WO2004106230A1 - 金属の複合酸化物の製造方法 - Google Patents
金属の複合酸化物の製造方法 Download PDFInfo
- Publication number
- WO2004106230A1 WO2004106230A1 PCT/JP2004/007753 JP2004007753W WO2004106230A1 WO 2004106230 A1 WO2004106230 A1 WO 2004106230A1 JP 2004007753 W JP2004007753 W JP 2004007753W WO 2004106230 A1 WO2004106230 A1 WO 2004106230A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- oxide
- alkaline earth
- composite oxide
- metal salt
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 68
- 239000002184 metal Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 59
- -1 alkali metal salt Chemical class 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 30
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 30
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 28
- 238000000605 extraction Methods 0.000 claims description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 239000010937 tungsten Substances 0.000 claims description 15
- 239000010955 niobium Substances 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 239000002440 industrial waste Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910001021 Ferroalloy Inorganic materials 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims 3
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 238000010671 solid-state reaction Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 31
- 239000003513 alkali Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000010298 pulverizing process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract 1
- 238000003801 milling Methods 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 32
- 235000017550 sodium carbonate Nutrition 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000000706 filtrate Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 19
- 229910052742 iron Inorganic materials 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 238000002076 thermal analysis method Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 238000009835 boiling Methods 0.000 description 10
- 235000010216 calcium carbonate Nutrition 0.000 description 10
- 235000011181 potassium carbonates Nutrition 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 229910052845 zircon Inorganic materials 0.000 description 8
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 8
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910001935 vanadium oxide Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910001257 Nb alloy Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-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
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
- C01B13/185—Preparing mixtures of oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/40—Electric properties
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a metal oxide and / or a precursor thereof or a metal oxide.
- the present invention relates to a method for producing a composite oxide with Z or an alkaline earth metal.
- mechanochemical treatment As a method of causing a reaction without heating, mechanochemical treatment is known.
- the treatment generally involves mechanical energy applied to the solid material, for example, shear, compression, impact, crushing, bending, stretching, etc., causing the surface of the solid material to undergo a physicochemical change, and the gas, liquid material existing around the solid material. It is a method of affecting the chemical state by causing a chemical change to the surface or directly inducing or promoting a chemical change between them and the surface of the solid material.
- mechanical energy applied to the solid material for example, shear, compression, impact, crushing, bending, stretching, etc.
- a method for leaching an indium-containing compound has been proposed in which an indium-containing compound is subjected to mechanochemical treatment in the presence of a ceramic powder and then leached into a low-concentration acid at room temperature.
- Japanese Unexamined Patent Publication No. 2001-111 A method has also been proposed in which quicklime is mixed with coal ash and subjected to mechanochemical treatment to produce a hydraulically treated product powder.
- the mechanochemical treatment is based on the fact that the reaction proceeds by point contact at the active point on the surface of the solid material that has been updated by impact or the like. Therefore, to increase the reaction amount, that is, increase the product, it is necessary to continue the treatment for a long time and take measures to repeat the surface renewal, which is basically unsuitable for industrial-scale production. It is. Disclosure of the invention
- the present inventor has applied the treatment to the reaction between an oxide of a valuable metal and an alkali (earth) metal salt. It has been found that when the treatment product is heated to a specific temperature, the reaction proceeds at an unexpected rate. That is, the inventor of the present invention has intensively studied a method of increasing the productivity by taking advantage of the mechanochemical treatment.
- the coexisting alkali (earth) metal salt is heated so as to be in contact with the surface, the alkali (earth) metal salt diffuses from the solid surface of the oxide of the valuable metal to the inside, and even inside the solid.
- FIG. 1 is a view showing a result of a thermal analysis of a co-ground product of vanadium-containing magnetite of Example 1 of the present invention.
- FIG. 2 is a view showing a result of a thermal analysis of the pulverized Huobn's nioballoy of Example 2 of the present invention.
- FIG. 3 is a view showing a result of a thermal analysis of a co-ground product of iron niobate of Example 2 of the present invention.
- FIG. 4 is a view showing a result of a thermal analysis of a co-ground product of iron niobate of Example 3 of the present invention.
