heating etc. one or
More than one.The highest calcining heat is between 600 DEG C to 1100 DEG C, preferably at 850 DEG C to 1050 DEG C
Between, more preferably between 900 DEG C to 1000 DEG C, and keep 0.5 hour extremely in the highest calcining heat
5.0 hours, preferably 1.0 hours to 3.0 hours, more preferably between 1.5 hours to 2.5 hours.Forge
The heating rate burnt may be set between 200 DEG C/h to 1200 DEG C/h, preferably at 300 DEG C/h extremely
Between 600 DEG C/h.
One-level (the U.S. clinical pathology that described washing step specifies according to GB GB 6682-2000
Can the Type I of CAP suitable) pure water carries out drip washing, with remove be attached to zirconia powder surface can
Molten cation and anion.
Described granulation step, can add according to GB GB 6682-2000 regulation Zirconium powder
One-level (the Type I of U.S. clinical pathology meeting CAP is suitable) pure water carries out wet type physical pulverization, thing
Manage the toughener that can also add including nano-particle including aluminium oxide etc. when pulverizing and/or include polyethylene
The binding agents such as alcohol, polyacrylic acid, polymethylacrylic acid, paraffin, cellulose and its derivates, until
After obtaining the particle diameter wanted, then it is spray-dried.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use nothing
Between machine acid or inorganic base regulation pH to 5.0 to 8.0, transpiring moisture separates out ammonium salt.It is specifically grasped
As: the solution A and the solution B that prepare in step (2) and step (4) are mixed, adds
Enter mineral acid example hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid etc. or inorganic base such as ammonium hydroxide etc. or carbamide is adjusted
Control its pH so that its pH is between 5.0 to 8.0, preferably between 6.0 to 7.5, more preferably exist
Between 6.5 to 7.5.Evaporate above-mentioned solution until the solids content forming serosity is more than or equal to 50%,
Preferably greater than or equal to 70%, more preferably equal to or greater than 90%.And the water of evaporation is reclaimed by condensation
Point, and the Water Cycle of recovery is used any step needing water of above-mentioned zirconium oxide production technology
Suddenly.Above-mentioned serosity is dried process, it is possible to prepare ammonium salt.
Conventional mineral acid example hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid etc.；Conventional inorganic base such as ammonium hydroxide,
I.e. ammonia.
This step can make this method reclaim ammonium salt while prepared Zirconium powder, and condensation is obtained
Water circulation to zirconium oxide production technology.The most both can increase economic benefit, production can have been reduced again
The technique impact on environment.
According to the product obtained by the zirconia powder preparation that the present invention provides, its key component is
ZrO2+HfO2+MxOy, wherein MxOyFor metal-oxide, its content is less than or equal to 15 moles of %,
Preferably between 2 moles of % to 8 mole of %, more preferably between 2.5 moles of % to 3.5 mole of %, M
One or more in yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements, described main one-tenth
Divide and account for the mass percent of Zirconium powder more than 90%.Other metal-oxides, as silicon dioxide,
Ferrum oxide, aluminium oxide, Cs2O, cobalt oxide, strontium oxide, oxidation polonium, radium oxide, urania,
Thorium oxide, plutonium oxide, fracium oxide etc., every kind of mass fraction accounting for described Zirconium powder less than or etc.
In 0.01%, preferably lower than or equal to 0.005%, more preferably less than or equal to 0.001%；Chlorine unit quality
Amount percentage ratio is less than or equal to 0.05%.
Described Zirconium powder, the ratio radiation activity recorded according to ISO 13356:2008 is less than or equal to
100Bq/kg, preferably lower than or equal to 50Bq/kg.Wherein four directions and cube crystalline phase content more than or
Equal to 90%, preferably greater than or equal to 95%, more preferably equal to or greater than 99%.
Described Zirconium powder, the ratio radiation activity recorded according to ISO 13356:2008 is less than or equal to
100Bq/kg, preferably lower than or equal to 50Bq/kg.Its four directions and cube crystalline phase content more than or etc.
In 90%, preferably greater than or equal to 95%, more preferably equal to or greater than 99%.
Described metal-oxide MxOy, M be selected from yttrium (Y), calcium (Ca), magnesium (Mg), cerium (Ce),
The one of the elements such as praseodymium (Pr), vanadium (V), molybdenum (Mo), titanium (Ti) or a combination thereof, x and y be greater than 0 and
Integer less than or equal to 10, its molar percentage accounting for key component refers to the value being calculated as follows out.
The content of described four directions and cube crystalline phase refers to utilize the powder x-ray diffraction (XRD) recorded
(111) and (11-1) face of monocline crystalline phase in collection of illustrative plates, (111) face of tetragonal phase, cube crystalline phase
The diffracted intensity in (111) face, be calculated as follows the value obtained.
