CN1077603C - Recovering method of valuable composition from rare earth element-containing material and alloy powder obtained therefrom - Google Patents
Recovering method of valuable composition from rare earth element-containing material and alloy powder obtained therefrom Download PDFInfo
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- CN1077603C CN1077603C CN99106463A CN99106463A CN1077603C CN 1077603 C CN1077603 C CN 1077603C CN 99106463 A CN99106463 A CN 99106463A CN 99106463 A CN99106463 A CN 99106463A CN 1077603 C CN1077603 C CN 1077603C
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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
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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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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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 method for recovering a valued composition from rare earth element-containing substances is that the rare earth element-containing substances is treated in order, followed by: (1) rubbing, acid washing and drying; or (2) rubbing, calcium reduction treatment, water washing for removing calcium and calcium and drying; or (3) rubbing, acid washing, calcium reduction treatment, water washing for removing calcium and calcium and drying; or (4) rubbing, acid washing, calcium reduction treatment, water washing for removing calcium, acid washing, water washing and drying. The powdered valued composition recyclable is easily used as a sintered body raw material by the incorporation of a proper conditioning alloy without separation into each constituent element simple substance.
Description
The present invention relates to from the sintering waste material that contains rare earth element to reclaim the method for valuable component, and by the powdered alloy that contains rare earth element that this recovery method obtained.
Sputtering target materials such as sintered magnets such as Sm-Co base, Nd-Fe-B base and Tb-Fe base contain rare earth element component.Mainly by the normal pressure-sintered acquisition of formed body, target mainly obtains by pressure sintering sintered magnet.Under the situation of these agglomerated materials, the waste material that have waste material that substandard products form, when the goods of combination discarded, forms etc.Particularly in sputtering target material, be difficult to by the whole target of sputter completely consumed, after use, the residual agglomerated material of a part has become waste material.
Because rare earth element comparatively costliness and natural resource is limited, from these waste materials, reclaim valuable composition and utilize said composition again that utilization is important for resources effective.
For this reason, up to now, mainly carried out a kind of method that contained component is separated from each other by hydrometallurgical technology.Simultaneously, also has a kind of this component of utilizing again as a kind of method that is used for the dissolved mother alloy.
Yet, in these traditional methods, use known metallurgical technology as basic fundamental and make that condition is suitable may be handled, but have problems such as the value of the product that needs complicated step and formation is very low.
For example, hydrometallurgical is one of traditional recovery method, and at expensive element, when being the main ingredient of waste material as rare earth metal, cobalt metal etc., hydrometallurgical is a preferable methods comparatively.But,,, under with the situation of compound that reclaims, need be reduced into the material that reclaims the step of metal as alloy raw material as forms such as oxide compounds because the form of material to be recycled is a compound.
Simultaneously, the dry process method is another kind of traditional method, is that under the situation of method metallurgy, rare earth element is discharged in slag in removing the purification process of impurity, therefore, must be in other step from slag the separating rare-earth metal component.Simultaneously, be difficult to thoroughly remove the oxygen of q.s, so that utilize this component as the dissolved basic material from the component that reclaims.
Therefore, an object of the present invention is to provide a kind of valuable method for compositions that from the sintering waste material that contains rare earth element, reclaims, can obtain pulverous valuable composition, said composition can be easily by adding suitable compensator alloy, again as the raw material of agglomerated material, not needing to resemble in traditional method every kind of single component of element is not separated and purify.
That is to say that the method for the recovery valuable constituent of the present invention that achieves the above object is a kind ofly to contain the sintering waste material of rare earth element by grinding, the material that makes grinding is through cleanup acid treatment, and dry handled material reclaims valuable method for compositions.
Simultaneously, the valuable method for compositions of another kind of recovery of the present invention is a kind of sintering waste material that contains rare earth element by grinding, the material of grinding is handled through calcium reduction, wash handled material then with the calcium oxide of removing formation and residual calcium, material after the dry washing reclaims valuable method for compositions.
Simultaneously, another method that from the sintering waste material that contains rare earth element, reclaims valuable composition of the present invention be below the valuable method for compositions of a kind of like this recovery, the sintering waste material that promptly contains rare earth element by grinding, make the material that is ground through cleanup acid treatment, the material that cleanup acid treatment is crossed is handled through calcium reduction, the material handled of washing reduction is with the calcium oxide of removing formation and residual calcium, the material after drying is washed then.
Simultaneously, another method that reclaims valuable composition from the sintering waste material that contains rare earth element of the present invention is the valuable method for compositions of a kind of recovery of following process, promptly grind the sintering waste material that contains rare earth element, make the material that is ground through cleanup acid treatment, material after the cleanup acid treatment is handled through calcium reduction, the material handled of washing reduction is to remove calcium oxide and residual calcium then, material process cleanup acid treatment, washing back and the dry material of washing that washing was handled.
The valuable composition that each method by method of the present invention reclaims is, for example, R-Fe-B base alloy (wherein, R represents a kind of rare earth element), particularly a kind of atomic ratio that contains is Nd
2Fe
14The alloy of B composition phase.
Describe the present invention below in detail.
The sintering waste material that contains rare earth element of each processing that can be by recovery method of the present invention comprises the metal sintering material that contains rare earth element; The sintered magnet that contains rare earth element is as R-Fe-B base sintered magnet (wherein, the rare earth element of R representative except that Nd), Nd-Fe-B base sintered magnet, Sm-Co base sintered magnet, their improved composition; With Tb-Fe-Co base target.
In the present invention, at first grind the sintering waste material contain rare earth element, as above-mentioned agglomerated material etc.In this case, in order to prevent oxidation, preferably mechanical mill contains the sintering waste material of rare earth element in inert atmosphere, and this material is ground to, for example, and about 100 μ m or littler particle size.
Because many sintering waste materials that contain rare earth element have absorption and release hydrogen and follow the character of volume change, when utilizing these character, material can be handled generation from disintegration (self-collapse) by carrying out absorption of hydrogen processing or absorption of hydrogen and release, if necessary, can control the particle size of disintegration material to the size that requires by mechanical mill.
The oxygen level that is used for the raw material of agglomerated material must be low.But the oxygen level of useless agglomerated material is bigger usually, is about 0.2～0.8wt%.
Can think that the part that oxygen level is big in agglomerated material is behind the powder surface zone of easy oxidation when sintering and the sintering on the oxygen accumulative structure crystal boundary.In the present invention, in the cleanup acid treatment after grinding, the oxide compound of existence and oxide film are dissolved in the crystal boundary (having gathered oxygen partially at this) of powder surface zone and structure falls, and carrying out this processing is in order to reduce oxygen level.
In the cleanup acid treatment step, not only can reduce oxygen level, and reduce carbon content unnecessary in the agglomerated material.
The sintering waste material that the condition of cleanup acid treatment can be suitable for containing rare earth element becomes its target product, and the cleanup acid treatment condition is had no particular limits.But because pH is when low, rare earth element component is dissolved unintentionally, preferably with pH buffered soln such as diluted acid or acetic acid control pH value.Even can not sufficiently reduce oxygen level, also can reduce oxygen level by the calcium reduction processing.
After cleanup acid treatment or washing processing, must remove by drying and anhydrate, in case oxidation etc. takes place, still, used method and apparatus is had no particular limits.
For the calcium reduction processing of abrasive substance, using particle or sheet metal calcium is economical and easy the processing, and the calcium reduction processing can replace cleanup acid treatment or carry out after cleanup acid treatment.As for other material, also can use hydrolith.Add-on as the calcium of reductive agent is not particularly limited, but will decides according to the oxygen concn of material to be restored, preferably the consumption of calcium is equivalent to reduce required amount at least.By in inert atmosphere or vacuum, keep reasonable time to reduce processing at the mixture of following abrasive substance of the temperature of the fusing point that is at least calcium and calcium.
Reduzate after the reduction processing is poured in the water into the reduzate disintegration.Remaining calcium metal component becomes calcium hydroxide in water, produce hydrogen simultaneously, and by reduction, the disintegrating property of product in water improves, and this makes valuable component good with separating of calcium.By repeating decant and slurrying again (repulp) washing, the calcium oxide of formation and remaining calcium components such as calcium metal can be removed effectively.In addition, if necessary, when in system, adding water-soluble flux components such as calcium chloride in advance, improved the disintegration character of reaction product.
Handle even carry out calcium reduction, oxygen concn takes place sometimes increase, this is considered to because disintegration in water or decant and the surface oxidation of the valuable composition of generation causes when slurrying is washed again.In this case, effectively after grinding contained the sintering waste material of rare earth element, the material after the grinding passed through cleanup acid treatment again through calcium reduction processing, the disintegration in water, washing.
In addition, before calcium reduction, when the carbon concentration of the material after the grinding to be restored is high, form owing to have the trace as carbonate such as lime carbonate of low solubility in reduction reaction, the removal of oxygen and carbon can not fully be carried out sometimes.In this case, after grinding, carry out cleanup acid treatment again, might fully reduce oxygen level by material after the grinding is handled through cleanup acid treatment, calcium reduction.
The valuable composition that is obtained is a powder type, forms by this powder is mixed with control with the powdered alloy for preparing separately for the composition that obtains to require, and this powder can be again as the raw material powder of producing sintered article.The powdered alloy of forming for control has no particular limits.But, because in the processing that reduces oxygen level (this is a main purpose of the present invention), the rare earth component is gone out by acidleach, so the powder that at least a control is formed is the powdered alloy that contains rare earth element.
Powdered alloy as the control composition, can use the powdered alloy that obtains by various known methods, the dissolving casting polishing of these known methods as after dissolving and casting, grinding, obtain the thin ribbon shaped goods and grind the liquid quench polishing of these thin goods by the roll-type chilling after the dissolving, directly obtain the atomization of powder by the injection-cooling after the dissolving, as water atomization or aerosolization method, obtain the reduction-diffusion process of powdered alloy etc. by calcium reduction etc.
Then, by the present invention of the following example practice interpretation.
Embodiment 1
As the sintering waste material that contains rare earth element, use the waste material of the sputtering target material that is used for Tb-Fe-Co base magneto-optic disk that obtains by means of reduction-diffusion process as the rare earth alloy powder of raw material by the pressure sintering sintering.The form of this waste material substandard products of fragmentation when handling forms.
The cobalt (Co) of the terbium that consists of 49.8wt% (Tb) of this waste material, the iron (Fe) of 46.1wt%, 4.12wt%, the calcium (Ca) of 0.09wt%, the oxygen (O) of 0.25wt%, the carbon (C) of 0.012wt%.By the EPMA quantitative analysis, the structure of waste material is made of the Tb-Fe-Co alloy phase (terbium of the iron of about 45～52wt%, the cobalt of about 3～4wt% and about 42～49wt%) of a kind of Fe-Co alloy phase (iron of about 93wt%～96wt% and the cobalt of about 4wt%～7wt%), a kind of Tb-Fe-Co alloy phase (terbium of the iron of about 65～68wt%, the cobalt of about 2～5wt% and about 23～25wt%) of low terbium concentration, a kind of medium terbium concentration and a kind of Tb-Fe-Co alloy phase (terbium of the iron of about 35～37wt%, the cobalt of about 5～6wt% and about 57～60wt%) of high terbium concentration.
This target waste material is placed in the stove, and the air with in the argon gas replacement stove replaces argon gas with hydrogen again, in hydrogen stream furnace temperature is brought up to about 300 ℃, and system is incubated 30 minutes under this temperature.Then, the hydrogen in the stove is replaced with argon gas, behind cool to room temperature, take out product, obtaining particle size is 500 μ m or littler powder.
The powder that is obtained is joined in the deionized water, form the slurry that 30g/ rises concentration, by under stirring condition, dripping 10 times of aqueous acetic acids its pH value is adjusted to 5, and carry out about 5 minutes cleanup acid treatment to slurry volume.Then, after replacing with deionized water and washing, filter this product, with the water in the ethanol substitution product, dry in a vacuum this product obtains a kind of powdered alloy.
The cobalt of the terbium that consists of 47.8wt% of the powdered alloy that is obtained, the iron of 47.2wt%, 5.36wt%, the calcium of 0.07wt%, the oxygen of 0.07wt% and the carbon of 0.008wt%.This composition shows, compares with the target composition before handling, and the terbium amount reduces 2wt%, and the oxygen amount reduces 0.18wt%.The structure of the powdered alloy that is obtained with handle before target on the structure that confirms identical.
The powdered alloy that reclaims is mixed mutually with the terbium metal powder, and ratio is respectively 98wt% and 2wt%, and purpose is to obtain the terbium of 49.8wt%, behind thorough mixing, produces target by pressure sintering.
The cobalt of the terbium that consists of 49.7wt% of the target of gained, the iron of 46.3wt%, 4.18wt%, the calcium of 0.07wt%, the oxygen of 0.07wt% and the carbon of 0.009wt%, the structure of this alloy are also identical with processing structure before.
Therefore, as can be seen, the sputtering target material waste material of the Tb-Fe-Co base magneto-optic disk that becomes substandard products that generation is broken when handling is recovered as valuable material and can reuses.
Embodiment 2
As the sintering waste material that contains rare earth element, use the alloy that obtains by reduction-diffusion process to be used as the SmCo of raw material production
5The base sintered magnet waste material, this waste material be the magnetization before the magnet forming step in owing to size deviation becomes substandard products.It consists of the samarium (Sm) of 34.8wt%, the cobalt (Co) of 65.1wt%, the calcium (Ca) of 0.06wt%, the oxygen (O) of 0.18wt% and the carbon (C) of 0.011wt%.By hydrogen treat used among the embodiment 1 this agglomerated material being ground to particle size is 500 μ m or littler, crushing grinding in argon gas again.The oxygen concn of the abrasive flour that is obtained is 0.16wt%, and this is lower than the oxygen concn of agglomerated material, but also is not enough to use powder after this grinding as the agglomerating raw material.
4 orders or littler) and the Calcium Chloride Powder Anhydrous (CaCl of 20wt% then, by the calcium metal of powder after grinding and 10wt% (Ca, particle size:
2, particle size: thorough mixing 300 orders or littler), this mixture is placed in the stainless steel vessel, in argon atmospher,, the powder that is obtained is handled through the reduction of carrying out with calcium 1,000 ℃ of insulation 3 hours.
After cooling, reaction product is ground to particle size is about 10mm, be added to the water forming under the condition that concentration is the slurry that rises of 30g/, stir then and make its disintegration in water.After isolating the calcium component by decant, resistates was stirred 10 minutes, be 10 or lower until pH value, when the water washing process of slurrying again of repeated application draining, water filling and stirring, wash by slurrying again that to make the pH value 4 times be 10 or lower.Replace water in the slurry by the method identical with alcohol, after drying, reclaim the powdered alloy of gained with embodiment 1.
The oxygen concn of the powdered alloy that is obtained is 0.09wt%, and this is as the enough oxygen concns of raw material for sintering.The composition of other component is the samarium of 33.1wt%, the cobalt of 65.8wt%, the calcium of 0.07wt%, the carbon of 0.013wt%, and the concentration of samarium is lowered, and forms near SmCo
5Stoichiometric composition.
Is this powdered alloy that 40.2wt%, cobalt concentration are that 58.9wt%, oxygen concn are that 0.06wt%, calcium concn are that 0.08wt%, carbon concentration are that the 0.010wt% powdered alloy mixes with 79.2: 21.7 weight ratio with the samarium concentration that obtains by reduction-diffusion process, form a kind of powdered alloy, it consists of the samarium of 34.9wt%, the cobalt of 64.9wt%, the calcium of 0.07wt%, the oxygen of 0.08wt% and the carbon of 0.012wt%, obtains SmCo at the powdered alloy from such formation
5During based sintered fuel, obtained to consist of the agglomerated material of the carbon of the oxygen of calcium, 0.18wt% of cobalt, the 0.06wt% of samarium, the 64.8wt% of 34.8wt% and 0.012wt%, this with handle before the composition of waste material identical.
Therefore, as can be seen, be used for SmCo
5SmCo in the agglomerated material of base magnet
5Be recovered as valuable material mutually and can reuse.
Embodiment 3
As the sintering waste material that contains rare earth element, use the alloy that obtains by reduction-diffusion process to be used as the SmCo of raw material production
5The waste material of base sintered magnet, this waste material are to become substandard products because of size deviation in the magnet forming step before magnetization.In addition, its form with embodiment 2 in identical.
This agglomerated material is placed in the stove and by hydrogen treat used among the embodiment 1 with embodiment 2 in identical method grind, be 500 μ m or littler powder (the hydrogen-gasified effect Ginding process identical) thereby obtain particle size with embodiment 2.
In addition, be this powder crushing grinding to particle size in argon atmospher 300 μ m or littler.
4 orders or littler) and the Calcium Chloride Powder Anhydrous (CaCl of 20wt% then, by the calcium metal of powder after grinding and 10wt% (Ca, particle size:
2, particle size: thorough mixing 300 orders or littler), this mixture is placed in the stainless steel vessel, in argon atmospher,, the powder that is obtained is handled through the reduction of carrying out with calcium 1,000 ℃ of insulation 3 hours.
After cooling, reaction product is ground to particle size is about 10mm, be added to the water forming under the condition that concentration is the slurry that rises of 30g/, stir then and make its disintegration in water.After isolating the calcium component by decant, resistates was stirred 10 minutes, be 10 or lower until pH value, when the water washing process of slurrying again of repeated application draining, water filling and stirring, wash by slurrying again that to make the pH value 4 times be 10 or lower.Replace water in the slurry by the method identical with alcohol, after drying, reclaim the powdered alloy of gained with embodiment 1.
The oxygen concn of the powdered alloy that is obtained is 0.08wt%, and this is as the enough oxygen concns of raw material for sintering.The samarium that consists of 33.2wt% of other component, the cobalt of 65.7wt%, the calcium of 0.06wt%, the carbon of 0.014wt%, the concentration of samarium is lowered, and forms near SmCo
5Stoichiometric composition.
Is this powdered alloy that 40.2wt%, cobalt concentration are that 58.9wt%, oxygen concn are that 0.06wt%, calcium concn are that 0.08wt%, carbon concentration are that the 0.010wt% powdered alloy mixes with 75.7: 24.3 weight ratio with the samarium concentration that obtains by reduction-diffusion process, form a kind of powdered alloy, it consists of the samarium of 34.9wt%, the cobalt of 64.0wt%, the calcium of 0.06wt%, the oxygen of 0.09wt% and the carbon of 0.013wt%, obtains SmCo at the powdered alloy from such formation
5During based sintered fuel, obtained to consist of the agglomerated material of the carbon of the oxygen of calcium, 0.18wt% of cobalt, the 0.06wt% of samarium, the 64.9wt% of 34.8wt% and 0.012wt%, this with handle before the composition of waste material identical.
Therefore, as can be seen, be used for SmCo
5SmCo in the agglomerated material of base magnet
5Be recovered as valuable material mutually and can reuse.
Embodiment 4
Substandard products agglomerated material among the embodiment 2 is carried out the processing identical with embodiment 2, but different is after calcium reduction is handled, carry out with embodiment 1 in identical cleanup acid treatment, the result is, the oxygen concn of the powdered alloy that is obtained becomes 0.05wt%, and this powdered alloy is a kind of good powdered alloy that has far below the oxygen concn that is applicable to raw materials for sintering.The samarium that consists of 33.1wt% of other component, the cobalt of 65.9wt%, the calcium of 0.06wt%, the carbon of 0.011wt%.
From here as can be seen, after calcium reduction, carry out cleanup acid treatment, improved quality as valuable material.
Embodiment 5
Substandard products agglomerated material among the embodiment 2 is carried out the processing identical with embodiment 2, but different is before calcium reduction is handled, carry out with embodiment 1 in identical cleanup acid treatment, the result is, the oxygen concn of the powdered alloy that is obtained becomes 0.05wt%, the samarium that consists of 33.1wt% of other component, the cobalt of 65.9wt%, the calcium of 0.06wt%, the carbon of 0.005wt%.
From as can be seen, be used for the SmCo of magnet here
5In the based sintered fuel, by carried out cleanup acid treatment before calcium reduction, this agglomerated material has become the valuable material that has less carbon content and improved quality.
Embodiment 6
Agglomerated material from the fragmentation that is used for Nd-Fe-B base magnet, it consists of the neodymium (Nd) of 31.2wt%, the dysprosium (Dy) of 1.1wt%, the boron (B) of 1.1wt%, the oxygen (O) of 0.58wt%, the carbon (C) of 0.41wt%, by with embodiment 2 in identical Ginding process to have obtained a kind of particle size be 100 μ m or littler powder.
The cleanup acid treatment of carrying out through the method identical at this powder with embodiment 1, but different be that the pH value becomes 4 when reclaiming a kind of powder, oxygen concn is 0.43wt%, carbon concentration is 0.031wt%.This carbon concentration is enough low.But as Nd-Fe-B base alloy materials, oxygen concn is too high.
Then, 4 orders or littler) and the Calcium Chloride Powder Anhydrous of 20wt% (particle size: thorough mixing 300 orders or littler) by the calcium metal of this powdered alloy and 10wt% (particle size:, this mixture is placed in the stainless steel vessel, in argon atmospher, 1,000 ℃ is incubated 3 hours, and the reduction of carrying out carrying out with calcium is handled.After cooling, reaction product is ground to particle size is about 10mm, be added to the water forming under the condition that concentration is the slurry that rises of 30g/, stir then and make its disintegration in water.After isolating the calcium component by decant, resistates was stirred 10 minutes, be 10 or lower until pH value, when the water washing process of slurrying again of repeated application draining, water filling and stirring, wash by slurrying again that to make the pH value 7 times be 10 or lower.
When the powdered alloy of a part of gained reclaimed with the water in the ethanol replacement slurry and by vacuum-drying, the neodymium that consists of 26.5wt% of this powdered alloy, the dysprosium of 1.12wt%, the boron of 1.02wt%, the oxygen of 0.27wt%, this oxygen concn were slightly high.
In addition, before calcium reduction, carry out the processing identical, carry out ethanol and replace with this cleanup acid treatment, and when reclaiming powder by vacuum-drying, composition becomes the neodymium of 26.2wt%, the dysprosium of 1.13wt%, the boron of 1.01wt%, the oxygen of 0.14wt%, and this oxygen concn is enough low.Simultaneously, the concentration of carbon is 0.018wt%, and the concentration of calcium is 0.03wt%, and therefore, the concentration of these impurity is enough low.The bigger part of the powdered alloy that is obtained is by Nd
2Fe
14B
1The powdered alloy that principal crystalline phase constitutes, this is the phase that Nd-Fe-B base magnet produces magnetic.
Be 85.4wt% at this powdered alloy with neodymium concentration, have Nd mutually and Nd
2Fe
14The Nd-Fe alloy of the eutectic structure of phase mixes with 94: 6 weight ratio, and when the mixture of common powder metallurgic method prepared sintered magnet, it was that 43.2MG Oe and coercivity H j are the high-performance of 14.0kOe that the property list of the magnet that is obtained reveals maximum magnetic flux energy density (BH) max.
Therefore, as can be seen, become valuable material, and used the magnet of powdered alloy to have the magnetic properties of realistic scale with composition of having adjusted powdered alloy from the hypoxemia principal crystalline phase powdered alloy that is used for the recovery of magnets N d-Fe-B based sintered fuel.
As mentioned above, the invention provides a kind of from containing the sintering waste material of rare earth element, as reclaiming valuable method for compositions and a kind of application method of described salvage material in Sm base or Nd base rare earth element permanent magnet and the Tb-Fe-Co based sputtering target material etc.By the present invention, reclaimed the more most sintering waste material that contains rare earth element, and separated not needing to resemble in traditional method and the every kind of component of purifying, therefore, method of the present invention has high economic worth.Simultaneously, adjust composition by mixing suitable alloy, Recycled materials can easily be regenerated as the agglomerating raw material, and the goods that obtain have enough performances.
Claims (43)
1, a kind ofly from the sintering waste material that contains rare earth element, reclaims valuable method for compositions, comprise and grind a kind of sintering waste material that contains rare earth element, the material that grinds making is through after the cleanup acid treatment, and the dry material of being washed obtains a kind of valuable composition.
2, a kind of recovery method of the valuable material according to claim 1, wherein, the said sintering waste material that contains rare earth element is a kind of metal sintering material that contains rare earth element.
3, a kind of recovery method of the valuable material according to claim 2, wherein, the said sintering waste material that contains rare earth element is the sintered magnet that contains rare earth element.
4, a kind of recovery method of the valuable material according to claim 3, wherein, the said sintering waste material that contains rare earth element is a kind of R-Fe-B base sintered magnet or a kind of Nd-Fe-B sintered magnet, wherein, R represents a kind of rare earth element except Nd.
5, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 1, wherein, the valuable composition that is reclaimed is a R-Fe-B base alloy, wherein, R represents a kind of rare earth element.
6, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 5, wherein, the valuable composition that is reclaimed is the alloy of a kind of Nd2Fe14B of containing composition (representing with atomic ratio) phase.
7, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 1, wherein, said grinding is undertaken by the mechanical means in rare gas element.
8, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 1, wherein, said cleanup acid treatment is carried out with the pH buffered soln that contains diluted acid or acetic acid.
9, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material, comprise and grind the sintering waste material that contains rare earth element, the material of said grinding is handled through calcium reduction, remove at the handled material of washing after the calcium oxide and residual calcium of formation, material after the dry washing obtains a kind of valuable composition.
10, a kind of method of the valuable material of recovery according to claim 9, wherein, the said sintering waste material that contains rare earth element is a kind of metal sintering material that contains rare earth element.
11, a kind of recovery method of the valuable material according to claim 10, wherein, the said sintering waste material that contains rare earth element is the sintered magnet that contains rare earth element.
12, a kind of recovery method of the valuable material according to claim 11, wherein, the said sintering waste material that contains rare earth element is a kind of R-Fe-B base sintered magnet or a kind of Nd-Fe-B base sintered magnet, and wherein, R represents a kind of rare earth element except Nd.
13, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 9, wherein, the valuable composition that is reclaimed is a R-Fe-B base alloy, wherein, R represents a kind of rare earth element.
14, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 13, wherein, the valuable composition that is reclaimed is a kind of Nd of containing
2Fe
14The alloy of B composition (representing) phase with atomic ratio.
15, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 9, wherein, said grinding is undertaken by the mechanical means in rare gas element.
16, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 9, wherein, it is particle or sheet metal calcium or hydrolith that said calcium reduction is handled used calcium.
17, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 9, wherein, said calcium reduction is handled under the temperature of the fusing point that is at least said calcium, in inert atmosphere or vacuum the material after grinding and the mixture of calcium is carried out.
18, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 9, wherein, by repeat decant and again the slurrying washing carry out the removal processing of calcium component.
19, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 9, wherein, after in the material of the grinding that will handle through calcium reduction, adding the water-soluble flux component in advance, carry out the removal of said calcium component and handle.
20, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material, comprise and grind the sintering waste material that contains rare earth element, the material that makes said grinding is through cleanup acid treatment, the material that cleanup acid treatment is crossed is handled through calcium reduction, material after washing reduction is handled is removed after the calcium oxide and residual calcium of formation, material after the dry washing obtains a kind of valuable composition.
21, a kind of method of the valuable material of recovery according to claim 20, wherein, the said sintering waste material that contains rare earth element is a kind of metal sintering material that contains rare earth element.
22, a kind of recovery method of the valuable material according to claim 21, wherein, the said sintering waste material that contains rare earth element is the sintered magnet that contains rare earth element.
23, a kind of recovery method of the valuable material according to claim 22, wherein, the said sintering waste material that contains rare earth element is a kind of R-Fe-B base sintered magnet or a kind of Nd-Fe-B base sintered magnet, and wherein, R represents a kind of rare earth element except Nd.
24, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 20, wherein, the valuable composition that is reclaimed is a R-Fe-B base alloy, wherein, R represents a kind of rare earth element.
25, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 24, wherein, said valuable composition is a kind of Nd of containing
2Fe
14The alloy of B composition (representing) phase with atomic ratio.
26, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 20, wherein, said grinding is undertaken by the mechanical means in rare gas element.
27, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 20, wherein, said cleanup acid treatment is to carry out with the pH value buffered soln that contains diluted acid or acetic acid.
28, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 20, wherein, it is particle or sheet metal calcium or hydrolith that said calcium reduction is handled used calcium.
29, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 20, wherein, said calcium reduction is handled under the temperature of the fusing point that is at least said calcium, in inert atmosphere or vacuum the material after grinding and the mixture of calcium is carried out.
30, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 20, wherein, by repeat decant and again the slurrying washing carry out the removal processing of calcium component.
31, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 20, wherein, after in the material of the grinding that will handle through calcium reduction, adding the water-soluble flux component in advance, carry out the removal of said calcium component and handle.
32, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material, comprise and grind the sintering waste material that contains rare earth element, make the material that ground through cleanup acid treatment, the material that cleanup acid treatment is crossed is handled through calcium reduction, material after washing reduction is handled is removed after the calcium oxide and residual calcium of formation, make the material of washing through cleanup acid treatment again, after washing, the material of dry washing.
33, a kind of method of the valuable material of recovery according to claim 32, wherein, the said sintering waste material that contains rare earth element is a kind of metal sintering material that contains rare earth element.
34, a kind of recovery method of the valuable material according to claim 33, wherein, the said sintering waste material that contains rare earth element is the sintered magnet that contains rare earth element.
35, a kind of recovery method of the valuable material according to claim 34, wherein, the said sintering waste material that contains rare earth element is a kind of R-Fe-B base sintered magnet or a kind of Nd-Fe-B base sintered magnet, and wherein, R represents a kind of rare earth element except Nd.
36, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 32, wherein, the valuable composition that is reclaimed is a R-Fe-B base alloy, wherein, R represents a kind of rare earth element.
37, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 36, wherein, the valuable composition that is reclaimed is a kind of Nd of containing
2Fe
14The alloy of B composition (representing) phase with atomic ratio.
38, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 32, wherein, said grinding is undertaken by the mechanical means in rare gas element.
39, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 32, wherein, said cleanup acid treatment is to carry out with the pH buffered soln that contains diluted acid or acetic acid.
40, a kind of method that reclaims valuable material from the sintering waste material that contains rare earth element according to claim 32, wherein, it is particle or sheet metal calcium or hydrolith that said calcium reduction is handled used calcium.
41, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 32, wherein, said calcium reduction is handled under the temperature of the fusing point that is at least said calcium, in inert atmosphere or vacuum the material after grinding and the mixture of calcium is carried out.
42, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 32, wherein, by repeat decant and again the slurrying washing carry out the removal processing of calcium component.
