CN1026016C - 从矿石萃取钪的方法 - Google Patents
从矿石萃取钪的方法 Download PDFInfo
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- CN1026016C CN1026016C CN89109624A CN89109624A CN1026016C CN 1026016 C CN1026016 C CN 1026016C CN 89109624 A CN89109624 A CN 89109624A CN 89109624 A CN89109624 A CN 89109624A CN 1026016 C CN1026016 C CN 1026016C
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- scandium
- resistates
- lanthanon
- organic phase
- yttrium
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- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 87
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 19
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 claims abstract description 6
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011260 aqueous acid Substances 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 20
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 20
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 17
- 229910052776 Thorium Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- -1 poly-alkyl phosphate Chemical compound 0.000 claims description 10
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012808 vapor phase Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 150000003325 scandium Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000004576 sand Substances 0.000 abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 2
- 239000012071 phase Substances 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- 150000002910 rare earth metals Chemical class 0.000 description 11
- 229910052705 radium Inorganic materials 0.000 description 10
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002925 low-level radioactive waste Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- 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 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- QFFMXYURYVMWLF-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].[Zr+4].[Hf+4] Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Zr+4].[Hf+4] QFFMXYURYVMWLF-UHFFFAOYSA-J 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000010423 industrial mineral Substances 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/10—Roasting processes in fluidised form
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/212—Scandium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/218—Yttrium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
