CN111653406A - Method for recycling permanent magnet material ultrafine powder and molding waste and product thereof - Google Patents
Method for recycling permanent magnet material ultrafine powder and molding waste and product thereof Download PDFInfo
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- CN111653406A CN111653406A CN202010610306.4A CN202010610306A CN111653406A CN 111653406 A CN111653406 A CN 111653406A CN 202010610306 A CN202010610306 A CN 202010610306A CN 111653406 A CN111653406 A CN 111653406A
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- H—ELECTRICITY
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- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B22F2003/248—Thermal after-treatment
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Abstract
The invention discloses a method for recycling ultrafine powder and/or molding waste of a Re-Fe-B permanent magnet material, which comprises the steps of profiling and sintering the ultrafine powder and the molding waste which are fully mixed, wherein the proportion of the ultrafine powder in the total mass of the ultrafine powder and the molding waste is less than 50 wt%. The invention also discloses a product prepared by the recycling method and application thereof. The method integrates the process of recovering the ultrafine powder and the molding waste of the RE-FE-B permanent magnet material such as rare earth neodymium iron boron, not only can well retain the value of the rare earth in the ultrafine powder and the molding waste, but also does not need to burn and oxidize the ultrafine powder, has no potential safety hazard, and has the advantages of large treatment capacity, high recovery rate, no environmental pollution, short treatment process period, lower cost and contribution to industrial large-scale production. When the product prepared by the method is applied to preparing products such as rare earth neodymium iron boron and the like, good magnetic performance indexes can be kept.
Description
Technical Field
The invention relates to a method for recycling permanent magnet material ultrafine powder and molding waste and a product.
Background
The RE-FE-B series permanent magnet material ultrafine powder (such as rare earth neodymium iron boron ultrafine powder) is ultrafine powder with the particle size D50 of about 1 mu m generated in the process of powder preparation by neodymium iron boron powder metallurgy, the rare earth neodymium iron boron ultrafine powder contains about 50 percent of total rare earth, has high activity and is easy to oxidize; these characteristics cause the ultrafine powder to have certain danger and difficulty in storage and use. At present, except a few low-grade products, the superfine powder of the neodymium iron boron enterprise can be added into normal powder according to a small adding proportion, and oil sludge is burnt and poured in most cases. In order to save resources and improve the utilization rate of waste resources, the method has important practical significance for recycling the neodymium iron boron ultrafine powder. The processing mode of the rare earth neodymium iron boron ultrafine powder industry generally adopts direct air combustion oxidation, and then serves as a raw material for extracting rare earth, and the raw material is supplied to rare earth separation enterprises for recycling through a rare earth separation method.
CN201710936762.6 discloses a method for recycling rare earth neodymium iron boron ultrafine powder, wherein a method for fully oxidizing rare earth neodymium iron boron ultrafine powder to obtain oxidized particles, and then adding the oxidized particles of the ultrafine powder to normal powder is provided. Because the neodymium iron boron ultrafine powder is oxidized, the rare earth value of the neodymium iron boron ultrafine powder is seriously lost.
CN201710786334.X discloses a method for recycling ultrafine powder of sintered neodymium iron boron material, wherein the neodymium iron boron ultrafine powder is used as a part of smelting raw materials, oxygen content which is not beneficial to magnetic materials is introduced in the treatment mode, and combustible potential safety hazard exists in the ultrafine powder adding process. Meanwhile, the source components of the ultrafine powder are unstable, the alloy components are difficult to master, and the large-scale production is not facilitated.
CN201310113826.4 discloses a neodymium iron boron magnetic material with superfine powder and a preparation method thereof, wherein the neodymium iron boron superfine powder is added into normal magnetic powder to prepare neodymium iron boron products, but the amount of neodymium iron boron superfine powder treated in one step in this way is small, which is not beneficial to large-scale production.
The molding waste of the rare earth neodymium iron boron is the waste generated in the molding process of the neodymium iron boron alloy powder. Due to the influence of technical limitation and uncontrollable factors, a certain amount of waste materials including unqualified blanks, cracked blanks, damaged blanks and the like are inevitably generated in the processing process of the neodymium iron boron product, and the waste materials are difficult to directly use, so that a large amount of raw materials are wasted. Along with the improvement of neodymium iron boron product productivity, produce neodymium iron boron waste material also greatly increased, how to handle neodymium iron boron waste material effectively is the technological problem that need solve urgently in the neodymium iron boron product production field. At present, the main method for recycling the waste materials is direct scrapping, when the waste materials are sold and used for extracting neodymium, praseodymium and other rare earth elements, the method has low value for sintered neodymium iron boron manufacturers, and the production cost is increased.
