CN104789991B - Method and device for preparing high-purity rare earth metal through electrolytic refining and in-situ directional solidification - Google Patents
Method and device for preparing high-purity rare earth metal through electrolytic refining and in-situ directional solidification Download PDFInfo
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- CN104789991B CN104789991B CN201510239832.3A CN201510239832A CN104789991B CN 104789991 B CN104789991 B CN 104789991B CN 201510239832 A CN201510239832 A CN 201510239832A CN 104789991 B CN104789991 B CN 104789991B
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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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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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Abstract
The invention relates to a method and device for preparing high-purity rare earth metal through electrolytic refining and in-situ directional solidification. The device comprises an electrolytic furnace and an ingot furnace which are arranged on a rack, wherein a protective atmosphere cover is arranged at a furnace mouth of the electrolytic furnace, an air inlet pipe, an air outlet pipe and a through hole are distributed on the protective atmosphere cover, and a consumable anode penetrates through the through hole; the consumable anode is fixedly arranged on an automatic lift feeding device on the rack; the lower part of a hearth of the electrolytic furnace is provided with a funnel-shaped insulated lining; an upper cooling water jacket is distributed outside the wall of the electrolytic furnace, and an electromagnetic stirring device is distributed at the lower part of the outer side of the upper cooling water jacket; an ingot cavity located on the ingot furnace aligns to an outlet of the funnel-shaped insulated lining, the lower part of the ingot cavity is matched with a sliding dummy bar, and the bottom of the dummy bar is connected with an ingot drawing bar and is communicated with a cathode conducting wire of a power source; and a lower cooling water jacket is distributed outside the wall of the ingot furnace. Constant-voltage or constant-current electrolysis can be carried out under the conditions that the temperature ranges from 900 DEG C to 1200 DEG C, the voltage ranges from 5V to 30V, and the current ranges from 1000A to 1200A. The high-purity rare earth metal can be prepared continuously and automatically.
Description
Technical field
The present invention relates to a kind of preparation method of high pure rare earth metals and device, more particularly to one kind has protective atmosphere
Under " lower the negative electrode electrorefining of falling three-layer-liquid magnetic agitation in-situ directional solidification refine automatic stripping come out of the stove " integration
The synchronous continuous method and apparatus producing high pure rare earth metals.
Background technology
In recent years, high pure rare earth metals are widely used in nuclear industry, superconductor industry, semi-conductor industry and electronics industry etc.
High and advanced industry, and demand increases year by year.But rare earth metal and metal impurities, nonmetallic inclusion, such as fe, c etc., have very strong
Binding ability, and the compound being formed has a strong impact on the performances such as the electricity of rare earth metal, power, magnetic, so rare earth metal carries in recent years
Pure technology is a popular study hotspot.
Begin one's study the method for Purification of Rare Earth Metals from late 1960s, the purification technique of current rare earth metal is main
There are solid phase electromigration, outer gettering, liquid phase outer gettering, electrolytic refining process, electron-beam process, vacuum distillation method, region
Smelting process etc. is several individual or integrated processes are used for Purification of Rare Earth Metals.The principle of its Purification of Rare Earth Metals is broadly divided into two kinds:
A kind of is the impurity element being purified in rare earth metal to be carried out with redistribution reduce impurity concentration and reach the purpose of purification；Another
Kind it is from being purified metal direct " removal " impurity element and reach the effect of purification.
Wherein solid phase electromigration is Purification of Rare Earth Metals under Low Temperature Solid-Phase, be remove interstitial impurity and part metals miscellaneous
Matter more effective method, but the requirement of shape, operating condition and impurity content to raw material for this method is harsh, leads to product
The problems such as long the production cycle, be not suitable for producing in enormous quantities.
The method that another kind is purified metals is outer gettering, and the method is using metallic matrix intermediate gap impurity adhesion very
Foreign gas differential pressure drop in system to extremely low, made the foreign gas in metallic matrix separate out, realizes dilute by strong active substance
The purification of earth metal, but this method be only applicable to purify some fusing points higher as the element such as er, y it is impossible to towards most of rare earths
Element, in this way has larger limitation.And the outer gettering of liquid phase is a kind of improved method externally inhaling method, it is will be thick
Rare earth metal is placed in crucible together with calcium, is jointly sealed in the iron ware in inert gas atmosphere, heats and keep anti-
Vessel temp is answered to be 870 DEG C, the response time should exceed 12 hours, and in whole course of reaction, liquid rare earth metal is in calcium melt and calcium
In steam.But the effect of Purification of Rare Earth Metals is unsatisfactory, the such as thulium such as tb, dy Metal Substrate after completion of the reaction
In body, oxygen content increases, this is because after calcium and rare earth form alloy, the impurity oxygen in calcium absorption rare earth forms calcium oxide,
But impurity oxygen is not released, it is not reaching to the purpose purifying, in this way may not apply in the production of reality.
Electrolytic refining process is the method carrying out Purification of Rare Earth Metals in selected electrolysis molten salt system, and its anode is slightly dilute
Earth metal.This method makes anode rare earth metal preferentially be dissolved in fused salt with ionic state form under certain condition, is subsequently deposited upon
The purpose of purification is reached on negative electrode, has preferable effect for removing the metal impurities such as fe, al, mg, but to gas and
Nonmetallic inclusion refining effect is not good；The position put due to current Rare Earth Electrolysis refine groove anodic-cathodic adopt upper cathodic and
The configuration mode of lower anode, this is very high to the crucible using and electrolyte purity requirement, and can not continuously produce；Electrolysis essence
The rare earth metal produced is to be come out of the stove using artificial batch (-type) in liquid form, and which has rare earth metal liquid and comes out of the stove the time
Long, pure rare-earth metals oxidation is serious, the shortcomings of, heavy losses cell body heat big to the fluctuation of groove condition, reduces high pure rare earth metals
The efficiency producing and product quality, therefore current electrolytic refining process has the larger defect of ratio, only rests on laboratory at present
Stage.
Content of the invention
The present invention seeks in view of the shortcomings of the prior art, a kind of electrorefining and in-situ directional solidification preparation are provided
The method and apparatus of high pure rare earth metals, it is simple to operate, can continuously, automatically prepare high pure rare earth metals.
Technical scheme: a kind of electrorefining and in-situ directional solidification prepare the device of high pure rare earth metals, bag
Include the electrolytic furnace being installed in frame and ingot furnace, electrolytic furnace and ingot furnace are linked together by securing member by upper-lower position,
The stockhole of electrolytic furnace is provided with protective atmosphere cover, protective atmosphere cover is affixed with electrolytic furnace, protective atmosphere cover is furnished with air inlet
Pipe and escape pipe, are additionally provided with through hole thereon, through hole are installed with consumable anode, seal between through hole and consumable anode；Consumable anode
Connect with power anode wire, consumable anode is fixed on automatic lifting feed arrangement, and automatic lifting feed arrangement is installed on machine
On frame；The bottom of electrolytic furnace burner hearth is provided with funnel-form insulated liner；It is disposed with cooling jacket outside the furnace wall of electrolytic furnace, on
Lower disposed outside cooling jacket has electromagnetic mixing apparatus, and electromagnetic mixing apparatus arrangement height is highly identical with insulated liner；
Ingot furnace is provided with ingot casting chamber, the exit centering of ingot casting chamber and funnel-form insulated liner, and the bottom in ingot casting chamber is furnished with drawing of slip
Spindle blade, the bottom of dummy bar is connected stripping bar and is connected with power cathode wire；It is disposed with lower cooling outside the furnace wall of ingot furnace
Water jacket.
The field frequency of described electromagnetic mixing apparatus is 3～10hz, and stir current is 100～300a.
A kind of method that electrorefining and in-situ directional solidification prepare high pure rare earth metals, sequentially include the following steps: one,
When electrolysis starts, open the upper and lower cooling jacket water valve of electrolytic furnace and ingot furnace simultaneously, cooling water flow 20～40l/h, preferably
30l/h；Dummy bar is placed in ingot furnace ingot casting chamber and is fixed on stripping bar, described dummy bar is resistance to rare earth metal corrosion
Tungsten bar or molybdenum bar, preferably tungsten bar；
2nd, the liquid having melted in advance rare earth alloy and molten salt electrolyte are added in electrolytic furnace burner hearth, liquid rare earth
Alloy floats on formation liquid rare earth alloy pond on molten salt electrolyte；In the presence of cooling water, molten salt electrolyte is in burner hearth
Wall solidification forms the protective layer stove side of certain thickness and shape；Cover protective atmosphere cover, be passed through protective gas, by thick rare earth gold
Belong to consumable anode to be immersed in liquid rare earth alloy pond, open automatic lifting feed arrangement, switch on power and start to be electrolysed；
3rd, gradually converge shape below the rare earth metal molten salt electrolyte in electrolytic furnace separating out by electrorefining purification
During the rare earth metal molten bath of one-tenth 5 ± 1cm height, open electromagnetic mixing apparatus, the magnetic field of electromagnetic agitation is 3～10hz, stirred
In journey, stir current controls in 100～300a；Start simultaneously at stripping, stripping speed range of accommodation is 1mm/s～10mm/s, rare earth
Liquid rare earth metal in metal bath constantly flows in the ingot casting chamber of ingot furnace, gradually orients solidifying in the presence of cooling water
Gu, the high pure rare earth metals ingot casting of generation is from ingot casting chamber lower exit port continuous synchronization pull-out stove, and is constantly cut into strand
Transport；
Described electrolytic condition: it is 900～1200 DEG C in temperature, preferably 1000 DEG C, voltage 5v～30v, electric current 1000a～
Carry out constant voltage or constant-current electrolysis under the conditions of 1200a.
Described liquid rare earth alloy is re-m, and m is one of sn, al, mg, preferably sn, and liquid rare earth alloy pond is in stove
Thorax inner height is 1 5cm, preferably 3cm.
Described molten salt electrolyte is rare earth fluoride and lithium fluoride fused salt mixt, and its mass ratio is rare earth fluoride: lithium fluoride=
(9.5-5): (0.5-5), is optimal with 9:1, height in burner hearth for the molten salt electrolyte is 30～50cm, preferably 40cm.
Described protective gas is argon or nitrogen, preferably argon.
The positive effect of the present invention:
(1) apparatus of the present invention optimize electrode configuration mode, invented upper plug type composite anode and liquid rare earth metal is made
For the continuous electrolysis of the falling three-layer-liquid refine pond of lower negative electrode, its advantage is to achieve thick rare earth metal by automatic lifting feed arrangement
Consumable anode Automatic continuous charging it is ensured that electrorefining purification be persistently normally carried out；And it is high-purity that electrorefining goes out
Rare earth metal can directly continuously converge in the rare earth metal molten bath of invention device middle and lower part, so both ensure that pole span
Good scope, reduces decomposition voltage, prevents liquid pure rare-earth metals oxidation by air again, improves current efficiency.
(2) apparatus of the present invention are by lower negative electrode in-situ directional solidification technology, by electrorefining and directional solidification refine melt for
Integrally, it is truly realized the slitless connection of two kinds of refines, not only make the pure rare-earth metals after electrorefining pass through orientation in situ solidifying
Admittedly having obtained continuously purifying further, and the high pure rare earth metals after directional solidification refine being capable of automatic synchronization by stripping bar
Continuously come out of the stove it is achieved that the purpose of high pure rare earth metals serialization and automated production.
(3) in rare earth metal refining process, electrorefining and directional solidification refine all seal apparatus of the present invention at one
Carry out with the environment of protective gas, it is to avoid the secondary oxidation of rare earth metal.Further, since being then provided with cold outside furnace wall
But water jacket, in the presence of cooling water, electrolyte forms the protective layer stove side of certain thickness and shape in fire door and inwall solidification,
The electrolysis of rare earth metal and ingot casting is made all to carry out in the environment of same sealing, the stove side being formed can also effectively stop electricity
The corrosion of solution confrontation stove inwall, it is to avoid the secondary pollution to rare earth metal solution for the stove inwall, not only increases the use of furnace wall
Life-span, and improve the purity of rare earth metal product to greatest extent.
(4) periphery in rare earth metal molten bath for the apparatus of the present invention is provided with electromagnetic induction agitating device, in electromagnetic agitation
Under effect, the rare earth metal liquid strengthening solid liquid interface forward position is not changed with continuously not continuing, thus reducing the thickness of diffusion layer, has
Beneficial to the more rapid diffusion transfer of the impurity element in solid phase in liquid phase, accelerate impurity element in the alternate segregation speed of solid-liquid
Degree, thus improve the efficiency of directional solidification Refining and the purity of rare earth metal.
Brief description
Accompanying drawing is the structural representation of apparatus of the present invention.
In figure reference: 1 positive wire, 2 protective atmosphere covers, 3 air inlet pipe, the tight bolt of 4 cover bodies, 5 top outlet pipes, 6
Electrolytic furnace, 7 insulated liner, 8 high pure rare earth metals ingot castings, 9 tight bolts, 10 bottom outlet pipes, 11 dummy bars, 12 cathode wires,
13 consumable anodes, 14 sealing rings, 15 escape pipes, 16 liquid rare earth alloy ponds, 17 molten salt electrolytes, cooling jacket on 18,19 is dilute
Earth metal molten bath, 20 electromagnetic mixing apparatus (electromagnetic induction coil), 21 top water inlet pipes, 22 times cooling jackets, 23 stove sides, 24 castings
Ingot stove, 25 times water inlet pipes, 26 stripping bars.
Specific embodiment
The present invention can be implemented according to following instance, the term being used in the present invention, unless otherwise specified, typically
There is the implication that those of ordinary skill in the art are generally understood that it should be appreciated that these embodiments present invention solely for the purpose of illustration,
Rather than limit the scope of the present invention by any way, below in an example, the content not described in detail is public in this area
The routine techniquess known.
The present invention can not also adopt automatic lifting feed arrangement (existing fexible unit), but to be adjusted certainly by manual
Consumption anode inserts the depth in liquid rare earth alloy pond in electrolytic furnace burner hearth, and now consumable anode is directly installed on frame by clip
On.
Embodiment one:
As shown in drawings, before energising, open apparatus of the present invention two-part cooling water valve up and down, cooling water flow simultaneously
30l/h, dummy bar tungsten bar is placed in ingot furnace ingot casting chamber as negative electrode.By the liquid alloy having melted in advance nd-sn and molten
Salt electrolyte mass ratio (ndf3: lif=9:0.9) it is added in electrolytic furnace, cover protective atmosphere cover, be passed through ar gas shielded gas
Body, the electrolyte now melting is placed in the intermediate layer of electrolytic furnace, and the height of electrolyte is 30cm, the highly liquid alloy for 2cm
Nd-sn floats on electrolyte, and 98.52% thick nd metal anode is immersed in liquid nd-sn alloy pond；Open automatic lifting
Feed arrangement, at 1100 DEG C of temperature, switches on power and carries out constant-current electrolysis refine, and anodic current density is 0.9a/cm2, electricity
The rare earth metal nd that solution Refining goes out gradually separates out above dummy bar, converges and forms molten bath；When rare earth metal molten bath liquid
When face rises to 5cm, open electromagnetic mixing apparatus, the magnetic field of electromagnetic agitation is 5hz, and in whipping process, stir current controls
150a；Start simultaneously at stripping, stripping speed is 3mm/s, the now setting rate phase of the speed of separating out of pure rare-earth metals and ingot casting
When, and then guaranteeing that rare earth metal bath surface height keeps constant, the high pure rare earth metals ingot casting of generation goes out below ingot casting chamber
Outside mouthful continuous synchronization pull-out stove, and constantly cut into strand and transported, averagely can be produced high pure rare earth metals nd about per hour
3kg (99.95%), wherein impurity element see table:
Impurity content (× 10 before and after table 1 electrorefining-5)
| Impurity | o | n | h | c | fe | cu | ni | mn | cr | zn | pb | bi | ti |
| Before refine | 400 | 70 | 57 | 39 | 7.3 | 22 | 1.8 | 1 | 0.9 | 1 | 1.8 | 1 | 0.2 |
| After refine | 100 | 1 | 0.8 | 1.6 | 0.6 | 0.5 | 0.2 | 0.1 | 0.2 | 0.1 | 0 | 0 | 0 |
Embodiment two:
As shown in drawings, before energising, open apparatus of the present invention two-part cooling water valve up and down, cooling water flow simultaneously
30l/h, dummy bar tungsten bar is placed in ingot furnace ingot casting chamber as negative electrode.By the liquid alloy having melted in advance la-mg and molten
Salt electrolyte mass ratio (laf3: lif=9:1) it is added in electrolytic furnace, cover protective atmosphere cover, be passed through ar gas shielded gas
Body, the electrolyte now melting is placed in the intermediate layer of electrolytic furnace, and the height of electrolyte is 30cm, the highly liquid alloy for 2cm
La-mg floats on electrolyte, and 98.58% thick la metal consumable anode is immersed in liquid la-mg alloy pond；Open automatically
Vertical feed device, at 1000 DEG C of temperature, switches on power and carries out constant-current electrolysis refine, and anodic current density is 0.8a/
cm2, the rare earth metal la that electrorefining purifies out gradually separates out above dummy bar, converges and forms rare earth metal molten bath.When
When rare earth metal bath surface rises to 5cm, open electromagnetic mixing apparatus, the magnetic field of electromagnetic agitation is 5hz, stirs in whipping process
Mix current control in 150a；Start simultaneously at stripping, stripping speed is 2mm/s, the now speed of separating out of pure rare-earth metals and ingot casting
Setting rate quite, and then guarantee that rare earth metal bath surface height keeps constant, the high pure rare earth metals ingot casting of generation from
Outside ingot casting chamber lower exit port continuous synchronization pull-out stove, and constantly cut into strand and transported, averagely can be produced rare earth per hour
Metal la about 2.8kg (99.96%), wherein impurity element see table:
Impurity content (× 10 before and after table 2 electrorefining-5)
| Impurity | o | n | h | c | fe | cu | ni | mn | cr | zn | pb | bi | ti |
| Before refine | 380 | 50 | 43 | 35 | 6.9 | 18 | 1.6 | 2 | 1.5 | 1.2 | 2.0 | 0.8 | 0.3 |
| After refine | 87.5 | 0.9 | 1.2 | 2.3 | 0.5 | 0.1 | 0.1 | 0.3 | 0.2 | 0.2 | 0.1 | 0 | 0 |
Embodiment three:
As shown in drawings, before energising, open apparatus of the present invention two-part cooling water valve up and down, cooling water flow simultaneously
35l/h, dummy bar tungsten bar is placed in ingot furnace ingot casting chamber as negative electrode.By the liquid alloy having melted in advance pr-al and molten
Salt electrolyte mass ratio (prf3: lif=9:1.2) it is added in electrolytic furnace, cover protective atmosphere cover, be passed through ar gas shielded gas
Body, the electrolyte now melting is placed in the intermediate layer of electrolytic furnace, and the height of electrolyte is 35cm, the highly liquid alloy for 2cm
Pr-al floats on electrolyte, and 98.46% thick pr metal consumable anode is immersed in liquid pr-al alloy pond；Open automatically
Vertical feed device, at 1100 DEG C of temperature, switches on power and carries out constant-current electrolysis refine, and anodic current density is 1a/cm2,
The rare earth metal pr that electrorefining purifies out gradually separates out above dummy bar, converges and forms rare earth metal molten bath；Work as rare earth
When metal bath liquid level rises to 5cm, open electromagnetic mixing apparatus, the magnetic field of electromagnetic agitation is 5hz, in whipping process, stir electricity
Flow control is in 150a；Start simultaneously at stripping, stripping speed is 3.5mm/s, now the speed of separating out of pure rare-earth metals and ingot casting
Setting rate quite, and then guarantees that rare earth metal bath surface height keeps constant, and the high pure rare earth metals ingot casting of generation is from casting
Outside ingot chamber lower exit port continuous synchronization pull-out stove, and constantly cut into strand and transported, averagely can be produced rare earth gold per hour
Belong to pr about 3.2kg (99.95%), wherein impurity element see table:
Impurity content (× 10 before and after table 3 electrorefining-5)
| Impurity | o | n | h | c | fe | cu | ni | mn | cr | zn | pb | bi | ti |
| Before refine | 440 | 80 | 67 | 45 | 8.2 | 25 | 2.2 | 4.3 | 2.1 | 1.6 | 1.8 | 1.2 | 0.5 |
| After refine | 92 | 1.1 | 0.7 | 1.2 | 0.8 | 0.3 | 0.3 | 0.2 | 0.1 | 0.1 | 0 | 0 | 0 |
Claims (3)
1. the method preparing high pure rare earth metals using electrorefining and in-situ directional solidification device, is characterized in that: by following step
Suddenly carry out: one, when electrolysis starts, open the upper and lower cooling jacket water valve of electrolytic furnace and ingot furnace, cooling water flow 20 simultaneously
～40l/h；Dummy bar is placed in ingot furnace ingot casting chamber and is fixed on stripping bar, described dummy bar is resistance to rare earth metal corrosion
Tungsten bar or molybdenum bar；
2nd, the liquid having melted in advance rare earth alloy and molten salt electrolyte are added in electrolytic furnace burner hearth, liquid rare earth alloy
Float on formation liquid rare earth alloy pond on molten salt electrolyte；In the presence of cooling water, molten salt electrolyte coagulates in inboard wall of burner hearth
Solid becomes the protective layer stove side of certain thickness and shape；Cover protective atmosphere cover, be passed through protective gas, by thick rare earth metal certainly
Consumption anode is immersed in liquid rare earth alloy pond, opens automatic lifting feed arrangement, switches on power and starts to be electrolysed；
3rd, gradually converge formation 5 below the rare earth metal molten salt electrolyte in electrolytic furnace separating out by electrorefining purification
During the rare earth metal molten bath of ± 1cm height, open electromagnetic mixing apparatus, the magnetic field of electromagnetic agitation is 3～10hz, in whipping process
Stir current controls in 100～300a；Start simultaneously at stripping, stripping speed range of accommodation is 1mm/s～10mm/s, rare earth metal
Liquid rare earth metal in molten bath constantly flows in the ingot casting chamber of ingot furnace, gradually directional solidification in the presence of cooling water,
The high pure rare earth metals ingot casting generating is from ingot casting chamber lower exit port continuous synchronization pull-out stove, and is constantly cut into strand fortune
Walk；
Described electrolytic condition: be 900～1200 DEG C in temperature, carry out under the conditions of voltage 5v～30v, electric current 1000a～1200a
Constant voltage or constant-current electrolysis；
Described liquid rare earth alloy is re-m, and m is one of sn, al, mg, and liquid rare earth alloy pond in burner hearth inner height is
1—5cm；
Described molten salt electrolyte is rare earth fluoride and lithium fluoride fused salt mixt, rare earth fluoride: lithium fluoride mass ratio is 9.5-5:
0.5-5, height in burner hearth for the molten salt electrolyte is 30～50cm；
Described electrorefining and in-situ directional solidification device include electrolytic furnace and the ingot furnace being installed in frame, electrolytic furnace and
Ingot furnace is linked together by securing member by upper-lower position, and the stockhole of electrolytic furnace is provided with protective atmosphere cover, shielding gas
Atmosphere cover is affixed with electrolytic furnace, protective atmosphere cover is furnished with air inlet pipe and escape pipe, is additionally provided with through hole thereon, through hole is installed with certainly
Consumption anode, seals between through hole and consumable anode；Consumable anode is connected with power anode wire, and consumable anode is fixed on automatic lifting
On feed arrangement, automatic lifting feed arrangement is installed in frame；The bottom of electrolytic furnace burner hearth is provided with funnel-form insulated liner；
It is disposed with cooling jacket outside the furnace wall of electrolytic furnace, the lower disposed outside upper cooling jacket has electromagnetic mixing apparatus, electromagnetism
Agitating device arrangement height is highly identical with insulated liner；Ingot furnace is provided with ingot casting chamber, ingot casting chamber and funnel-form insulated liner
Exit centering, the bottom in ingot casting chamber is furnished with the dummy bar of slip, and the bottom of dummy bar is connected stripping bar and simultaneously led with power cathode
Line connects；It is disposed with lower cooling jacket outside the furnace wall of ingot furnace.
2. the method preparing high pure rare earth metals according to claim 1, is characterized in that: described protective gas is argon
Or nitrogen.
3. the method preparing high pure rare earth metals according to claim 1, is characterized in that: before energising, opens electricity simultaneously
Solution stove and ingot furnace two-part cooling water valve up and down, cooling water flow 30l/h, dummy bar tungsten bar is placed in ingot furnace ingot casting chamber
Middle as negative electrode；By the liquid alloy having melted in advance la-mg and molten salt electrolyte laf in mass ratio3: lif=9:1 is added to
In electrolytic furnace, cover protective atmosphere cover, be passed through ar gas shielded gas, the electrolyte now melting is located at the centre of electrolytic furnace
Layer, the height of electrolyte is 30cm, and the liquid alloy la-mg highly for 2cm floats on electrolyte, by 98.58% thick la gold
Belong to consumable anode to be immersed in liquid la-mg alloy pond；Open automatic lifting feed arrangement, at 1000 DEG C of temperature, connect electricity
Source carries out constant-current electrolysis refine, and anodic current density is 0.8a/cm2, the rare earth metal la that electrorefining purifies out gradually exists
The top of dummy bar separates out, and converges and forms rare earth metal molten bath；When rare earth metal bath surface rises to 5cm, open electromagnetism
Agitating device, the magnetic field of electromagnetic agitation is 5hz, and in whipping process, stir current controls in 150a；Start simultaneously at stripping, stripping speed
Spend for 2mm/s, now the setting rate of the speed of separating out of pure rare-earth metals and ingot casting quite, and then guarantees rare earth metal molten bath liquid
Face height keeps constant, the high pure rare earth metals ingot casting of generation from ingot casting chamber lower exit port continuous synchronization pull-out stove, and by not
Disconnected cut into strand and transport, averagely can produce rare earth metal la2.8kg, purity 99.96% per hour.
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| CN105908218B (en) * | 2016-04-26 | 2017-11-03 | 中国科学院金属研究所 | A kind of high pure rare earth metals and its production and use |
| CN106636880A (en) * | 2016-12-13 | 2017-05-10 | 中国科学院金属研究所 | Extra-low oxygen rare earth alloy and use |
| EP3339480B1 (en) * | 2016-12-21 | 2021-01-13 | Sintef TTO AS | Electrochemical production of rare earth alloys and metals comprising a liquid anode |
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| ITTO970080A1 (en) * | 1997-02-04 | 1998-08-04 | Marco Vincenzo Ginatta | PROCEDURE FOR THE ELECTROLYTIC PRODUCTION OF METALS |
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