Wherein, I is the diffracted intensity of corresponding lattice, subscript m, t and c refer to respectively monocline, four directions and cube
Crystalline phase.As the zirconium oxide of structural ceramic material with tetragonal phase for the most preferable.Its crystalline phase, outward appearance (face
Normal complexion light transmittance) and water resistant heat deterioration performance depend in building-up process add solid solution burning
The kind of thing and amount.
Chlorine element mass percent refers to, by the Zirconium powder of certain massWith HNO3
Clearing up at 150 DEG C with the mixed acid of HF and the silver nitrate aqueous solution of excess, zirconium powder body to be oxidized is complete
After dissolving, measure surplus by methods such as induced plasma emission spectrum (ICP) or Atomic Absorption (AS)
Remaining Ag+Amount, thus inverse goes out the chlorine ions in Zirconium powderFurther according to following formula
The value calculated.
In described Zirconium powder, owing to hafnium is difficult to separate with zirconium, therefore hafnium is always deposited with certain proportion
, do not affect Zirconium powder properties.
If the content of metallic additions is the lowest, just it is not enough to stop zirconic Tetragonal to single
The conversion of monoclinic phase, the tetragonal content causing zirconium oxide product is on the low side.If on the other hand metal adds
If the content of thing is the highest, then metallic additions can be caused in the segregation at zirconia grains edge, impact
The sintering character of Zirconium powder.In order to improve biocompatibility and the safety of zirconia ceramics powder body,
The metals content impurity beyond above-mentioned metal-oxide additive should be reduced, particularly to pottery as far as possible
The influential aluminium oxide of sintering character, silicon oxide, the influential ferrum oxide of outward appearance on pottery, and
Content on the ratio radiation influential caesium of activity, cobalt, strontium, radium, uranium and the thorium etc. of pottery.
The Zirconium powder that the present invention provides can prepare press body by compacting sintering, and therefore its composition and ratio are put
Penetrate activity identical with described Zirconium powder.This press body, can prepare ceramic material further, its tool
There are excellent mechanical performance and biocompatibility, lower than radiation activity.Described ceramic material, the suitableeest
For as bioceramic material, the life-span is long, radiates low, is used for example as grinding blank into artificial tooth processing,
Concrete such as orthodontic bracket, or artificial bone turned blank, specifically such as bioceramices such as artificial femur joints
Material.
It is below embodiment:
Embodiment 1
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the zirconium oxychloride solution of 0.5mol/L, heating occur chemical reaction so that zirconium sun from
Son changes into zirconium oxide, zirconium hydroxide or its hydrate, reacts to zirconium cationic monomer conversion 98.8%, system
Zirconium reactant mixture must be contained.
Reacting by heating temperature 150 DEG C, pressure 0.41MPa.
(2) by step (1) prepare containing zirconium reactant mixture, regulate pH=1.0 with ammonia, so
Rear employing is centrifuged 30 minutes under 6000 × g centrifugal force, carries out solid-liquid separation process, obtains containing zirconium solid
Body and solution A.
(3) the solid pure water containing zirconium prepared in step (2) being configured to mass concentration is 45%
Containing zirconium serosity, and to add relative to key component be 5.6 moles of % Yttrium chloride(Y2Cl6)s.
(4) by step (3) prepares containing zirconium serosity, use ammonia regulation pH=8.5, then exist
It is centrifuged 30 minutes under 4000 × g centrifugal force, carries out solid-liquid separation process, obtain main component precursor solid
And solution B.
(5) spray after the main component precursor solid pure water prepared in step (4) being configured to serosity
Mist is dried and calcines, and i.e. prepares described Zirconium powder after washing pelletize.
Described calcining step, in air atmosphere, uses electrical heating.The highest calcining heat 1000 DEG C,
Keep 2.0 hours in the highest calcining heat.The heating rate of calcining can be set as 300 DEG C/h.
One-level (the U.S. clinical pathology that described washing step specifies according to GB GB 6682-2000
Can the Type I of CAP suitable) pure water carries out drip washing 3 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of a diameter of 6mm with 2mm, add toughener during physical pulverization
Aluminum oxide nanoparticle (particle diameter is between 10 to 20nm) and binding agent polyacrylic acid, until averagely
After particle diameter is less than 1.0 microns, then it is spray-dried, obtains the powder body that mean diameter is 3.5 microns.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use ammonia
Water regulation pH=7.0, evaporates above-mentioned solution until the solids content forming serosity is 95%.And by cold
The solidifying moisture reclaiming evaporation, uses appointing of above-mentioned zirconium oxide production technology by the Water Cycle of recovery
What is the need for and want the step of water.Above-mentioned serosity is dried process, ammonium chloride can be prepared, production
Ammonium chloride is 96% relative to the response rate of chlorine element in raw material basic zirconium chloride.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+Y2O3, Y2O3The molar percentage accounting for main component is 2.8%, and described main component accounts for
The mass percent of Zirconium powder is 99.9%.Containing other metal oxide contents, specifically it is shown in Table 1,
Chlorine element mass percent is 0.035%.
Other metal oxide contents of table 1 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, the ratio radiation activity recorded according to ISO 13356:2008 is 80Bq/kg.
