CN85108786A - The electrolysis process of preparation rare earth metals or its alloy and implement the device of this method - Google Patents
The electrolysis process of preparation rare earth metals or its alloy and implement the device of this method Download PDFInfo
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- CN85108786A CN85108786A CN198585108786A CN85108786A CN85108786A CN 85108786 A CN85108786 A CN 85108786A CN 198585108786 A CN198585108786 A CN 198585108786A CN 85108786 A CN85108786 A CN 85108786A CN 85108786 A CN85108786 A CN 85108786A
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
Abstract
The invention relates to the preparation technology of electrolysis rare earth metal or rare-earth-based alloy molten salt electrolyte and implement the electrolyzer of this technology.According to this invention, at first be a kind of electrolytic solution, it has a kind of rare-earth metal chloride at least, at least a basic metal or alkaline earth metal chloride and at least a basic metal or alkaline metal fluoride cpd.According to the present invention, electrolyzer has a basin 2, and the vertical bearing of trend of basin runs in and puts conduit 3.
Description
The invention relates to the preparation method of electrolysis rare earth metal or rare-earth-based alloy molten salt electrolyte, and the device of realizing this technology.
This term of rare earths (RE) of this paper narration is meant any element except samarium, europium, ytterbium in yttrium family and the lanthanide.
At present, the melting media of electrolysis rare-earth metal chloride, particularly existing problem is that productive rate is very low during the melting media of electrolysis neodymium.This is because under the situation that rare-earth metal chloride exists, the solubleness of metal is very high.This method, at T.KU RITA(Denku Kagaku, 1,967 35 the volume, the 7th phase, 496-501 page or leaf) paper in description is arranged.That piece paper proposes, and by the molten salt electrolyte that Neodymium trichloride and Repone K are formed, productive rate does not reach 20% pure neodymium.
First purpose of the present invention is to realize that the electrolysis process under the technical scale condition prepares rare earth metals.
Second purpose of the present invention is that the Process that is fit to plant-scale preparation rare earth based alloy is provided.
At last, another object of the present invention provides the device of the above-mentioned technology of energy specific implementation.
For such purpose, according to the present invention, electrolysis rare earth metal or rare earth based alloy and preparation technology who contains at least a metal that is selected from rare earths and transition metal fusion saline solution and feature are to use a kind of electrolytic solution to comprise a kind of muriate of rare earth metal, the electrolytic solution of the fluorochemical of at least a basic metal or alkaline earth metal chloride and at least a basic metal or alkaline-earth metal at least.
The special concrete device of selecting for use according to the present invention, this electrolytic solution contains lithium at least and makes basic metal.
In addition, the present invention also relates to the electrolyzer of the above-mentioned electrolytic solution industry of specific implementation, it is characterized in that containing a basin, the bottom of jar puts in a delivery pipe, and the interior transverse section of pipe is less than the transverse section of basin.
The special concrete device according to the present invention, delivery pipe is aimed at the bottom centre of jar.
Method of the present invention can be produced the alloy of highly purified metal or high rare earth metals content under industrialized condition, and can obtain surpassing 80% productive rate.
From following narration and specific and unrestricted concrete device that technology is implemented, can more easily estimate characteristics of the present invention and advantage.
Fig. 1 is a sectional schematic diagram according to first concrete device of electrolytic process of the present invention.
Fig. 2 is the sectional schematic diagram according to second concrete device of electrolyzer of the present invention.
As mentioned above, the present invention relates to the preparation of rare earth metal and rare earth based alloy, be applied to especially be prepared by neodymium chloride the method for neodymium metal, in fact, improved significantly especially the productive rate of neodymium.
The present invention also relates to the preparation of alloy, especially the preparation of meodymium-base alloy.
Can be with the alloy of said method preparation, neodymium-lanthanum for example, the alloy between the alloy between neodymium-cerium or neodymium-praseodymium rare earths or one or more rare earth metals and the metal selected from one group of magnesium-yttrium-transition metal. The transition metal that can adopt comprises having all metals that fusing point is higher than electrolytic cell fuse salt liquid temp. For example, this temperature can change between 650 ℃-1100 ℃. Iron, cobalt, nickel and chromium are the examples of these transition metal, according to the present invention, especially can prepare following alloy: neodymium-iron, lanthanum-iron, neodymium-lanthanum-iron and praseodymium-iron.
According to the present invention, the first step of this technology is the rare-earth metal chloride of preparation metallic forms, to contain the polynary first step that rare earth alloys are taked be that preparation contains the molten electrolyte that each rare-earth metal chloride mixes in order to produce, and these chloride water content are got by weight preferably should be less than 6%.
The electrolyte that is used for electrolytic cell operation except rare-earth metal chloride or chloride, also should contain one or more alkali metal or alkaline earth metal chloride and one or more alkali metal or alkali earth metal fluoride.
Having found that, is favourable with lithium as alkali metal. In electrolyte, exist lithium halide can improve significantly productive rate.
At last, according to preferred embodiment of the present invention, electrolyte contains a kind of lithium fluoride and lithium chloride at least. Like that, usually, obtain best productive rate.
Electrolyte middle rare earth metal chloride or chloride ratio can change between 10%-70% by weight, especially between 15% and 45%.
In addition, the weight ratio between alkali metal or alkaline earth metal chloride or chloride and a kind of fluoride or the multiple fluoride is preferably between 1.5: 1 and 3: 1 and changes.
At last, using content at least is that 15% a kind of fluorochemical or the electrolytic solution of multiple fluorochemical are favourable.
In the electrolysis procedure process, the temperature of electrolytic solution will be higher than the melt temperature of electrolytic solution.
Usually, the temperature of electrolytic solution is from 650 ℃-1100 ℃, especially between 700 ℃ and 900 ℃.
About the detailed conditions of electrolysis procedure, will narrate hereinafter.
About electrode, the general graphite anode that uses of device, the character of negative electrode can change according to the type of prepared product.
When a kind of pure rare earth of preparation family metal, preferably use tungsten to make negative electrode.It also is possible using and making negative electrode with the rare earth metals identical materials of preparation.The negative electrode of same type is usually used in preparing the alloy that various rare earth metals are formed.
When a kind of rare earth based alloy that contains transition metal of preparation, negative electrode will be the negative electrode of a consumable, and this negative electrode is to be made by the alloy of transition metal or rare earth metal-transition metal of the same race of being produced.
Terminal voltage between the electrode is generally the 4-10 volt.The current density of negative electrode (cod) can be at 70 peace/decimetres
2With 100 dutiful rice
2Between change.Particularly at 100 peace/decimetres
2With 250 peace/decimetres
2Between, anodic current density (aod) is generally at 50-250 peace/decimetre
2Between change.
In addition, find to have 1.01 * 10 at least in the gas phase
4The Pa(0.1 normal atmosphere) under the condition that chlorine dividing potential drop exists, be favourable for the electrolysis procedure that is carried out.In this case, according to reaction TORCl+Cl
2→ TRCl
3+ 1/2O
2, the oxychloride that exists in the electrolytic solution transforms; In fact, oxychloride is introduced into as the impurity of rare-earth metal chloride.At this moment, used initial product can be to contain oxychloride content by weight at the rare earths muriate more than 25%.
Narrate the following examples now.At the 10-25 mm dia, have in the alumina crucible of graphite anode and carry out described experiment; In routine 1-4, interpole gap is 65 millimeters, and each electrolysis procedure obtains the metal that is produced after the crucible cooling.The composition of electrolytic solution is represented with weight percent (%).
The metal productive rate of regulation, the rare earth metal and the rare-earth metal chloride (TRCl of expression gained
3) ratio.
The production of embodiment 1 neodymium metal
Go up the molten mixture of the following composition of electrolysis 800 grams at the tungsten cathode of 850 ℃ of temperature (φ=4 millimeter): Neodymium trichloride 13.3%; Lithium chloride 62%; Lithium fluoride 24.7%.With being equivalent to cathode current density (cod) is 690 peace/decimetres
2With anodic current density be 60 peace/decimetres
2(aod) strength of current I is to carry out electrolysis procedure in 8.5 peaces.Terminal voltage is between the 4.6-5.0 volt between electrode.Electrolysis 4 hours, the metal productive rate is 40%, obtains 24.1 gram metals.The content of the neodymium of this metal, lithium, tungsten be respectively 98%, 0.07% and＜1%.
The production of the neodymium-iron alloy of embodiment 2 low iron contents
The composition of electrolytic solution (800 gram) is in close proximity to the used blended composition of embodiment 1 electrolysis: Neodymium trichloride 13%; Lithium chloride 62%; Lithium fluoride 25%.730 ℃ of temperature with contain on 65 negative electrodes that the gram neodymiums/iron alloy is done of 20% iron (preparing with calciothermics system this alloy before) and carry out electrolysis procedure.Electrically contact by rod iron.Faradaic current intensity is high, be 25 peaces, but this is equivalent to low cathode current density (110 peace/decimetres
2); Anodic current density 250 peace/decimetres
2After the electrolysis one hour 20 minutes, obtain the metal (the metal productive rate is 80.4%) of 48 grams, this metal contains neodymium 89% at least, iron 8.7% and lithium 0.1%.
The production of embodiment 3 neodymiums-iron alloy
Identical (Neodymium trichloride that contains oxychloride 7.5% and water 2.7%) that the material of electrolytic solution and composition and used temperature and example 2 are considered.Faradaic current intensity is lower (13.5 peace).On the negative electrode that is connected to form by (consumption) iron net and steel, cathode current density is 100 peace/decimetres
2The anodic current density value is 135 peace/decimetres
2After the electrolysis two hours 30 minutes, obtain the metal (the metal productive rate is 84%) of 50 grams; This metal contains neodymium 85% at least, iron 12% and lithium 0.7%.
(embodiment 4-8) if metal is 100%, presses TRCl in the following embodiments
3The required in theory corresponding time, draw the persistence of electrolysis procedure.
The production of embodiment 4 pure lanthanums
At first, use the fused solution of following composition: Lanthanum trichloride: 13%; Lithium chloride: 62%; Lithium fluoride: 25%.Used negative electrode is a tungsten bar, and cathode current density is 690 peace/decimetres
2, anodic current density is 60 peace/decimetres
2When temperature was 800 ℃, interpole gap was 65 millimeters.After time arrived, generation lanthanum content was at least 95% metal, and the metal productive rate is 33%.
The production of embodiment 5 lanthanums-iron alloy
The composition of electrolytic solution is as follows: Lanthanum trichloride: 25%; Lithium chloride: 53%; Lithium fluoride: 22%.Used negative electrode is an iron staff, and cathode current density is 165 peace/decimetres
2, anodic current density is 215 peace/decimetres
2, pole gap is 60 millimeters, and temperature is 840 ℃, and the time produces the alloy that contains lanthanum 92% and iron 7% after reaching 1.5 hours.
The production of embodiment 6 ammoniums-lanthanum alloy
It at first is the electrolytic solution of following composition: Neodymium trichloride: 26%; Lanthanum trichloride: 9%; Lithium chloride: 46%; Lithium fluoride: 19%.Negative electrode is a tungsten bar, and negative electrode is 235 peace/decimetres
2, interpole gap is 63 millimeters, and temperature is 860 ℃, and after electrolytic process reaches 0.7 hour, obtain the alloy of following composition: neodymium content is 81%; Lanthanum is 18%; Lithium is: 0.1%.
The production of embodiment 7 neodymiums-lanthanum-iron alloy
The composition of electrolytic solution is as follows: Neodymium trichloride: 15%; Lanthanum trichloride 10%; Lithium chloride: 53%; Lithium fluoride: 22%.
Negative electrode is an iron staff, and negative electrode is 100 peace/decimetres
2, negative electrode is 142 peace/decimetres
2, pole gap is 40 millimeters, and temperature is 750 ℃, and after electrolysis time reached 1.5 hours, obtain the following alloy of forming: neodymium content was 55%; Lanthanum is 37%; Iron is 9.2%; Lithium is 0.5%, and the metal productive rate is 74%.
The production of embodiment 8 praseodymiums-iron alloy
Use the electrolytic solution of following composition: praseodymium chloride: 25%; Lithium chloride 53%; Lithium fluoride 22%.Used identical of negative electrode and example 7.Cod is 100 peace/decimetres
2Aod is 140 peace/decimetres
2, interpole gap is 45 millimeters, and the temperature of electrolytic solution is 750 ℃, and after electrolysis procedure reaches 1.5 hours, obtain the alloy of following composition: praseodymium content is 86%; Iron is 12%; Lithium is 0.5%; The metal productive rate is 60%.
The production of embodiment 9 pure lanthanums
Use the electrolytic solution of following composition: Lanthanum trichloride 30%; Repone K 38.6%; Lithium chloride 31.4%.Anode is a graphite, and negative electrode is the lanthanum that is connected with steel.Cod is 55 peace/decimetres
2, aod is 130 peace/decimetres
2, pole gap is 40 millimeters, and the temperature of electrolytic solution is 690 ℃, and electrolysis obtains 67 gram metals after 3 hours 31 minutes, and the metal productive rate is 56%.
Embodiment 10
This be one with neodymium-iron example that has the pass, the composition of electrolytic solution changes.In all cases, anode is a graphite, and negative electrode is an iron staff.
Its result is narrated in following table, wherein
T-represents the temperature of electrolytic solution, and unit is ℃
T-represents the time length of electrolysis procedure as defined above;
Di-represents interpole gap, with " millimeter " expression;
D-represents metal productive rate as defined above.
Embodiment 11:
This is to prepare relevant example with gadolinium-iron alloy.
Use the electrolytic solution of following composition: Gadolinium trichloride: 26%; Lithium chloride: 52.3%; Lithium fluoride: 21.7%.
Anode is a graphite, and negative electrode is an iron, and the temperature of electrolytic solution is 940 ℃, and anode is 89 peace/decimetres
2, interpole gap is 46 millimeters, after electrolysis procedure reaches 0.94 hour, obtain the alloy of following composition: gadolinium concentrations is 86%; Iron level is 14%; The metal productive rate is 42%.
The device of these methods is implemented in narration below.
According to electrolyzer of the present invention, be to design like this, the metal or alloy that promptly allows to be generated is poured out or is bled off in its bottom.So, in the bottom of equipment, there is one to extract out or discharge region, collect the product that generates in discharge region with sedimentation.Design the zone of this shape, mean that metal or alloy belongs to discharge easily.
With reference now to accompanying drawing,, represented here is electrolyzer 1, this electrolyzer by the first half 2, be generally garden tubular narrow-necked earthen jar and Lower Half is formed, Lower Half is the discharge region of conduit 3.The interior transverse section of discharge region is less than the transverse section of the first half, and preferably by the center of vertical aligning narrow-necked earthen jar, the conduit with transverse section of garden tubular is made.Conduit 3 preferably leads to the first half at 4 centers, electrolyzer first half bottom.
In order to be easy to emission product, can make 4 downward-sloping a little about 10 ° of angles, bottom.
The first half of electrolyzer is equipped with electirc radiation, electrically contact or the heating unit of electro-induction, or gas or fuel oil stove heating unit.
Fig. 1 and Fig. 2 illustrate two specific installations of discharge region.
About Fig. 1, discharge region or conduit 3 are by joining region 5, and three different zones in central section 6 and outside 7 districts are formed.Central section and other two districts are with valve 8 and opened in 9 minutes, and valve 8 and 9 is master switchs and shakes control.Determined in the above described manner regional 6 form a deposition space.Each all is provided with heating unit 5 districts and 6 districts, for example the device of electric heating pattern.
About used size, can point out the diameter in 6 districts and highly depend on the frequency that product discharges.Usually, the height in 6 districts can be 2.5-6 times of 5 districts height.
The discharge region 3 that Fig. 2 represents also is made up of three zones.These three zones are: joining region 10, central section 11 and outside area 12.Zone 11 characteristics are, its section is less than the section of regional 3 remaining parts, particularly 10 districts.Distinguish 12 status two portions: the part 13 and outside 14 close with 11 districts.These two portions owing to contain independently heating unit, therefore, come down to distinguishing each other.
Heating unit also is equipped with in 11 districts.For part 13 and 14, preferably use contact or the radiating heating unit is induction heaters of arbitrary form about part 14, and 11 districts are individual coll(-tube) heater, for example heating units of oil fuel or gaseous combustion type of furnace formula.
The diameter of discharge region also depends on the frequency of electrolyzer product discharging, and the diameter in 10 districts and 12 districts preferably equates, is about 2-4 doubly with 11 district's diameter ratios.As for height, approach the height in 10,11 and 13 districts substantially, than the big 3-5 of height of part 3 times.
Whole electrolyzer is made by resisting electrolyte resistance temperature and corrosion resistant material.Because electrolyzer contains different materials, the appropriate materials that can recommend is a cast iron, particularly foliate gray iron or spheroidal graphite cast iron, also can with contain chromium or nickel or preferably neodymium-alloying with silicon cast iron.
According to the present invention, electrolyzer can be with different electrode forms and different arrangement of electrodes.
In general, use graphite to make anode, about negative electrode, its character is decided by to be produced the kind of product.As previously mentioned, to the preparation rare earth metals, make negative electrode with tungsten; To the alloy that preparation is discussed, just make negative electrode with the consumption negative electrode or the rare earth metals-transition metal alloy of transition metal.
Usually, electrolyzer uses the negative electrode of a garden cylindricality, and it vertically puts into the narrow-necked earthen jar device, preferably is placed on the center of narrow-necked earthen jar.Particularly when the discharge region of electrolyzer be when making by garden tubular conduit, for the negative electrode that will dispose, the center of perpendicular alignmnet conduit is favourable.
In the equipment that the present invention mentions, negative electrode is hollow and the garden cylindricality, can pass through the centre portions of the sky of negative electrode, provides the rare earths muriate to electrolyzer.
At last, the negative electrode of usage level also is fine, and can use multi-form anode.
See that as Fig. 1 anode is owing to form with the garden post 15 of one or more vertical placements, these garden posts are configured in around the negative electrode, also can make the garden post 15 of use-case 6.
In the equipment of Fig. 2, anode also can constitute with the ring 17 of garden cylindricality, and garden cylindricality ring is aimed at the center of negative electrode 16, and anode also can be fan-shaped and need not annular with ring.
Be noted that it at last in electrolyzer, electrode will reasonably install, that is: the bottom of negative electrode more is close to storage narrow-necked earthen jar and bottom than an anode or a plurality of anodic bottom.
Now, the working method of narration said apparatus.
Mode with distributor is supplied with the rare-earth metal chloride material to electrolyzer continuously, under the situation of above-mentioned hollow cathode, and the centre portions of muriate iontophoresis electrode.
In the electrolysis procedure process, the metal or alloy of generation is fallen the bottom of storage narrow-necked earthen jar, and periodically discharges in discharge region.
Under device situation shown in Figure 1, open valve 8, shut-off valve 9 allows metal or alloy to be full of 6 districts fully, and one time loading operation finishes, and shut-off valve 8 is also opened valve 9, so that material flows to outside area 7.
When with device shown in Figure 2, program is as follows: the part 14 in 12 districts keeps cold state, that is to say that it maintains and is lower than the electrolyzer melt temperature.Metal or alloy leaves and is deposited on part 13,10 districts, 11 districts and just in heated 13 districts.Then, 11 districts are cooled very soon, and generate acromorph there.Promptly heat the outside 14 in 12 districts, so that pour out the product of collecting in 13 districts.Then, cooling 13 districts and 14 districts, so that generate fresh acromorph in 12 districts, 11 districts are heat temperature raising gradually.
Can estimate: above-mentioned device can be used for any electrolysis of molten electrolyte, and this electrolytic final product finishes to collect with deposition.So, the electrolyzer that its application is not limited to describe among the present invention.
The present invention never is limited to the equipment of only narrating as embodiment, if particularly these equipment are to use in the scope that claim is protected, the present invention includes the technical equivalents thing of the equipment of being described and all devices of combination thereof.
Claims (19)
1, the preparation method of the electrolytic solution of the alloy salts of electrolysis rare earth metals or a kind of metal selected by rare earths at least and transition metal, it is characterized in that it being to adopt to contain to have a kind of rare-earth metal chloride at least, the electrolytic solution of at least a alkaline earth metal chloride and at least a basic metal or alkaline-earth metal fluoride.
2, the method for the above-mentioned alloy of preparation according to claim 1 is characterized in that making negative electrode with the alloy of transition metal or rare earth metal and transition metal.
3,, it is characterized in that using and contain lithium at least as alkali-metal electrolytic solution according to claim 1 or 3 described methods.
4, according to described method one of in the claim 1 to 3, it is characterized in that containing at least a kind of lithium chloride and lithium fluoride.
5, according to one of aforesaid right requirement described method, in the electrolytic solution that it is characterized in that using, the weight ratio between basic metal or alkaline earth metal chloride or muriate and a kind of fluorochemical or the multiple fluorochemical changed between 1.5: 1 and 3: 1.
6, according to the method for one of aforesaid right requirement, it is characterized in that the electrolytic solution that uses contains one or more fluorochemicals of at least 15% ratio.
7,, it is characterized in that the electrolytic solution that uses ammonium chloride to form according to described method one of in claim 1 or the claim 3 to 6.
8,, it is characterized in that the electrolytic solution that uses Neodymium trichloride to form, and the transition metal that choosing is selected is an iron according to described method one of in the claim 2 to 6.
9, one of require described method according to aforesaid right, it is characterized in that the electrolytic solution that uses contains one or more rare-earth metal chlorides, its ratio be 10%-70%(by weight).
10,, it is characterized in that between 650 ℃-1100 ℃ of temperature, carrying out electrolysis procedure according to the method one of in the claim 7 to 9.
11, according to each the method described in the claim 1 to 9, it is characterized in that in the chlorine dividing potential drop at least 1.01 * 10
4Carry out electrolysis procedure under pascal's's (0.1 normal atmosphere) the condition.
12, implement the electrolyzer of the employed molten salt electrolyte of each method in the aforesaid right requirement, it is characterized in that it has a basin, a discharge tube is stretched in the bottom of jar, and the interior section of two conduits is less than the section of jar.
13, electrolyzer according to claim 12 is characterized by the center that above-mentioned conduit leads to tank bottom.
14, according to claim 12 or 13 described electrolyzers, it is characterized in that being equipped with a columniform negative electrode.
15,, it is characterized in that anode is made up of one or more right cylinders that are configured in around the negative electrode according to the electrolyzer one of in the claim 12 to 14.
16,, it is characterized in that anode is that ring by centering adjustment constitutes according to described electrolyzer one of in the claim 12 to 14.
17, according to described electrolyzer one of in the claim 12 to 16, it is characterized in that the center of negative electrode with the above-mentioned conduit of perpendicular alignmnet.
18,, it is characterized in that above-mentioned conduit is at vertical two valves of configuration of definite deposition space according to described electrolyzer one of in the claim 12 to 17.
19, according to described electrolyzer one of in the claim 12 to 14, it is characterized in that some section of above-mentioned conduit is less than remaining section.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8418700 | 1984-12-07 | ||
| FR8418700A FR2574434B1 (en) | 1984-12-07 | 1984-12-07 | PROCESS FOR THE ELECTROLYTIC PREPARATION OF RARE EARTHS OR THEIR ALLOYS AND DEVICE FOR CARRYING OUT SAID METHOD |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85108786A true CN85108786A (en) | 1986-11-05 |
Family
ID=9310347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198585108786A Pending CN85108786A (en) | 1984-12-07 | 1985-12-04 | The electrolysis process of preparation rare earth metals or its alloy and implement the device of this method |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0184515B1 (en) |
| JP (1) | JPS61159593A (en) |
| KR (1) | KR910009402B1 (en) |
| CN (1) | CN85108786A (en) |
| AT (1) | ATE45597T1 (en) |
| AU (1) | AU591080B2 (en) |
| CA (2) | CA1276585C (en) |
| DE (1) | DE3572371D1 (en) |
| ES (1) | ES8705050A1 (en) |
| FR (1) | FR2574434B1 (en) |
| MY (1) | MY102430A (en) |
| NO (1) | NO172989C (en) |
| ZA (1) | ZA859360B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966661A (en) * | 1986-12-23 | 1990-10-30 | Showa Denko Kabushiki Kaisha | Process for preparation of neodymium or neodymium alloy |
| WO1993013247A1 (en) * | 1986-12-23 | 1993-07-08 | Hideo Tamamura | Process for producing neodymium or alloy thereof |
| JPH0243391A (en) * | 1988-08-01 | 1990-02-13 | Japan Metals & Chem Co Ltd | Production of nd-fe mother alloy |
| FR2661425B1 (en) * | 1990-04-27 | 1992-12-04 | Pechiney Recherche | PROCESS FOR THE ELECTROLYTIC PREPARATION IN THE MEDIUM OF MOLTEN FLUORIDES, LANTHANE OR ITS ALLOYS WITH NICKEL. |
| CN102449201A (en) * | 2009-05-26 | 2012-05-09 | 住友化学株式会社 | Process for producing refined metal or metalloid |
| CN103572329B (en) * | 2012-07-31 | 2016-01-20 | 有研稀土新材料股份有限公司 | A kind of fusion electrolysis prepares the method for rare earth alloys |
| CN113481545B (en) * | 2016-12-16 | 2023-07-14 | 包头稀土研究院 | Lanthanum-iron alloy |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR430116A (en) * | 1911-04-01 | 1911-10-09 | Anton Kratky | Process for the preparation of cerium and similar metals and their alloys |
| US2961387A (en) * | 1957-09-18 | 1960-11-22 | Timax Corp | Electrolysis of rare-earth elements and yttrium |
| US3729397A (en) * | 1970-09-25 | 1973-04-24 | Molybdenum Corp | Method for the recovery of rare earth metal alloys |
| JPS4843774A (en) * | 1971-10-07 | 1973-06-23 | ||
| US4139427A (en) * | 1977-09-09 | 1979-02-13 | Th. Goldschmidt Ag | Europium chloride enrichment process |
-
1984
- 1984-12-07 FR FR8418700A patent/FR2574434B1/en not_active Expired
-
1985
- 1985-12-04 EP EP85402404A patent/EP0184515B1/en not_active Expired
- 1985-12-04 DE DE8585402404T patent/DE3572371D1/en not_active Expired
- 1985-12-04 CN CN198585108786A patent/CN85108786A/en active Pending
- 1985-12-04 AT AT85402404T patent/ATE45597T1/en not_active IP Right Cessation
- 1985-12-05 NO NO854899A patent/NO172989C/en unknown
- 1985-12-06 CA CA000497041A patent/CA1276585C/en not_active Expired - Fee Related
- 1985-12-06 AU AU50850/85A patent/AU591080B2/en not_active Ceased
- 1985-12-06 ZA ZA859360A patent/ZA859360B/en unknown
- 1985-12-06 ES ES549652A patent/ES8705050A1/en not_active Expired
- 1985-12-06 JP JP60273569A patent/JPS61159593A/en active Granted
- 1985-12-06 KR KR1019850009185A patent/KR910009402B1/en not_active IP Right Cessation
-
1987
- 1987-03-18 MY MYPI87000320A patent/MY102430A/en unknown
-
1990
- 1990-05-04 CA CA000615726A patent/CA1318882C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ES8705050A1 (en) | 1987-04-16 |
| ES549652A0 (en) | 1987-04-16 |
| ATE45597T1 (en) | 1989-09-15 |
| KR860005054A (en) | 1986-07-16 |
| FR2574434B1 (en) | 1989-04-21 |
| MY102430A (en) | 1992-06-30 |
| JPS61159593A (en) | 1986-07-19 |
| NO172989B (en) | 1993-06-28 |
| CA1276585C (en) | 1990-11-20 |
| NO854899L (en) | 1986-06-09 |
| NO172989C (en) | 1993-10-06 |
| FR2574434A1 (en) | 1986-06-13 |
| KR910009402B1 (en) | 1991-11-15 |
| DE3572371D1 (en) | 1989-09-21 |
| JPH0440435B2 (en) | 1992-07-02 |
| ZA859360B (en) | 1986-08-27 |
| AU5085085A (en) | 1986-06-12 |
| EP0184515B1 (en) | 1989-08-16 |
| CA1318882C (en) | 1993-06-08 |
| AU591080B2 (en) | 1989-11-30 |
| EP0184515A1 (en) | 1986-06-11 |
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