CN104805292B - 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
- Publication number
- CN104805292B CN104805292B CN201510181745.7A CN201510181745A CN104805292B CN 104805292 B CN104805292 B CN 104805292B CN 201510181745 A CN201510181745 A CN 201510181745A CN 104805292 B CN104805292 B CN 104805292B
- Authority
- CN
- China
- Prior art keywords
- neodymium
- praseodymium
- fluoride
- rare earth
- salt electrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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 the separation of valuable constituent and recovery method, specifically a kind of praseodymium in a kind of rare earth waste
The separation of valuable constituent and recovery method in neodymium molten-salt electrolysis waste material, it is more particularly to a kind of to adopt low concentration of salt Acid leaching, will
Valuable constituent is separated into liquid phase in praseodymium neodymium molten-salt electrolysis waste material（Praseodymium chloride neodymium）And solid phase（Praseodymium fluoride neodymium）Separation and return
Receiving method.
Background technology
Rare earth element due to its special electronic structure, the feature such as the 4f tracks with underfill electronics and lanthanide contraction,
And there is light not available for many other elements, electricity, magnetic and heat effect, and it is referred to as " treasure-house of new material ", it is widely used in
The industries such as permanent magnetism, metallurgy, polishing powder, fluorescent material, catalyst, function ceramics, rubber and plastics auxiliaries and hydrogen storage material, therefore, rare earth is again
There is the good reputation of " industrial monosodium glutamate ".Especially in recent years the development of information technology is continuously increased to the demand of Nd-Fe-B permanent magnet material, causes
Make the demand of praseodymium neodymium metal also increasing.At present, rare earth oxide-fluoride system electrolysis process has become current production
The most important and topmost production technology of rare earth metal and alloy.The waste cell melt of 5 ﹪ or so can be produced in electrolytic process, its
Total amount of rare earth is about 60 ﹪～85 ﹪, is a kind of mixture, and major part is rare earth fluoride and rare earth oxide in composition, and
A small amount of rare earth metal.
Due to this useless electricity based on rare earth fluoride of recycling that the structure of rare earth fluoride is highly stable, traditional
Xie Zhi, common processing means are concentrated sulfuric acid roasting methods.Its molecular structure is opened under conditions of high-temperature and highly acidity, is obtained
To solubility sulfuric acid rare earth, then through a series of processes such as purification by liquid extraction, crystalline deposit and calcination, finally with rare earth oxide shape
Formula is reclaimed.Not only technique is miscellaneous, and process is more, and yield is low, and HF, the SO produced in roasting process2It is difficult to reclaim Deng gas, environment
Pollution is big, and fluorine element therein is also not used.
Patent No. 201010505807.2, entitled one kind separates and recovers rare earth from molten salt electrolysis wastes
The patent of the method for element discloses a kind of method that rare earth element is separated and recovered from molten salt electrolysis wastes, and it is using strong
The mode of alkali roasting is destroying the molecular structure of rare earth fluoride.Its essence is exactly by the dense sulfur in traditional roasting process of sulfuric acid
Acid is substituted for calcium hydroxide to carry out roasting, then Jing dissolving with hydrochloric acid, and extract and separate, the technique of crystalline deposit reaches recovering rare earth
The purpose of element, while the fluorine in waste material is transformed into calcium fluoride.Although the technique avoid the waste gas of technique generation to environment
Pollution, but the result of calcification baking causes calcium constituent is incorporated in system, and the content of CaO has exceeded 10g/ in sour molten feed liquid
L, subsequently has to drag for rare earth deliming using the means of extraction, and technological process is long, and processing cost is high.
The content of the invention
It is an object of the invention to provide a kind of separation of praseodymium neodymium molten-salt electrolysis waste material valuable constituent and recovery method, special
It is not a kind of using low concentration of salt Acid leaching, valuable constituent in praseodymium neodymium molten-salt electrolysis waste material is separated into into liquid phase（Praseodymium chloride
Neodymium）And solid phase（Praseodymium fluoride neodymium）Separation and recovery method.
The present invention adopts the following technical scheme that and realizes its goal of the invention have in a kind of praseodymium neodymium molten-salt electrolysis waste material
The separation method of valency composition, it comprises the following steps：
(1) Feedstock treating：The waste material of praseodymium neodymium metal generation is produced as raw material with fused salt electrolysis process, after raw material is crushed
Obtain powder；
(2) it is beaten：By weight, by step, (1) gained powder presses solid-to-liquid ratio 1：1～2 adds pure water stirring to be mixed into slurry；
(3) leach：Under room temperature concentration is added for the hydrochloric acid of 1.0mol/L～2.0mol/L, side toward step (2) gained slurry
Edged stir, to solution pH value be 1.0～1.5 when, stop acid adding, continue stirring reaction 2h～4h, be filtrated to get containing fluorination
The filtering residue of praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
For the benefit of in slurry dissolvable oxides especially non-rare earth impurity composition is leached, the present invention step (1) in,
The granularity of the powder is more than 325 mesh.
For the benefit of the acid soluble impurities and oxide slag in slurry are leached in solution, the present invention step (3) in, stop
After acid adding, first serosity is warmed up to into 60 DEG C～80 DEG C, is further continued for stirring reaction 2h～4h.
The recovery method of valuable constituent in a kind of praseodymium neodymium molten-salt electrolysis waste material, it comprises the following steps：
(1) Feedstock treating：The waste material of praseodymium neodymium metal generation is produced as raw material with fused salt electrolysis process, after raw material is crushed
Obtain powder；
(2) it is beaten：By weight, by step, (1) gained powder presses solid-to-liquid ratio 1：1～2 adds pure water stirring to be mixed into slurry；
(3) leach：Under room temperature concentration is added for the hydrochloric acid of 1.0mol/L～2.0mol/L, side toward step (2) gained slurry
Edged stir, to solution pH value be 1.0～1.5 when, stop acid adding, continue stirring reaction 2h～4h, be filtrated to get containing fluorination
The filtering residue of praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium；
(4) filtering residue is processed：Filtering residue Jing containing praseodymium fluoride neodymium is washed to into neutrality, is dried at 60 DEG C～80 DEG C, be fluorinated
Praseodymium neodymium；
(5) filtrate is processed：Praseodymium oxalate neodymium, gained oxalic acid are obtained using Oxalic Acid Method crystalline deposit to the filtrate of chloride containing praseodymium neodymium
Praseodymium neodymium calcination at 950 DEG C, decomposition obtains praseodymium neodymium oxide.
For the benefit of in slurry dissolvable oxides especially non-rare earth impurity composition is leached, the present invention step (1) in,
The granularity of the powder is more than 325 mesh.
For the benefit of the acid soluble impurities and oxide slag in slurry are leached in solution, the present invention step (3) in, stop
After acid adding, first serosity is warmed up to into 60 DEG C～80 DEG C, is further continued for stirring reaction 2h～4h.
For using water wisely, reduces cost, the present invention step (4) in, when washing to filtering residue, (2) wash water return to step is beaten
Section is done pure water and is used.
Due to adopting above-mentioned technical proposal, the present invention preferably realizes goal of the invention, using rare earth fluoride not with salt
The characteristic of acid reaction, takes low concentration of salt Ore Leaching soluble impurity and oxide, is not required to destroy fluorine under high-temperature strong acid or highly basic
Change rare earth structure, reach the purpose for recycling valuable constituent, compare with highly basic roasting method with traditional concentrated sulfuric acid roasting method, reduce
Roasting process, also without extraction process, with process is simple, flow process is short, low cost, high income follow-up feed liquid, environment friend
Good the characteristics of, and efficiently recycled fluorine element therein.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1：
The separation method of valuable constituent in a kind of praseodymium neodymium molten-salt electrolysis waste material, it comprises the following steps：
(1) Feedstock treating：The waste material of praseodymium neodymium metal generation is produced as raw material with fused salt electrolysis process, after raw material is crushed
Obtain powder；
The invention will be further described by taking the molten salt electrolysis wastes of Hunan Rare Earth Factory as an example for the present embodiment, the electricity
The total amount of rare earth and the major impurity content analysis result such as (unit of table 1 of solution matter waste material：﹪)：
Table 1 is electrolysed Scrap analysis result
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 80.65 | 0.49 | 0.02 | 1.14 | 0.50 |
For the benefit of in slurry dissolvable oxides especially non-rare earth impurity composition is leached, the present invention step (1) in,
The granularity of the powder is more than 325 mesh.
The granularity of powder described in the present embodiment is 400 mesh.
(2) it is beaten：By weight, by step, (1) gained powder presses solid-to-liquid ratio 1：1～2 adds pure water stirring to be mixed into slurry；
(3) leach：Under room temperature concentration is added for the hydrochloric acid of 1.0mol/L～2.0mol/L, side toward step (2) gained slurry
Edged stir, to solution pH value be 1.0～1.5 when, stop acid adding, continue stirring reaction 2h～4h, be filtrated to get containing fluorination
The filtering residue of praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
The present embodiment takes the ㎏ of powder 1 into beaker, adds 2 ㎏ pure water mix homogeneously, stirs under room temperature while adding
The hydrochloric acid of 1mol/L, until final ph stops acid adding when being maintained at 1.0～1.5, continues stirring reaction 2h, is filtrated to get fluorine-containing
Change the filtering residue of praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
The recovery method of valuable constituent in a kind of praseodymium neodymium molten-salt electrolysis waste material, it comprises the following steps：
(1) Feedstock treating：The waste material of praseodymium neodymium metal generation is produced as raw material with fused salt electrolysis process, after raw material is crushed
Obtain powder；
The invention will be further described by taking the molten salt electrolysis wastes of Hunan Rare Earth Factory as an example for the present embodiment, the electricity
The total amount of rare earth and the major impurity content analysis result such as (unit of table 1 of solution matter waste material：﹪)：
Table 1 is electrolysed Scrap analysis result
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 80.65 | 0.49 | 0.02 | 1.14 | 0.50 |
For the benefit of in slurry dissolvable oxides especially non-rare earth impurity composition is leached, the present invention step (1) in,
The granularity of the powder is more than 325 mesh.
The granularity of powder described in the present embodiment is 400 mesh.
(2) it is beaten：By weight, by step, (1) gained powder presses solid-to-liquid ratio 1：1～2 adds pure water stirring to be mixed into slurry；
(3) leach：Under room temperature concentration is added for the hydrochloric acid of 1.0mol/L～2.0mol/L, side toward step (2) gained slurry
Edged stir, to solution pH value be 1.0～1.5 when, stop acid adding, continue stirring reaction 2h～4h, be filtrated to get containing fluorination
The filtering residue of praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium；
(4) filtering residue is processed：Filtering residue Jing containing praseodymium fluoride neodymium is washed to into neutrality, is dried at 60 DEG C～80 DEG C, be fluorinated
Praseodymium neodymium；
For using water wisely, reduces cost, the present invention step (4) in, when washing to filtering residue, (2) wash water return to step is beaten
Section is done pure water and is used.
(5) filtrate is processed：Praseodymium oxalate neodymium, gained oxalic acid are obtained using Oxalic Acid Method crystalline deposit to the filtrate of chloride containing praseodymium neodymium
Praseodymium neodymium calcination at 950 DEG C, decomposition obtains praseodymium neodymium oxide.
The present embodiment takes the ㎏ of powder 1 into beaker, adds 2 ㎏ pure water mix homogeneously, stirs under room temperature while adding
The hydrochloric acid of 1mol/L, until final ph stops acid adding when being maintained at 1.0～1.5, continues stirring reaction 2h, is filtrated to get fluorine-containing
Change the filtering residue of praseodymium neodymium and the filtrate of chloride containing praseodymium neodymium.