- FIG. 5 is a diagram showing a result of a thermal analysis of a co-ground product of ore containing manganese heavy stone of Example 4 of the present invention.
- FIG. 6 is a view showing a result of a thermal analysis of a co-ground product of ore containing scheelite in Example 5 of the present invention.
- FIG. 7 is a view showing a result of a thermal analysis of a co-milled product of the nickel silicate ore of Example 6 of the present invention.
- FIG. 8 is a diagram showing a result of a thermal analysis of a co-milled ore containing zircon of Example 7 of the present invention.
- FIG. 9 is a view showing a result of a thermal analysis of a kneaded material containing vanadium-containing magnetite of Comparative Example 2 of the present invention.
- the present invention is based on the periodic table 13 group 4, group 4, group 5, group 6, group 7, cobalt and nickel. Reacting an oxide of at least one metal selected from the group consisting of Z and Z or a precursor thereof or a substance containing them with an alkali metal salt and z or an alkaline earth metal salt to form the metal and alkali metal And / or a method for producing a composite oxide with an alkaline earth metal, comprising: mixing the oxide of the metal and / or a precursor thereof or a substance containing the same with the alkali metal and Z or an alkaline earth metal salt.
- the metal oxide and Z or its precursor or a substance containing them are co-ground until the particle diameter becomes 1 O ⁇ m or less, and the co-ground product is brought to a temperature of 200 ° C or more.
- the method for producing a composite oxide according to the present invention comprises the steps of: forming at least one metal selected from the group consisting of Groups 13, 4, 5, 6, 7, cobalt and nickel, alkali metal, and Z; Alternatively, it is preferable that the composite oxide is recovered in the aqueous solvent by extraction from a reaction product containing the composite oxide with the alkaline earth metal using an aqueous solvent.
- the substance containing the metal oxide is preferably ore, concentrate, incinerated ash, industrial waste, or general waste.
- the precursor of the metal oxide is preferably a ferroalloy, an alloy, a metal salt, or a sulfide of the metal.
- the metal oxide is preferably vanadium, zirconium, niobium, nickel or tungsten.
- the alkali metal salt and the Z or alkaline earth metal salt are preferably a carbonate, a halide, a sulfate, a borate or a hydroxide.
- the alkali metal salt and Z or alkaline earth metal salt are preferably sodium carbonate, potassium carbonate, sodium sulfate, calcium carbonate, or sodium hydroxide.
- the reaction between the metal oxide and / or a precursor thereof or a substance containing the metal oxide and the alkali metal and Z or an alkaline earth metal salt is 250 or more, It is preferable to carry out the reaction in a temperature range lower than the lower one of the decomposition temperature and the melting temperature of the alkali metal and Z or the alkaline earth metal salt.
- the type and structure of the mill used in the present invention are not particularly limited as long as the oxide of valuable metal and Z or its precursor or a substance containing these can be milled to 10 m or less.
- a kneader such as a pressure kneader or a two-roll mill, a vibration mill, a rotating ball mill, or the like can be used.
- Preferred is a vibratory mill.
- the particle size of the raw material is not crushed to a median value of 10 m or less, preferably 5 m or less, the number of active points on the surface of the raw material is small, and the amount of alkali (earth) metal salt in contact with the active point is also small.
- the progress of the solid-phase reaction between the raw material and the alkali (earth) metal salt on the raw material surface during co-milling becomes insufficient, and a stable interface is not formed.
- a stable interface is not formed, so that it becomes difficult for the alkali (earth) metal salt to penetrate into the raw material, , And the progress of the solid-phase reaction becomes insufficient. Therefore, it is very important to co-mill the raw materials until the median value becomes 10 m or less, preferably 5 m or less.
- the median value is a particle size having a median value on a mass basis in the particle size distribution of the raw material.
- the particle size distribution can be obtained on a mass basis by using a laser diffraction method, and the median particle size in this particle size distribution is mesian. Value.
- the oxide of a valuable metal that is an object of the present invention is at least one metal oxide selected from the group consisting of Group 13, Group 4, Group 5, Group 6, Group 7, cobalt and nickel. And a substance containing Z or a precursor thereof, or an oxide of the metal and / or a precursor thereof.
- Group 3 metals are gallium, indium, thallium, group 4 metals are zirconium, group 5 metals are vanadium, niobium, tantalum, group 6 metals are chromium, molybdenum, tungsten, and group 7 metals are Technetium, rhenium, etc.
- the substance containing an oxide of a valuable metal of interest in the present invention includes ore, concentrate, Incinerated ash, industrial waste, and general waste.
- the ore is a vanadium-containing ore, a chromium-containing ore, a zircon-containing ore, a niobium-containing ore, a nickel-containing ore, a tungsten ore
- the concentrate is a mineral in the ore, a vanadate-containing ore, chromium It is a concentrate of iron ore, zircon, scheelite (silite), nickel silicate ore (garnierite), iron spar, and manganese spar (orfuramite).
- Industrial waste is waste such as soot, slag, waste catalyst, scrap, coal ash, electronic components and materials.
- the precursor of the valuable metal oxide is a compound that can be converted into the valuable metal oxide, and is a compound such as a ferroalloy, an alloy, a metal salt, or a sulfide.
- metal salts include carbonates, halides, sulfates, borates, silicates, aluminates, and hydroxides.
- the alloys include tungsten in the mouth, niobium in the mouth, ferrovanadium, nickel in the mouth, and molybdenum in the mouth. For example, in the case where a composite oxide of niobium is to be obtained, a niobium alloy having a ferrite content containing about two-thirds of niobium is preferable.
- the alkali metal salt and the Z or alkaline earth metal salt that react with the oxide of the valuable metal include carbonates, halides, sulfates, borates and the like.
- hydroxides and oxides are also included in the metal salts for convenience. Of course, these mixtures can also be used.
- the alkali metal is preferably sodium or potassium, and the alkaline earth metal is calcium. Demuka is preferred.
- alkali metal salts and z or alkaline earth metal salts specifically, carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, hydroxides such as sodium hydroxide and potassium hydroxide, and bicarbonate Examples include bicarbonates such as sodium, octogenides such as sodium chloride and lithium fluoride, and borates such as sodium borate and sodium metaborate. Particularly preferred are sodium carbonate and potassium carbonate.
- the alkali (earth) metal salt is used in an amount equal to or greater than the theoretical molar amount at which a complex oxide is formed by reacting with a valuable metal oxide.
- This molar ratio varies depending on the target composite oxide. For example, when a composite oxide having a specific composition is obtained using one kind of metal salt and one kind of valuable metal oxide, they are mixed in a theoretical molar ratio, co-ground, and then reacted. Just fine.
- an oxide of a valuable metal or the like contained in the complex oxide is used to improve the efficiency of the reaction. It is preferable to use an alkali (earth) metal salt having a molar ratio of 1.2 to 3 times the theoretical molar ratio.
- the co-milled product in the mill or the co-milled product taken out from the mill is heated. Heating promotes the diffusion of the metal salt or its decomposition product from the solid surface of the co-ground product, that is, the valuable metal oxide, into the solid. However, it is presumed that the solid-phase reaction proceeds inside the valuable metal oxide.
- the heating is performed to promote the diffusion of the alkali (earth) metal salt or its decomposition product from the solid surface of the valuable metal oxide after co-milling to the solid interior. Therefore, it is preferable to carry out the reaction promptly after co-milling.However, even if the time until the start of heating after co-milling is long, the completion time of the solid phase reaction for producing the composite oxide is prolonged. Yes, the heating step may be appropriately controlled from the viewpoint of work management. However, when a deliquescent alkali (earth) metal salt is used, if the time until the start of heating after co-grinding is long, the formation of complex oxides will be delayed. Since the reaction may not proceed, it is preferable to appropriately control the process according to the raw material and the alkali (earth) metal salt.
- the heating method is not particularly limited, but for example, a method in which the co-milled product is put into a general electric heating furnace and electric heating is performed is simple. Not only this method, but also a method of flowing hot air into the furnace containing the co-pulverized flame product, a method of heating the furnace wall of the furnace containing the co-pulverized product from the outside and radiantly heating the co-pulverized product May be.
