JPWO2016031699A1 - Scandium separation method - Google Patents
Scandium separation method Download PDFInfo
- Publication number
- JPWO2016031699A1 JPWO2016031699A1 JP2016545486A JP2016545486A JPWO2016031699A1 JP WO2016031699 A1 JPWO2016031699 A1 JP WO2016031699A1 JP 2016545486 A JP2016545486 A JP 2016545486A JP 2016545486 A JP2016545486 A JP 2016545486A JP WO2016031699 A1 JPWO2016031699 A1 JP WO2016031699A1
- Authority
- JP
- Japan
- Prior art keywords
- scandium
- aqueous
- solution
- acid
- separating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 350
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims abstract description 348
- 238000000926 separation method Methods 0.000 title claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 102
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000010936 titanium Substances 0.000 claims abstract description 77
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 77
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 61
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 42
- 239000011550 stock solution Substances 0.000 claims abstract description 37
- 230000002378 acidificating effect Effects 0.000 claims abstract description 34
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 73
- 239000007864 aqueous solution Substances 0.000 claims description 67
- 239000011347 resin Substances 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 51
- 239000003960 organic solvent Substances 0.000 claims description 46
- 239000013522 chelant Substances 0.000 claims description 44
- 239000003125 aqueous solvent Substances 0.000 claims description 31
- 230000001376 precipitating effect Effects 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 description 30
- 238000001179 sorption measurement Methods 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 16
- 239000012535 impurity Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000000605 extraction Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000003929 acidic solution Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000010979 pH adjustment Methods 0.000 description 14
- 238000011282 treatment Methods 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 238000000638 solvent extraction Methods 0.000 description 12
- 239000012670 alkaline solution Substances 0.000 description 11
- 239000000292 calcium oxide Substances 0.000 description 11
- 235000012255 calcium oxide Nutrition 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- -1 zirconium ions Chemical class 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 239000000920 calcium hydroxide Substances 0.000 description 10
- 235000011116 calcium hydroxide Nutrition 0.000 description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 10
- 230000003472 neutralizing effect Effects 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 238000010828 elution Methods 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 235000011054 acetic acid Nutrition 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 150000007522 mineralic acids Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 230000000737 periodic effect Effects 0.000 description 6
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 6
- 150000001339 alkali metal compounds Chemical class 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 5
- 229910001863 barium hydroxide Inorganic materials 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 5
- 239000001095 magnesium carbonate Substances 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229940093915 gynecological organic acid Drugs 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052776 Thorium Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical class CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
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- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 1
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- HJSRRUNWOFLQRG-UHFFFAOYSA-N propanedioic acid Chemical compound OC(=O)CC(O)=O.OC(=O)CC(O)=O HJSRRUNWOFLQRG-UHFFFAOYSA-N 0.000 description 1
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- 235000017550 sodium carbonate Nutrition 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
- C22B59/00—Obtaining rare earth metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
スカンジウムの分離方法は、少なくともスカンジウム、チタン、ジルコニウムを含む水性原液に酸又はアルカリを混合してｐＨを１．０〜２．０の範囲に調整することにより、スカンジウムを液相に含み、チタン及びジルコニウムを固相に含む、スカンジウム含有水性懸濁液を得る工程を備えている。スカンジウム含有水性懸濁液は、固液分離により、チタン及びジルコニウムと、スカンジウムを含む酸性液とに分離することができる。The method for separating scandium includes mixing scandium in the liquid phase by mixing acid or alkali with an aqueous stock solution containing at least scandium, titanium, and zirconium to adjust the pH to a range of 1.0 to 2.0. A step of obtaining a scandium-containing aqueous suspension containing zirconium in a solid phase. The scandium-containing aqueous suspension can be separated into titanium and zirconium and an acidic liquid containing scandium by solid-liquid separation.
Description
本発明は、少なくともスカンジウム、チタン、ジルコニウムを含む水性原液からスカンジウムとチタン、ジルコニウムとを分離し、粗スカンジウムを回収する方法に関する。更に、本発明は、この粗スカンジウムを用いて、キレート樹脂吸着工程、有機溶媒抽出工程を経て、高純度のスカンジウムを製造する方法に関する。 The present invention relates to a method of recovering crude scandium by separating scandium, titanium, and zirconium from an aqueous stock solution containing at least scandium, titanium, and zirconium. Furthermore, the present invention relates to a method for producing high purity scandium using this crude scandium through a chelate resin adsorption step and an organic solvent extraction step.
スカンジウムは、遷移金属元素の一つで、イットリウムと共に希土類元素に分類される。スカンジウムは、例えばアルミニウム合金の添加剤、ニッケル・アルカリ蓄電池の陽極の改良剤のほかに、ヨウ化スカンジウムをメタルハライドランプに封入して用いたり、酸化ジルコニウムの安定化剤等に用いられ、スカンジア安定化ジルコニアは固体酸化物燃料電池の電解質に利用されている。 Scandium is one of transition metal elements and is classified as a rare earth element together with yttrium. For example, in addition to aluminum alloy additives and nickel / alkaline battery anode improvers, scandium can be used by encapsulating scandium iodide in metal halide lamps, zirconium oxide stabilizers, etc. Zirconia is used as an electrolyte for solid oxide fuel cells.
スカンジウムは比較的希少な金属であり、トルトベイト石等に含まれているが産出量が少ないため、チタン鉱石やニッケル酸化鉱等の残滓から分離回収している。例えば、特許文献１には、チタン鉱石を塩素化した固体状残渣を酸液に浸出し濾過して、不溶残渣を除去したスカンジウム含有液を得、次いで、前記のスカンジウム含有液をＴＢＰ（トリブチルホスフェート）を含む有機溶媒に接触させてスカンジウムを選択的に抽出し、塩酸で逆抽出し、アンモニア液を添加し析出させて高純度のスカンジウムを回収することを記載している（実施例１）。 Scandium is a relatively rare metal and is contained in tortbaitite, etc., but it is produced in small quantities, so it is separated and recovered from residues such as titanium ore and nickel oxide ore. For example, in Patent Document 1, a solid residue obtained by chlorinating titanium ore is leached in an acid solution and filtered to obtain a scandium-containing solution from which insoluble residues have been removed, and then the scandium-containing solution is converted to TBP (tributyl phosphate). In this example, scandium is selectively extracted by contacting with an organic solvent containing a), back-extracted with hydrochloric acid, ammonia solution is added and precipitated to recover high-purity scandium (Example 1).
また、特許文献２は、ニッケルとスカンジウムを含有する酸化鉱石からニッケルとスカンジウムを回収する方法において、（１）酸化鉱石を高温高圧下で酸により浸出してニッケルとスカンジウムを含む浸出液を得る浸出工程と、（２）浸出液に中和剤を加えてｐＨを２〜４の範囲に調整することにより、浸出液中の鉄とアルミニウムを沈殿物として除去する第一中和工程と、（３）第一中和工程で沈殿物を除去した後の溶液に、中和剤を加えてｐＨを４超〜７．５の範囲に調整することにより溶液中のスカンジウムを沈殿物として回収する第二中和工程と、（４）更に中和剤を加えてｐＨを７．５超に調整することにより、溶液中のニッケルを沈殿物として回収する第三中和工程とからなることを特徴とする、酸化鉱石からニッケルとスカンジウムを回収する方法を記載している。 Patent Document 2 discloses a method for recovering nickel and scandium from an oxide ore containing nickel and scandium. (1) A leaching step of leaching the oxide ore with an acid under high temperature and high pressure to obtain a leachate containing nickel and scandium. And (2) a first neutralization step in which iron and aluminum in the leachate are removed as precipitates by adding a neutralizing agent to the leachate and adjusting the pH to a range of 2 to 4, and (3) first Second neutralization step of recovering scandium in the solution as a precipitate by adding a neutralizing agent to the solution after removing the precipitate in the neutralization step and adjusting the pH to a range of more than 4 to 7.5. And (4) a third neutralization step in which nickel in the solution is recovered as a precipitate by adjusting the pH to more than 7.5 by adding a neutralizing agent. From nickel and ska It describes a method for recovering indium.
前記の特許文献１では、チタン鉱石を塩素化した固体状残渣を酸液に浸出し、次いで、ＴＢＰ（トリブチルホスフェート）を含む有機溶媒に接触させてスカンジウムを選択的に抽出する方法を開示しているが、スカンジウム含有液には、チタン鉱石由来のチタン、ジルコニウム等の不純物が含まれているため、スカンジウムを選択的に有機溶媒に抽出することができず、そのため、この後の処理を行っても高純度のスカンジウムが製造できないという問題がある。また、特許文献２では、浸出液に中和剤を加えてｐＨを２〜４の範囲に調整することにより鉄とアルミニウムを沈殿させ、その後にｐＨを４超〜７．５の範囲に調整することによりスカンジウムを沈殿させるが、鉱石由来のチタン、ジルコニウムが存在する場合はｐＨを２〜４に調整するとスカンジウムもチタン、ジルコニウムとともに共沈殿することから、その後にｐＨを４超〜７．５の範囲に調整してもスカンジウムの収率が低下したり、鉱石由来の鉄（第一鉄）、マンガン等の不純物の混入が避けられないなどの問題がある。 Patent Document 1 discloses a method of selectively extracting scandium by leaching a solid residue obtained by chlorinating titanium ore in an acid solution and then contacting with an organic solvent containing TBP (tributyl phosphate). However, since the scandium-containing liquid contains impurities such as titanium and zirconium derived from titanium ore, scandium cannot be selectively extracted into an organic solvent. However, there is a problem that high purity scandium cannot be produced. In Patent Document 2, a neutralizing agent is added to the leachate to adjust the pH to a range of 2 to 4, thereby precipitating iron and aluminum, and then adjusting the pH to a range of more than 4 to 7.5. In the case where ore-derived titanium or zirconium is present, if the pH is adjusted to 2 to 4, scandium coprecipitates with titanium and zirconium, and then the pH is in the range of more than 4 to 7.5. Even if it adjusts to, there are problems that the yield of scandium is reduced, and that impurities such as iron (ferrous iron) and manganese derived from ore cannot be avoided.
本発明者らは、スカンジウムを含む溶液から、高効率かつ簡便に行うことのできるスカンジウムの分離又は回収の方法を研究した結果、少なくともスカンジウム、チタン、ジルコニウムのイオンを含む水性原液とアルカリを混合してｐＨを１．０〜２．０の範囲に調整しチタン、ジルコニウムを析出させたり、あるいは、少なくともスカンジウム、チタン、ジルコニウムの沈殿析出物を含む水性原液と酸とを混合してｐＨを１．０〜２．０の範囲に調整しスカンジウムを溶解させたりすると（チタン、ジルコニウム分離工程）、スカンジウム及びチタンと、ジルコニウムとを効率よく分離することができることを見出した。尚、チタン、ジルコニウム分離工程によって得られる懸濁液（スカンジウムを液相に含み、チタン及びジルコニウムを固相に含む懸濁液）を、スカンジウム含有懸濁液と呼ぶことがある。 As a result of studying a method for separating or recovering scandium that can be efficiently and easily performed from a solution containing scandium, the present inventors have mixed an aqueous stock solution containing at least scandium, titanium, and zirconium ions with an alkali. The pH is adjusted to 1.0 to 2.0 to precipitate titanium and zirconium, or an aqueous stock solution containing at least a precipitate of scandium, titanium and zirconium and an acid are mixed to adjust the pH to 1. It has been found that when scandium is dissolved in a range of 0 to 2.0 (titanium and zirconium separation step), scandium and titanium and zirconium can be efficiently separated. A suspension obtained by the titanium / zirconium separation step (a suspension containing scandium in the liquid phase and titanium and zirconium in the solid phase) may be referred to as a scandium-containing suspension.
次に、前記のスカンジウム含有懸濁液を固液分離し、分離後の溶液（スカンジウムを含む酸性液）にアルカリを混合してｐＨを３．５〜７．０の範囲に調整しスカンジウムを析出させ、次いで、固液分離すると（第１スカンジウム析出・分離工程）、スカンジウムの析出物を分離することができることを見出した。このスカンジウム析出物は、純度の低い粗スカンジウム化合物である。 Next, the above scandium-containing suspension is solid-liquid separated, and alkali is mixed with the separated solution (an acidic liquid containing scandium) to adjust the pH to a range of 3.5 to 7.0, thereby precipitating scandium. Then, when solid-liquid separation (first scandium precipitation / separation step), it was found that scandium precipitates can be separated. This scandium deposit is a crude scandium compound with low purity.