Filtering residue is washed to into neutrality, is dried at 80 DEG C, obtain praseodymium fluoride neodymium 542.8g.Its composition analysis result is shown in Table 2
(unit：﹪)：
Table 2：The praseodymium fluoride neodymium analysis result of embodiment 1
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 81.50 | 0.15 | 0.08 | 0.24 | 0.17 |
The filtrate 6.50L of chloride containing praseodymium neodymium is obtained, concentration (TREO) is 55.7g/L, is added after 75 DEG C are heated to filtrate
Saturated oxalic acid solution carries out crystalline deposit, praseodymium oxalate neodymium is filtered to obtain, after gained praseodymium oxalate neodymium is with hot wash 3 times, in Muffle furnace
In calcination 2h at 950 DEG C, decomposition obtains praseodymium neodymium oxide 351.2g.Its composition analysis result is shown in Table 3 (units：﹪)：
Table 3：The praseodymium neodymium oxide analysis result of embodiment 1
| TREO | Pr6O11 | Nd2O3 | SO4 2- | Cl- | Fe2O3 | SiO2 | CaO | Al2O3 |
| 99.15 | 18.18 | 81.75 | 0.017 | 0.030 | 0.014 | 0.005 | 0.048 | 0.020 |
Calculated by above-mentioned data, it is known that the weight of institute's recovering rare earth（REO）For 542.8 × 81.50 ﹪+351.2 ×
99.15 ﹪=790.60g, the total recovery of rare earth is 98.02 ﹪.
Embodiment 2：
For the benefit of the acid soluble impurities and oxide slag in slurry are leached in solution, and the present invention is in praseodymium neodymium fused salt electricity
Solution waste material in valuable constituent separation method the step of (3) in, stop acid adding after, first serosity is warmed up to into 60 DEG C～80 DEG C, followed by
Continuous stirring reaction 2h～4h.
For the benefit of the acid soluble impurities and oxide slag in slurry are leached in solution, and the present invention is in praseodymium neodymium fused salt electricity
Solution waste material in valuable constituent recovery method the step of (3) in, stop acid adding after, first serosity is warmed up to into 60 DEG C～80 DEG C, followed by
Continuous stirring reaction 2h～4h.
The present embodiment stops after acid adding, will serosity be warmed up to 60 DEG C, continue stirring reaction 2h, pH value is almost unchanged,
It is filtrated to get the filtrate of the filtering residue containing praseodymium fluoride neodymium and chloride containing praseodymium neodymium.
Filtering residue is washed to into neutrality, is dried at 60 DEG C, obtain praseodymium fluoride neodymium 540.5g.Its composition analysis result is shown in Table 4
(unit：﹪)：
Table 4：The praseodymium fluoride neodymium analysis result of embodiment 2
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 82.01 | 0.10 | 0.06 | 0.05 | 0.06 |
The filtrate 6.30L of chloride containing praseodymium neodymium is obtained, concentration (TREO) is 56.0g/L, is added after 75 DEG C are heated to filtrate
Saturated oxalic acid solution carries out crystalline deposit, praseodymium oxalate neodymium is filtered to obtain, after gained praseodymium oxalate neodymium is with hot wash 3 times, in Muffle furnace
In at 950 DEG C calcination 2h, decomposition obtain praseodymium neodymium oxide 347.8g, quality is up to state standards.Its composition analysis result is shown in Table 5
(unit：﹪)：
Table 5：The praseodymium neodymium oxide analysis result of embodiment 2
| TREO | Pr6O11 | Nd2O3 | SO4 2- | Cl- | Fe2O3 | SiO2 | CaO | Al2O3 |
| 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 same embodiment 1.
The present invention using rare earth fluoride not with the characteristic of hydrochloric acid reaction, take low concentration of salt Ore Leaching soluble impurity and
Oxide, is not required to destroy rare earth fluoride structure under high-temperature strong acid or highly basic, the purpose for recycling valuable constituent is reached, with tradition
Concentrated sulfuric acid roasting method is compared with highly basic roasting method, reduces roasting process, follow-up feed liquid also without extraction process, with technique
Simply, flow process is short, low cost, high income, the characteristics of environmental friendliness, and has efficiently recycled fluorine element therein.