CN201510193474.7 discloses a method for recycling neodymium iron boron forming waste, which comprises the steps of heating and drying treatment in a demagnetizing furnace, hydrogen crushing treatment, ICP detector detection, mixing of hydrogen crushing powder and an antioxidant, air flow grinding, fine grinding, forming, isostatic pressing, sintering, aging treatment and the like, so as to obtain neodymium iron boron blanks. CN201410671262.0 discloses a method for recycling sintered neodymium iron boron molding waste, which comprises the steps of crushing the molding waste generated in the molding pressing and isostatic pressing processes of sintered neodymium iron boron, and sieving the molding waste with a sieve larger than or equal to 60 meshes to obtain waste fine powder; and then adding the mixture into a jet mill for dispersion, mixing the mixture with the same series of normal neodymium iron boron fine powder, an antioxidant and gasoline, carrying out orientation pressing under the protection of nitrogen, charging and sintering, and tempering to obtain a sintered neodymium iron boron blank. The methods mainly relate to a recovery mode of single neodymium iron boron forming waste materials, and the problem of neodymium iron boron ultrafine powder cannot be solved simultaneously.
Disclosure of Invention
The invention aims to solve the technical problems that the existing method for recycling the superfine powder generated in the production process of RE-FE-B series permanent magnetic materials such as rare earth neodymium iron boron and the recycling of molding waste (namely the molding waste of the RE-FE-B series permanent magnetic materials such as rare earth neodymium iron boron) has the defects of larger potential safety hazard, low recycling rate, large environmental pollution, long period, serious loss of the rare earth value of the neodymium iron boron superfine powder, inconvenience for large-scale production, overhigh recycling treatment cost and the like, and provides a method for recycling the superfine powder and the molding waste of the RE-FE-B series permanent magnetic materials (such as the rare earth neodymium iron boron) and a product prepared by the recycling method. The recycling method of the invention integrates the process of recycling the ultrafine powder and the molding waste of the RE-FE-B permanent magnet material such as the rare earth neodymium iron boron, not only can well reserve the value of the ultrafine powder of the RE-FE-B permanent magnet material (such as the rare earth neodymium iron boron) and the rare earth in the molding waste of the RE-FE-B permanent magnet material such as the neodymium iron boron, but also does not need to burn and oxidize the ultrafine powder, has no potential safety hazard, has large treatment capacity and high recovery rate of the ultrafine powder and the molding waste, has no pollution to the environment, short treatment process period and lower cost, and is beneficial to industrial large-scale production. When the product obtained by the method is applied to preparing products such as rare earth neodymium iron boron and the like, good magnetic performance indexes can be kept.
In the prior art, various ways of treating and recovering ultrafine powder and molding waste of RE-FE-B permanent magnet materials such as rare earth neodymium iron boron are adopted, but the defects of low utilization rate, high treatment cost, inconvenience for large-scale production and the like exist more or less. Through a large number of experiments, the inventor of the invention firstly mixes the ultrafine powder of the RE-FE-B permanent magnet material (such as neodymium iron boron) and the molding waste material at a certain proportion and dosage, and particularly after mixing the ultrafine powder and the molding waste material under a certain condition and recycling the mixture, and unexpectedly finds that the method can well retain the rare earth value in the ultrafine powder of the RE-FE-B permanent magnet material (such as rare earth neodymium iron boron) and the molding waste material of the RE-FE-B permanent magnet material (such as neodymium iron boron), and can make up the defects of the existing recycling treatment methods.
In order to solve the above technical problems, a first aspect of the present invention provides a method for recycling ultrafine powder of a RE-FE-B-based permanent magnetic material and/or molding waste of a RE-FE-B-based permanent magnetic material, comprising the steps of compacting and sintering the ultrafine powder of the RE-FE-B-based permanent magnetic material and the molding waste of the RE-FE-B-based permanent magnetic material, which are mixed thoroughly, the molding waste of the RE-FE-B-based permanent magnetic material being crushed molding waste;
wherein the ratio of the ultrafine powder of the RE-FE-B-based permanent magnet material to the total mass of the ultrafine powder of the RE-FE-B-based permanent magnet material and the molding waste of the RE-FE-B-based permanent magnet material is 50 wt% or less, and for example, the ratio may be 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%. The inventor finds in the experimental process that when the proportion of the superfine powder of the RE-FE-B series permanent magnet material, such as rare earth neodymium iron boron superfine powder, is higher than 50 wt%, the superfine powder is easy to oxidize and difficult to control, and finally the obtained product cannot be formed. The inventors of the present invention tried to prepare ultrafine powders or molding wastes by mixing them with conventional neodymium-iron-boron products, respectively, and then press molding and sintering them, and found that the desired products could not be finally obtained, and they had to be subjected to complicated processes and their addition amounts were limited.
In the present invention, the sufficient mixing may be performed under the condition of inert gas and/or nitrogen. In the invention, the ultrafine powder of the RE-FE-B permanent magnetic material can be loaded in a gas-tight qualified container so as to be kept under the atmosphere condition of inert gas and/or nitrogen. The inert gas may be argon or the like.
In the present invention, the time for the sufficient mixing may be 20 to 240min, for example, 180 min. The inventor finds that uneven mixing can be caused when the mixing time is too short, and resources are wasted when the mixing time is too long in the experimental process, so that the mixing time is generally controlled to be 20-240 min. The mixing may be by conventional mixing means in the art, such as mixing using a blender or the like.
In the present invention, an antioxidant may be added to the superfine powder of the RE-FE-B permanent magnet material in a proportion of 0.5 wt% or less, for example, in a proportion of 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, to prevent the superfine powder of the RE-FE-B permanent magnet material (e.g., rare earth neodymium iron boron) from being oxidized. The inventor finds that when the addition proportion of the antioxidant is higher than 0.5 wt%, carbon element is easy to be introduced, the carbon content of the final product is increased, and the RE-FE-B series permanent magnet material Hcj is seriously deteriorated due to the excessively high carbon content. The time for mixing the antioxidant and the ultrafine powder of the RE-FE-B series permanent magnet material (such as rare earth neodymium iron boron) can be 20-240min, such as 120 min. The inventor finds that uneven mixing can be caused when the mixing time is too short, and resources are wasted when the mixing time is too long in the experimental process, so that the mixing time is generally controlled to be 20-240 min. In the present invention, the antioxidant may be conventional in the art, and may be alkylphenol ethoxylate, diethyl malonate, gasoline and/or commercially available antioxidant.
In the present invention, the RE-FE-B permanent magnetic material may be conventional in the art, and is generally RE composed of rare earth elements2Fe14The B type compound is a main phase, such as rare earth neodymium iron boron.
In the present invention, the composition of the ultra-fine powder of the RE-FE-B based permanent magnetic material may be conventional in the art, and may include, for example, 40 to 50% PrNd, 1 to 1.5% dysprosium (Dy), 0.3 to 0.5% aluminum (Al), 0.2 to 0.4% copper (Cu), 1 to 2% cobalt (Co), 0.1 to 0.3% gallium (Ga), 0.7 to 0.9% boron (B), and the balance iron (FE).
The molding waste in the art generally has a certain strength and shape, and thus it is often mentioned to subject the molding waste to a shredding or crushing process, either manually or mechanically. Generally, the crushing of the molding waste of the RE-FE-B permanent magnet material may further include a sieving process, and finally, the crushed molding waste is in the form of large-particle-size molding waste powder.
In the present invention, the composition of the molding scrap may be conventional in the art, and may be, for example, 30.5 to 31% PrNd, 0.2 to 0.4% Al, 0.2 to 0.3% Cu, 0.5 to 1% Co, 0.1 to 0.15% Ga, 0.92 to 0.97% B, and the balance Fe.
In the present invention, the step of profiling (i.e. press forming) may be conventional in the art, and may be, for example, profiling under conditions where the strength of the orienting magnetic field is higher than 1.4T. The press molding may be generally performed by using an orientation molding press, and the molding is not limited by the type, specification, density, size, etc. of the equipment, and the equipment having a large green compact size is preferable. The pressed compact obtained after pressing can also be subjected to isostatic pressing.
In the present invention, the sintering step can be performed by conventional methods in the art, wherein the sintering temperature can be 900-. The temperature is slightly lower than the temperature of the conventional sintering in the field, and the inventor finds in experiments that when the sintering temperature is higher than 1020 ℃, the adhesion of the obtained product is high, and the production operation is not easy to carry out; while the sintering effect is not achieved at temperatures below 900 ℃.
In the present invention, the product obtained after the above sintering step is usually a blank (a blank of a RE-FE-B permanent magnet material (e.g., a blank of a neodymium iron boron magnet)), and can be generally prepared into a powder by mechanical crushing, hydrogen crushing and/or jet milling, so that the powder can be used for powder blending, and mass production is facilitated. The particle size D50 of the powder may be conventional in the art, for example, 2-5 μm, such as 4.8 μm. The mechanical crushing may be, for example, crushing by means of a hammer crusher or a jaw crusher. The hydrogen crushing may be performed by a rotary hydrogen crushing furnace. The dehydrogenation temperature for the hydrogen fragmentation can be, for example, 520 ± 50 ℃. The step of jet milling is conventional in the art and preferably is oxygen-free.
In a preferred embodiment of the present invention, the method for recycling ultra-fine powder of the RE-FE-B based permanent magnet material and/or molding waste of the RE-FE-B based permanent magnet material comprises the steps of:
1) filling the superfine powder of the RE-FE-B series permanent magnet material, the components of which are 40-50% of PrNd, 1-1.5% of Dy, 0.3-0.5% of Al, 0.2-0.4% of Cu, 1-2% of Co, 0.1-0.3% of Ga, 0.7-0.9% of B and the balance of Fe, into a container with qualified air tightness, filling inert gas such as argon or nitrogen for protection, adding 0.4 wt% of antioxidant, and mixing for 120 min;
crushing and sieving molding waste of the RE-FE-B system permanent magnet material, which comprises 30.5-31% of PrNd, 0.2-0.4% of Al, 0.2-0.3% of Cu, 0.5-1% of Co, 0.1-0.15% of Ga, 0.92-0.97% of B and the balance of Fe, in an inert gas such as argon or nitrogen protection environment to obtain powder of the molding waste (with large granularity); then adding the ultrafine powder into the molding waste according to the mass ratio of 30 wt%;
2) mixing the molding waste added with the ultrafine powder for 180min to obtain mixed powder of the ultrafine powder and the molding waste;
3) pressing the mixed powder by an orientation forming press, wherein the intensity of the orientation magnetic field is more than 1.4T;
4) carrying out isostatic pressing and sintering on the pressed blank obtained after the pressing to obtain a blank, wherein the sintering temperature is 950 ℃;
5) crushing the obtained blank by a hammer crusher or a jaw crusher, treating the crushed blank by a rotary hydrogen crushing furnace to perform hydrogen crushing dehydrogenation at the temperature of 520 ℃, and then performing jet milling to prepare powder, wherein oxygen is not supplemented in the jet milling, and the particle size D50 of the obtained powder is 4.8 mu m.
In order to solve the above technical problems, a second aspect of the present invention provides a product obtained by the recycling method according to the first aspect of the present invention.
In order to solve the technical problem, the invention also provides a preparation method of the RE-FE-B series permanent magnetic material, and the raw materials of the RE-FE-B series permanent magnetic material comprise the product prepared by the second aspect of the invention.
Preferably, the preparation method comprises the step of pressing and sintering the fully mixed product prepared by the second aspect of the invention and other raw materials for preparing the Re-Fe-B series permanent magnet material.
The raw materials for preparing the Re-Fe-B permanent magnetic material can be conventional in the field, and can be 25% of PrNd, 2-2.5% of Dy, 0.5% of Ho, 3% of Gd, 0.3-0.4% of Al, 0.25-0.3% of Cu, 1.5-2% of Co, 0.15% of Ga, 0.93-0.99% of B and the balance of Fe. The product prepared by the second aspect of the invention and the raw materials for preparing the Re-Fe-B series permanent magnetic material can be 25 percent of the product prepared by the second aspect of the invention, 25 percent of PrNd, 2-2.5 percent of Dy, 0.5 percent of Ho, 3 percent of Gd, 0.3-0.4 percent of Al, 0.25-0.3 percent of Cu, 1.5-2 percent of Co, 0.15 percent of Ga, 0.93-0.99 percent of B and the balance of Fe, wherein the percentages are mass percentages; and then fully mixing the raw materials to prepare mixed powder, and using the mixed powder in the subsequent steps.
Wherein the profiling may be conventional in the art, for example using an orientation profiling press, the orientation magnetic field strength may be above 1.6T, for example. The pressed compact obtained after the pressing can also be subjected to the step of isostatic pressing.
The sintering step can be conventional in the art, the sintering temperature can be 1060 +/-20 ℃, and the sintering time can be 3 h.
Wherein, the sintering process can be further followed by an aging step which is conventional in the field, and preferably comprises primary aging and secondary aging, wherein the temperature of the primary aging is preferably 920 +/-50 ℃, and the time is preferably 3 h; the temperature of the secondary aging is preferably 480 +/-50 ℃, and the time is preferably 4 h.
In a preferred embodiment of the present invention, the method for preparing the RE-FE-B permanent magnetic material, such as the rare earth neodymium iron boron, comprises the following steps:
1) mixing 25% of the product prepared by the second aspect of the invention, 25% of PrNd, 2-2.5% of Dy, 0.5% of Ho, 3% of Gd, 0.3-0.4% of Al, 0.25-0.3% of Cu, 1.5-2% of Co, 0.15% of Ga, 0.93-0.99% of B and the balance of Fe for 240min to prepare mixed powder; the percentage is mass percentage;
2) pressing the obtained mixed powder by an orientation forming press to obtain a pressed blank, wherein the orientation magnetic field intensity is more than 1.6T;
3) and (3) carrying out isostatic pressing and sintering on the obtained pressed compact, wherein the sintering temperature and time are 1060 ℃ and 3h respectively, and then carrying out primary aging and secondary aging, wherein the primary aging temperature and time are 920 ℃ and 3h respectively, and the secondary aging temperature and time are 480 ℃ and 4h respectively.
In order to solve the technical problem, the invention also provides a product (RE-FE-B series permanent magnetic material such as rare earth neodymium iron boron) prepared by the preparation method.
In order to solve the technical problem, the invention also provides an application of the product prepared by the second aspect of the invention in preparing RE-FE-B series permanent magnetic materials. The RE-FE-B series permanent magnetic material is preferably rare earth neodymium iron boron.
In the present invention, the "comprising or including" may mean that other components exist in addition to the components listed later; it may also mean "consisting of … …", i.e. including only the ingredients listed later without the presence of other ingredients.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the recycling method of the invention integrates the process of recycling the ultrafine powder and the molding waste of the RE-FE-B permanent magnet material (such as rare earth neodymium iron boron), the method not only can well reserve the value of the rare earth in the ultrafine powder of the RE-FE-B permanent magnet material (such as rare earth neodymium iron boron) and the molding waste of the RE-FE-B permanent magnet material (such as neodymium iron boron), but also does not need to burn and oxidize the ultrafine powder, has no potential safety hazard, and has large treatment capacity, high recovery rate, no environmental pollution, short treatment process period, lower cost and contribution to industrial large-scale production. When the product obtained by the method is applied to preparing products such as rare earth neodymium iron boron and the like, good magnetic performance indexes can be kept.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1 Recycling method of rare earth NdFeB ultrafine powder and Molding waste
1. The rare earth neodymium iron boron ultrafine powder (the components are 40-50% PrNd, 1-1.5% Dy, 0.3-0.5% Al, 0.2-0.4% Cu, 1-2% Co, 0.1-0.3% Ga, 0.7-0.9% B and the balance Fe) is loaded in a container with qualified air tightness, inert gas argon is filled for protection, 0.4 wt% alkylphenol polyoxyethylene ether, a mixture of diethyl malonate and gasoline (which is a conventional antioxidant formula in the field) is added, and the materials are mixed for 120 min.
Molding waste materials which comprise 30.5-31% of PrNd, 0.2-0.4% of Al, 0.2-0.3% of Cu, 0.5-1% of Co, 0.1-0.15% of Ga, 0.92-0.97% of B and the balance of Fe in percentage by mass are crushed and sieved under the protection of inert gas argon to obtain large-granularity molding waste material powder; then adding the rare earth neodymium iron boron ultrafine powder into the molding waste according to the proportion of 30 wt% of the total weight.
2. Mixing the molding waste added with the rare earth neodymium iron boron ultrafine powder for 180min to obtain mixed powder of the rare earth ultrafine powder and the molding waste powder;
3. the mixed powder obtained by mixing the rare earth ultrafine powder and the molding waste powder is pressed and molded by an orientation molding press, and the intensity of the orientation magnetic field is more than 1.4T;
4. performing isostatic pressing and sintering on the pressed blank obtained after the pressing and forming to obtain a blank, wherein the sintering temperature is 950 ℃;
5. crushing the obtained blank by a hammer crusher or a jaw crusher, then treating the crushed blank by a rotary hydrogen crushing furnace to perform hydrogen crushing dehydrogenation at the temperature of 520 ℃, and then performing jet milling to prepare powder, wherein oxygen is not supplemented by the jet milling, and the particle size D50 of the obtained powder is 4.8 mu m. The obtained powder (namely the rare earth neodymium iron boron alloy powder) is used for powder mixing.
Example 2 preparation of sintered NdFeB (i.e., rare earth NdFeB)
1. Adding the rare earth neodymium-iron-boron alloy powder obtained in the example 1 into 25 wt% of PrNd, 2-2.5% of Dy, 0.5% of Ho, 3% of Gd, 0.3-0.4% of Al, 0.25-0.3% of Cu, 1.5-2% of Co, 0.15% of Ga, 0.93-0.99% of B and the balance of Fe according to the addition proportion of 25 wt%, wherein the percentages are mass percentages, and mixing for 240 min;
2. pressing the obtained mixed powder by an orientation forming press, wherein the orientation magnetic field intensity is more than 1.6T;
3. isostatic pressing and sintering the obtained pressed compact into a blank, wherein the sintering process is 1060 ℃ for 3h, then primary aging is carried out at 920 ℃ for 3h, and secondary aging is carried out at 480 ℃ for 4 h;
4. magnetic properties were measured by PFM pulsed magnetic field magnetometer with Br 12.3KGs, Hcj 25.3KOe, and Hk/Hcj 98.3%. The magnetic property meets the use requirement.
Comparative example 1
In the step 1 of the example 1, the rare earth neodymium iron boron ultrafine powder is added into the molding waste according to the proportion that the total percentage by weight is higher than 50 wt%, and the rest steps are the same as the example 1, so that the rare earth neodymium iron boron ultrafine powder is easy to oxidize and is not easy to control, and finally the obtained product cannot be molded.
Claims (10)
1. A method for recycling ultrafine powder of a Re-Fe-B permanent magnet material and/or molding waste of a RE-FE-B permanent magnet material is characterized by comprising the steps of compacting and sintering the ultrafine powder of the RE-FE-B permanent magnet material and the molding waste of the RE-FE-B permanent magnet material which are fully mixed, wherein the molding waste of the RE-FE-B permanent magnet material is crushed molding waste;
wherein the proportion of the ultrafine powder of the RE-FE-B permanent magnet material to the total mass of the ultrafine powder of the RE-FE-B permanent magnet material and the molding waste of the RE-FE-B permanent magnet material is less than 50 wt%.
2. The recycling method according to claim 1, wherein the sufficient mixing is performed under the condition of inert gas and/or nitrogen, and the inert gas is preferably argon;
and/or the time for intensive mixing is 20-240min, for example 180 min;
and/or the RE-FE-B series permanent magnet material is rare earth neodymium iron boron;
and/or the proportion of the ultrafine powder of the RE-FE-B permanent magnet material to the total mass of the ultrafine powder of the RE-FE-B permanent magnet material and the molding waste of the RE-FE-B permanent magnet material is 30 wt%.
3. The recycling method of claim 1, wherein the ultra-fine powder of RE-FE-B based permanent magnetic material comprises 40-50% PrNd, 1-1.5% Dy, 0.3-0.5% Al, 0.2-0.4% Cu, 1-2% Co, 0.1-0.3% Ga, 0.7-0.9% B, and the balance FE;
and/or the superfine powder of the RE-FE-B series permanent magnet material also comprises an antioxidant with the addition ratio of less than 0.5 wt%, such as 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt% and 0.5 wt%; the time for mixing the antioxidant and the superfine powder of the RE-FE-B series permanent magnet material is preferably 20-240min, for example 120 min; the antioxidant is alkylphenol polyoxyethylene, diethyl malonate and/or gasoline;
and/or, the forming waste material of the RE-FE-B series permanent magnet material is crushed and then screened;
and/or the molding waste material of the RE-FE-B series permanent magnet material comprises 30.5-31% of PrNd, 0.2-0.4% of Al, 0.2-0.3% of Cu, 0.5-1% of Co, 0.1-0.15% of Ga, 0.92-0.97% of B and the balance of Fe.