更に、前記の工程で得たスカンジウム含有水性懸濁液又はスカンジウムを含む酸性液又はスカンジウム析出物を溶解した水系溶液（第１水系溶液）は、チタンやジルコニウムのように、スカンジウムと選択性の低い吸着種が分離されているので、これらの何れか１つとキレート樹脂とを接触させ、スカンジウムを吸着させることで、キレート樹脂へのスカンジウムの吸着を促進し、スカンジウムの純度を高めることができることを見出した。 Furthermore, the aqueous solution (first aqueous solution) in which the scandium-containing aqueous suspension obtained in the above step, the acidic solution containing scandium or the scandium precipitate is dissolved is low in selectivity with scandium like titanium and zirconium. Since the adsorbed species are separated, it is found that by adhering any one of these to a chelate resin and adsorbing scandium, the adsorption of scandium to the chelate resin can be promoted and the purity of scandium can be increased. It was.
加えて、前記の工程で得たスカンジウム含有水性懸濁液又はスカンジウムを含む酸性液又はスカンジウム析出物を溶解した水系溶液（第１水系溶液）を、キレート樹脂に接触させ、スカンジウムを吸着させ、次いで、吸着したスカンジウムを水系溶媒に溶離して第２水系溶液を得る工程（キレート樹脂吸着・溶離工程）、前記の各工程で得たスカンジウム含有水性懸濁液又はスカンジウムを含む酸性液又は各種水系溶液を、抽出剤を含む有機溶媒に接触させ、スカンジウムを有機溶媒に抽出させてスカンジウム含有有機溶液を得る工程（有機溶媒抽出工程）、スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第３水系溶液を得る工程（逆抽出工程）、更に、前記の各工程で得たスカンジウム含有水性懸濁液又はスカンジウムを含む酸性液又は各種水系溶液又はスカンジウム含有有機溶液と、析出剤を含む水系溶媒とを接触させ、スカンジウムを析出させ、次いで、固液分離によりスカンジウムを回収する工程（第２スカンジウム析出・回収工程）を選択的に行うことにより、スカンジウムの純度を高めていくことができることを見出し、本発明を完成した。 In addition, the scandium-containing aqueous suspension obtained in the above step or the aqueous solution (first aqueous solution) in which the scandium-containing acidic solution or scandium precipitate is dissolved is brought into contact with the chelate resin, and scandium is adsorbed. , A step of eluting the adsorbed scandium into an aqueous solvent to obtain a second aqueous solution (chelate resin adsorption / elution step), an aqueous solution containing scandium obtained in each of the above steps, or an acidic solution or various aqueous solutions containing scandium Is contacted with an organic solvent containing an extractant, scandium is extracted into the organic solvent to obtain a scandium-containing organic solution (organic solvent extraction step), and scandium in the scandium-containing organic solution is back-extracted into an aqueous solvent. 3 Step of obtaining an aqueous solution (back extraction step), and further, the scandium-containing aqueous suspension or scandium obtained in each of the above steps A step of contacting an acidic liquid containing various liquids or various aqueous solutions or scandium-containing organic solutions with an aqueous solvent containing a precipitating agent to precipitate scandium, and then recovering scandium by solid-liquid separation (second scandium precipitation / recovery step) It was found that the purity of scandium can be increased by selectively carrying out (3)), and the present invention was completed.
すなわち、本発明は、
（１）少なくともスカンジウム、チタン、ジルコニウムを含む水性原液を準備する工程と、前記水性原液に酸又はアルカリを混合してｐＨを１．０〜２．０の範囲に調整することにより、スカンジウムを液相に含み、チタン及びジルコニウムを固相に含む、スカンジウム含有水性懸濁液を得る工程とを備えるスカンジウムの分離方法、
（２）好ましい実施態様１ 前記スカンジウム含有水性懸濁液を固液分離してチタン及びジルコニウムを除去した酸性液に、アルカリを混合してｐＨを３．５〜７．０の範囲に調整することにより、スカンジウムを析出させる工程と、固液分離により、析出したスカンジウムを分離する工程とをさらに備える、スカンジウムの分離方法、
（３）好ましい実施態様２ 前記スカンジウム含有水性懸濁液又はこれを固液分離した酸性液又は前記析出したスカンジウムを溶解した第１水系溶液と、キレート樹脂とを接触させることにより、キレート樹脂にスカンジウムを吸着させる工程と、キレート樹脂に吸着したスカンジウムを水系溶媒に溶離して第２水系溶液を得る工程とをさらに備える、スカンジウムの分離方法、
（４）好ましい実施態様３ 前記スカンジウム含有水性懸濁液、又はこれを固液分離した酸性液、又は前記析出したスカンジウムを溶解した第１水系溶液、又は前記溶離したスカンジウムを含む第２水系溶液と、抽出剤を含む有機溶媒とを接触させることにより、スカンジウムを有機溶媒に抽出してスカンジウム含有有機溶液を得る工程と、スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第３水系溶液を得る工程とをさらに備える、スカンジウムの分離方法、
（５）好ましい実施態様４ 前記スカンジウム含有水性懸濁液を固液分離した酸性液、又は前記析出したスカンジウムを溶解した第１水系溶液、又は前記溶離したスカンジウムを含む第２水系溶液、又は前記スカンジウムを抽出したスカンジウム含有有機溶液、又は前記スカンジウムを逆抽出した第３水系溶液と、析出剤を含む水系溶媒とを接触させることにより、スカンジウムを析出させる工程と、固液分離により、スカンジウムを回収する工程とをさらに備える、スカンジウムの分離方法、などである。That is, the present invention
(1) A step of preparing an aqueous stock solution containing at least scandium, titanium, zirconium, and a solution of scandium by adjusting the pH to a range of 1.0 to 2.0 by mixing acid or alkali with the aqueous stock solution. A method for separating scandium comprising the steps of: obtaining a scandium-containing aqueous suspension comprising a phase and titanium and zirconium in the solid phase;
(2) Preferred embodiment 1 The pH is adjusted to a range of 3.5 to 7.0 by mixing alkali with an acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension and removing titanium and zirconium. The method of separating scandium, further comprising the step of precipitating scandium and the step of separating the precipitated scandium by solid-liquid separation,
(3) Preferred Embodiment 2 By contacting the chelate resin with the scandium-containing aqueous suspension, the acidic solution obtained by solid-liquid separation of the scandium-containing aqueous suspension, or the first aqueous solution in which the precipitated scandium is dissolved, the chelate resin is scandium. A method for separating scandium, further comprising: adsorbing scandium adsorbed on the chelate resin; and eluting the scandium adsorbed on the chelate resin into an aqueous solvent to obtain a second aqueous solution;
(4) Preferred embodiment 3 The above-mentioned scandium-containing aqueous suspension, an acidic liquid obtained by solid-liquid separation thereof, a first aqueous solution in which the precipitated scandium is dissolved, or a second aqueous solution containing the eluted scandium A step of extracting scandium into an organic solvent by contacting with an organic solvent containing an extractant to obtain a scandium-containing organic solution; and a third aqueous solution by back-extracting scandium in the scandium-containing organic solution into an aqueous solvent. A method for separating scandium, further comprising:
(5) Preferred Embodiment 4 An acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension, a first aqueous solution in which the precipitated scandium is dissolved, a second aqueous solution containing the eluted scandium, or the scandium The scandium is recovered by bringing the scandium into contact with an organic solution containing the extracted scandium or a third aqueous solution obtained by back-extracting the scandium and an aqueous solvent containing a precipitating agent, and solid-liquid separation. And a process for separating scandium.
本発明のスカンジウムの分離方法は、少なくともスカンジウム、チタン、ジルコニウムを含む水性原液を用いて、スカンジウムとチタン、ジルコニウムとを効率よく分離することができる。これにより、不純物のチタン、ジルコニウムの混入を低く抑えることができ、高効率かつ簡便にスカンジウムを分離することができる。また、前記の固液分離したスカンジウムを含む酸性液にアルカリを混合してｐＨを３．５〜７．０の範囲に調整しスカンジウムを析出させ、次いで、固液分離すると、スカンジウムの析出物を分離することができ、これにより、不純物の鉄（第一鉄）、マンガン等の混入を低く抑えることができ、高効率かつ簡便にスカンジウムを回収することができる。これらの方法により得られた粗スカンジウムは、不純物の含有量が少ないため、その後のキレート樹脂吸着・溶離工程、有機溶媒抽出工程、逆抽出工程、スカンジウム析出工程等を行う際の不純物を除去するための負担が少なく、各工程を効率的に行うことができる。特に、チタン、ジルコニウム等の不純物が除去されていることにより、キレート樹脂へのスカンジウムの吸着を促進することができ、結果として、スカンジウムの純度を高めることが可能となる。 The method for separating scandium of the present invention can efficiently separate scandium from titanium and zirconium using an aqueous stock solution containing at least scandium, titanium and zirconium. Thereby, contamination of titanium and zirconium as impurities can be kept low, and scandium can be separated easily and efficiently. Further, alkali is mixed with the above-mentioned acidic liquid containing scandium that has been separated into solid and liquid to adjust the pH to a range of 3.5 to 7.0, thereby precipitating scandium. Thus, it is possible to keep impurities such as iron (ferrous iron) and manganese from being mixed low, and scandium can be recovered efficiently and easily. Since the crude scandium obtained by these methods has a low impurity content, it removes impurities during the subsequent chelate resin adsorption / elution step, organic solvent extraction step, back extraction step, scandium precipitation step, etc. Each process can be performed efficiently. In particular, removal of impurities such as titanium and zirconium can promote the adsorption of scandium to the chelate resin, and as a result, the purity of scandium can be increased.
本発明の方法は、チタン鉱石を塩素化した残滓を水に懸濁した液、チタン鉱石を酸で浸出した残滓を水に懸濁した液を用いて、スカンジウムを分離・回収するのに最適である。 The method of the present invention is optimal for separating and recovering scandium using a solution obtained by suspending a residue obtained by chlorinating titanium ore in water and a solution obtained by suspending a residue obtained by leaching titanium ore with an acid. is there.
本発明は、少なくともスカンジウム、チタン、ジルコニウムを含む水性原液に酸又はアルカリを混合してｐＨを１．０〜２．０の範囲に調整し、スカンジウムを液相に含み、チタン及びジルコニウムを固相に含む、スカンジウム含有水性懸濁液とすることで、チタン、ジルコニウムとスカンジウムとを分離する方法である。 In the present invention, an aqueous stock solution containing at least scandium, titanium and zirconium is mixed with an acid or alkali to adjust the pH to a range of 1.0 to 2.0, scandium is contained in the liquid phase, and titanium and zirconium are solid-phased. Is a method of separating titanium, zirconium and scandium by preparing an aqueous suspension containing scandium.
（１）水性原液を準備する工程について
水性原液は、スカンジウムイオンを含む溶液や水酸化スカンジウム、酸化スカンジウムを含むスラリー等のスカンジウムを含む水性液であって、スカンジウムのほかに、チタン、ジルコニウムを含んでいる。チタン、ジルコニウムはイオンの状態であってもよく、水酸化物や酸化物等の化合物の状態であってもよい。また、スカンジウム以外の希土類元素（イットリウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウム）を含んでいてもよく、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、ニオブ、モリブデン、テクネチウム、ルテニウム、ロジウム、パラジウム、銀等の遷移金属元素を含んでいてもよく、トリウム、ウラン等の放射性元素を含んでいてもよく、そのほかのアルカリ金属元素、アルカリ土類金属元素、亜鉛、カドミウム等の周期表第１２族元素、ホウ素、アルミニウム、ガリウム、インジウム等の周期表第１３族元素、ケイ素、ゲルマニウム、スズ等の周期表第１４族元素、リン、ヒ素、アンチモン、ビスマス等の周期表第１５族元素、セレン、テルル等の周期表第１６族元素、フッ素、塩素等の周期表第１７族元素等の典型元素を含んでいてもよい。チタン、ジルコニウムのほかに、バナジウム及びスカンジウム以外の希土類元素から選ばれる少なくとも一種の金属を含むものが本発明の効果が得られやすいため好ましい。水性原液中のスカンジウムの濃度には特段の制限はなく、任意の濃度の水性原液を用いることができる。一般に、高濃度の水性原液（５００〜５００００ｍｇ／Ｌ程度）を用いれば、高い収率でスカンジウムを回収しやすい。本発明の方法によれば、スカンジウム濃度が低いもの（１〜５００ｍｇ／Ｌ程度）であっても、十分にスカンジウムを精製し、分離し、回収することができる。一方、スカンジウム以外の元素の濃度についても特段の制限はない。一般に、不純物成分が少なく、その濃度が低ければ（例えば、チタン、ジルコニウム、バナジウムがそれぞれ１０００ｍｇ／Ｌ以下程度であれば）、スカンジウムの精製は行い易い。本発明の方法によれば、不純物成分（チタン、ジルコニウム、バナジウム等）の濃度が比較的高い場合（１０００ｍｇ／Ｌを超える場合）でも、十分にスカンジウムを精製し、分離し、回収することができる。更に、スカンジウム以外の希土類元素の濃度についても特段の制限はないが、それぞれ０〜１０００ｍｇ／Ｌ程度であると好ましい。水性原液は、どのようなｐＨ域のものでも使用できる。原液のｐＨが６以上であれば予め酸を混合して６以下に調整するのが好ましく、ｐＨが２以下に調整しておくのがより好ましい。ｐＨが２以上であると、スカンジウム、チタン、ジルコニウムは水酸化物等の沈殿析出物のスラリーの状態であるが、ｐＨが２以下の強酸性域であると、スカンジウム、チタン、ジルコニウム等は溶解し溶液になっているため取り扱い易く、ｐＨが１以下であるとより好ましく、０．５以下のものが品質の安定性がよいため更に好ましい。(1) Step of preparing an aqueous stock solution The aqueous stock solution is an aqueous solution containing scandium such as a solution containing scandium ions, a slurry containing scandium hydroxide or scandium oxide, and contains titanium and zirconium in addition to scandium. It is out. Titanium and zirconium may be in an ionic state or a compound such as a hydroxide or an oxide. It may also contain rare earth elements other than scandium (yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), vanadium, chromium May contain transition metal elements such as manganese, iron, cobalt, nickel, copper, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, and may contain radioactive elements such as thorium, uranium, Other Periodic Table Group 12 Elements such as Alkali Metal Elements, Alkaline Earth Metal Elements, Zinc, Cadmium, etc., Periodic Table Group 13 Elements such as Boron, Aluminum, Gallium, Indium, Periodic Tables of Silicon, Germanium, Tin, etc. Including typical elements such as Group 4 elements, Periodic Table Group 15 elements such as phosphorus, arsenic, antimony, and bismuth, Periodic Table Group 16 elements such as selenium and tellurium, and Periodic Group 17 elements such as fluorine and chlorine May be. In addition to titanium and zirconium, those containing at least one metal selected from rare earth elements other than vanadium and scandium are preferable because the effects of the present invention can be easily obtained. There is no particular limitation on the concentration of scandium in the aqueous stock solution, and an aqueous stock solution having an arbitrary concentration can be used. Generally, if a high-concentration aqueous stock solution (about 500 to 50000 mg / L) is used, scandium can be easily recovered with a high yield. According to the method of the present invention, even if the scandium concentration is low (about 1 to 500 mg / L), scandium can be sufficiently purified, separated, and recovered. On the other hand, there is no particular limitation on the concentration of elements other than scandium. Generally, when there are few impurity components and the concentration is low (for example, when titanium, zirconium, and vanadium are each about 1000 mg / L or less), scandium is easily purified. According to the method of the present invention, even when the concentration of impurity components (titanium, zirconium, vanadium, etc.) is relatively high (over 1000 mg / L), scandium can be sufficiently purified, separated, and recovered. . Further, the concentration of rare earth elements other than scandium is not particularly limited, but is preferably about 0 to 1000 mg / L. The aqueous stock solution can be used in any pH range. If the pH of the stock solution is 6 or more, it is preferable to adjust the pH to 6 or less by mixing an acid in advance, and more preferably to adjust the pH to 2 or less. When the pH is 2 or more, scandium, titanium, and zirconium are in a slurry state of precipitates such as hydroxide, but when the pH is 2 or less, scandium, titanium, and zirconium are dissolved. Since it is a solution, it is easy to handle, and it is more preferable that the pH is 1 or less, and a pH of 0.5 or less is more preferable because the quality is stable.
水性原液は、少なくともスカンジウム、チタン、ジルコニウムを含み、例えば、次のような水性液を用いることができる。なお、酸性液とはｐＨが概ね６以下のもの、中性液とはｐＨが概ね６〜８のもの、アルカリ性液とはｐＨが概ね８以上のものを指す。本発明では、鉱石を酸で溶解した液、具体的にはチタン鉱石を塩素化した残滓を水に懸濁した液や、鉱石の残滓を酸で溶解した液、具体的にはチタン鉱石を酸で浸出した残滓を水に懸濁した液を用いるのがより好ましい。
１）スカンジウムを含む鉱石等の材料を酸で溶解した酸性液、この酸性液にアルカリを混合した酸性液、中性液又はアルカリ性液
２）スカンジウムを含む鉱石等の材料を酸で溶解した液を加水分解又は中和して他の金属成分を精製した後の酸性液、あるいは他の金属成分を精製した後の残滓を酸で溶解した酸性液、この酸性液にアルカリを混合した酸性液、中性液又はアルカリ性液
３）スカンジウムを含む鉱石等の材料をアルカリで溶解したアルカリ性液、このアルカリ性液に酸を混合した酸性液、中性液又はアルカリ性液
４）スカンジウムを含む鉱石等の材料をアルカリで溶解した液を加水分解又は中和して他の金属成分を精製した後のアルカリ性液、このアルカリ性液に酸を混合した酸性液、中性液又はアルカリ性液
５）スカンジウムを含む鉱石等の材料をアルカリで溶解した液を加水分解又は中和して他の金属成分を精製した後の残滓をアルカリ又は酸で溶解したアルカリ性液、中性液又は酸性液
６）１）〜５）の酸性液やアルカリ性液に含まれるスカンジウムをイオン交換樹脂（キレート樹脂）で吸着溶離したり、沈殿分離するなどしてスカンジウムを粗精製した後の酸性液、中性液又はアルカリ性液
７）１）〜５）の酸性液やアルカリ性液に含まれるスカンジウムをイオン交換樹脂（キレート樹脂）で吸着溶離したり、沈殿分離するなどしてスカンジウムを粗精製した水酸化スカンジウム、酸化スカンジウム等を含むスラリーにアルカリ又は酸を混合して得られたアルカリ性液、中性液又は酸性液The aqueous stock solution contains at least scandium, titanium, and zirconium. For example, the following aqueous solution can be used. The acidic liquid has a pH of about 6 or less, the neutral liquid has a pH of about 6 to 8, and the alkaline liquid has a pH of about 8 or more. In the present invention, a solution obtained by dissolving an ore with an acid, specifically, a solution obtained by suspending a residue obtained by chlorinating a titanium ore in water, a solution obtained by dissolving an ore residue with an acid, specifically, a titanium ore by an acid. It is more preferable to use a liquid obtained by suspending the residue leached in step (b) in water.
1) An acidic liquid obtained by dissolving a material such as ore containing scandium with an acid, an acidic liquid obtained by mixing an alkali with this acidic liquid, a neutral liquid or an alkaline liquid 2) A liquid obtained by dissolving a material such as ore containing scandium with an acid Acidic liquid after hydrolysis or neutralization to purify other metal components, or acidic liquid in which the residue after purifying other metal components is dissolved with acid, acidic liquid in which alkali is mixed with this acidic liquid, 3) An alkaline solution obtained by dissolving a material such as an ore containing scandium with an alkali, an acidic solution obtained by mixing an acid with the alkaline solution, a neutral solution or an alkaline solution 4) an alkali such as an ore containing scandium. The alkaline solution after hydrolyzing or neutralizing the solution dissolved in step 2 to purify other metal components, an acidic solution obtained by mixing an acid with this alkaline solution, a neutral solution or an alkaline solution 5) Scandium An alkaline solution, a neutral solution or an acidic solution obtained by dissolving a residue obtained by hydrolyzing or neutralizing a solution obtained by dissolving a material such as mu ore with an alkali and purifying other metal components with an alkali or an acid. 5) Acidic, neutral or alkaline liquids after scandium is roughly purified by adsorbing and eluting the scandium contained in the acidic or alkaline liquids with an ion exchange resin (chelate resin) or by precipitation separation. Slurry containing scandium hydroxide, scandium oxide, etc. obtained by roughly purifying scandium by adsorbing and eluting the scandium contained in the acidic liquid and alkaline liquid of 1) to 5) with an ion exchange resin (chelate resin) or by separating it by precipitation. Alkaline liquid, neutral liquid or acidic liquid obtained by mixing alkali or acid with
スカンジウムを含む材料としては、種々の鉱石、鉱石から他の金属成分を精錬した後の残滓のほかに、スカンジウムを含むアルミニウム合金、ニッケル・アルカリ蓄電池の陽極、メタルハライドランプ、固体酸化物燃料電池の電解質、スカンジア安定化ジルコニア等のセラミックス等の各種材料や廃棄物を使用することができる。鉱石として、例えば、トルトベイト石、金鉱石、銀鉱石、銅鉱石、鉛鉱石、ビスマス鉱石、スズ鉱石、アンチモン鉱石、水銀鉱石、亜鉛鉱石、鉄鉱石、クロム鉱石、マンガン鉱石、タングステン鉱石、モリブデン鉱石、ヒ素鉱石、ニッケル鉱石、コバルト鉱石、ウラン鉱石、トリウム鉱石、リン鉱石、硫黄鉱石 、バリウム鉱石、カルシウム鉱石、マグネシウム鉱石、ストロンチウム鉱石 、ベリリウム鉱石、アルミニウム鉱石、チタン鉱石等が挙げられ、鉄鉱石、ニッケル鉱石、チタン鉱石、マンガン鉱石、スズ鉱石、アルミニウム鉱石等のスカンジウムを多く含んでいる鉱石が好ましい。鉱石等の材料を溶解する酸あるいは酸性に調整する酸は、制限なく用いることができ、塩酸、硫酸、硝酸、フッ酸、王水等の無機酸や酢酸等の有機酸を用いることができる。鉱石等の材料を酸で溶解した液を加水分解したり中和したりして他の金属成分を精錬した後の液を用いることもできる。例えば、ラテライト鉱のニッケル酸化鉱に硫酸を添加して加圧浸出することによって得られる浸出液、その浸出液からニッケル分を取り出した後の液を用いることができる。また、ルチル鉱、チタン鉄鉱等のチタン鉱石や鉄鉱石に硫酸、塩酸、硝酸、フッ酸、王水等の無機酸、酢酸等の有機酸で溶解した溶解液、その溶解液を加水分解、中和してチタン分、鉄分を取り出した後の液等を用いることができる。また、鉱石中の他の金属を塩素化し気体として取り出した後の残滓を酸で溶解した液を用いることができ、例えば、ルチル鉱、チタン鉄鉱等のチタン鉱石や鉄鉱石を塩素ガスで塩素化し塩化チタン、塩化鉄を取り出した後の残滓を硫酸、塩酸、硝酸、フッ酸、王水等の無機酸、酢酸等の有機酸で溶解した溶解液、その溶解液を加水分解してチタン分、鉄分を取り出した後の液等を用いることができる。また、ｐＨ調整に用いるアルカリは、制限なく用いることができ、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属化合物、水酸化カルシウム（消石灰)、水酸化マグネシウム、水酸化バリウム等のアルカリ土類金属水酸化物、酸化カルシウム（生石灰）、酸化マグネシウム、酸化バリウム等のアルカリ土類金属酸化物、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等のアルカリ土類金属化合物、アンモニア、アミン類等を用いることができる。鉱石等の材料をアルカリで溶解した液やそれを加水分解したり中和したりして他の金属成分を精錬した後の液を用いることもできる。 As materials containing scandium, various ores, residues after refining other metal components from ores, aluminum alloys containing scandium, anodes of nickel / alkali storage batteries, metal halide lamps, electrolytes of solid oxide fuel cells Various materials such as ceramics such as scandia-stabilized zirconia and wastes can be used. As ores, for example, tortue bait, gold ore, silver ore, copper ore, lead ore, bismuth ore, tin ore, antimony ore, mercury ore, zinc ore, iron ore, chromium ore, manganese ore, tungsten ore, molybdenum ore, Arsenic ore, nickel ore, cobalt ore, uranium ore, thorium ore, phosphorus ore, sulfur ore, barium ore, calcium ore, magnesium ore, strontium ore, beryllium ore, aluminum ore, titanium ore etc., iron ore, nickel Ores containing a large amount of scandium such as ores, titanium ores, manganese ores, tin ores, and aluminum ores are preferred. An acid that dissolves materials such as ores or an acid that is adjusted to be acidic can be used without limitation, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia, and organic acids such as acetic acid can be used. A liquid obtained by refining other metal components by hydrolyzing or neutralizing a liquid obtained by dissolving a material such as ore with an acid can also be used. For example, a leachate obtained by adding sulfuric acid to a nickel oxide ore of laterite ore and leaching under pressure, or a solution obtained by removing nickel from the leachate can be used. Also, a solution in which titanium ore such as rutile or titanite or iron ore is dissolved with an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, or aqua regia, or an organic acid such as acetic acid, and the solution is hydrolyzed. The liquid etc. after taking out titanium content and iron content by summing can be used. In addition, it is possible to use a solution obtained by dissolving the residue after chlorinating other metals in the ore as a gas with an acid, for example, chlorinating titanium ore such as rutile or titanite or iron ore with chlorine gas. Titanium chloride, the residue after taking out iron chloride is dissolved in an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, aqua regia, etc., an organic acid such as acetic acid, The liquid etc. after taking out iron content can be used. Moreover, the alkali used for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, calcium hydroxide (slaked lime), water Alkaline earth metal hydroxides such as magnesium oxide and barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide and barium oxide, and alkaline earth metals such as calcium carbonate, magnesium carbonate and barium carbonate Compounds, ammonia, amines and the like can be used. A solution obtained by dissolving a material such as ore with an alkali or a solution obtained by refining other metal components by hydrolyzing or neutralizing the same can also be used.
一方、鉱石等の材料をアルカリで溶解する場合は、そのアルカリ性溶解液、そのアルカリ性溶解液を加水分解や中和して他の金属を取り出した後のアルカリ性液等を用いることができ、それに酸を混合して酸性液、中性液又はアルカリ性液とすることができる。鉱石等の材料を溶解するアルカリあるいはｐＨ調整に用いるアルカリは、制限なく用いることができ、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属化合物、水酸化カルシウム（消石灰)、水酸化マグネシウム、水酸化バリウム等のアルカリ土類金属水酸化物、酸化カルシウム（生石灰）、酸化マグネシウム、酸化バリウム等のアルカリ土類金属酸化物、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等のアルカリ土類金属化合物、アンモニア、アミン類等を用いることができる。鉱石等の材料をアルカリで溶解した液やそれを加水分解したり中和したりして他の金属成分を精錬した後の液を用いることもできる。ｐＨを酸性に調整する酸は、制限なく用いることができ、塩酸、硫酸、硝酸、フッ酸、王水等の無機酸や酢酸等の有機酸を用いることができ、前記の鉱石等の材料を溶解した酸性液を用いてもよい。 On the other hand, when materials such as ores are dissolved with alkali, the alkaline solution, the alkaline solution after hydrolysis or neutralization of the alkaline solution and taking out other metals can be used. Can be mixed into an acidic liquid, a neutral liquid or an alkaline liquid. Alkalis for dissolving materials such as ores or alkalis used for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, water Alkaline earth metal hydroxides such as calcium oxide (slaked lime), magnesium hydroxide, barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide, barium oxide, calcium carbonate, magnesium carbonate, carbonic acid Alkaline earth metal compounds such as barium, ammonia, amines and the like can be used. A solution obtained by dissolving a material such as ore with an alkali or a solution obtained by refining other metal components by hydrolyzing or neutralizing the same can also be used. The acid that adjusts the pH to acid can be used without limitation, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia, and organic acids such as acetic acid can be used. A dissolved acidic solution may be used.
水性原液は、予めスカンジウムを粗精製したものを用いてもよい。スカンジウムの粗精製は、前記の酸性液やそれを調製するために得られたアルカリ性液を用いて、それに含まれるスカンジウムを従来の方法で、例えば、イオン交換樹脂（キレート樹脂）で吸着し、次いで、イオン交換樹脂（キレート樹脂）から溶離によって、あるいは、ｐＨ調整などして沈殿分離処理して得られた水酸化スカンジウム、酸化スカンジウム等を水に分散するなどして、スカンジウムの濃度を高めることができる。このように粗精製した液と酸又はアルカリを加えてｐＨ調整した溶液も水性原液として用いることができる。また、スカンジウム含有液のｐＨを一旦７以上として水酸化スカンジウムを析出させ、そのスラリーを酸又はアルカリと混合してｐＨを調整した液を水性原液として用いることができ、必要に応じて調整した水性原液を分別して用いるのが好ましい。 As the aqueous stock solution, one obtained by roughly purifying scandium in advance may be used. The rough purification of scandium is performed by adsorbing scandium contained in the acidic solution and the alkaline solution obtained for preparing the same in a conventional manner, for example, with an ion exchange resin (chelate resin), The concentration of scandium can be increased by dispersing scandium hydroxide, scandium oxide, etc. obtained by elution from an ion exchange resin (chelate resin) or by precipitation separation treatment by adjusting pH, etc. in water. it can. A solution whose pH is adjusted by adding the roughly purified solution and acid or alkali can be used as the aqueous stock solution. In addition, the scandium-containing liquid once has a pH of 7 or more to precipitate scandium hydroxide, and the slurry can be mixed with an acid or alkali to adjust the pH as an aqueous stock solution. The stock solution is preferably used separately.
（２）チタン、ジルコニウム分離工程について
本発明では、少なくともスカンジウム、チタン、ジルコニウムを含む水性原液とアルカリを混合してｐＨを１．０〜２．０の範囲に調整し、チタン、ジルコニウムを固相に含み、スカンジウムを液相に含む、スカンジウムを含む水性懸濁液を得る。水性原液のｐＨを１．０未満から１．０〜２．０にすることにより、チタン、ジルコニウムの沈殿を析出させることができる。ｐＨ調整を１．０より低くすると、チタン、ジルコニウムの沈殿が不十分で、多くのチタン、ジルコニウムが水性原液中に残留する。また、ｐＨ調整を２．０より高くするとチタン、ジルコニウムの沈殿にスカンジウムの沈殿が混入してしまうため、スカンジウムの回収率が低下する。ｐＨ調整するアルカリは、制限なく用いることができ、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属化合物、水酸化カルシウム（消石灰)、水酸化マグネシウム、水酸化バリウム等のアルカリ土類金属水酸化物、酸化カルシウム（生石灰）、酸化マグネシウム、酸化バリウム等のアルカリ土類金属酸化物、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等のアルカリ土類金属化合物、アンモニア、アミン類等を用いることができる。鉱石等の材料をアルカリで溶解した液を加水分解したり中和したりして他の金属成分を精錬した後の液を用いることもできる。ｐＨ調整の際の温度は、適宜設定することができ、例えば、２〜１００℃程度が好ましく、５〜７０℃程度がより好ましい。(2) Titanium and zirconium separation step In the present invention, an aqueous stock solution containing at least scandium, titanium and zirconium and an alkali are mixed to adjust the pH to a range of 1.0 to 2.0, and titanium and zirconium are solid-phased. And an aqueous suspension containing scandium containing scandium in the liquid phase. By setting the pH of the aqueous stock solution to less than 1.0 to 1.0 to 2.0, titanium and zirconium precipitates can be deposited. When the pH adjustment is lower than 1.0, precipitation of titanium and zirconium is insufficient, and much titanium and zirconium remain in the aqueous stock solution. Further, when the pH adjustment is higher than 2.0, scandium precipitates are mixed into titanium and zirconium precipitates, and the scandium recovery rate is lowered. The alkali for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, calcium hydroxide (slaked lime), magnesium hydroxide, Alkaline earth metal hydroxides such as barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide and barium oxide, alkaline earth metal compounds such as calcium carbonate, magnesium carbonate and barium carbonate, ammonia , Amines and the like can be used. A liquid obtained by refining other metal components by hydrolyzing or neutralizing a liquid obtained by dissolving a material such as ore with an alkali can also be used. The temperature at the time of pH adjustment can be set suitably, for example, about 2-100 degreeC is preferable and about 5-70 degreeC is more preferable.
本発明の別の方法では、少なくともスカンジウム、チタン、ジルコニウムを含む水性原液と酸を混合してｐＨを１．０〜２．０の範囲に調整しスカンジウムを溶解する。水性原液のｐＨを２．０より大きいところから１．０〜２．０にすることにより、スカンジウムが溶解し、一方のチタン、ジルコニウムの沈殿析出物がそのままの状態を維持した状態とすることができる。ｐＨ調整を１．０より低くすると、チタン、ジルコニウムの沈殿が溶解し、多くのチタン、ジルコニウムが水性原液中に溶解する。また、ｐＨ調整を２．０より高くするとスカンジウムの沈殿が残りチタン、ジルコニウムの沈殿に混入してしまうため、スカンジウムの回収率が低下する。ｐＨを酸性に調整する酸は、制限なく用いることができ、塩酸、硫酸、硝酸、フッ酸、王水等の無機酸や酢酸等の有機酸を用いることができ、前記の鉱石等の材料を溶解した酸性液を用いてもよい。ｐＨ調整の際の温度は、適宜設定することができ、例えば、２〜１００℃程度が好ましく、５〜７０℃程度がより好ましい。 In another method of the present invention, an aqueous stock solution containing at least scandium, titanium, and zirconium and an acid are mixed to adjust the pH to a range of 1.0 to 2.0 and dissolve scandium. By adjusting the pH of the aqueous stock solution to a value from 2.0 to 1.0 to 2.0, the scandium dissolves, and the precipitate of one of the titanium and zirconium may be maintained as it is. it can. When the pH adjustment is lower than 1.0, titanium and zirconium precipitates are dissolved, and a large amount of titanium and zirconium are dissolved in the aqueous stock solution. Further, when the pH adjustment is higher than 2.0, scandium precipitates remain and are mixed into titanium and zirconium precipitates, so that the scandium recovery rate decreases. The acid that adjusts the pH to acid can be used without limitation, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia, and organic acids such as acetic acid can be used. A dissolved acidic solution may be used. The temperature at the time of pH adjustment can be set suitably, for example, about 2-100 degreeC is preferable and about 5-70 degreeC is more preferable.
（３）第１スカンジウム析出・分離の各工程について（好ましい実施態様１）
前記のチタン、ジルコニウム分離工程で得たスカンジウムを含む水性懸濁液を固液分離してチタン及びジルコニウムを除去し、除去後の水溶液（酸性液）にアルカリを混合してｐＨを３．５〜７．０の範囲に調整するのが好ましい。スカンジウムを含む酸性液のｐＨを３．５〜７．０にすることにより、スカンジウムの沈殿が析出し、それを固液分離することができる。ｐＨ調整を３．５より低くすると、スカンジウムの沈殿が不十分で、多くのスカンジウムが酸性液中に残留する。また、ｐＨ調整を７．０より高くすると鉄（第一鉄）、マンガン等の沈殿が析出し、スカンジウムの沈殿に混入してしまうため、スカンジウムの純度が低下するので、上記ｐＨ範囲が好ましい。ｐＨ調整するアルカリは、制限なく用いることができ、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属化合物、水酸化カルシウム（消石灰)、水酸化マグネシウム、水酸化バリウム等のアルカリ土類金属水酸化物、酸化カルシウム（生石灰）、酸化マグネシウム、酸化バリウム等のアルカリ土類金属酸化物、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等のアルカリ土類金属化合物、アンモニア、アミン類等を用いることができる。ｐＨ調整の際の温度は、適宜設定することができ、例えば、２〜１００℃程度が好ましく、５〜７０℃程度がより好ましい。スカンジウムを含む水性懸濁液の固液分離、又は、スカンジウムの析出物を含む液の固液分離は、何れも通常の方法を用いることができ、例えば、濾過機、静置分離機、遠心分離機等を用いることができる。回収した沈殿物は、必要に応じて乾燥し、及び／又は焼成する。固液分離の対象が前記水性懸濁液の場合、沈殿物の乾燥、及び／又は焼成によって酸化チタン、酸化ジルコニウムの粉末等を回収できる。また、固液分離の対象がスカンジウム析出物を含む液の場合、沈殿物の乾燥、及び／又は焼成によって酸化スカンジウムの粉末を回収することができる。(3) Each step of first scandium precipitation / separation (preferred embodiment 1)
The aqueous suspension containing scandium obtained in the titanium and zirconium separation step is subjected to solid-liquid separation to remove titanium and zirconium, and an alkali is mixed with the aqueous solution (acid solution) after removal to adjust the pH to 3.5 to It is preferable to adjust to the range of 7.0. By setting the pH of the acidic solution containing scandium to 3.5 to 7.0, scandium precipitates, and it can be separated into solid and liquid. When the pH adjustment is lower than 3.5, precipitation of scandium is insufficient and much scandium remains in the acidic liquid. Moreover, since the precipitation of iron (ferrous iron), manganese, etc. will precipitate and it will mix in scandium precipitation when pH adjustment is made higher than 7.0, since the purity of scandium falls, the said pH range is preferable. The alkali for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, calcium hydroxide (slaked lime), magnesium hydroxide, Alkaline earth metal hydroxides such as barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide and barium oxide, alkaline earth metal compounds such as calcium carbonate, magnesium carbonate and barium carbonate, ammonia , Amines and the like can be used. The temperature at the time of pH adjustment can be set suitably, for example, about 2-100 degreeC is preferable and about 5-70 degreeC is more preferable. For solid-liquid separation of an aqueous suspension containing scandium, or solid-liquid separation of a liquid containing scandium precipitates, any ordinary method can be used. For example, a filter, a stationary separator, or a centrifugal separator. A machine or the like can be used. The collected precipitate is dried and / or calcined as necessary. When the target of solid-liquid separation is the aqueous suspension, titanium oxide, zirconium oxide powder, etc. can be recovered by drying and / or firing the precipitate. Moreover, when the object of solid-liquid separation is a liquid containing scandium precipitates, the scandium oxide powder can be recovered by drying and / or firing the precipitates.
（４）キレート樹脂吸着・溶離の各工程について（好ましい実施態様２）
前記のチタン、ジルコニウム分離工程で得たスカンジウムを含む水性懸濁液、又はこれを固液分離した酸性液や、スカンジウム析出工程で得たスカンジウム析出物を水系溶媒に溶解した第１水系溶液を、キレート樹脂に接触させ、スカンジウムを吸着させ、次いで、吸着したスカンジウムを水系溶媒に溶離して、第２水系溶液を得ることができる。スカンジウム析出物を溶解する水系溶媒は、硫酸水溶液、塩酸水溶液、硝酸水溶液などの公知の酸や、炭酸ナトリウム水溶液、炭酸アンモニウム水溶液などの公知のアルカリを用いることができる。コストやハンドリング面から酸が好ましく、濃度はスカンジウムの溶解度が十分高ければ特に限定はされないが、スカンジウムをより高濃度で回収したければ、より高濃度であることが好ましく、例えば７０％硫酸がより好ましい。(4) Each step of chelate resin adsorption / elution (Preferred embodiment 2)
An aqueous suspension containing scandium obtained in the titanium and zirconium separation step, or an acidic solution obtained by solid-liquid separation of the suspension, and a first aqueous solution in which the scandium precipitate obtained in the scandium precipitation step is dissolved in an aqueous solvent. The second aqueous solution can be obtained by contacting the chelate resin to adsorb scandium and then eluting the adsorbed scandium into the aqueous solvent. As the aqueous solvent for dissolving the scandium precipitate, a known acid such as a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a nitric acid aqueous solution, or a known alkali such as a sodium carbonate aqueous solution or an ammonium carbonate aqueous solution can be used. Acid is preferable from the viewpoint of cost and handling, and the concentration is not particularly limited as long as the solubility of scandium is sufficiently high. However, if scandium is recovered at a higher concentration, a higher concentration is preferable, for example, 70% sulfuric acid is more preferable. preferable.
キレート樹脂は、従来公知のものを用いることができ、スカンジウムの吸着量が大きいキレート樹脂が好ましい。スカンジウムの吸着量が大きいキレート樹脂の官能基としては、イミノジ酢酸、チオウレア、ポリアミン系、アミノリン酸、メチルグルカミン、アミノオキシム、ホスホン酸、スルホン酸、カルボン酸等があり、これらを単独あるいは複数種有する樹脂を用いることができる。スカンジウムを吸着したキレート樹脂は、必要に応じて溶離槽に移し、硫酸、塩酸、硝酸、酢酸や、炭酸ナトリウムや炭酸アンモニウムなどの公知の溶離剤と接触させることでスカンジウムを水系溶媒中に溶離させる。スカンジウム吸着槽、溶離槽は、通常の反応槽、カラム等を用い、通液方法等は適宜選択することができる。吸着槽、溶離槽の液温は、適宜設定することができ、例えば、２〜８０℃程度が好ましく、５〜５０℃程度がより好ましい。キレート樹脂からのスカンジウムの溶離に用いる水系溶媒は、水又は水に必要に応じてアルコール等の有機溶媒を混合したものであり、有機溶媒の含有量は１０質量％以下程度が好ましい。 A conventionally well-known thing can be used for chelate resin, and chelate resin with a large amount of scandium adsorption | suction is preferable. The functional group of the chelate resin with a large amount of scandium adsorption includes iminodiacetic acid, thiourea, polyamine, aminophosphoric acid, methylglucamine, aminooxime, phosphonic acid, sulfonic acid, carboxylic acid, and the like. The resin which has can be used. The chelate resin adsorbed with scandium is transferred to an elution tank as necessary, and is contacted with a known eluent such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, sodium carbonate or ammonium carbonate to elute scandium in an aqueous solvent. . As the scandium adsorption tank and the elution tank, a normal reaction tank, a column and the like can be used, and a liquid passing method and the like can be appropriately selected. The liquid temperature of an adsorption tank and an elution tank can be set suitably, For example, about 2-80 degreeC is preferable and about 5-50 degreeC is more preferable. The aqueous solvent used for elution of scandium from the chelate resin is water or a mixture of water and an organic solvent such as alcohol as necessary, and the content of the organic solvent is preferably about 10% by mass or less.
（５）有機溶媒抽出工程、逆抽出工程の各工程について（好ましい実施態様３）
前記の（２）〜（４）の各工程で得たスカンジウムを含む水系溶液（前記のチタン、ジルコニウム分離工程で得られたスカンジウムを含む水性懸濁液、又はこれを固液分離した酸性液、又は第１水系溶液、又は第２水系溶液）を、抽出剤を含む有機溶媒に接触させ、スカンジウムを有機溶媒に抽出してスカンジウム含有有機溶液を得た後に、スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して、第３水系溶液を得る工程である。(5) About each process of an organic-solvent extraction process and a back extraction process (Preferred embodiment 3)
An aqueous solution containing scandium obtained in each of the above steps (2) to (4) (an aqueous suspension containing scandium obtained in the titanium or zirconium separation step, or an acid solution obtained by solid-liquid separation of this, Or the first aqueous solution or the second aqueous solution) is brought into contact with an organic solvent containing an extractant to extract scandium into the organic solvent to obtain a scandium-containing organic solution, and then the scandium in the scandium-containing organic solution is converted into an aqueous solution. This is a step of obtaining a third aqueous solution by back extraction into a solvent.
スカンジウムを含む水系溶液として、スカンジウム析出物を水系溶媒に溶解したもの（第１水系溶液）を用いる場合には、必要に応じて、水系溶液に酸又はアルカリを混合してｐＨを４．０〜７．０の範囲に調整すると、抽出量が大きくなるため好ましい。水系溶液のｐＨを前記の範囲とすると、スカンジウムが主に抽出され、不純物元素は殆ど抽出されず、分離することができる。ｐＨが４．０より低いとスカンジウムの抽出量が減少し、収率の低下を招くため好ましくない。７．０より高いと不純物元素の抽出量が増加し、分離効率が悪くなるため好ましくない。好ましいｐＨは５．０〜６．５である。ｐＨを酸性に調整する酸としては、制限なく用いることができ、塩酸、硫酸、硝酸、フッ酸、王水等の無機酸や酢酸等の有機酸を用いることができ、前記の鉱石等の材料を溶解した酸性液を用いてもよい。ｐＨを調整するためのアルカリとしては、アルカリ性を呈するものであれば制限なく用いることができ、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属化合物、水酸化カルシウム（消石灰)、水酸化マグネシウム、水酸化バリウム等のアルカリ土類金属水酸化物、酸化カルシウム（生石灰）、酸化マグネシウム、酸化バリウム等のアルカリ土類金属酸化物、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等のアルカリ土類金属化合物、アンモニア、アミン類等を用いることができ、鉱石等の材料をアルカリで溶解した液を用いてもよい。 When using an aqueous solution containing scandium in which a scandium precipitate is dissolved in an aqueous solvent (first aqueous solution), an acid or alkali is mixed with the aqueous solution as necessary to adjust the pH to 4.0 to 4.0. Adjustment to a range of 7.0 is preferable because the amount of extraction increases. When the pH of the aqueous solution is in the above range, scandium is mainly extracted, and the impurity element is hardly extracted and can be separated. When the pH is lower than 4.0, the amount of scandium extracted is decreased, and the yield is lowered. If it is higher than 7.0, the extraction amount of the impurity element is increased, and the separation efficiency is deteriorated. A preferred pH is 5.0 to 6.5. The acid that adjusts the pH to acid can be used without limitation, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia, and organic acids such as acetic acid can be used. You may use the acidic liquid which melt | dissolved. The alkali for adjusting the pH can be used without limitation as long as it exhibits alkalinity, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, etc. , Alkaline earth metal hydroxides such as calcium hydroxide (slaked lime), magnesium hydroxide, barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide, barium oxide, calcium carbonate, magnesium carbonate In addition, alkaline earth metal compounds such as barium carbonate, ammonia, amines and the like can be used, and a solution obtained by dissolving a material such as ore with an alkali may be used.
スカンジウムを含む水系溶液と、抽出剤を含む有機溶媒とを混合して、スカンジウムと抽出剤から形成される錯体を有機溶媒に抽出する。抽出剤は、従来公知のものを用いることができ、例えば、カルボン酸及び／又はその塩（以下にカルボン酸系抽出剤ということがある）が好ましい。カルボン酸はカルボキシ基を有する有機酸であり、カルボン酸塩としてはナトリウム、カリウム、アンモニウム等の塩が挙げられ、スカンジウムと錯体を形成するものであれば使用できる。具体的にはカルボン酸系抽出剤としてネオデカン酸系、バーサチック酸系、ナフテン酸系、オレイン酸系、ラウリン酸系等の公知の抽出剤を用いることができ、ナフテン酸及び／又はネオデカン酸が好ましく用いられる。抽出剤の割合は適宜設定することができ、カルボン酸系抽出剤の割合は有機溶媒に対して１〜５０質量％が好ましく、５〜２０質量％がより好ましい。また、有機相と水相との界面に第三相が生成することを抑制するために、界面調節剤を添加してもよい。界面調節剤としては、ノニルフェノール、１−デカノール、イソデカノール、１−オクタノール、２−エチルヘキサノール等の長鎖アルキル化合物や、リン酸トリブチル（ＴＢＰ）等のリン酸アルキル化合物等が一例として挙げられる。界面調節剤の添加量は適宜設定することができ、通常、有機溶媒に対して１〜５０質量％が好ましく、５〜４０質量％がより好ましい。スカンジウムの溶媒抽出操作は、任意の液液接触装置を用いて、スカンジウムを含む溶液（前記水性懸濁液、又は前記酸性液、又は前記第１水系溶液、又は前記第２水系溶液）と、抽出剤や必要に応じて界面調節剤を含む有機溶媒とを適当な温度で一定時間、公知の手順で液液接触させ、次いで静置分離又は遠心分離によって抽出剤相と液相とに分離することにより行うことができる。液液接触装置としては、例えば遠心抽出機、ミキサー、振とう機、分液漏斗や、多段式の液液接触装置、より具体的には向流のミキサーセトラーが挙げられ、連続法、回分法のいずれであってもよい。また、処理温度は、抽出操作前の各種水系溶液及び抽出剤を含む有機溶媒の温度を保持するように設定することが好ましいが、有機溶媒の引火点、相分離速度、抽出剤相の安定性などの点から、通常、２０〜７０℃に保つのが好ましい。溶媒抽出は１回に限ることはなく、数回に分けて行ってもよい。 An aqueous solution containing scandium and an organic solvent containing an extractant are mixed to extract a complex formed from scandium and the extractant into the organic solvent. A conventionally well-known thing can be used for an extractant, For example, carboxylic acid and / or its salt (Hereinafter, it may be called a carboxylic acid type extractant.) Is preferable. Carboxylic acid is an organic acid having a carboxy group, and examples of the carboxylate include salts such as sodium, potassium, and ammonium, and any salt that forms a complex with scandium can be used. Specifically, known extractants such as neodecanoic acid, versatic acid, naphthenic acid, oleic acid, and lauric acid can be used as the carboxylic acid-based extractant, and naphthenic acid and / or neodecanoic acid are preferred. Used. The ratio of the extractant can be appropriately set, and the ratio of the carboxylic acid-based extractant is preferably 1 to 50% by mass, and more preferably 5 to 20% by mass with respect to the organic solvent. Moreover, in order to suppress that a 3rd phase produces | generates in the interface of an organic phase and an aqueous phase, you may add an interface regulator. Examples of the surface modifier include long chain alkyl compounds such as nonylphenol, 1-decanol, isodecanol, 1-octanol and 2-ethylhexanol, and alkyl phosphate compounds such as tributyl phosphate (TBP). The addition amount of the interfacial modifier can be appropriately set, and is usually preferably 1 to 50% by mass and more preferably 5 to 40% by mass with respect to the organic solvent. The solvent extraction operation of scandium is performed by using any liquid-liquid contact device and extracting a solution containing scandium (the aqueous suspension, the acidic liquid, the first aqueous solution, or the second aqueous solution) and A liquid-liquid contact with an agent and, if necessary, an organic solvent containing a surface modifier at a suitable temperature for a certain period of time by a known procedure, and then separating into an extractant phase and a liquid phase by stationary separation or centrifugation. Can be performed. Examples of the liquid-liquid contact device include a centrifugal extractor, a mixer, a shaker, a separatory funnel, a multistage liquid-liquid contact device, more specifically, a countercurrent mixer settler, a continuous method, a batch method. Any of these may be used. In addition, the treatment temperature is preferably set so as to maintain the temperature of the organic solvent containing various aqueous solutions and the extractant before the extraction operation, but the flash point of the organic solvent, the phase separation rate, and the stability of the extractant phase. From the point of view, it is usually preferable to keep the temperature at 20 to 70 ° C. The solvent extraction is not limited to once, and may be performed in several steps.
有機溶媒としては特段制限なく用いることができ、例えば、トルエン、ベンゼン、キシレン、エチルベンゼン、ジエチルベンゼン、イソプロピルベンゼン、アミルベンゼン、ジアミルベンゼン、アミルトルエン、クロロベンゼン、ブロモベンゼン、ｏ−ジクロロベンゼン、ｏ−クロロトルエン、ｐ−クロロトルエン等の芳香族系炭化水素化合物類；ケロシン、ｎ−ペンタン、ｎ−ヘキサン、イソヘキサン、ｎ−ヘプタン、イソヘプタン、ｎ−オクタン、イソオクタン、ｎ−デカン、ｎ−ドデカン、シクロヘキサン、クロロホルム、テトラクロロメタン、クロロエタン、１，１−ジクロロエタン、１，２−ジクロロエタン、１，１，１−トリクロロエタン、１，１，２−トリクロロエタン、２−クロロプロパン、１，２−ジクロロプロパン、１，２，３−トリクロロプロパン、１−クロロヘキサン、石油エーテル、石油ベンジン、リグロイン、ｎ−パラフィン等の脂肪族系炭化水素化合物類；アイソパー（エクソン モービル コーポレーション社登録商標）、ソルベッソ（エクソン モービル コーポレーション社登録商標）等の工業用希釈剤などが一例として挙げられる。また、これらの有機溶媒は１種又は２種以上を混合して使用してもよい。 The organic solvent can be used without any particular limitation. For example, toluene, benzene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamylbenzene, amyltoluene, chlorobenzene, bromobenzene, o-dichlorobenzene, o-chloro Aromatic hydrocarbon compounds such as toluene and p-chlorotoluene; kerosene, n-pentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, n-dodecane, cyclohexane, Chloroform, tetrachloromethane, chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 2-chloropropane, 1,2-dichloropropane, 1 Aliphatic hydrocarbon compounds such as 2,3-trichloropropane, 1-chlorohexane, petroleum ether, petroleum benzine, ligroin, and n-paraffin; Isopar (registered trademark of Exxon Mobil Corporation), Solvesso (registered by Exxon Mobil Corporation) An example is an industrial diluent such as a trademark. Moreover, you may use these organic solvents 1 type or in mixture of 2 or more types.
前記の抽出したスカンジウムを含むスカンジウム含有有機溶液と水系溶媒とを混合して、スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して、第３水系溶液を得る。逆抽出に用いる水系溶媒は、水又は水に必要に応じてアルコール等の有機溶媒を混合したものであり、有機溶媒の含有量は１０質量％以下程度が好ましい。逆抽出に用いる水系溶媒は、塩酸、硫酸、硝酸等の無機酸、酢酸等の有機酸を用いて酸性にするのが好ましい。スカンジウムの逆抽出操作は、前記の液液接触装置を用いて、有機溶媒と水系溶媒とを適当な温度で一定時間、公知の手順で液液接触させ、次いで静置分離又は遠心分離によって抽出剤相と液相とに分離することにより行うことができる。液液接触装置としては、例えば遠心抽出機、ミキサー、振とう機、分液漏斗や、多段式の液液接触装置、より具体的には向流のミキサーセトラーや遠心抽出機が挙げられ、連続法、回分法のいずれであってもよい。逆抽出は１回に限ることはなく、数回に分けて行ってもよい。また、有機溶媒抽出工程と逆抽出工程は１回に限ることはなく、数回繰り返すことによりスカンジウムの濃度を高めることができるため好ましい。このようにして、有機溶媒抽出工程、逆抽出工程を行うと、スカンジウムの純度は９９.０質量％以上となり、好ましくは９９．５質量％以上とすることができる。 The scandium-containing organic solution containing the extracted scandium and an aqueous solvent are mixed, and the scandium in the scandium-containing organic solution is back-extracted into the aqueous solvent to obtain a third aqueous solution. The aqueous solvent used for the back extraction is water or a mixture of water and an organic solvent such as alcohol as necessary, and the content of the organic solvent is preferably about 10% by mass or less. The aqueous solvent used for back extraction is preferably acidified using an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid. The scandium back-extraction operation is performed by bringing the organic solvent and the aqueous solvent into contact with each other at a suitable temperature for a certain period of time by a known procedure using the above-described liquid-liquid contact device, and then by means of stationary separation or centrifugation. It can be performed by separating into a phase and a liquid phase. Examples of the liquid-liquid contact device include a centrifugal extractor, a mixer, a shaker, a separatory funnel, a multi-stage liquid-liquid contact device, more specifically, a counter-current mixer settler and a centrifugal extractor. Either the method or the batch method may be used. The back extraction is not limited to once, and may be performed in several steps. In addition, the organic solvent extraction step and the back extraction step are not limited to once, and it is preferable because the concentration of scandium can be increased by repeating several times. Thus, when the organic solvent extraction step and the back extraction step are performed, the purity of scandium is 99.0% by mass or more, and preferably 99.5% by mass or more.
（６）第２スカンジウム析出・回収の各工程について（好ましい実施態様４）
前記の（２）〜（５）の各工程で得たスカンジウムを含む溶液（スカンジウム含有水性懸濁液を固液分離した酸性液、又は第１水系溶液、又は第２水系溶液、又はスカンジウム含有有機溶液又は逆抽出した第３水系溶液）と析出剤を含む液（水系溶媒）とを混合しスカンジウムを析出させ、固液分離によりスカンジウムを沈殿物として回収する工程である。例えば、スカンジウム含有有機溶液と析出剤とを混合して、スカンジウムを析出させるのが好ましく、このように有機溶媒抽出工程の後に直ぐに析出工程を行っても、スカンジウムの純度は９９.０質量％以上となり、好ましくは９９．５質量％以上とすることができる。(6) Each step of second scandium precipitation / recovery (preferred embodiment 4)
A solution containing scandium obtained in each of the above steps (2) to (5) (an acid solution obtained by solid-liquid separation of a scandium-containing aqueous suspension, a first aqueous solution, a second aqueous solution, or a scandium-containing organic material) This is a step of mixing a solution or a back-extracted third aqueous solution) and a liquid containing a precipitating agent (aqueous solvent) to precipitate scandium and recovering scandium as a precipitate by solid-liquid separation. For example, it is preferable to mix scandium-containing organic solution and a precipitating agent to precipitate scandium. Thus, even when the precipitation step is performed immediately after the organic solvent extraction step, the purity of scandium is 99.0% by mass or more. And preferably 99.5% by mass or more.
析出剤は、従来公知のものを用いることができ、例えば、カルボン酸及び／又はその塩（以下にカルボン酸系析出剤ということがある）が好ましい。カルボン酸はカルボキシ基を有するカルボン酸であり、カルボン酸塩としてはナトリウム、カリウム、アンモニウム等の塩が挙げられ、スカンジウムを析出するものであれば使用できる。具体的にはカルボン酸系析出剤としてギ酸（メタン酸）、酢酸（エタン酸）、プロピオン酸（プロパン酸）、酪酸（ブタン酸）、吉草酸（ペンタン酸）、カプロン酸（ヘキサン酸）、エナント酸（ヘプタン酸）、カプリル酸（オクタン酸）等の脂肪酸、乳酸（２−ヒドロキシプロパン酸）、リンゴ酸（２−ヒドロキシブタン二酸）、クエン酸（２−ヒドロキシプロパントリカルボン酸）等のヒドロキシ酸、シュウ酸（エタン二酸）、マロン酸（プロパン二酸）、コハク酸（ブタン二酸）グルタル酸（ペンタン二酸）、アジピン酸（ヘキサン二酸）、フマル酸（（Ｅ）−ブタ−２−エン二酸）、マレイン酸（（Ｚ）−ブタ−２−エン二酸）等のジカルボン酸等やそれらの塩を用いることができ、シュウ酸等のジカルボン酸及び／又はその塩が好ましい。析出剤の割合は適宜設定することができ、スカンジウムに対してカルボン酸系析出剤の割合は、１．０〜５．０モルが好ましく、１．５〜３．０モルがより好ましい。スカンジウムの析出操作は、析出装置を用いて、スカンジウムと析出剤とを適当な温度で一定時間、公知の手順で接触させて反応析出させる。得られた沈殿物はカルボン酸スカンジウム等の化合物であり、必要に応じて分別して回収する。分別操作は通常の装置で行うことができ、濾過機、静置分離機、遠心分離機等を用いることができる。回収した沈殿物は、必要に応じて乾燥し、及び／又は焼成すると酸化スカンジウム等の粉末として回収することができるため好ましい。乾燥条件、焼成条件は適宜設定することができ、例えば乾燥温度は８０〜１５０℃程度が適当であり、乾燥時間は１〜２４時間程度が適当である。また、例えば焼成温度は、３００〜１２００℃程度であればよく、焼成時間は１〜２４時間程度が適当である。このようにして、有機溶媒抽出工程、逆抽出工程、カルボン酸析出工程を行うと、スカンジウムの純度は９９.３質量％以上とすることができ、好ましくは９９．７質量％以上、より好ましくは９９．９質量％とすることができる。特にトリウム、ウランを含む水性原液から、高度にスカンジウムを分離することができる。 A conventionally well-known thing can be used for a depositing agent, for example, carboxylic acid and / or its salt (Hereinafter, it may be called a carboxylic acid type depositing agent.) Is preferable. Carboxylic acid is a carboxylic acid having a carboxy group, and examples of the carboxylate include salts such as sodium, potassium, and ammonium, and any salt that precipitates scandium can be used. Specifically, formic acid (methanoic acid), acetic acid (ethanoic acid), propionic acid (propanoic acid), butyric acid (butanoic acid), valeric acid (pentanoic acid), caproic acid (hexanoic acid), enanthate Acids (heptanoic acid), fatty acids such as caprylic acid (octanoic acid), hydroxy acids such as lactic acid (2-hydroxypropanoic acid), malic acid (2-hydroxybutanedioic acid), citric acid (2-hydroxypropanetricarboxylic acid) Oxalic acid (ethanedioic acid), malonic acid (propanedioic acid), succinic acid (butanedioic acid) glutaric acid (pentanedioic acid), adipic acid (hexanedioic acid), fumaric acid ((E) -buta-2 -Endioic acid), maleic acid ((Z) -but-2-enedioic acid) and the like and salts thereof, dicarboxylic acids such as oxalic acid and / or salts thereof are preferred. Arbitrariness. The proportion of the precipitating agent can be appropriately set, and the proportion of the carboxylic acid-based precipitating agent with respect to scandium is preferably 1.0 to 5.0 mol, and more preferably 1.5 to 3.0 mol. For the scandium precipitation, a precipitation apparatus is used to cause scandium and a precipitating agent to come into contact with each other at a suitable temperature for a certain period of time by a known procedure for reaction precipitation. The obtained precipitate is a compound such as scandium carboxylate, and is collected by separation as necessary. The fractionation operation can be performed with a normal apparatus, and a filter, a stationary separator, a centrifuge, or the like can be used. The recovered precipitate is preferably dried and / or calcined as necessary because it can be recovered as a powder of scandium oxide or the like. The drying conditions and firing conditions can be set as appropriate. For example, the drying temperature is suitably about 80 to 150 ° C., and the drying time is suitably about 1 to 24 hours. For example, the firing temperature may be about 300 to 1200 ° C., and the firing time is suitably about 1 to 24 hours. Thus, when the organic solvent extraction step, the back extraction step, and the carboxylic acid precipitation step are performed, the purity of scandium can be set to 99.3% by mass or more, preferably 99.7% by mass or more, more preferably It can be 99.9 mass%. In particular, scandium can be highly separated from an aqueous stock solution containing thorium and uranium.
このようにして回収したスカンジウムが、カルボン酸スカンジウムであれば、それを更に酸に溶解し、ジルコニウム化合物と共沈殿物を形成させ、それを焼成してスカンジア安定化ジルコニアを製造することができる。また、乾燥や焼成して回収した水酸化スカンジウム、酸化スカンジウム等の粉末は、酸化ジルコニウムと混合し焼成してスカンジア安定化ジルコニアを製造することができる。回収したスカンジウムは不純物が少なく純度が高いため、それを用いたスカンジア安定化ジルコニアは固体酸化物燃料電池の電解質に有用である。また、酸化スカンジウムを還元して金属にしたり、ヨウ化してヨウ化スカンジウム等の化合物として用いることもできる。 If the scandium recovered in this manner is scandium carboxylate, it can be further dissolved in an acid to form a coprecipitate with the zirconium compound, which can be calcined to produce scandia-stabilized zirconia. Further, scandia hydroxide and scandium oxide powder recovered by drying or firing can be mixed with zirconium oxide and fired to produce scandia-stabilized zirconia. Since the recovered scandium has few impurities and high purity, scandia-stabilized zirconia using the scandium is useful as an electrolyte for a solid oxide fuel cell. Further, scandium oxide can be reduced to a metal, or iodinated to be used as a compound such as scandium iodide.
以下、本発明を実施例、比較例により説明するが、本発明はそれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to those Examples.
実施例１
チタン鉱石を塩素化した残滓を水に懸濁してｐＨ１未満とし、スカンジウムを溶解させた水性原液１３Ｌを得た（試料Ａ）。次いで、水酸化ナトリウムを混合してｐＨ１．５とし、７０℃で１５分撹拌した後、室温まで冷却してスカンジウムを含む水性懸濁液とし、このスカンジウム含有水性懸濁液を減圧濾過して固形分を取り除き、スカンジウムを含有する酸性液１４Ｌを得た（試料Ｂ）。スカンジウムを含有する酸性液（試料Ｂ）に室温で水酸化ナトリウムを添加してｐＨ４に調整した後、１時間撹拌した。これをヌッチェで減圧濾過して固形分を回収し、ヌッチェに純水を追加して濾過を続け、濾液の導電率が１ｍＳ／ｃｍ未満となるまで固形分の洗浄を行った。Example 1
Residue obtained by chlorinating titanium ore was suspended in water to a pH of less than 1, and 13 L of an aqueous stock solution in which scandium was dissolved was obtained (Sample A). Next, sodium hydroxide is mixed to pH 1.5 and stirred at 70 ° C. for 15 minutes, and then cooled to room temperature to obtain an aqueous suspension containing scandium. The scandium-containing aqueous suspension is filtered under reduced pressure to form a solid The portion was removed to obtain 14 L of an acidic liquid containing scandium (Sample B). Sodium hydroxide was added to an acidic liquid containing scandium (sample B) at room temperature to adjust the pH to 4, followed by stirring for 1 hour. This was filtered under reduced pressure with a Nutsche to recover the solid content, and pure water was added to the Nutsche to continue the filtration, and the solid content was washed until the conductivity of the filtrate was less than 1 mS / cm.
洗浄した固形分を７０％の硫酸に添加して溶解し、最終的にｐＨ０．７となるよう硫酸を用いて微調整して、スカンジウムを含有する水系溶液（第１水系溶液）（試料Ｃ）３Ｌを得た。 An aqueous solution containing scandium (first aqueous solution) (sample C) is prepared by adding the washed solid content to 70% sulfuric acid and dissolving it, and finely adjusting it with sulfuric acid so that the final pH is 0.7. 3 L was obtained.
前記の水性原液と、チタン・ジルコニウム除去後のスカンジウム溶解液（試料Ａ、Ｂ及びＣ）の各元素濃度を誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＡＥＳ若しくはＭＰ−ＡＥＳ）で分析した。その結果を表１に示す。この結果から、本発明の処方で、不純物元素が分離され、スカンジウムを濃縮できることが分かった。 The elemental concentrations of the aqueous stock solution and the scandium solution (samples A, B, and C) after removal of titanium and zirconium were analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES). The results are shown in Table 1. From this result, it was found that the impurity element was separated and scandium could be concentrated in the formulation of the present invention.
実施例２
チタン鉱石を塩素化した残滓を水に懸濁してｐＨ１未満とし、スカンジウムを溶解させた水性原液１０Ｌを得た（試料Ｄ）。次いで、炭酸カルシウムを混合してｐＨ４とし、更に塩酸（１０％）を４０℃で添加してｐＨ１．０とした後、室温まで冷却してスカンジウムを含む水性懸濁液とし、このスカンジウム含有水性懸濁液を減圧濾過して固形分を取り除き、スカンジウムを含有する酸性液１５Ｌを得た（試料Ｅ）。スカンジウムを含有する酸性液（試料Ｅ）に室温で水酸化カルシウムを添加してｐＨ４に調整した後、１時間撹拌した。これをヌッチェで減圧濾過して固形分を回収し、ヌッチェに純水を追加して濾過を続け、濾液の導電率が１ｍＳ／ｃｍ未満となるまで固形分の洗浄を行った。Example 2
The residue obtained by chlorinating titanium ore was suspended in water to a pH of less than 1 to obtain 10 L of an aqueous stock solution in which scandium was dissolved (sample D). Next, calcium carbonate is mixed to pH 4, and hydrochloric acid (10%) is added at 40 ° C. to pH 1.0, and then cooled to room temperature to obtain an aqueous suspension containing scandium. The turbid liquid was filtered under reduced pressure to remove solids, and 15 L of acidic liquid containing scandium was obtained (Sample E). After adjusting the pH to 4 by adding calcium hydroxide to an acidic solution (sample E) containing scandium at room temperature, the mixture was stirred for 1 hour. This was filtered under reduced pressure with a Nutsche to recover the solid content, and pure water was added to the Nutsche to continue the filtration, and the solid content was washed until the conductivity of the filtrate was less than 1 mS / cm.
洗浄した固形分を塩酸に添加して溶解し、最終的にｐＨ０．７となるよう塩酸を用いて微調整して、スカンジウムを含有する水系溶液（第１水系溶液）（試料Ｆ）１Ｌを得た。 The washed solid content is added to hydrochloric acid to be dissolved, and finely adjusted with hydrochloric acid so that the final pH is 0.7, thereby obtaining 1 L of an aqueous solution (first aqueous solution) (sample F) containing scandium. It was.
前記の水性原液と、チタン・ジルコニウム除去後のスカンジウム溶解液（試料Ｄ、Ｅ及びＦ）の各元素濃度を誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＡＥＳ若しくはＭＰ−ＡＥＳ）で分析した。その結果を表２に示す。この結果から、本発明の処方で、不純物元素が分離され、スカンジウムを濃縮できることが分かった。 The elemental concentrations of the aqueous stock solution and the scandium solution (samples D, E, and F) after removal of titanium and zirconium were analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES). The results are shown in Table 2. From this result, it was found that the impurity element was separated and scandium could be concentrated in the formulation of the present invention.
キレート樹脂によるスカンジウム濃縮処理への影響
前記の方法によってスカンジウムと共存する不純物を低減することで、キレート樹脂や溶媒抽出などの公知の分離工程の効率が向上する。一例としてキレート樹脂へのスカンジウム吸着特性を実施例３に示す。Effect of chelate resin on scandium concentration treatment By reducing impurities coexisting with scandium by the above-described method, the efficiency of known separation processes such as chelate resin and solvent extraction is improved. As an example, the scandium adsorption property to the chelate resin is shown in Example 3.
実施例３
実施例２で得た、スカンジウム含有水系溶液（第１水系溶液）（試料Ｆ）と、公知のキレート樹脂（官能基：アミノリン酸）とを表３に示す体積比で密閉容器に入れ、２４時間ボトルローラーで混合してスカンジウム等の吸着を行った。吸着処理後に溶液とキレート樹脂を分離し、溶液中のスカンジウム濃度を、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＡＥＳ若しくはＭＰ−ＡＥＳ）で分析した。吸着処理の前後の溶液のスカンジウム濃度から、キレート樹脂１Ｌあたりのスカンジウム吸着容量を算出した。その結果を表３に示す。Example 3
The scandium-containing aqueous solution (first aqueous solution) (sample F) obtained in Example 2 and a known chelate resin (functional group: aminophosphoric acid) were placed in a sealed container at a volume ratio shown in Table 3 for 24 hours. Mixing with a bottle roller adsorbed scandium and the like. After the adsorption treatment, the solution and the chelate resin were separated, and the scandium concentration in the solution was analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES). The scandium adsorption capacity per liter of the chelate resin was calculated from the scandium concentration of the solution before and after the adsorption treatment. The results are shown in Table 3.
本発明のチタン・ジルコニウム分離後のスカンジウム溶解液が、公知の各種キレート樹脂を用いた精製処理に広く適用できることを確認するため、公知の各種キレート樹脂への適用試験を実施例４で行った。 In order to confirm that the scandium solution after separation of titanium and zirconium of the present invention can be widely applied to purification treatments using various known chelating resins, an application test to various known chelating resins was conducted in Example 4.
実施例４
実施例２において、試料Ｄに代えて、スカンジウム、チタン、ジルコニウム等を溶解させた水性原液（試料Ｇ、ｐＨ１未満）を用いたこと以外は実施例２と同様にして、スカンジウム含有酸性液（試料Ｈ）を得た。尚、試料Ｈは、ｐＨ調整によるスカンジウムの析出、濾過、洗浄、酸への再溶解の工程を経ていないものであり、実施例２に記載の試料Ｅに対応する。Example 4
In Example 2, a scandium-containing acidic solution (sample) was used in the same manner as in Example 2 except that an aqueous stock solution (sample G, pH less than 1) in which scandium, titanium, zirconium and the like were dissolved was used instead of sample D. H) was obtained. Sample H does not go through the steps of scandium precipitation by pH adjustment, filtration, washing, and re-dissolution in acid, and corresponds to Sample E described in Example 2.
次いで、試料Ｈと表４に示した公知の各種キレート樹脂とを、体積比率２０：１で密閉容器に入れ、２４時間ボトルローラーで混合してスカンジウム等の吸着を行った（試料Ｉ、Ｊ、Ｋ）。吸着処理後に溶液とキレート樹脂を分離し、溶液中のスカンジウム濃度を、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＡＥＳ若しくはＭＰ−ＡＥＳ）で分析した。吸着処理の前後の溶液のスカンジウム濃度から、キレート樹脂１Ｌあたりのスカンジウム吸着容量を算出した。その結果を表５に示す。 Next, sample H and various known chelate resins shown in Table 4 were placed in a sealed container at a volume ratio of 20: 1 and mixed with a bottle roller for 24 hours to adsorb scandium or the like (samples I, J, K). After the adsorption treatment, the solution and the chelate resin were separated, and the scandium concentration in the solution was analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES). The scandium adsorption capacity per liter of the chelate resin was calculated from the scandium concentration of the solution before and after the adsorption treatment. The results are shown in Table 5.
比較例１
実施例２で本発明の分離処理を行っていない、スカンジウム水性原液（試料Ｄ）と、公知のキレート樹脂（官能基：アミノリン酸、実施例３で使用したものと同じ）とを表６に示す体積比で密閉容器に入れ、２４時間ボトルローラーで混合してスカンジウム等の吸着を行った。吸着処理後に溶液とキレート樹脂を分離し、溶液中のスカンジウム濃度を、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＡＥＳ若しくはＭＰ−ＡＥＳ）で分析した。吸着処理の前後の溶液のスカンジウム濃度から、キレート樹脂１Ｌあたりのスカンジウム吸着容量を算出した。その結果を表６に示す。Comparative Example 1
Table 6 shows the scandium aqueous stock solution (sample D) not subjected to the separation treatment of the present invention in Example 2 and a known chelate resin (functional group: aminophosphoric acid, the same as that used in Example 3). It put into the airtight container by volume ratio, and mixed with the bottle roller for 24 hours, and adsorb | sucked scandium etc. was performed. After the adsorption treatment, the solution and the chelate resin were separated, and the scandium concentration in the solution was analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES). The scandium adsorption capacity per liter of the chelate resin was calculated from the scandium concentration of the solution before and after the adsorption treatment. The results are shown in Table 6.
キレート樹脂を用いた濃縮処理では、目標となる元素（ここではスカンジウム）の樹脂への最大吸着量が、濃縮効率を示す一つの指標となる。実施例３と比較例１のスカンジウム吸着等温線を図１に示す。実施例３では、スカンジウム吸着量は最大で２．８ｇ／ＬＲＥＳＩＮを示しており、接触させるスカンジウム含有水系溶液（第１水系溶液）の量を増すことで、更に吸着量が向上する傾向を示している。一方比較例１より、本発明のチタン、ジルコニウム除去工程を行わないと、スカンジウム吸着容量は０．１ｇ／ＬＲＥＳＩＮで飽和している。これは、スカンジウムと選択性の低い吸着種（チタンやジルコニウム）が多量に含まれるために、キレート樹脂へのスカンジウム吸着を阻害することによる。In the concentration treatment using a chelate resin, the maximum adsorption amount of the target element (here, scandium) to the resin is one index indicating the concentration efficiency. The scandium adsorption isotherms of Example 3 and Comparative Example 1 are shown in FIG. In Example 3, the maximum amount of scandium adsorbed was 2.8 g / L RESIN. By increasing the amount of scandium-containing aqueous solution (first aqueous solution) to be brought into contact, the amount of adsorption was further improved. ing. On the other hand, from Comparative Example 1, the scandium adsorption capacity is saturated at 0.1 g / L RESIN unless the titanium and zirconium removal step of the present invention is performed. This is because scandium and a low-selectivity adsorption species (titanium and zirconium) are contained in a large amount, thereby inhibiting scandium adsorption on the chelate resin.
また、表５の結果から試料Ｉ、Ｊ、Ｋの３種の樹脂１ＬあたりのＳｃ吸着容量は何れも０．２ｇ／ＬＲＥＳＩＮ以上となった。これは比較例１に示した吸着容量０．１ｇ／ＬＲＥＳＩＮに比べて十分高く、本発明のチタン・ジルコニウム分離工程が、様々なキレート樹脂を用いた精製処理への適用が可能であり、且つ、精製効率の向上に寄与することを示している。Further, from the results of Table 5, the Sc adsorption capacity per 1 L of the three types of resins of Samples I, J, and K was 0.2 g / L RESIN or more. This is sufficiently higher than the adsorption capacity of 0.1 g / L RESIN shown in Comparative Example 1, and the titanium / zirconium separation step of the present invention can be applied to purification treatments using various chelate resins. This indicates that it contributes to the improvement of purification efficiency.
なお、キレート樹脂に接触させ、スカンジウムを吸着させた後に、吸着したスカンジウムを水系溶媒に溶離する工程（溶離工程）、更に、前記の各工程で得たスカンジウムを含む水性懸濁液又は酸性液又は各種水系溶液を、抽出剤を含む有機溶媒に接触させ、スカンジウムを有機溶媒に抽出させる工程（有機溶媒抽出工程）、次いで、水系溶媒に逆抽出する工程（逆抽出工程）、更に、前記の各工程で得たスカンジウムを含む酸性液又は各種水系溶液又はスカンジウム含有有機溶液と、析出剤を含む水系溶媒とを接触させ、スカンジウムを析出させ、次いで、固液分離する工程（第２スカンジウム析出・回収工程）を選択的に行うことにより、スカンジウムの純度を更に高めていくことができることを確認した。 In addition, after making the chelate resin contact and adsorbing scandium, a step of eluting the adsorbed scandium into an aqueous solvent (elution step), and further, an aqueous suspension or acidic liquid containing scandium obtained in each of the above steps or Various aqueous solutions are brought into contact with an organic solvent containing an extractant and scandium is extracted into the organic solvent (organic solvent extraction step), then back extracted into the aqueous solvent (back extraction step), A step of contacting the acidic liquid or various aqueous solutions or scandium-containing organic solutions obtained in the step with an aqueous solvent containing a precipitating agent to precipitate scandium, followed by solid-liquid separation (second scandium precipitation / recovery It was confirmed that the purity of scandium can be further increased by selectively performing the step (step).
本発明の方法で回収したスカンジウムは濃縮されており、且つチタン、ジルコニウム等の不純物が低減できていることから、このような粗スカンジウム液から種々の精製プロセスを適用して高純度のスカンジウムを得るのに好適である。 Since scandium recovered by the method of the present invention is concentrated and impurities such as titanium and zirconium can be reduced, high purity scandium is obtained by applying various purification processes from such crude scandium liquid. It is suitable for.
Claims (17)
前記水性原液に酸又はアルカリを混合してｐＨを１．０〜２．０の範囲に調整することにより、スカンジウムを液相に含み、チタン及びジルコニウムを固相に含む、スカンジウム含有水性懸濁液を得る工程とを備えるスカンジウムの分離方法。Preparing an aqueous stock solution containing at least scandium, titanium, and zirconium;
A scandium-containing aqueous suspension containing scandium in the liquid phase and titanium and zirconium in the solid phase by adjusting the pH to a range of 1.0 to 2.0 by mixing acid or alkali with the aqueous stock solution. And a method for separating scandium.
固液分離により、析出したスカンジウムを分離する工程とをさらに備える、請求項１に記載のスカンジウムの分離方法。A step of precipitating scandium by adjusting the pH to a range of 3.5 to 7.0 by mixing an alkali with an acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension to remove titanium and zirconium. When,
The method for separating scandium according to claim 1, further comprising a step of separating precipitated scandium by solid-liquid separation.
前記キレート樹脂に吸着したスカンジウムを水系溶媒に溶離して第２水系溶液を得る工程とをさらに備える、請求項２に記載のスカンジウムの分離方法。A step of adsorbing scandium to the chelate resin by bringing the first aqueous solution in which the precipitated scandium is dissolved into contact with the chelate resin;
The method for separating scandium according to claim 2, further comprising a step of eluting scandium adsorbed on the chelate resin into an aqueous solvent to obtain a second aqueous solution.
前記キレート樹脂に吸着したスカンジウムを水系溶媒に溶離して第２水系溶液を得る工程とをさらに備える、請求項１に記載のスカンジウムの分離方法。A step of adsorbing scandium to the chelate resin by contacting the scandium-containing aqueous suspension or an acidic liquid obtained by solid-liquid separation of the suspension and the chelate resin;
The method for separating scandium according to claim 1, further comprising a step of eluting the scandium adsorbed on the chelate resin into an aqueous solvent to obtain a second aqueous solution.
前記スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第３水系溶液を得る工程とをさらに備える、請求項１に記載のスカンジウムの分離方法。A step of extracting scandium into the organic solvent to obtain a scandium-containing organic solution by contacting the scandium-containing aqueous suspension or an acidic liquid obtained by solid-liquid separation of the suspension and an organic solvent containing an extractant; and
The scandium separation method according to claim 1, further comprising a step of back-extracting scandium in the scandium-containing organic solution into an aqueous solvent to obtain a third aqueous solution.
前記スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第３水系溶液を得る工程とをさらに備える、請求項２に記載のスカンジウムの分離方法。A step of extracting scandium into the organic solvent to obtain a scandium-containing organic solution by contacting the first aqueous solution in which the precipitated scandium is dissolved and an organic solvent containing an extractant;
The method for separating scandium according to claim 2, further comprising a step of back-extracting scandium in the scandium-containing organic solution into an aqueous solvent to obtain a third aqueous solution.
前記スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第３水系溶液を得る工程とをさらに備える、請求項３又は４に記載のスカンジウムの分離方法。Contacting the eluted second aqueous solution containing scandium with an organic solvent containing an extractant to extract scandium into the organic solvent to obtain a scandium-containing organic solution;
The scandium separation method according to claim 3 or 4, further comprising a step of back-extracting scandium in the scandium-containing organic solution into an aqueous solvent to obtain a third aqueous solution.
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項１に記載のスカンジウムの分離方法。A step of precipitating scandium by contacting an acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension and an aqueous solvent containing a precipitation agent;
The method for separating scandium according to claim 1, further comprising a step of recovering scandium by solid-liquid separation.
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項２に記載のスカンジウムの分離方法。A step of precipitating scandium by bringing the first aqueous solution in which the precipitated scandium is dissolved into contact with an aqueous solvent containing a precipitating agent;
The method for separating scandium according to claim 2, further comprising a step of recovering scandium by solid-liquid separation.
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項３又は４に記載のスカンジウムの分離方法。A step of precipitating scandium by bringing the second aqueous solution containing the eluted scandium into contact with an aqueous solvent containing a precipitating agent;
The method for separating scandium according to claim 3, further comprising a step of recovering scandium by solid-liquid separation.
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項５〜７のいずれか１項に記載のスカンジウムの分離方法。A step of precipitating scandium by bringing the scandium-containing organic solution extracted from the scandium into contact with an aqueous solvent containing a precipitating agent;
The method for separating scandium according to claim 5, further comprising a step of recovering scandium by solid-liquid separation.
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項８〜１０のいずれか１項に記載のスカンジウムの分離方法。A step of precipitating scandium by contacting a third aqueous solution back-extracted with the scandium and an aqueous solvent containing a precipitating agent;
The method for separating scandium according to any one of claims 8 to 10, further comprising a step of recovering scandium by solid-liquid separation.
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| JP6900677B2 (en) * | 2017-01-11 | 2021-07-07 | 住友金属鉱山株式会社 | How to make scandium oxide |
| JP6666288B2 (en) * | 2017-03-13 | 2020-03-13 | Ｊｘ金属株式会社 | Rare metal recovery method |
| CN112041043B (en) * | 2018-05-07 | 2022-09-13 | 力拓铁钛加拿大公司 | Process for flushing metal contaminants from an acidic scandium-containing solution |
| CN110541081A (en) * | 2019-09-02 | 2019-12-06 | 中国恩菲工程技术有限公司 | method for treating laterite-nickel ore |
| JP7463181B2 (en) | 2020-04-22 | 2024-04-08 | Ｊｘ金属株式会社 | How to recover rare metals |
| CN113584327B (en) * | 2021-06-28 | 2022-10-28 | 中国恩菲工程技术有限公司 | Method for purifying scandium oxide |
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| AU2015310078A1 (en) | 2017-02-02 |
| CN106460092B (en) | 2018-09-28 |
| WO2016031699A1 (en) | 2016-03-03 |
| TW201615846A (en) | 2016-05-01 |
| CN106460092A (en) | 2017-02-22 |
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