Embodiment 3：
The present embodiment takes the ㎏ of powder 1 into beaker, adds 2 ㎏ pure water mix homogeneously, stirs under room temperature while adding
The hydrochloric acid of 2mol/L, until final ph stops acid adding when being maintained at 1.0～1.5, serosity is warmed up to 60 DEG C, continues stirring reaction
2h, pH value is almost unchanged；It is filtrated to get filtering residue and filtrate.
Filtering residue is washed to into neutrality, is dried at 70 DEG C, obtain praseodymium fluoride neodymium 534.9g.Its composition analysis result is shown in Table 6
(unit：﹪)：
Table 6：The praseodymium fluoride neodymium analysis result of embodiment 3
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 82.50 | 0.06 | 0.05 | 0.07 | 0.05 |
The filtrate 3.21L of chloride containing praseodymium neodymium is obtained, concentration (TREO) is 110.5g/L, is added after 75 DEG C are heated to filtrate
Saturated oxalic acid solution carries out crystalline deposit, praseodymium oxalate neodymium is filtered to obtain, after gained praseodymium oxalate neodymium is with hot wash 3 times, in Muffle furnace
In at 950 DEG C calcination 2h, decomposition obtain praseodymium neodymium oxide 349.9g, quality is up to state standards.Its composition analysis result is shown in Table 7
(unit：﹪)：
Table 7：The praseodymium neodymium oxide analysis result of embodiment 3
| TREO | Pr6O11 | Nd2O3 | SO4 2- | Cl- | Fe2O3 | SiO2 | CaO | Al2O3 |
| 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 same embodiment 1,2.
Embodiment 4：
The present embodiment takes the ㎏ of powder 1 into beaker, adds 2 ㎏ pure water mix homogeneously, stirs under room temperature while adding
The hydrochloric acid of 2mol/L, until final ph stops acid adding when being maintained at 1.0～1.5, serosity is warmed up to 60 DEG C, continues stirring reaction
4h, pH value is almost unchanged；It is filtrated to get filtering residue and filtrate.
Filtering residue is washed to into neutrality, is dried at 80 DEG C, obtain praseodymium fluoride neodymium 533.8g.Its composition analysis result is shown in Table 8
(unit：﹪)：
Table 8：The praseodymium fluoride neodymium analysis result of embodiment 4
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 82.40 | 0.05 | 0.04 | 0.07 | 0.05 |
The filtrate 3.19L of chloride containing praseodymium neodymium is obtained, concentration (TREO) is 112.0g/L, is added after 75 DEG C are heated to filtrate
Saturated oxalic acid solution carries out crystalline deposit, praseodymium oxalate neodymium is filtered to obtain, after gained praseodymium oxalate neodymium is with hot wash 3 times, in Muffle furnace
In at 950 DEG C calcination 2h, decomposition obtain praseodymium neodymium oxide 353.1g, quality is up to state standards.Its composition analysis result is shown in Table 9
(unit：﹪)：
Table 9：The praseodymium neodymium oxide analysis result of embodiment 4
| TREO | Pr6O11 | Nd2O3 | SO4 2- | Cl- | Fe2O3 | SiO2 | CaO | Al2O3 |
| 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 same embodiment 1,2.
Embodiment 5：
The present embodiment takes the ㎏ of powder 1 into beaker, adds 2 ㎏ pure water mix homogeneously, stirs under room temperature while adding
The hydrochloric acid of 2mol/L, until final ph stops acid adding when being maintained at 1.0～1.5, serosity is warmed up to 80 DEG C, continues stirring reaction
2h, pH value is almost unchanged；It is filtrated to get filtering residue and filtrate.
