CN111154980B - Neodymium iron boron waste solution electrolytic regeneration method - Google Patents
Neodymium iron boron waste solution electrolytic regeneration method Download PDFInfo
- Publication number
- CN111154980B CN111154980B CN202010079981.9A CN202010079981A CN111154980B CN 111154980 B CN111154980 B CN 111154980B CN 202010079981 A CN202010079981 A CN 202010079981A CN 111154980 B CN111154980 B CN 111154980B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- iron boron
- neodymium iron
- solution
- waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/58—Construction or demolition [C&D] waste
Abstract
The invention belongs to the field of renewable resources, and particularly relates to an electrolytic regeneration method of a neodymium iron boron waste solution. The method firstly removes the anticorrosive coating on the surface of the neodymium iron boron disassembled waste, and then gathers the waste into a whole by virtue of the magnetism of the neodymium iron boron and uses the whole as the anode of an electrolysis system. During the electrolysis process, the anode is dissolved, and rare earth and iron ions enter the solution. Wherein, iron ions are separated out at the cathode to become high-purity iron; the rare earth elements are enriched in the electrolyte in an ionic state. And recovering the rare earth elements in the electrolyte in a solvent extraction mode after the electrolysis is finished, and producing rare earth oxides or further producing rare earth metals. The method can directly recover high-purity electrolytic iron products in the electrolytic process, and then extract and separate the rare earth ions such as Nd, La and Dy remained in the electrolyte, so that the process has low requirement on temperature, can be carried out at normal temperature, and realizes high value-added utilization of iron and rare earth.
Description
Technical Field
The invention belongs to the field of renewable resources, and relates to an electrolytic regeneration method of a neodymium iron boron waste solution.
Background
Rare earth is a precious and key strategic resource and plays a vital role in various fields of industry, military and life. With the increasing demand for high-performance magnetic materials in various countries, more and more rare earths are used to produce rare earth permanent magnetic materials typified by neodymium-iron-boron permanent magnets. The content of rare earth in the neodymium iron boron permanent magnet waste is about 30 percent and is far higher than that of the rare earth in the raw ore, and the potential regeneration value is higher. If the chain can be effectively recycled, the chain has positive effects on the whole industrial chain. The recycling of rare earth elements is realized, and the development of a regeneration technology aiming at the waste neodymium iron boron is urgently needed. According to the invention, the rare earth elements in the neodymium iron boron permanent magnet can be directly extracted and separated without component adjustment through a normal-temperature solution electrolysis method, and meanwhile, high-added-value comprehensive recovery of the rare earth permanent magnet material can be realized by producing high-purity electrolytic pure iron as a byproduct.
The Chinese patent CN105931781B discloses a method for recycling sintered neodymium iron boron recycled waste, belonging to the technical field of rare earth permanent magnet materials. Mechanically crushing and screening clean NdFeB waste materials such as machine-processed cutting leftover materials and electroplating unqualified products to obtain large-particle magnetic powder (the size of a screen is 60-300 meshes), and performing orientation molding in an atmospheric environmentThe density of the prepared product is 6.0g/cm3The blank of (2) is subjected to vacuum heat treatment to obtain a high-performance NdFeB permanent magnet. The raw material magnetic powder is about hundred micron-sized magnetic powder obtained by crushing NdFeB recovered waste, and the storage of the magnetic powder, the orientation forming process of the magnet and the storage of the formed blank can be carried out in an atmospheric environment.
Therefore, the neodymium iron boron waste materials are directly recycled, and impurity elements mixed in the magnet cannot be removed.
The Chinese invention patent CN108359798A discloses a method for rapidly and efficiently recycling neodymium iron boron waste. The method comprises the following steps: collecting waste materials of the neodymium iron boron magnet; the method comprises the following steps of (1) dividing the waste into massive and powdery wastes, wherein oil sludge in the powdery wastes is pretreated; pressing the powdery waste into blocks, charging into a furnace, and adding a deoxidizer according to the adding proportion of the powdery waste and the blocky waste; smelting, reducing and deoxidizing oxides of other alloy elements except rare earth in the waste by utilizing rare earth metal and deoxidizer in the massive waste; smelting reduction can be carried out in a medium-frequency induction furnace or an electric arc furnace; obtaining ferroalloy products and furnace slag after smelting; crushing the furnace slag, and then carrying out molten salt electrolysis to obtain mixed rare earth metal or rare earth ferroalloy; and detecting the chemical components of the iron alloy and the rare earth alloy to obtain the alloy component composition and the impurity content of the cast ingot, and providing the cast ingot to a neodymium iron boron manufacturer to be used as a raw material or used as an intermediate alloy for other purposes after the cast ingot is qualified through inspection.
Chinese patent CN109385528A discloses a method for recovering rare earth in waste permanent magnets, which comprises the following steps: (1) demagnetizing the waste neodymium iron boron permanent magnet, placing the obtained non-magnetic neodymium iron boron material and the prepared charcoal in a reactor, then placing the reactor in a high-temperature furnace together, introducing argon, heating for carbon/hydrogenation reaction, and finally cooling the sample to room temperature along with the furnace to obtain neodymium iron boron-carbon/hydrogen alloy; (2) crushing the alloy obtained in the step (1) until the particle size is less than or equal to 45 mu m, then putting the crushed alloy into deionized water for full hydrolysis, and separating the hydrolysis product to obtain rare earth hydroxide; (3) recovering rare earth oxide: and (3) oxidizing and roasting the rare earth hydroxide obtained in the step (2) in a muffle furnace, and then cooling the rare earth hydroxide along with the furnace to obtain the rare earth oxide.
The chinese invention patent CN104087755A discloses a method for recovering rare earth elements from neodymium iron boron waste. The invention comprises the following steps: (1) uniformly mixing aluminum fluoride powder and cryolite powder according to the mass ratio of 1: 1-1: 10 to obtain a cryolite-aluminum fluoride mixture; (2) crushing the neodymium iron boron waste into particles with the particle size of 4-6 mm, and embedding the particles in a cryolite-aluminum fluoride mixture; (3) placing the cryolite-aluminum fluoride mixture embedded with the neodymium iron boron waste in an electric furnace, and reacting at 900-1200 ℃ for 3-12 h; (4) and (3) carrying out solid-liquid separation on the product obtained by the reaction to respectively obtain solid residues and molten salt, wherein the solid residues are waste steel, and the molten salt is a mixture of the rare earth fluoride-cryolite-aluminum fluoride. The aluminum fluoride in the invention can selectively extract unoxidized rare earth elements in neodymium iron boron waste, and the cryolite can better dissolve the rare earth which is oxidized into oxides, so the recovery rate of the rare earth is greatly improved.
Therefore, the existing neodymium iron boron pyrogenic regeneration technology cannot separate the separation of rare earth elements, cannot produce high-grade rare earth products, cannot utilize iron at a high value, and can only realize the degraded utilization of neodymium iron boron.
The Chinese patent CN109554549A discloses a method for recovering rare earth in neodymium iron boron waste by high-temperature high-pressure leaching. Oxidizing and roasting the neodymium iron boron waste, leaching the neodymium iron boron waste at high temperature and high pressure by hydrochloric acid, and leaching Fe in the leaching solution2+Oxidizing, removing impurities and purifying to obtain rare earth chloride leachate; and the rare earth chloride leachate can be used as a subsequent process and a product raw material, rare earth is obtained through extraction and separation, and rare earth carbonate is prepared through precipitation or rare earth oxide is prepared through precipitation-roasting.
The invention Chinese patent CN107794373A discloses a comprehensive treatment method of waste neodymium iron boron magnetic material, which utilizes the acid solubility of neodymium iron boron, does not need strict granularity requirement (less than or equal to 5mm), the waste neodymium iron boron magnetic material can be completely dissolved in sulfuric acid solution, various differences of the dissolved substances are utilized to separate rare earth, iron and nonferrous metal, oil phase is recycled by oil-water separation, and the rare earth is sulfuric acid rare earth complex salt precipitate and partial enrichment for rare earth separation as raw materials; the nonferrous metal is in a sulfide state and can be further enriched and purified; the ferrous sulfate is in solution state, and can be used for producing iron oxide red pigment by ammonia process.
The Chinese invention patent CN106319249A discloses a method for recovering rare earth from neodymium iron boron waste, which is mainly characterized in that the oxidability and the weak acidity of hydrogen peroxide are utilized, mixed acid with a certain proportion is adopted to dissolve the neodymium iron boron waste, an NdFeB hydrogen crushing device is utilized to crush the neodymium iron boron waste, after the acid leaching is completed, N503 is utilized to extract iron elements in a leaching solution, then P507 is utilized to extract single rare earth metal ions, and oxalic acid and potassium carbonate are utilized to precipitate corresponding rare earth metal ions respectively, so that the rare earth metal is further purified.
The Chinese patent CN102011020A discloses a method for recovering rare earth elements from neodymium iron boron waste, which comprises the following steps: mixing neodymium iron boron waste with water and then grinding; oxidizing the ground neodymium iron boron waste; carrying out secondary grinding on the oxidation product; adding acid for leaching; solid-liquid separation; extracting to remove iron; chloridizing rare earth, and extracting and separating rare earth; extracting to remove aluminum; and (4) precipitating and burning. By applying the method, the content of non-rare earth elements such as C, S, O in the metal is reduced, the recovery rate of the rare earth is increased by 5-8%, and the value of the recovered rare earth product is improved.
The invention patent CN102776375A relates to a method for recovering rare earth from waste neodymium iron boron materials. The method comprises the steps of firstly, finely grinding and crushing neodymium iron boron waste materials, and then separating undissolved B elements by utilizing a hydrochloric acid preferential dissolution method; adjusting the pH value of the obtained liquid to 2.0-3.0 by using ammonia water; adding an ammonium sulfide solution into a water bath at 50-70 ℃, fully precipitating metal cation impurities under the action of ammonium sulfide, and reacting for more than 2 hours; performing centrifugal filtration, wherein the filtrate mainly contains rare earth ions and chloride ions; hydrochloric acid is added into the filtrate dropwise until no bubbles are generated, and the filtrate is heated for more than 10 min.
The invention Chinese patent CN109439912A discloses a method for one-step comprehensive recovery of neodymium iron boron waste acid leaching slag by flash reduction, which is characterized in that neodymium iron boron waste acid leaching slag and a fluxing agent are mixed uniformly and sprayed into a high-temperature vertical reaction tower space together with reducing gas through a nozzle, most of iron oxides in the materials are reduced into metallic iron, a small amount of unreduced iron is reduced into metallic iron when passing through a hot coke layer arranged above a sedimentation tank, rare earth oxides in the materials are not reduced, and the rare earth oxides and the added fluxing agent form a rare earth slag phase. After standing and layering, the molten iron and the rare earth slag are discharged from the tap hole and the slag discharge hole respectively, and the flue gas is discharged from the flue.
The invention Chinese patent CN109439913A discloses a method for comprehensively recovering neodymium iron boron waste acid leaching residues by flash reduction, which is characterized in that the neodymium iron boron waste acid leaching residues are dried and sprayed into a high-temperature vertical reaction tower space together with reducing gas through a nozzle, the reducing atmosphere is controlled, iron oxides in materials are reduced into metallic iron or ferroferric oxide, and rare earth oxides in the materials are not reduced. And magnetic separation is carried out on the reduction product to obtain an iron-rich phase and a rare earth-rich phase respectively. The invention realizes the high-efficiency enrichment and separation of rare earth and iron in the neodymium iron boron waste acid leaching residue.
Therefore, the existing wet recovery technology for neodymium iron boron has low utilization efficiency of iron, and only can produce iron products with low value, even can remove iron.
In summary, the rare earth elements in the neodymium iron boron waste can be recovered by means of high temperature, high pressure, strong acid and the like in the prior art, but there is still room for improvement in the aspects of rare earth product grade, separation between rare earth elements, high value-added utilization of iron elements and the like.
Disclosure of Invention
The invention provides an electrolytic regeneration method of a neodymium iron boron waste solution. Firstly, an anticorrosive layer on the surface of the neodymium iron boron waste is removed, and then the waste fragments are gathered into a large-size anode by utilizing the magnetism of the waste fragments. In the electrolytic process, rare earth and iron in the neodymium iron boron waste material in the anode area are dissolved into the electrolyte in an ionic state by utilizing an electric field. Wherein ferrous ions are separated out at the cathode in the form of simple substance iron, and rare earth ions are remained in the electrolyte. And the obtained rare earth-rich electrolyte is subjected to solvent extraction separation and rare earth recovery, and then rare earth elements are classified and recovered.
An electrolytic regeneration method of neodymium iron boron waste solution is characterized in that: the neodymium iron boron waste is used as an anode, and dilute sulfuric acid, dilute nitric acid or rare earth and iron sulfate and nitrate are used as electrolyte; the neodymium iron boron scrap scraps are gathered into a whole by virtue of magnetism and used as an anode, and high-purity iron or inert conductive materials are used as a cathode; electrolyzing the solution at room temperature to make the rare earth and iron ions in the neodymium iron boron waste enter the solution; wherein, iron ions are separated out at the cathode and recovered in the form of high-purity iron; the rare earth elements are enriched in the electrolyte in an ionic state; after the electrolysis is finished, the rare earth elements in the electrolyte are recovered by extraction, and the high-purity rare earth oxide is produced by precipitation, filtration and ignition.
Further, the anode in the electrolytic cell is neodymium iron boron waste. If the waste particle size is small, the waste fragments are magnetically agglomerated into larger volume anodes.
Further, the electrolytic recovery process of the neodymium iron boron waste is carried out in dilute acid or salt solution at room temperature; wherein the dilute acid is a dilute solution of strong acids such as sulfuric acid, nitric acid and the like, and the pH value is 0.9-4.1; the salt solution is strong acid salt such as divalent or trivalent iron, sulfate and nitrate of rare earth elements, and the concentration is 0.28 mol/L-3.9 mol/L.
Further, in the process of electrolyzing the neodymium iron boron waste, the current density is 19mA/cm2～520mA/cm2Controlling the cathode iron production state by adjusting the current within the range, and respectively recovering blocky, spongy or granular high-purity electrolytic iron.
Furthermore, the rare earth elements after electrolysis are left in the electrolyte and can be converted into high-purity rare earth oxides with the content of more than 99.9 percent after the treatment of extraction, precipitation, filtration, ignition and the like.
Furthermore, the extracted electrolyte can be reused in the electrolysis process without adding any chemical reagent.
The invention can be used for treating neodymium iron boron waste scraps, and converts rare earth metals and iron into high-concentration solution by electrolysis. Wherein, iron ions are separated out at the cathode and recovered in a high-purity iron form; the rare earth salt remains in solution for subsequent separation and recovery by extraction. The differences from the prior art are reflected in:
(1) raw materials. The prior art mainly treats neodymium iron boron waste materials with low oxidation degree and small pollution degree, and generally needs to be demagnetized before disposal. Neodymium iron boron scraps which are low in purity and difficult to demagnetize cannot be treated;
(2) the treatment temperature. The existing electrochemical rare earth regeneration process generally needs to be realized in molten salt at high temperature, and the separation between rare earth elements can not be realized generally. The invention provides a method for electrolyzing solution at normal temperature, and the process has low requirement on temperature.
(3) And (4) resource utilization rate. The existing neodymium iron boron waste disposal process can only recover low-grade rare earth mixture, can not realize the separation of rare earth elements, and has low utilization efficiency of iron, even can not be completely utilized; the method for performing solution electrolysis at normal temperature can directly recover high-purity electrolytic iron products in the electrolysis process, and can realize high value-added utilization of iron and rare earth by extracting and separating rare earth ions such as Nd, La and Dy remained in the electrolyte.
Drawings
FIG. 1 shows a process flow of an electrolytic regeneration method of a neodymium iron boron waste solution.
Detailed Description
The following examples are provided to illustrate the practice of the present invention, but are not intended to limit the scope of the invention.
Example 1:
refrigerator door magnetic stripe debris, major components (multiple test range values) are: TFe 61.62-63.12%, Nd 21.31-22.97%, Pr 3.03-3.86%, La 1.39-1.72%, B9.16-10.03%; with FeSO4·7H2O preparing a solution with the concentration of 0.98-1.03 mol/L as an electrolytic solution; the electrolysis temperature is room temperature (12-27 ℃); the anode of the electrolytic cell is the scraps of the magnetic strip of the refrigerator door, and the cathode is a high-purity iron plate; the pH value of electrolysis is 2.5-3.62, and the current density is 20mA/cm2～200mA/cm2(initial to final process values).
The use process comprises the following steps:
(1) and an electrode. Weighing 500g of neodymium iron boron waste, gathering scraps by virtue of waste magnetism, and placing the scraps in an anode basket; cleaning the surface of the high-purity iron plate; placing the anode basket and the cathode plate in electrolyte;
(2) and (3) an electrolyte. With FeSO4·7H2O is prepared into the mixture with 3L concentration of 1mol/LElectrolyte is put in the electrolytic tank. Adjusting the pH to 2.5 with dilute sulfuric acid;
(3) and (4) electrolyzing. The circuit is switched on to control the current density. Connecting a constant current power supply, and regulating the current to 1A;
(4) and collecting the product. Collecting and washing cathode spongy high-purity iron, and actually measuring the Fe content to be 99.87-99.91%; after the electrolyte is tempered, the rare earth in the electrolyte is recovered in an extraction mode, and the obtained product has Nd purity after precipitation, filtration and ignition2O3 99.99％、La2O3 99.91％、Dy2O3 99.92％。
Example 2:
the magnetic block for motor disassembly comprises the following main components (multiple test range values): TFe 61.73% -63.09%, Nd21.47% -22.85%, Pr 3.14% -3.89%, La 1.34% -1.68%, B9.22% -10.01%; with FeSO4·7H2O preparing a solution with the concentration of 0.99-1.05 mol/L as an electrolytic solution; the electrolysis temperature is room temperature (12-27 ℃); the anode of the electrolytic cell is a motor disassembling magnetic block, and the cathode of the electrolytic cell is a high-purity titanium plate; the electrolysis pH is 2.5-3.62, and the current density is 20mA/cm2～500mA/cm2(initial to final process values).
The use process comprises the following steps:
(1) and an electrode. Weighing neodymium iron boron waste 512g, gathering two magnetic blocks by virtue of waste magnetism, and connecting the two magnetic blocks to a power supply anode; cleaning the surface of a high-purity titanium plate; placing the anode magnetic block and the cathode plate in electrolyte;
(2) and (3) an electrolyte. With FeSO4·7H2O is prepared into 3L electrolyte with the concentration of 1mol/L and is placed in an electrolytic cell. Adjusting the pH to 2.5 with dilute sulfuric acid;
(3) and (4) electrolyzing. The circuit is switched on to control the current density. Connecting a constant current power supply, and regulating the current to 5A;
(4) and collecting the product. Unloading the blocky high-purity iron from the cathode titanium plate, and measuring the Fe content to be 99.92-99.93% by a subtraction method; after the electrolyte is tempered, the rare earth elements in the electrolyte are recovered in an extraction mode, and the obtained product with the purity of Nd is obtained by precipitation, filtration and ignition2O3 99.99％、La2O3 99.95％、Dy2O3 99.91％。
Example 3:
the scrap neodymium iron boron permanent magnet fragments comprise the following main components: 62.87 to 62.95 percent of TFe, 22.39 to 22.57 percent of Nd22.39, 3.26 to 2.31 percent of Pr, 1.42 to 1.59 percent of La and 9.45 to 9.46 percent of B; with FeSO4·7H2Preparing FeSO with the concentration of 1.51-1.53 mol/L from O4The solution is used as an electrolytic solution; the electrolysis temperature is room temperature (15-28 ℃); the anode of the electrolytic cell is a waste neodymium iron boron magnetic block, and the cathode of the electrolytic cell is a high-purity titanium plate; the electrolysis pH is 2.5-3.62, and the current density is 20mA/cm2～200mA/cm2(initial to final process values).
The use process comprises the following steps:
(1) raw material (anode material) preparation. Cutting to obtain 3-5 g of neodymium iron boron magnetic blocks, polishing by using a polisher to remove pollutants on the surfaces of the magnetic blocks to expose fresh surfaces, weighing and recording the weight of the magnetic blocks;
(2) and preparing a cathode material. Taking a small piece of pure iron sheet, shearing the small piece of pure iron sheet regularly, wiping off impurities on the surface, weighing and recording the weight of the small piece of pure iron sheet;
(3) and (4) preparing an electrode. The platinum sheets of the cathode and the anode electrodes need to be wiped clean, so that the pollutants are prevented from generating resistance and influencing the current efficiency. Then the materials of the cathode and the anode are tightly connected with the electrodes;
(4) and preparing an electrolyte. 69.5g of FeSO are weighed out4·7H2The O medicament is poured into 500mL of deionized water and stirred until dissolved, and 0.5mol/L ferrous sulfate solution is prepared;
(5) and adjusting the pH value of the electrolyte. Diluting a small amount of concentrated sulfuric acid by 100 times, adding the diluted sulfuric acid into electrolyte by a dropper in a dropwise manner, and simultaneously, measuring the pH value by using a pH meter until the pH value is reduced to 2.51;
(6) and (5) building an electrolysis device. The cell was rinsed clean with deionized water prior to the preparation of the feedstock. Pouring the electrolyte into an electrolytic cell, respectively placing two electrodes into two sides of the electrolytic cell, and screwing a screw plug;
(7) and adjusting the temperature of the electrolyte. Setting the temperature of the water bath kettle as the temperature determined by the test, putting the electrolytic bath into the water bath kettle after the water temperature in the water bath kettle reaches the determined temperature, enabling the temperature of the electrolyte to be consistent with the ambient water temperature, and then switching on the power supply;
(8) the circuit is completed. And connecting a constant current power supply, regulating the current to 0.31A, and reading and recording the initial time of energization.
(9) And collecting the electrolyte. And (4) removing the electrolysis device, and washing the cathode high-purity iron powder and the residual anode material with deionized water. The content of high-purity Fe is 99.86-99.90%; collecting the electrolyte, filtering, and weighing and recording the anode mud as a filter cake after filtering. Recovering rare earth in an extraction mode after the electrolyte is tempered, precipitating, filtering and firing to obtain Nd product with purity2O399.99％、La2O3 99.91％、Dy2O3 99.95％。
Claims (6)
1. An electrolytic regeneration method of neodymium iron boron waste solution is characterized in that: the neodymium iron boron waste is used as an anode, and dilute sulfuric acid, dilute nitric acid or rare earth and iron sulfate and nitrate are used as electrolyte; the neodymium iron boron scrap scraps are gathered into a whole by virtue of magnetism and used as an anode, and high-purity iron or inert conductive materials are used as a cathode; electrolyzing the solution at room temperature to make the rare earth and iron ions in the neodymium iron boron waste enter the solution; wherein ferrous ions are separated out at the cathode and recovered in the form of high-purity iron; the rare earth elements are enriched in the electrolyte in an ionic state; after the electrolysis is finished, the rare earth elements in the electrolyte are recovered by extraction, and the high-purity rare earth oxide is produced by precipitation, filtration and ignition.
2. The electrolytic regeneration method of neodymium iron boron waste solution as claimed in claim 1, characterized in that: the anode in the electrolytic cell is neodymium iron boron waste, and waste fragments are gathered into a larger-size anode by virtue of magnetism.
3. The solution electrolytic regeneration method of neodymium iron boron waste as claimed in claim 1, characterized in that: the electrolytic recovery process of the neodymium iron boron waste is carried out in dilute acid or salt solution at room temperature; wherein the dilute acid is dilute solution of sulfuric acid and nitric acid, and the pH value is 0.9-4.1; the salt solution is sulphate and nitrate of bivalent or trivalent iron and rare earth elements, and the concentration is 0.28 mol/L-3.9 mol/L.
4. The electrolytic regeneration method of neodymium iron boron waste solution as claimed in claim 1, characterized in that: in the process of electrolyzing the neodymium iron boron waste, the current density is 19mA/cm2～520mA/cm2Controlling the cathode iron production state by adjusting the current within the range, and respectively recovering blocky, spongy or granular high-purity electrolytic iron.
5. The electrolytic regeneration method of neodymium iron boron waste solution as claimed in claim 1, characterized in that: the rare earth elements after electrolysis are left in the electrolyte and can be converted into high-purity rare earth oxides with the content of more than 99.9 percent after extraction, precipitation, filtration and burning treatment.
6. The electrolytic regeneration method of neodymium iron boron waste solution as claimed in claim 1, characterized in that: the extracted electrolyte can be reused in the electrolysis process without adding any chemical reagent.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010079981.9A CN111154980B (en) | 2020-02-04 | 2020-02-04 | Neodymium iron boron waste solution electrolytic regeneration method |
| JP2020048099A JP7076149B2 (en) | 2020-02-04 | 2020-03-18 | Electrolytic regeneration method of Nd-Fe-B scrap solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010079981.9A CN111154980B (en) | 2020-02-04 | 2020-02-04 | Neodymium iron boron waste solution electrolytic regeneration method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111154980A CN111154980A (en) | 2020-05-15 |
| CN111154980B true CN111154980B (en) | 2021-04-16 |
Family
ID=70565260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010079981.9A Active CN111154980B (en) | 2020-02-04 | 2020-02-04 | Neodymium iron boron waste solution electrolytic regeneration method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP7076149B2 (en) |
| CN (1) | CN111154980B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113957250B (en) * | 2021-09-18 | 2023-05-30 | 内蒙古大学 | Environment-friendly recycling method for rare earth permanent magnet alloy waste |
| CN113846221B (en) * | 2021-09-18 | 2023-05-30 | 内蒙古大学 | Environment-friendly recycling method for neodymium-iron-boron alloy waste |
| CN114427042B (en) * | 2022-01-28 | 2023-02-03 | 江苏南方永磁科技有限公司 | Draw separator of high-purity rare earth oxide from neodymium iron boron waste material |
| CN115818692B (en) * | 2022-12-07 | 2024-03-26 | 北京科技大学 | Method for separating rare earth salt from ferrous sulfate-containing mixed solution |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5967384A (en) * | 1982-10-07 | 1984-04-17 | Sumitomo Metal Mining Co Ltd | Method for recovering valuable metal from alloy containing rare earth elements |
| JPH0533074A (en) * | 1991-07-26 | 1993-02-09 | Tdk Corp | Method for reuse of ni-coated rare earth alloy |
| US5362459A (en) * | 1993-05-17 | 1994-11-08 | Pure-Etch Co. | Neodymium recovery process |
| CN104169471A (en) | 2012-07-19 | 2014-11-26 | 吉坤日矿日石金属株式会社 | Method for recovering rare earth from rare earth element-containing alloy |
| JP6348796B2 (en) | 2013-07-25 | 2018-06-27 | 国立大学法人横浜国立大学 | Recovery method of rare earth elements using ionic liquid |
| CN103540756B (en) * | 2013-10-29 | 2016-06-29 | 中南大学 | A kind of method processing waste and old neodymium iron boron material dissolution rare earth |
| CN105238929B (en) * | 2014-10-06 | 2017-07-04 | 永州市零陵远达新材料有限公司 | A kind of recovery of waste and old Nd-Fe-B permanent magnet material middle rare earth and utilization |
| CN106319575B (en) * | 2016-11-02 | 2018-04-17 | 江西理工大学 | A kind of method of neodymium iron boron greasy filth waste material electrolytic preparation Nd Fe B alloys |
| CN108359798A (en) * | 2017-06-03 | 2018-08-03 | 江西离子型稀土工程技术研究有限公司 | A method of rapidly and efficiently recycling neodymium iron boron waste material |
| CN109161934B (en) * | 2018-11-13 | 2019-12-31 | 内蒙古科技大学 | Method for separating rare earth elements in neodymium iron boron alloy waste and directly preparing rare earth metals |
| CN110592378B (en) * | 2019-04-30 | 2021-05-04 | 内蒙古科技大学 | Method for recovering rare earth and iron from ultrafine powder waste generated in neodymium iron boron production process |
-
2020
- 2020-02-04 CN CN202010079981.9A patent/CN111154980B/en active Active
- 2020-03-18 JP JP2020048099A patent/JP7076149B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP7076149B2 (en) | 2022-05-27 |
| JP2021123788A (en) | 2021-08-30 |
| CN111154980A (en) | 2020-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111154980B (en) | Neodymium iron boron waste solution electrolytic regeneration method | |
| CN106756084B (en) | Method for extracting noble metal by taking iron-based material as trapping agent | |
| Sun et al. | Spent lead-acid battery recycling in China–A review and sustainable analyses on mass flow of lead | |
| Tanaka et al. | Recycling of rare earths from scrap | |
| CN102011020B (en) | Method for recovering rare earth elements from neodymium-iron-boron wastes | |
| Tao et al. | Formation cause, composition analysis and comprehensive utilization of rare earth solid wastes | |
| CN110607537B (en) | Method for synchronously and efficiently extracting rare earth and iron from high-value recycled neodymium iron boron waste | |
| CN102719674A (en) | Method for extracting rare earth from oxidized neodymium iron boron waste | |
| CN107623152B (en) | Applying waste lithium ionic power battery resource recycle method | |
| CN112680598A (en) | Method for low-cost clean treatment of waste lithium ion battery anode material | |
| CN104169471A (en) | Method for recovering rare earth from rare earth element-containing alloy | |
| WO2020151478A1 (en) | Method for recovering rare earth element from neodymium-iron-boron scrap by means of extraction with liquid metal bismuth | |
| CN107299219A (en) | A kind of resource utilization method of electroplating sludge | |
| WO2020215857A1 (en) | Method for extracting rare earth element from neodymium-iron-boron waste by means of metal lead liquid-liquid separation | |
| CN112941321B (en) | Method for strengthening leaching reaction of neodymium iron boron magnet by combining electrochemical anodic oxidation with ionic flocculant | |
| CN106282568A (en) | A kind of method being enriched with platinum group metal from spent automotive exhaust catalysts metallic carrier | |
| CN108330276A (en) | Method for preparing high-purity iron powder using iron vitriol slag and products thereof and application | |
| CN109136996B (en) | Method for preparing Mg-Nd base intermediate alloy by using neodymium iron boron waste | |
| CN109609776A (en) | A method of copper cobalt in copper vessel slag is extracted using waste cathode of aluminum electrolytic cell carbon block | |
| WO2018168471A1 (en) | Production method for metallic manganese | |
| CN113846221B (en) | Environment-friendly recycling method for neodymium-iron-boron alloy waste | |
| US20230124749A1 (en) | Ammonium complex system-based method for separating and purifying lead, zinc, cadmium, and copper | |
| CN115652077A (en) | Method for selectively separating and recovering lithium and manganese from waste lithium manganate battery | |
| CN114231744A (en) | Method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries | |
| CN112813278A (en) | Recovery processing method of copper dross |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |