CN107268031B - The electrochemistry recovery method of heavy rare earth metalloid - Google Patents
The electrochemistry recovery method of heavy rare earth metalloid Download PDFInfo
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- CN107268031B CN107268031B CN201710198074.4A CN201710198074A CN107268031B CN 107268031 B CN107268031 B CN 107268031B CN 201710198074 A CN201710198074 A CN 201710198074A CN 107268031 B CN107268031 B CN 107268031B
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- rare earth
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 222
- -1 rare earth metalloid Chemical class 0.000 title claims abstract description 167
- 229910052752 metalloid Inorganic materials 0.000 title claims abstract description 153
- 238000000034 method Methods 0.000 title claims description 43
- 238000011084 recovery Methods 0.000 title claims description 41
- 230000005518 electrochemistry Effects 0.000 title claims description 4
- 239000008139 complexing agent Substances 0.000 claims abstract description 91
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 88
- 230000009467 reduction Effects 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 229910052691 Erbium Inorganic materials 0.000 claims description 61
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 41
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 239000004471 Glycine Substances 0.000 claims description 21
- 229910052775 Thulium Inorganic materials 0.000 claims description 16
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 16
- 230000000052 comparative effect Effects 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 229960001484 edetic acid Drugs 0.000 claims description 8
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 239000010842 industrial wastewater Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 claims description 3
- 229930002839 ionone Natural products 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 238000005363 electrowinning Methods 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 45
- 238000002474 experimental method Methods 0.000 description 34
- 238000007740 vapor deposition Methods 0.000 description 32
- 238000002484 cyclic voltammetry Methods 0.000 description 23
- 238000004064 recycling Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910001004 magnetic alloy Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- MYYPUXZNVLDNLK-UHFFFAOYSA-N [Ni].[Co].S(O)(O)(=O)=O Chemical compound [Ni].[Co].S(O)(O)(=O)=O MYYPUXZNVLDNLK-UHFFFAOYSA-N 0.000 description 1
- MNZHBXZOPHQGMD-UHFFFAOYSA-N acetic acid;azane Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O MNZHBXZOPHQGMD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention solves the previous technical problem that can not recycle heavy rare earth metalloid by electrochemical means from the solution containing heavy rare earth class due to low reduction potential, heavy rare earth metalloid ion-ligand complex compound is formed between heavy rare earth metalloid ion and complexing agent by adding complexing agent in the various industry solution containing heavy rare earth metalloid, and heavy rare earth metalloid ionic metal is recycled by electrochemical means, so that having the advantages that can be not only environmentally friendly in the solution containing heavy rare earth metalloid but also to recycle heavy rare earth metalloid in high yield.
Description
Technical field
The present invention relates to recycle heavy rare earth metalloid by electrochemical means from the solution containing heavy rare earth metalloid
Method is more specifically related to by adding complexing agent in the various industry solution containing heavy rare earth metalloid come dilute in weight
Heavy rare earth metalloid ion-ligand complex compound is formed between great soil group metal ion and complexing agent, to recycle by electroreduction
The method of heavy rare earth metalloid.
Background technique
Rare earth metal is the general name for the microelement of the sophisticated industry including generator and battery of new generation.
Include minimal amount of rare earth metal in the earth earth's crust, currently, supplies a considerable amount of rare earth metals by China, but have such as
With the trend of generally the wanted weaponization of petroleum.Therefore, many developed countries are striving to find new resource supplier, close simultaneously
It infuses to by recycling previous used rare earth metal come the exploitation for the method reused.
Term rare earth is as the scandium (Sc) of 3A race, yttrium (Y) in the periodic table of chemical element and plus atomic number
The general name of totally 17 kinds of elements of 57 to 71 15 kinds of lanthanide series.Rare earth metal can be divided into as light rare earth metalloid element
Scandium (Sc), lanthanum (La), cerium (Ce), praseodymium (Pr), the neodymium (Nd), promethium (Pm), samarium of (Light Rare Earth Element, LREE)
(Sm), europium (Eu) and yttrium (Y), gadolinium as heavy rare earth metalloid element (Heavy Rare Earth Element, HREE)
(Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu).
Since the chemical property of rare-earth substance is similar, thus it is difficult to be separated by common chemical analysis operation,
And the natively output in a manner of being mutually mixed, and its yield is few.EU Committee (EC:European
Commission) by delivering entitled " key raw material (the Critical raw materials for of European Union in 2010
The EU) " report, 14 kinds of rare earth metals are divided into the substance that market is difficult to persistently supply according to demand.
2010, US Geological Survey (USGS:US geological Survey) extrapolated economically minable
The global reserves of rare earth metal are 99000000 tons (REO benchmark: rare earth oxide (Rare earth oxide)).Relatively
In 124000 tons as 2009 gross annual output amounts, above-mentioned estimated amount is not a small amount of reserves, from now on, in rare earth metal
Mining and smelt the aspect development of the technology and increase of demand, it is about 50000000 that the yield of exploitation can be added by, which extrapolating,
Ton.
Estimate that about 40% or so in whole reserves of global rare earth metal is imbedded in China, in terms of output, estimates
The 97% of meter whole world rare earth metal produced originates from China.
From after 1972, China starts the smelting and isolation technics of developing rare earth metal alone, currently, in above-mentioned neck
In domain, China has top technology and experience.24 mining companies and more than 100 a smelting companies are runed in China.
In order to protect rare earth metal resource, Chinese Government is just being applicable in new control and guilding principle.New policy it is basic
Rare-earth Industry is considered as in country by frame, important a part of long-term industry development plan.The policy includes to rare earth resources
Comparison strength protection and environmental pollution control.2010, Chinese technical industry portion issued entitled " Rare-earth Industry
Into standard (Entry Criterions for Rare Earth Industry) " bill, assume overall responsibility for smelting in the control
And separate smallest size, equipment, flowing and the fixed assets ratio of facility, for the guilding principle of environmentally friendly facility.According to upper
New bill is stated, smelts and separation facility needs the annual ore that can at least handle 8000 tons or more, only for bastnaesite
(bastnaesite) facility needs to handle 5000 tons or more of ore every year.China in order to protect this country rare earth eka-gold
Belong to resource and adjusts the market price and the output of rare earth metal is adjusted.According to " 2009-2015 year terres rares
Annual minable most ore amounts were set within 13000-15000 tons, in above-mentioned period by metal industry development plan "
It is interior, the development rights and mining right of new mineral products may not be provided.Also, for the smelting in current operation and company is separated, is also wanted
It is asked to further increase production efficiency.Plan is only allowed raw with regulation by reducing the small-sized smelting company in illegal operation
A company more than the 20 of production capacity power.In addition to China, the related rare earth metal company runed concentrate on European Union (EU) and
Japan, Japanese firm mainly produce magnetic alloy substance (NdFeB, magnetisable material) using rare earth metal, and European is several
Company produces catalyst using rare earth metal and prepares magnetic alloy substance.But in rare earth metal application industry
Many fields are also by Chinese companies' tenant's leading position.Under present case, mining and Smelting Part are almost 100% by Chinese ridge
Disconnected, the other countries in addition to China only grasp a part (20%) in the production field of magnetic alloy substance.
Rare earth metal is mainly for the preparation of magnetic material, catalyst, battery and high efficiency light-emitting body.Current trends are,
Cerium is used as glass matt additive, also uses the conjunction comprising rare earth metal when manufacturing the cooling end of high speed rotation turbine
Gold, and think the further demand that can also have to rare earth from now on.Also, it is current, using a large amount of in terms of manufacturing magnetic material
Rare earth, when manufacturing hybrid vehicle and when electric car, wind turbine, need terbium (Tb), dysprosium (Dy), praseodymium (Pr) and neodymium
(Nd).It is therefore expected that the demand to this 4 kinds of rare earth metals can sharply increase from now on.When manufacturing high efficiency light-emitting body, need
Europium (Eu), samarium (Sm), terbium (Tb), cerium (Ce), erbium (Er) etc., in particular, supply falls short of demand for estimated europium and terbium meeting at present, yttrium (Y) and lanthanum
(La) a possibility that supply falls short of demand is also proposed according to the rare earth policy of China and whether develop new rare earth.In particular, in addition to system
High efficiency light-emitting body is made, in the refinement industry of petroleum, lanthanum also functions to very important effect, it is contemplated that for the time being as catalyst
It is difficult to find out the method that can replace lanthanum.
As described above, since to have become reality to the export restrictions of rare earth metal stable dilute it is necessary to make for China
The supply and demand measure of great soil group metal needs to develop the technology that can replace rare earth metal or Ke Xunhuanliyong as above-mentioned measure
The technology of rare earth metal.But it is prepared in the multiple fields such as magnetic material, catalyst, battery, high efficiency light-emitting body currently
In the case where continuing to increase to the use of rare earth metal, however, it is difficult to while multiple ensuring that rare earth metal can be replaced
Technology.Therefore, it as achievable and feasible measure, needs to support in policy and rare earth metal is recycled and recycled
Technology.
As the method recycled to input rare earth metal in the manufacturing process of magnetic material, have by right
The method that waste material is melted to recycle the rare earth metal of elementary state；The method recycled with oxide form；Utilize chlorination
The method that magnesium comes Selective Separation neodymium and dysprosium；The additional method etc. for adding 1% neodymium to be sintered after crushing neodymium magnetic material,
But these methods the practicality due to the rate of recovery etc. is very low is also very low so far.
As the research in relation to being recycled to rare earth metal included in Ni-HM battery, there is Japanese national oil gas
It will be from the thermal decomposition in Ni-HM battery to the research of lanthanum and cerium recycled, Germany with mineral metal products (JOGMEC) company
The research of recovering rare earth metalloid in the slag generated in the process, China to be utilized retrieval of sulfuric acid nickel cobalt/rare earth metal
Research etc., but not yet it is suitable for industry aspect so far.
As the research in relation to being recycled to the rare earth used in illuminator and television set (TV), there is Ou Silang public
Take charge of the research of the technical aspect recycled to the yttrium and europium that are usually used in the display of television set, computer, electric light.
It the present invention relates to the use of electrochemical means recovering rare earth metalloid from industrial wastewater, especially recycling heavy rare earth eka-gold
The method of category.Under normal circumstances, the reduction potential of heavy rare earth metalloid (Er, Yb, Tm) is extremely low (E0=2.2~﹣ of ﹣ 2.3V).
This indicates that the tendency to be aoxidized is very big and restores required overpotential and becomes larger.If also, the hydrone of aqueous solution and electricity
Son is in contact, then can be reduced to hydrogen and hydroxide ion, and reduction potential at this time is relatively higher than the reduction of heavy rare earth element
Current potential (E0=﹣ 0.8277V).That is, this is indicated in the mistake for recycling heavy rare earth metalloid by electrochemical means from industrial wastewater
Cheng Zhong largely can generate hydrogen in electrode surface and heavy rare earth metalloid not be deposited, thus be difficult to make heavy rare earth metalloid from
Son reduction.
In this regard, the present inventor is in order to solve the technical problem of the electrochemistry recovery method of heavy rare earth metalloid as described above
And pass through and be continually striving to, finally, complete by the way that in the solution containing heavy rare earth metalloid, more specifically, containing, weight is dilute
Complexing agent is added in the various industry solution of great soil group metal to form heavy rare earth between heavy rare earth metalloid ion and complexing agent
Metalloid ion-ligand complex compound, so as to recycle heavy rare earth metalloid ionic metal by electrochemical means
The present invention.
Summary of the invention
It is an object of the present invention to which electrification can not be passed through from the solution containing heavy rare earth class due to low reduction potential by overcoming
Mode recycles the previous technical problem of heavy rare earth metalloid, and can pass through electrification from the solution containing heavy rare earth metalloid
The method that mode recycles heavy rare earth metalloid.
To achieve the goals above, the present invention provides through add in the various industry solution containing heavy rare earth metalloid
Complexing agent to form heavy rare earth metalloid ion-ligand complex compound between heavy rare earth metalloid ion and complexing agent, and passes through
The method that electrochemical means recycle heavy rare earth metalloid ionic metal.
The present invention overcomes can not pass through electrochemical means from the solution containing heavy rare earth class due to low reduction potential to return
The previous technical problem for receiving heavy rare earth metalloid is complexed by adding in the various industry solution containing heavy rare earth metalloid
Agent to form heavy rare earth metalloid ion-ligand complex compound between heavy rare earth metalloid ion and complexing agent, and passes through electrification
Mode recycles heavy rare earth metalloid ionic metal, so that having can be in the solution containing heavy rare earth metalloid
Not only environmental protection but also in high yield come the advantages of recycling heavy rare earth metalloid.
Detailed description of the invention
Fig. 1 is the schematic diagram of three electrolysis also original system, and (a) of Fig. 1 is partially that titanium foil (Ti foil) a is used workmanship
Make the schematic diagram of the three electrolysis also original system of electrode, (b) of Fig. 1 is partially the schematic diagram of working electrode b.
Fig. 2 is to be used as RECl contained in the RE-Cl solution of sample in three electrolysis also original system3.6H2O powder.
Fig. 3 is in the case where heavy rare earth metalloid ion is erbium, by cyclic voltammetry based on complexing agent
The chart of current density.
Fig. 4 is in the case where heavy rare earth metalloid ion is thulium, by cyclic voltammetry based on complexing agent
The chart of current density.
Fig. 5 is in the case where heavy rare earth metalloid ion is ytterbium, by cyclic voltammetry based on complexing agent
The chart of current density.
Fig. 6 a, Fig. 6 b and Fig. 6 c be illustrated respectively in heavy rare earth metalloid ion be erbium in the case where, when pH be respectively 1,7 and
Pass through the current density (Current Density) based on complexing agent of cyclic voltammetry when 12.
Fig. 7 indicates to pass through each of cyclic voltammetry according to the presence or absence of erbium in the case where pH is 4 and 7
The current density of complexing agent.
Fig. 8 shows using erbium as heavy rare earth metalloid element, using iminodiacetic acid, RE-Cl as complexing agent
In the case that the pH of solution is 4 and potential range is 0~-4V, by rest potential experiment vapor deposition in working electrode (titanium foil)
The fine structure of object is deposited.
Fig. 9 is to indicate using erbium as heavy rare earth metalloid element, using iminodiacetic acid, RE- as complexing agent
In the case that the pH of Cl solution is 7 and potential range is 0~-4V, by rest potential experiment vapor deposition in working electrode (titanium foil)
Vapor deposition object fine structure.
Figure 10 is to indicate using erbium as heavy rare earth metalloid element, using glycine, RE-Cl solution as complexing agent
PH be 7 and in the case that potential range is 0~-4V, by rest potential experiment vapor deposition in the vapor deposition of working electrode (titanium foil)
The fine structure of object.
Figure 11 is to indicate in the case where pH is 4 and 7, when using iminodiacetic acid and glycine as complexing agent
The result of the erbium content (wt% and at%) in object is deposited.
Figure 12 is to use erbium as heavy rare earth metalloid element, using iminodiacetic acid, pH condition as complexing agent
Voltage-to-current CV curve in the case where being set as 4 and 7 and execute cyclic voltammetry in the potential range of 0~-5.5V.
Figure 13 is to indicate using erbium as heavy rare earth metalloid element, using iminodiacetic acid, RE- as complexing agent
In the case that the pH of Cl solution is 7 and potential range is 0~-5.5V, by rest potential experiment vapor deposition in working electrode (titanium
Foil) vapor deposition object fine structure.
Figure 14 is to indicate using erbium as heavy rare earth metalloid element, using iminodiacetic acid, RE- as complexing agent
In the case that the pH of Cl solution is 7 and potential range is 0~-5.5V, by rest potential experiment vapor deposition in working electrode (titanium
Foil) vapor deposition object in erbium content (wt% and at%).
Figure 15 is to indicate to measure going back for erbium when potential range is set as -5.0V, -5.5V, -6.0V, -6.5V, -7.0V
The result of former degree.
Figure 16 is the variation for indicating the reduction potential of the heavy rare earth changed based on solution temperature.
Specific embodiment
Hereinafter, the present invention is explained in more detail.
The present invention provides the recovery method of heavy rare earth metalloid, and it includes containing that the recovery method of above-mentioned heavy rare earth metalloid, which utilizes,
There is the electrolytic reduction device of the solution of heavy rare earth metalloid ion, working electrode and comparative electrode to recycle heavy rare earth metalloid,
The recovery method of above-mentioned heavy rare earth metalloid includes: step a, added in the solution containing heavy rare earth metalloid ion it is a kind of with
On when forming complex compound with heavy rare earth metalloid complexing agent of the log value range within 3 to 32 of stability constant K formed again
Rare-earth metal ion-ligand complex；And step b, it is electrochemically handled to recycle heavy rare earth metalloid.
Above-mentioned heavy rare earth metalloid ion can be for selected from being made of erbium (Er) ion, thulium (Tm) ion and ytterbium (Yb) ion
One or more of group heavy rare earth metalloid ion, preferably erbium ion.
Before above-mentioned steps a, the recovery method of above-mentioned heavy rare earth metalloid, which may also include, will contain heavy rare earth metalloid
The pH range of the solution of ion is adjusted to 13 hereinafter, be specifically adjusted to 1 to 12, is more specifically adjusted to 3 to 10, further
The step of being specifically adjusted to 4 to 7.
Temperature condition when recycling above-mentioned heavy rare earth metalloid can be 40 DEG C or more, 45 DEG C or more, 50 DEG C or more, 55
DEG C or more, 60 DEG C or more, 65 DEG C or more, 70 DEG C or more, 75 DEG C or more, 80 DEG C or more, 85 DEG C or more and 90 DEG C or more, specifically
Ground can carry out in the range of 50 DEG C to 90 DEG C.In the case where recycling under above-mentioned temperature range, heavy rare earth class can be improved
The recycling yield of metal.
Above-mentioned complexing agent can for selected from by glycine (Glycine), ethylenediamine tetra-acetic acid (EDTA,
Ethylenediaminetetraacetic acid), iminodiacetic acid (IDA, Iminodiacetic acid) and three second of ammonia
The complexing agent of one or more of the group of sour (NTA, Nitrilotriacetic acid) composition can be specifically glycine
Or more specifically as complexing agent, iminodiacetic acid can be used in iminodiacetic acid.
In the step b in the recovery method of above-mentioned heavy rare earth metalloid, electrochemical treatments can be electroreduction, electrolysis
One of extraction, electrorefining and electrolysis, it is further preferred that can be electroreduction.
Above-mentioned working electrode can be Ti electrode.
Above-mentioned comparative electrode can be platinum electrode.
In one embodiment of the present invention, can also utilize includes the solution containing heavy rare earth metalloid ion, work
Three electrolysis reduction apparatus of electrode, reference electrode and comparative electrode.
As a further embodiment of the invention, heavy rare earth recycling electrolytic reduction system, above-mentioned heavy rare earth recycling are provided
Include the solution containing heavy rare earth metalloid ion, working electrode and comparative electrode with electrolytic reduction system, is containing heavy rare earth
The log value model of more than one stability constant K when forming complex compound with heavy rare earth metalloid is added in the solution of metalloid ion
The complexing agent being trapped among within 3 to 32 makes heavy rare earth metalloid vapor deposition in working electrode by carrying out electroreduction later.
In above-mentioned heavy rare earth recycling electrolytic reduction system, heavy rare earth metalloid ion can for selected from by erbium ion,
The heavy rare earth metalloid ion of one or more of the group of thulium ion and ytterbium ion composition can be specifically erbium ion.
In above-mentioned heavy rare earth recycling electrolytic reduction system, as complexing agent, it can be used selected from by glycine, ethylenediamine
Specifically glycine can be used in the complexing agent of one or more of the group of tetraacethyl, iminodiacetic acid and nitrilotriacetic acid composition
Or more specifically iminodiacetic acid can be used in iminodiacetic acid.
In above-mentioned heavy rare earth recycling electrolytic reduction system, working electrode can be Ti electrode.
In above-mentioned heavy rare earth recycling electrolytic reduction system, comparative electrode can be platinum electrode.
As another embodiment of the present invention, the recovery system of heavy rare earth metalloid, above-mentioned heavy rare earth metalloid are provided
Recovery system by electroreduction processing come from the industrial wastewater containing heavy rare earth metalloid ion and complexing agent recycle weight
Rare earth metal, the recovery system of above-mentioned heavy rare earth metalloid include: (a) waste water tank, (b) comparative electrode, (c) working electrode and
(d) potentiostat.
Above-mentioned heavy rare earth metalloid ion can be for selected from by ruthenium ion, gadolinium ion, terbium ion, dysprosium ion, holmium ion, erbium
The heavy rare earth metalloid ion of one or more of the group of ion, thulium ion, ytterbium ion and lutetium ion composition, it is specifically, above-mentioned
Heavy rare earth metalloid ion is the heavy rare earth eka-gold selected from one or more of the group being made of erbium ion, thulium ion and ytterbium ion
Belong to ion, more specifically, above-mentioned heavy rare earth metalloid ion is erbium ion.
Above-mentioned complexing agent is selected from the group being made of glycine, ethylenediamine tetra-acetic acid, iminodiacetic acid and nitrilotriacetic acid
One or more of complexing agent, specifically, above-mentioned complexing agent be in the group being made of glycine and iminodiacetic acid
More than one complexing agent, more specifically, above-mentioned complexing agent be iminodiacetic acid.
Also, in an embodiment of the recovery system in above-mentioned heavy rare earth metalloid, above-mentioned work (Working) electrode
For titanium matter electrode.
Hereinafter, by embodiment and experimental example come the present invention will be described in detail.
But following embodiment and experimental example be only used for illustrate the present invention, and the contents of the present invention be not limited to it is following
Embodiment and experimental example.
Embodiment: three electrolysis restore (electroreduction) system
Three electrolysis also original system used in the present invention includes potentiostat (Potentiostat), work electricity
Pole, comparative electrode, benchmark (Reference) electrode and RE-Cl solution (rare earth (Rare Earth)-chloride as sample
Solution).Fig. 1 is the schematic diagram of three electrolysis also original system, and (a) of Fig. 1 is partially three electricity by titanium foil as working electrode
The schematic diagram of pole electrolytic reduction system, (b) of Fig. 1 are partially the schematic diagram of working electrode.Constant potential used in the present invention
Instrument is that Iviumstat and Gamry equipment has used stud (Titanium rod, (r=as working electrode in three electrodes
5mm, l=2mm)) or titanium foil (2mm × 2mm) as comparative electrode used gauze platinum electrode (Platinum mesh
Electrode), as reference electrode, the pre-filled Calomel reference electricity of the accumet standard of fischer (Fisher) company has been used
Pole W/PIV (accumet standard pre-filled calomel reference electrode W/PIV).As examination
The RE-Cl solution of sample is the simulated solution for including rare-earth metal ion and the mineral products waste water with low pH, by basic
Mixing RECl as shown in Figure 2 in solution (mixed solution of distilled water and hydrochloric acid)36H2O powder prepares above-mentioned RE-Cl solution.
As the heavy rare earth metalloid element in RE-Cl solution, erbium, thulium and ytterbium have been used respectively.In the present invention, with
As described above structure judges suitably to be complexed to implement cyclic voltammetry (Cyclic Voltammetry) and potentiostatic method
After agent type and pH appropriate, the reduction situation of counterweight rare earth metal element and whether practical vapor deposition is observed.
In the test piece for being used as working electrode, stud is being manufactured with the size of Φ 10mm × 150mm, and with 20mm × 2mm
The size of × 0.1mm after manufacturing titanium foil, brings the portion for making to be reacted with real solution by adhering to insulating cement in test piece
Divide and maintains Φ 10mm × 2mm and 2mm × 2mm × 0.1mm size respectively.Ultrasonic cleaning is implemented to made test piece,
Later by adequately dry to come into operation in an experiment.
Hereinafter, the type of complexing agent, pH etc. are implemented experiment as experimental variation in a manner of following experimental example.
Experimental example 1: the cyclic voltammetry based on complexing agent (Complexing agents) is tested
Complexing agent is the organic compound combined in circular arrangement structure with metal ion, in embodiment 1 really
The complexing agent of guarantor to be used for three electrolysis also original system is glycine, ethylenediamine tetra-acetic acid, iminodiacetic acid and ammonia
Triacetic acid.And the above-mentioned complexing agent of 2M is used.The pH of basic solution (mixed solution of hydrochloric acid and distilled water) is fixed as 1,
And RECl is added in above-mentioned basic solution3.6H2O powder prepares RE-Cl solution.As the heavy rare earth class in RE-Cl solution
Metal ion has used erbium, thulium and ytterbium, and the concentration of above-mentioned each metal ion is set as 1M.Stud is used as working electrode,
As a control group, identical with other conditions, and it is condition to be tested that complexing agent, which is only not used,.
Fig. 3, Fig. 4, Fig. 5 are respectively to be lied prostrate in the case where heavy rare earth metalloid ion is respectively erbium, thulium and ytterbium by circulation
The result of the current density based on complexing agent of peace method measurement.
In the case where heavy rare earth metalloid ion is erbium, thulium and ytterbium, other than glycine, it is complexed in these cases
Agent is not almost dissolved (a small amount of to be dissolved) in the state that pH is 1.In order to observe the heavy rare earth class based on complexing agent type
Relationship between the reduction of metal ion considers to use stability constant.
Each heavy rare earth metalloid ion and for the stability constant (stability between the complexing agent of experiment
Constant) such as table 1.
Table 1
Stability constant between heavy rare earth metalloid ion and complexing agent
For erbium, thulium and ytterbium to be considered in interior multiple complexing agents, the combination of complexing agent and heavy rare earth metalloid ion
The stability constant of reaction shows Gao Shui according to the sequence of glycine, iminodiacetic acid, nitrilotriacetic acid and ethylenediamine tetra-acetic acid
Flat stability constant, can be confirmed, the high low mode of this stability constant draws specific mould in the result of Fig. 3 to Fig. 5
Formula.That is, according to Fig. 3 to Fig. 5's as a result, can be confirmed, the case where relative to unused complexing agent, be equivalent to have it is high steady
In the case where the ethylenediamine tetra-acetic acid or nitrilotriacetic acid of the complexing agent of permanent number, the gradient for going back virgin curve increases, reduction potential
It is mobile to positive direction；The case where relative to unused complexing agent, is being equivalent to the complexing agent with relatively low stability constant
In the case where glycine, iminodiacetic acid, the gradient decline of virgin curve is gone back, reduction potential is mobile to negative direction.
Can be confirmed by above-mentioned experiment, can according to the stability constant between heavy rare earth metalloid ion and complexing agent come
It observes specific mode, but due to the different solubility of the complexing agent based on pH, and generates the reduction negative interaction of a large amount of hydrogen,
To be difficult to confirm influence in terms of can directly explaining complexing agent to heavy rare earth metalloid ionic metal is made as a result, thus with
As under type has carried out additional experiment by increasing pH.
Experimental example 2: the cyclic voltammetry experiment based on pH condition
In addition to adjusting the pH of RE-Cl solution using KOH and being fixed as the heavy rare earth metalloid ion of RE-Cl solution
Except erbium, other all conditions are identical as the cyclic voltammetry experiment condition based on complexing agent of experimental example 1.Institute in the present invention
The RE-Cl solution used is the simulated solution of mineral products waste water, thus while initial waste has acidity, but in view of being neutralized
The reduction situation of processing, erbium when being 1 and 7 to pH is observed, and is implemented when pH is 12 to be compared
The reduction experiment of erbium.
Fig. 6 a, Fig. 6 b and Fig. 6 c be illustrated respectively in heavy rare earth metalloid ion be erbium in the case where, when pH be respectively 1,7 and
Pass through the current density based on complexing agent of cyclic voltammetry when 12.
When pH is 4 or more, it can be confirmed that complexing agent is dissolved, and observe that pH more increases, then the yield of hydrogen
It is remarkably decreased with the noise of current density plot.When pH is 7, it is mobile to positive direction to confirm reduction potential, and observe
The current potential for starting reduction is equivalent to about 0.5V to negative direction is mobile.When pH is 12, observe that reduction potential is mobile to negative direction,
And the current potential for starting reduction is equivalent to about 0.8V to negative direction is mobile.The reduction situation of erbium when in order to be further 7 to pH
Following experiment is carried out explicitly stated, additional.
It is -4.0V increasing the electric potential scanning range of cyclic voltammetry in additional experiment, and by working electrode from titanium
After stick replaces with titanium foil, the movement for going back virgin curve of each complexing agent of the presence or absence based on erbium is observed.
Fig. 7 indicates to pass through each of cyclic voltammetry according to the presence or absence of erbium in the case where pH is 4 and 7
The current density of complexing agent.
When iminodiacetic acid and Er (III) form complex compound, confirm in the case where pH is 4 and pH is 7, two kinds
The positive direction mobile range for going back virgin curve in situation is maximum, but only in Er (the III)-iminodiacetic acid for forming complex compound
In the case where solution, reduction vapor deposition object is formed in titanium foil and (passes through X-ray energy dispersion spectrum (Energy dispersive X-ray
Spectroscopy, EDS or EDX) come checking as a result, detecting the up to erbium of 97.04wt%).
Experimental example 3: rest potential experiment
Rest potential experiment condition such as the following table 2.
Table 2
Rest potential experiment condition
Fig. 8 shows using erbium as heavy rare earth metalloid element, using iminodiacetic acid, RE-Cl as complexing agent
In the case that the pH of solution is 4 and potential range is 0~-4V, by rest potential experiment vapor deposition in working electrode (titanium foil)
The fine structure of object is deposited.
Fig. 9 is to indicate using erbium as heavy rare earth metalloid element, using iminodiacetic acid, RE- as complexing agent
In the case that the pH of Cl solution is 7 and potential range is 0~-4V, by rest potential experiment vapor deposition in working electrode (titanium foil)
Vapor deposition object fine structure.
Figure 10 is to indicate using erbium as heavy rare earth metalloid element, using glycine, RE-Cl solution as complexing agent
PH be 7 and in the case that potential range is 0~-4V, by rest potential experiment vapor deposition in the vapor deposition of working electrode (titanium foil)
The fine structure of object.
In the case where pH is 1, even if in voltage range, vapor deposition object is not deposited on titanium foil using any complexing agent.
PH be 4 in the case where, by iminodiacetic acid be used as complexing agent when, can be confirmed -2.5V, -
Object vapor deposition is deposited in the case where 3.0V, -3.5V, -4.0V on titanium foil.
In the case where pH is 7, when glycine is used as complexing agent, can be confirmed in -3.0V, -3.5V, -4.0V
In the case where object vapor deposition is deposited on titanium foil, in the case where iminodiacetic acid is used as complexing agent, it can be identified that-
Object vapor deposition is deposited in the case where 2.5V, -3.0V, -3.5V, -4.0V on titanium foil.
Experimental example 4: the confirmation to the content of erbium in vapor deposition object
It is examined by X-ray energy dispersion spectrum (Energy dispersive X-ray spectroscopy, EDS or EDX)
It is surveying as a result, the element that detects is erbium, oxygen, potassium, chlorine and titanium out of vapor deposition object.
Figure 11 is to indicate in the case where pH is 4 and 7, when using iminodiacetic acid and glycine as complexing agent
The result of the erbium content (wt%) in object is deposited.
It can be confirmed, in the case where coming as complexing agent using iminodiacetic acid, the erbium content being deposited in object is whole
It is higher by 2-3 times or more when body ratio is using glycine, and is difficult to observe by the tendentiousness of the erbium content based on current potential.
Hereinafter, iminodiacetic acid is used as complexing agent come the current potential in the case where pH is 4 and pH is 7 in 0~-5.5V
Cyclic voltammetry experiment has been carried out in range.
Experimental example 5: using erbium as heavy rare earth metalloid element, uses iminodiacetic acid, pH 4 as complexing agent
And 7, the cyclic voltammetry experiment that potential range carries out in the case where 0~-5.5V
Cyclic voltammetry experiment condition such as the following table 3.
Table 3
Cyclic voltammetry experiment condition
Figure 12 is to use erbium as heavy rare earth metalloid element, using iminodiacetic acid, pH condition as complexing agent
It is set as 4 and 7 and the voltage-to-current CV song in the potential range of 0~-5.5V in the case where execution cyclic voltammetry
Line.
Electric current is caused excessively to increase because of hydrogen reducing, thus the incrementss of electric current are higher than the case where pH is 4 and pH is 7
Situation is respectively formed vapor deposition object in the case where pH is 4 and 7, but the surface state of vapor deposition object when pH is 4 is bad, and because producing
Raw hydrogen and there is a phenomenon where vapor deposition object is stripped, on the contrary, vapor deposition object when pH is 7 is in apparent good order and condition, and because of hydrogen
Yield it is few and there is a phenomenon where vapor deposition object be stripped.
Experimental example 6: erbium is being used as heavy rare earth metalloid element, is using iminodiacetic acid as complexing agent, pH is
7, the rest potential experiment that potential range carries out in the case where being 0~-5.5V
Rest potential experiment condition such as table 4.
Table 4
Rest potential experiment condition
Figure 13 is to indicate using erbium as heavy rare earth metalloid element, using iminodiacetic acid, RE- as complexing agent
In the case that the pH of Cl solution is 7 and potential range is 0~-5.5V, by rest potential experiment vapor deposition in working electrode (titanium
Foil) vapor deposition object fine structure.
Figure 14 is to indicate using erbium as heavy rare earth metalloid element, using iminodiacetic acid, RE- as complexing agent
In the case that the pH of Cl solution is 7 and potential range is 0~-5.5V, by rest potential experiment vapor deposition in working electrode (titanium
Foil) vapor deposition object in erbium content (wt% and at%).
According to Figure 14, pass through X-ray energy dispersion spectrum (Energy dispersive X-ray in the case where pH is 7
Spectroscopy, EDS or EDX) come the surface analysis to rest potential implemented as a result, the Wt% and At% of erbium can be confirmed
Show increased tendency.
Experimental example 7: erbium is being used as heavy rare earth metalloid element, is using iminodiacetic acid as complexing agent, pH is
7, the experiment that potential range carries out in the case where being -5~-7V
Due to not finding out diffusion boundary in the case where applicable previous -5V rest potential below, thus by applying more
Big overpotential observes diffusion terminal conditions.The condition for restoring erbium ion sufficiently can be found out by predicting.
The experimental results are shown inthe following table, and the absolute value for substantially showing applied rest potential more increases, then is reduced
Er amount more increases.(referring to Fig.1 5)
Table 5
Experimental example 8: erbium is being used as heavy rare earth metalloid element, is using iminodiacetic acid as complexing agent, pH is
7, potential range is 0~-7.0V, the cyclic voltammetry experiment that solution temperature carries out in the case where 25~65 DEG C
Cyclic voltammetry experiment condition such as the following table 6 under high temperature.
Table 6
Cyclic voltammetry experiment condition
Figure 16 is to use erbium as heavy rare earth metalloid element, to use iminodiacetic acid, pH as complexing agent
Voltage-to-current CV curve when cyclic voltammetry is carried out in the case that condition is 7, potential range is 0~-7.0V.As based on
Want parameter by solution temperature from when being changed to 65 DEG C for 25 DEG C, it, can be within the scope of the reduction potential of electroreduction that erbium occurs
Observe the changed state of circulating current voltage curve.
Experimental result, the combination situation for showing heavy rare earth and complexing agent change with the variation of solution temperature,
Heavy rare earth reduction potential is also mobile (shift) to positive direction as a result,.It can from the circulating current voltage curve based on temperature of Figure 16
Know, it is mobile to positive direction for reaching the reduction potential of identical reduction current as the temperature increases, to improve heavy rare earth
The electrolytic reduction efficiency of metalloid.
Claims (22)
1. a kind of recovery method of heavy rare earth metalloid, using including the solution containing heavy rare earth metalloid ion, working electrode
And the electrolytic reduction device of comparative electrode recycles heavy rare earth metalloid, the feature of the recovery method of above-mentioned heavy rare earth metalloid exists
In, comprising:
Step a, addition is stablized when forming complex compound with heavy rare earth metalloid in the solution containing heavy rare earth metalloid ion
More than one complexing agents of the log value range of constant K within 3 to 32 form heavy rare earth metalloid ion-ligand complex compound；
And
Step b is electrochemically handled to recycle heavy rare earth metalloid.
2. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that above-mentioned heavy rare earth metalloid from
Son is selected from being made of ruthenium ion, gadolinium ion, terbium ion, dysprosium ion, holmium ion, erbium ion, thulium ion, ytterbium ion and lutetium ion
One or more of group heavy rare earth metalloid ion.
3. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that above-mentioned heavy rare earth metalloid from
Son is the heavy rare earth metalloid ion selected from one or more of the group being made of erbium ion, thulium ion and ytterbium ion.
4. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that above-mentioned heavy rare earth metalloid from
Son is erbium ion.
5. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that before above-mentioned steps a, on
The recovery method for stating heavy rare earth metalloid further includes that the pH of the solution containing heavy rare earth metalloid ion is adjusted to 13 is below
Step.
6. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that before above-mentioned steps a, on
The recovery method for stating heavy rare earth metalloid further includes the step that the pH of the solution containing heavy rare earth metalloid ion is adjusted to 1 to 12
Suddenly.
7. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that before above-mentioned steps a, on
The recovery method for stating heavy rare earth metalloid further includes the step that the pH of the solution containing heavy rare earth metalloid ion is adjusted to 3 to 10
Suddenly.
8. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that before above-mentioned steps a, on
The recovery method for stating heavy rare earth metalloid further includes the step that the pH of the solution containing heavy rare earth metalloid ion is adjusted to 4 to 7
Suddenly.
9. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that added in above-mentioned steps a
The complexing agent added is selected from one of the group being made of glycine, ethylenediamine tetra-acetic acid, iminodiacetic acid and nitrilotriacetic acid
Above complexing agent.
10. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that added in above-mentioned steps a
The complexing agent added is the complexing agent selected from one or more of the group being made of glycine and iminodiacetic acid.
11. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that added in above-mentioned steps a
The complexing agent added is iminodiacetic acid.
12. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that the electrification in above-mentioned steps b
Processing is learned selected from one or more of the group being made of electroreduction, electroextraction, electrorefining and electrolysis.
13. the recovery method of heavy rare earth metalloid according to claim 1, which is characterized in that the electrochemistry of above-mentioned steps b
Processing is electroreduction.
14. a kind of recovery system of heavy rare earth metalloid, by electroreduction processing come from containing heavy rare earth metalloid ion and
Heavy rare earth metalloid is recycled in the industrial wastewater of complexing agent, the recovery system of above-mentioned heavy rare earth metalloid is characterised by comprising:
(a) waste water tank, (b) comparative electrode, (c) working electrode and (d) potentiostat, when forming complex compound with heavy rare earth metal, institute
The log value range for stating the stability constant K of complexing agent is 3 to 32.
15. the recovery system of heavy rare earth metalloid according to claim 14, which is characterized in that above-mentioned heavy rare earth metalloid
Ion is selected from by ruthenium ion, gadolinium ion, terbium ion, dysprosium ion, holmium ion, erbium ion, thulium ion, ytterbium ion and lutetium ion group
At one or more of group heavy rare earth metalloid ion.
16. the recovery system of heavy rare earth metalloid according to claim 14, which is characterized in that above-mentioned heavy rare earth metalloid
Ion is the heavy rare earth metalloid ion selected from one or more of the group being made of erbium ion, thulium ion and ytterbium ion.
17. the recovery system of heavy rare earth metalloid according to claim 14, which is characterized in that above-mentioned heavy rare earth metalloid
Ion is erbium ion.
18. the recovery system of heavy rare earth metalloid according to claim 14, which is characterized in that above-mentioned complexing agent be selected from
The complexing agent of one or more of the group being made of glycine, ethylenediamine tetra-acetic acid, iminodiacetic acid and nitrilotriacetic acid.
19. the recovery system of heavy rare earth metalloid according to claim 14, which is characterized in that above-mentioned complexing agent be selected from
The complexing agent of one or more of the group being made of glycine and iminodiacetic acid.
20. the recovery system of heavy rare earth metalloid according to claim 14, which is characterized in that above-mentioned complexing agent is imido
Base oxalic acid.
21. the recovery system of heavy rare earth metalloid according to claim 14, which is characterized in that above-mentioned working electrode is titanium
Material electrode.
22. the recovery system of heavy rare earth metalloid according to claim 14, which is characterized in that above-mentioned comparative electrode is platinum
Electrode.
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| KR1020160038986A KR101714965B1 (en) | 2016-03-31 | 2016-03-31 | Electrochemical Recovery Method of Heavy Rare Earth Metals |
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| SI3660174T1 (en) * | 2018-11-27 | 2022-01-31 | Institut "Jozef Stefan" | A method for recovery of nd2fe14b grains from bulk sintered nd-fe-b magnets and/or magnet scraps by electrochemical etching |
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| US6306276B1 (en) * | 1997-10-08 | 2001-10-23 | Univ California | Aqueous electrodeposition of rare earth and transition metals |
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| CN102140662A (en) * | 2011-01-18 | 2011-08-03 | 浙江大学 | Method for preparing NaYF4: yb, er up-conversion fluorescent material by electrodeposition |
| CN102719864A (en) * | 2012-06-28 | 2012-10-10 | 上海大学 | Method for preparing cerium-containing zinc coating |
| CN103014761A (en) * | 2012-12-22 | 2013-04-03 | 广州有色金属研究院 | Method for electrolytically reducing europium |
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| US3932225A (en) * | 1971-11-03 | 1976-01-13 | Hahn-Meitner-Institut Fur Kernforschung Berlin Gmbh | Process for separately recovering uranium, transuranium elements, and fission products of uranium from atomic reactor fuel |
| US6306276B1 (en) * | 1997-10-08 | 2001-10-23 | Univ California | Aqueous electrodeposition of rare earth and transition metals |
| CN1485466A (en) * | 2002-09-27 | 2004-03-31 | 长沙高新技术产业开发区英才科技有限 | Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material |
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| CN102140662A (en) * | 2011-01-18 | 2011-08-03 | 浙江大学 | Method for preparing NaYF4: yb, er up-conversion fluorescent material by electrodeposition |
| CN102719864A (en) * | 2012-06-28 | 2012-10-10 | 上海大学 | Method for preparing cerium-containing zinc coating |
| CN103014761A (en) * | 2012-12-22 | 2013-04-03 | 广州有色金属研究院 | Method for electrolytically reducing europium |
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