Filtering residue is washed to into neutrality, is dried at 60 DEG C, obtain praseodymium fluoride neodymium 533.0g.Its composition analysis result is shown in Table 10
(unit：﹪)：
Table 10：The praseodymium fluoride neodymium analysis result of embodiment 5
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 82.30 | 0.06 | 0.05 | 0.05 | 0.06 |
The filtrate 3.01L of chloride containing praseodymium neodymium is obtained, concentration (TREO) is 119.2g/L, is added after 75 DEG C are heated to filtrate
Saturated oxalic acid solution carries out crystalline deposit, praseodymium oxalate neodymium is filtered to obtain, after gained praseodymium oxalate neodymium is with hot wash 3 times, in Muffle furnace
In at 950 DEG C calcination 2h, decomposition obtain praseodymium neodymium oxide 354.0g, quality is up to state standards.Its composition analysis result is shown in Table
11 (units：﹪)：
Table 11：The praseodymium neodymium oxide analysis result of embodiment 5
| TREO | Pr6O11 | Nd2O3 | SO4 2- | Cl- | Fe2O3 | SiO2 | CaO | Al2O3 |
| 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 same embodiment 1,2.
Embodiment 6：
The present embodiment takes the ㎏ of powder 1 into beaker, adds 2 ㎏ pure water mix homogeneously, stirs under room temperature while adding
The hydrochloric acid of 2mol/L, until final ph stops acid adding when being maintained at 1.0～1.5, serosity is warmed up to 80 DEG C, continues stirring reaction
4h, pH value is almost unchanged；It is filtrated to get filtering residue and filtrate.
Filtering residue is washed to into neutrality, is dried at 75 DEG C, obtain praseodymium fluoride neodymium 532.5g.Its composition analysis result is shown in Table 12
(unit：﹪)：
Table 12：The praseodymium fluoride neodymium analysis result of embodiment 6
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 82.35 | 0.05 | 0.04 | 0.06 | 0.04 |
The filtrate 2.98L of chloride containing praseodymium neodymium is obtained, concentration (TREO) is 121.1g/L, is added after 75 DEG C are heated to filtrate
Saturated oxalic acid solution carries out crystalline deposit, praseodymium oxalate neodymium is filtered to obtain, after gained praseodymium oxalate neodymium is with hot wash 3 times, in Muffle furnace
In at 950 DEG C calcination 2h, decomposition obtain praseodymium neodymium oxide 354.1g, quality is up to state standards.Its composition analysis result is shown in Table
13 (units：﹪)：
Table 13：The praseodymium neodymium oxide analysis result of embodiment 6
| TREO | Pr6O11 | Nd2O3 | SO4 2- | Cl- | Fe2O3 | SiO2 | CaO | Al2O3 |
| 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 same embodiment 1,2.
Embodiment 7：
The present embodiment takes the ㎏ of powder 1 into beaker, adds 2 ㎏ pure water mix homogeneously, stirs under room temperature while adding
The hydrochloric acid of 2mol/L, until final ph stops acid adding when being maintained at 1.0～1.5, serosity is warmed up to 75 DEG C, continues stirring reaction
4h, pH value is almost unchanged；It is filtrated to get filtering residue and filtrate.
Filtering residue is washed to into neutrality, is dried at 80 DEG C, obtain praseodymium fluoride neodymium 540.0g.Its composition analysis result is shown in Table 14
(unit：﹪)：
Table 14：The praseodymium fluoride neodymium analysis result of embodiment 7
| TREO | Fe2O3 | SiO2 | CaO | Al2O3 |
| 82.05 | 0.04 | 0.04 | 0.05 | 0.04 |
The ㎏ of filtrate 2.92 of chloride containing praseodymium neodymium is obtained, concentration (TREO) is 120.3g/L, is added after 75 DEG C are heated to filtrate
Entering saturated oxalic acid solution carries out crystalline deposit, praseodymium oxalate neodymium is filtered to obtain, after gained praseodymium oxalate neodymium is with hot wash 3 times, in Muffle
In stove at 950 DEG C calcination 2h, decomposition obtain praseodymium neodymium oxide 346.6g, quality is up to state standards.Its composition analysis result is shown in
(the unit of table 15：﹪)：
Table 15：The praseodymium neodymium oxide analysis result of embodiment 7
| TREO | Pr6O11 | Nd2O3 | SO4 2- | Cl- | Fe2O3 | SiO2 | CaO | Al2O3 |
| 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 same embodiment 1,2.