Described Zirconium powder, the result characterized with X-ray diffraction shows, the inventive method prepares
Zirconium powder is calcined 2 hours at 1000 DEG C, and its crystalline phase is the Tetragonal of 100%, according to thanking to Le equation
The grain size that (Scherrer equation) calculates is 28.3nm.
Embodiment 2
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the zirconium nitrate solution of 1.2mol/L, there is chemical reaction in heating so that zirconium cation turns
Chemical conversion zirconium oxide, zirconium hydroxide or its hydrate, reaction, to zirconium cationic monomer conversion 99.2%, prepares and contains
Zirconium reactant mixture.
Reacting by heating temperature 250 DEG C, pressure 1.5MPa.
(2) by step (1) prepare containing zirconium reactant mixture, regulate pH=1.6 with carbamide, so
After under 6000 × g centrifugal force centrifugal 30 minutes, carry out solid-liquid separation process, obtain containing zirconium solid and
Solution A.
(3) the solid pure water containing zirconium prepared in step (2) being configured to mass concentration is 50%
Containing zirconium serosity, and add relative to the Yttrium chloride(Y2Cl6) that key component is 5.0 moles of %.
(4) by step (3) prepares containing zirconium serosity, use ammonia regulation pH=8.0, then exist
It is centrifuged 30 minutes under 5000 × g centrifugal force, carries out solid-liquid separation process, obtain main component precursor solid
And solution B.
(5) the main component precursor solid prepared in step (4) is vacuum dried and calcines, washing
Described Zirconium powder is i.e. prepared after pelletize.
Described calcining step, in air atmosphere, uses electrical heating.The highest calcining heat 950 DEG C,
The highest calcining heat keeps 2.5 hours.The heating rate of calcining can be set as 200 DEG C/h.
One-level (the U.S. clinical pathology that described washing step specifies according to GB GB 6682-2000
Can the Type I of CAP suitable) pure water carries out drip washing 3 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of a diameter of 6mm with 2mm, add toughener during physical pulverization
Aluminum oxide nanoparticle (particle diameter 10 to 20nm) and adhesive polyethylene alcohol, until mean diameter is little
After 1.0 microns, then it is spray-dried.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use ammonia
Water regulation pH=8.0, evaporates above-mentioned solution until the solids content forming serosity is 90%.And by cold
The solidifying moisture reclaiming evaporation, uses appointing of above-mentioned zirconium oxide production technology by the Water Cycle of recovery
What is the need for and want the step of water.Above-mentioned serosity is dried process, ammonium nitrate can be prepared, prepared
Ammonium nitrate is 97% relative to the response rate of the nitrate anion of zirconium nitrate.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+Y2O3, wherein Y2O3The molar percentage accounting for main component is 2.5%, described mainly
Composition accounts for the mass percent 99.9% of Zirconium powder.Containing other metal-oxides, specifically it is shown in Table 2,
Chlorine element mass percent is 0.043%.
Other metal oxide contents of table 2 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 75Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 99.5%.
Embodiment 3
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the zirconium oxychloride solution of 0.3mol/L, heating occur chemical reaction so that zirconium sun from
Son changes into zirconium oxide, zirconium hydroxide or its hydrate, reacts to zirconium cationic monomer conversion 98.2%, system
Zirconium reactant mixture must be contained.
Reacting by heating temperature 400 DEG C, pressure 3.25MPa.
(2) by step (1) prepare containing zirconium reactant mixture, regulate pH=1.8 with ammonia, so
After under 6000 × g centrifugal force centrifugal 30 minutes, carry out solid-liquid separation process, obtain containing zirconium solid and
Solution A.
(3) the solid pure water containing zirconium prepared in step (2) being configured to mass concentration is 60%
Containing zirconium serosity, and add the Yttrium chloride(Y2Cl6) relative to 7.0 moles of % of key component.
(4) by step (3) prepares containing zirconium serosity, use ammonia regulation pH=7.0 value, then
Centrifugal, carry out sucking filtration with the cellulose membrane that aperture is 0.1 micron as filter membrane, reach the mesh of solid-liquid separation
, obtain main component precursor solid and solution B.
(5) the main component precursor solid prepared in step (4) is air-dried in room temperature and calcines, wash
Described Zirconium powder is i.e. prepared after washing pelletize.
Described calcining step, in air atmosphere, uses electrical heating.The highest calcining heat 900 DEG C,
The highest calcining heat keeps 3.0 hours.The heating rate of calcining is set as 450 DEG C/h.
