CN115094253B - Praseodymium neodymium metal polishing waste recycling method - Google Patents
Praseodymium neodymium metal polishing waste recycling method Download PDFInfo
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Abstract
The invention belongs to the technical field of rare earth metal smelting, and particularly relates to a praseodymium-neodymium metal polishing waste recycling method. The recycling treatment method of the praseodymium and neodymium metal polishing waste adopts the procedures of mesh screen, magnetic separation, acidification, oxalic acid precipitation and calcination to recycle rare earth elements, fluorine and iron in the praseodymium and neodymium metal polishing waste. The praseodymium neodymium oxide and praseodymium neodymium fluoride obtained by the recycling method provided by the invention have higher purity, and have higher recovery rate to praseodymium, neodymium, fluorine and iron, the recovery rate to rare earth elements is more than 93%, the recovery rate to fluorine is more than 85%, and the recovery rate to iron is 90-98%. The recovery processing method provided by the invention is simple and easy to operate, and is easy to industrialize.
Description
Technical Field
The invention belongs to the technical field of rare earth metal smelting, and particularly relates to a praseodymium-neodymium metal polishing waste recycling method.
Background
Praseodymium-neodymium metal is a raw material for preparing the neodymium-iron-boron magnetic material, is favored by industrial production because of superior magnetic properties of neodymium-iron-boron, and increases along with the increase of the demand of the neodymium-iron-boron material. In the process of preparing praseodymium and neodymium metals, polishing treatment is required to be carried out on the praseodymium and neodymium metals, waste materials are generated in the polishing treatment process, and the waste materials contain a large amount of iron, part of praseodymium and neodymium metals and a small amount of lithium, fluorine and carbon elements. The accumulation of a large amount of waste not only occupies a large amount of space, but also causes the waste of resources such as rare earth elements, iron elements and the like; and the accumulated large amount of waste materials can be spontaneous-burned in hot weather, so that potential safety hazards are generated.
In order to reduce resource waste and promote resource recycling, a process for recycling praseodymium-neodymium metal polishing waste is needed at present.
Disclosure of Invention
In view of the above, the invention provides a praseodymium neodymium metal polishing waste recycling method, which can recycle iron, fluorine and rare earth elements in waste materials, thereby reducing resource waste.
In order to solve the technical problems, the invention provides a praseodymium neodymium metal polishing waste recycling method, which comprises the following steps:
screening praseodymium neodymium metal polishing scraps by a mesh screen to obtain oversize products and undersize products;
carrying out magnetic separation on the undersize to obtain magnetic separation iron and rare earth waste;
firstly mixing the oversize material, the magnetic iron and the first acid solution, and carrying out first acidification to obtain solid iron and a first leaching solution;
second mixing the rare earth waste and a second acid solution, and performing second acidification to obtain an acid insoluble substance and a second leaching solution;
thirdly mixing the first leaching solution, the second leaching solution and the third acid solution to obtain a clear solution;
fourthly, mixing the clarified solution with oxalic acid solution for coprecipitation, and calcining solid obtained by coprecipitation to obtain praseodymium neodymium oxide;
and fifthly, mixing the acid insoluble matter with a fourth acid solution, performing third acidification, and calcining the solid after the third acidification to obtain praseodymium neodymium fluoride.
Preferably, the first mixing further includes: washing the oversize material to obtain washed solid and washing liquid; the water-washed solids, the magnetic iron and the first acid solution are first mixed.
Preferably, the magnetic separation process further comprises adding the washing liquid.
Preferably, the first acid solution comprises an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the molar concentration of the first acid solution is 0.5-1 mol/L.
Preferably, the first acidification time is 50-70 min;
the pH value of the first acidified solution system is 1-2.
Preferably, the second acid solution comprises an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the molar concentration of the second acid solution is 0.5-8 mol/L;
preferably, the second acidification time is 1-5 h;
the pH value of the second acidified solution system is 1-2.
Preferably, the third acid solution comprises hydrochloric acid aqueous solution, sulfuric acid aqueous solution or nitric acid aqueous solution, and the molar concentration of the third acid solution is 5-6 mol/L; the concentration of the acid in the third mixed solution is 0.1-0.5 mol/L.
Preferably, the fourth acid solution comprises an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution and an aqueous nitric acid solution, and the concentration of the fourth acid solution is 6-8 mol/L; the mass ratio of the acid insoluble matter to the fourth acid solution is 1:5-10.
Preferably, the mass percentage of iron in the praseodymium-neodymium metal polishing waste is 70-85%, the mass percentage of praseodymium-neodymium element in the praseodymium-neodymium metal polishing waste is 13-29%, the mass percentage of fluorine in the praseodymium-neodymium metal polishing waste is 0.8-2.0%, and the mass percentage of carbon in the praseodymium-neodymium metal polishing waste is 0.01-0.05%.