4. The recycling method according to claim 1, wherein the profiling is a profiling performed under a condition that the oriented magnetic field strength is higher than 1.4T;
and/or, the profiling is performed using an orientation profiling press;
and/or the pressed blank obtained after pressing is also subjected to isostatic pressing;
and/or, the sintering temperature is 900-;
and/or, the sintering process further comprises a crushing step, preferably mechanical crushing, hydrogen crushing and/or jet milling; the particle size D50 of the powder obtained after crushing is preferably 2-5 μm, for example 4.8 μm; the dehydrogenation temperature of the hydrogen fragmentation is preferably 520 +/-50 ℃; the jet mill is preferably not supplemented with oxygen.
5. The recycling method according to claim 1, wherein the recycling method comprises the steps of:
1) filling the superfine powder of the RE-FE-B series permanent magnet material, the components of which are 40-50% of PrNd, 1-1.5% of Dy, 0.3-0.5% of Al, 0.2-0.4% of Cu, 1-2% of Co, 0.1-0.3% of Ga, 0.7-0.9% of B and the balance of Fe, into a container with qualified air tightness, filling inert gas or nitrogen for protection, adding 0.4 wt% of antioxidant, and mixing for 120 min;
crushing and sieving molding waste of the RE-FE-B system permanent magnet material, which comprises 30.5-31% of PrNd, 0.2-0.4% of Al, 0.2-0.3% of Cu, 0.5-1% of Co, 0.1-0.15% of Ga, 0.92-0.97% of B and the balance of Fe, in an inert gas or nitrogen protection environment to obtain powder of the molding waste; then adding the ultrafine powder into the molding waste according to the mass ratio of 30 wt%;
2) mixing the molding waste added with the ultrafine powder for 180min to obtain mixed powder of the ultrafine powder and the molding waste;
3) pressing the mixed powder by an orientation forming press, wherein the intensity of the orientation magnetic field is more than 1.4T;
4) carrying out isostatic pressing and sintering on the pressed blank obtained after the pressing to obtain a blank, wherein the sintering temperature is 950 ℃;
5) crushing the obtained blank by a hammer crusher or a jaw crusher, treating the crushed blank by a rotary hydrogen crushing furnace to perform hydrogen crushing dehydrogenation at the temperature of 520 ℃, and then performing jet milling to prepare powder, wherein oxygen is not supplemented in the jet milling, and the particle size D50 of the obtained powder is 4.8 mu m.
6. A product produced by the recycling method according to any one of claims 1 to 5.
7. A method for preparing RE-FE-B series permanent magnetic material, wherein the raw material comprises the product of claim 6.
8. The production method according to claim 7, comprising a step of compacting and sintering the product, which is sufficiently mixed, with a raw material for producing a Re-Fe-B-based permanent magnet material;
preferably:
the preparation method comprises the steps of pressing and sintering the raw materials which are fully mixed, namely 25% of the product, 25% of PrNd, 2-2.5% of Dy, 0.5% of Ho, 3% of Gd, 0.3-0.4% of Al, 0.25-0.3% of Cu, 1.5-2% of Co, 0.15% of Ga, 0.93-0.99% of B and the balance of Fe; the percentage is mass percentage;
and/or, the profiling is performed when the oriented magnetic field strength is higher than 1.4T;
and/or, the profiling is performed using a sample forming press;
and/or the pressed blank obtained after pressing is subjected to isostatic pressing;
and/or the sintering temperature is 1060 +/-20 ℃;
and/or the sintering time is 3 h;
and/or the sintering process further comprises an aging step, preferably comprises primary aging and secondary aging, wherein the temperature of the primary aging is preferably 920 +/-50 ℃, and the time is preferably 3 h; the temperature of the secondary aging is preferably 480 +/-50 ℃, and the time is preferably 4 h.
9. A product obtained by the production method according to claim 7 or 8.
10. Use of a product according to claim 6 for the preparation of RE-FE-B based permanent magnetic materials;
preferably, the RE-FE-B series permanent magnet material is rare earth neodymium iron boron.
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