CN1796608A - Method and equipment for purifying ytterbium and gathering thulium and lutetium - Google Patents
Method and equipment for purifying ytterbium and gathering thulium and lutetium Download PDFInfo
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- CN1796608A CN1796608A CN 200410101606 CN200410101606A CN1796608A CN 1796608 A CN1796608 A CN 1796608A CN 200410101606 CN200410101606 CN 200410101606 CN 200410101606 A CN200410101606 A CN 200410101606A CN 1796608 A CN1796608 A CN 1796608A
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- ytterbium
- thulium
- lutetium
- solution
- sulfuric acid
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- 229910052769 Ytterbium Inorganic materials 0.000 title claims abstract description 43
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052775 Thulium Inorganic materials 0.000 title claims abstract description 31
- 229910052765 Lutetium Inorganic materials 0.000 title claims abstract description 30
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 5
- 239000012141 concentrate Substances 0.000 claims abstract 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract 2
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000746 purification Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 28
- 238000000605 extraction Methods 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000003014 ion exchange membrane Substances 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- KVCOOBXEBNBTGL-UHFFFAOYSA-H ytterbium(3+);trisulfate Chemical compound [Yb+3].[Yb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KVCOOBXEBNBTGL-UHFFFAOYSA-H 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- NYEODMYOBSNUDJ-UHFFFAOYSA-N S(O)(O)(=O)=O.[Lu] Chemical compound S(O)(O)(=O)=O.[Lu] NYEODMYOBSNUDJ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- JYXGEPNZGMUFEK-UHFFFAOYSA-N [Lu].[Yb].[Tm] Chemical compound [Lu].[Yb].[Tm] JYXGEPNZGMUFEK-UHFFFAOYSA-N 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 2
- 238000006722 reduction reaction Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 229910000497 Amalgam Inorganic materials 0.000 description 5
- 229910001362 Ta alloys Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- KACAUYDQOUENGF-UHFFFAOYSA-N [Ta].[Ru].[Ir] Chemical compound [Ta].[Ru].[Ir] KACAUYDQOUENGF-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- 210000005056 cell body Anatomy 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
This invention relates to a electrolysis method and facility for the purification of ytterbium and concentration of thulium and lutetium, in which ytterbium is reduced to bivalence and separated from the thulium-ytterbium-lutetium concentrates. As for the facility, hydrargyrum is adopted as cathode and ruthenium-iridium-titanium alloy is adopted as anode, with an anion exchange membrane separating the two parts. During the electrolysis, a sulfuric acid solution of thulium-ytterbium-lutetium concentrate with a pH valute of 0.1~4.0 serves as cathode liquid and an aqueous sulfuric acid solution with a proton concentration of 0.1~3.0mol/L serves as anode liquid. This method greatly reduces the manufacture cost and is simplified in both the process technique and actual operation.
Description
Technical field
The present invention relates to the method and apparatus of a kind of electrolytic reduction purifying ytterbium and gathering thulium and lutetium.
Background technology
Heavy rare earth element (thulium, ytterbium, lutetium) has many good characteristics, and begun to be applied in the hi-tech field of functional materials, but because at present thulium, ytterbium, the separating technology cost height of lutetium, treatment capacity are little, cause its price high for a long time, seriously limited the research and the application development of heavy rare earths.At present, thulium, ytterbium, lutetium enriched substance mainly adopt extraction process, chromatography and reduction method (amalgamation process, electrolytic process and metallothermics) to carry out.
Chinese patent literature CN 1131200 has reported a kind of method with hybrid extraction system extracting and separating thulium, ytterbium, lutetium, though having overcome chromatography, this method produces the main drawback that exists in high-purity heavy rare earths technology, processing condition have been simplified, making production cost extract the drip washing chromatography has had significantly reduction, but still has problems such as the extraction agent occupancy is big, separation efficiency is not high.Also there is the article report to mix use separately or with other acidic phosphorus extractant with novel extraction agent Cyanex272, to reduce extraction and back extraction acidity, improve the separation factor between thulium, ytterbium, lutetium, but because the little and easy emulsification of price height, loading capacity of Cyanex272, thereby also be difficult to reach the requirement of optimizing technology.
Chromatography comprises extraction chromatography and ion-exchange chromatography, but because the extraction chromatography exchange process is slow, processing power is little, the production cycle is long, wastewater discharge is big simultaneously, and the reagent price is expensive, though can obtain a small amount of ultra-pure product, be difficult to satisfy the industrial production requirement of large-tonnage product.
Because the main component in thulium, ytterbium, the lutetium enriched substance is a ytterbium, it has reducible characteristic, thereby reduction method extraction ytterbium is a kind of feasible production method.The rare earth method of reducing mainly contains methods such as amalgam reduction extraction process, metallothermic reduction, electrolytic reduction.The amalgam reduction extraction process generally adopts the amalgam of alkali-metal that the ytterbium in acetic acid or the sulphosalicylic acid solution is reduced into metal and is extracted into and forms the ytterbium amalgam in the mercury.The ytterbium amalgam is again through oxidation, washing, pickling, ammonia precipitation process or oxalic acid precipitation, obtains the ytterbium product of certain purity after the calcination, can obtain higher yield through circular treatment repeatedly, but reduction extraction in the production process and postprocessing working procedures complexity.
The metallothermic reduction method is to adopt cheap lanthanum or cerium metal under vacuum condition ytterbium at first to be reduced and distill, and collects and obtains the ytterbium metal, and thulium, lutetium exist with oxide form respectively, extract or stratography after acid is molten.This method equipment complexity, process control cost height is simultaneously because the restriction of equipment scale can't realize industrialization at present.
Utilize the variable valence characteristic (trivalent ytterbium can be reduced into divalence, and there are very big difference in the physicochemical property of divalence ytterbium and other trivalent rare earth ions) of ytterbium, can from the mixture of thulium, ytterbium, lutetium, separate ytterbium.There is the article report to do negative electrode with the mercury metal electrode, iron plate is done the electrolytic reduction process of anodic ytterbium, but when doing anode with iron plate, iron loses two electronics at anode and becomes ferrous ion and enter solution, owing to participating in reaction, iron enters solution, cause anolyte must change over time, cause certain waste, thereby and iron ion be penetrated into negative electrode by anion-exchange membrane and polluted catholyte.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art part, with electrolytic reduction, utilize ytterbium to have the character of appraising at the current rate, adopt anion-exchange membrane to make membranous electrolyzer, make negative electrode with mercury metal, the ruthenium-iridium-tantalum alloy network is made anodic one cover electrolyzer, ytterbium is reduced to the divalence state in sulfuric acid system, form precipitation with sulfuric acid, thereby reach and thulium, the isolating purpose of lutetium.Gained thulium, lutetium mixture and then obtain separating with extracting process.Because the treatment capacity that reduction is carried behind the ytterbium reduces greatly, and the separation factor of thulium, lutetium is relatively large, adopts extracting process to be easy to realize high-purity cheaply thulium, lutetium production.
Processing method of the present invention may further comprise the steps:
A. the preparation of negative electrode earth solution: with the sulphuric acid soln of thulium, ytterbium, lutetium enriched substance, concentration is the solution of 0.05-1.0mol/L, and the pH of solution is 0.1-4.0, and the concentration of solution is more preferably greater than 0.2mol/L, and pH is more preferably greater than 2.0;
B. the preparation of anolyte: Dilution of sulphuric acid is become [H
+] be the aqueous solution of 0.1-3.0mol/L, [H
+] more preferably greater than 1mol/L;
C. earth solution and aqueous sulfuric acid were put in the electrolyzer cathode and anode chamber in 1: 1 by volume;
D. electrolysis: be that more preferably greater than 20 ℃, the whipping appts that starts negative electrode stirs under 5-80 ℃ the situation in temperature, stirring velocity is at 10-600rpm, more preferably greater than 60rpm; Carry out electrolysis for negative electrode and anodal closure, voltage is 2.0-10.0V, more preferably greater than 5.0V;
E. separate: treat to stop after the electrolysis fully, solution, ytterbium sulfate precipitation are separated with mercury, solution advances extraction tank and carries out extracting and separating thulium and lutetium;
F. washing: the ytterbium sulfate precipitation that obtains is washed 1-10 time, more preferably greater than 5 times.
Wherein the sulphuric acid soln of thulium, ytterbium, lutetium enriched substance can obtain through sulfuric acid dissolution with carbonate, oxyhydroxide or the oxide compound of thulium, ytterbium, lutetium enriched substance, is preferably the carbonate of thulium, ytterbium, lutetium enriched substance.
For achieving the above object, equipment of the present invention is constructed as follows: it comprises cell body, negative electrode, anode, between negative electrode and anode ion-exchange membrane is arranged, and is divided into cathode compartment and anolyte compartment, and described cell body is a closed system, described anode ruthenium-iridium-tantalum alloy electrode, negative electrode is the mercury metal electrode, and ion-exchange membrane is an anion-exchange membrane, adorns agitator in the cathode compartment, has an anolyte import, the anolyte outlet has a catholyte import, the catholyte outlet.
The present invention compared with former Processes and apparatus, had following advantage:
1, simple in structure, disassembly, cleaning are convenient in the cathode and anode chamber;
2, cell body is a closed system, has avoided the volatilization of mercury and the oxidation of wandering and divalence ytterbium, can not pollute environment;
3, positive electricity ruthenium-iridium-tantalum alloy mesh electrode has very been avoided anodic consumption, need not frequently change anolyte, has reduced cost, and anolyte can not polluted yet simultaneously;
4, ytterbium and sulfuric acid form precipitation, are easy to realize and the separating of thulium, lutetium;
5, technological process is simple, is easy to control.
Following examples describe in further detail the present invention, but never constitute any limitation of the invention.
