CN104805292A - Method for separating and recovering valuable components from rare earth praseodymium-neodymium fused salt electrolysis waste - Google Patents
Method for separating and recovering valuable components from rare earth praseodymium-neodymium fused salt electrolysis waste Download PDFInfo
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Abstract
The invention discloses a separating and recovering method for separating valuable components in rare earth praseodymium-neodymium fused salt electrolysis waste into a liquid phase (praseodymium-neodymium chloride) and a solid phase (praseodymium-neodymium fluoride) by adopting leaching by low-concentration hydrochloric acid. The method is characterized by comprising steps of raw materials processing, beating and leaching to obtain filter residues containing praseodymium-neodymium fluoride and filtrate containing praseodymium-neodymium chloride; the filter residues containing praseodymium-neodymium fluoride are washed to neutral and dried at the temperature of 60-80 DEG C to obtain praseodymium-neodymium fluoride; the filtrate containing praseodymium-neodymium chloride is subjected to crystallization and precipitation with an oxalic acid method to obtain praseodymium-neodymium oxalate, and the obtained praseodymium-neodymium oxalate is burnt at the temperature of 950 DEGC and degraded to obtain praseodymium-neodymium oxide. By means of the characteristic that rare earth fluoride does not react with hydrochloric acid, the low-concentration hydrochloric acid is used for leaching soluble impurities and oxides, a rare earth fluoride structure is not required to be damaged with high-temperature strong acid or strong base, and the valuable components are recycled; compared with the traditional concentrated sulfuric acid roasting method or strong base roasting method, the method omits a roasting process, a follow-up feed liquid is not required to be subjected to an extraction process, so that the method has the characteristics of simple process, short process flow, low cost, high yield and environment-friendliness, and the fluorine element is recycled efficiently.
Description
Technical field
The present invention relates to separation and the recovery method of valuable constituent in a kind of rare earth waste, the specifically separation of valuable constituent and recovery method in a kind of praseodymium neodymium fused salt electrolysis waste material, particularly relate to and a kind of adopt low concentration of salt Acid leaching, valuable constituent in praseodymium neodymium fused salt electrolysis waste material is separated into being separated and recovery method of liquid phase (praseodymium chloride neodymium) and solid phase (praseodymium fluoride neodymium).
Background technology
Rare earth element is due to its special electronic structure, there is the feature such as 4f track and lanthanide contraction of underfilling electronics, and optical, electrical, the magnetic had not available for other elements many and heat effect, be called as " treasure-house of novel material ", be widely used in the industries such as permanent magnetism, metallurgy, polishing powder, fluorescent material, catalyzer, function ceramics, rubber and plastics auxiliaries and hydrogen storage material, therefore, rare earth has again the good reputation of " industrial monosodium glutamate ".Especially in recent years the demand of development to Nd-Fe-Bo permanent magnet material of information technology constantly increases, and causes the demand of praseodymium neodymium metal also increasing.At present, rare earth oxide-fluoride system electrolysis process has become current most important and topmost production technique of producing rare earth metal and alloy.Can produce the waste cell melt of about 5 ﹪ in electrolytic process, its total amount of rare earth is about 60 ﹪ ~ 85 ﹪, is a kind of mixture, and in composition, major part is rare earth fluorine and rare earth oxide, and a small amount of rare earth metal.
Because the structure of rare earth fluorine is highly stable, this waste cell melt based on rare earth fluorine of traditional recycling, common process means are concentrated sulfuric acid roasting methods.Namely under the condition of high-temperature and highly acidity, open its molecular structure, obtain solubility sulfuric acid rare earth, then through a series of processes such as purification by liquid extraction, crystalline deposit and calcinations, finally reclaim with rare earth oxide form.Not only technique is mixed, and process is many, and yield is low, and HF, SO of producing in roasting process
2be difficult to reclaim Deng gas, environmental pollution is large, and fluorine element wherein is also not used.
The patent No. is 201010505807.2, denomination of invention is a kind of a kind of method that patent discloses Separation and Recovery rare earth element from molten salt electrolysis wastes of method of Separation and Recovery rare earth element from molten salt electrolysis wastes, and it adopts the mode of highly basic roasting to destroy the molecular structure of rare earth fluorine.Its essence is exactly that the vitriol oil in traditional roasting process of sulfuric acid is replaced to calcium hydroxide to carry out roasting, and then through dissolving with hydrochloric acid, extracting and separating, the technique of crystalline deposit reaches the object of recovering rare earth element, and the fluorine simultaneously in waste material makes the transition as Calcium Fluoride (Fluorspan).Although this technique avoids the waste gas of technique generation to the pollution of environment, but the result of calcification baking causes calcium constituent to be incorporated in system, and in acid-soluble feed liquid, the content of CaO has exceeded 10g/L, follow-up having to adopts the means of extraction to drag for rare earth deliming, technical process is long, and processing cost is high.
Summary of the invention
The object of this invention is to provide a kind of separation and recovery method of praseodymium neodymium fused salt electrolysis waste material valuable constituent, particularly a kind ofly adopt low concentration of salt Acid leaching, valuable constituent in praseodymium neodymium fused salt electrolysis waste material is separated into being separated and recovery method of liquid phase (praseodymium chloride neodymium) and solid phase (praseodymium fluoride neodymium).
The present invention adopts following technical scheme to realize its goal of the invention, and the separation method of valuable constituent in a kind of praseodymium neodymium fused salt electrolysis waste material, it comprises the following steps:
(1) Feedstock treating: produce the waste material of praseodymium neodymium metal generation for raw material with fused salt electrolysis process, obtain powder by after raw material crushing;
(2) pull an oar: by weight, by step (1) gained powder add pure water by solid-to-liquid ratio 1:1 ~ 2 and be uniformly mixed form slurry;
(3) leach: under room temperature, in step (2) gained slurry, add the hydrochloric acid that concentration is 1.0mol/L ~ 2.0mol/L, limit edged stirs, and when the pH value to solution is 1.0 ~ 1.5, stops acid adding, continue stirring reaction 2h ~ 4h, filter and obtain the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
For the benefit of in slurry dissolvable oxides especially non-rare earth impurity composition leached, the present invention step (1) in, the granularity of described powder is more than 325 orders.
Acid soluble impurities for the benefit of in slurry and oxide slag leach in solution, the present invention step (3) in, stop after acid adding, first slurries be warmed up to 60 DEG C ~ 80 DEG C, then continue stirring reaction 2h ~ 4h.
A recovery method for valuable constituent in praseodymium neodymium fused salt electrolysis waste material, it comprises the following steps:
(1) Feedstock treating: produce the waste material of praseodymium neodymium metal generation for raw material with fused salt electrolysis process, obtain powder by after raw material crushing;
(2) pull an oar: by weight, by step (1) gained powder add pure water by solid-to-liquid ratio 1:1 ~ 2 and be uniformly mixed form slurry;
(3) leach: under room temperature, in step (2) gained slurry, add the hydrochloric acid that concentration is 1.0mol/L ~ 2.0mol/L, limit edged stirs, and when the pH value to solution is 1.0 ~ 1.5, stops acid adding, continue stirring reaction 2h ~ 4h, filter and obtain the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium;
(4) filter residue process: by the filter residue of fluorinated praseodymium neodymium through being washed to neutrality, dries, obtains praseodymium fluoride neodymium at 60 DEG C ~ 80 DEG C;
(5) filtrate process: adopt Oxalic Acid Method crystalline deposit to obtain praseodymium oxalate neodymium, the calcination at 950 DEG C of gained praseodymium oxalate neodymium to the filtrate of chloride containing praseodymium neodymium, decompose and obtain praseodymium neodymium oxide.
For the benefit of in slurry dissolvable oxides especially non-rare earth impurity composition leached, the present invention step (1) in, the granularity of described powder is more than 325 orders.
Acid soluble impurities for the benefit of in slurry and oxide slag leach in solution, the present invention step (3) in, stop after acid adding, first slurries be warmed up to 60 DEG C ~ 80 DEG C, then continue stirring reaction 2h ~ 4h.
For water saving, reduce costs, the present invention step (4) in, when filter residue is washed, wash water return step (2) the section of making beating do pure water use.
Owing to adopting technique scheme, the present invention achieves goal of the invention preferably, utilize rare earth fluorine not with the characteristic of hydrochloric acid reaction, take low concentration of salt Ore Leaching soluble impurity and oxide compound, rare earth fluoride structure is destroyed under not needing high-temperature strong acid or highly basic, reach the object recycling valuable constituent, compare with highly basic roasting method with traditional concentrated sulfuric acid roasting method, decrease roasting process, follow-up feed liquid does not also need extraction process, there is technique simple, flow process is short, cost is low, yield is high, eco-friendly feature, and recycle fluorine element wherein efficiently.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
A separation method for valuable constituent in praseodymium neodymium fused salt electrolysis waste material, it comprises the following steps:
(1) Feedstock treating: produce the waste material of praseodymium neodymium metal generation for raw material with fused salt electrolysis process, obtain powder by after raw material crushing;
The invention will be further described for the molten salt electrolysis wastes of Hunan Rare Earth Factory for the present embodiment, and the total amount of rare earth of this ionogen waste material and major impurity content analysis result are as table 1 (unit: ﹪):
Table 1 electrolysis Scrap analysis result
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 80.65 | 0.49 | 0.02 | 1.14 | 0.50 |
For the benefit of in slurry dissolvable oxides especially non-rare earth impurity composition leached, the present invention step (1) in, the granularity of described powder is more than 325 orders.
The granularity of powder described in the present embodiment is 400 orders.
(2) pull an oar: by weight, by step (1) gained powder add pure water by solid-to-liquid ratio 1:1 ~ 2 and be uniformly mixed form slurry;
(3) leach: under room temperature, in step (2) gained slurry, add the hydrochloric acid that concentration is 1.0mol/L ~ 2.0mol/L, limit edged stirs, and when the pH value to solution is 1.0 ~ 1.5, stops acid adding, continue stirring reaction 2h ~ 4h, filter and obtain the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
The present embodiment gets powder 1 ㎏ in beaker, add 2 ㎏ pure water to mix, under room temperature, stir the hydrochloric acid adding 1mol/L, until stop acid adding when final ph remains on 1.0 ~ 1.5, continue stirring reaction 2h, filter and obtain the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
A recovery method for valuable constituent in praseodymium neodymium fused salt electrolysis waste material, it comprises the following steps:
(1) Feedstock treating: produce the waste material of praseodymium neodymium metal generation for raw material with fused salt electrolysis process, obtain powder by after raw material crushing;
The invention will be further described for the molten salt electrolysis wastes of Hunan Rare Earth Factory for the present embodiment, and the total amount of rare earth of this ionogen waste material and major impurity content analysis result are as table 1 (unit: ﹪):
Table 1 electrolysis Scrap analysis result
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 80.65 | 0.49 | 0.02 | 1.14 | 0.50 |
For the benefit of in slurry dissolvable oxides especially non-rare earth impurity composition leached, the present invention step (1) in, the granularity of described powder is more than 325 orders.
The granularity of powder described in the present embodiment is 400 orders.
(2) pull an oar: by weight, by step (1) gained powder add pure water by solid-to-liquid ratio 1:1 ~ 2 and be uniformly mixed form slurry;
(3) leach: under room temperature, in step (2) gained slurry, add the hydrochloric acid that concentration is 1.0mol/L ~ 2.0mol/L, limit edged stirs, and when the pH value to solution is 1.0 ~ 1.5, stops acid adding, continue stirring reaction 2h ~ 4h, filter and obtain the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium;
(4) filter residue process: by the filter residue of fluorinated praseodymium neodymium through being washed to neutrality, dries, obtains praseodymium fluoride neodymium at 60 DEG C ~ 80 DEG C;
For water saving, reduce costs, the present invention step (4) in, when filter residue is washed, wash water return step (2) the section of making beating do pure water use.
(5) filtrate process: adopt Oxalic Acid Method crystalline deposit to obtain praseodymium oxalate neodymium, the calcination at 950 DEG C of gained praseodymium oxalate neodymium to the filtrate of chloride containing praseodymium neodymium, decompose and obtain praseodymium neodymium oxide.
The present embodiment gets powder 1 ㎏ in beaker, add 2 ㎏ pure water to mix, under room temperature, stir the hydrochloric acid adding 1mol/L, until stop acid adding when final ph remains on 1.0 ~ 1.5, continue stirring reaction 2h, filter and obtain the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
Filter residue is washed to neutrality, dries at 80 DEG C, obtain praseodymium fluoride neodymium 542.8g.Its composition analysis result is in table 2 (unit: ﹪):
Table 2: embodiment 1 praseodymium fluoride neodymium analytical results
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 81.50 | 0.15 | 0.08 | 0.24 | 0.17 |
Obtain the filtrate 6.50L of chloride containing praseodymium neodymium, concentration (TREO) is 55.7g/L, add saturated oxalic acid solution after 75 DEG C are heated to filtrate and carry out crystalline deposit, filter to obtain praseodymium oxalate neodymium, gained praseodymium oxalate neodymium is with after hot wash 3 times, calcination 2h at 950 DEG C in retort furnace, decomposes and obtains praseodymium neodymium oxide 351.2g.Its composition analysis result is in table 3 (unit: ﹪):
Table 3: embodiment 1 praseodymium neodymium oxide analytical results
| TREO | Pr 6O 11 | Nd 2O 3 | SO 4 2- | Cl - | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 99.15 | 18.18 | 81.75 | 0.017 | 0.030 | 0.014 | 0.005 | 0.048 | 0.020 |
Calculated by above-mentioned data, the weight (REO) of known institute recovering rare earth is 542.8 × 81.50 ﹪+351.2 × 99.15 ﹪=790.60g, and the total recovery of rare earth is 98.02 ﹪.
Embodiment 2:
Acid soluble impurities for the benefit of in slurry and oxide slag leach in solution, the step of the present invention's separation method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material (3) in, after stopping acid adding, first slurries are warmed up to 60 DEG C ~ 80 DEG C, then continue stirring reaction 2h ~ 4h.
Acid soluble impurities for the benefit of in slurry and oxide slag leach in solution, the step of the present invention's recovery method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material (3) in, after stopping acid adding, first slurries are warmed up to 60 DEG C ~ 80 DEG C, then continue stirring reaction 2h ~ 4h.
The present embodiment is warmed up to 60 DEG C by slurries after stopping acid adding, and continue stirring reaction 2h, pH value is almost unchanged, filters and obtains the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
Filter residue is washed to neutrality, dries at 60 DEG C, obtain praseodymium fluoride neodymium 540.5g.Its composition analysis result is in table 4 (unit: ﹪):
Table 4: embodiment 2 praseodymium fluoride neodymium analytical results
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 82.01 | 0.10 | 0.06 | 0.05 | 0.06 |
Obtain the filtrate 6.30L of chloride containing praseodymium neodymium, concentration (TREO) is 56.0g/L, add saturated oxalic acid solution after 75 DEG C are heated to filtrate and carry out crystalline deposit, filter to obtain praseodymium oxalate neodymium, gained praseodymium oxalate neodymium is with after hot wash 3 times, in retort furnace at 950 DEG C calcination 2h, decompose obtain praseodymium neodymium oxide 347.8g, quality is up to state standards.Its composition analysis result is in table 5 (unit: ﹪):
Table 5: embodiment 2 praseodymium neodymium oxide analytical results
| TREO | Pr 6O 11 | Nd 2O 3 | SO 4 2- | Cl - | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 99.35 | 18.20 | 81.65 | 0.017 | 0.033 | 0.015 | 0.005 | 0.049 | 0.018 |
Calculated by above-mentioned data, the total recovery of rare earth is 98.09 ﹪.
Remaining with embodiment 1.
The present invention utilize rare earth fluorine not with the characteristic of hydrochloric acid reaction, take low concentration of salt Ore Leaching soluble impurity and oxide compound, under not needing high-temperature strong acid or highly basic, destroy rare earth fluoride structure, reach the object recycling valuable constituent, compare with highly basic roasting method with traditional concentrated sulfuric acid roasting method, decrease roasting process, follow-up feed liquid does not also need extraction process, there is technique simple, flow process is short, and cost is low, and yield is high, eco-friendly feature, and recycled fluorine element wherein efficiently.
Embodiment 3:
The present embodiment gets powder 1 ㎏ in beaker, adds 2 ㎏ pure water and mixes, stir the hydrochloric acid adding 2mol/L under room temperature, until stop acid adding when final ph remains on 1.0 ~ 1.5, slurries are warmed up to 60 DEG C, and continue stirring reaction 2h, pH value is almost unchanged; Filtration obtains filter residue and filtrate.
Filter residue is washed to neutrality, dries at 70 DEG C, obtain praseodymium fluoride neodymium 534.9g.Its composition analysis result is in table 6 (unit: ﹪):
Table 6: embodiment 3 praseodymium fluoride neodymium analytical results
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 82.50 | 0.06 | 0.05 | 0.07 | 0.05 |
Obtain the filtrate 3.21L of chloride containing praseodymium neodymium, concentration (TREO) is 110.5g/L, add saturated oxalic acid solution after 75 DEG C are heated to filtrate and carry out crystalline deposit, filter to obtain praseodymium oxalate neodymium, gained praseodymium oxalate neodymium is with after hot wash 3 times, in retort furnace at 950 DEG C calcination 2h, decompose obtain praseodymium neodymium oxide 349.9g, quality is up to state standards.Its composition analysis result is in table 7 (unit: ﹪):
Table 7: embodiment 3 praseodymium neodymium oxide analytical results
| TREO | Pr 6O 11 | Nd 2O 3 | SO 4 2- | Cl - | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 99.30 | 18.21 | 81.70 | 0.015 | 0.032 | 0.012 | 0.002 | 0.050 | 0.010 |
Calculated by above-mentioned data, the total recovery of rare earth is 97.80 ﹪.
Remaining with embodiment 1,2.
Embodiment 4:
The present embodiment gets powder 1 ㎏ in beaker, adds 2 ㎏ pure water and mixes, stir the hydrochloric acid adding 2mol/L under room temperature, until stop acid adding when final ph remains on 1.0 ~ 1.5, slurries are warmed up to 60 DEG C, and continue stirring reaction 4h, pH value is almost unchanged; Filtration obtains filter residue and filtrate.
Filter residue is washed to neutrality, dries at 80 DEG C, obtain praseodymium fluoride neodymium 533.8g.Its composition analysis result is in table 8 (unit: ﹪):
Table 8: embodiment 4 praseodymium fluoride neodymium analytical results
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 82.40 | 0.05 | 0.04 | 0.07 | 0.05 |
Obtain the filtrate 3.19L of chloride containing praseodymium neodymium, concentration (TREO) is 112.0g/L, add saturated oxalic acid solution after 75 DEG C are heated to filtrate and carry out crystalline deposit, filter to obtain praseodymium oxalate neodymium, gained praseodymium oxalate neodymium is with after hot wash 3 times, in retort furnace at 950 DEG C calcination 2h, decompose obtain praseodymium neodymium oxide 353.1g, quality is up to state standards.Its composition analysis result is in table 9 (unit: ﹪):
Table 9: embodiment 4 praseodymium neodymium oxide analytical results
| TREO | Pr 6O 11 | Nd 2O 3 | SO 4 2- | Cl - | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 99.25 | 18.21 | 81.74 | 0.013 | 0.038 | 0.011 | 0.003 | 0.047 | 0.010 |
Calculated by above-mentioned data, the total recovery of rare earth is 98.00 ﹪.
Remaining with embodiment 1,2.
Embodiment 5:
The present embodiment gets powder 1 ㎏ in beaker, adds 2 ㎏ pure water and mixes, stir the hydrochloric acid adding 2mol/L under room temperature, until stop acid adding when final ph remains on 1.0 ~ 1.5, slurries are warmed up to 80 DEG C, and continue stirring reaction 2h, pH value is almost unchanged; Filtration obtains filter residue and filtrate.
Filter residue is washed to neutrality, dries at 60 DEG C, obtain praseodymium fluoride neodymium 533.0g.Its composition analysis result is in table 10 (unit: ﹪):
Table 10: embodiment 5 praseodymium fluoride neodymium analytical results
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 82.30 | 0.06 | 0.05 | 0.05 | 0.06 |
Obtain the filtrate 3.01L of chloride containing praseodymium neodymium, concentration (TREO) is 119.2g/L, add saturated oxalic acid solution after 75 DEG C are heated to filtrate and carry out crystalline deposit, filter to obtain praseodymium oxalate neodymium, gained praseodymium oxalate neodymium is with after hot wash 3 times, in retort furnace at 950 DEG C calcination 2h, decompose obtain praseodymium neodymium oxide 354.0g, quality is up to state standards.Its composition analysis result is in table 11 (unit: ﹪):
Table 11: embodiment 5 praseodymium neodymium oxide analytical results
| TREO | Pr 6O 11 | Nd 2O 3 | SO 4 2- | Cl - | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 99.40 | 18.22 | 81.72 | 0.016 | 0.036 | 0.014 | 0.004 | 0.050 | 0.011 |
Calculated by above-mentioned data, the total recovery of rare earth is 98.03 ﹪.
Remaining with embodiment 1,2.
Embodiment 6:
The present embodiment gets powder 1 ㎏ in beaker, adds 2 ㎏ pure water and mixes, stir the hydrochloric acid adding 2mol/L under room temperature, until stop acid adding when final ph remains on 1.0 ~ 1.5, slurries are warmed up to 80 DEG C, and continue stirring reaction 4h, pH value is almost unchanged; Filtration obtains filter residue and filtrate.
Filter residue is washed to neutrality, dries at 75 DEG C, obtain praseodymium fluoride neodymium 532.5g.Its composition analysis result is in table 12 (unit: ﹪):
Table 12: embodiment 6 praseodymium fluoride neodymium analytical results
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 82.35 | 0.05 | 0.04 | 0.06 | 0.04 |
Obtain the filtrate 2.98L of chloride containing praseodymium neodymium, concentration (TREO) is 121.1g/L, add saturated oxalic acid solution after 75 DEG C are heated to filtrate and carry out crystalline deposit, filter to obtain praseodymium oxalate neodymium, gained praseodymium oxalate neodymium is with after hot wash 3 times, in retort furnace at 950 DEG C calcination 2h, decompose obtain praseodymium neodymium oxide 354.1g, quality is up to state standards.Its composition analysis result is in table 13 (unit: ﹪):
Table 13: embodiment 6 praseodymium neodymium oxide analytical results
| TREO | Pr 6O 11 | Nd 2O 3 | SO 4 2- | Cl - | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 99.45 | 18.18 | 81.75 | 0.018 | 0.030 | 0.012 | 0.003 | 0.037 | 0.015 |
Calculated by above-mentioned data, the total recovery of rare earth is 98.04 ﹪.
Remaining with embodiment 1,2.
Embodiment 7:
The present embodiment gets powder 1 ㎏ in beaker, adds 2 ㎏ pure water and mixes, stir the hydrochloric acid adding 2mol/L under room temperature, until stop acid adding when final ph remains on 1.0 ~ 1.5, slurries are warmed up to 75 DEG C, and continue stirring reaction 4h, pH value is almost unchanged; Filtration obtains filter residue and filtrate.
Filter residue is washed to neutrality, dries at 80 DEG C, obtain praseodymium fluoride neodymium 540.0g.Its composition analysis result is in table 14 (unit: ﹪):
Table 14: embodiment 7 praseodymium fluoride neodymium analytical results
| TREO | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 82.05 | 0.04 | 0.04 | 0.05 | 0.04 |
Obtain filtrate 2.92 ㎏ of chloride containing praseodymium neodymium, concentration (TREO) is 120.3g/L, add saturated oxalic acid solution after 75 DEG C are heated to filtrate and carry out crystalline deposit, filter to obtain praseodymium oxalate neodymium, gained praseodymium oxalate neodymium is with after hot wash 3 times, in retort furnace at 950 DEG C calcination 2h, decompose obtain praseodymium neodymium oxide 346.6g, quality is up to state standards.Its composition analysis result is in table 15 (unit: ﹪):
Table 15: embodiment 7 praseodymium neodymium oxide analytical results
| TREO | Pr 6O 11 | Nd 2O 3 | SO 4 2- | Cl - | Fe 2O 3 | SiO 2 | CaO | Al 2O 3 |
| 99.35 | 18.25 | 81.66 | 0.017 | 0.035 | 0.013 | 0.002 | 0.042 | 0.016 |
Calculated by above-mentioned data, the total recovery of rare earth is 97.60 ﹪.
Remaining with embodiment 1,2.
Claims (7)
1. the separation method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material, is characterized in that it comprises the following steps:
(1) Feedstock treating: produce the waste material of praseodymium neodymium metal generation for raw material with fused salt electrolysis process, obtain powder by after raw material crushing;
(2) pull an oar: by weight, by step (1) gained powder add pure water by solid-to-liquid ratio 1:1 ~ 2 and be uniformly mixed form slurry;
(3) leach: under room temperature, in step (2) gained slurry, add the hydrochloric acid that concentration is 1.0mol/L ~ 2.0mol/L, limit edged stirs, and when the pH value to solution is 1.0 ~ 1.5, stops acid adding, continue stirring reaction 2h ~ 4h, filter and obtain the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
2. the separation method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material according to claim 1, it is characterized in that step (1) in, the granularity of described powder is more than 325 orders.
3. the separation method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material according to claim 1, it is characterized in that step (3) in, after stopping acid adding, first slurries are warmed up to 60 DEG C ~ 80 DEG C, then continue stirring reaction 2h ~ 4h.
4. the recovery method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material, is characterized in that it comprises the following steps:
(1) Feedstock treating: produce the waste material of praseodymium neodymium metal generation for raw material with fused salt electrolysis process, obtain powder by after raw material crushing;
(2) pull an oar: by weight, by step (1) gained powder add pure water by solid-to-liquid ratio 1:1 ~ 2 and be uniformly mixed form slurry;
(3) leach: under room temperature, in step (2) gained slurry, add the hydrochloric acid that concentration is 1.0mol/L ~ 2.0mol/L, limit edged stirs, and when the pH value to solution is 1.0 ~ 1.5, stops acid adding, continue stirring reaction 2h ~ 4h, filter and obtain the filter residue of fluorinated praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium;
(4) filter residue process: by the filter residue of fluorinated praseodymium neodymium through being washed to neutrality, dries, obtains praseodymium fluoride neodymium at 60 DEG C ~ 80 DEG C;
(5) filtrate process: adopt Oxalic Acid Method crystalline deposit to obtain praseodymium oxalate neodymium, the calcination at 950 DEG C of gained praseodymium oxalate neodymium to the filtrate of chloride containing praseodymium neodymium, decompose and obtain praseodymium neodymium oxide.
5. the recovery method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material according to claim 4, it is characterized in that step (1) in, the granularity of described powder is more than 325 orders.
6. the recovery method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material according to claim 4, it is characterized in that step (3) in, after stopping acid adding, first slurries are warmed up to 60 DEG C ~ 80 DEG C, then continue stirring reaction 2h ~ 4h.
7. the recovery method of valuable constituent in praseodymium neodymium fused salt electrolysis waste material according to claim 4, it is characterized in that step (4) in, when filter residue is washed, wash water return step (2) the section of making beating do pure water and use.
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| CN105567985A (en) * | 2015-12-28 | 2016-05-11 | 江苏金石稀土有限公司 | Recovery method of rare earth metal electrolysis fused salt slag |
| CN114921668A (en) * | 2022-06-30 | 2022-08-19 | 包头稀土研究院 | Method for reducing rare earth content in rare earth iron boron waste hydrochloric acid preferential-dissolution iron slag |
| CN116043016A (en) * | 2022-07-19 | 2023-05-02 | 江苏南方永磁科技有限公司 | Preparation method and application of neodymium oxide |
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