CN108470616A - It is a kind of to prepare Nd using neodymium iron boron solid waste2Fe14The method of the nano combined magnetic powders of B/ α-Fe - Google Patents
It is a kind of to prepare Nd using neodymium iron boron solid waste2Fe14The method of the nano combined magnetic powders of B/ α-Fe Download PDFInfo
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- CN108470616A CN108470616A CN201810208373.6A CN201810208373A CN108470616A CN 108470616 A CN108470616 A CN 108470616A CN 201810208373 A CN201810208373 A CN 201810208373A CN 108470616 A CN108470616 A CN 108470616A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- 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
- H01F1/10—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 non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
- H01F1/11—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 non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
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- H—ELECTRICITY
- 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
Abstract
The invention belongs to rare earth permanent magnet spent material recycling fields, disclose a kind of utilization neodymium iron boron solid waste preparation Nd2Fe14The method of the nano combined magnetic powders of B/ α Fe.Neodymium iron boron solid waste is dissolved after cleaned, dry, comminution pretreatment with strong acid solution, insoluble matter is filtered off, acquired solution prepares nanocrystalline mixed oxide by Microwave Irradiation Assisted Chemical synthetic method, sol-gal process or spray pyrolysis；The nanocrystalline mixed oxide of gained is restored by reducing agent, obtains Nd2Fe14The nano combined magnetic powders of B/ α Fe.The method and process of the present invention is simple, economic and environment-friendly, avoids the shortcomings of conventional wet metallurgical process is long, energy consumption is big, seriously polluted, while realizing the utilization of waste material high value, obtained Nd2Fe14The nano combined magnetic powder crystal grain of B/ α Fe is tiny, ingredient is uniform, has stronger exchange-coupling interaction.
Description
Technical field
The invention belongs to rare earth permanent magnet spent material recycling fields, and in particular to a kind of to be prepared using neodymium iron boron solid waste
Nd2Fe14The method of the nano combined magnetic powders of B/ α-Fe.
Background technology
Neodymium iron boron, which is permanent-magnet material, has high-coercive force, high remanent magnetism and high energy product, is referred to as " permanent magnetism king ".As third
For rare earth permanent magnet, neodymium iron boron is widely used in motor.Compared with conventional motors, neodymium iron boron motor have light weight, it is efficient,
The advantages that controllability is strong, cost-effective, energy conservation and environmental protection, has been widely used in electronic information, auto industry, Medical Devices, energy
The various fields such as source traffic.Meanwhile with the reduction of the raising of neodymium iron boron comprehensive performance and production cost, application gradually extends
And enter many emerging fields.Under energy-saving and environment-friendly social theme, the following wind-power electricity generation, new-energy automobile and energy saving household electrical appliances
Etc. industries will grow rapidly, Nd-Fe-B rare-earth permanent magnet will have more vast market prospect.
Under the huge market demand, neodymium iron boron yield keeps steady growth.It will produce in neodymium iron boron magnetic body production process
About 40% waste material contains a large amount of rare earth elements, great utility value in these waste materials.Rare earth is known as " industrial vitamin ", " work
The title of industry gold ".In recent years since reserves are in an emergency, state of the neodymium iron boron supply in constant tension, the exploitation profit of rare earth resources
With there is the present situations such as waste exploitation for a long time.
Neodymium-iron-boron manufacturing method mainly has two kinds of sintering and bonding, and wherein sintered magnet accounts for 90% or more, is waste material
Main source.The technological process of production of sintered NdFeB is as follows：Raw material → pretreatment → dispensing → melting → powder processed → at
Magnetize type → sintering → tempering heat treatment → mechanical processing and be surface-treated → → performance detection → packaging → product.Entire production
Each step can all generate waste material or defect ware in the process.(1) various raw material are generated in pre-treatment of raw material and proportioning process
Waste, such as metal simple-substance neodymium, iron, boron, dysprosium and cobalt and mixture ferro-boron, mischmetal and praseodymium neodymium alloy etc.；(2) traditional
It is just broken in technique, in break, can all generate the clast of variable grain size in ball milling pulverizing process per level-one, it is most of at present to use
Hydrogen is quick-fried, airflow milling powder, and grain size, which is more than the particle of demand size, during handling herein can return to airflow milling after-treatment, be less than
Demand grain size is separated, and constitutes a part for waste material；(3) magnetic field orientating and when die mould, it is easy to generate demoulding and make
At cracking or unfilled corner etc. loss object；(4) in sintering and drawing process, generation stress removal is incomplete, magnetic property does not reach
The defect wares such as mark；(5) machining and wire cutting, polishing, polishing and the generations such as coating is unqualified in surface treatment process is broken
Bits and defect ware；(6) in preparation process caused by anti-oxidation measure deficiency defect ware.The entire production process of sintered NdFeB
In will produce about 40% waste material, wherein machining processes generate 35%, other processes 5%.It is most of in addition to small part greasy filth
Waste material is solid.These solid waste ingredients are more simple, and only surface portion oxidation and contamination greasy dirt, physical method removes surface
After greasy dirt, the raw material for preparing regeneration neodymium iron boron can be used as.
The recovery process of neodymium iron boron waste material is mainly hydrometallurgy at present, such as sulfuric acid double salt precipitation, the excellent molten method of hydrochloric acid, vulcanization
Object impurity removal method, full extraction process etc., above-mentioned technique obtain high-purity single rare earth oxide and need complicated interminable flow, expends
A large amount of acid and organic solvent, and the significant wastage of ferro element is caused, reduce the meaning of neodymium iron boron waste material recycling.
Invention content
In place of the above shortcoming and defect of the existing technology, neodymium iron is utilized the purpose of the present invention is to provide a kind of
Boron solid waste prepares Nd2Fe14The method of the nano combined magnetic powders of B/ α-Fe.This method can shorten technological process, reduce recycling
Cost, the Nd that synthetic ingredient is uniform, crystal grain is tiny2Fe14The nano combined magnetic powders of B/ α-Fe.
The object of the invention is achieved through the following technical solutions：
It is a kind of to prepare Nd using neodymium iron boron solid waste2Fe14The method of the nano combined magnetic powders of B/ α-Fe, including following step
Suddenly：
(1) cleaned, the dry, comminution pretreatment by neodymium iron boron solid waste；
(2) the pretreated neodymium iron boron solid waste of step (1) is dissolved with strong acid solution, filters off insoluble matter, gained is molten
Liquid prepares nanocrystalline mixed oxide by Microwave Irradiation Assisted Chemical synthetic method, sol-gal process or spray pyrolysis；
(3) nanocrystalline mixed oxide obtained by step (2) is restored by reducing agent, obtains Nd2Fe14- Fe nanometers of B/ α are multiple
Close magnetic powder.
Preferably, the crushing described in step (1) refers to being crushed to grain size<400μm.
Preferably, strong acid described in step (2) refers at least one of nitric acid, hydrochloric acid, sulfuric acid.
Preferably, ferro element, boron element and dilute are additionally added in pretreated neodymium iron boron solid waste described in step (2)
The soluble-salt of at least one of earth elements element.It can be used for adjusting the ratio of the nano-crystal oxide generated, and then adjust
Ingredient, tissue and the performance of final magnetic powder.
Preferably, Microwave Irradiation Assisted Chemical synthetic method described in step (2) the specific steps are：It is added also into acquired solution
Former agent glycine, is put into microwave reactor after stirring and dissolving is uniform and reacts, and obtains nanocrystalline mixed oxide.
Preferably, sol-gal process described in step (2) the specific steps are：Citric acid is added into acquired solution, adds
Thermal agitation is reacted, and is then allowed to stand cooling, is obtained gel, gel is placed in oven and dried to obtain xerogel；At xerogel heat
Reason obtains nanocrystalline mixed oxide.