The invention provides a praseodymium neodymium metal polishing waste recycling method, which comprises the following steps: screening praseodymium neodymium metal polishing scraps by a mesh screen to obtain oversize products and undersize products; carrying out magnetic separation on the undersize to obtain magnetic separation iron and rare earth waste; firstly mixing the oversize material, the magnetic iron and the first acid solution, and carrying out first acidification to obtain solid iron and a first leaching solution; second mixing the rare earth waste and a second acid solution, and performing second acidification to obtain an acid insoluble substance and a second leaching solution; thirdly mixing the first leaching solution, the second leaching solution and the third acid solution to obtain a clear solution; fourthly, mixing the clarified solution with oxalic acid solution for coprecipitation, and calcining solid obtained by coprecipitation to obtain praseodymium neodymium oxide; and fifthly, mixing the acid insoluble matter with a fourth acid solution, performing third acidification, and calcining the solid after the third acidification to obtain praseodymium neodymium fluoride. The invention adopts the procedures of mesh screen, magnetic separation, acidification, oxalic acid precipitation and calcination to recycle rare earth elements and iron in praseodymium and neodymium metal polishing waste, and the recovery rate of the rare earth elements is more than 94 percent, the recovery rate of fluorine is more than 85 percent and the recovery rate of the iron is 90-97 percent. The recovery processing method provided by the invention is simple and easy to operate, and is easy to industrialize.
Drawings
Fig. 1 is a schematic process flow diagram of recycling praseodymium-neodymium metal polishing waste in embodiment 1.
Detailed Description
The invention provides a praseodymium neodymium metal polishing waste recycling method, which comprises the following steps:
screening praseodymium neodymium metal polishing scraps by a mesh screen to obtain oversize products and undersize products;
carrying out magnetic separation on the undersize to obtain magnetic separation iron and rare earth waste;
firstly mixing the oversize material, the magnetic iron and the first acid solution, and carrying out first acidification to obtain solid iron and a first leaching solution;
second mixing the rare earth waste and a second acid solution, and performing second acidification to obtain an acid insoluble substance and a second leaching solution;
thirdly mixing the first leaching solution, the second leaching solution and the third acid solution to obtain a clear solution;
fourthly, mixing the clarified solution with oxalic acid solution for coprecipitation, and calcining solid obtained by coprecipitation to obtain praseodymium neodymium oxide;
and fifthly, mixing the acid insoluble matter with a fourth acid solution, performing third acidification, and calcining the solid after the third acidification to obtain praseodymium neodymium fluoride.
The invention screens praseodymium neodymium metal polishing scraps to obtain oversize products and undersize products. In the invention, the mass percentage of iron in the praseodymium-neodymium metal polishing waste is preferably 70-85%, more preferably 75-80%; the praseodymium-neodymium element mass percentage content in the praseodymium-neodymium metal polishing waste is preferably 13-29%, more preferably 15-28%; the content of fluorine in the praseodymium-neodymium metal polishing waste is 0.8-2.0%, more preferably 1.0-1.8%, and the content of carbon in the praseodymium-neodymium metal polishing waste is preferably 0.01-0.05%, more preferably 0.02-0.03%. In the invention, the mass percentage of praseodymium-neodymium fluoride in the praseodymium-neodymium metal polishing waste is preferably 1.0-3.0%, more preferably 1.5-2.5%; the mass percentage of praseodymium neodymium oxide in the praseodymium neodymium metal polishing waste is preferably 13-20%, more preferably 15-18%.
The invention adopts a chemical method to detect REO (rare earth element) and F, fe content in praseodymium-neodymium metal polishing waste, and adopts a carbon detector to detect C content; the REO content is preferably measured by a total amount method; the invention preferably adopts a distillation method to measure the fluorine content; the invention preferably adopts a redox method to measure the iron content.
In the invention, the particle size of iron in the praseodymium-neodymium metal polishing waste is preferably distributed in a gradient manner. In the present invention, the gradient distribution of particle sizes includes a first particle size and a second particle size. In the present invention, the first particle diameter is preferably 0.15 to 1.0mm, more preferably 0.18 to 1.0mm; the second particle diameter is preferably 0.05 to 0.12mm, more preferably 0.08 to 0.12mm. In the present invention, the iron of the first particle size is preferably 90 to 99% by mass, more preferably 93 to 96% by mass of all iron; the iron of the second particle diameter is preferably 1 to 10% by mass, more preferably 3 to 8% by mass of the total iron.
In the present invention, the mesh size of the mesh screen for mesh screen is preferably 60 to 100 mesh, more preferably 80 to 90 mesh. The invention can separate and treat iron with the grain size ranging from 0.15 to 1.0mm through the mesh screen. In the present invention, the mesh screen is preferably vibration screening.
After the oversize is obtained, the invention preferably carries out water washing on the oversize to obtain water washing solid and washing liquid. In the present invention, the mass ratio of the oversize material to water is preferably 1:4 to 6, more preferably 1:5. In the present invention, the water washing is capable of removing impurities adsorbed on the surface of the oversize product. In the present invention, the impurities preferably include praseodymium neodymium metal, praseodymium neodymium fluoride, and praseodymium neodymium oxide.
In the present invention, the water-washed solid is preferably iron beads.
After the undersize is obtained, the undersize is magnetically separated to obtain magnetic iron and rare earth waste. In the present invention, when the oversize product is washed with water, the washing liquid after washing is preferably subjected to magnetic separation together with the undersize product.
In the present invention, the magnetic separation is preferably wet magnetic separation. In the present invention, the material to be magnetically separated and water are preferably mixed before wet magnetic separation. In the invention, the mass ratio of the material to be magnetically separated to water is preferably 1:10-15, more preferably 1:11-13. In the invention, the strength of the magnetic separation is preferably 900-1100 gauss, more preferably 1000 gauss; the magnetic separation time is preferably 30 to 60 minutes, more preferably 40 to 50 minutes.
The invention can separate and remove iron in the undersize through magnetic separation; the rare earth waste comprises praseodymium neodymium metal, praseodymium neodymium oxide, praseodymium neodymium fluoride, carbon and lithium.
In the invention, the rare earth waste is preferably soaked in the solvent after magnetic separation. In the present invention, the soaking time is preferably 5 to 7 days, more preferably 6 days. In the invention, the rare earth waste is prevented from generating pungent odor in the subsequent second acidification process after being soaked.
After the oversize product and the magnetic iron are obtained, the oversize product, the magnetic iron and the first acid solution are mixed for the first time, and the first acidification is carried out to obtain solid iron and first leaching liquid. In the present invention, the first mixing preferably includes the steps of:
dispersing the oversize material and the magnetic iron in water to obtain slurry;
a first acid solution is added to the slurry.
The invention disperses the oversize and the magnetic iron in water to obtain slurry. The invention preferably carries out water washing on the oversize material, and disperses the washed solid and the magnetic iron in water to obtain suspension. In the present invention, the mass ratio of the total mass of the oversize and the magnetic iron to the water is preferably 1 to 2:8, more preferably 1 to 3:6. In the present invention, the dispersion is preferably performed under stirring, and the stirring speed is preferably 100 to 300r/min, more preferably 150 to 200r/min. In the present invention, the stirring time is preferably 10 to 20 minutes, more preferably 12 to 18 minutes.
After the slurry is obtained, the present invention adds a first acid solution to the slurry. In the present invention, the first acid solution preferably includes an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, or an aqueous nitric acid solution, more preferably an aqueous hydrochloric acid solution. In the present invention, the aqueous hydrochloric acid solution is preferably an industrial aqueous hydrochloric acid solution. In the present invention, the molar concentration of the first acid solution is preferably 0.5 to 1mol/L, more preferably 0.6 to 0.8mol/L. In the present invention, the addition is preferably by a peristaltic pump to deliver the first acid solution to the vessel containing the slurry. In the present invention, the time of the first acidification is preferably 50 to 70min, more preferably 60 to 65min. In the present invention, the pH of the first acidified solution system is preferably 1 to 2, more preferably 1.3 to 1.8. In the present invention, the first acidification is preferably performed under stirring at a rotation speed of preferably 100 to 300r/min, more preferably 150 to 200r/min
In the present invention, the first acidification further preferably includes: and carrying out solid-liquid separation on the first acidified system to obtain solid iron and a first leaching solution. In the present invention, the solid-liquid separation is preferably filtration.
In the present invention, the solid iron is preferably washed with water after the first acidification. In the invention, the water washing removes rare earth elements and acid solution on the surface of the solid iron.
In the invention, the screen material and the rare earth element (praseodymium neodymium metal) in the magnetic iron can react with acid to generate rare earth ions in the first acidification process; the invention controls the acid solution not to react with a large amount of iron by controlling the concentration and the volume of the acid solution added and the time of the first acidification. The praseodymium neodymium oxide and praseodymium neodymium fluoride particles in the praseodymium neodymium metal polishing waste are removed by screening and washing.
In the invention, the content of rare earth elements in the solid iron is less than 0.1%; the solid iron can be directly recycled. In the invention, the first leaching solution contains a large amount of praseodymium and neodymium ions and a small amount of ferrous ions.
After the rare earth waste is obtained through magnetic separation, the rare earth waste is mixed with a second acid solution for the second time, and the acid insoluble matter and a second leaching solution are obtained through the second acidification. In the present invention, the second mixing preferably includes the steps of:
mixing the rare earth waste with water to obtain slurry;
and dropwise adding a second acid solution into the slurry.
The invention mixes the rare earth waste with water to carry out size mixing to obtain sizing agent. In the present invention, the water is preferably water for soaking rare earth waste after magnetic separation. In the invention, the mass ratio of the rare earth waste to the water is preferably 1:2-5, more preferably 1:3-4. In the present invention, the mixing is preferably performed under stirring at a rotation speed of preferably 100 to 300r/min, more preferably 150 to 200r/min; the stirring time is preferably 5 to 20 minutes, more preferably 10 to 15 minutes.
After the slurry is obtained, the second acid solution is dropwise added into the slurry. In the present invention, the second acid solution preferably includes an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, or an aqueous nitric acid solution, more preferably an aqueous hydrochloric acid solution; the molar concentration of the second acid solution is preferably 0.5 to 8mol/L, more preferably 2 to 6mol/L. In the present invention, the aqueous hydrochloric acid solution is preferably an industrial aqueous hydrochloric acid solution. In the present invention, the time of the second acidification is preferably 1 to 5 hours, more preferably 2 to 3 hours. In the present invention, the pH of the second leaching solution is preferably 0.8 to 1.2, more preferably 1.
In the invention, the acid insoluble substance is praseodymium neodymium fluoride; reacting praseodymium neodymium metal and praseodymium neodymium oxide in the rare earth waste through a second acidification second acid solution to generate praseodymium neodymium ions; the second leaching solution comprises a large amount of praseodymium and neodymium ions and a small amount of ferrous iron.
After the first leaching solution and the second leaching solution are obtained, the first leaching solution, the second leaching solution and the third acid solution are mixed in a third way to obtain a clear solution. In the present invention, the third mixing preferably includes the steps of:
mixing the first leaching solution and the second leaching solution to obtain a mixed leaching solution;
mixing the leaching solution with a third acid solution.
The invention mixes the first leaching solution and the second leaching solution to obtain mixed leaching solution. In the present invention, the total mass concentration of praseodymium and neodymium ions in the mixed leachate is preferably 30 to 110g/L, more preferably 50 to 100g/L. In the present invention, the mass concentration of iron in the mixed leachate is preferably less than 30g/L, more preferably less than 20g/L. The mode of the mixing is not particularly limited in the present invention, as long as the mixing can be performed uniformly.
After the mixed leaching solution is obtained, the mixed leaching solution and the third acid solution are mixed. In the present invention, the third acid solution preferably includes an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, or an aqueous nitric acid solution, more preferably an aqueous hydrochloric acid solution; the molar concentration of the third acid solution is preferably 5 to 6mol/L, more preferably 5.5 to 5.9mol/L; in the present invention, the aqueous hydrochloric acid solution is preferably an industrial aqueous hydrochloric acid solution. In the present invention, the temperature of the third mixture is preferably 5 to 50 ℃, more preferably 10 to 45 ℃. The mode of the mixing is not particularly limited in the present invention, as long as the mixing can be performed uniformly.
In the present invention, the concentration of the acid in the third mixed solution is preferably 0.1 to 0.5mol/L, more preferably 0.2 to 0.3mol/L.
In the invention, the third acid solution with the larger molar concentration is used for dissolving small particles (praseodymium and neodymium fluoride) suspended in the first leaching solution and the second leaching solution, the fluoride ions and the praseodymium and neodymium ions dissolved after the molar concentration of the third acid solution is reduced are hydrolyzed and then polymerized into larger suspended particles (praseodymium and neodymium fluoride) in an acidic solution with the smaller molar concentration (low acidity), so that the particles are sunk, and the mixed solution of the first leaching solution and the second leaching solution is clarified.
After the clear solution is obtained, the clear solution and the oxalic acid solution are mixed for the fourth time, coprecipitation is carried out, and solid obtained by coprecipitation is calcined to obtain praseodymium neodymium oxide. In the present invention, the oxalic acid solution is preferably an industrial oxalic acid solution; the mass concentration of the oxalic acid solution is preferably 50-200 g/L, more preferably 80-180 g/L, and the temperature of the oxalic acid solution is preferably 10-60 ℃, more preferably 15-50 ℃. . In the present invention, the molar ratio of oxalic acid in the oxalic acid solution to rare earth element (REO) in the clarified solution is preferably 2.0 to 2.2:1, more preferably 2.05 to 2.15:1. The invention has no special requirement on the fourth mixing, so long as the fourth mixing can be uniformly mixed.
In the present invention, the time of the coprecipitation is preferably 60 to 90 minutes, more preferably 70 to 80 minutes. The end point of the coprecipitation is preferably judged by detecting the content of rare earth elements in the supernatant, specifically, the supernatant is mixed with oxalic acid solution, and the condition that no precipitation is generated is that the coprecipitation reaction is complete.
In the present invention, the coprecipitation step further preferably includes: the co-precipitated system was filtered to give a solid. The invention has no special requirement on the filtration, and adopts the conventional filtration mode in the field. The invention preferably washes the filter residue obtained by filtration to remove oxalic acid solution and ferrous ions on the surface. In the present invention, the washing solvent is preferably water. In the present invention, the pH of the post-washing liquid is preferably 7. In the present invention, the washed washing liquid can be used to dilute an aqueous industrial hydrochloric acid solution to obtain the desired concentration of the aqueous hydrochloric acid solution. The invention fully utilizes the solvent of each treatment step to realize no wastewater discharge in the whole treatment process, thereby achieving the effects of energy conservation and emission reduction.
In the invention, the filtrate obtained by filtration contains a large amount of hydrochloric acid and a small amount of oxalic acid and ferrous ions. In the present invention, the filtrate obtained by filtration is preferably diluted to a desired concentration to be used as the first acid solution or the second acid solution. The invention fully utilizes byproducts of each step, realizes no waste generation in the whole treatment process, and realizes the recycling of resources.
In the present invention, the temperature of the calcination is preferably 900 to 950 ℃, more preferably 920 to 950 ℃; the calcination time is preferably 2 to 6 hours, more preferably 3 to 5 hours.
In the invention, the solid obtained by coprecipitation is praseodymium neodymium oxalate. And calcining praseodymium neodymium oxalate to generate praseodymium neodymium oxide. The generated praseodymium neodymium oxide can be directly recycled. In the present invention, the content of iron in the solid obtained by the coprecipitation is preferably less than 0.05%.
After the acid insoluble matter is obtained, the acid insoluble matter and a fourth acid solution are mixed in a fifth mode, third acidification is carried out, and the solid after the third acidification is calcined, so that praseodymium neodymium fluoride is obtained. In the present invention, the fourth acid solution preferably includes an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution or an aqueous nitric acid solution, more preferably an aqueous hydrochloric acid solution; the concentration of the fourth acid solution is preferably 6 to 8mol/L, more preferably 6 to 7mol/L. In the present invention, the aqueous hydrochloric acid solution is preferably an industrial aqueous hydrochloric acid solution. In the present invention, the mass ratio of the acid-insoluble matter to the fourth acid solution is preferably 1:5 to 10, more preferably 1:6 to 8. In the present invention, the time of the third acidification is preferably 12 to 24 hours, more preferably 18 to 20 hours.
The invention can remove iron in the acid insoluble substances through third acidification. In the present invention, the third acidification step further preferably includes:
carrying out solid-liquid separation on the third acidified system;
and washing, drying and calcining the solid obtained by solid-liquid separation in sequence.
The invention carries out solid-liquid separation on the system after the third acidification. In the present invention, the solid-liquid separation is preferably filtration. The invention has no special requirement on the filtration, and can be realized by adopting a conventional mode in the field.
In the present invention, the liquid obtained by solid-liquid separation is preferably subjected to post-treatment. In the present invention, the post-treatment preferably includes the steps of:
and (3) sequentially oxidizing and extracting the liquid obtained by solid-liquid separation, and taking a water phase.
In the present invention, the oxidation is preferably performed by introducing air into a liquid obtained by solid-liquid separation to oxidize ferrous ions into ferric ions. In the present invention, the extraction extractant is preferably an N235 extractant. The invention can remove ferric ions in the liquid obtained by solid-liquid separation through extraction, and can remove 80-90% of the total content of ferric ions in the acid solution through extraction. . The aqueous phase obtained by extraction is an acid solution. The acid solution is preferably diluted and then used as the first acid solution or the second acid solution, so that the acid solution is fully recycled, and the recycling of resources is realized.
The invention sequentially washes, dries and calcines the solid obtained by solid-liquid separation. In the present invention, the washing solvent is preferably an aqueous hydrochloric acid solution, and the molar concentration of the aqueous hydrochloric acid solution is preferably 0.5 to 1mol/L, more preferably 0.5 to 0.8mol/L. The invention can remove ferrous ions on the surface of the acid insoluble substances after washing.
In the present invention, the temperature of the drying is preferably 100 to 105 ℃, more preferably 103 to 105 ℃; the drying time is preferably 4 to 8 hours, more preferably 5 to 7 hours.
In the present invention, the temperature of the calcination is preferably 750 to 800 ℃, more preferably 750 to 780 ℃; the calcination time is preferably 2 to 5 hours, more preferably 3 to 4 hours.
The invention can remove carbon in acid insoluble substances through calcination to improve the purity of praseodymium neodymium fluoride. In the present invention, the content of iron in the praseodymium neodymium fluoride is preferably less than 0.05%.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
The praseodymium neodymium metal polishing waste is recycled according to the flow of FIG. 1.
The compositions of praseodymium-neodymium metal polishing wastes are shown in Table 1.
TABLE 1 Pr-Nd metal polishing waste composition
Screening: screening 20.0kg of praseodymium neodymium metal polishing waste by a vibrating screen (the aperture of the screen used is 80 meshes), wherein the quality of the undersize is 4.5kg, and the quality of the oversize is 15.5kg;
TABLE 2 Components in praseodymium neodymium metal polishing wastes after screening
| Screening profile | Composition of the components | REO | F | C | Fe | Li | Other impurities |
| Screen feeding | Mass percent (%) | 4.8 | 0.1 | 0.01 | 95.0 | 0.02 | 0.07 |
| Screen blanking | Mass percent (%) | 66.24 | 7.58 | 0.6 | 24.23 | 1.27 | 0.08 |
2. Washing: 15.5kg of oversize material is put into a tray inclined at 30 ℃, 80L of tap water is used for washing, the washed washing liquid flows into a 100L reaction kettle below the tray, and iron beads (water washing solids) are left in the tray;
3. wet magnetic separation: adding 60L of washing liquid in the step 2 into a 100L reaction kettle, starting a stirring paddle, adding 4.5kg of undersize, stirring at a rotating speed of 150r/min, opening a bottom valve of the reaction kettle after stirring is started, slowly adding the slurry into a magnetic separator (the magnetic separator is provided with two outlets, one is an iron outlet and the other is a rare earth waste outlet), carrying out magnetic separation according to the intensity of 1000 gauss, transferring magnetic separation iron from the iron outlet into a 50L plastic barrel, transferring rare earth waste from the rare earth waste outlet into the 100L plastic barrel, and controlling the magnetic separation time to be 50min;
4. soaking the rare earth waste for 7 days by utilizing water after wet magnetic separation;
5. first acidification (acidified iron): adding tap water into a 50L reaction kettle, stopping adding the tap water without a stirring paddle, starting the stirring paddle, adding the iron beads in the step 2 and the magnetic iron in the step 3, stirring for 10min at a rotating speed of 150r/min, then adding a hydrochloric acid solution with a molar concentration of 1.0mol/L into the reaction kettle by adopting a peristaltic pump, and acidizing (stirring at a rotating speed of 160 r/min) for 0.6 h (the pH value of a solution system after acidizing is 1.3), so as to obtain solid iron and a first leaching solution; filtering and air-drying when the pH value of the leaching solution is 1 to obtain 15.34kg of solid iron (the rare earth element content is 0.06%) and a first leaching solution;
6. second acidification (acidification of rare earth waste): pumping 5L of water subjected to wet magnetic separation in the step 3 into a 50L reaction kettle through a peristaltic pump, starting a stirring paddle, pouring rare earth waste into the reaction kettle, stirring for 10min at a rotating speed of 200r/min, and then adding 6.0mol/L hydrochloric acid into the reaction kettle by adopting the peristaltic pump to acidify for 1 hour (the pH value of a solution system after acidification is 1.4) to obtain an acid insoluble substance and a second leaching solution; pumping the first leaching solution and the second leaching solution into a plastic barrel of 50L, starting stirring, adding a hydrochloric acid aqueous solution with the molar concentration of 5.0mol/L into a reaction kettle by adopting a peristaltic pump, stopping adding the hydrochloric acid aqueous solution when the molar concentration of hydrogen ions in the mixed solution is 0.2mol/L, and standing for clarifying for 12 hours;
7. co-precipitation: mixing the leaching solutions in the steps 5 and 6 at 45 ℃ to obtain 33L of mixed leaching solution with the total praseodymium and neodymium ion concentration of 78.6 g/L; adding pure water into a 100L reaction kettle, stirring after the pure water is not stirred by a stirring paddle, adding a clear solution and 19.84L of oxalic acid solution with the mass concentration of 200g/L and the temperature of 50 ℃ into the reaction kettle at the same time, and performing coprecipitation (mixing supernatant and oxalic acid solution, and indicating complete coprecipitation reaction when no precipitate is generated) for 80min; filtering the coprecipitated system; washing the filtered solid with water until the pH value of the washed solution is 7, and calcining at 950 ℃ for 3 hours to obtain praseodymium neodymium oxide, wherein the total mass of the praseodymium neodymium oxide is 2.56kg;
8. third acidification (highly purified acid insoluble): adding hydrochloric acid solution with the molar concentration of 8.0mol/L into a reaction kettle, wherein the mass ratio of the hydrochloric acid solution to the acid insoluble matter is 6:1, acidifying the acid insoluble matter by using the hydrochloric acid solution for 18 hours, and filtering; washing the filtered solid (iron oxide content less than 0.05% by mole, calculated here using iron oxide) with an aqueous hydrochloric acid solution of 0.5 mol/L; drying the washed solid at 105 ℃ for 5 hours, and calcining at 750 ℃ for 4 hours to obtain praseodymium neodymium fluoride, wherein the total mass of the praseodymium neodymium fluoride is 1.18kg;
9. waste acid recycling: the mass concentration of ferrous iron in the hydrochloric acid after impurity removal in the step 8 is 1.8g/L, oxygen is blown into the liquid through an air compressor, and ferrous iron in the liquid is converted intoFerric iron is extracted by N235 to remove Fe 3+ After that, the iron content in the liquid is 0.18g/L, tap water can be added to dilute the liquid into hydrochloric acid with the concentration of 6.0mol/L, and the hydrochloric acid can be used as dilute concentration hydrochloric acid in the steps 5 and 6 of the next batch treatment, so that the recycling of resources is achieved;
10. recycling the wastewater: the supernatant produced in the step 7 can be used as the dilute hydrochloric acid to dissolve rare earth in the step 6 for treating the lower batch, and the washing water in the step 8 can be used as the dilute hydrochloric acid to dissolve rare earth in the steps 5 and 6 for treating the lower batch, so that the consumption of hydrochloric acid is saved and the cost is saved; and 7, diluting the hydrochloric acid concentration of the batch material in the treatment of the washing water, and realizing the functions of energy conservation and emission reduction, wherein no waste water is discharged in the whole process.
Example 2
The praseodymium and neodymium metal polishing waste is recycled and treated according to the method of the embodiment 1, except that the first acidification time is 0.8h, the hydrochloric acid concentration is 0.8mol/L, the second acidification time is 2.0h, the third acidification time is 19h, the hydrochloric acid generated in the step 7 of the embodiment 1 is used for acidification in the step 6, the hydrochloric acid concentration is 1.62mol/L, the hydrochloric acid generated in the step 9 of the embodiment 1 is used for acidification in the step 8, and in coprecipitation, the leaching solutions of the steps 5 and 6 are mixed at 60 ℃ to obtain 74L of mixed leaching solution with the total concentration of praseodymium and neodymium ions of 35 g/L; adding pure water into a 150L reaction kettle, stirring after the pure water passes through a stirring paddle, adding a clear solution and 26L of oxalic acid solution with the mass concentration of 150g/L and the temperature of 45 ℃ into the reaction kettle at the same time, and performing coprecipitation (mixing supernatant and oxalic acid solution, and indicating complete coprecipitation reaction when no precipitate is generated) for 70min; 15.02kg of solid (rare earth element mass percentage content is 0.08%) iron, 2.53kg of praseodymium neodymium oxide and 1.12kg of praseodymium neodymium fluoride are obtained.
Example 3
The praseodymium neodymium metal polishing waste is recycled according to the flow of FIG. 1.
The compositions of praseodymium-neodymium metal polishing wastes are shown in Table 3.
TABLE 3 Pr-Nd metal polishing waste composition
| Composition of the components | REO | F | C | Fe | Li | Other impurities |
| Mass percent (%) | 20.05％ | 0.98％ | 0.09％ | 78.62％ | 0.21％ | 0.05％ |
1. Screening: screening 20.0kg of praseodymium neodymium metal polishing waste by a vibrating screen (the aperture of the screen used is 90 meshes), wherein the quality of the undersize is 3.23kg, and the quality of the oversize is 16.77kg; the components of the oversize and undersize are shown in table 4;
TABLE 4 Components in post-Screen Pr-Nd metal polishing waste
| Screening profile | Composition of the components | REO | F | C | Fe | Li | Other impurities |
| Screen feeding | Mass percent (%) | 9.71 | 0.1 | 0.01 | 90.1 | 0.03 | 0.05 |
| Screen blanking | Mass percent (%) | 73.73 | 5.56 | 0.50 | 19.0 | 1.15 | 0.06 |
2. Washing: placing 16.77kg of oversize product into a tray inclined at 30 ℃, washing with 100L of tap water, flowing the washed washing liquid into a 150L reaction kettle below the tray, and retaining iron beads (water washing solid) in the tray;
3. wet magnetic separation: adding 60L of washing liquid in the step 2 into a 100L reaction kettle, starting a stirring paddle, adding 3.23kg of undersize, stirring at a rotating speed of 200r/min, opening a bottom valve of the reaction kettle after stirring is started, slowly adding the slurry into a magnetic separator (the magnetic separator is provided with two outlets, one is an iron outlet and the other is a rare earth waste outlet), carrying out magnetic separation according to the intensity of 900 gauss, transferring magnetic separation iron from the iron outlet into a 50L plastic barrel, transferring rare earth waste from the rare earth waste outlet into the 100L plastic barrel, and controlling the magnetic separation time to be 60min;
4. soaking the rare earth waste for 6 days by utilizing water after wet magnetic separation;
5. first acidification (acidified iron): adding tap water into a 100L reaction kettle, stopping adding the tap water by a stirring paddle, starting the stirring paddle, adding the iron beads in the step 2 and the magnetic iron in the step 3, stirring for 10min, adding 120L hydrochloric acid solution with the molar concentration of 0.6mol/L into the reaction kettle by a peristaltic pump, and acidifying (with stirring at the rotating speed of 160 r/min) for 0.7 h (the pH value of the acidified solution system is 1.5), so as to obtain solid iron and a first leaching solution; filtering and air-drying the leachate when the pH value of the leachate is 1 to obtain 14.62kg of solid iron (the content of rare earth elements is 0.07) and a first leachate;
6. second acidification (acidification of rare earth waste): pumping 5L of water subjected to wet magnetic separation in the step 3 into a 20L reaction kettle through a peristaltic pump, stopping adding the water after the water is removed by a stirring paddle, starting the stirring paddle, pouring rare earth waste into the reaction kettle, stirring the water for 10min at a rotating speed of 150r/min, and adding 8.5L of 6.0mol/L hydrochloric acid into the reaction kettle by a peristaltic pump to acidify for 1.5 hours (the pH value of a solution system after acidizing is 1.8) to obtain an acid insoluble substance and a second leaching solution; pumping the first leaching solution and the second leaching solution into a 100L plastic barrel, starting stirring, adding hydrochloric acid aqueous solution with the molar concentration of 7.0mol/L into a reaction kettle by adopting a peristaltic pump, stopping adding the hydrochloric acid aqueous solution when the molar concentration of hydrogen ions in the mixed solution is 0.3mol/L, and standing for clarifying for 15 hours;
7. co-precipitation: mixing the leaching solutions in the steps 5 and 6 at 45 ℃ to obtain 81L of mixed leaching solution with the total concentration of praseodymium and neodymium ions of 40 g/L; adding pure water into a 200L reaction kettle, stirring after the pure water is not stirred by a stirring paddle, simultaneously adding the clarified solution and 63L of oxalic acid solution with the mass concentration of 80g/L into the reaction kettle, and performing coprecipitation (mixing supernatant and oxalic acid solution, and indicating complete coprecipitation reaction when no precipitate is generated) for 80min; filtering the coprecipitated system; washing the filtered solid with water until the pH value of the washed solution is 7, and calcining at 950 ℃ for 5 hours to obtain praseodymium neodymium oxide, wherein the total mass of the praseodymium neodymium oxide is 3.21kg;
8. third acidification (highly purified acid insoluble): adding hydrochloric acid solution with the molar concentration of 8.0mol/L into a reaction kettle, wherein the mass ratio of the hydrochloric acid solution to the acid insoluble matter is 13:1, acidifying the acid insoluble matter by using the hydrochloric acid solution for 20 hours, and filtering; washing the filtered solid (iron oxide content less than 0.05% by mole, calculated here using iron oxide) with an aqueous hydrochloric acid solution having a molar concentration of 0.8 mol/L; drying the washed solid at 105 ℃ for 6 hours, and calcining at 750 ℃ for 3 hours to obtain praseodymium neodymium fluoride, wherein the total mass of the praseodymium neodymium fluoride is 0.68kg;
9. waste acid recycling: the mass concentration of ferrous iron in hydrochloric acid after impurity removal in the step 8 is 1.0g/L, oxygen is blown into the liquid through an air compressor, ferrous iron in the liquid is converted into ferric iron, and Fe is removed through N235 extraction 3+ After that, the iron content in the liquid is 0.12g/L, tap water can be added to dilute the liquid into hydrochloric acid with the concentration of 6.0mol/L, and the hydrochloric acid can be used as dilute concentration hydrochloric acid in the steps 5 and 6 of the next batch treatment, so that the recycling of resources is achieved;
10. recycling the wastewater: the supernatant produced in the step 7 can be used as the rare earth dissolved by the dilute hydrochloric acid in the step 6 for treating the lower batch and the washing water in the step 8 can be used as the rare earth dissolved by the dilute hydrochloric acid in the steps 5 and 6 for treating the lower batch, so that the consumption of the hydrochloric acid is reduced and the cost is saved; and 7, diluting the hydrochloric acid concentration of the batch material in the treatment of the washing water, and realizing the functions of energy conservation and emission reduction, wherein no waste water is discharged in the whole process.
Example 4
Praseodymium neodymium metal polishing waste is recycled and treated according to the method of the embodiment 2, except that the first acidification time is 0.9h, the second acidification time is 2.5h, the third acidification time is 18h, and the hydrochloric acid treated in the step 8 of the embodiment 2 is used for acidification in the step 5; in coprecipitation, the leaching solutions in the steps 5 and 6 are mixed at 40 ℃ to obtain 79L of mixed leaching solution with the total praseodymium and neodymium ion concentration of 40 g/L; adding pure water into a 150L reaction kettle, stirring after the pure water is not stirred by a stirring paddle, adding a clear solution and 41L of oxalic acid solution with the mass concentration of 120g/L and the temperature of 45 ℃ into the reaction kettle at the same time, and performing coprecipitation (mixing supernatant and oxalic acid solution, and indicating complete coprecipitation reaction when no precipitate is generated) for 60min; 14.46kg of solid (rare earth element mass percentage content is 0.08%) iron, 3.13kg of praseodymium neodymium oxide and 0.67kg of praseodymium neodymium fluoride are obtained.
Example 5
The praseodymium and neodymium metal polishing waste is recycled and treated according to the method of the embodiment 2, and the difference is that the first acidification time is 1.0h, the hydrochloric acid concentration is 1.0mol/L, the second acidification time is 3.0h, the third acidification time is 20h, and in the coprecipitation, the leaching solution of the steps 5 and 6 is mixed at 35 ℃ to obtain 66.5L of mixed leaching solution with the total concentration of praseodymium and neodymium ions of 46.4 g/L; adding pure water into a 150L reaction kettle, stirring after the pure water is not stirred by a stirring paddle, adding a clear solution and 46L of oxalic acid solution with the mass concentration of 100g/L and the temperature of 45 ℃ into the reaction kettle at the same time, and performing coprecipitation (mixing supernatant and oxalic acid solution, and indicating complete coprecipitation reaction when no precipitate is generated) for 60min; 14.15kg of solid (rare earth element content of 0.09%) iron, 3.05kg of praseodymium neodymium oxide and 0.65kg of praseodymium neodymium fluoride are obtained.
The components of praseodymium neodymium oxide and praseodymium neodymium fluoride in examples 1 to 5 were examined by a conventional chemical method, and the results are shown in Table 5.
Components in praseodymium neodymium oxide and praseodymium neodymium fluoride recovered in Table 5
The recovery rate was calculated and the results are shown in Table 6.
TABLE 6 recovery rates for examples 1-5
As can be seen from the combination of tables 5 and 6, the praseodymium neodymium oxide and praseodymium neodymium fluoride obtained by the recovery treatment method provided by the invention have higher purity and higher recovery rates of praseodymium, neodymium and iron.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. A praseodymium neodymium metal polishing waste recycling method comprises the following steps:
screening praseodymium neodymium metal polishing scraps by a mesh screen to obtain oversize products and undersize products;
carrying out magnetic separation on the undersize to obtain magnetic separation iron and rare earth waste;
firstly mixing the oversize material, the magnetic iron and the first acid solution, and carrying out first acidification to obtain solid iron and a first leaching solution, wherein the molar concentration of the first acid solution is 0.5-1 mol/L, and the first acidification time is 50-70 min;
second mixing the rare earth waste and a second acid solution, and performing second acidification to obtain an acid insoluble substance and a second leaching solution;
thirdly mixing the first leaching solution, the second leaching solution and the third acid solution to obtain a clear solution;
fourthly, mixing the clarified solution with oxalic acid solution for coprecipitation, and calcining solid obtained by coprecipitation to obtain praseodymium neodymium oxide;
and fifthly, mixing the acid insoluble matter with a fourth acid solution, performing third acidification, and calcining the solid after the third acidification to obtain praseodymium neodymium fluoride.
2. The recycling method according to claim 1, wherein the first mixing step further comprises: washing the oversize material to obtain washed solid and washing liquid; the water-washed solids, the magnetic iron and the first acid solution are first mixed.
3. The recovery processing method according to claim 2, further comprising adding the washing liquid to the magnetic separation process.
4. The recovery processing method according to claim 1, wherein the first acid solution includes an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, or an aqueous nitric acid solution.
5. The recovery process of claim 1 or 4, wherein the pH of the first acidified solution system is from 1 to 2.
6. The recovery processing method according to claim 1, wherein the second acid solution comprises an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the molar concentration of the second acid solution is 0.5 to 8mol/L.
7. The recovery treatment method according to claim 1 or 6, wherein the second acidification time is 1 to 5 hours;
the pH value of the second acidified solution system is 1-2.
8. The recovery processing method according to claim 1, wherein the third acid solution comprises an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the molar concentration of the third acid solution is 5 to 6mol/L; the concentration of the acid in the third mixed solution is 0.1-0.5 mol/L.
9. The recovery processing method according to claim 1, wherein the fourth acid solution comprises an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution and an aqueous nitric acid solution, and the concentration of the fourth acid solution is 6 to 8mol/L; the mass ratio of the acid insoluble matter to the fourth acid solution is 1:5-10.
10. The recycling method according to claim 1, wherein the content of iron in the praseodymium-neodymium metal polishing waste is 70-85% by mass, the content of praseodymium-neodymium element in the praseodymium-neodymium metal polishing waste is 13-29% by mass, the content of fluorine in the praseodymium-neodymium metal polishing waste is 0.8-2.0% by mass, and the content of carbon in the praseodymium-neodymium metal polishing waste is 0.01-0.05% by mass.
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