CN1013888B - Process and equipment for prepn. of dysprosium-neodymium alloy - Google Patents
Process and equipment for prepn. of dysprosium-neodymium alloyInfo
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- CN1013888B CN1013888B CN 89103793 CN89103793A CN1013888B CN 1013888 B CN1013888 B CN 1013888B CN 89103793 CN89103793 CN 89103793 CN 89103793 A CN89103793 A CN 89103793A CN 1013888 B CN1013888 B CN 1013888B
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- dysprosium
- electrolysis
- ionogen
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Abstract
The present invention relates to a technological method and a device for preparing dysprosium-neodymium alloys in the technical field of rare earth fire metallurgy. The present invention adopts a fluoride electrolyte system and uses oxides as raw materials, and dysprosium-neodymium alloys containing 2 to 10 wt% of dysprosium is prepared by a salt melting electrolysis method in a purpose-made graphitic cell. The alloy has the advantages of low melting point, stable component and low impurity content, and can become ideal raw materials for preparing Nd-Fe-B permanent magnetic materials with high coercive force. The present invention has the advantages of simple technological device, continuous production, less investment and obvious effect, and is suitable for being adopted by township enterprises and individual factories.
Description
A kind of preparation technology's method and device thereof that relates to the dy-nd alloys of rare earth pyrometallurgy technical field.
As everyone knows, the rare earth metal dysprosium is the important interpolation element of preparation high-performance Ne-Fe-B permanent-magnet material; Because the adding of dysprosium can improve the coercive force and the use temperature of Nd-Fe-Bo permanent magnet material greatly,, the demand of metal dysprosium, neodymium metal is also day by day all increased in recent years along with the develop rapidly of science and technology and the continuous expansion of rare earth permanent magnet Application Areas.
Because metal dysprosium character is active; fusing point height (1409 ℃) can only adopt the preparation of metallothermic reduction method so far; promptly under high temperature (greater than fusing point) high vacuum (or argon shield); adopt more active basic metal or alkaline-earth metal to make reductive agent; the compound of reduction dysprosium makes metal dysprosium; this method need be with special equipment and expensive reductive agent, so production cost is very high, can't mass production.
There is the people once to adopt consumable iron cathode electrolytic process at present, prepared dysprosium iron, the neodymium Dy-Fe alloy.But do not solve the stable control problem of composition so far, do not realize large scale continuous prod yet.Strength of current 100A, the longest electrolysis time 16 hours obtains dy-nd alloys and is no more than 3Kg, (referring to EP, Patents, NO0229516).
The purpose of this invention is to provide a kind of preparation technology's method of dy-nd alloys and be the device of the designed manufacturing of this method, this alloy ingredient is stable, fusing point is low, but with this device continuous production, the needs of permanent magnetism industry have been satisfied, its technical indicator is: strength of current is 1600A, and the longest electrolysis time is 72～300 hours, the dy-nd alloys 90～360Kg that obtains.The fluctuation of the content of dysprosium is below 1% in the alloy.
The present invention is achieved in that
Adopted graphitic cell, the graphite tube anode, the molybdenum bar negative electrode, and the mixture that has adopted neodymium fluoride-dysprosium fluoride-lithium fluoride-barium fluoride is as ionogen, adopt the mixture of Neodymium trioxide and dysprosium oxide to do raw material, (1100 ℃～1150 ℃) molten salt electrolysis makes and contains dysprosium 3～10%(% meter by weight under the high temperature) dy-nd alloys, its electrolytic process is as follows:
(A) under the high temperature, Neodymium trioxide, dysprosium oxide be dissolved at first that electrolysis of fluorides matter is molten stops, and dissociates:
(B) under the direct current electric field action, positive and negative ion is respectively to the moon, anode movement, and on electrode, carry out the selectivity exoelectrical reaction.
The anode principal reaction is:
The negative electrode principal reaction is:
Certainly the anode motion removes O
2-Also has F
-, but because F
-Deposition potential compare O
2-Deposition potential corrigendum, therefore be difficult on anode, discharging and separate out; The same Nd that removes to cathode motion
3+, D
3+Outer Li in addition
+, Ba
2+Deng, also because Li
+, Ba
2+Deposition potential compare Nd
3+, Dy
3+More negative, therefore be difficult on negative electrode, separating out.So its electrolytic result is Nd, Dy separates out and forms alloy, is collected in the alloy receptor of negative electrode below.
Advantage of the present invention is:
(1) dy-nd alloys and the existing single Metal Melting that adopts Technology of the present invention and device to prepare is legal (promptly two kinds of single metals of preparing in advance with electrolytic process or hot reducing method, be fused together under the high temperature) compare with hot reducing method (promptly adopting under the reductive agent high temperature two kinds of single metallic compounds of reduction to make the method for alloy), simplified technology, saved reductive agent, avoid use by reductive agent to the impurity that alloy brings, greatly reduced production cost;
(2) present method has been selected the alloy ingredient of neodymium as dysprosium for use, and because of the two all is a rare earth element, performance is close, the deposition potential under the high temperature also close (1000 ℃ the time, Nd/Nd
3+Electropotential is 0.28V, Dy/Dy
3+Electropotential is 0.42V) so be easier to obtain stable alloy ingredient;
(3) product of the present invention contains dysprosium about 3～10% (weight percentage) and has lower fusing point (1000～1100 ℃), therefore realized low-temperature electrolytic, its electrolysis temperature is 1050 ℃～1150 ℃, and this will reduce that the cell construction material at high temperature is corroded and to the pollution of alloy;
(4) alloy ingredient dysprosium and neodymium all are the main raw materials of Nd-Fe-Bo permanent magnet material or add element, and the dysprosium in the neodymium-iron-boron magnetic material, the ratio of neodymium composition was near 1: 10, and as seen adopting alloy product of the present invention to produce the high-performance Ne-Fe-B material is economical rationality;
(5) equipment of the present invention's employing is simple, easy to operate, produces continuously less investment, instant effect.
(6) processing method of the present invention and device thereof can be applied to the preparation of single light rare earth metal (lanthanum, cerium, praseodymium, neodymium) and norium.
In sum, it is ideal that alloy product of the present invention is used to prepare the high-performance Ne-Fe-B magneticsubstance, it is advanced that molten salt electrolysis of the present invention prepares the dy-nd alloys novel process, if can be used for industrial production and will obtain favorable economic benefit and social benefit.
The concrete structure of invention is provided by following embodiment and accompanying drawing thereof.
Fig. 1 is the preparation dy-nd alloys apparatus structure synoptic diagram that proposes according to the present invention.
Fig. 2 is the preparation technology's method flow diagram according to dy-nd alloys proposed by the invention.
The drawing explanation:
Electrolyzer (1), cast iron cover (2), asbestos powder lagging material (3), graphite anode tube (4), thermopair (5), negative electrode conducting plates (6), anode conducting plate (7), molybdenum negative electrode (8), alloy receptor (9), Neodymium trioxide (10), dysprosium oxide (11), Quilonum Retard (12), barium carbonate (13), dysprosium fluoride (14), neodymium fluoride (15), lithium fluoride (16), barium fluoride (17), electrolysis raw material (18), ionogen (19), carbonic acid gas (20), dy-nd alloys (21).
Below in conjunction with accompanying drawing in detail concrete processing method of the present invention and device are described in detail.
Preparation technology's method of dy-nd alloys adopts molten salt electrolysis, its technical process as shown in Figure 2, its step is as follows:
The electrolytical preparation of the first step:
It is to have selected neodymium fluoride (15) for use that molten salt electrolysis prepares dy-nd alloys, dysprosium fluoride (14), lithium fluoride (16), barium fluoride (17) is as ionogen (19), and these products can't be supplied on the current market in a large number, therefore can use Neodymium trioxide (10) respectively, dysprosium oxide (11), Quilonum Retard (12), barium carbonate (13) is made raw material, voluntarily preparation.With the fluorochemical that makes according to a certain percentage, as: neodymium fluoride (15) is 72～82%, and dysprosium fluoride (14) is 2～10%, lithium fluoride (16) is 5～15%, barium fluoride (17) is 5～10%, and (aforementioned proportion all % meter) by weight mixes obtaining ionogen (19).
The second step fused salt electrolysis
At first the ionogen (19) for preparing is added 3% rare earth oxide (18) during electrolysis, (Neodymium trioxide and dysprosium oxide mixture by a certain percentage), put into electrolyzer (1) together, adopt direct current striking type of heating, make ionogen (19) the local heating fusing that contains 3% rare earth oxide, make ionogen (19) the self-conductive heating of its fusing then, melt until whole ionogen (19), and reach electrolysis temperature (1050～1150 ℃ time) and begin normal electrolysis, will keep anodic current density in the electrolytic process less than 1A/cm
2, cathode current density is near 10A/cm
2, along with dy-nd alloys (19) will continuously replenish electrolysis raw material (18) constantly separating out on the negative electrode in melt, the raw material composition is 2～10%Dy
2O
3And 90～98%Nd
2O
3(all % counts by weight).And regularly use the titanium spoon from alloy receptor (9), to scoop out dy-nd alloys (21), and inject pig mold, be cooled to ingot, the natural emptying of the carbonic acid gas that generates on the anode (20).
The apparatus structure details designed according to aforesaid method:
The present invention carries out in 1600A electrolyzer (1), and its trench structure as shown in Figure 1; Adopted the plumbago crucible of external diameter Φ 500mm to do electrolyzer (1); The crucible skin is surrounded by cast iron cover (2), is used for protecting plumbago crucible to prevent oxidation; Be filled with asbestos powder lagging material (3) between crucible and the iron cover; Diameter is that the special graphite anode tube (4) of Φ 300mm is done anode, and anode is inaccurate to be contacted with plumbago crucible; The anode tube is connected with positive source by anode conducting plate (7), contact is connected the elongated molybdenum bar of negative electrode (8) about by Φ 30mm and makes between anode tube and the conducting plates (7), and be connected with power cathode by negative electrode conducting plates (6), the molybdenum negative electrode is connected with conducting plates (6) contact, negative electrode below, plumbago crucible bottom center have molybdenum alloyage receptor (9), thermopair (5) inserts the plumbago crucible wall from the electrolyzer side bottom, carries out thermometric.
Embodiment 1. preparation contains Dy2.6～2.9(weight) the dy-nd alloys 70Kg of %.
This example has adopted high temperature electrolyser as shown in Figure 1 (1), the external diameter of its plumbago crucible is Φ 500mm, internal diameter is Φ 350mm, graphite anode tube external diameter is Φ 300mm, internal diameter is Φ 200mm, the elongated molybdenum bar of diameter of phi 30mm is done negative electrode (8), the plumbago crucible bottom center is equipped with diameter of phi 200mm, the molybdenum crucible of high 120mm is made alloy receptor (9), and its electrolytic condition is as shown in table 1, and Faradaic current is 1600A, time length is 72h, make dy-nd alloys 70Kg, because of raw material uses up blowing out, alloy ingredient sees Table 2 at last.
Embodiment 2. preparation contains dysprosium 9～10%(% meter by weight) dy-nd alloys 360Kg.
This example has adopted and example 1 identical electrolysis trench structure and schedule of operation, and electrolytic condition sees Table 1, and disposable continuous production 13 days makes dy-nd alloys 360Kg, contains dysprosium 9～10% in the alloy, and (% meter by weight) its Chemical Composition sees Table 2.
Table 1. electrolytic condition and technical indicator
Example 1 example 2
Electricity
Separate LiF 5～15 5～15
Matter BaF
25～10 5～10
Group NdF
377～82 72～77
Become DyF
32～3 8～10
（%）
Add
Material Nd
2O
3120 420
Amount Dy
2O
34 45
（Kg）
Close
Gold Nd 96 89
Become Dy 2.6～2.9 9.1～9.7
Part other 1.1～1.4 1.3～1.9
（%）
Average Faradaic current (A) 1,600 1600
Average cell voltage (V) 11 11
The continuous electrolysis time (h) 72 300
Alloy output (Kg) 90 360
Anodic current density (A/cm
2)＜1＜1
Cathode current density (A/cm
2)～10～10
Current efficiency (%) 58 53
Electrolysis temperature (C) 1050-1150 1050-1150
Table 2. alloy composition (%)
∑RE????Nd????Dy????Fe????C????Si????Ca
Execute example 1.＞98 96 2.6～2.9 0.16 0.11 0.08＜0.05
Execute example 2＞98 89 9.1～9.7 0.32 0.12 0.07＜0.05
Claims (2)
1, a kind of preparation technology's method that adopts the molten salt electrolysis preparation to contain dysprosium 3-10% dy-nd alloys is characterized in that adopting following technical process:
A. select electrolysis of fluorides matter (19) system for use, its ionogen (19) proportioning is: neodymium fluoride (15) NdF
3Be 72～82%, dysprosium fluoride (14) DyF
3Be 2～10%, lithium fluoride (16) LiF is 5～15%, barium fluoride (17) BaF
2Be 5～10%, (all % counts by weight);
B. to ionogen (19) in, add 3% rare earth oxide (18) (all % counts by weight) before the normal electrolysis, and employing direct current striking type of heating, make ionogen (19) the local heating fusing that contains 3% oxide compound, make the ionogen self-conductive heating of its fusing then, until whole ionogen (19) fusing finishing beginning electrolysis;
During C. normal electrolysis, melt temperature maintains between 1050 ℃～1150 ℃, and anodic current density is less than 1A/cm
2, cathode current density is near 10A/cm
2
D. in the electrolytic process, add the electrolysis raw material of Neodymium trioxide (10) and dysprosium oxide (11) continuously, the raw material composition is 2～10%Dy
2O
3And 90～98%Nd
2O
3(all % counts by weight);
E. the dy-nd alloys (21) of the last electrolysis generation of negative electrode (8) falls into alloy receptor (9), need from alloy receptor (9), dy-nd alloys (21) to be scooped out with the titanium spoon, inject pig mold, be cooled to ingot, the natural emptying of carbonic acid gas (20) that anode (4) generates.
2, implement the described square law device of claim 1, it is characterized in that: electrolyzer (1) is made by plumbago crucible, the outside is surrounded by cast iron cover (2), be filled with asbestos powder lagging material (3) between cast iron cover (2) and the plumbago crucible, special graphite anode tube (4) is connected with positive source by plumbago crucible insertion suitable for reading and by anode conducting plate (7); Molybdenum negative electrode (8) is positioned at the central authorities of anode tube (4) and is connected with power cathode by negative electrode conducting electrode (6); Molybdenum alloyage receptor (9) places negative electrode below, plumbago crucible bottom center position; Thermopair (5) inserts the plumbago crucible wall from electrolyzer (1) side bottom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103793 CN1013888B (en) | 1989-06-09 | 1989-06-09 | Process and equipment for prepn. of dysprosium-neodymium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103793 CN1013888B (en) | 1989-06-09 | 1989-06-09 | Process and equipment for prepn. of dysprosium-neodymium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040399A CN1040399A (en) | 1990-03-14 |
| CN1013888B true CN1013888B (en) | 1991-09-11 |
Family
ID=4855287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89103793 Expired CN1013888B (en) | 1989-06-09 | 1989-06-09 | Process and equipment for prepn. of dysprosium-neodymium alloy |
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443640C (en) * | 2005-12-30 | 2008-12-17 | 重庆大学 | Apparatus and method for adding element during metal smelting process |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003221351A1 (en) * | 2002-03-13 | 2003-09-22 | Santoku Corporation | Process for producing r-iron alloy |
| CN103924265A (en) * | 2014-04-28 | 2014-07-16 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Method for preparing rare-earth dysprosium alloy by molten salt electrolysis |
| CN105420762B (en) * | 2015-11-25 | 2018-11-16 | 成都先进金属材料产业技术研究院有限公司 | Cell construction and molten salt electrolysis method |
| CN106400057A (en) * | 2016-12-06 | 2017-02-15 | 中南大学 | Energy-efficient rare earth metal electrolytic bath |
| CN106811644A (en) * | 2016-12-16 | 2017-06-09 | 包头稀土研究院 | Neodymium-iron alloy and preparation method thereof |
| CN108950605A (en) * | 2018-08-27 | 2018-12-07 | 王福刚 | A kind of method of quaternary molten salt system electrolytic preparation rare earth metal or alloy |
| CN111778524B (en) * | 2020-07-28 | 2021-06-04 | 巴彦淖尔市亿鑫新材料有限责任公司 | Leak-proof rare earth metal electrolytic tank device |
-
1989
- 1989-06-09 CN CN 89103793 patent/CN1013888B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443640C (en) * | 2005-12-30 | 2008-12-17 | 重庆大学 | Apparatus and method for adding element during metal smelting process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1040399A (en) | 1990-03-14 |
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