CN100449240C - Method and device for melting rare earth magnet scrap and primary molten alloy of rare earth magnet - Google Patents
Method and device for melting rare earth magnet scrap and primary molten alloy of rare earth magnet Download PDFInfo
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- CN100449240C CN100449240C CNB998163597A CN99816359A CN100449240C CN 100449240 C CN100449240 C CN 100449240C CN B998163597 A CNB998163597 A CN B998163597A CN 99816359 A CN99816359 A CN 99816359A CN 100449240 C CN100449240 C CN 100449240C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/003—Dry processes only remelting, e.g. of chips, borings, turnings; apparatus used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
- C22B9/226—Remelting metals with heating by wave energy or particle radiation by electric discharge, e.g. plasma
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/08—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces heated electrically, with or without any other source of heat
- F27B3/085—Arc furnaces
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/10—Details, accessories, or equipment peculiar to hearth-type furnaces
- F27B3/24—Cooling arrangements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A magnet for increasing a yield attained during a process in which, when separating metals from scraps occurring during a rare earth magnet production process, alloy materials for rare earth magnet are melt-refined so as to positively separate oxides and then subjected to a secondary melting by using a vacuum high-frequency induction melting furnace; wherein part or all of the scraps (3) are charged into an insulated (2) water-cooled crucible (1) or a refractory crucible (7, 21, 22) and subjected to twin plasma arc (10A, 10b) melting and tungsten arc or migration arc (15) melting.
Description
Technical field
The invention relates to the employing fusion technology, make the high alloy of oxygen concentrations such as scrap that in the manufacturing process of rare earth element magnet, produces utilize method again, with utilizing the smelting apparatus that uses in the method again, and the method that adopts secondary smelting is at the rare earth element magnet melting once alloy of state modulated that can melting coupernick raw material (to call " magnet alloy " in the following text).
Background technology
Recently, the requirement of the NdFeB system that magnetic properties is good and the rare-earth sintered magnet of SmCo system increases, and follows, and the scrap amount that produces in the manufacturing process of magnet also increases.As these scrap, the shape defective work that produces because of reasons such as blemish when the sintering defective work that produces in sintering circuit, machining can be arranged for example, the scrap such as coating defective work that in the coating operation, produce because of reasons such as pin holes.In addition, make rare earth element magnet with alloy in Efco-Northrup furnace in vacuum or the inert atmosphere during melting, the residue that oxygen concentration is high in crucible is attached on the refractory lining and residual.Though these are smelting slags, be also included within the scrap of broad sense.On the other hand, the scrap of the powder shaped that in cutting, grinding and sintering body process, produces.These scrap as general method, are to adopt the method for sour dissolution extraction to carry out the recovery of useful metals such as rare earth element with when cutting used water and the powder of the abrasive material state of sneaking into and existing.
Owing to yet there are no the recovery method that proposes economy so far for sintering defective work, shape defective work, coating defective work, so, producer at magnet, perhaps occur in the future utilizing method to lay in again because of believing, perhaps, for example, employing is in the such occasion that contains the many alloys of high price Co of the scrap of SmCo system, adopt electro-smelting, the Sm that makes easy oxidation is oxidized and move in the slag, only the so-called molten refined method that is recovered as metal of Co.Equally be that metal Sm and Zr high price, useful then be not recovered with Co this moment.Technology about melting rare earth element magnet scrap has the spy to open flat 8-31624 communique, according to this explanation, because during with high frequency melting, electric arc melting, plasma melting, Huo Xing rare earth metal scorification extremely, the rare-earth separating metalloid is difficult from slag, so proposed to limit the method that the addition of the new raw material of relative scrap carries out melting again.
But, because no matter SmCo system, NdFeB are that a kind of occasion, in the operation of making magnet, all the alloys that contain many extremely active rare earth elements to be broken into fine powder, pass through the shaping sintering circuit again, so in scrap, there are many fine oxides, directly in the high-frequency induction smelting furnace during melting, the recovery rate of metal is extremely low, establishes as yet as effective reutilization technology with them.Particularly, exist following problem with smelting process: because the growing amount of slag is many, the molten metal surface is covered by slag, makes to observe the molten metal situation and measure the temperature difficulty; Because this slag adheres to and increases in that the crucible inwall is strong, makes the internal volume of crucible become narrow and small, becomes the reason of input raw material palisade hanging; Also have, the regular operational difficulty that strips the slag that adheres on the employed crucible inwall, make the lifetime of crucible etc.
To adopting the low reason of occasion recovery rate of common high-frequency induction smelting furnace melting rare earth element magnet scrap, the present inventor resolves, the result thinks, the rare-earth oxide that contains in former scrap melts the body when separated from scrap, and the part of the metal of molten condition also together is involved in the slag, and perhaps metal is suspended state in oxide, recovery rate is worsened, perhaps the part of the metal that oxygen concentration is high exists with scoriform, because the increase of the apparent quantity of slag, so recovery rate worsens.
Above-mentioned spy opens flat 8-31624 number method, constitute element as the initial liquation of metal (the alloy)-so-called new raw material of principal component-make owing to be first melting with rare earth element magnet, and then the method for fusing scrap, so belong to the so-called purifying method of molten oxide is actively removed in employing by fusion smelting process again.
And in plasma arc, have with the electrode of spray gun as negative pole, will be by the melting thing as the mobile model arc of anode with the spray gun electrode is had two types of non-moving type arc at the two poles of the earth as anode, spray gun self as negative pole, nozzle.
Recently, methods (opening flat 2-199028 number, spy with reference to the spy opens flat 3-8739 number, spy and open flat 7-126019 number, spy and open flat 8-5247 number) different with said method, produced plasma arc by negative electrode spray gun that is provided with respectively and anode spray gun has been proposed.To be called two spray gun plasmas with the plasma that this method produces.
For example, above-mentioned spy opens the melting method that flat 7-126019 number method has proposed not sneak into the quartz glass of container impurity, the energy density of wherein said plasma is wanted to spread granular silica on high and the container before fusion comprehensively, is important to reaching desired effect.In addition, the spy opens flat 3-5247 number and has narrated, and when burning ash of discarded object etc. carried out fusion, two spray gun plasma methods were good by restarting that easy this point sets out.Thus, well-known, existing pair of spray gun plasmamelt process brought excellent results for the melting of oxidation system material and discarded object.
Disclosure of an invention
The objective of the invention is to, when separating in all rare earth element magnet scrap of residue etc. in the crucible that the scrap that metal is produced from the manufacturing process at rare earth element magnet produces during with melting rare earth element magnet raw material, by the molten refined method of the agglomeration separation of actively pushing forward oxide is provided, oxide is partly separated to be removed, make when using raw material with vacuum high-frequency induction smelting furnace secondary smelting rare earth element magnet thereafter, can access extremely good recovery rate.
First method of the present invention is the method for smelting of the scrap of rare earth element magnet, it is characterized in that, scrap at the melting once rare earth element magnet, obtain in the method for rare earth element magnet production of raw material for use, the scrap of rare earth element magnet packed into to be made in part or all adiabatic cold-crucible or refractory material system crucible of molten metal maintaining part, adopt be positioned at above-mentioned crucible above the scrap of the plasma gun melting rare earth element magnet that constitutes by at least 1 antianode and negative electrode that is provided with.
In addition, smelting apparatus for the terres rares scrap of implementing first method of the present invention, it is characterized in that, in the plasma arc melting stove that has the plasma gun that is made of 1 antianode and negative electrode at least, configuration makes part or all the adiabatic cold-crucible or the refractory material system crucible of molten metal maintaining part.
Second method of the present invention is the method for smelting of the scrap of rare earth element magnet, it is characterized in that, scrap at the melting once rare earth element magnet obtains in the method for rare earth element magnet production of raw material for use, the scrap of the rare earth element magnet molten metal maintaining part of packing into is had in the crucible of heat insulating part and water-cooled part, with the scrap of tungsten electrode arc or mobile model plasma arc melting rare earth element magnet.
In addition, the smelting apparatus for the terres rares scrap of implementing second method of the present invention is characterized in that, in tungsten electrode arc or mobile model plasma arc stove, configuration molten metal maintaining part includes the crucible of heat insulating part and water-cooled part.
Third party's method of the present invention is the method for smelting of the scrap of rare earth element magnet, it is characterized in that, scrap at the melting once rare earth element magnet obtains in the method for rare earth element magnet production of raw material for use, with the scrap of rare earth element magnet pack into the molten metal maintaining part have adiabatic structure crucible in, use first electrode of the adiabatic face that covers this crucible in the part and the tungsten electrode arc that between second electrode that disposes above this crucible, produces or mobile model plasma arc to come the scrap of melting rare earth element magnet.
In addition, smelting apparatus for the terres rares scrap of implementing third party's method of the present invention, it is characterized in that, this device is by in tungsten electrode arc or mobile model plasma arc stove, and comprising by the molten metal maintaining part has first electrode of the crucible of adiabatic structure, the local adiabatic face that covers this crucible and second electrode that disposes constitutes above this crucible.
In addition, the alloy of rare earth element magnet scrap melting once of the present invention, this alloy is the alloy that the rare earth element magnet scrap that the present invention relates to of melting once constitutes, it is characterized in that, about formed alloy is SmCo system, and Sm and Ce add up to that 10～40wt%, Nd are that 5wt% is following, Fe is that 25wt% is following, Cu is that 4～10wt%, Zr are that 1～4wt%, oxygen are that 0.1wt% is following, all the other interstitial elements based on the deironing of the unavoidable impurities of Co, the deoxidation of cause what rare earth element magnet manufacturing process in addition and cause what melting once.
Moreover, this alloy is the alloy of the melting once of rare earth element magnet scrap, it is characterized in that, about NdFeB system, Nd, Pr and Dy add up to that 20～35wt%, B are that 0.9～1.2wt%, Al are that 0.1～1wt%, Co are that 5wt% is following, Cu is that 0.5wt% is following, Nb is that 1wt% is following, oxygen is that 0.1wt% is following, all the other interstitial elements based on the deironing of the unavoidable impurities of Fe, the deoxidation of cause what rare earth element magnet manufacturing process in addition and cause what melting once.
The achievement that these inventions are obtained is briefly described as follows.
(1) resulting melting once alloy owing to carried out the agglomeration separation of oxide, is used the melting of vacuum high-frequency induction smelting furnace thereafter, so can make the recovery rate when utilizing again high.
(2) owing to part or all thermal insulation of crucible, so the agglomeration separation of oxide in advance, the thermal efficiency improves, and when the melting amount increased, smelting time had also shortened.Therefore, the unit power consumption amount reduces and the productivity ratio raising.
(3) because the composition of an ingot is even, thereby the composition of standard secondary ingot correctly, the quality of sintered magnet is kept well.
Below describe the present invention in detail and reach the method that above-mentioned achievement adopts.
At first, common item in the 1st～the 3rd method of the present invention is described.
During with general tungsten electrode arc smelting furnace or the melting of mobile model plasma arc melting stove because with respect to the arc spray gun, with the melting raw material as directly to the utmost point, so employing is carried out with the scull vacuum arc melting method of copper cold-crucible usually.In the method, on the inner face of cold-crucible, generate the shell (scull) of solidification layer by raw material self.Like this, under the condition of solidification layer coexistence, when with the scrap of NdFeB system or SmCo based magnet during, the temperature of molten metal is fully raise by the alloy melting point have any problem with common arc-melting furnace or plasma melting furnace melting.When keeping low melt temperature to carry out melting in this case, the deoxygenation refining effect is insufficient.Therefore, the rate of recovery when resulting 1 ingot is carried out 2 meltings is below 70%, becomes extremely low.
In contrast, the scrap of rare earth element magnet packed into make in part or all crucible of making by refractory material, during with two spray gun plasma arcs, tungsten electrode arc, mobile model plasma arc melting, can make fused mass be in high temperature, found that, promoted the agglomeration separation come-up of the rare-earth oxide that exists in scrap, oxygen separates refining effect and significantly improves.Under this occasion, because the insulation effect of the refractory material of crucible part, so not residual scull, the scull attenuation of water-cooled part in addition, and the temperature of molten metal is improved more than 200 ℃ satisfactorily by melting point.Find in addition, when the temperature difference of the melting point of fused mass and rare earth alloy material is more than 200 ℃ the time, become active significantly in the convection current of divided oxide essential molten metal in refining.When setting such condition, the separation of the oxide that exists in scrap can have good effect.The difference in specific gravity of general rare earth element magnet alloy and its rare-earth oxide is little, and it is difficult that the come-up of oxide is separated.This is the same with the reason that does not reduce oxygen in existing smelting process.But, at the crucible that adopts adiabatic structure and adopt when keeping high temperature under the situation of the plasma that can concentrate jumbo energy and since with the temperature difference of melting point more than 200 ℃, the viscosity of alloy is very low.Therefore can think, combine, because the cohesion of oxide and come-up are carried out separating sharp of causing with the mixing effect that produces because of the heating scrap.
In the present invention, so-called " thermal insulation " be meant with common cold-crucible by the metal that is the good conductor of heat constitute as prerequisite, will be opposite with it heat non-conductor and use.Its result does not generate scull at this heat insulating part.Specifically, maintaining part for the molten metal of crucible, or be in the part of cold-crucible of copper etc. in integral body, the non-conductor of stationary heat makes insulation, or the non-conductor part that makes the metal part of crucible water-cooled and heat is in conjunction with constituting or the whole non-conductor with heat of crucible being constituted.Non-conductor as heat is a refractory material, can enumerate that aluminum oxide, zirconia matter, yittrium oxide matter, oxidation are calcareous, magnesia etc. with and the product that burn till of composite oxides.In these refractory materials, be only from economy, durability aluminum oxide refractory material.Also have, aluminium enters such the sneaking into of metal from refractory material, takes to control the not too high method of temperature that makes the molten bath from the heat of plasma arc input, just it can be suppressed at below the scope that goes wrong.
In addition, the thermal insulation of the part of cold-crucible is to make the thermal insulation of crucible molten metal maintaining part in the scope of the phenomenons such as expansion that produce above-mentioned molten bath.Adiabatic zone, is more preferred from more than 30% to be good more than 20% with respect to the inner area of crucible, and good again is more than 50%.Moreover both can make the inner area of crucible all adiabatic, also can make integral body is the refractory material crucible.In the occasion of refractory material crucible, also can be at the inboard of metal container made (furnace shell) refractory lining (furnace lining).No matter this refractory material that is used for furnace lining is that typing refractory material or amorphous refractory are all right.Furnace shell also can be made the chuck water-cooled.
This method as described above is not owing to aspect the high rare earth element magnet scrap of melting oxygen concentration advantage being arranged, be very wise move so new metal is added in the melting raw material.But, few at the scrap generation of magnet manufacturing works, have under the situation of surplus energy at smelting apparatus, also can be with in the part of new metal, the melting raw material of packing into below the best 30 weight %.This occasion can adopt terres rares foundry alloy such as rare earth metal such as armos iron, electrolytic iron, neodymium or neodymium iron and ferro-boron etc. as new metal.
In smelting process of the present invention, even the time that makes molten metal prolong maintenance is carried out the agglomeration separation of oxide, also little than the effect of temperature, do not wish like this from the viewpoint of productivity ratio, so, for the agglomeration separation of accelerating oxidation thing, make the molten metal temperature remain on more than 200 ℃ of melting point of the scrap of rare earth element magnet, more hope is that the high temperature more than 300 ℃ is good.
In the method, at crucible the also residual scull of occasion of water-cooled part is arranged, still, to compare scull thin with the occasion of common cold-crucible, owing in the part of configuration flame retardant coatings such as bottom, do not generate scull, so, can make the melting amount many.After emitting liquation, raw material is next time packed in the residual scull, can continue melting.At this moment, scull is retracted on the raw material next time of packing into, and produces the gap between the crucible.When the electric conductivity of scull and crucible worsens, produce electric arc betwixt, make the melting loss of crucible part,, can be equipped with the conducting parts of the metal made from pure iron plate etc. for crucible and the certain conducting of scull that makes anode-side.
The occasion that molten metal is emitted from crucible, not all to emit liquation, but only emit a part of liquation, the residual fraction of molten metal is remained in the crucible, the rare earth element magnet scrap of melting raw material is appended when packing in it, because raffinate is full of the space of appending the raw material block of packing into, sheet etc., so, can make the whole energising of tungsten electrode and raw material really.Thus, the energising of tungsten electrode arc or mobile model plasma arc is restarted and is become easily, can carry out semi-continuous melting, can boost productivity.In addition, after sending into that thing is molten and finishing, the suitable charging feedstock that appends adopts to make molten metal by the method that the liquation mouth overflows of emitting that is provided with in crucible edge portion, has omitted toppling over of crucible, continuation refining that also can be continuous.
In method of the present invention, when stopping to switch on when emitting liquation, owing to capping oxide slag on molten surface, it is the layer of poorly conductive, so energising becomes difficult again.But, before liquation solidifies fully, during charging feedstock, form conducting parts by raw material, so can continue energising owing to can break this slag blanket.
The speciality of first method of the present invention is described then.
Two spray gun plasmas are made of 1 antianode and cathode electrode at least, and for this reason, crucible there is no need electric conductivity.The setting of each spray gun will be inserted from its front end of top of smelting furnace burner hearth towards melting kettle according to: spray gun, melting atmosphere is without prejudice, inserts that angle can change and the position of above-below direction also can be adjusted etc.The voltage of plasma gun, electric current, input power are necessary to change range of choice according to per 1 batch melting amount and smelting time.Generally along with the increase of melting amount, along with the shortening of smelting time, be necessary to improve plasma current, power output.For example, the occasion 150～300kW of the scrap of the per 1 crowd of 50Kg of melting is suitable.Occasion 400～the 600kW of the scrap of melting 200Kg is suitable.
Secondly, the feature of the 2nd method of the present invention is described.
General when adopting tungsten electrode arc smelting furnace or the melting of mobile model plasma arc melting stove and since with respect to arc pistol with the melting raw material as directly to the utmost point, so employing is carried out with the scull vacuum arc melting method of copper cold-crucible usually.In the method, generate the shell (scull) of solidification layer at the inner face of cold-crucible by raw material self, the raw material of sending into the scull inboard is by melting.When making the part of cold-crucible adiabatic with refractory material etc., the molten bath also broadens and deeply.Thus, can easily the raise temperature of molten metal.Therefore, the liquation and the high crucible residue convection current therein of oxygen concentration of rare earth element magnet scrap have been promoted.And since oxide come-up become easily, so can promote molten refined significantly by the agglomeration separation of the selection of oxide.
Continue, the speciality of the 3rd method of the present invention is described.
This method adopts the crucible structure different with the 2nd method.That is, the liquation maintaining part of crucible is made the thermal insulation structure that covers with refractory material, select to make the structure that is covered by metal electrode (the 1st electrode) of refractory material part.Because of the whole of liquation maintaining part cover with refractory material, become easier so improve the temperature of liquation, can improve the separation refining effect of smelting efficiency, oxygen.This occasion is in order to ensure energising, with the coating fire-resistant material face of metal electrode part.
It is good that plate electrode is used in such covering.In the occasion of using the plate-shape metal electrode, after when crucible bottom was provided with more than one hole portion, the temperature of liquation rose, the separation of oxygen fully carries out, utilize hole portion top and fusing of its peripheral metal electrode and disappearance, extract molten metal out, that is, can emit liquation.This occasion, the cycle time of emitting liquation can be by the tungsten electrode arc of control during from melting or the heat of mobile model plasma arc input, perhaps also adjusts by material, the thickness of selected following metal electrode.Like this, the occasion of the mode of liquation is taken out in employing from the bottom, after the molten metal of desired amount is emitted, in order to prevent that slag sneaking into, making in molten metal from having more slag residual in crucible, employing pourer stopper etc. is blocked out the liquation mouth, can obtain the very favourable melting once ingot of refining effect.
Material as metal electrode can adopt iron electrode.Particularly because to adopt as the rare earth element magnet raw material be that the poor iron steel material of the carbon etc. of objectionable impurities can prevent the pollution of these elements, so wish the iron electrode of use technical pure.In addition, can use the electrode made from niobium, molybdenum, the contour melting point metal of tantalum and their alloy.Under this occasion, with use oxidation aluminum refractory material occasion prevent that sneaking into of aluminium is the same, by controlling the heat of importing by tungsten electrode arc or mobile model plasma arc, the temperature height within reason that makes the molten bath, can constitute the metallic element of these electrodes to being suppressed at below the scope that goes wrong by sneaking into of melting thing.
Then, relevant melting once alloy of the present invention is described.The melting once alloy of rare earth element magnet scrap of the present invention is the shape of ingot.Because their are as the ingot of the 1～50kg in the secondary smelting stove that can directly pack into, so followingly describe to being called " ingot ".An ingot oxygen concentration of the present invention significantly reduces with the scrap state, also lower significantly than ingot of existing vacuum melting.Analyze the composition of this ingot, decide proportioning like that,, in inert atmosphere, carry out secondary smelting, cast, make the magnet alloy with usual way with common vacuum Efco-Northrup furnace according to the composition that combines with new raw material and achieve the goal.
Because the oxygen content in the metal tails off in melting once, with vacuum Efco-Northrup furnace secondary smelting the time, the metal of the scoriform that remaining not separating oxide causes in metal partly reduces, so the rate of recovery can improve widely.
At this moment, the addition of an ingot that is obtained by the rare earth element magnet scrap must consider that following problem decides.Here it is, in scrap, used lubricant when resulting from the magnetic field of magnet manufacturing process drawing, the concentration of carbon is also uprised, in addition since in melting once the decarburization major part can not be expected value, so the typical carbon content in ingot is up to more than 0.04%.And the magnet of only founding by new raw material with the common less than 0.04% of the carbon content of alloy, be typically about 0.02%.Like this, when the addition of an ingot was too much, the carbon content in the ingot of secondary smelting also increased, and used the characteristic of its magnet that obtains as raw material to be adversely affected.When considering the restriction that causes because of this carbon content, the ratio that an ingot that can obtain with this method is below 50% weight, all the other are new raw material is carried out secondary smelting.
As described above, in the present invention, will with ingot and new raw material mutually the ingot of the secondary smelting of mixed smelting as the magnet alloy.On the other hand, also can be only with ingot as magnet with the ratio that limits this alloy in alloy, the pulverizing mixed processes when magnet is thereafter made.
In the composition of an ingot of the present invention, 15～40% the rare earth element and the principal component of all the other parts are that Fe is the resulting composition range of scrap of the most general grade of melting of regulation.Oxygen is sneaked into as impurity in the manufacturing process of rare earth element magnet, particularly pulverizing process or sintering circuit, still, is the important achievement of reaching of the invention described above owing to make its reduction, so be limited to below 0.1%.With the composition of alloy, B, Al, Co, Cu, the Nd of Fe, Cu, Zr and Nd (can use Pr, Dy replaces a part)-Fe-B based magnet of Sm-Co based magnet etc. are arranged, as magnet no matter how much they can effectively utilize the composition as magnet usefulness alloy.Generally speaking, in the Sm-Co based magnet, Co is 40～60%, and Fe is 10～25%, and Cu is 4～10%, and Zr is below 4%, and in the Nd-Fe-B based magnet, B is 0.9～1.2%, and Al is 0.1～1.5%.Have, the occasion of sintered magnet is sneaked into carbon at magnet in the alloy powder forming process again, and still, as described above, these remain in ingot as inexpungible impurity almost.And if adopt the method for an ingot as described above and new raw material and usefulness, carbon content can allow to 0.1%.
In relevant method of smelting of the present invention, sneak into trace element, for example except that Al etc. from above-mentioned various refractory materials, come the metals such as Fe of the metal electrode that uses in comfortable the 3rd method.This Fe becomes the neccessary composition of magnet with alloy.Al is the element that is harmful to magnetic characteristic in the Sm-Co based magnet, on the other hand, allows a small amount of the existence as alloying element in the Nd-Fe-B based magnet, still, is harmful to magnetic characteristic in the time of too much.Therefore its content is for good below 1%.
The simple explanation of accompanying drawing.
Fig. 1 is the sectional drawing that is expressed as an embodiment of the water jacketed copper crucible of implementing the present invention's the 1st, the 2nd method.
Fig. 2 is the sectional drawing that is expressed as an embodiment of the refractory material system crucible of implementing the present invention's the 1st method.
Fig. 3 is the figure of an embodiment of expression the 1st smelting apparatus of the present invention that uses two spray gun plasma arc melting stoves.
Fig. 4 is the figure of expression about an embodiment of the of the present invention the 2nd and the 3rd smelting apparatus of use mobile model plasma arc melting stove.
Fig. 5 is the oblique view that is expressed as an embodiment of the water jacketed copper crucible that possesses conducting parts of implementing the present invention's the 2nd method.
Fig. 6 is the figure that is expressed as an embodiment of the refractory material system crucible of implementing the present invention's the 3rd method.
Fig. 7 is the figure that is expressed as another embodiment of the refractory material system crucible of implementing the present invention's the 3rd method.
Fig. 8 still is expressed as the figure of another embodiment of the refractory material system crucible of implementing the present invention's the 3rd method.
The explanation of working of an invention mode
The following embodiment of implementing the smelting apparatus of the inventive method with reference to description of drawings.
The 1st figure has represented to be for the integral body of implementing the inventive method the crucible of water-cooling structure made of copper.
Among the figure, 1 is that copper crucible, 2 is that refractory plate, 3 is that raw material, 4 is that cooling water inlet, 5 is that cooling water stream, 6 is coolant outlet.As shown in the figure, owing to only use refractory plate 2 in the bottom of crucible 1, sidewall is still the former state of cold-crucible, so get by the input heat of plasma with by the thermal balance that the thermal insulation of refractory plate 2 brings, can form dark molten bath.In addition, only make the adiabatic use amount that can reduce the refractory material of high price in bottom, the simple shape of refractory material, durability are also good, and because cheap, become the also good method of smelting of economy.
The 2nd figure is expressed as to implement refractory material system crucible of the present invention.Here holding refractory material system crucible in canister, among the figure, 7 is alumina crucible, and 9 is iron ware.Fill alumina powder 8 between the gap of crucible and container.
The 3rd figure represents an embodiment of two spray gun plasma melting furnaces.Among the figure, 10 is plasma gun, takes this to produce between anode spray gun 10a and negative electrode spray gun 10b plasma 11.
The 4th figure represents mobile model plasma arc melting stove.15 is plasma gun among the figure, and the stock yard of taking this in the spray gun and the copper crucible 1 of packing into produces plasma arc.The tungsten electrode arc smelting furnace is to possess the structure that replaces this plasma spray gun 15 with tungsten electrode, and this electrode and stock yard produce electric arc.Also have 16 to be the raw material pipe of packing into.
The 5th figure represents to be provided with the crucible of conducting parts 17.Conducting parts 17 be with bend to iron plate etc. copy the crucible interior shape and disposing like that of contacting the water jacketed copper crucible inwall.In the inboard of the residual scull of rare earth element magnet scrap next time can being packed into according to the melting of this law, after emitting liquation, carry out melting.
At this moment because of being contracted in of residual scull produces the gap between crucible because this also is to cause electric conductivity to worsen and the crucible melting loss, so for the conducting parts 17 of the conducting of the crucible that prevents from that this phenomenon from taking place, be provided with to guarantee anode-side and scull for good.Also have, in the 5th figure, show the crucible of the plasma arc stove that use is made of 3 plasma gunes, with respectively between 2 spray guns the configuration conducting parts 3 conducting parts are set like that.Like this, when conducting parts 17 being set, can also obtaining and make that scull portion is little, insulation is big, improve security, can also increase the melting amount corresponding to spray gun.The used metal of this conducting parts dissolves a part in scull, still, in order to ensure energising, only otherwise removing scull can make melting continue, just there is no need to take out and replace.
In the 6th figure of the form of implementation of representing the 3rd method of the present invention, metal electrode 20 is the plate electrodes that for example cover crucible bottom, the side wall portion 22 of crucible is separated on above-below direction with bottom 21, with side wall portion 22 and bottom 21 clamping plate electrodes 20, make and to guarantee from the peripheral part of electrode 20 to the such structure of power supply energising.Perhaps, the cave is set, inserts stick electrode within it, also can guarantee energising in crucible bottom.Make the occasion of such crucible structure, behind the scrap of melting rare earth element magnet, topple over crucible and emit liquation.In addition, as shown in Figure 8, also can be formed in crucible bottom 21 and be provided with the crucible structure of emitting liquation mouth 25.
The best mode that carries out an invention
Embodiment 1 (the 1st inventive embodiment)
With NdFeB based magnet scrap with (assay value: Nd+Pr-29.0wt%, Dy-2.5wt%, Al-0.32wt%, B-1.03wt%, O-0.66wt%, C-0.04wt%, all the other are Fe) as raw material, the two spray gun plasma arc melting stoves (the 2nd figure) that make the 50KW of the adiabatic water jacketed copper crucible (the 1st figure) in bottom with the sintering oxidation aluminium sheet are disposed in employing, make argon plasmaization carry out melting, obtain ingot one time.
The assay value of an ingot: Nd+Pr-25.2wt%, Dy-2.1wt%, Al-0.34wt%, B-1.00wt%, O-0.018wt%, C-0.04wt%, all the other are Fe.
Every batch melting amount is 1.5kg, and being 1200～1250 ℃, melt temperature according to the melting point of this alloy highly rises to 1550 ℃ than it more than 300 ℃.The internal diameter of crucible 1 is that 170mm, the degree of depth are 70mm, and having disposed thickness in its bottom is the alumina sintering plate 2 of 20mm.
Also have, calculate the melting once recovery rate divided by charging feedstock weight with finished weight.Smelting time in this pair spray gun plasma arc melting stove is 13 minutes, and the melting power of an ingot is 2.8kWh/kg.Because the crucible bottom thermal insulation, so smelting time is short, melting power is also little.
As raw material, in argon gas atmosphere, carry out melting with resulting alloy with vacuum high-frequency induction smelting furnace.At this moment, usually an ingot is added in the new raw material, become coupernick and form, still, here in order to study recovery rate, making full dose only is that an ingot carries out melting.The averaged oxygen assay value of the melting recovery rate of an ingot that obtains and secondary smelting recovery rate and an ingot is shown in table 1.
As shown in table 1, make scrap melting under two spray gun plasma arcs, when carrying out the high-frequency induction melting with the significantly reduced ingot of oxygen concentration, the generation of slag is few, and the average recovery rate that has obtained with only with the new raw material melting time is 95% approaching secondary smelting recovery rate.
Embodiment 2 (the 2nd inventive embodiment)
With the scrap of the NdFeB based magnet that in embodiment 1, uses as raw material, configuration alumina crucible (the 2nd figure), melting in two spray gun plasma arc stoves of the 50kW identical with embodiment 1 obtains ingot one time.The assay value of an ingot: Nd+Pr-25.0wt%, Dy-2.2wt%, Al-0.38wt%, B-0.99wt%, O-0.019wt%, C-0.04wt%, all the other are Fe.Every batch melting amount is 1.5kg, and melt temperature is 1550 ℃, and is all identical with embodiment 1.The configuration internal diameter is that 170mm, the degree of depth are 70mm, and thickness is the alumina crucible 7 of 30mm.The time of this melting is 12 minutes, and the melting power of an ingot is 2.6kWh/kg.Similarly to Example 1, smelting time weak point and melting power are also little.At this moment melting recovery rate and average oxygen concentration are shown in table 1.These values and embodiment 1 can access too with high recovery rate, the significantly reduced ingot of oxygen concentration.
Comparative example 1
The NdFeB based magnet scrap and the new raw material that in embodiment 1, use with the vacuum high-frequency induction smelting furnace melting of 15kW.The melting amount is 5kg, is 50% corresponding to the addition of new raw material scrap.The melting recovery rate of a resulting ingot and averaged oxygen assay value are shown in table 1. to be also had, the average recovery rate of the melting yield of supposition new raw material is 95% during only with the new raw material melting, calculate the recovery rate of only obtaining with the melting of scrap by the mode of comparing with whole recovery rate, the melting recovery rate is with this value representation.
The method of utilizing again as scrap, with new raw material, directly melting obtains the occasion of magnet with alloy in Efco-Northrup furnace, the generating capacity of slag is many, operating difficulties, recovery rate is also low, and the composition of the alloy that obtains is also unstable.
Comparative example 2
As raw material,, obtain ingot one time with the scrap of the NdFeB based magnet that in embodiment 1, uses with melting 5kg in the vacuum high-frequency induction smelting furnace of 15kW.The assay value of an ingot: Nd+Pr-25.0wt%, Dy-2.3wt%, Al-0.35wt%, B-1.01wt%, O-0.020wt%, C-0.04wt%, all the other are Fe.
Identical with embodiment 1, this ingot is used the melting of vacuum high-frequency induction smelting furnace once more.Identical with embodiment 1, the melting recovery rate and the averaged oxygen assay value of trying to achieve is shown in table 1, the table 2.
Comparative example 3
As raw material, adopt two spray gun plasma arc melting stove melting 1.5kg with the scrap of the NdFeB based magnet that in embodiment 1, uses, obtain ingot one time with the 50kW of the water jacketed copper crucible of complete heat without cease.The assay value of an ingot: Nd+Pr-28.0wt%, Dy-2.4wt%, Al-0.32wt%, B-1.02wt%, O-0.42wt%, C-0.04wt%, all the other are Fe.Can the melting melting point in this device be 1200～1250 ℃ scrap, still because crucible is not adiabatic, institute so that melt temperature can not fully improve and stop at 1300 ℃.Scull is also thick, becomes scull about half of the raw material of packing into and remains in the crucible.The time of melting is 22 minutes in this plasma arc smelting furnace, is 13kWh/kg corresponding to the melting power of an ingot.
Identical with embodiment 1, with the vacuum high-frequency induction smelting furnace melting of this ingot.Identical with embodiment 1, the melting recovery rate and the averaged oxygen assay value of trying to achieve is shown in Table 1.
As shown in table 1 like that the oxygen assay value in ingot is very high, and deoxidation effect is insufficient.With the occasion of scrap melting in possessing the plasma arc stove of common cold-crucible, because not adiabatic, can not keep reaching high temperature to melting, so the separation of oxide is insufficient, obviously, the oxygen concentration in ingot is high in the same old way.Therefore, low for the secondary smelting recovery rate of Efco-Northrup furnace, be same level with the direct melting of scrap the time.
The melting recovery rate of table 1 ingot, oxygen assay value
| Melting once recovery rate (%) | Oxygen assay value (wt%) | Secondary smelting recovery rate (%) | Compound recovery rate (%) | |
| |
94 | 0.018 | 92 | 86.5 |
| |
95 | 0.019 | - | - |
| Comparative example 1 | 64 | 0.021 | - | - |
| Comparative example 2 | 57 | 0.020 | 94 | 53.6 |
| Comparative example 3 | 50 | 0.42 | 69 | 34.5 |
Embodiment 3 (the 2nd inventive embodiment)
With the NdFeB based magnet scrap (assay value of in embodiment 1, using: Nd+Pr-29.0wt%, Dy-2.5wt%, Al-0.32wt%, B-1.03wt%, O-0.66wt%, C-0.04wt%) 6kg is as raw material, the tungsten electrode arc smelting furnace that makes the 30kW of the adiabatic water jacketed copper crucible (the 1st figure) in bottom with the sintering oxidation aluminium sheet is disposed in employing, in argon gas atmosphere, carry out melting, obtain ingot one time.The assay value of an ingot: Nd+Pr-25.1wt%, Dy-2.2wt%, Al-0.32wt%, B-1.02wt%, O-0.018wt%, C-0.04wt%, all the other are Fe.
Every batch melting amount is 1.5kg, because the melting point of this alloy is 1300 ℃, melt temperature is higher 300 ℃ and rise to 1600 ℃ than it.The internal volume of crucible 1 is that diameter is that 110mm, the degree of depth are 70mm, and having disposed thickness in its bottom is the alumina sintering plate 2 of 20mm.
Smelting time in this arc-melting furnace is 11 minutes, and the melting power of an ingot is 1.5kWh/kg.Because the crucible bottom thermal insulation, so smelting time is short, melting power is also little.
As raw material, use the melting in argon gas atmosphere of vacuum high-frequency induction smelting furnace with resulting alloy.At this moment, usually an ingot is added to making the coupernick composition in the new raw material, still, here in order to study recovery rate, making full dose is that an ingot carries out melting.The averaged oxygen assay value of the melting recovery rate of an ingot that obtains and secondary smelting recovery rate and an ingot is shown in table 2.
As shown in table 2, make scrap melting under high-temperature electric arc, when carrying out the high-frequency induction melting with the significantly reduced ingot of oxygen concentration, the generation of slag is few, and the average recovery rate that has obtained with only with the new raw material melting time is 95% approaching secondary smelting recovery rate.
Embodiment 4 (second inventive embodiment)
With shown in Figure 5, be provided with the employing pure iron plate (thick 1mm, the wide 15mm that contact with the water jacketed copper crucible inwall, 3) the crucible of conducting parts replace the crucible (the 1st figure) that in embodiment 3, uses, the NdFeB based magnet scrap that will use in embodiment 1 carries out melting, obtains with the assay value of ingot next time.Nd+Pr-26.0wt%, Dy-2.4wt%, Al-0.33wt%, B-1.00wt%, O-0.016wt%, C-0.04wt%, all the other are Fe.Also have, repeat melting does not also have crucible fully more than 30 times melting loss.
The occasion of conducting parts is set like this, because will be by in the minimum limit of being controlled at of the electric arc between melting thing and cold-crucible, so, even carrying out melt back, crucible also is difficult to melting loss, thus the raising that can make durability obtain leaping.Though the part of pure iron plate and scull is being welded, remain in the scull side, because of the influence of fusing into the variation that ingot causes composition is negligible level.
Embodiment 5 (second inventive embodiment)
As raw material, adopt the plasma arc melting stove that makes the water jacketed copper crucible shown in the 1st figure of bottom thermal insulation with the sintering oxidation aluminium sheet with the identical scrap 5kg of the NdFeB based magnet that in embodiment 1, uses, in argon gas atmosphere, carry out melting, obtain ingot one time.Melt temperature is got 1600 ℃ identical with embodiment.The assay value of an ingot is, Nd+Pr-24.8wt%, and Dy-2.1wt%, Al-0.35wt%, B-0.98wt%, O-0.018wt%, C-0.04wt%, all the other are Fe.
In addition, use the method identical, become coupernick with this ingot melting and casting with embodiment 3.Similarly to Example 1, try to achieve the melting recovery rate, measure the averaged oxygen assay value of an ingot, it is shown in table 2.As shown in table 2, even in the plasma arc melting stove, make scrap melting at high temperature, also the same with embodiment 3, can access oxygen concentration and significantly reduce and high secondary smelting recovery rate.
Embodiment 6 (the 2nd inventive embodiment)
In vacuum high-frequency induction smelting furnace after the melting, (Sm-31.6wt%, Fe-4.6wt%, Zr-2.0wt%, O-2.8wt%, all the other are Co with residue residual in the crucible with SmCo based magnet alloy materials.) with disposing the tungsten electrode arc smelting furnace that makes the 30kW of the adiabatic water jacketed copper crucible (Fig. 1) in bottom with the sintering oxidation aluminium sheet, in argon gas atmosphere, carry out melting, can reclaim the part of metal.The melting amount is 1.5kg, and the melting recovery rate of an ingot that obtains is 75%, and the composition analysis value is Sm-15.0wt%, Fe-28.0wt%, Cu-4.6wt%, Zr-2.5wt%, O-0.021wt%, all the other are Co.Clearly show by this result, in the manufacturing of SmCo coupernick, even the hyperoxia concentration residue in the Efco-Northrup furnace crucible, when high-temperature electric arc carries out melting, also can reduce oxygen content significantly, make high price metal part such as Co but also Sm and Zr not only divide as the metal that can re-use, can reclaim with high recovery rate.
Embodiment 7 (second inventive embodiment)
The new raw material 10% that will contain the significant Nd metal of oxidation joins in the NdFeB based magnet scrap that uses in embodiment 3, uses the method identical with embodiment 3 to obtain ingot one time.The oxygen assay value of this ingot fully is reduced to the degree that does not have significant difference with embodiment 1.
Embodiment 8 (the 1st inventive embodiment)
With the scrap 45kg of the NdFeB based magnet that in embodiment 1, uses as raw material, employing dispose with sintered alumina cylinder 23 make the sidepiece thermal insulation, only the plasma arc melting stove of 300kW of the crucible as shown in Figure 8 of water-cooled copper plate 24 is made in the bottom, in argon gas atmosphere, carry out melting, obtain ingot one time.The assay value of an ingot is, Nd+Pr-25.8wt%, and Dy-2.3wt%, Al-0.34wt%, B-1.00wt%, O-0.018wt%, C-0.04wt%, all the other are Fe.
Melt temperature is got 1600 ℃ identical with embodiment 3.Crucible 1 is that internal diameter is that 320mm, the degree of depth are that 150mm, thickness are the sintered alumina cylinder 23 of 30mm, has disposed water-cooled copper plate 24 in its bottom.
Moreover, the same with embodiment 3, become coupernick with this ingot melting and casting.As shown in table 2, in the method, make scrap melting at high temperature, oxygen concentration is significantly reduced and obtain high secondary smelting recovery rate.
The melting recovery rate of an ingot of table 2, oxygen assay value
| Melting once recovery rate (%) | Oxygen assay value (wt%) | Secondary smelting recovery rate (%) | Compound recovery rate (%) | |
| |
94 | 0.018 | 92 | 86.5 |
| |
94 | 0.016 | - | - |
| |
93 | 0.017 | 91 | 84.6 |
| Embodiment 8 | 94 | 0.015 | 98 | 92 |
| Comparative example 1 | 64 | 0.021 | - | - |
| Comparative example 2 | 57 | 0.020 | 94 | 53.6 |
| Comparative example 3 | 45 | 0.53 | 67 | 30.2 |
Embodiment 9 (the 2nd inventive embodiment)
Melting NdFeB based magnet scrap raw material similarly to Example 6, go out liquation after, before this liquation solidifies fully, under the situation of not destroying argon gas atmosphere, append charging feedstock, the melting of switching on once again.When the liquation in the crucible became full, the crucible that fascinates was emitted its part, in addition, because of chasing after the dress raw material, thus can be continuous carry out melting.In addition and since crucible top emit liquation mouth place metal freezing, have unusual arc to fly to this part at the energising initial stage, so, this partial coagulation metal is cut an osculum makes out the liquation mouth.
Adopt method melting like this also can obtain an ingot identical with embodiment 8.
Embodiment 10 (the 3rd inventive embodiment)
With the scrap 45kg of the NdFeB based magnet that in embodiment 3, uses as raw material, employing dispose with the sintered alumina cylinder make the sidepiece thermal insulation and also with the sintering oxidation aluminium sheet also make the bottom adiabatic, portion is provided with the plasma arc melting stove of 300kW of the crucible shown in the 6th figure of pure circular slab made of iron as conducting parts within it, in argon gas atmosphere, carry out melting, obtain ingot one time.
Melt temperature is got 1600 ℃ identical with embodiment 1.Crucible 1 is that internal diameter is that 320mm, the degree of depth are that 150mm, thickness are the sintered alumina cylinder 10 of 30mm, and having disposed external diameter in its bottom is that 320mm, thickness are the sintered alumina circular slab of 30mm, and side has disposed the pure iron circular slab of 0.5mm within it.
Also obtained an ingot identical in the method with embodiment 6.
Embodiment 11 (the 3rd inventive embodiment)
With the scrap of the NdFeB based magnet that in embodiment 3, uses as raw material, employing dispose the central authorities that make the sidepiece thermal insulation with sintered alumina cylinder 22 and be used in the bottom leave ring-shaped sintered alumina plate 21 thermal insulation of emitting molten metal mouth 25, side is provided with the plasma arc melting stove of 300kw of crucible as shown in Figure 8 of the circular slab 20 of pure pure iron made of iron portion as conducting parts within it, carries out melting in argon gas atmosphere.The central authorities of iron plate destruction, liquation are released to the bottom during melting, obtain ingot one time in the casting mold that its underpart is provided with.The assay value of an ingot is, Nd+Pr-25.5wt%, and Dy-2.2wt%, Al-0.35wt%, B-1.01wt%, O-0.018wt%, C-0.04wt%, all the other are Fe.
In the present embodiment, except the sintering oxidation aluminium sheet of bottom is that internal diameter is that 100mm, external diameter are that 320mm, thickness are the ring-type of 30mm, use the condition identical to carry out melting with embodiment 10.Use the method, because slag and a part of metal are residual in crucible, so, obtain slag and be involved in ingot of few 40kg.
Embodiment 12 (the 3rd inventive embodiment)
After molten metal is emitted in melting under the condition identical with embodiment 10, the slag that residual top, frozen metal exists in crucible of pruning of part exposes with after guaranteeing that conducting parts divides the metal level of downside, appends charging feedstock, the melting of switching on again, and repeatedly by this method operation.At this moment, owing to the furnace charge that emptying aperture is also arranged in the central authorities of remaining frozen metal, so, adopt the method charging feedstock of placing iron foil or iron plate consent in this occasion.Adopt this method can obtain an ingot identical with embodiment 10.
The possibility of utilizing on the industry
As described above because the effective ways that the oxygen concentration in the rare earth element magnet scrap is reduced, so limited the as much as possible use amount of scrap, and new raw material together melting can not meet the demands. Adopt when of the present invention, owing to there is not such restriction, make the scrap that in present magnet manufacturing process, produces can good, the economic recycling of efficient. Therefore, realized the increase of efficient utilization of resource and output.
Claims (25)
1. the method for smelting of a rare earth element magnet scrap, it is characterized in that, at the scrap of melting once rare earth element magnet, obtain making rare earth element magnet with in the method for raw material, the scrap (3) of rare earth element magnet is packed in part or all adiabatic cold-crucible (1) or refractory material system crucible (7) of liquation maintaining part (2), with the scrap of plasma gun (10) the melting rare earth element magnet of forming by 1 antianode and negative electrode at least of the top of being arranged to be positioned at above-mentioned crucible (1); Wherein, during the scrap of the above-mentioned rare earth element magnet of melting, make liquation remain the high high temperature more than 200 ℃ of fusing point than the scrap of this rare earth element magnet.
2. the method for smelting of the described rare earth element magnet scrap of claim 1 is characterized in that, will carry out melting by constituting with rare earth element magnet more than a kind in the scrap that new raw material that element forms as the metal of principal component joins above-mentioned rare earth element magnet.
3. the method for smelting of claim 1 or 2 described rare earth element magnet scrap, it is characterized in that, emit the part of liquation of the rare earth element magnet scrap of melting, when the liquation of residual fraction exists with not solidified state in above-mentioned crucible, replenish the scrap of the rare earth element magnet of packing into, continue energising.
4. the method for smelting of a rare earth element magnet scrap, it is characterized in that, at the scrap of melting once rare earth element magnet, obtain in the method for rare earth element magnet production of raw material for use, the scrap (3) of the rare earth element magnet liquation maintaining part of packing into is had in the crucible (1) of heat insulating part (2) and water-cooled part, with the scrap of tungsten electrode arc or mobile model plasma arc (15) melting rare earth element magnet; Wherein during the scrap of the above-mentioned rare earth element magnet of melting, make liquation remain the high high temperature more than 200 ℃ of fusing point than the scrap of this rare earth element magnet.
5. the method for smelting of the described rare earth element magnet scrap of claim 4 is characterized in that, will carry out melting by constituting with rare earth element magnet more than a kind in the scrap that new raw material that element forms as the metal of principal component adds above-mentioned rare earth element magnet.
6. the method for smelting of claim 4 or 5 described rare earth element magnet scrap, it is characterized in that, emit the part of liquation of the rare earth element magnet scrap of melting, when the liquation of residual fraction exists with not solidified state in above-mentioned crucible, replenish the scrap of the rare earth element magnet of packing into, continue energising.
7. the method for smelting of a rare earth element magnet scrap, it is characterized in that, at the scrap of melting once rare earth element magnet, obtain making rare earth element magnet with in the method for raw material, the scrap (3) of the rare earth element magnet liquation maintaining part of packing into is had in the crucible (1) of adiabatic structure (21,22), make first electrode (20) of the adiabatic face that covers this crucible partly and between second electrode (15) that disposes above this crucible, produce tungsten electrode arc or mobile model plasma arc, come the scrap of melting rare earth element magnet thus; Wherein during the scrap of the above-mentioned rare earth element magnet of melting, make liquation remain the high high temperature more than 200 ℃ of scrap fusing point than this rare earth element magnet.
8. the method for smelting of the described rare earth element magnet scrap of claim 7 is characterized in that, will carry out melting by constituting with rare earth element magnet more than a kind in the scrap that new raw material that element forms as the metal of principal component adds above-mentioned rare earth element magnet.
9. the method for smelting of claim 7 or 8 described rare earth element magnet scrap is characterized in that, covers above-mentioned the 1st electrode (20) of the liquation bleed hole of the bottom that connects above-mentioned crucible (1), and after the whole meltings of above-mentioned rare earth element magnet scrap, melting is in liquation.
10. the method for smelting of the described rare earth element magnet scrap of claim 9 is characterized in that, the liquation that makes above-mentioned rare earth element magnet scrap does not sneak in the liquation stream of emitting the slag blanket on the liquation of above-mentioned rare earth element magnet scrap when above-mentioned liquation bleed hole is emitted.
11. the smelting apparatus of a rare earth element magnet scrap, it is characterized in that, in the plasma arc melting stove that has the plasma gun (10) that constitutes by 1 antianode and negative electrode at least, the cold-crucible (1) or the refractory material system crucible (7) of the thermal insulation more than 20% that makes the liquation maintaining part have been disposed, this refractory material be selected from that aluminum oxide, zirconia matter, yittrium oxide matter, oxidation are calcareous, magnesia, with and the refractory material of the product that burn till of composite oxides, this device can remain on liquation the high high temperature more than 200 ℃ of fusing point than rare earth element magnet scrap.
12. the smelting apparatus of the described rare earth element magnet scrap of claim 11 is characterized in that, disposes refractory plate (2) as above-mentioned heat insulating part to cover the whole mode of above-mentioned crucible bottom.
13. the smelting apparatus of a rare earth element magnet scrap, it is characterized in that, in tungsten electrode arc or mobile model plasma arc stove (15), the crucible (1) that configuration liquation maintaining part has heat insulating part and water-cooled part, wherein for the thermal insulation more than 20% of liquation maintaining part, this device can remain on liquation the high high temperature more than 200 ℃ of fusing point than rare earth element magnet scrap.
14. the smelting apparatus of the described rare earth element magnet scrap of claim 13 is characterized in that, disposes the part of metallic plate (17) as electrode in the mode of the part of the sidewall of crucible that covers above-mentioned water-cooled part.
15. the smelting apparatus of claim 13 or 14 described rare earth element magnet scrap is characterized in that, disposes refractory plate (2) as above-mentioned heat insulating part to cover the whole mode of above-mentioned crucible bottom.
16. the smelting apparatus of a rare earth element magnet scrap, it is characterized in that, in tungsten electrode arc or mobile model plasma arc stove (15), comprise the liquation maintaining part have be selected from that aluminum oxide, zirconia matter, yittrium oxide matter, oxidation are calcareous, magnesia, with and the crucible of the thermal insulation structure (21,22) of the product that burn till of composite oxides, cover first electrode (20) of adiabatic face of this crucible and second electrode (15) that is configured in this crucible top partly, this device can remain on liquation the high high temperature more than 200 ℃ of fusing point than rare earth element magnet scrap.
17. the smelting apparatus of the described rare earth element magnet scrap of claim 16 is characterized in that, forms the liquation discharge port that connects above-mentioned crucible bottom.
18. the melting once alloy of a rare earth element magnet scrap, it is characterized in that, it is to make with the method for smelting of the described rare earth element magnet scrap of claim 1, represent that with weight percent Sm and Ce add up to that 10～40wt%, Nd are that 5wt% is following, Fe is that 25wt% is following, Cu is that 4～10wt%, Zr are that 1～4wt%, oxygen are that 0.1wt% is following, all the other are based on Co, result from unavoidable impurities beyond the deoxygenation of rare earth element magnet manufacturing process and the deironing intrusion element in addition of melting once of resulting from addition.
19. the melting once alloy of a rare earth element magnet scrap, it is characterized in that, it is to make with the method for smelting of the described rare earth element magnet scrap of claim 1, represent Nd with weight percent, Pr and Dy add up to 20～35wt%, B is 0.9～1.2wt%, Al is 0.1～1wt%, Co is below the 5wt%, Cu is below the 0.5wt%, Nb is below the 1wt%, oxygen is below the 0.1wt%, all the other are based on Fe, result from unavoidable impurities beyond the deoxygenation of rare earth element magnet manufacturing process in addition, and result from intrusion element beyond the deironing of melting once.
20. the melting once alloy of claim 18 or 19 described rare earth element magnet scrap is characterized in that, above-mentioned unavoidable impurities is the C below 0.1%.
21. the melting once alloy of claim 18 or 19 described rare earth element magnet scrap is characterized in that rare earth element magnet is a sintered magnet.
22. the melting once alloy of a rare earth element magnet scrap, it is characterized in that, it is to make with the method for smelting of the described rare earth element magnet scrap of claim 4, represent that with weight percent Sm and Ce add up to that 10～40wt%, Nd are that 5wt% is following, Fe is that 25wt% is following, Cu is that 4～10wt%, Zr are that 1～4wt%, oxygen are that 0.1wt% is following, all the other are based on Co, result from unavoidable impurities beyond the deoxygenation of rare earth element magnet manufacturing process and the deironing intrusion element in addition of melting once of resulting from addition.
23. the melting once alloy of a rare earth element magnet scrap, it is characterized in that, it is to make with the method for smelting of the described rare earth element magnet scrap of claim 4, represent Nd with weight percent, Pr and Dy add up to 20～35wt%, B is 0.9～1.2wt%, Al is 0.1～1wt%, Co is below the 5wt%, Cu is below the 0.5wt%, Nb is below the 1wt%, oxygen is below the 0.1wt%, all the other are based on Fe, result from unavoidable impurities beyond the deoxygenation of rare earth element magnet manufacturing process in addition, and result from intrusion element beyond the deironing of melting once.
24. the melting once alloy of a rare earth element magnet scrap, it is characterized in that, it is to make with the method for smelting of the described rare earth element magnet scrap of claim 7, represent that with weight percent Sm and Ce add up to that 10～40wt%, Nd are that 5wt% is following, Fe is that 25wt% is following, Cu is that 4～10wt%, Zr are that 1～4wt%, oxygen are that 0.1wt% is following, all the other are based on Co, result from unavoidable impurities beyond the deoxygenation of rare earth element magnet manufacturing process and the deironing intrusion element in addition of melting once of resulting from addition.
25. the melting once alloy of a rare earth element magnet scrap, it is characterized in that, it is to make with the method for smelting of the described rare earth element magnet scrap of claim 7, represent Nd with weight percent, Pr and Dy add up to 20～35wt%, B is 0.9～1.2wt%, Al is 0.1～1wt%, Co is below the 5wt%, Cu is below the 0.5wt%, Nb is below the 1wt%, oxygen is below the 0.1wt%, all the other are based on Fe, result from unavoidable impurities beyond the deoxygenation of rare earth element magnet manufacturing process in addition, and result from intrusion element beyond the deironing of melting once.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP370740/98 | 1998-12-25 | ||
| JP37074098 | 1998-12-25 | ||
| JP370740/1998 | 1998-12-25 | ||
| JP1680599 | 1999-01-26 | ||
| JP16805/1999 | 1999-01-26 | ||
| JP16805/99 | 1999-01-26 | ||
| US13715699P | 1999-06-01 | 1999-06-01 | |
| US13715599P | 1999-06-01 | 1999-06-01 | |
| US60/137,155 | 1999-06-01 | ||
| US60/137,156 | 1999-06-01 |
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| CN100449240C true CN100449240C (en) | 2009-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB998163597A Expired - Fee Related CN100449240C (en) | 1998-12-25 | 1999-12-24 | Method and device for melting rare earth magnet scrap and primary molten alloy of rare earth magnet |
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| Country | Link |
|---|---|
| JP (1) | JP4263366B2 (en) |
| CN (1) | CN100449240C (en) |
| WO (1) | WO2000039514A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102492848B (en) * | 2011-12-22 | 2014-10-08 | 张森 | Method for recovering NdFeB waste material by cold crucible induction smelting technology |
| CN104651612B (en) * | 2013-11-19 | 2017-06-20 | 荆门市格林美新材料有限公司 | The method of molten rare earth waste recovery rare earth |
| DE102014206223A1 (en) | 2014-04-01 | 2015-10-01 | Fme Freiberger Metallrecycling Und Entwicklungsdienstleistungen Gmbh | Process for the recovery of rare earths from rare earth-containing compositions |
| DE102014224015B4 (en) | 2014-11-25 | 2019-07-04 | Fme Freiberger Metallrecycling Und Entwicklungsdienstleistungen Gmbh | Process for the recovery of rare earths from rare earth-containing phosphors |
| CN108754163A (en) * | 2018-07-31 | 2018-11-06 | 邳州市尕星医药技术服务有限公司 | A method of the Extraction of rare earth metal from rare earth waste |
| CN108977674A (en) * | 2018-07-31 | 2018-12-11 | 邳州市尕星医药技术服务有限公司 | A method of the Extraction of rare earth oxide from Rare Earth Electrolysis waste material |
| KR102122428B1 (en) * | 2019-07-12 | 2020-06-19 | 주식회사 알인텍 | Method of recycling raw material of cast alnico magnet and method of making the cast alnico magnet |
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| JPH0533077A (en) * | 1991-07-26 | 1993-02-09 | Tdk Corp | Method for reuse of ni-coated rare earth alloy |
| WO1993020252A1 (en) * | 1992-03-31 | 1993-10-14 | Mannesmann Ag | Method and device for processing free-flowing materials |
| JPH06185879A (en) * | 1992-10-19 | 1994-07-08 | Nippon Steel Corp | Method for operating complex type arc furnace facility |
| JPH085247A (en) * | 1994-06-15 | 1996-01-12 | Tsukishima Kikai Co Ltd | Plasma type fusion furnace |
| JPH0831624A (en) * | 1994-07-15 | 1996-02-02 | Sumikin Morikoopu Kk | Melting method of rare earth magnet scrap |
| JPH0924326A (en) * | 1995-07-10 | 1997-01-28 | Konica Corp | Method for coating cylindrical base material and device therefor |
| JPH0942850A (en) * | 1995-07-28 | 1997-02-14 | Ishikawajima Harima Heavy Ind Co Ltd | Direct current arc furnace |
| JPH09257221A (en) * | 1996-03-22 | 1997-09-30 | Takuma Co Ltd | Plasma melting furnace and melting method of molten article |
| JPH1047861A (en) * | 1996-08-06 | 1998-02-20 | Nisshin Steel Co Ltd | Electric furnace |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3377906B2 (en) * | 1996-03-11 | 2003-02-17 | 株式会社タクマ | Method for preventing decrease in fluidity of molten slag in plasma melting furnace |
-
1999
- 1999-12-24 WO PCT/JP1999/007264 patent/WO2000039514A1/en active Application Filing
- 1999-12-24 CN CNB998163597A patent/CN100449240C/en not_active Expired - Fee Related
- 1999-12-24 JP JP2000591371A patent/JP4263366B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0533077A (en) * | 1991-07-26 | 1993-02-09 | Tdk Corp | Method for reuse of ni-coated rare earth alloy |
| WO1993020252A1 (en) * | 1992-03-31 | 1993-10-14 | Mannesmann Ag | Method and device for processing free-flowing materials |
| JPH06185879A (en) * | 1992-10-19 | 1994-07-08 | Nippon Steel Corp | Method for operating complex type arc furnace facility |
| JPH085247A (en) * | 1994-06-15 | 1996-01-12 | Tsukishima Kikai Co Ltd | Plasma type fusion furnace |
| JPH0831624A (en) * | 1994-07-15 | 1996-02-02 | Sumikin Morikoopu Kk | Melting method of rare earth magnet scrap |
| JPH0924326A (en) * | 1995-07-10 | 1997-01-28 | Konica Corp | Method for coating cylindrical base material and device therefor |
| JPH0942850A (en) * | 1995-07-28 | 1997-02-14 | Ishikawajima Harima Heavy Ind Co Ltd | Direct current arc furnace |
| JPH09257221A (en) * | 1996-03-22 | 1997-09-30 | Takuma Co Ltd | Plasma melting furnace and melting method of molten article |
| JPH1047861A (en) * | 1996-08-06 | 1998-02-20 | Nisshin Steel Co Ltd | Electric furnace |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000039514A9 (en) | 2001-10-04 |
| WO2000039514A1 (en) | 2000-07-06 |
| JP4263366B2 (en) | 2009-05-13 |
| CN1335925A (en) | 2002-02-13 |
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