WO2020215857A1 - Procédé d'extraction d'un élément des terres rares à partir de déchets de néodyme-fer-bore au moyen d'une séparation liquide-liquide de plomb métal - Google Patents

Procédé d'extraction d'un élément des terres rares à partir de déchets de néodyme-fer-bore au moyen d'une séparation liquide-liquide de plomb métal Download PDF

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WO2020215857A1
WO2020215857A1 PCT/CN2020/074814 CN2020074814W WO2020215857A1 WO 2020215857 A1 WO2020215857 A1 WO 2020215857A1 CN 2020074814 W CN2020074814 W CN 2020074814W WO 2020215857 A1 WO2020215857 A1 WO 2020215857A1
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rare earth
lead
liquid
metal
ndfeb
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Chinese (zh)
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何杰
孙小钧
陈斌
赵九洲
江鸿翔
张丽丽
郝红日
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中国科学院金属研究所
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • 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

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  • the invention belongs to the field of metal resource recycling and reuse, and specifically relates to a method for extracting rare earth elements from neodymium iron boron waste by metal lead liquid-liquid separation.
  • Rare earth elements have unique physical and chemical properties and are widely used in the development and innovation of science and technology, and the global demand for rare earth metal resources is increasing year by year. Especially in recent years, new technologies dedicated to reducing energy consumption and developing renewable energy have become significantly more dependent on rare earth resources. Rare earth elements are widely used in new materials such as permanent magnet materials, luminescent materials, hydrogen storage alloys, nickel-hydrogen battery electrode materials, polishing and catalysts. In particular, neodymium iron boron permanent magnet materials (containing about 30wt.% of rare earths) need to consume a large amount of rare earths, and the annual consumption is close to half of my country's total rare earth consumption, resulting in extremely unbalanced utilization of rare earth resources in my country.
  • rare earth permanent magnet samarium cobalt developed in 1967 to the third generation of rare earth permanent magnet NdFeB developed in 1983, the rare earth elements used are samarium, praseodymium, neodymium, terbium, dysprosium, lanthanum, cerium, and gadolinium , Holmium, erbium, yttrium, etc.
  • the third-generation neodymium iron boron rare earth permanent magnet material has the advantages of light weight, small size, strong magnetism, extremely high magnetic energy, easy access to raw materials, and low price. It has developed extremely rapidly. It is the most cost-effective permanent magnet material so far.
  • the field of magnetism is known as the "magnet king". It is widely used in hard disk drives, wind power generation, electric power steering, hybrid and electric vehicles, electric bicycles, consumer electronics and household appliances.
  • NdFeB permanent magnet materials are still used in elevators, magnetic separation and magnetic refrigeration equipment.
  • rare earth permanent magnetic materials mainly include sintered NdFeB (91.4%), bonded NdFeB (6.7%), hot-pressed/hot-deformed NdFeB (0.6%) and sintered samarium cobalt (accounting for 0.6%). 1.3%) Four categories. In 2017, the global NdFeB permanent magnet output was nearly 200,000 tons, of which China accounted for about 85%.
  • NdFeB waste mainly comes from: 1The waste produced during the preparation of the NdFeB material and 2The waste produced in the end of the NdFeB material due to the failure of the used device.
  • the production and preparation process of rare earth NdFeB permanent magnet materials mainly include: batching, alloy smelting, hydrogen crushing, jet milling, magnetic field orientation forming, isostatic pressing, oil stripping, sintering, machining and other links and processes.
  • Various processes in the production process of NdFeB permanent magnet materials will produce a certain amount of waste or waste products, mainly including: the loss of raw materials in the pretreatment process of raw materials, and the neodymium produced by severe oxidation during the induction melting process.
  • the service life of voice coil motors is 8 years
  • the service life of hybrid/electric vehicles is 15 years
  • the service life of consumer motors is 15 years
  • the service life of wind power motors is 20 years.
  • China's installed wind power capacity exceeded 188GW, and each installed capacity of 1.5MW requires approximately 1 ton of neodymium iron boron permanent magnets. Since 2000, my country's installed wind power capacity has increased year by year, especially in the past 10 years.
  • the total amount of scrapped rare earth NdFeB permanent magnets in the world was 50,000 to 70,000 tons, and China accounted for more than 70%, and the scrap volume increased year by year.