Preferably, spray pyrolysis described in step (2) the specific steps are：By acquired solution it is agitated after spray
It is dry, obtain presoma；Presoma heat treatment desalination is obtained into oxide, nanocrystalline mixed oxide is obtained after ball milling.
Preferably, described in step (3) by reducing agent restore the specific steps are：By nanocrystalline mixed oxide and admittedly
Body reducing agent mixes pressure-like, the high temperature reduction under vacuum state or protective gas atmosphere, or uses gaseous reducing agent will be nanocrystalline
Mixed oxide is placed in the reduction of reducing gas atmosphere high temperature；The temperature of the high temperature reduction is 800~1150 DEG C, the reaction time
For 1~6h.
The method of the present invention has the following advantages that and advantageous effect：
(1) method of the invention is to recycle all valuable elements in neodymium iron boron solid waste together, is avoided individually
The complicated procedures of forming of rare-earth separating, reduces cost.
(2) the preparation method reaction time of the invention is short and ingredient even tissue is not necessarily to consumption compared with conventional wet recycles
Take a large amount of acid and organic solvent, has the advantages that flow is short, pollutes less, is simple for process.
(3) present invention gained reduzate is Nd2Fe14The nano combined magnetic powders of B/ α-Fe, subsequently can be by controlling technique item
Part adjusts two-phase proportion, crystallite dimension, coupling condition, which has huge development space, has extensive
Application prospect.
(4) present invention gained regenerates Nd2Fe14The nano combined magnetic powders of B/ α-Fe are with content of rare earth is low, remanent magnetism is high, thermostabilization
The good advantage of property, can be used as the raw material of bonded permanent magnet, heat distortion magnet, can also be used as high-coercive force magnetic fluid application, have
High regeneration value.
Description of the drawings
Fig. 1 is that gained regenerates Nd after step (3) reduction in embodiment 12Fe14The XRD diagram of the nano combined magnetic powders of B/ α-Fe.
Fig. 2 and Fig. 3 is respectively gained regeneration Nd after 1 step of embodiment (3) reduction2Fe14The nano combined magnetic powders of B/ α-Fe
MH schemes and SEM figures.
Fig. 4 is that gained regenerates Nd after step (3) reduction in embodiment 22Fe14The XRD diagram of the nano combined magnetic powders of B/ α-Fe.
Fig. 5 and Fig. 6 is respectively gained regeneration Nd after 2 step of embodiment (3) reduction2Fe14The nano combined magnetic powders of B/ α-Fe
MH schemes and SEM figures.
Fig. 7 is that 3 step of embodiment (3) cleaning is preceding regenerates Nd with gained after cleaning2Fe14The MH of the nano combined magnetic powders of B/ α-Fe
Figure.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
The present embodiment prepares regeneration Nd using neodymium iron boron solid waste as raw material, with Microwave Irradiation Assisted Chemical synthetic method2Fe14B/α-
The nano combined magnetic powders of Fe, specific preparation process are as follows：
(1) neodymium iron boron solid waste 3g is taken, is sequentially placed into 30ml ethanol solutions and deionized water, is cleaned by ultrasonic respectively
10min is repeated 3 times；Sample after cleaning is placed in drying box, 80 DEG C, dry 1h；Sample after drying is crushed with airflow milling
To grain size<400 μm of powder.
(2) powder in step (1) is placed in beaker, and the HNO of 4mol/L is added3Solution 50ml fully dissolves, filter
Remove insoluble matter；Reducing agent glycine 3g is added into obtained solution, stirring makes it fully dissolve；Then obtained solution is put
Enter in microwave reactor, power 800W, reacts 10min, obtain nanocrystalline mixed oxide.
(3) phase composition for the nanocrystalline mixed oxide that determination step (2) obtains matches according to chemical formula and calculates theoretical institute
Need the amount of calcium hydride, actual interpolation amount:Theoretical additive amount=1.1:1, it is placed in ground and mixed in agate mortar, particle together
Degree control is at 100~200 μm；Above-mentioned reactant is placed in pressure-like in mold, oxide is made to be come into full contact with calcium hydride.It will press
Reactant be put into tube furnace and carry out reduction reaction.Reaction is carried out in the case where argon gas protects high temperature, 850 DEG C of reaction temperature, heat preservation
2h.Continue after having reacted ventilation be cooled to room temperature after, blow-on sampling.Obtained reduzate is placed in 50ml methanol solutions and stirs
Cleaning, 400r/min stir 30min, are filtered after being repeated 3 times, and remove calcium oxide and calcium hydroxide.Product after cleaning is placed in
In vacuum drying chamber, 50 DEG C are warming up to, dry 8h obtains regeneration Nd2Fe14The nano combined magnetic powders of B/ α-Fe.
Gained regenerates the XRD diagram of nano combined magnetic powder as shown in Figure 1, mixing as seen from the figure after the present embodiment step (3) reduction
It closes oxide and is reduced to Nd2Fe14B and α-Fe composite magnetic powders.Gained regenerates Nd after reduction2Fe14The nano combined magnetic powders of B/ α-Fe
MH figure and SEM figure respectively it is as shown in Figures 2 and 3.Nd is regenerated as seen from Figure 22Fe14The saturation magnetic of the nano combined magnetic powders of B/ α-Fe
Change intensity Ms=15.48emu//g, coercivity Hc=2293Oe.Nd is regenerated as seen from Figure 32Fe14The nano combined magnetic powders of B/ α-Fe
Size is about 20~200nm.
Embodiment 2
The present embodiment adds a certain amount of rare earth element and boron element according to neodymium iron boron solid waste element species and content,
Regeneration Nd is prepared with Microwave Irradiation Assisted Chemical synthetic method2Fe14The nano combined magnetic powders of B/ α-Fe, specific preparation process are as follows：
(1) neodymium iron boron solid waste 3g is taken, is sequentially placed into 30ml ethanol solutions and deionized water, is cleaned by ultrasonic respectively
10min is repeated 3 times；Sample after cleaning is placed in drying box, 80 DEG C, dry 1h；Sample after drying is crushed with airflow milling
To grain size<400 μm of powder, the element species and content of analysed for powder waste material；
(2) with Nd15Fe77B8A certain amount of Nd (NO are added into the raw material of step (1) for target component3)3And H3BO3.It will
Mixed-powder is placed in beaker, and the HNO of 4mol/L is added3Solution 50ml fully dissolves, and filters off insoluble matter；To obtained solution
Middle addition reducing agent glycine 3g, stirring make it fully dissolve；Obtained solution is put into microwave reactor, power 800W,
10min is reacted, nanocrystalline mixed oxide is obtained.
(3) phase composition for the nanocrystalline mixed oxide that determination step (2) obtains matches according to chemical formula and calculates theoretical institute
Need the amount of calcium hydride, actual interpolation amount:Theoretical additive amount=1.1:1, it is placed in ground and mixed in agate mortar, particle together
Degree control is at 100~200 μm；Above-mentioned reactant is placed in pressure-like in mold, oxide is made adequately to be contacted with calcium hydride.It will pressure
Good reactant, which is put into tube furnace, carries out reduction reaction.Reaction is carried out in the case where argon gas protects high temperature, and 950 DEG C of reaction temperature is protected
Warm 2h.Continue after having reacted ventilation be cooled to room temperature after, blow-on sampling；Obtained reduzate is placed in 50ml methanol solutions
Stirring and washing, 400r/min stir 30min, are filtered after being repeated 3 times, and remove calcium oxide and calcium hydroxide；By the product after cleaning
It is placed in vacuum drying chamber, is warming up to 50 DEG C, dry 8h obtains regeneration Nd2Fe14The nano combined magnetic powders of B/ α-Fe.
The XRF test results of neodymium iron boron solid waste after being crushed in the present embodiment step (1) are as shown in table 1.
1 neodymium iron boron solid waste element species of table and content table
| Element | Fe | Nd | Gd | Pr | Ce | Al | It is other |
| Content/wt% | 63.93 | 23.85 | 4.05 | 2.39 | 0.68 | 0.58 | 0.85 |
The XRD diagram of gained composite magnetic powder is as shown in Figure 4 after the present embodiment step (3) reduction.Mixed oxide as seen from the figure
It is reduced to Nd2Fe14B and α-Fe composite magnetic powders.The MH figures of gained composite magnetic powder and SEM scheme respectively such as Fig. 5 and Fig. 6 institutes after reduction
Show.Nd is regenerated as seen from Figure 52Fe14The saturation magnetization M of the nano combined magnetic powders of B/ α-Fes=20.14emu//g, coercivity Hc
=6299Oe.Nd is regenerated as seen from Figure 62Fe14The size of the nano combined magnetic powders of B/ α-Fe is about 20~200nm.
Embodiment 3
The present embodiment synthesizes to obtain high-coercive force using neodymium iron boron solid waste as raw material with Microwave Irradiation Assisted Chemical synthetic method
Regenerate Nd2Fe14The nano combined magnetic powders of B/ α-Fe.Specific preparation process is as follows：
(1) neodymium iron boron solid waste 3g is taken, is sequentially placed into 30ml ethanol solutions and deionized water, is cleaned by ultrasonic respectively
10min is repeated 3 times；Sample after cleaning is placed in drying box, 80 DEG C, dry 1h；Sample after drying is crushed with airflow milling
To grain size<400 μm of powder, the element species and content of analysed for powder waste material；
(2) with Nd15Fe77B8A certain amount of Nd (NO are added into the raw material of step (1) for target component3)3And H3BO3.It will
Mixed-powder is placed in beaker, and the HNO of 4mol/L is added3Solution 50ml fully dissolves, and filters off insoluble matter；To obtained solution
Middle addition reducing agent glycine 3g, stirring make it fully dissolve；Obtained solution is put into microwave reactor, power 900W,
10min is reacted, nanocrystalline mixed oxide is obtained.
(3) phase composition for the nanocrystalline mixed oxide that determination step (2) obtains matches according to chemical formula and calculates theoretical institute
Need the amount of calcium hydride, actual interpolation amount:Theoretical additive amount=1.1:1, it is placed in ground and mixed in agate mortar, particle together
Degree control is at 100~200 μm；Above-mentioned reactant is placed in pressure-like in mold, oxide is made adequately to be contacted with calcium hydride.It will pressure
Good reactant, which is put into tube furnace, carries out reduction reaction.Reaction is carried out in the case where argon gas protects high temperature, and 1050 DEG C of reaction temperature is protected
Warm 2h.Continue after having reacted ventilation be cooled to room temperature after, blow-on sampling；Obtained reduzate is placed in 50ml methanol solutions
Stirring and washing, 400r/min stir 30min, are filtered after being repeated 3 times, and remove calcium oxide and calcium hydroxide；By the product after cleaning
It is placed in vacuum drying chamber, is warming up to 50 DEG C, dry 8h obtains regeneration Nd2Fe14The nano combined magnetic powders of B/ α-Fe.
Magnetic property of the nano combined magnetic powder of gained before and after cleaning deliming is as shown in table 2.
2 nano combined magnetic powder of table cleans the magnetic property before and after deliming
| Sample | Ms(emu/g) | Br(T) | Hc(kOe) |
| Before cleaning | 52.88 | 0.35 | 11.303 |
| After cleaning | 112.20 | 0.73 | 10.276 |
Nd is regenerated before cleaning obtained by the present embodiment and after cleaning2Fe14The MH figures of B/ α-Fe composite magnetic powders are as shown in Figure 7.By
Saturation magnetization is significantly promoted after table 2 and Fig. 7 can be seen that cleaning deliming, and coercivity is declined slightly.
Embodiment 4
The present embodiment prepares regeneration Nd using neodymium iron boron solid waste as raw material, with sol-gal process2Fe14- Fe nanometers of B/ α are multiple
Magnetic powder is closed, specific preparation process is as follows：
(1) neodymium iron boron solid waste 3g is taken, is sequentially placed into 30ml ethanol solutions and deionized water, is cleaned by ultrasonic respectively
10min is repeated 3 times；Sample after cleaning is placed in drying box, 80 DEG C, dry 1h；Sample after drying is crushed with airflow milling
To grain size<400 μm of powder.
(2) powder in step (1) is placed in beaker, and the HNO of 4mol/L is added3Solution 50ml fully dissolves, filter
Remove insoluble matter；Appropriate citric acid is added into solution to stir evenly, is then heated to 80 DEG C, stirs 1h, is cooled to 20 DEG C
Obtain colloidal sol；Above-mentioned colloidal sol is put into 120 DEG C of heat preservation 2h in baking oven, obtains gel；It is heat-treated 2h by 800 DEG C in hydrogel air,
Obtain nano-crystal oxide powder；
(3) phase composition for the nanocrystalline mixed oxide that determination step (2) obtains matches according to chemical formula and calculates theoretical institute
Need the amount of calcium hydride, actual interpolation amount:Theoretical additive amount=1.1:1, it is placed in ground and mixed in agate mortar, particle together
Degree control is at 100~200 μm；Above-mentioned reactant is placed in pressure-like in mold, oxide is made to be come into full contact with calcium hydride.It will press
Reactant be put into tube furnace and carry out reduction reaction.Reaction is carried out in the case where argon gas protects high temperature, 850 DEG C of reaction temperature, heat preservation
2h.Continue after having reacted ventilation be cooled to room temperature after, blow-on sampling.Obtained reduzate is placed in 50ml methanol solutions and stirs
Cleaning, 400r/min stir 30min, are filtered after being repeated 3 times, and remove calcium oxide and calcium hydroxide.Product after cleaning is placed in
In vacuum drying chamber, 50 DEG C are warming up to, dry 8h obtains regeneration Nd2Fe14The nano combined magnetic powders of B/ α-Fe.
Embodiment 5
The present embodiment prepares regeneration Nd using neodymium iron boron solid waste as raw material, with spray pyrolysis2Fe14- Fe nanometers of B/ α are multiple
Magnetic powder is closed, specific preparation process is as follows：
(1) neodymium iron boron solid waste 3g is taken, is sequentially placed into 30ml ethanol solutions and deionized water, is cleaned by ultrasonic respectively
10min is repeated 3 times；Sample after cleaning is placed in drying box, 80 DEG C, dry 1h；Sample after drying is crushed with airflow milling
To grain size<400 μm of powder.
(2) powder in step (1) is placed in beaker, and the HNO of 4mol/L is added3Solution 50ml fully dissolves, filter
Remove insoluble matter；It will be spray-dried to obtain presoma with Mini Spray-Drier after above-mentioned solution magnetic agitation 2h；Presoma is existed
800 DEG C of heat treatment 2h desalinations obtain oxide in air, and the tiny nano-crystal oxide powder of size is obtained after ball milling.
(3) phase composition for the nanocrystalline mixed oxide that determination step (2) obtains matches according to chemical formula and calculates theoretical institute
Need the amount of calcium hydride, actual interpolation amount:Theoretical additive amount=1.1:1, it is placed in ground and mixed in agate mortar, particle together
Degree control is at 100~200 μm；Above-mentioned reactant is placed in pressure-like in mold, oxide is made to be come into full contact with calcium hydride.It will press
Reactant be put into tube furnace and carry out reduction reaction.Reaction is carried out in the case where argon gas protects high temperature, 850 DEG C of reaction temperature, heat preservation
2h.Continue after having reacted ventilation be cooled to room temperature after, blow-on sampling.Obtained reduzate is placed in 50ml methanol solutions and stirs
Cleaning, 400r/min stir 30min, are filtered after being repeated 3 times, and remove calcium oxide and calcium hydroxide.Product after cleaning is placed in
In vacuum drying chamber, 50 DEG C are warming up to, dry 8h obtains regeneration Nd2Fe14The nano combined magnetic powders of B/ α-Fe.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (9)
1. a kind of preparing Nd using neodymium iron boron solid waste2Fe14The method of the nano combined magnetic powders of B/ α-Fe, it is characterised in that including
Following steps：
(1) cleaned, the dry, comminution pretreatment by neodymium iron boron solid waste；
(2) the pretreated neodymium iron boron solid waste of step (1) is dissolved with strong acid solution, filters off insoluble matter, acquired solution is logical
It crosses Microwave Irradiation Assisted Chemical synthetic method, sol-gal process or spray pyrolysis and prepares nanocrystalline mixed oxide；
(3) nanocrystalline mixed oxide obtained by step (2) is restored by reducing agent, obtains Nd2Fe14The nano combined magnetic of B/ α-Fe
Powder.
2. a kind of utilization neodymium iron boron solid waste according to claim 1 prepares Nd2Fe14The nano combined magnetic powders of B/ α-Fe
Method, it is characterised in that：Crushing described in step (1) refers to being crushed to grain size<400μm.
3. a kind of utilization neodymium iron boron solid waste according to claim 1 prepares Nd2Fe14The nano combined magnetic powders of B/ α-Fe
Method, it is characterised in that：Strong acid described in step (2) refers at least one of nitric acid, hydrochloric acid, sulfuric acid.
4. a kind of utilization neodymium iron boron solid waste according to claim 1 prepares Nd2Fe14The nano combined magnetic powders of B/ α-Fe
Method, it is characterised in that：Be additionally added in pretreated neodymium iron boron solid waste described in step (2) ferro element, boron element and
The soluble-salt of at least one of rare earth element element.
5. a kind of utilization neodymium iron boron solid waste according to claim 1 prepares Nd2Fe14The nano combined magnetic powders of B/ α-Fe
Method, it is characterised in that：Microwave Irradiation Assisted Chemical synthetic method described in step (2) the specific steps are：It is added into acquired solution
Reducing agent glycine is put into microwave reactor after stirring and dissolving is uniform and reacts, and obtains nanocrystalline mixed oxide.
6. a kind of utilization neodymium iron boron solid waste according to claim 1 prepares Nd2Fe14The nano combined magnetic powders of B/ α-Fe
Method, it is characterised in that：Sol-gal process described in step (2) the specific steps are：Citric acid is added into acquired solution, adds
Thermal agitation is reacted, and is then allowed to stand cooling, is obtained gel, gel is placed in oven and dried to obtain xerogel；At xerogel heat
Reason obtains nanocrystalline mixed oxide.
7. a kind of utilization neodymium iron boron solid waste according to claim 1 prepares Nd2Fe14The nano combined magnetic powders of B/ α-Fe
Method, it is characterised in that：Spray pyrolysis described in step (2) the specific steps are：By acquired solution it is agitated after spray
Mist is dried, and presoma is obtained；Presoma heat treatment desalination is obtained into oxide, nanocrystalline mixed oxide is obtained after ball milling.
8. a kind of utilization neodymium iron boron solid waste according to claim 1 prepares Nd2Fe14The nano combined magnetic powders of B/ α-Fe
Method, it is characterised in that：Described in step (3) by reducing agent restore the specific steps are：By nanocrystalline mixed oxide with
Solid reductant mixes pressure-like, the high temperature reduction under vacuum state or protective gas atmosphere, or uses gaseous reducing agent by nanometer
Brilliant mixed oxide is placed in the reduction of reducing gas atmosphere high temperature；The temperature of the high temperature reduction is 800~1150 DEG C, when reaction
Between be 1~6h.
9. a kind of utilization neodymium iron boron solid waste according to claim 6 prepares Nd2Fe14The nano combined magnetic powders of B/ α-Fe
Method, it is characterised in that：The solid reductant is calcium hydride.
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