43, a kind of method that from the sintering waste material that contains rare earth element, reclaims valuable material according to claim 32, wherein, after in the material of the grinding that will handle through calcium reduction, adding the water-soluble flux component in advance, carry out the removal of said calcium component and handle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12871298A JPH11319752A (en) | 1998-05-12 | 1998-05-12 | Recovery of valued composition from rare earth element-containing substance and alloy powder obtained thereby |
| JP128712/98 | 1998-05-12 | ||
| JP128712/1998 | 1998-05-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1237643A CN1237643A (en) | 1999-12-08 |
| CN1077603C true CN1077603C (en) | 2002-01-09 |
Family
ID=14991573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99106463A Expired - Fee Related CN1077603C (en) | 1998-05-12 | 1999-05-12 | Recovering method of valuable composition from rare earth element-containing material and alloy powder obtained therefrom |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH11319752A (en) |
| CN (1) | CN1077603C (en) |
| DE (1) | DE19922144C2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107922997A (en) * | 2015-08-26 | 2018-04-17 | 日立金属株式会社 | Separate light rare earth elements and the useful method of heavy rare earth element |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11329811A (en) * | 1998-05-18 | 1999-11-30 | Sumitomo Special Metals Co Ltd | Raw material powder for r-fe-b magnet and manufacture of r-fe-b based magnet |
| DE19843883C1 (en) * | 1998-09-24 | 1999-10-07 | Vacuumschmelze Gmbh | Method for recycling of permanent magnets forming part of scrap material |
| JP4240679B2 (en) * | 1999-09-21 | 2009-03-18 | ソニー株式会社 | Method for producing sputtering target |
| JP4243461B2 (en) * | 2002-08-06 | 2009-03-25 | 学校法人千葉工業大学 | Rare earth metal recovery method |
| US8118906B2 (en) | 2007-10-29 | 2012-02-21 | Heraeus Inc. | Methodology for recycling Ru and Ru-alloy deposition targets and targets made of recycled Ru and Ru-based alloy powders |
| JP4846771B2 (en) * | 2008-08-12 | 2011-12-28 | Ｊｆｅミネラル株式会社 | Pretreatment method for rare earth element recovery from waste fluorescent lamp and method for collecting rare earth element using solid matter obtained by the pretreatment method |
| KR101414967B1 (en) * | 2012-03-22 | 2014-07-04 | 한국생산기술연구원 | Nd Extraction Metod From Rare Earth element |
| CN105026607B (en) * | 2013-01-28 | 2017-05-31 | 吉坤日矿日石金属株式会社 | Rare-earth magnet sputtering target and its manufacture method |
| CN103103361B (en) * | 2013-02-28 | 2014-11-26 | 包头稀土研究院 | Method for preparing rare earth oxide from rare earth polishing powder waste |
| CN103343234B (en) * | 2013-07-19 | 2015-01-14 | 北京工业大学 | Method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation |
| EP3807913A1 (en) * | 2018-06-18 | 2021-04-21 | ABB Schweiz AG | Method for producing a magnetic powder |
| CN109847892A (en) * | 2019-03-20 | 2019-06-07 | 兰州大学 | A kind of reduction-diffusion process prepares the deimpurity device of terres rares-transition metal alloy |
| CN111876787B (en) * | 2020-07-22 | 2022-03-15 | 宁波江丰电子材料股份有限公司 | Treatment process of copper phosphorus evaporation material |
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- 1998-05-12 JP JP12871298A patent/JPH11319752A/en active Pending
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- 1999-05-12 DE DE1999122144 patent/DE19922144C2/en not_active Expired - Fee Related
- 1999-05-12 CN CN99106463A patent/CN1077603C/en not_active Expired - Fee Related
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| JPS58193331A (en) * | 1982-05-04 | 1983-11-11 | Hitachi Metals Ltd | Treatment of alloy power of rare earth element-cobalt |
| CN1062232A (en) * | 1990-12-04 | 1992-06-24 | 北京科技大学 | Produce the method for rare-earth iron-boron permanent magnetic material with the rare-earth iron-boron waste material |
| CN1119216A (en) * | 1994-09-22 | 1996-03-27 | 泰兴市君泰稀土实业有限公司 | Process for preparing neodymium and neodymium-dysprosium compounds by recovering waste neodymium-iron-boron |
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| CN107922997A (en) * | 2015-08-26 | 2018-04-17 | 日立金属株式会社 | Separate light rare earth elements and the useful method of heavy rare earth element |
| CN107922997B (en) * | 2015-08-26 | 2020-05-05 | 日立金属株式会社 | Process useful for separating light rare earth elements from heavy rare earth elements |
| US10865463B2 (en) | 2015-08-26 | 2020-12-15 | Hitachi Metals, Ltd. | Useful method for separating light rare earth elements and heavy rare earth elements |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1237643A (en) | 1999-12-08 |
| DE19922144A1 (en) | 1999-11-25 |
| DE19922144C2 (en) | 2001-11-15 |
| JPH11319752A (en) | 1999-11-24 |
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