  • NdFeB rare earth permanent magnet materials the content of rare earth elements such as praseodymium, neodymium, and dysprosium is as high as 25-30%, and the rest are mainly metallic iron, cobalt, nickel, and element boron. If a large number of waste NdFeB rare earth permanent magnets cannot be recycled efficiently and greenly, not only will they produce a large number of pollution sources and secondary pollution, but also cause waste of resources, which goes against the development of circular economy.
  • the recovery of metal elements from waste NdFeB rare earth permanent magnet materials not only contributes to ecological environment protection, but also alleviates the resource shortage caused by the extremely unbalanced utilization of rare earth resources, and promotes the efficient recycling and sustainable development of rare earth resources in my country . This is of great significance to environmental protection and the development of a benign recycling economy of rare earths.
  • the recycling of NdFeB permanent magnet waste mainly includes two treatment methods: wet method and fire method.
  • the wet method mainly includes 4 steps: 1 dissolving the waste with chemical reagents, so that the metal ions are distributed in the solution, that is, leaching; 2 separating the leaching solution from the residue; 3 using ion exchange, solvent extraction or other chemical precipitation methods to make the leaching Liquid purification and separation; 4Extract compounds from the purified solution.
  • the sulfate double salt precipitation method, the sulfide precipitation method, the hydrochloric acid solution method, the hydrochloric acid solution method, and the oxalic acid precipitation method have been developed at home and abroad.
  • Literature 1 Lihecheng, Research on the Preparation of Neodymium Oxide, Rare Metals and Cemented Carbides, 03:4-7, 1997) reported the use of sulfuric acid-double salt method to recover rare earths from neodymium iron boron waste and prepare neodymium oxide products.
  • Literature 2 Choen Yunjin, Recovery of Rare Earth and Cobalt in NdFeB Waste Residue by Full Extraction Method, 06:10-12, 2004
  • the NdFeB waste was dissolved in hydrochloric acid by the hydrochloric acid total solution method, and the iron was adjusted by adjusting the PH value. Separated from rare earth elements.
  • Literature 3 (Yin Xiaowen, etc., Study on the Recovery of Rare Earth Elements in NdFeB Waste by Oxalate Precipitation Method, Rare Metals, 06:1093-1098, 2014) reported that NdFeB waste was dissolved in concentrated hydrochloric acid by the oxalic acid precipitation method. Oxalic acid is added to the leaching solution to obtain the precipitation of rare earth oxalate, which separates the rare earth from iron.
  • the Chinese invention patent (a method for recovering and extracting rare earth oxides from neodymium iron boron waste, publication number CN107012330A) discloses a method for recovering and extracting rare earth oxides from neodymium iron boron waste, which uses crushing-incineration-cleaning -Acid dissolution-extraction-roasting process to obtain rare earth oxides.
  • a Chinese invention patent (a method for recovering rare earths from NdFeB waste, publication number CN106319249A) discloses a method for recovering rare earths from NdFeB waste.
  • NdFeB uses hydrogen peroxide and oxidizing and weak acid to make NdFeB
  • N503 is used to extract the iron element in the solution first
  • P507 is used to extract the rare earth elements
  • oxalic acid and potassium carbonate are used to respectively precipitate the corresponding rare earth ions.
  • the Chinese invention patent (Method for recovering rare earth from NdFeB waste, publication number CN103146925A) discloses a method for recovering rare earth from NdFeB waste, which includes the steps of roasting-acid dissolution-separation-burning, and the filtrate is modified Rare earth oxides are obtained after attapulgite and hydrogen peroxide treatment, centrifugal slag removal, extraction separation, precipitation separation and other processes.
  • the Chinese invention patent (Method for recovering rare earth elements from NdFeB waste, publication number CN102011020A) discloses a method for recovering rare earth elements from NdFeB waste.
  • the steps are: mixing NdFeB waste with water and grinding, After oxidation and grinding of NdFeB, secondary grinding of oxidation products, acid leaching, solid-liquid separation, extraction and removal of iron, rare earth chloride, extraction and separation of rare earths, extraction and removal of aluminum, precipitation and burning, etc.
  • Fire treatment is mainly divided into glass slag method, alloy method, chlorination method, selective oxidation method, slag finance method, etc.
  • Saito et al. used the glass slag method and used boron oxide as the oxidant to oxidize the rare earth elements in the NdFeB waste into neodymium oxide, and the boron oxide was reduced to boron as a simple substance and entered into the iron to form an iron-boron alloy.
  • Uda used FeCl 2 as the chlorinating agent.
  • the rare earth elements in the neodymium iron boron waste were chlorinated at 800°C, and then the rare earth chlorides were recovered by vacuum distillation.
  • the purpose of the present invention is to provide a metal lead liquid-liquid separation method for extracting rare earth elements from neodymium iron boron waste, which has short process flow, high efficiency, no need for harsh chemical reagents, zero emission, and environmental protection.
  • a metal lead liquid-liquid separation method for extracting rare earth elements from neodymium iron boron waste, which has short process flow, high efficiency, no need for harsh chemical reagents, zero emission, and environmental protection.
  • using the thermodynamic properties of rare earth elements and lead and iron elements to solve the comprehensive and efficient recovery and recycling of NdFeB waste including rare earth, iron and boron elements.
  • a method for separating and extracting rare earth elements from NdFeB waste by metal lead liquid-liquid separation is carried out according to the following steps:
  • Step 1 Clean the dirt on the surface of the NdFeB waste material and dry it;
  • Step 2 Construct Fe-Pb immiscible separation system from NdFeB waste and metallic lead extractant
  • Step 3 Place the NdFeB waste in a crucible for melting metallic lead, and stir the melt in the crucible to make the NdFeB waste fully contact the metallic lead liquid;
  • Step 4 controlling the temperature of the metal material in the crucible, the rare earth elements are enriched in the metallic lead liquid to form a lead rare earth alloy melt, and the residual NdFeB scrap is in the form of iron-boron alloy;
  • Step 5 separating the lead-rare earth alloy melt from the iron-boron alloy, and separating the rare earth from the lead metal in the lead-rare earth alloy by vacuum evaporation or selective oxidation.
  • the chemical composition of the NdFeB waste recovered in step 1 mainly includes: rare earth elements Nd, Pr, La, Ce, Dy, Tb, One or more of Gd, Ho, Er, Y, one or more of transition metal elements Fe, Ni, Co, Mn, Cu, Nb, Zn, and other elements B, Al, Sn, One or more of Ga.
  • the metal lead extractant used in step 2 is a lead alloy containing lead and one or more of silver, magnesium and calcium.
  • the lead content is not less than 50wt.%.
  • the lead content of the metal lead extractant is not less than 98wt.%.
  • step 3 in the method for separating and extracting rare earth elements from NdFeB waste by metal lead liquid-liquid separation, in step 3, in the ratio of NdFeB waste and metal lead extractant, the weight ratio of NdFeB waste and metal lead is W Nd-Fe-B /W Pb varies from 0.1 to 10.
  • the weight ratio W Nd-Fe-B /W Pb of NdFeB waste to metal lead is within a range of 0.5-5.
  • the material of the crucible and the stirring rod for melting the metal lead is pure iron, alumina or graphite.
  • the heating temperature of the metal material in the crucible is between 1327°C and 1450°C.
  • the iron-boron alloy is composed of transition metals with a weight percentage of not less than 97% Fe and one or more of Ni, Co, Mn, Cu, Nb, Zn, and boron B with a weight percentage of 1 to 2%, used in steel or neodymium as a master alloy after refining Production of boron permanent magnet materials.
  • the lead-rare earth alloy obtained by separation in step 5 uses selective oxidation to separate the metal Pb in the Pb-RE alloy from various rare earth metals; or Based on the fact that the metal Pb vapor pressure is higher than the rare earth metal at the same temperature, vacuum distillation technology is used to separate the metal Pb from the rare earth metal in the Pb-RE alloy.
  • the remaining mixed rare earth contains one or two of Nd, Pr, Dy, and Tb Above, the intermediate alloy is used to produce NdFeB permanent magnet materials.
  • the design idea of the present invention is:
  • Rare earth has the reputation of "industrial vitamin" and is widely used in the preparation of rare earth permanent magnets, polishing, hydrogen storage, catalysis and other materials.
  • NdFeB rare earth permanent magnets are used in hard disk drives, motors, wind power generation, new energy vehicles, etc. Key material.
  • these rare earth materials such as neodymium iron boron permanent magnet materials
  • waste materials such as sludge and scraps are generated.
  • these products containing key rare-earth materials such as computers, motors, automobiles, etc.
  • the present invention helps to reduce the pressure of waste on the ecological environment.
  • Rare earth permanent magnet materials are widely used in electronic appliances, industrial motors, wind power generation, electric vehicles, automobiles and other products. With the continuous advancement of science and technology and the upgrading of products, these products have gradually become solid waste. If the rare earth permanent magnet waste is improperly handled in the process of recycling, the secondary pollution caused will bring great harm to the ecological environment and pose a great threat to animals, plants and humans. For example, the acidity and alkalinity of groundwater and soil are seriously exceeding the standard; a large amount of smoke and dust are generated, causing serious pollution to the atmosphere. It can be seen that exploring new technologies and processes for NdFeB waste recycling and developing the comprehensive and efficient separation and recycling of NdFeB waste has significant environmental benefits.
  • the present invention uses metallic lead to separate and extract rare earth metals in NdFeB waste, and enables various metal elements in NdFeB waste to be efficiently recycled and reused, so as to realize the recovery and reuse of NdFeB permanent magnet waste .
  • the one-step clean and efficient separation and extraction of rare earth elements such as neodymium and iron and boron from neodymium iron boron waste are realized. This not only can effectively alleviate the resource shortage caused by the extremely unbalanced application of rare earth elements, but also promote the efficient recycling and sustainable development of rare earth resources in my country, which has long-term strategic significance.
  • Figure 1(a)-(c) is a schematic diagram of the selective distribution of rare earth element RE in the liquid phase separation system (L 1 +L 2 ) to efficiently separate and recover rare earth elements in NdFeB waste.
  • Figure 1 (a) shows the rare earth element RE dissolved in L 1 in the separation system
  • Figure 1 (b) shows the rare earth element RE dissolved in L 2 in the separation system
  • Figure 1 (c) shows the rare earth element RE distribution Near the interface of the two separated phases L 1 and L 2 .
  • Figures 2(a)-(d) are schematic diagrams of the specific implementation process of extracting rare earth elements from neodymium iron boron waste using metallic lead.
  • Figure 2(a) shows the liquid-liquid separation to form two liquid phases rich in Fe and Pb
  • Figure 2(b) shows the lower Pb-rich lead-rare earth alloy melt is introduced into a metal crucible container through the melt diversion port.
  • Figure 2(c) shows the upper Fe-rich iron-boron alloy melt
  • Figure 2(d) shows the Fe-rich iron-boron alloy melt introduced into another metal crucible container from the melt orifice.
  • Figure 3 is a schematic diagram of the vacuum distillation separation of Pb-RE alloy, that is, the saturated vapor pressure logP(Pa)-temperature T(°C) relationship diagram of metal Pb and rare earth elements Nd, Pr, Dy, Tb.
  • Figure 4 is a schematic diagram of the selective oxidation and separation of Pb-RE alloy, that is, the free energy of formation of metal elements Pb and rare earth elements Nd, Pr, Dy, Tb and other oxides ⁇ G (kJ/mol)-temperature T (°C) relationship diagram .
  • Figure 5 is a microstructure diagram of the lower Pb-RE alloy melt enriched with rare earth elements after cooling and solidification.
  • Fig. 6 shows the solidified structure morphology of the Fe-B alloy remaining after the NdFeB waste is extracted with the rare earth elements by the liquid metal Pb.
  • Figure 7 shows the solidification structure of the lead-rare earth alloy after the lead-rare-earth alloy melt is filled with air to selectively oxidize the rare-earth elements therein and the rare-earth elements are oxidized and floated.
  • the present invention provides a method for efficiently separating and recovering rare earth elements in neodymium iron boron waste materials, using the selective distribution law of rare earth elements in the separation system to achieve extraction and separation of rare earth metal elements from neodymium iron boron waste materials.
  • the rare earth element RE (Nd, Pr, Dy, etc.) in the NdFeB scrap is separated from the transition metal TM (Fe, Co, Ni, Cu, etc.) efficiently, and almost all the rare earth elements are enriched in the liquid state.
  • the metal Pb a Pb-RE alloy melt is formed.
  • the method for separating rare earth elements in NdFeB waste with metallic lead liquid-liquid is the key to constructing a liquid-liquid separation system from NdFeB waste and metallic lead extractant, that is, the metallic lead extractant and The NdFeB waste materials contact to form a liquid-liquid contact surface (rather than a liquid-solid contact surface).
  • a liquid-liquid contact surface (rather than a liquid-solid contact surface).
  • the diffusion distance of rare earth elements to the metal lead extractant is reduced, and the rare earth elements are quickly and fully enriched in the metal lead extractant, so that no less than 95% of the rare earth elements are enriched in the metal lead extractant within 5-30 minutes ; Then the mechanical vibration technology is used to promote the rapid separation of the liquid iron-boron alloy and the liquid lead-rare earth alloy with the difference in density to form the upper and lower layers.
  • a liquid-solid separation system is formed between the liquid metal lead and the NdFeB waste (that is, the NdFeB waste is Solid). Specifically, under the condition of 800°C, a liquid-solid reaction interface is formed between the liquid metal lead and the solid NdFeB, and the interface is maintained at 800°C for 2 hours to cause a diffusion reaction between the two. Then, the diffusion couple was observed and analyzed. The results showed that a diffusion reaction occurred at the liquid-solid interface. The rare earth elements in the solid NdFeB diffused into the liquid metal lead.
  • the thickness of the rare earth element diffusion layer in the solid NdFeB was about 2.5 mm. If other conditions remain unchanged, the holding time is increased from 2 hours to 5 hours. At this time, it is observed that the thickness of the rare earth element diffusion layer in the solid NdFeB is about 4.5mm, and in the thickness region of the solid NdFeB diffusion layer, the rare earth neodymium The content is still about 5-7% mass content.
  • the method first melts the metallic lead Pb in an induction heating furnace; then adds the NdFeB waste to the liquid metal lead, and heats it to a certain temperature so that the rare earth elements in the NdFeB waste quickly diffuse into the metal lead liquid, in order to achieve Efficient and rapid extraction of rare earth elements in NdFeB waste materials can heat up the melting of NdFeB waste materials and cause liquid-liquid separation to form two immiscible solution phases of lead-rich rare earth Pb-RE and iron-rich Fe-B; hold for a certain period of time Afterwards, the rare earth elements in the NdFeB waste are fully enriched in the liquid metal lead to form a lead-rare earth Pb-RE alloy melt, and the rare earth elements in the NdFeB waste are extracted by the metal lead liquid and the residue is iron boron Fe-B alloy; finally, based on the difference in density between the two, the Pb-RE alloy melt is separated from the Fe-B iron-boron alloy.
  • Fe-B iron-boron alloy can be recycled as an intermediate alloy for the production of neodymium iron-boron permanent magnet materials or as an intermediate alloy for the production of special steel; the metals Pb and RE in the lead-rare earth Pb-RE alloy can be vacuum evaporated or selectively oxidized Law separation.
  • Step 1 Clean the dirt on the surface of the NdFeB waste material and dry it;
  • Step 2 Construct Fe-Pb immiscible separation system from NdFeB waste and metallic lead extractant
  • Step 3 Place the NdFeB waste in a crucible for melting metallic lead, and stir the melt in the crucible to make the NdFeB waste fully contact the metallic lead liquid;
  • Step 4 controlling the temperature of the metal material in the crucible, the rare earth elements are enriched in the metallic lead liquid to form a lead rare earth alloy melt, and the residual NdFeB scrap is in the form of iron-boron alloy;
  • Step 5 separating the lead and rare earth Pb-RE alloy melt from the iron-boron Fe-B alloy, and then using vacuum evaporation or selective oxidation to separate the rare earth from the lead metal in the lead rare earth alloy.
  • the vapor pressures of the metals Pb and RE are different.
  • the saturation vapor pressure-temperature diagram of metal Pb and rare earth elements Nd, Pr, Dy, Tb the vapor pressures of Pb, Nd, Pr, Dy and other metal elements in the Pb-RE alloy melt are different at the same temperature.
  • Vacuum is used Distillation method separates various metals, and then obtains pure metal element with a purity of more than 99wt%; or based on the highest vapor pressure of metal Pb at the same temperature, vacuum evaporation technology is used to first separate the Pb element in the Pb-RE alloy, and then the remaining mixed rare earth ( Containing Nd, Dy, Pr, etc.) to be recycled as a master alloy for the production of NdFeB permanent magnet materials.
  • the free energy of formation of oxides such as metal Pb and rare earth elements RE (Nd, Pr, Dy, Tb) is different.
  • the rare earth elements preferentially oxidize to form oxides, so that the liquid metal Pb is separated from the rare earth elements RE.
  • the remaining NdFeB waste is an iron-boron alloy, and the rare earth elements are distributed in the metal lead Pb liquid.
  • the temperature is about 1350°C
  • the NdFeB waste material melts and forms a liquid-liquid immiscible system with the metallic lead liquid. After separation, it solidifies to form a lead rare earth alloy ( Figure 5) and an iron-boron alloy ( Figure 6).
  • Analysis shows that the total mass percentage of transition metals Fe, Co, Ni, Cu, etc. in the Fe-rich metal melt is above 98%, and the total mass percentage of rare earth elements Nd, Pr, and Dy is between 0.1 to 1.5%.
  • the invention can comprehensively recover light rare earth elements Nd, Pr, etc., heavy rare earth elements Dy, etc., transition metals Fe, Co, Ni, etc. and boron B elements in neodymium iron boron waste in one step, so that the metal resource separation and extraction process is improved. Simplified, has the characteristics of high efficiency, energy saving, zero emission, environmental friendliness, etc., and has economic and environmental benefits.
  • the rare earth strong magnet neodymium iron boron scraps purchased on the market are first demagnetized, and then the surface stains are cleaned, and dried for use.
  • Configure NdFeB waste and metallic lead Pb in a weight ratio of 1:1 weigh out 500 grams of NdFeB waste and metallic lead, for a total mixture of 1,000 grams.
  • the Fe-rich liquid phase floats up under the action of gravity, while the Pb-rich liquid phase sinks, forming a layered structure of Fe-rich and Pb-rich liquid phases.
  • the upper layer is neodymium iron.
  • the boron waste is extracted by the metal Pb solution to form a Fe-rich iron-boron alloy melt 4, and the lower layer is the rare earth element enriched into the liquid metal Pb to form a Pb-rich lead rare earth alloy melt 5, as shown in Figure 2(a). Start the stopper rod 1, and move the stopper rod 1 upwards by 6-8mm.
  • the lower Pb-rich Pb-rare earth alloy melt 5 flows out through the melt diversion port 6, and the metal crucible container 7 below the crucible 2 is used to hold the Pb-rich Lead rare earth alloy melt 5, see Figure 2(b).
  • the upper Fe-rich iron-boron alloy melt 4 is left, and the stopper rod 1 is activated to reset and guide the melt Orifice 6 is plugged, see Figure 2(c).
  • the weight percentage of rare earth elements is 13.36%
  • the metal Pb weight percentage is 86.14%
  • the metal Fe weight percentage is 0.4%
  • the metal Co weight percentage is 0.03%
  • the metal Ni weight percentage is 0.07%.
  • the weight percentage of rare earth elements (Nd, Pr, Dy) totals 0.28%
  • the weight percentage of metal Pb is 0.06%
  • the weight percentage of metal Fe is 94.76%
  • the weight percentage of metal Co It is 1.92%
  • the weight percentage of metal Ni is 1.77%
  • the weight percentage of element B is 1.21%.
  • the rare earth strong magnet neodymium iron boron scraps purchased on the market are first demagnetized, and then the surface stains are cleaned, and dried for use.
  • the Fe-rich liquid phase floats up under the action of gravity, while the Pb-rich liquid phase sinks, forming a layered structure of Fe-rich and Pb-rich liquid phases.
  • the upper layer is neodymium iron.
  • the boron waste is extracted by the metal Pb solution to form a Fe-rich iron-boron alloy melt 4, and the lower layer is the rare earth element enriched into the liquid metal Pb to form a Pb-rich lead rare earth alloy melt 5, as shown in Figure 2(a). Start the stopper rod 1, and move the stopper rod 1 upwards by 6-8mm.
  • the lower Pb-rich Pb-rare earth alloy melt 5 flows out through the melt diversion port 6, and the metal crucible container 7 below the crucible 2 is used to hold the Pb-rich Lead rare earth alloy melt 5, see Figure 2(b).
  • the upper Fe-rich iron-boron alloy melt 4 is left, and the stopper rod 1 is activated to reset and guide the melt Orifice 6 is plugged, see Figure 2(c).
  • the weight percentage of rare earth elements (Nd, Pr, Dy) is 32.73%, the metal Pb weight percentage is 66.68%, the metal Fe weight percentage is 0.48%, and the metal Co weight percentage is The percentage content is 0.04%, and the metal Ni weight percentage is 0.07%.
  • the weight percentage of rare earth elements (Nd, Pr, Dy) is 0.93%, the weight percentage of metal Pb is 0.08%, the weight percentage of metal Fe is 94.16%, and the weight percentage of metal Co. It is 1.89%, the weight percentage of metal Ni is 1.75%, and the weight percentage of element B is 1.19%.
  • the rare earth strong magnet neodymium iron boron scraps purchased on the market are first demagnetized, and then the surface stains are cleaned, and dried for use.
  • Configure NdFeB waste and metallic lead Pb in a weight ratio of 2:1 weigh 800 grams of NdFeB waste and 400 grams of metallic lead, for a total mixture of 1200 grams.
  • the Fe-rich liquid phase floats up under the action of gravity, while the Pb-rich liquid phase sinks, forming a layered structure of Fe-rich and Pb-rich liquid phases.
  • the upper layer is neodymium iron.
  • the boron waste is extracted by the metal Pb solution to form a Fe-rich iron-boron alloy melt 4, and the lower layer is the rare earth element enriched into the liquid metal Pb to form a Pb-rich lead rare earth alloy melt 5, as shown in Figure 2(a). Start the stopper rod 1, and move the stopper rod 1 upwards by 6-8mm.
  • the lower Pb-rich Pb-rare earth alloy melt 5 flows out through the melt diversion port 6, and the metal crucible container 7 below the crucible 2 is used to hold the Pb-rich Lead rare earth alloy melt 5, see Figure 2(b). Then, air was charged into the lead-rare earth alloy melt at a flow rate of 5 liters/min. The rare earth elements were preferentially oxidized and the rare earth oxides floated up. After being filled with air for 4 minutes, the lead-rare earth alloy melt was cooled and solidified.
  • the metal Pb weight percentage was 96.81%
  • the metal Fe weight percentage was 0.83%
  • the metal Co weight percentage was 0.08%.
  • the weight percentage of metal Ni is 0.12%.
  • the weight percentage of rare earth elements (Nd, Pr, Dy) is 1.31%
  • the weight percentage of metal Pb is 0.11%
  • the weight percentage of metal Fe is 93.62%
  • the weight percentage of metal Co It is 1.92%
  • the weight percentage of metal Ni is 1.84%
  • the weight percentage of element B is 1.2%.

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Abstract

L'invention concerne un procédé d'extraction d'un élément des terres rares à partir de déchets de néodyme-fer-bore au moyen d'une séparation liquide-liquide de plomb métal, comprenant tout d'abord le chauffage et la fusion de plomb métal dans un creuset ; puis l'immersion des déchets de néodyme-fer-bore dans le plomb métal liquide, l'élément des terres rares dans les déchets de néodyme-fer-bore étant enrichi dans la masse fondue de plomb métal liquide dans certaines conditions de température pour former une masse fondue d'alliage de plomb-terres rares, les déchets de néodyme-fer-bore restants étant présents sous forme d'alliage fer-bore ; et enfin, la séparation de la masse fondue d'alliage de plomb-terres de l'alliage fer-bore, l'alliage fer-bore Fe-B pouvant être utilisé en tant que matériau d'alliage intermédiaire après raffinage, et des métaux tels que Pb et Nd dans l'alliage de plomb-terres rares étant dissociés par évaporation sous vide ou oxydation sélective.
PCT/CN2020/074814 2019-04-22 2020-02-12 Procédé d'extraction d'un élément des terres rares à partir de déchets de néodyme-fer-bore au moyen d'une séparation liquide-liquide de plomb métal WO2020215857A1 (fr)

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CN110066924B (zh) * 2019-04-22 2020-07-10 中国科学院金属研究所 一种金属铅液-液分离提取钕铁硼废料中稀土元素的方法
CN111778399B (zh) * 2020-01-06 2022-05-27 中南大学 一种熔体萃取分离回收废旧钴基高温合金中镍钴的方法
CN111172399A (zh) * 2020-01-19 2020-05-19 中南大学 一种利用金属熔体萃取处理铜钴合金的方法

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