- the heating temperature can be appropriately determined depending on the type of the oxide of the valuable metal, etc. However, if the temperature is lower than 200 ° C., it takes a long time to diffuse in a solid, and therefore, it is not preferable when industrially performed. It is necessary to heat the mixture to at least ° C, preferably at least 250 ° C.
- the upper limit of the heating temperature must be lower than the lower of the decomposition temperature or melting temperature of the alkali metal salt and / or the earth metal salt. Heating to a higher temperature will give unnecessary heat energy, which is not only economically disadvantageous, but also causes the alkali metal salt and Z or alkaline earth metal salt to become non-solid and volatilize or melt. Therefore, it is not preferable because it causes corrosion and adhesion of reaction products due to heating of the heating furnace.
- a composite oxide as a final product can be obtained in a state where the impurities are mixed.
- the composite oxide obtained by the solid phase reaction is water-soluble, an aqueous solvent is added to the heated solid phase reaction product to extract the composite oxide as an aqueous solution according to a standard method, and this is filtered.
- the extraction temperature is preferably set so as to obtain a high-concentration solution in consideration of the temperature dependence of the solubility of the composite oxide in order to increase the extraction concentration and perform the extraction efficiently.
- the complex oxide can be separated and recovered by dissolving and removing substances other than the composite oxide with an acid or alkali according to a standard method. .
- the recovered complex oxides are reduced to valuable metal oxides that make up the composite oxides, and further to valuable metals, according to a standard method.
- the extraction rate of the composite oxide is calculated by the following equation.
- the powder having a particle size of 300 m or more obtained by sieving was re-pulverized. This pulverization was repeated until the powder having a particle diameter of 300 m or more disappeared to obtain a crushed concentrate having a median particle diameter of 32.3 im.
- the median particle size was measured using a laser diffraction particle size analyzer (Cil as Company, HR850B), 1 g of the concentrate after milling and 0.05 g of sodium hexamephosphate as a dispersant were added to 400 ml of ion-exchanged water, and dispersed by an ultrasonic homogenizer for 5 minutes. The particle size was measured in a quartz cell and calculated. table 1
- the concentration of vanadium in the filtrate and the residue was measured by the ICP method, and the absolute amount of vanadium in the residue and in the filtrate was determined to be 35 mg and 696, respectively, based on the concentration, the residual mass and the liquid volume (250 ml). mg and the extraction ratio of vanadium was calculated by the following formula. The extraction rate was as high as 95.2%.
- Niobium alloy with an elemental composition (excluding oxygen: mass%) by the ICP method shown in Table 2 was coarsely ground to 0.3 mm or less in advance, and then the average particle size was 200 mesh using the vibrating mill of Example 1. (75 m)
- the following components were pulverized so as to be 50% by mass to obtain pulverized Nioballoy with a median particle size of 71.0 m.
- thermobalance the change in mass of the ferronioballoy 5 Omg after the pulverization was measured at a heating rate of 1 OK / min under an air flow of 200 ml / min.
- the results are shown in a graph (FIG. 2) in which the horizontal axis represents temperature, the left vertical axis represents mass, and the right vertical axis represents differential calorific value. From Fig. 2, it can be seen that at about 900 ° C, the mass increase of Nioballoy at the mouth stopped, and the oxidation ended.
- the mass change of 50 mg of the mixture containing iron niobate and sodium carbonate after the co-milling was measured at a heating rate of 1 OK / min under a 20 Oml / min air flow using a thermobalance.
- the results are shown in Darraf (Fig. 3) with the horizontal axis representing temperature, the left vertical axis representing mass, and the right vertical axis representing differential calorific value. From FIG. 3, it can be seen that the mass loss of the mixture started at 400 ° C., ended at 780 ° C., and at the same time, an endothermic peak appeared at 780 ° C.
- Example 2 200 g of the iron-niobate-containing mixture after cooling in Example 2 and 200 g of sodium carbonate were added to the vibrating mill of Example 1 and 280 alumina poles (19 mm in diameter) were added. Co-milling was performed at 1200 n) m for 120 minutes. The particle size of the mixture containing iron niobate and sodium carbonate after co-milling was 2.5 zm in median particle size.