One-level (the U.S. clinical pathology that described washing step specifies according to GB GB 6682-2000
Can the Type I of CAP suitable) pure water carries out drip washing 3 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of diameter 6mm with 2mm, add toughener oxygen during physical pulverization
Change aluminum nanoparticles (particle diameter is between 10 to 20nm) and binding agent polymethylacrylic acid, until
After being less than 1.0 microns to particle diameter, then it is spray-dried.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use ammonia
Water regulation pH=7.5, evaporates above-mentioned solution until the solids content forming serosity is 70%.And by cold
The solidifying moisture reclaiming evaporation, uses appointing of above-mentioned zirconium oxide production technology by the Water Cycle of recovery
What is the need for and want the step of water.Above-mentioned serosity is dried process, ammonium chloride can be prepared, prepared
Ammonium chloride is 95% relative to the response rate of the chloride ion of basic zirconium chloride.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+Y2O3, wherein Y2O3The molar percentage accounting for main component is 3.5%, described mainly
Composition accounts for the mass percent 99.9% of Zirconium powder.Containing other metal-oxides, specifically it is shown in Table 3,
Chlorine element mass percent is 0.038%.
Other metal oxide contents of table 3 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 68Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 98.7%.
Embodiment 4
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the Disulfatozirconic acid. solution of 2.0mol/L, there is chemical reaction in heating so that zirconium cation
Change into zirconium oxide, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion 95.3%%, system
Zirconium reactant mixture must be contained.
Reacting by heating temperature 110 DEG C, pressure 0.15MPa.
(2) by step (1) prepare containing zirconium reactant mixture, regulate pH=0.56 with ammonia, so
After under 6000 × g centrifugal force centrifugal 30 minutes, carry out solid-liquid separation process, obtain containing zirconium solid and molten
Liquid A.
(3) the solid pure water containing zirconium prepared in step (2) being configured to mass concentration is 70%
Containing zirconium serosity, and add relative to the Yttrium chloride(Y2Cl6) that key component is 4.0 moles of %.
(4) by step (3) prepares containing zirconium serosity, use ammonia regulation pH=6.0, then exist
It is centrifuged 30 minutes under 6000 × g centrifugal force, carries out solid-liquid separation process, obtain main component precursor solid
And liquor B.
(5) the main component precursor solid prepared in step (4) is spray-dried and calcines, clean
Described Zirconium powder is i.e. prepared after pelletize.
Described calcining step, in nitrogen atmosphere, uses electrical heating.The highest calcining heat 1100 DEG C,
Keep 0.5 hour in the highest calcining heat.The heating rate of calcining can be set as 600 DEG C/h.
One-level (the U.S. clinical pathology that described washing step specifies according to GB GB 6682-2000
Can the Type I of CAP suitable) pure water carries out drip washing 3 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of a diameter of 6mm with 2mm, add toughener during physical pulverization
Aluminum oxide nanoparticle (particle diameter is between 10 to 20nm) and binding agent carboxymethyl cellulose, until
Obtain particle diameter less than after 1.0 microns, then be spray-dried.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use ammonia
Water regulation pH=6.5, evaporates above-mentioned solution until the solids content forming serosity is 50%.And by cold
The solidifying moisture reclaiming evaporation, uses appointing of above-mentioned zirconium oxide production technology by the Water Cycle of recovery
What is the need for and want the step of water.Above-mentioned serosity is dried process, ammonium sulfate can be prepared, obtain
Ammonium sulfate is 98% relative to the response rate of the sulfate radical in Disulfatozirconic acid..
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+Y2O3, wherein Y2O3The molar percentage accounting for main component is 2.0%, described mainly
Composition accounts for the mass percent 99.9% of Zirconium powder.Containing other metal-oxides, specifically it is shown in Table 4,
Chlorine element mass percent is 0.026%.
Other metal oxide contents of table 4 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 95Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 95%.
Embodiment 5
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the zirconium oxychloride solution of 5.0mol/L, heating occur chemical reaction so that zirconium sun from
Son changes into zirconium oxide, zirconium hydroxide or its hydrate, reacts to zirconium cationic monomer conversion 90%, system
Zirconium reactant mixture must be contained.
Reacting by heating temperature 80 DEG C, pressure 0.1MPa.
(2) by step (1) prepare containing zirconium reactant mixture, regulate pH=0.1 with ammonia, so
After, under 6000 × g centrifugal force centrifugal 30 minutes, carry out solid-liquid separation process, obtain containing zirconium solid and molten
Liquid A.
(3) the solid pure water containing zirconium prepared in step (2) being configured to mass concentration is 20%
Containing zirconium serosity, and add relative to the Yttrium chloride(Y2Cl6) that key component is 6.0 moles of % and 12.0 moles of %
Titanium chloride.
(4) by step (3) prepares containing zirconium serosity, use sodium hydroxide regulation pH=10.5, so
Rear employing 4000 × g centrifugal force carries out solid-liquid separation process in 30 minutes, obtains main component precursor
Solid and solution B.
(5) spray after the main component precursor solid pure water prepared in step (4) being configured to serosity
Mist is dried and calcines, and i.e. prepares described Zirconium powder after washing pelletize.
Described calcining step, in air atmosphere, uses electrical heating.The highest calcining heat 850 DEG C,
The highest calcining heat keeps 5.0 hours.The heating rate of calcining can be set as 1200 DEG C/h.
One-level (the U.S. clinical pathology meeting that described cleaning step specifies according to GB GB 6682-2000
The Type I of CAP is suitable) pure water carries out drip washing 5 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of a diameter of 6mm with 2mm, add toughener during physical pulverization
Aluminum oxide nanoparticle (particle diameter is between 10 to 20nm) and binding agent polyacrylic acid, until obtaining
After particle diameter is less than 1.0 microns, then it is spray-dried.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use urine
Element regulation pH=6.0, evaporates above-mentioned solution until the solids content forming serosity is 92%.And lead to then
Cross condensation and reclaim the moisture of evaporation, the Water Cycle of recovery is used above-mentioned zirconium oxide production technology
Any step needing water.Above-mentioned serosity is dried process, ammonium chloride can be prepared,
To ammonium chloride relatively and in basic zirconium chloride the response rate of chloride ion be 97%.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+TiO2+Y2O3, wherein TiO2And Y2O3The molar percentage accounting for main component respectively is
12.0% and 3.0%, described main component accounts for the mass percent 99.8% of Zirconium powder.Containing other gold
Belonging to oxide, be specifically shown in Table 5, chlorine element mass percent is 0.045%.
Other metal oxide contents of table 5 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 98Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 90.5%.
Embodiment 6
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the zirconium oxychloride solution of 0.1mol/L, heating occur chemical reaction so that zirconium sun from
Son changes into zirconium oxide, zirconium hydroxide or its hydrate, reacts to zirconium cationic monomer conversion 99.9%, system
Zirconium reactant mixture must be contained.
Reacting by heating temperature 40 DEG C, pressure 0.1MPa.
(2) by step (1) prepare containing zirconium reactant mixture, regulate pH=2.0 with HCl, so
After under 6000 × g centrifugal force centrifugal 30 minutes, carry out solid-liquid separation process, obtain containing zirconium solid and
Solution A.
(3) the solid pure water containing zirconium prepared in step (2) being configured to mass concentration is 5% contain
Zirconium serosity, and to add relative to key component be 6.0 moles of % Yttrium chloride(Y2Cl6)s and the magnesium chloride of 5.0 moles of %.
(4) by step (3) prepares containing zirconium serosity, use sodium hydroxide regulation pH=11.0, so
After under 3000 × g centrifugal force centrifugal 30 minutes, carry out solid-liquid separation process, before obtaining main component
Body solid and solution B.
(5) by step (4) prepare 110 DEG C of oven drying at low temperatures of main component precursor solid and calcine,
Described Zirconium powder is i.e. prepared after washing pelletize.
Described calcining step, in air atmosphere, uses electrical heating.The highest calcining heat 600 DEG C,
The highest calcining heat keeps 5.0 hours.The heating rate of calcining is set as 300 DEG C/h.
One-level (the U.S. clinical pathology that described washing step specifies according to GB GB 6682-2000
Can the Type I of CAP suitable) pure water carries out drip washing 3 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of a diameter of 6mm with 2mm, add toughener during physical pulverization
Aluminum oxide nanoparticle (particle diameter is between 10 to 20nm) and binding agent POLYPROPYLENE GLYCOL, until obtaining
After particle diameter is less than 1.0 microns, then it is spray-dried.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use ammonia
Water regulation pH=5.0, evaporates above-mentioned solution until the solids content forming serosity is 95%.And lead to then
Cross condensation and reclaim the moisture of evaporation, the Water Cycle of recovery is used above-mentioned zirconium oxide production technology
Any step needing water.Above-mentioned serosity is dried process, ammonium chloride can be prepared,
To ammonium chloride be 97% relative to the response rate of chloride ion in basic zirconium chloride.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+MgO+Y2O3, wherein MgO and Y2O3Account for the molar percentage of main component respectively
Being 5.0 moles of % and 3.0 moles of %, described main component accounts for the mass percent of Zirconium powder
99.87%.Containing other metal-oxides, being specifically shown in Table 6, chlorine element mass percent is 0.039%.
Other metal oxide contents of table 6 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 76Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 92.1%.
Embodiment 7
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the zirconium oxychloride solution of 0.6mol/L, heating occur chemical reaction so that zirconium sun from
Son changes into zirconium oxide, zirconium hydroxide or its hydrate, reacts to zirconium cationic monomer conversion 99.7%, system
Zirconium reactant mixture must be contained.
Reacting by heating temperature 50 C, pressure 0.1MPa.
(2) by step (1) prepare containing zirconium reactant mixture, regulate pH=0.23 with ammonia, so
After under 6000 × g centrifugal force centrifugal 30 minutes, carry out solid-liquid separation process, obtain containing zirconium solid and
Solution A.
(3) the solid pure water containing zirconium prepared in step (2) being configured to mass concentration is 35%
Containing zirconium serosity, and to add relative to key component be 16.0 moles of % Yttrium chloride(Y2Cl6)s.
(4) by step (3) prepares containing zirconium serosity, use ammonia regulation pH value=8.5, then
It is centrifuged 30 minutes under 4000 × g centrifugal force, carries out solid-liquid separation process, obtain main component precursor
Solid and solution B.
(5) spray after the main component precursor solid pure water prepared in step (4) being configured to serosity
Mist is dried and calcines, and i.e. prepares described Zirconium powder after washing pelletize.
Described calcining step, in air atmosphere, uses electrical heating.The highest calcining heat 1050 DEG C,
Keep 1.5 hours in the highest calcining heat.The heating rate of calcining is set as 300 DEG C/h.
One-level (the U.S. clinical pathology that described washing step specifies according to GB GB 6682-2000
Can the Type I of CAP suitable) pure water carries out drip washing 3 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of a diameter of 6mm with 2mm, add toughener during physical pulverization
Aluminum oxide nanoparticle (particle diameter is between 10 to 20nm) and binding agent polyacrylic acid, until obtaining
After particle diameter is less than 1.0 microns, then it is spray-dried.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use ammonia
Water regulation pH=7.0, evaporates above-mentioned solution until the solids content forming serosity is 92%.And by cold
The solidifying moisture reclaiming evaporation, uses appointing of above-mentioned zirconium oxide production technology by the Water Cycle of recovery
What is the need for and want the step of water.Above-mentioned serosity is dried process, ammonium chloride can be prepared, obtain
Ammonium chloride is 99% relative to the response rate of the chloride ion in basic zirconium chloride.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+Y2O3, wherein Y2O3The molar percentage accounting for main component is 8.0%, described mainly
Composition accounts for the mass percent 99.9% of Zirconium powder.Containing other metal-oxides, specifically it is shown in Table 7,
Chlorine element mass percent is 0.047%.
Other metal oxide contents of table 7 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 45Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 99.9%.
Embodiment 8
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the zirconium oxychloride solution of 2.5mol/L, heating occur chemical reaction so that zirconium sun from
Son changes into zirconium oxide, zirconium hydroxide or its hydrate, reacts to zirconium cationic monomer conversion 94.8%, system
Zirconium reactant mixture must be contained.
Reacting by heating temperature 105 DEG C, pressure 0.12MPa.
(2) by step (1) prepare containing zirconium reactant mixture, regulate pH=0.46 with ammonia, so
After under 6000 × g centrifugal force centrifugal 30 minutes, carry out solid-liquid separation process, obtain containing zirconium solid and
Solution A.
(3) the solid pure water containing zirconium prepared in step (2) being configured to mass concentration is 40%
Containing zirconium serosity, and to add relative to key component be 6.0 moles of % Yttrium chloride(Y2Cl6)s and the chlorination of 8.0 moles of %
Cerium.
(4) by step (3) prepares containing zirconium serosity, use ammonia regulation pH value=9.0, then
It is centrifuged 30 minutes under 4000 × g centrifugal force, carries out solid-liquid separation process, obtain main component precursor
Solid and solution B.
(5) spray after the main component precursor solid pure water prepared in step (4) being configured to serosity
Mist is dried and calcines, and i.e. prepares described Zirconium powder after washing pelletize.
Described calcining step, in air atmosphere, uses electrical heating.The highest calcining heat 1000 DEG C,
Keep 1.0 hours in the highest calcining heat.The heating rate of calcining is set as 300 DEG C/h.
One-level (the U.S. clinical pathology that described washing step specifies according to GB GB 6682-2000
Can the Type I of CAP suitable) pure water carries out drip washing 3 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of a diameter of 6mm with 2mm, add toughener during physical pulverization
Aluminum oxide nanoparticle (particle diameter is between 10 to 20nm) and binding agent polyacrylic acid, until obtaining
After particle diameter is less than 1.0 microns, then it is spray-dried.
(6) solution A prepared in step (2) and step (4) and solution B are merged, use ammonia
Water regulation pH=7.3, evaporates above-mentioned solution until the solids content forming serosity is 95%.And by cold
The solidifying moisture reclaiming evaporation, uses appointing of above-mentioned zirconium oxide production technology by the Water Cycle of recovery
What is the need for and want the step of water.Above-mentioned serosity is dried process, ammonium chloride can be prepared, obtain
Ammonium chloride is 98% relative to the response rate of the chloride ion in basic zirconium chloride.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+CeO2+Y2O3, wherein CeO2And Y2O3Account for the molar percentage of main component respectively
Being 8.0% and 3.0%, it is 99.7% that described main component accounts for the percent mass of Zirconium powder.Containing other
Metal-oxide, is specifically shown in Table 8, and chlorine element mass percent is 0.047%.
Other metal oxide contents of table 8 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 45Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 99.9%.
Embodiment 9
The preparation method of a kind of Zirconium powder, same as in Example 1, only step (2) pH is adjusted
Control is to 1.0.
The ammonium chloride prepared according to the method described above, it is relative to the recovery of chloride ion in basic zirconium chloride
Rate is 98%.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+Y2O3, Y2O3The molar percentage accounting for main component is 3.0%, and described main component accounts for
The mass percent of Zirconium powder is 99.9%.Containing other metal oxide contents, specifically it is shown in Table 9,
Chlorine element mass percent is 0.034%.
Other metal oxide contents of table 9 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 91Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 99.9%.
Embodiment 10
The preparation method of a kind of Zirconium powder, same as in Example 1, only step (4) pH is adjusted
Control is to 7.0.
The ammonium chloride prepared according to the method described above, it is relative to the recovery of chloride ion in basic zirconium chloride
Rate is 98%.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+Y2O3, Y2O3The molar percentage accounting for main component is 3.0%, and described main component accounts for
The mass percent of Zirconium powder is 99.9%.Containing other metal oxide contents, specifically it is shown in Table 10,
Chlorine element mass percent is 0.034%.
Other metal oxide contents of table 10 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 72Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 99.9%.
Embodiment 11 (comparative example)
The preparation method of a kind of Zirconium powder, comprises the following steps:
(1) by the basic zirconium chloride of 0.5mol/L, there is chemical reaction in heating so that zirconium cation turns
Chemical conversion zirconium oxide, zirconium hydroxide or its hydrate, reaction, to zirconium cationic monomer conversion 98.6%, prepares and contains
Zirconium reactant mixture.
Reacting by heating temperature 150 DEG C, pressure 0.41MPa.
(2) in step (1) prepare containing zirconium reactant mixture adds relative to key component be
6.0 moles of % Yttrium chloride(Y2Cl6)s.It is spray-dried after stirring and calcines, i.e. preparing after washing pelletize and compare use
Zirconium powder.
Described calcining step, in air atmosphere, uses electrical heating.The highest calcining heat 1000 DEG C,
Keep 2.0 hours in the highest calcining heat.The heating rate of calcining is set as 300 DEG C/h.
One-level (the U.S. clinical pathology meeting that described washing step specifies according to GB GB 6682-2000
The Type I of CAP is suitable) pure water carries out drip washing 3 times.
Described granulation step, can add pure water to Zirconium powder and carry out, put in ball grinder, with
Ball milling 5 hours together with the zirconia ball of a diameter of 6mm with 2mm, add binding agent during physical pulverization
Polyacrylic acid, until obtaining particle diameter less than after 1.0 microns, then is spray-dried.
The Zirconium powder prepared according to the method described above, its key component is
ZrO2+HfO2+Y2O3, wherein Y2O3The molar percentage accounting for main component is 3.0%, described mainly
Composition accounts for the mass percent 96.6% of Zirconium powder.Containing other metal-oxides, specifically it is shown in Table 11,
Chlorine element mass percent is 1.34%.
Other metal oxide contents of table 11 (mass fraction)
Note: detection is limited to 0.00001%
Described Zirconium powder, ratio radiation activity 357Bq/kg recorded according to ISO 13356:2008.
Wherein the content of four directions and cube crystalline phase is 85%.
Relatively understand the present invention to be removed by twice regulation and control pH and solid-liquid separation raw material contains
The impurity such as Si, Al, Fe and radioelement so that the impurity content of prepared Zirconium powder and ratio
Radiation activity significantly reduces, it is possible to fully meet the ISO 13356:2008 corresponding requirements to bioceramic.
Furthermore it is also possible to find out in second time centrifugal process, the yttrium presoma of interpolation almost without loss,
So the structural stability of final Zirconium powder is not had any impact.
The zirconic X-ray diffracting spectrum that embodiment 1 and comparative example 11 prepare, as shown in Figure 2.
From Figure 2 it can be seen that the Zirconium powder that comparative example 11 prepares is before being calcined, it is less than without at pH
Or the solid-liquid separation under the conditions of being more than or equal to 6.0 two equal to 2.0 and pH, except Si, Al, Fe
And the impurity such as radioelement will not be removed, and add during from the chloride ion of raw material and pH regulation and control
Acid or alkali can form crystallization in dry run.In calcination process subsequently, these impurity can turn
Turn to corrosivity and the environmental contaminants such as chlorine, hydrogen chloride, NOx.And the side of the embodiment of the present invention 1
The Zirconium powder that method prepares before being calcined, after twice solid-liquid separation, is just not detected by
The crystallization of ammonium chloride, also will not be formed in follow-up calcination process and have corrosiveness to equipment and to ring
The influential gas in border.
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention,
Not in order to limit the present invention, all made within the spirit and principles in the present invention any amendment, etc.
With replacement and improvement etc., should be included within the scope of the present invention.
Claims (12)
1. one kind produces Zirconium powder and the method for ammonium salt simultaneously, it is characterised in that include following step
Rapid:
(1) by zirconium precursor liquid solution, there is chemical reaction in heating so that zirconium is cation ic-converted to be become to aoxidize
Zirconium, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion more than or equal to 90%, prepare
Containing zirconium reactant mixture；Described zirconium precursor liquid solution, its zirconium cation concn is less than or equal to 5.0
mol/L；
(2) by step (1) prepare containing zirconium reactant mixture, with mineral acid, inorganic base or urine
Element regulation pH, less than or equal to 2.0, then carries out solid-liquid separation process, obtains containing zirconium solid and solution
A；
(3) the solid pure water containing zirconium prepared in step (2) is configured to mass concentration 5% to 70%
Between containing zirconium serosity, and according to required stoichiometric proportion to described containing in zirconium serosity add burning
Thing MxOyPresoma so that M in productxOyAccount for key component ZrO2Molar percentage less than or
Equal to one in yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements of 15 moles of %, M or
Multiple；
(4) by step (3) prepares containing zirconium serosity, regulate with mineral acid, inorganic base or carbamide
PH value be more than or equal to 6.0, then carry out solid-liquid separation process, obtain main component precursor solid and
Solution B；
(5) the main component precursor solid prepared in step (4) is dried and calcines, wash pelletize
After i.e. prepare Zirconium powder；
(6) solution A prepared in step (2) and step (4) and solution B are merged, use nothing
Machine acid or inorganic base regulation pH are between 5.0 to 8.0, and transpiring moisture separates out ammonium salt；
Described step (2), (4) and (6) uses ammonia or carbamide regulation pH value at least one times.
2. the method for claim 1, it is characterised in that step (1) described zirconium precursor body
For one or more in basic zirconium chloride, zirconium chloride, zirconium nitrate, Disulfatozirconic acid., zirconium carbonate and zirconium phosphate
Combination.
3. the method for claim 1, it is characterised in that described step (1) reaction temperature
Between 40 DEG C to 400 DEG C, pressure is between 0.1MPa to 3.25MPa.
4. method as claimed in claim 3, it is characterised in that described temperature is at 50 DEG C to 250 DEG C
Between, pressure is between 0.1MPa to 1.2MPa.
5. method as claimed in claim 4, it is characterised in that described temperature is at 80 DEG C to 150 DEG C
Between, pressure is between 0.1MPa to 0.5MPa.
6. the method for claim 1, it is characterised in that described step (5) calcining heat
Between 800 DEG C to 1100 DEG C, heating rate, between 200 DEG C/h to 1200 DEG C/h, maintains calcining
Maximum temperature 0.5 hour to 5 hours.
7. a Zirconium powder, it is characterised in that according to such as Claims 1-4 any one institute
Prepared by the method stated.
8. Zirconium powder as claimed in claim 7, it is characterised in that its key component is
ZrO2+HfO2+MxOy, wherein MxOyFor metal-oxide, its content accounts for key component ZrO2Rub
You are selected from yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium less than or equal to 15 moles of %, M by percentage ratio
One or more in element, described main component account for the mass percent of Zirconium powder 90% with
On, other metal-oxides every kind account for the mass fraction of described Zirconium powder less than or equal to 0.01%.
9. Zirconium powder as claimed in claim 8, it is characterised in that other burnings described
Thing is silicon dioxide, ferrum oxide, aluminium oxide, Cs2O, cobalt oxide, strontium oxide, oxidation polonium, oxygen
Change radium, urania, thorium oxide, plutonium oxide, fracium oxide.
10. Zirconium powder as claimed in claim 7, it is characterised in that wherein chlorine element quality
Percentage ratio is less than or equal to 0.05%.
11. Zirconium powders as claimed in claim 7, it is characterised in that described Zirconium powder
The ratio radiation activity recorded according to ISO13356:2008 is less than or equal to 100Bq/kg.
12. Zirconium powders as claimed in claim 7, it is characterised in that described Zirconium powder
Four directions and the content of cube crystalline phase more than or equal to 90%.
Priority Applications (1)
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| JP3265368B2 (en) * | 1991-06-13 | 2002-03-11 | 東ソー株式会社 | Method for producing zirconium oxide powder |
| CN103626492A (en) * | 2013-12-18 | 2014-03-12 | 江西赛瓷材料有限公司 | Scandia-stabilized zirconia powder for solid oxide fuel battery |
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| JPH06171943A (en) * | 1992-12-04 | 1994-06-21 | Tosoh Corp | Production of zirconium oxide powder |
| JPH06287019A (en) * | 1993-04-01 | 1994-10-11 | Tosoh Corp | Production of hydrated zirconia powder |
| JP2007015898A (en) * | 2005-07-08 | 2007-01-25 | Nippon Denko Kk | Method for manufacturing zirconium oxide powder and zirconium oxide powder |
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| JP3265368B2 (en) * | 1991-06-13 | 2002-03-11 | 東ソー株式会社 | Method for producing zirconium oxide powder |
| CN103626492A (en) * | 2013-12-18 | 2014-03-12 | 江西赛瓷材料有限公司 | Scandia-stabilized zirconia powder for solid oxide fuel battery |
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| 无团聚ZrO2-HfO2-Y2O3复合纳米粉体的制备;石刚等;《功能材料》;20061231;第37卷(第7期);1130-1133 * |
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