Claims (5)
1. in a kind of praseodymium neodymium molten-salt electrolysis waste material valuable constituent separation method, it is characterized in that it comprises the following steps：
(1) Feedstock treating：The waste material of praseodymium neodymium metal generation is produced as raw material with fused salt electrolysis process, powder is obtained after raw material is crushed
Material；
Step (1) in, the granularity of the powder is more than 325 mesh；
(2) it is beaten：By weight, by step, (1) gained powder presses solid-to-liquid ratio 1：1～2 adds pure water stirring to be mixed into slurry；
(3) leach：Under room temperature concentration is added for the hydrochloric acid of 1.0mol/L～2.0mol/L, side edged toward step (2) gained slurry
Stirring, to solution pH value be 1.0～1.5 when, stop acid adding, continue stirring reaction 2h～4h, be filtrated to get neodymium containing praseodymium fluoride
Filtering residue and chloride containing praseodymium neodymium filtrate.
2. in praseodymium neodymium molten-salt electrolysis waste material according to claim 1 valuable constituent separation method, it is characterized in that
Step (3) in, stop acid adding after, first serosity is warmed up to into 60 DEG C～80 DEG C, be further continued for stirring reaction 2h～4h.
3. in a kind of praseodymium neodymium molten-salt electrolysis waste material valuable constituent recovery method, it is characterized in that it comprises the following steps：
(1) Feedstock treating：The waste material of praseodymium neodymium metal generation is produced as raw material with fused salt electrolysis process, powder is obtained after raw material is crushed
Material；
Step (1) in, the granularity of the powder is more than 325 mesh
(2) it is beaten：By weight, by step, (1) gained powder presses solid-to-liquid ratio 1：1～2 adds pure water stirring to be mixed into slurry；
(3) leach：Under room temperature concentration is added for the hydrochloric acid of 1.0mol/L～2.0mol/L, side edged toward step (2) gained slurry
Stirring, to solution pH value be 1.0～1.5 when, stop acid adding, continue stirring reaction 2h～4h, be filtrated to get neodymium containing praseodymium fluoride
Filtering residue and chloride containing praseodymium neodymium filtrate；
(4) filtering residue is processed：Filtering residue Jing containing praseodymium fluoride neodymium is washed to into neutrality, is dried at 60 DEG C～80 DEG C, obtain praseodymium fluoride
Neodymium；
(5) filtrate is processed：Praseodymium oxalate neodymium, gained praseodymium oxalate neodymium are obtained using Oxalic Acid Method crystalline deposit to the filtrate of chloride containing praseodymium neodymium
The calcination at 950 DEG C, decomposition obtains praseodymium neodymium oxide.
4. according to claim 3 in praseodymium neodymium molten-salt electrolysis waste material valuable constituent recovery method, it is characterized in that in step
It is rapid (3) in, after stopping acid adding, first serosity is warmed up to into 60 DEG C～80 DEG C, be further continued for stirring reaction 2h～4h.