A. the preparation of negative electrode earth solution: after the carbonate of thulium, ytterbium, lutetium enriched substance added water and size mixing, use sulfuric acid dissolution, be mixed with the sulphuric acid soln of thulium, ytterbium, lutetium mixture, concentration is 0.2048mol/L, and the pH of regulator solution is 0.70;
B. the preparation of anolyte: sulfuric acid is diluted with water to [H
+] be the solution of 2.0mol/L;
C. get 1000ml earth solution and 1000ml aqueous sulfuric acid respectively, put in electric tank cathode chamber 13 and the anolyte compartment 14;
D. electrolysis: under 20 ℃ situation, the whipping appts 15 that starts negative electrode stirs, and stirring velocity carries out electrolysis for negative electrode 11 and positive electrode 6 energisings at 400rpm, and voltage is 7.0V;
E. separate: treat to stop after the electrolytic reduction rate reaches 90%, solution, ytterbium sulfate precipitation are separated with mercury, solution advances extraction tank and carries out extracting and separating thulium and lutetium;
F. washing: the precipitation that will obtain washes with water 8 times.
Raw materials used ytterbium content is 83.6%, reduction ratio＞90%, and the ytterbium purity that obtains is 99.6%
Accompanying drawing one is an equipment synoptic diagram of the present invention; Accompanying drawing two is a ruthenium-iridium-tantalum alloy mesh electrode synoptic diagram, and mesh is a rhombus.
Coding in the accompanying drawing one is respectively: the 1-current regulator power supply; The import of 2-catholyte, pneumatic outlet; The import of 3-anolyte, pneumatic outlet; The 4-volt ohm-milliammeter; The outlet of 5-anolyte; 6-ruthenium-iridium-tantalum alloy mesh electrode; The 7-ion-exchange membrane; The 8-saturated calomel electrode; The saturated KCl solution of 9-; The outlet of 10-catholyte; 11-mercury metal electrode; The 12-salt bridge; The 13-cathode compartment; The 14-anolyte compartment; The 15-whipping appts.
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410101606 CN1796608A (en) | 2004-12-21 | 2004-12-21 | Method and equipment for purifying ytterbium and gathering thulium and lutetium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410101606 CN1796608A (en) | 2004-12-21 | 2004-12-21 | Method and equipment for purifying ytterbium and gathering thulium and lutetium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1796608A true CN1796608A (en) | 2006-07-05 |
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ID=36817921
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|---|---|---|---|
| CN 200410101606 Pending CN1796608A (en) | 2004-12-21 | 2004-12-21 | Method and equipment for purifying ytterbium and gathering thulium and lutetium |
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| CN (1) | CN1796608A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102557205A (en) * | 2012-01-21 | 2012-07-11 | 杭州普普科技有限公司 | Novel method and apparatus for enriching and separating metal ions in sewage |
| CN103343230A (en) * | 2013-07-05 | 2013-10-09 | 南昌航空大学 | Valuable metal leaching process and device for waste lithium ion batteries |
| CN103469251A (en) * | 2013-08-26 | 2013-12-25 | 李戈登 | Novel process for fully separating rare earth elements |
| CN103718250A (en) * | 2011-07-15 | 2014-04-09 | Itm同位素技术慕尼黑股份公司 | Method for producing high-purity 177Lu compound added without carrier and 177Lu compound added without carrier |
| CN115637341A (en) * | 2022-11-03 | 2023-01-24 | 湖南稀土金属材料研究院有限责任公司 | Ytterbium oxide purification method |
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2004
- 2004-12-21 CN CN 200410101606 patent/CN1796608A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103718250A (en) * | 2011-07-15 | 2014-04-09 | Itm同位素技术慕尼黑股份公司 | Method for producing high-purity 177Lu compound added without carrier and 177Lu compound added without carrier |
| CN103718250B (en) * | 2011-07-15 | 2016-06-01 | Itm同位素技术慕尼黑股份公司 | The high purity that production carrier free is added177The method of Lu compound and carrier free are added177Lu compound |
| US9816156B2 (en) | 2011-07-15 | 2017-11-14 | ITM Isotopen Technologien München AG | Method of manufacturing non-carrier-added high-purity 177Lu compounds as well as non-carrier-added 177Lu compounds |
| CN102557205A (en) * | 2012-01-21 | 2012-07-11 | 杭州普普科技有限公司 | Novel method and apparatus for enriching and separating metal ions in sewage |
| CN103343230A (en) * | 2013-07-05 | 2013-10-09 | 南昌航空大学 | Valuable metal leaching process and device for waste lithium ion batteries |
| CN103343230B (en) * | 2013-07-05 | 2014-11-05 | 南昌航空大学 | Valuable metal leaching process and device for waste lithium ion batteries |
| CN103469251A (en) * | 2013-08-26 | 2013-12-25 | 李戈登 | Novel process for fully separating rare earth elements |
| CN115637341A (en) * | 2022-11-03 | 2023-01-24 | 湖南稀土金属材料研究院有限责任公司 | Ytterbium oxide purification method |
| CN115637341B (en) * | 2022-11-03 | 2024-03-12 | 湖南稀土金属材料研究院有限责任公司 | Ytterbium oxide purification method |
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