- the mass change of 5 Omg of the iron niobate-containing mixture and the sodium carbonate-containing mixture after co-milling was measured using a thermal stove at a heating rate of l OK / min under an air flow of 20 Oml / min. .
- the results are shown in a graph with temperature on the horizontal axis, mass on the left vertical axis, and differential calorie on the right vertical axis (Fig. 4). From FIG. 4, the mass loss of the mixture starts at 400 ° C. and ends at 800 ° C., and at the same time, an exothermic peak appears at 800 ° C. At the same time, an endothermic peak appears. In the case of the second embodiment, as shown in FIG. 3, only the exothermic peak is present, so that in the case of the third embodiment, it is estimated that some phase change has occurred.
- the mixture was placed 10 0 g containing the iron niobate-containing mixture and sodium carbonate obtained by co-milling the Matsufuru furnace, 1. heated 5 hours at 80 in an air atmosphere, and the sodium carbonate niobate iron F eNB0 4 After the solid-phase reaction was performed, the mixture was cooled. X-ray diffraction of the solid-phase reaction product after cooling yields a complex oxide of niobium, sodium orthoniobate. It was confirmed that lithium Na 3 Nb 4 was formed.
- the concentration of the niobium in the filtrate and the residue was measured by the ICP method. From the concentration, the residual mass and the liquid volume (250 ml), the absolute amount of the niobium in the filtrate and the filtrate was 0.06 g, respectively. And 5.38 g, and the extraction rate of niobium was calculated. The extraction rate was as high as 98.9%.
- the ore containing the iron-manganese heavy stone of the elemental composition (excluding oxygen: mass%) according to the ICP method shown in Table 3 was previously coarsely ground to 0.3 mm or less, and then averaged using the rotating pole mill of Example 1.
- the ore containing the pulverized iron-manganese heavy stone having a median particle diameter of 52.3 m was obtained by pulverizing the components having a particle size of 400 mesh (36 zm) or less to 80% by mass.
- 260 g of iron poles (19 mm in diameter) were added to 200 g of the ore containing the crushed iron manganese stone and potassium carbonate, at an amplitude of 4 mm and a rotation speed of 1200 rpm.
- Co-milling was performed for 90 minutes.
- the particle size of the mixture containing the ore and potassium carbonate after co-milling was 3.9 im in median particle size.
- the mass change of 5 Omg of the mixture containing the ore and potassium carbonate after co-milling was measured at a heating rate of 1 OK / min under a 200 ml / min air flow using a thermobalance.
- the results are shown in a graph (Fig. 5), with the horizontal axis representing temperature, the left vertical axis representing mass, and the right vertical axis representing differential calorific value.
- the significant endothermic weight loss up to 100 ° C is due to the evaporation of the water absorbed by potassium carbonate.
- the concentration of tungsten in the filtrate and the residue was measured by the ICP method. From the concentration, the amount of the residue and the amount of the solution (250 ml), the absolute amount of the composite oxide of tungsten in the residue and in the filtrate was 4 g and 4 g, respectively. 15. Calculated as lg and the extraction rate of tungsten was calculated. The extraction rate was as high as 97.4%.
- Ore containing scheelite with an elemental composition (excluding oxygen:% by mass) according to the ICP method shown in Table 4 was coarsely ground to 0.3 mm or less in advance, and the average particle size was measured using the rotary ball mill of Example 1.
- the ore containing pulverized scheelite with a median particle size of 49.0 m was obtained by pulverizing the components having a diameter of 400 mesh (36 m) or less to 80% by mass.
- Table 4 250 g of the crushed ore containing the scheelite and 80 g of sodium carbonate were added using the vibrating mill of Example 1 to 260 iron balls (19 mm in diameter) at an amplitude of 4 mm and a rotation speed of 120 Orpm for 1 hour. Co-milling was performed. The particle size of the mixture containing ore containing scheelite and sodium carbonate after co-milling was 3.1 m in median particle size. The mass change of 2 Omg of the mixture containing the ore and sodium carbonate after co-milling was measured at a heating rate of 2 K / min under a 20 Oml / min air flow using a thermobalance. The results are shown in a graph with temperature on the horizontal axis, mass on the left vertical axis, and differential calorific value on the right vertical axis ( Figure ⁇ ).
