CN1865514A - Process for preparing cell-class mischmetal by fused salt electrolysis process and device therefor - Google Patents
Process for preparing cell-class mischmetal by fused salt electrolysis process and device therefor Download PDFInfo
- Publication number
- CN1865514A CN1865514A CN 200610074437 CN200610074437A CN1865514A CN 1865514 A CN1865514 A CN 1865514A CN 200610074437 CN200610074437 CN 200610074437 CN 200610074437 A CN200610074437 A CN 200610074437A CN 1865514 A CN1865514 A CN 1865514A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- fused salt
- fluoride
- electrolyzer
- salt electrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a battery grade composite rare earth metal manufacturing technology and equipment of melting salt electrolytic method in the rare earth product preparing domain, which comprises the following steps: melting the blended rare earth oxide in the fluoride flux; ionizing; evolving Ren+ to reduce into Re on the tungsten cathode surface at (60-70V/M) DC electric field; oxidizing O2- into O2 on the graphite anode surface; reacting O2 and graphite to produce CO2 into the air. The electrolyser is made of carborundum connecting silicon nitride material, which reduces electrolyte fusing point and improves the fluidity and stability.
Description
One, technical field
The present invention relates to a kind of fused salt electrolysis process production cell-grade mixed rare earth metals and reach, belong to the rare-earth products preparation field.
Two, background technology
The technology of the domestic existing production norium of China generally adopts the electrolysis of fused chloride salt method, and the disadvantage of this method is exactly that the partition of the norium produced is very unstable, can not satisfy vast norium user's requirement; And can produce a large amount of HCl, Cl in process of production
2Deng toxic gas, serious environment pollution, residual Cl element absorption airborne moisture post-etching metal and influence the quality of Ni:H battery and application product thereof in the product.
Electrolyzer adopts silicon carbide to substitute graphite material in conjunction with silicon nitride material, and the C content in reduction and the elimination electrolysis rare earth metal prevents the fused salt seepage, improves the work-ing life of electrolyzer, has solved the Universal Problems of Rare Earth Production enterprise.
Three, summary of the invention
The technical problem that the present invention solves is: the product partition is stable, environmental protection and energy saving, production cost reduce; And can reduce and eliminate the C content in the electrolysis rare earth metal, prevent the fused salt seepage, improve the work-ing life of electrolyzer.
The technical solution step is as follows:
(1) being is raw material with the mixed rare-earth oxide, when temperature is 950～1050 ℃, mixed rare-earth oxide is added in the fluorochemical melt, and ionization takes place rare earth oxide immediately;
(2) under the effect of DC electric field 60-70V/M, electrolysis voltage 10V, electrolysis temperature are 980～1000 ℃, Re
N+Separate out on the tungsten cathode surface, be reduced to Re; O
2-Be oxidized to O on the graphite anode surface
2, and in graphite reaction generation CO
2Enter air;
Wherein: n=3～4;
(3) norium of Sheng Chenging is lanthanum, cerium, praseodymium, neodymium alloy, La26-30%, Ce50-54%, Pr3-7%, Nd13-17%.
Contain La in the mixed rare-earth oxide
2O
326-30%, CeO
250-54%, Pr
6O
113-7%, Nd
2O
313-17%.
Melt is the fluorochemical melt, and wherein the fluorochemical melt comprises rare earth fluorine, lithium fluoride, and its ratio is 5: 1.
Rare earth fluorine is lanthanum fluoride 47-53%, cerium fluoride 32-38%, praseodymium fluoride 2-4%, neodymium fluoride 8-14%.
Electrolyzer adopts silicon carbide to make in conjunction with silicon nitride material.
Quality product of the present invention has reached international like product level:
Current efficiency is greater than 65%, and the metal direct yield is greater than 95%.
Quality product: La 28 ± 2%, Ce 52 ± 2%, and Pr 5 ± 1%, and Nd 15 ± 1%, Fe≤0.15%, C≤0.05%, O≤0.01%, Si≤0.01%, W+Mo≤0.05%.
The present invention selects the ternary electrolyte system for use, reduces the ionogen fusing point, improves flowability and stable.Show as in actual production: norium separates fully with ionogen, avoids being mingled with, ionogen physical and chemical performance long-term stability.