5. according to claim 3 in praseodymium neodymium molten-salt electrolysis waste material valuable constituent recovery method, it is characterized in that in step
It is rapid (4) in, when washing to filtering residue, (2) wash water return to step is beaten section does pure water and uses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510181745.7A CN104805292B (en) | 2015-04-17 | 2015-04-17 | Method for separating and recovering valuable components from rare earth praseodymium-neodymium fused salt electrolysis waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510181745.7A CN104805292B (en) | 2015-04-17 | 2015-04-17 | Method for separating and recovering valuable components from rare earth praseodymium-neodymium fused salt electrolysis waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104805292A CN104805292A (en) | 2015-07-29 |
| CN104805292B true CN104805292B (en) | 2017-04-12 |
Family
ID=53690486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510181745.7A Active CN104805292B (en) | 2015-04-17 | 2015-04-17 | Method for separating and recovering valuable components from rare earth praseodymium-neodymium fused salt electrolysis waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104805292B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567985B (en) * | 2015-12-28 | 2017-11-24 | 江苏金石稀土有限公司 | A kind of recovery method of re metal electrolyzing fused salt slag |
| CN114921668B (en) * | 2022-06-30 | 2024-06-11 | 包头稀土研究院 | Method for reducing rare earth content in rare earth iron boron waste hydrochloric acid eutectoid 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5728355A (en) * | 1995-09-27 | 1998-03-17 | Santoku Metal Industry Co., Ltd. | Method for recovering reusable rare earth compounds |
| CN102011020B (en) * | 2009-12-14 | 2012-09-05 | 包头市玺骏稀土有限责任公司 | Method for recovering rare earth elements from neodymium-iron-boron wastes |
| CN101851000A (en) * | 2010-05-08 | 2010-10-06 | 益阳桃江金牛稀土厂 | Method for preparing rare-earth oxide |
| CN101956078B (en) * | 2010-10-13 | 2012-07-04 | 赣州鑫磊稀土新材料有限公司 | Method for separating and recycling rare-earth elements from molten salt electrolysis wastes of rare-earth metals |
-
2015
- 2015-04-17 CN CN201510181745.7A patent/CN104805292B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104805292A (en) | 2015-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6406675B2 (en) | Zinc recovery method from electric furnace steelmaking dust and zinc recovery device from electric furnace steelmaking dust | |
| US20160068929A1 (en) | EXTRACTION OF RARE EARTH METALS FROM NdFeB USING SELECTIVE SULFATION ROASTING | |
| CN104843761A (en) | Method for recovering rare earth from rare earth fluoride fused salt electrolysis waste with effects of environmental protection and low cost | |
| JP5913639B2 (en) | Method for producing indium oxide-tin oxide powder, method for producing ITO target, and method for producing indium hydroxide-metastannic acid mixture | |
| CN104805292B (en) | Method for separating and recovering valuable components from rare earth praseodymium-neodymium fused salt electrolysis waste | |
| JP5935098B2 (en) | Zinc production method | |
| CN107058738A (en) | The method that nickel sulfate is reclaimed from nickel slag | |
| CN104164567A (en) | Method for enriching and recycling niobium and tantalum from waste high-temperature alloy | |
| JP2014051718A (en) | Rare earth separation method and rare earth separation unit | |
| JP6656709B2 (en) | Manufacturing method of zinc ingot | |
| JP5596590B2 (en) | Method for separating and recovering metal elements from rare earth magnet alloy materials | |
| JP2010138490A (en) | Method of recovering zinc | |
| CN101314184A (en) | Method for recycling and preparing ultra-fine zinc dust from zinc dust containing material | |
| KR20190109082A (en) | Recovery method rare earth elements from waste RE:YAG crystal | |
| US20140251820A1 (en) | Method of recovering a metal from a solution | |
| KR101843951B1 (en) | Method for recovering indium from target waste containing indium | |
| WO2006084273A2 (en) | Process for hydrometallurgical treatment of electric arc furnace dust | |
| JPWO2018168471A1 (en) | Method for producing metal manganese | |
| JP7193136B2 (en) | Method for producing zinc carbonate | |
| CN114032396A (en) | Method for treating aluminum ash by low-temperature harmless wet method | |
| KR101959257B1 (en) | Method for increasing the circulation efficiency of Fe rich powder put into the recovery electric furnace by increasing of Zn recovery rate by high-efficiency multi-stage acid leaching hydrometallurgy and magnet separation of low-quality electric furnace dust | |
| Berhe et al. | Green extraction of niobium and tantalum from Kenticha tantalite ore using 1-ethyl-3-methyl imidazolium chloride ionic liquid | |
| JP2014218697A (en) | Method for producing zinc | |
| JP7565585B2 (en) | Zinc carbonate manufacturing method | |
| WO2023157826A1 (en) | Zinc recovery method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |