CN112447389A - Dysprosium oxide coated neodymium iron boron permanent magnet material composite powder, preparation method and system device thereof - Google Patents
Dysprosium oxide coated neodymium iron boron permanent magnet material composite powder, preparation method and system device thereof Download PDFInfo
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- 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
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- 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
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- 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
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Abstract
The invention provides dysprosium oxide coated neodymium iron boron permanent magnet material composite powder, a preparation method and a system device thereof, wherein the preparation method comprises the following steps: and mixing the neodymium iron boron particles in a fluidized state with a dysprosium source and a reaction gas, and reacting, and carrying out gas-solid separation on a reaction product to obtain the dysprosium oxide coated neodymium iron boron permanent magnet material composite powder. The invention adopts a fluidization process, so that the neodymium-iron-boron powder is fully contacted with a dysprosium source and reaction gas in a fluidized bed reaction device, a dynamic basis is provided for subsequent full reaction, the uniform distribution of the powder in a micro scale is realized, the uniformity of the permanent magnet in a macro scale is further ensured, and the coercive force and the temperature stability of the neodymium-iron-boron permanent magnet material are effectively improved.
Description
Technical Field
The invention belongs to the technical field of magnetic materials, and relates to dysprosium oxide coated neodymium iron boron permanent magnet material composite powder, a preparation method and a system device thereof.
Background
The neodymium iron boron rare earth permanent magnet material is widely applied to the fields of extra-high voltage direct current power supply systems, quick charging systems, electric automobile motors and the like due to the optimal magnetic energy product performance, and is the permanent magnet material which is most widely applied at present. One of the main applications of the neodymium iron boron rare earth permanent magnet material is to prepare a permanent magnet motor, compared with an alternating current asynchronous motor, the permanent magnet motor provides excitation by a permanent magnet, and the motor has a simple structure and good operation reliability; meanwhile, no exciting current and excitation loss exist, and the power density of the motor is high. At present, most of motors such as automobile starting motors, wind driven generators and the like adopt permanent magnet motors. In particular, in recent years, new energy vehicles such as electric vehicles have been developed in order to protect the environment and save resources. In new energy vehicles, including driving motors, generators, etc., neodymium iron boron rare earth permanent magnet materials are required. The neodymium iron boron permanent magnet is small in size and high in performance, can well reduce the quality of a motor, improves the efficiency of the motor, and is more suitable for miniaturization and light weight of an automobile. At present, in the motor installation vehicle of the new energy automobile in China, the installation proportion of the neodymium iron boron rare earth permanent magnet synchronous motor is up to 91.4%, and the neodymium iron boron rare earth permanent magnet synchronous motor occupies the largest share in the domestic market.
However, the neodymium iron boron rare earth permanent magnet material has poor thermal stability, so that the application of the neodymium iron boron rare earth permanent magnet material in the high-temperature field is severely limited. In recent years, with the rapid development of industries such as electric vehicles and wind power generation, how to improve the thermal stability of the neodymium iron boron rare earth permanent magnet material becomes a main problem in the field of industrial research.
At present, an effective method for improving the high-temperature magnetic performance of a magnet is to greatly improve the coercive force of the magnet, improve the anisotropy of a magnetic field by doping dysprosium oxide in a neodymium iron boron rare earth permanent magnet material, and effectively improve the coercive force and the temperature stability of the magnet.
CN104164646A A neodymium iron boron surface dysprosium penetration method, which is characterized in that: the method sequentially comprises the following steps: A. removing black skin and oil on the surface of the neodymium iron boron, cleaning and drying; B. mixing dysprosium oxide, dysprosium chloride and alcohol according to the proportion of 4-6 g: 0.01-0.03 g: 450-550 ml to form a mixed solution; C. putting the mixed solution formed in the step B into a water bath at the temperature of 30-100 ℃; b, placing the neodymium iron boron treated in the step A into the mixed solution, taking out the neodymium iron boron after 4-6 minutes, and drying the neodymium iron boron under the protection of nitrogen; D. c, wrapping the neodymium iron boron treated in the step C with an iron sheet, and carrying out vacuum aging treatment for 4-8 hours at 850-950 ℃; and then carrying out vacuum aging treatment for 4-8 hours at the temperature of 400-600 ℃.
CN110556243A discloses a dysprosium penetration method on the surface of neodymium iron boron, which comprises the following steps: (1) mixing dysprosium oxide powder with a sodium chloride solution to obtain a suspension, coating the suspension on the surface of neodymium iron boron, standing for 30min in an environment with the pressure of 5-10 MPa and the temperature of 170-300 ℃, taking out, washing away residues on the surface of the neodymium iron boron, and drying for later use; (2) mixing dysprosium oxide powder and an ethanol solution to form slurry, coating the slurry on the surface of the neodymium iron boron treated in the step (1), and quickly drying to obtain a semi-finished product; (3) and carrying out laser shock treatment on the surface of the semi-finished neodymium iron boron, then washing with deionized water, and drying.
CN110233036A A method for dysprosium penetration of neodymium iron boron magnet, comprising the following steps: s1, taking neodymium iron boron slices, crushing, adding dysprosium oxide powder, ball milling and refining, pressing into a blank, sintering and tempering to obtain a neodymium iron boron magnet; s2, washing the neodymium iron boron magnet with water, acid washing, ethanol washing and drying to complete the pretreatment of the neodymium iron boron magnet; s3, respectively ultrasonically dissolving dysprosium chloride, terbium chloride and aluminum chloride in ethanol, and stirring and mixing the dysprosium chloride, terbium chloride and aluminum chloride with sodium polyacrylate, polyurethane and ethanol to obtain dysprosium-permeated liquid; s4, adding part of the dysprosium penetration liquid into the container, adding the neodymium iron boron magnet, continuing adding the dysprosium penetration liquid until the liquid level of the dysprosium penetration liquid is higher than the interface of the neodymium iron boron magnet, heating the container, preserving heat, carrying out ultrasonic treatment, taking out and drying, wrapping with an iron sheet, carrying out vacuum aging treatment, and cooling to room temperature to finish the dysprosium penetration of the neodymium iron boron magnet.
Therefore, how to design and prepare the high-quality dysprosium oxide coated neodymium iron boron permanent magnet material composite powder ensures that components on a microscale are uniformly distributed, and becomes a problem to be solved urgently for improving the coercive force and the temperature stability of the neodymium iron boron rare earth permanent magnet material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide dysprosium oxide coated neodymium iron boron permanent magnet material composite powder, a preparation method and a system device thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of dysprosium oxide coated neodymium iron boron permanent magnet material composite powder, which comprises the following steps:
and mixing the neodymium iron boron particles in a fluidized state with a dysprosium source and a reaction gas, and reacting, and carrying out gas-solid separation on a reaction product to obtain the dysprosium oxide coated neodymium iron boron permanent magnet material composite powder.
The invention adopts a fluidization process, so that the neodymium-iron-boron powder is fully contacted with a dysprosium source and reaction gas in a fluidized bed reaction device, a dynamic basis is provided for subsequent full reaction, the uniform distribution of the powder in a micro scale is realized, the uniformity of the permanent magnet in a macro scale is further ensured, and the coercive force and the temperature stability of the neodymium-iron-boron permanent magnet material are effectively improved.
As a preferred technical solution of the present invention, the neodymium iron boron particles are fluidized in a protective atmosphere to obtain fluidized neodymium iron boron particles.
Preferably, the protective gas used in the protective atmosphere comprises at least one of nitrogen, argon or helium or a combination of two groups thereof.
According to the invention, the reaction is carried out in a protective atmosphere, so that the neodymium iron boron particles can be kept in a fluidized state, oxygen in the environment can be isolated, and the subsequent controllable coating of dysprosium oxide is facilitated.
Preferably, the particle size of the neodymium iron boron particles is 0.5-100 μm, for example, 0.5 μm, 1 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferred technical solution of the present invention, the mixing manner is: and respectively and independently introducing a dysprosium source and reaction gas into the protective atmosphere in which the neodymium-iron-boron particles in the fluidized state are positioned.
Preferably, the mixing temperature is 600-800 ℃, for example 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃ or 800 ℃, but not limited to the values listed, and other values not listed within the range of values are also applicable.
Preferably, the mixing time is 1min or more, for example 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.
As a preferred technical scheme of the invention, the dysprosium source is DyCl3。
Preferably, the dysprosium source is preheated and then mixed for reaction.
Preferably, the dysprosium source is preheated to 718-1500 ℃, for example 718 ℃, 720 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, or 1500 ℃, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the dysprosium source is conveyed into the reaction device through a carrier gas for mixing reaction.
Preferably, the gas velocity of the dysprosium source mixed with the carrier gas is 200-1500 mL/min, such as 200mL/min, 300mL/min, 400mL/min, 500mL/min, 600mL/min, 700mL/min, 800mL/min, 900mL/min, 1000mL/min, 1100mL/min, 1200mL/min, 1300mL/min, 1400mL/min, or 1500mL/min, but is not limited to the recited values, and other values within the range are equally applicable.
In a preferred embodiment of the present invention, the reaction gas is steam.
Preferably, the reaction gas is preheated and then mixed for reaction.
Preferably, the reaction gas is preheated to 0 to 100 ℃, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction gas is fed into the reaction device through a carrier gas to carry out mixing reaction.
Preferably, the gas velocity of the reaction gas mixed with the carrier gas is 75 to 500mL/min, for example, 75mL/min, 100mL/min, 150mL/min, 200mL/min, 250mL/min, 300mL/min, 350mL/min, 400mL/min, 450mL/min or 500mL/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The preparation method provided by the invention limits the mixing time and the mixing temperature, and the gas velocity of the dysprosium source and the reaction gas introduced into the fluidized bed reaction device, and realizes the purpose of uniformly depositing dysprosium oxide on the surface of the neodymium iron boron permanent magnet material and the regulation and control of the content of dysprosium oxide by adjusting the process parameters.
As a preferable technical scheme of the invention, the gas-solid separation method comprises gravity settling, centrifugal settling or filtering.
As a preferred technical solution of the present invention, the preparation method comprises:
carrying out fluidization treatment on neodymium iron boron particles with the particle size of 0.5-100 microns in a protective atmosphere to obtain neodymium iron boron particles in a fluidized state, wherein the protective atmosphere adopts protective gas comprising at least one of nitrogen, argon or helium or a combination of two groups of nitrogen, argon or helium;
(II) preheating a dysprosium source to 718-1500 ℃, mixing the preheated dysprosium source with carrier gas, and introducing the mixture into a protective atmosphere in which neodymium-iron-boron particles in a fluidized state are positioned at a gas speed of 200-1500 mL/min; meanwhile, preheating the reaction gas to 0-100 ℃, mixing the preheated reaction gas with a carrier gas, and introducing the mixture into a protective atmosphere in which the neodymium-iron-boron particles in a fluidized state are located at a gas speed of 75-500 mL/min, wherein the mixing temperature of the neodymium-iron-boron particles in the fluidized state, the dysprosium source and the reaction gas is 600-800 ℃, and the mixing time is more than or equal to 1 min;
and (III) after the reaction is finished, obtaining the dysprosium oxide coated neodymium iron boron permanent magnet material composite powder by gravity settling, centrifugal settling or filtering of the obtained reaction product.
In a second aspect, the invention provides dysprosium oxide-coated neodymium iron boron permanent magnet material composite powder prepared by the preparation method of the first aspect, wherein the mass fraction of dysprosium oxide in the dysprosium oxide-coated neodymium iron boron permanent magnet material composite powder is 0.1-3.0 wt.%.
The dysprosium oxide coated neodymium iron boron permanent magnet material composite powder provided by the invention is characterized in that a dysprosium oxide shell is uniformly coated on the surface of neodymium iron boron particles by combining a chemical vapor deposition principle and a fluidized bed process technology, and the uniform distribution of the microscale ensures the uniformity of the macroscale, so that the purpose is to improve the coercive force and the temperature stability of the neodymium iron boron permanent magnet material and ensure the component uniformity of a macroscopic permanent magnet motor.
In a third aspect, the invention provides a system device for preparing the dysprosium oxide coated neodymium iron boron permanent magnet material composite powder according to the first aspect, the system device comprises a fluidized bed reaction device, the bottom of the fluidized bed reaction device is externally connected with a protective gas inlet pipe, the lower part of the reaction device is respectively and independently externally connected with a dysprosium source generating device and a reaction gas inlet pipe, and the upper part of the fluidized bed reaction device is externally connected with a storage bin.
As a preferable technical scheme, the top of the fluidized bed reaction device is externally connected with a tail gas treatment device.
Preferably, a vaporizing device is arranged on the reaction gas inlet pipe.
Preferably, the fluidized bed reaction device is externally connected with a product collecting device.
The system refers to an equipment system, a system device or a production device.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts a fluidization process, so that the neodymium-iron-boron powder is fully contacted with a dysprosium source and reaction gas in a fluidized bed reaction device, a dynamic basis is provided for subsequent full reaction, the uniform distribution of the powder on a microscopic scale is realized, the uniformity of the permanent magnet on a macroscopic scale is further ensured, and the coercive force and the temperature stability of the neodymium-iron-boron permanent magnet material are effectively improved;
(2) the method for preparing the dysprosium oxide coated neodymium iron boron composite powder is simple, uniform in coating layer, controllable in thickness, low in cost and easy for large-scale batch production.
Drawings
Fig. 1 is a schematic structural diagram of a system device for preparing dysprosium oxide-coated neodymium iron boron magnetic material composite powder according to an embodiment of the present invention;
wherein, 1-a storage bin; 2-a fluidized bed reaction device; a 3-dysprosium source generating device; 4-a vaporization device; 5-a product collection device; 6-tail gas treatment device;
fig. 2 is an SEM image of the dysprosium oxide coated neodymium iron boron composite powder prepared in example 1 of the invention.
Detailed Description
It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be taken as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "disposed," "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In a specific embodiment, the present invention provides a system apparatus for preparing dysprosium oxide coated neodymium iron boron permanent magnet material composite powder, which comprises a fluidized bed reaction apparatus 2, wherein a protective gas inlet pipe is externally connected to the bottom of the fluidized bed reaction apparatus 2, the lower part of the reaction apparatus is respectively and independently externally connected with a dysprosium source generating apparatus 3 and a reaction gas inlet pipe, and a vaporizing apparatus 4 is arranged on the reaction gas inlet pipe, as shown in fig. 1. The external feed bin 1 in upper portion of fluidized bed reaction unit 2, the external tail gas processing apparatus 6 in top of fluidized bed reaction unit 2, the external product collection device 5 of fluidized bed reaction unit 2.
In another embodiment, the invention provides a preparation method of dysprosium oxide coated neodymium iron boron permanent magnet material composite powder, which comprises the following steps:
(1) carrying out fluidization treatment on neodymium iron boron particles with the particle size of 0.5-100 microns in a protective atmosphere to obtain neodymium iron boron particles in a fluidized state, wherein the protective atmosphere adopts protective gas comprising at least one of nitrogen, argon or helium or a combination of two groups of nitrogen, argon or helium;
(2) preheating a dysprosium source to 718-1500 ℃, mixing the preheated dysprosium source with a carrier gas, and introducing the mixture into a protective atmosphere in which neodymium-iron-boron particles in a fluidized state are located at a gas speed of 200-1500 mL/min; meanwhile, preheating the reaction gas to 0-100 ℃, mixing the preheated reaction gas with a carrier gas, and introducing the mixture into a protective atmosphere in which the neodymium-iron-boron particles in a fluidized state are located at a gas speed of 75-500 mL/min, wherein the mixing temperature of the neodymium-iron-boron particles in the fluidized state, the dysprosium source and the reaction gas is 600-800 ℃, and the mixing time is more than or equal to 1 min;
(3) and after the reaction is finished, the obtained reaction product is subjected to gravity settling, centrifugal settling or filtering to obtain the dysprosium oxide coated neodymium iron boron permanent magnet material composite powder.
Example 1
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing nitrogen as a protective gas into the fluidized bed reaction container to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in a protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 800 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 200 mL/min; preheating the reaction gas to 30 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 75 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 600 ℃ for 60 min;
(3) after the reaction is finished, performing gravity settling gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 0.2 wt.%.
Fig. 2 is an SEM image of the dysprosium oxide coated neodymium iron boron magnetic material composite powder prepared in this example, and it can be seen from fig. 2 that the surface of the neodymium iron boron powder is uniformly coated with a layer of dysprosium oxide film.
Example 2
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing argon gas into the fluidized bed reaction container as a protective gas to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in a protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 900 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 300 mL/min; preheating the reaction gas to 50 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 120 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 900 ℃ for 30 min;
(3) after the reaction is finished, performing centrifugal sedimentation gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 0.3 wt.%.
Example 3
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing helium gas serving as protective gas into the fluidized bed reaction container to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 1100 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 300 mL/min; preheating the reaction gas to 60 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 120 mL/min; dysprosium source and reaction gas are synchronously introduced into the fluidized bed reaction device 2 to react with the neodymium in a fluidized stateMixing iron and boron particles at 750 deg.C for 60 min;
(3) and after the reaction is finished, filtering and carrying out gas-solid separation to obtain the dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 0.8 wt.%.
Example 4
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing nitrogen as a protective gas into the fluidized bed reaction container to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in a protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 1300 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 400 mL/min; preheating the reaction gas to 80 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 200 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 800 ℃ for 90 min;
(3) after the reaction is finished, performing gravity settling gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 2.1 wt.%.
Example 5
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing argon gas into the fluidized bed reaction container as a protective gas to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in a protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 900 deg.C, feeding into fluidized bed reactor 2 by carrier gas, dysprosium source and carrierThe mixed gas speed of the gas is 500 mL/min; preheating the reaction gas to 60 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 200 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 680 ℃ for 120 min;
(3) after the reaction is finished, performing centrifugal sedimentation gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 1.6 wt.%.
Example 6
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing helium gas serving as protective gas into the fluidized bed reaction container to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 1400 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 800 mL/min; preheating the reaction gas to 80 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 500 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at 880 ℃ for 120 min;
(3) and after the reaction is finished, filtering for gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 2.7 wt.%.
Example 7
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing nitrogen as a protective gas into the fluidized bed reaction container to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in a protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 900 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 600 mL/min; preheating the reaction gas to 60 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 300 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 700 ℃ for 90 min;
(3) after the reaction is finished, performing gravity settling gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 1.7 wt.%.
Example 8
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing argon gas into the fluidized bed reaction container as a protective gas to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in a protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 1200 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 300 mL/min; preheating the reaction gas to 50 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 150 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 660 ℃ for 30 min;
(3) after the reaction is finished, performing centrifugal sedimentation gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 0.4 wt.%.
Example 9
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing helium gas serving as protective gas into the fluidized bed reaction container to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 900 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 600 mL/min; preheating the reaction gas to 40 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 200 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 850 ℃ for 45 min;
(3) and after the reaction is finished, filtering for gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 1.0 wt.%.
Example 10
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing argon gas into the fluidized bed reaction container as a protective gas to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in a protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 718 deg.C, and delivering into fluidized bed reactor 2 with carrier gas, wherein the mixed gas speed of dysprosium source and carrier gas is 200 mL/min; preheating the reaction gas to 10 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 75 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 600 ℃ for 60 min;
(3) after the reaction is finished, performing centrifugal sedimentation gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 0.1 wt.%.
Example 11
The embodiment provides a preparation method of dysprosium oxide coated neodymium iron boron magnetic material composite powder, which is performed in a system device shown in fig. 1 provided by the invention, and the preparation method comprises the following steps:
(1) introducing argon gas into the fluidized bed reaction container as a protective gas to enable the neodymium iron boron particles with the particle size of 1-3 mu m to be in a fluidized state in a protective atmosphere;
(2) DyCl of dysprosium source3Preheating to 1500 ℃, and then sending the mixture into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the dysprosium source and the carrier gas is 1500 mL/min; preheating the reaction gas to 100 ℃, and then conveying the reaction gas into a fluidized bed reaction device 2 by carrier gas, wherein the mixed gas speed of the reaction gas and the carrier gas is 500 mL/min; synchronously introducing a dysprosium source and reaction gas into the fluidized bed reaction device 2, and mixing with the neodymium-iron-boron particles in a fluidized state at the mixing temperature of 800 ℃ for 1 min;
(3) after the reaction is finished, performing centrifugal sedimentation gas-solid separation to obtain dysprosium oxide coated neodymium iron boron magnetic material composite powder, wherein the content of dysprosium oxide in the dysprosium oxide coated neodymium iron boron magnetic material composite powder is 0.4 wt.%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of dysprosium oxide coated neodymium iron boron permanent magnet material composite powder is characterized by comprising the following steps:
and mixing the neodymium iron boron particles in a fluidized state with a dysprosium source and a reaction gas, and reacting, and carrying out gas-solid separation on a reaction product to obtain the dysprosium oxide coated neodymium iron boron permanent magnet material composite powder.
2. The preparation method according to claim 1, wherein the neodymium iron boron particles are subjected to fluidization treatment in a protective atmosphere to obtain the neodymium iron boron particles in a fluidized state;
preferably, the protective gas used in the protective atmosphere comprises at least one of nitrogen, argon or helium or a combination of two groups of nitrogen, argon or helium;
preferably, the particle size of the neodymium iron boron particles is 0.5-100 μm.
3. The method according to claim 1 or 2, wherein the mixing is performed by: respectively and independently introducing a dysprosium source and reaction gas into a protective atmosphere in which the neodymium-iron-boron particles in a fluidized state are positioned;
preferably, the mixing temperature is 600-800 ℃;
preferably, the mixing time is more than or equal to 1 min.
4. The process according to any one of claims 1 to 3, wherein the source of dysprosium is DyCl3；
Preferably, the dysprosium source is preheated and then mixed for reaction;
preferably, the dysprosium source is preheated to 718-1500 ℃;
preferably, the dysprosium source is conveyed into the reaction device through a carrier gas for mixing reaction;
preferably, the gas velocity after the dysprosium source and the carrier gas are mixed is 200-1500 mL/min.
5. The production method according to any one of claims 1 to 4, wherein the reaction gas is water vapor;
preferably, the reaction gas is preheated and then is mixed for reaction;
preferably, the reaction gas is preheated to 0-100 ℃;
preferably, the reaction gas is sent into the reaction device through a carrier gas to carry out mixing reaction;
preferably, the gas velocity after the reaction gas and the carrier gas are mixed is 75-500 mL/min.
6. The process according to any one of claims 1 to 5, wherein the gas-solid separation comprises gravity settling, centrifugal settling or filtration.
7. The method according to any one of claims 1 to 6, wherein the method comprises:
the method comprises the following steps of (I) fluidizing neodymium iron boron particles with the particle size of 0.5-100 mu m in a protective atmosphere to obtain the neodymium iron boron particles in a fluidized state, wherein the protective atmosphere adopts protective gas comprising at least one of nitrogen, argon or helium or a combination of two groups of nitrogen, argon or helium;
(II) preheating a dysprosium source to 718-1500 ℃, mixing the preheated dysprosium source with carrier gas, and introducing the mixture into a protective atmosphere in which neodymium-iron-boron particles in a fluidized state are positioned at a gas speed of 200-1500 mL/min; meanwhile, preheating the reaction gas to 0-100 ℃, mixing the preheated reaction gas with a carrier gas, and introducing the mixture into a protective atmosphere in which the neodymium-iron-boron particles in a fluidized state are located at a gas speed of 75-500 mL/min, wherein the mixing temperature of the neodymium-iron-boron particles in the fluidized state, the dysprosium source and the reaction gas is 600-800 ℃, and the mixing time is more than or equal to 1 min;
and (III) after the reaction is finished, obtaining the dysprosium oxide coated neodymium iron boron permanent magnet material composite powder by gravity settling, centrifugal settling or filtering of the obtained reaction product.
8. The dysprosium oxide-coated neodymium iron boron permanent magnet material composite powder prepared by the preparation method of any one of claims 1 to 7 is characterized in that the mass fraction of dysprosium oxide in the dysprosium oxide-coated neodymium iron boron permanent magnet material composite powder is 0.1-3.0 wt.%.
9. A system device for preparing the dysprosium oxide coated neodymium iron boron permanent magnet material composite powder according to claim 8, wherein the system device comprises a fluidized bed reaction device, the bottom of the fluidized bed reaction device is externally connected with a protective gas inlet pipe, the lower part of the reaction device is respectively and independently externally connected with a dysprosium source generating device and a reaction gas inlet pipe, and the upper part of the fluidized bed reaction device is externally connected with a storage bin.
10. The system device according to claim 9, wherein the top of the fluidized bed reactor is externally connected with a tail gas treatment device;
preferably, a vaporizing device is arranged on the reaction gas inlet pipe;
preferably, the fluidized bed reaction device is externally connected with a product collecting device.
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