- the weight loss after 400 is due to the desorption of carbon dioxide from sodium carbonate, and desorption is completed at 600 ° C.
- Sodium carbonate has a melting point of 850 ° C and decomposes at higher temperatures. From the mass change, it is presumed that the solid-phase reaction involving carbon dioxide from sodium carbonate is proceeding from a surprisingly low temperature. 100 g of the mixture containing the ore and sodium carbonate after co-milling was put into a Matsufuru furnace, heated at 600 ° C in an air atmosphere for 1.5 hours, and cooled. We applied X-ray diffraction on a part of the cooling products, the generation of C a sodium tungstate lost as a composite oxide of WO 4 N a 2 W_ ⁇ 4 was observed. Therefore, considering the results of the thermal analysis, it is estimated that the solid phase reaction described below was completed by 600 ° C.
- the concentration of tungsten in the filtrate and the residue was measured by the ICP method. From the concentration, the amount of the residue and the amount of the solution (250 ml), the absolute amount of tungsten in the residue and in the filtrate was 13 g and 7.83, respectively. g and calculate the extraction rate of tungsten Calculated. The extraction rate was as high as 98, 4%.
- Nickel ore of the elemental composition (excluding oxygen: mass%) according to the ICP method shown in Table 5 was previously coarsely ground to 0.3 mm or less, and the average particle size was measured using the rotating pole mill of Example 1.
- the components of 400 mesh (36 m) or less were pulverized to 90% by mass to obtain pulverized silica nickel ore having a median particle size of 38.1 zxm.
- Table 5 300 g of the crushed silica nickel ore was put into a Matsufuru furnace, heated in an air atmosphere at 700 ° C. for 2 hours, dehydrated, and then cooled. Using the vibrating pole mill of Example 1, add 260 g of iron poles (19 mm in diameter) to 200 g of the silica nickel ore and 80 g of sodium sulfate after dehydration, and co-mill with an amplitude of 4 mm and a rotation speed of 1200 rpm for 2 hours. Was done. The particle size of the mixture containing the nickel silicate ore and sodium sulfate after co-milling was 2.1 m in median particle size.
- the mass change of 3 Omg of the mixture containing nickel nickel ore and sodium sulfate after co-milling was measured using a thermobalance at a heating rate of 1 OK / min under an air flow of 20 Oml / min. did.
- the results are shown in a graph (FIG. 7) in which the horizontal axis represents temperature, the left vertical axis represents mass, and the vertical axis represents differential calorific value.
- the weight loss after 520 ° C is due to the desorption of sulfur dioxide from sodium sulfate, which is completed at 660.
- the melting point of sodium sulfate is 880 ° C, and it decomposes at higher temperatures. From the mass change, it is presumed that the solid-phase reaction accompanied by the removal of sulfur dioxide from sodium sulfate proceeds from a lower temperature of 200 ° C or more than the decomposition of a simple substance.
- the nickel concentration of the filtrate and the residue was measured by the ICP method. From the concentration, the residual mass and the liquid volume (250 m), the absolute amount of Niggel in the residual and the filtrate was 0.16, respectively. g and 1.95 g, and the nickel extraction rate was calculated. The extraction rate was as high as 92.4%. 7753
- Ore containing zircon having an elemental composition (excluding oxygen: mass%) according to the ICP method shown in Table 6 150 g and 203 g of calcium carbonate were co-ground using the vibrating mill of Example 1 with 260 iron poles (diameter 19 mm) at an amplitude of 4 mm and a rotation speed of 1200 m for 2.5 hours. After co-milling, the mixture containing the ore containing zircon and calcium carbonate has a median particle size of 6.0. Met.
- the mass change of 50 mg of the mixture containing the ore containing zircon and calcium carbonate after co-milling was measured using a thermobalance. The measurement was performed at a heating rate of 101 (/ 111111). The results are shown in a graph (FIG. 8) in which the horizontal axis represents temperature, the left vertical axis represents mass, and the right vertical axis represents differential calorific value.
- the weight loss after 500 ° C is due to the desorption of carbon dioxide from calcium carbonate, and the desorption is completed at 730 ° C.
- the decomposition temperature of calcium carbonate is 825 ° C. From the change in mass, it is presumed that the solid-phase reaction involving the removal of carbon dioxide from calcium carbonate proceeds at a lower temperature of 190 ° C. or more than the decomposition of a simple substance.
- a mixture of the concentrate and sodium carbonate after co-milling with a median particle size of 4.3 m obtained by co-milling the concentrate and sodium carbonate in Example 1 was extracted with hot water without heating. Was done. The extraction rate is as low as 0.24% by weight. The surface of the extract is presumed metavanadate Natoriumu N a V0 3 is a composite oxide.
- Example 1 The concentrate having a median particle size of 32.3 m in Example 1 was further pulverized using the vibrating mill of Example 1 to obtain a pulverized product having a median particle size of 4.0 m.
- FIG. 9 shows that the mass reduction of the kneaded product started at 600 ° C., ended at 840 ° C., and at the same time, an endothermic peak appeared at 839 ° C.
- an alkali (earth) metal salt which is a eutectic agent, is heated from an oxide of a metal, Z or a precursor thereof, or a substance containing the metal, without melting, that is, an extremely high temperature.
- the reaction rate can be increased, and the selectivity is high, so that the productivity of the composite oxide of the valuable metal is extremely good.
- the valuable metal oxide can be efficiently separated and recovered from various ores, industrial waste, and general waste. It is expected to be used for manufacturing
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Abstract
Description
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EA200501889A EA007976B1 (ru) | 2003-05-30 | 2004-05-28 | Способ получения комплексных оксидов металла |
EP04735391A EP1630132A4 (en) | 2003-05-30 | 2004-05-28 | METHOD FOR PRODUCING METAL MIXED OXIDE |
US10/557,140 US8034319B2 (en) | 2003-05-30 | 2004-05-28 | Method for producing complex oxide of metal |
CN200480015073.2A CN1798699B (zh) | 2003-05-30 | 2004-05-28 | 金属复合氧化物的制造方法 |
AU2004242643A AU2004242643B2 (en) | 2003-05-30 | 2004-05-28 | Method for producing composite oxide of metal |
BRPI0410826-4A BRPI0410826B1 (pt) | 2003-05-30 | 2004-05-28 | processo para preparar àxido complexo de metal. |
CA002524774A CA2524774C (en) | 2003-05-30 | 2004-05-28 | Method for producing composite oxide of metal |
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JP2003-154410 | 2003-05-30 | ||
JP2003154410 | 2003-05-30 | ||
JP2004-147898 | 2004-05-18 | ||
JP2004147898A JP2005015327A (ja) | 2003-05-30 | 2004-05-18 | 金属の複合酸化物の製造方法 |
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US (1) | US8034319B2 (ja) |
EP (1) | EP1630132A4 (ja) |
JP (1) | JP2005015327A (ja) |
AU (1) | AU2004242643B2 (ja) |
BR (1) | BRPI0410826B1 (ja) |
CA (1) | CA2524774C (ja) |
EA (1) | EA007976B1 (ja) |
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JP2010100510A (ja) * | 2008-01-07 | 2010-05-06 | Sumitomo Chemical Co Ltd | チタン酸アルミニウムセラミックスの製造方法 |
WO2013071294A2 (en) * | 2011-11-10 | 2013-05-16 | Advanced Magnetic Processes Inc. | Magneto-plasma separator and method for separation |
CN113368851A (zh) * | 2021-06-09 | 2021-09-10 | 中国科学院青岛生物能源与过程研究所 | 一种制备氧化物负载金属的方法及应用 |
Citations (3)
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JPH08208226A (ja) * | 1994-11-30 | 1996-08-13 | Sumitomo Chem Co Ltd | 複合金属酸化物粉末の製造方法 |
JPH0952773A (ja) * | 1995-08-09 | 1997-02-25 | Nara Kikai Seisakusho:Kk | 複合酸化物セラミックスの製造方法 |
JP2003335523A (ja) * | 2002-05-20 | 2003-11-25 | Koji Sato | 酸化鉄と酸化チタンの複合酸化物の製造方法及びその酸化物 |
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US1535019A (en) * | 1920-09-18 | 1925-04-21 | Gen Electric | Metallurgical process |
US1652646A (en) * | 1922-03-30 | 1927-12-13 | William B Stoddard | Process of forming sodium tungstate |
US3320024A (en) * | 1963-07-05 | 1967-05-16 | Burwell Blair | Process of recovering high purity vanadium compositions |
BE756946R (fr) * | 1969-10-03 | 1971-04-01 | Continental Ore Corp | Procede de traitement de scories contenant du |
JPS4838817A (ja) | 1971-09-22 | 1973-06-07 | ||
ZA786478B (en) * | 1978-11-17 | 1980-02-27 | Anglo Amer Corp South Africa | Recovery of tungsten values from tungsten-bearing materials |
EP0324871A1 (en) * | 1988-01-19 | 1989-07-26 | The Dow Chemical Company | Process for preparing pigmentary titanium dioxide |
WO1993004207A1 (en) * | 1991-08-19 | 1993-03-04 | Commonwealth Scientific And Industrial Research Organisation | Zirconium extraction |
EP0714850B1 (en) * | 1994-11-30 | 1999-07-28 | Sumitomo Chemical Company, Limited | Method for producing double metal oxide powder |
US5882620A (en) | 1995-06-07 | 1999-03-16 | International Carbitech Industries, Inc. | Pyrometallurgical process for forming tungsten carbide |
JPH1171111A (ja) | 1997-08-25 | 1999-03-16 | Fumiyoshi Saito | 希土類金属化合物の抽出方法 |
JP3673960B2 (ja) | 1998-04-28 | 2005-07-20 | 東北電力株式会社 | 水硬性粉体の製造方法 |
JP4169871B2 (ja) | 1999-07-01 | 2008-10-22 | Dowaホールディングス株式会社 | In含有酸化物からのIn浸出方法 |
-
2004
- 2004-05-18 JP JP2004147898A patent/JP2005015327A/ja active Pending
- 2004-05-28 AU AU2004242643A patent/AU2004242643B2/en not_active Ceased
- 2004-05-28 BR BRPI0410826-4A patent/BRPI0410826B1/pt not_active IP Right Cessation
- 2004-05-28 US US10/557,140 patent/US8034319B2/en not_active Expired - Fee Related
- 2004-05-28 EP EP04735391A patent/EP1630132A4/en not_active Withdrawn
- 2004-05-28 WO PCT/JP2004/007753 patent/WO2004106230A1/ja active Application Filing
- 2004-05-28 CA CA002524774A patent/CA2524774C/en not_active Expired - Fee Related
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08208226A (ja) * | 1994-11-30 | 1996-08-13 | Sumitomo Chem Co Ltd | 複合金属酸化物粉末の製造方法 |
JPH0952773A (ja) * | 1995-08-09 | 1997-02-25 | Nara Kikai Seisakusho:Kk | 複合酸化物セラミックスの製造方法 |
JP2003335523A (ja) * | 2002-05-20 | 2003-11-25 | Koji Sato | 酸化鉄と酸化チタンの複合酸化物の製造方法及びその酸化物 |
Non-Patent Citations (1)
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See also references of EP1630132A4 * |
Also Published As
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BRPI0410826A (pt) | 2006-06-27 |
BRPI0410826B1 (pt) | 2013-04-09 |
AU2004242643B2 (en) | 2007-09-20 |
US20060275202A1 (en) | 2006-12-07 |
EA200501889A1 (ru) | 2006-06-30 |
CA2524774A1 (en) | 2004-12-09 |
AU2004242643A1 (en) | 2004-12-09 |
CA2524774C (en) | 2009-12-15 |
EA007976B1 (ru) | 2007-02-27 |
EP1630132A4 (en) | 2010-10-27 |
EP1630132A1 (en) | 2006-03-01 |
JP2005015327A (ja) | 2005-01-20 |
US8034319B2 (en) | 2011-10-11 |
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