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- C22B1/08—Chloridising roasting
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
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- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/32—Carboxylic acids
- C22B3/322—Oxalic acids
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- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
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Abstract
从锆英石萃取钪的方法，将锆英石砂送入一个约1000℃的流态化床氯化器，以产生一个蒸汽相(主要是氯化锆和氯化硅)和固态残余物，并从该固态残余物回收钪。即用酸的水溶液(例如HCl)浸出该残余物而形成含钪水溶液，接着使该水溶液与含辛烷基磷酸酯的有机相接触，聚烷基磷酸酯(例如磷酸三丁酯)将钪萃取到该有机相中，接着通过加入铵形成氢氧化钪沉淀使钪析出，焙烧该氢氧化钪，从而钪以氧化物形式被回收。
Description
本发明涉及从矿石萃取钪的方法。显然从来没有从锆英石矿石回收过钪。虽然存在钪矿石，但正如美国专利说明书2874039（Pruvot等人）所指出，这种矿石是稀少的，该美国专利说明书公开了一种从钪钇石矿石萃取钪的方法。在美国专利说明书2722471（Hirsch等人）、2812233（Duncan）和273547（Kasey）中论述了通过浸出（包括在一种情况下用盐酸）从矿石分离稀土的方法。在美国专利说明书2990244（Brown等人）、3159452（Lerner）和3087948（Carter等人）中论述了从钍（在一种情况下包含在酸浸出液中）分离稀土。在美国专利说明书2941867（Maurer）中论述了由钪氯化物还原成金属。
锆英石矿石被用于生产金属锆。通常使用下列操作使锆英石矿（锆英石矿）转变成金属锆：氯化、分离（以除去）、再氯化（按照类似最初氯化的方法）、还原、蒸馏（为了从锆中除去氯化镁和镁将其汽化）和两次（或三次）电弧熔炼，以形成锭。然后可以将锆锭加工成不同的形状。
不考虑氯化，美国专利说明书4244935（Dell）公开了一种利用液态焦化技术形成含金属一氧化物质的氯化物的方法。应该注意的是，用于
制取金属锆的工业方法是利用一种约1000℃的流态化床碳氯化过程（横断该床的温度变化显然达200℃左右），该方法生产一种比较不纯的含铪的四氯化锆和副产物四氯化硅（该四氯化硅富产物利用梯度冷凝较容易分离）。美国专利说明书3895097（Langenhoff等人）也公开了一种使金属氧化物与氯反应的方法。
由于天然存在的锆矿石通常含通常含1-3%的氧化铪（相对于氧化锆），所以分离步骤是需要的。为了使金属锆符合作为核反应堆材料的要求，铪含量必须首先降至低水平，以使高的分子吸收截面的作用减至最小程度。由于这两种元素的化学性十分相似，因此这种分离过程是困难的。为了实现这种分离已经研究出一些技术，在美国普遍使用的技术包括利用甲基·异丁基酮对氧化氧锆的硫氰酸盐络合物水溶液进行液-液萃取（通常如美国专利说明书2938679（Overholser）所述），同时如美国专利说明书3006719（Miller）所述，在溶剂萃取之前除去铁杂质。
工业上通过使气态四氯化锆与熔融镁反应进行还原生成金属锆（为较多孔的通常所说的“海绵”状）。在例如美国专利说明书4440384、4511399、4556420、461336、4613366、4637831和4668287中已经提出关于该还原方法的改进。
关于从海绵锆去除氯化镁和镁（借助它们的汽化）的“蒸馏”通常在约1050-1100℃下进行（注意，但是美国专利说明书4711644（Kwon等人）指出通过在约934℃下蒸馏可以降低铁含量）。
通常利用自耗电极真空电弧熔炼从多孔蒸馏海绵制成凝固锭（通常破碎蒸馏的海绵，然后将其压制成圆片，以后例如将这些圆片焊接在一起而形成自耗电极）。美国专利说明书4539688（Weber）公开了一种改进的自耗电极。
当然，希望从废流中回收物质。例如，美国专利说明书4650652（Naitou等人）叙述了一种从废稀土磷中回收高纯稀土氧化物的方法（该方法利用废稀土磷溶解在过量酸中，然后添加草酸而得到稀土草酸盐沉淀物，冲洗并烘干这种沉淀物）。
按照本发明，一种用于从矿石萃取钪的方法包括将锆英石砂送入一个800-1250℃的流态化床氯化器，以形成主要含氯化锆和氯化硅的蒸汽相以及固态残余物，而回收的富集在该固态残余物中的钪。
存在于锆英石矿石中的极低量的钪富集在残余物中使能够经济而方便地从锆英石矿石回吸钪。
最好该方法是生产金属锆的一部分，从而钪是锆生产一种副产物。
通常钪主要是以氯化钪形式存在于残余物中，而从该残余物中回收氯化钪最好如此进行，即用酸的水溶液（例如盐酸）浸出该残余物，以形成一种含钪水溶液，然后使所产生的水溶液与一种含聚烷基磷酸酯的有机相接触，该聚烷基磷酸酯（例如磷酸三丁酯）将钪萃取到有机相中。然后可以通过加入铵使钪沉淀而形成氢氧化钪沉淀物，焙烧氢氧化钪，以使钪能以一种氧化物形式被回收。
本发明还包括一种从锆英石砂提取锆和钪的方法，该方法包括将锆英石砂送入一个800-1250℃的流态化床氯化器，以使氯化锆和氯化硅从锆英石砂中挥发并形成一种含钪化合物和其他固体颗粒的残余物，从残余物的其他固体颗粒中分离出钪化合物，收集氯化锆以及处理氯化锆，以生产金属锆。
通常该残余物也含有钇和镧系元素，而钇和镧系元素也可以从该残余物中回收，所用方法或者是通过用酸浸出钇和镧系元素，从而，与钪一起进入含钪水溶液（在这种情况下，通过加入铵，钇和镧系元素可以与钪一起沉淀，焙烧钇和镧系元素并与钪一起回收），或者是通过水溶液与一种含聚烷基磷酸酯的有机相接触而生成含钪有机相和含钇和镧系元素的含水相。在后一种情况下，通过焙烧该有机相，钪以氧化物形式被回收，而通过早独焙烧含水相，钇和镧系元素以氧化物形式也被回收。
通过用醇（最好走甲醇）浸出该残余物而生成一种含钪的醇溶液，也可以从该残余物中回收氯化钪。然后所留下的残余物可以再返回氯化器。通常，在用醇浸出后，可以将该醇溶液与草酸接触，以沉淀出钪、钍和镧系元素的草酸盐，于是得到纯化的钪、钍和镧系元素的氯化物。可以蒸馏该醇并再返回到浸出步骤。
为了能更清楚地了解本发明，下面将通过实施例并参照附图描述本发明的一个合适的具体实施方案，附图是一个萃取方法流程图，在流程图中使用水溶液浸出并从镧系元素中分离回收钪。
如上所述，钪矿石是比较稀少的。钪通常存在镧系元素矿石中（术语“稀土”通常用于镧系元素，
而这个术语有时作为包括钇而使用，而偶尔也作为包括钪而使用，按照本文的使用，“稀土”将习惯包括钇，但不包括钪）。然而，在稀土矿石中显然没有发现钪的大量富集并且显然从来没有在任何矿床中发现大量钪。钪的缺乏已导致很高的价格，这就限制钪的应用。
与许多其他工业矿物相比，锆英石砂是相当纯的矿物。全部杂质含量仅约1%（锆英石砂是约99%二氧化锆、二氧化铪和二氧化硅）。所存在的杂质大多数具有挥发性氯化物并与锆-铪四氯化物和四氯化硅一起进入蒸汽流。约2000ppm的杂质不具有挥发性氯化物并富集在矿石氯化器（一般称为初始氯化器”）的残余物中。非挥发性氯化物通常是碱金属的，例如钠的，碱土金属的，例如钙的和稀土金属的氯化物。意想不到的是，尽管有1000℃的氯化器标称操作温度和800-850℃的氯化钪纯化温度，但大部分钪最终归于非挥发性残余物中。还应当注意的是，即使在低于800℃时，氯化钪应具有大的蒸汽压，然而不清楚为什么氯化钪保留在残余物中，也许通过与某种其他非挥发性氯化物形成某种复盐而降低了氯化钪的蒸汽压。
应该注意的是，在氯化器条件下钍是非挥发性的，而钍及其衰变产物镭也聚集在带有镭的残余物中，使该残余物具有每克约为4000微微居里的放射性。由于分离矿石主要部分的浓缩作用，物料中的钍和镭含量应是这样的，即应使所得残余物必须作为低水平放射性废物进行处理。
在上述流态化床氯化器操作中，必须防止汽态化床聚集超过约10%的非挥发性氯化物，因为这些氯化物在氯化器温度下通常是液态的，流化床会变成“粘性的”，并且由于盐的聚集将不能完全“流态化”。为氯化器由于非挥发性氯化物聚集而停止运转时，流化床通常含约70%焦炭、20%锆英石和10-12%非挥发性氯化物。过去上述残余物的处理费用已超过100000美元。如果停止运转时该床全部是非挥发性物质，则可能有500∶1的浓度，但是当仅有10-12%的非挥发性物质时，该浓度约是50∶1-60∶1。
虽然分析结果表明残余的钪含量仅是约0.0065%，但本发明的计算表明，如果钪归于残余物，则钪应该约占残余物的0.4%使用本发明方法对钪作试验性分离，回收了约占残余物0.34%的钪。因为残余物也含有稀土（镧系元素和钇，尤其是镥和铥），所以这些元素也可以收回收钪的副产物形式从该残余物中被回收。另外，在为了回收钪（并且通常也回收稀土）而对残余物进行处理的过程中，最好也除去钍和镭，以便既防止它们进入产物也避免放射性残余物处理的问题。
下面将参照实施例举例说明本发明，其中实施例1包括残余物浸出和形成四股合钪、稀土、镭和钍的分离流，而实施例2仅形成两股流，第一股带有镭，而第二股带有钪、钇、镧系元素和钍。
实施例1
按照通用的方法（标称1000℃）氯化锆英石砂，如此获得的初始氯化器的残余物，用6摩尔浓度的HCl、在没有外部加热的条件下浸出24小时（1Kg残余物/1升6摩尔浓度的HCl）。过滤该浸出的溶液。在120℃下烘干沥滤出的固体颗粒并返回到氯化系统。用0.001摩尔浓度的BaCl2和0.001摩尔浓度的H2SO4处理该浸出溶液。过滤该溶液，以除去以在BaSO4上形式存在的镭。使过滤出的溶液与TBP（磷酸三丁酯）接触，以选择性地萃取钪。用0.1摩尔浓度的HCl反萃取TBP溶液。使贫钪的含水相与TOPO（三辛基氧磷）/乙烷接触，以选择性地萃取钍。用0.1摩尔浓度的HCl反萃取钍。这些萃取物可以单独分开或递流，这取决于所要求的分离程度。剩下的无钪、钍和镭，但含有镧系元素和钇的溶液用NH3（水）处理至pH值为10并过滤，在600℃焙烧镧系元素的氢氧化物，以得到氧化物。钍和镭的反萃取物同样也随镧系元素溶液转变成氧化物。钪样品是大于99%的纯SC2O3并占残余物重量的0.34%，唯一的附图是这个实施例的流程图。
实施例2
按照实施例1通过过滤BaSO4可以得到钪、钇镧系元素和钍的混合氧化物。用氨水将过滤出的溶液处理至pH值为10，然后过滤并在600℃焙烧混合的氢氧化物。
虽然使用这种方法能够从锆英石矿石中回收钪，但是，当然最好作为生产金属锆工序的一部分来进行，同时伴随钪从初始氧化器的残余物中回收（这种残余物已经在低水平放射性废物处理点预先进行处理）。最好稀土、钍和镭作为附带副产物而分别回收。因此，本方法将通过将放射性元素集中
成小体积商品形式以降低残余物去除的费用，将允许残余物的某些组分（碳和锆英石，在没有“粘性的”非挥发性氯化物时，如果是通过醇浸出进行分离，则氯化锆也被返回）返回到初始氢氧化器的供料中，并且将回收具有重大价值的副产物（尤其是钪、和铥，它们通常以氧化物形式分别约占残余物重量的0.4%、0.25%和0.2%）。
Claims (14)
1、一种从矿石萃取钪的方法，其特征在于，将含钪锆英石矿石送入一个800-1250℃的流态化床氯化器，以形成主要含氯化锆和氯化硅的蒸汽相及固态含钪残余物，并回收富集在该固态残余物中的钪化合物。
2、按照权利要求1的方法，其特征在于，将所说的蒸汽相从含钪残余物中分离后再将蒸汽相氯化锆与蒸汽相氯化硅分开，然后将氯化锆加工成金属锆，在此钪是锆生产的副产物。
3、按照权利要求1或2的方法，其特征在于，钪主要以氯化钪形式存在于残余物中，通过用酸的水溶液浸出该残余物而形成含钪水溶液，从该残余物中回收氯化钪。
4、按照权利要求3的方法，其特征在于，所说的酸是盐酸。
5、按照权利要求3的方法，其特征在于，用酸浸出后接着将该水溶液与含聚烷基磷酸酯的有机相接触，该聚烷基磷酸酯将钪离子萃取到该有机相中。
6、按照权利要求5的方法，其特征在于，有机相中的聚烷基磷盐酯是磷酸三丁酯。
7、按照权利要求5或6的方法，其特征在于，在钪萃取到上述有机相中之后，通过加入铵而形成氢氧化钪沉淀来沉淀出钪，将该氢氧化钪焙烧，由此钪以氧化物形式被回收。
8、按照权利要求2的方法，其特征在于，钪主要以氯化钪形式存在于残余物中，通过用醇浸出该残余物而形成含钪醇溶液，从该残余物中回收氯化钪。
9、按照权利要求8的方法，其特征在于，所说的醇是甲醇，并且所剩下的残余物返回到氯化器中。
10、按照权利要求8和9的方法，其特征在于，用醇浸出后接着将该醇溶液与草酸接触而生成钪、钍和镧系元素的草酸盐沉淀，并在该醇溶液中保留锆、硅和铁的氯化物，由此得到纯的钪、钍和镧系元素的氯化物。
11、按照权利要求2的方法，其特征在于，钪以氯化钪形式存在于残余物中，通过用酸浸滤该残余物而形成水溶液，以使上述氯化钪与其它固体颗粒分离，接着使该溶液与有机相接触而将钪萃取到该有机相中，继而焙烧上述萃取的钪，从而钪以氧化物形式被回收。
12、按照权利要求11的方法，其特征在于，该残余物中也含有钇和镧系元素，它们也从残余物中进行回收。
13、按照权利要求12的方法，其特征在于，钇和镧系元素借助酸与钪一起被浸出到含钪水溶液中，通过加入铵使钇和镧系元素与上述钪一起沉淀成为混合氢氧化物，焙烧上述钇和镧系元素混合氢氧化物并与上述钪一起回收。
14、按照权利要求12的方法，其特征在于，钇和镧系元素借助酸与钪一起被浸出到含上述钪的水溶液中，接着使该水溶液与含聚烷基磷酸酯的有机相接触，形成含钪的有机相和含钇和镧的含水相，然后焙烧被萃取的钪，由此钪以氧化物形式被回收，继而焙烧该含水相，从而钇和镧系元素以氧化物形式被回收。
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| EP2802675B1 (en) * | 2012-01-10 | 2020-03-11 | Orbite Aluminae Inc. | Processes for treating red mud |
| JP2015518414A (ja) | 2012-03-29 | 2015-07-02 | オーバイト アルミナ インコーポレイテッドＯｒｂｉｔｅ Ａｌｕｍｉｎａｅ Ｉｎｃ． | フライアッシュ処理プロセス |
| JP5403115B2 (ja) * | 2012-06-19 | 2014-01-29 | 住友金属鉱山株式会社 | スカンジウムの分離精製方法 |
| RU2597096C2 (ru) | 2012-07-12 | 2016-09-10 | Орбит Алюминэ Инк. | Способы получения оксида титана и различных других продуктов |
| US9163297B2 (en) | 2012-08-07 | 2015-10-20 | Justin Langley | Method for the integration of carbochlorination into a staged reforming operation as an alternative to direct residue oxidation for the recovery of valuable metals |
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| CA2891427C (en) | 2012-11-14 | 2016-09-20 | Orbite Aluminae Inc. | Methods for purifying aluminium ions |
| US9970078B2 (en) | 2012-12-17 | 2018-05-15 | Element 21 Pty Limited | Method for producing a solid scandium-containing material of enhanced scandium content |
| CN103436700B (zh) * | 2013-08-19 | 2014-06-18 | 连云港市丽港稀土实业有限公司 | 一种用复合萃取剂从钛氯化烟尘和熔盐氯化渣中提取钪的方法 |
| JP5884840B2 (ja) * | 2014-01-27 | 2016-03-15 | 住友金属鉱山株式会社 | スカンジウム塩化物及びスカンジウム酸化物の製造方法 |
| AU2016200868B2 (en) | 2015-02-10 | 2021-05-13 | Scandium International Mining Corporation | Systems and processes for recovering scandium values from laterite ores |
| CA2993331C (en) * | 2015-07-21 | 2022-07-12 | Hazen Research, Inc. | Recovery of rare earths from concentrates containing fluorine |
| CN107082443B (zh) * | 2017-04-21 | 2019-03-01 | 山西城市动力新能源有限公司 | 一种固体燃料电池用氧化钪的制备方法 |
| BR112020003080A2 (pt) | 2017-08-14 | 2020-08-25 | Hendrickson Usa, L.L.C. | montagem de suspensão com proteção de acionador de freio a disco |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2824783A (en) * | 1953-02-27 | 1958-02-25 | Donald F Peppard | Separation of scandium from aqueous solutions |
| US2931705A (en) * | 1957-09-18 | 1960-04-05 | Columbia Southern Chem Corp | Process for preparing zirconium chlorides |
| US2952513A (en) * | 1958-01-14 | 1960-09-13 | Du Pont | Production of zirconium and silicon chlorides |
| US3383181A (en) * | 1965-04-08 | 1968-05-14 | American Potash & Chem Corp | Process of halogenating a phosphate ore |
| DE2311213C2 (de) * | 1973-03-07 | 1975-03-13 | Th. Goldschmidt Ag, 4300 Essen | Verwendung von Chlorkohlenwasserstoffen zur Chlorierung von oxidischen Verbindungen |
| SU866416A1 (ru) * | 1979-12-07 | 1981-09-23 | Московский Ордена Трудового Красного Знамени Институт Стали И Сплавов | Способ хроматографического выделени сканди |
| JPS60122718A (ja) * | 1983-12-08 | 1985-07-01 | Nippon Pureeteingu Kk | サマリウムの回収方法 |
| US5049363A (en) * | 1989-08-03 | 1991-09-17 | Westinghouse Electric Corp. | Recovery of scandium, yttrium and lanthanides from titanium ore |
-
1988
- 1988-12-30 US US07/292,035 patent/US5039336A/en not_active Expired - Lifetime
-
1989
- 1989-12-08 AU AU45972/89A patent/AU620948B2/en not_active Ceased
- 1989-12-28 FR FR8917368A patent/FR2641287B1/fr not_active Expired - Lifetime
- 1989-12-29 CN CN89109624A patent/CN1026016C/zh not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US5039336A (en) | 1991-08-13 |
| AU620948B2 (en) | 1992-02-27 |
| FR2641287A1 (fr) | 1990-07-06 |
| AU4597289A (en) | 1990-07-05 |
| FR2641287B1 (fr) | 1992-10-09 |
| CN1043752A (zh) | 1990-07-11 |
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