In addition because present anode electrolytic cell structure is a column, so complicated operation, energy consumption height, and be unfavorable for effective electrolysis of electrolyzer different depths makes raw material amass bottom at electrolyzer deeply, has reduced yield.
Electrolyzer adopts silicon carbide to substitute graphite material in conjunction with silicon nitride material, and the C content in reduction and the elimination electrolysis rare earth metal prevents the fused salt seepage, improves the work-ing life of electrolyzer.
The present invention not only can reduce cost, and the foreign matter content of product is also very low, and environmental protection and energy saving are innovative production technique.
Four, description of drawings
Cell construction synoptic diagram of the present invention;
Five, embodiment
Embodiment 1
The present invention is with rare earth oxide (La
2O
323-33%, CeO
247-57%, Pr
6O
113-7%, Nd
2O
312-18%) be raw material, rare earth fluorine (lanthanum fluoride 48-52%, cerium fluoride 33-37%, praseodymium fluoride 2-4%, neodymium fluoride 9-13%), lithium fluoride binary system are ionogen, the solubleness of oxide compound in melt is 2～5%, utilize tungsten cathode electrolysis mixed rare-earth oxide, obtain battery grade mischmetal.
Fused salt electrolysis process is produced the equipment of battery grade mischmetal; comprise that shell 1, lagging material 2, interior protective shell 3, negative electrode 4, silicon carbide are in conjunction with silicon nitride material electrolyzer 5, anode 6, receptor 7; the anode 6 that invests electrolyzer 5 internal surfaces is shaped as back taper, and electrolyzer 5 adopts silicon carbide in conjunction with silicon nitride material.Electrolyzer 5 is through thorough drying, and connect graphite starting the arc heating in electrolyzer 5 with making the arc machine, ionogen was slowly added electrolyzer 5 by 5: 1 after the mixed, after treating that fused salt all melts, when electrolysis liquid surface reaches anode 6 middle and upper parts, temperature is in the time of 950～1050 ℃, insert tungsten cathode 4 and carry out electrolysis, oxide compound adds by automatic charging equipment equal and quantitative (110-130g/min), under the effect of DC electric field (62-68V/m), electrolysis voltage 9～11V, electrolysis temperature are 950～1050 ℃, and electrolysis time is 160～200 minutes, Re
N+Separate out on tungsten cathode 4 surfaces, be reduced to Re; O
2-Be oxidized to O on graphite anode 6 surfaces
2, and in graphite reaction generation CO
2Enter air.
Wherein: n=3～4;
After 160～200 minutes, dip metal liquid in the receptor 7, and liquid is poured into the ingot mould ingot casting with the titanium spoon.
The norium that generates is lanthanum, cerium, praseodymium, neodymium alloy, La23-33%, Ce47-57%, Pr3-7%, Nd12-18%.
Embodiment 2
The present invention is with rare earth oxide (La
2O
326-30%, CeO
250-54%, Pr
6O
113-7%, Nd
2O
313-17%) be raw material, rare earth fluorine (lanthanum fluoride 49-51%, cerium fluoride 34-36%, praseodymium fluoride 2-4%, neodymium fluoride 10-11%), lithium fluoride binary system are ionogen, the solubleness of oxide compound in melt is 2～5%, utilize tungsten cathode electrolysis mixed rare-earth oxide, obtain battery grade mischmetal.
Fused salt electrolysis process is produced the equipment of battery grade mischmetal; comprise that shell 1, lagging material 2, interior protective shell 3, negative electrode 4, silicon carbide are in conjunction with silicon nitride material electrolyzer 5, anode 6, receptor 7; the anode 6 that invests electrolyzer 5 internal surfaces is shaped as back taper, and electrolyzer 5 adopts silicon carbide in conjunction with silicon nitride material.Electrolyzer 5 is through thorough drying, and connect graphite starting the arc heating in electrolyzer 5 with making the arc machine, ionogen was slowly added electrolyzer 5 by 5: 1 after the mixed, after treating that fused salt all melts, when electrolysis liquid surface reaches anode 6 middle and upper parts, temperature is in the time of 950～1050 ℃, insert cloudy 4 utmost points of tungsten and carry out electrolysis, oxide compound adds by automatic charging equipment equal and quantitative (120g/min), under the effect of DC electric field (64-66V/m), electrolysis voltage 10V, electrolysis temperature are 980～1000 ℃ ℃, and electrolysis time is 180 minutes, Re
N+Separate out on tungsten cathode 4 surfaces, be reduced to Re; O
2-Be oxidized to O on graphite anode 6 surfaces
2, and in graphite reaction generation CO
2Enter air.
Wherein: n=3～4;
After 180 minutes, dip metal liquid in the receptor 7, and liquid is poured into the ingot mould ingot casting with the titanium spoon.
The norium that generates is lanthanum, cerium, praseodymium, neodymium alloy, La26-30%, Ce50-54%, Pr3-7%, Nd13-17%.
Claims (5)
1, fused salt electrolysis process is produced cell-grade mixed rare earth metals, it is characterized in that:
(1) being is raw material with the mixed rare-earth oxide, when temperature is 920～1080 ℃, mixed rare-earth oxide is added in the fluorochemical melt, and ionization takes place rare earth oxide immediately;
(2) under the effect of DC electric field 60-70V/m, electrolysis voltage 8～12V, electrolysis temperature are 920～1080 ℃, Re
N+Separate out on the tungsten cathode surface, be reduced to Re; O
2-Be oxidized to O on the graphite anode surface
2, and in graphite reaction generation CO
2Enter air;
Wherein: n=3～4;
(3) norium of Sheng Chenging is the alloy of lanthanum, cerium, praseodymium, neodymium, La 22-34%, Ce46-58%, Pr 2-8%, Nd 11-19%.
2, fused salt electrolysis process according to claim 1 is produced mixed rare earth metals, it is characterized in that: contain La in the mixed rare-earth oxide
2O
322-34%, CeO
246-58%, Pr
6O
112-8%, Nd
2O
311-19%.
3, fused salt electrolysis process according to claim 1 is produced mixed rare earth metals, and it is characterized in that: melt is the fluorochemical melt, and wherein the fluorochemical melt comprises rare earth fluorine, lithium fluoride, and its ratio is 5: 1.
4, fused salt electrolysis process according to claim 3 is produced mixed rare earth metals, and it is characterized in that: rare earth fluorine is lanthanum fluoride 47-53%, cerium fluoride 32-38%, praseodymium fluoride 2-4%, neodymium fluoride 8-14%.
5, a kind of fused salt electrolysis process is produced the equipment of battery grade mischmetal; comprise that shell (1), lagging material (2), interior protective shell (3), negative electrode (4), silicon carbide are in conjunction with silicon nitride material electrolyzer (5), anode (6), receptor (7); the anode (6) that invests electrolyzer (5) internal surface is shaped as back taper, it is characterized in that: electrolyzer (5) adopts silicon carbide in conjunction with silicon nitride material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610074437 CN1865514A (en) | 2006-04-09 | 2006-04-09 | Process for preparing cell-class mischmetal by fused salt electrolysis process and device therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610074437 CN1865514A (en) | 2006-04-09 | 2006-04-09 | Process for preparing cell-class mischmetal by fused salt electrolysis process and device therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1865514A true CN1865514A (en) | 2006-11-22 |
Family
ID=37424657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610074437 Pending CN1865514A (en) | 2006-04-09 | 2006-04-09 | Process for preparing cell-class mischmetal by fused salt electrolysis process and device therefor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1865514A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230195A (en) * | 2011-07-15 | 2011-11-02 | 包头市玺骏稀土有限责任公司 | Method for dipping special graphite anode for rare earth electrolysis |
| CN101845641B (en) * | 2009-12-21 | 2012-01-25 | 内蒙古科技大学 | Immersion-type rare earth electrolyzer |
| CN104109882A (en) * | 2013-04-19 | 2014-10-22 | 北京有色金属研究总院 | Electrolysis tank and electrolysis technology used to prepare rare earth metal and alloy thereof |
| CN105648230A (en) * | 2015-04-24 | 2016-06-08 | 洛阳高新永杰钨钼材料有限公司 | Tungsten cathode |
| CN107227468A (en) * | 2017-07-31 | 2017-10-03 | 赣州市恒源科技股份有限公司 | A kind of automatic electrolysis installation of rare earth metal |
-
2006
- 2006-04-09 CN CN 200610074437 patent/CN1865514A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845641B (en) * | 2009-12-21 | 2012-01-25 | 内蒙古科技大学 | Immersion-type rare earth electrolyzer |
| CN102230195A (en) * | 2011-07-15 | 2011-11-02 | 包头市玺骏稀土有限责任公司 | Method for dipping special graphite anode for rare earth electrolysis |
| CN104109882A (en) * | 2013-04-19 | 2014-10-22 | 北京有色金属研究总院 | Electrolysis tank and electrolysis technology used to prepare rare earth metal and alloy thereof |
| CN104109882B (en) * | 2013-04-19 | 2016-12-28 | 北京有色金属研究总院 | For preparing electrolysis bath and the electrolysis process of rare earth metal and alloy thereof |
| CN105648230A (en) * | 2015-04-24 | 2016-06-08 | 洛阳高新永杰钨钼材料有限公司 | Tungsten cathode |
| CN107227468A (en) * | 2017-07-31 | 2017-10-03 | 赣州市恒源科技股份有限公司 | A kind of automatic electrolysis installation of rare earth metal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2014019513A2 (en) | Rare earth metal, rare earth metal alloy and method for the preparation of same by molten salt electrolysis | |
| CN1827860A (en) | Process and apparatus for producing Dy-Fe alloy by molten salt electrolysis method | |
| CN105624737B (en) | A kind of method for preparing magnesium-rare earth and rare-earth yttrium neodymium magnesium alloy | |
| US7744814B2 (en) | Method for producing a magnesium-lanthanum praseodymium cerium intermediate alloy | |
| CN102618883B (en) | Method for direct electrolytic refining of crude lead | |
| CN1936085A (en) | Method for preparing aluminium and aluminium alloy by low temperature molten-salt electrolysis | |
| CN1163637C (en) | Process for producing rare earth metals | |
| CN1837411A (en) | Method for preparing refractory active metal or alloy | |
| CN1865514A (en) | Process for preparing cell-class mischmetal by fused salt electrolysis process and device therefor | |
| CN101117723A (en) | Method for preparing Gd-Mg intermediate alloy by fluorination system coelectrodeposition | |
| CN102220606B (en) | Preparation method of silicon particles by inert anode molten salt electrolysis | |
| WO2013185539A1 (en) | Inert alloy anode used for aluminum electrolysis and preparation method therefor | |
| CN107794551B (en) | A kind of copper dysprosium intermediate alloy and preparation method thereof of fused salt electrolysis codeposition preparation | |
| CN101054686A (en) | Process for purifying zinc from casting zinc residue | |
| CN105603461A (en) | Method of preparing praseodymium-neodymium-dysprosium-terbium quaternary alloy by molten salt electrolysis | |
| CN112921360B (en) | Method for preparing rare earth metal by molten salt electrolysis | |
| CN100588732C (en) | Process for preparing magnesium-lithium-dysprosium alloy by fused salt electrolysis | |
| CN107287470B (en) | A kind of lead storage battery grid alloy and preparation method comprising nanometer tungsten carbide material | |
| CN1013888B (en) | Process and equipment for prepn. of dysprosium-neodymium alloy | |
| CN105177632B (en) | It is rare earth modified to prepare copper aluminium rare earth intermediate alloy molten salt electrolysis method and alloy | |
| CN103484895B (en) | A kind of electrolgtic aluminium inert alloy anode and preparation method thereof | |
| CN108717975A (en) | A kind of preparation method of negative material, battery and its negative material | |
| CN104962954A (en) | Method for preparing rare earth-aluminum-copper interalloy by fused salt electrolysis and alloy thereof | |
| CN101302594B (en) | Mg-Li-Ce-La alloy and fused salt electrolysis preparation thereof | |
| CN103132108B (en) | Method for preparing heat resistance magnesia-alumina-neodymium alloy through electrolysis in fused salt system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |