CN104878204A - Leaching Method Of Neodymium From Permanent Magnet Containing Neodymium - Google Patents

Leaching Method Of Neodymium From Permanent Magnet Containing Neodymium Download PDF

Info

Publication number
CN104878204A
CN104878204A CN201510059269.1A CN201510059269A CN104878204A CN 104878204 A CN104878204 A CN 104878204A CN 201510059269 A CN201510059269 A CN 201510059269A CN 104878204 A CN104878204 A CN 104878204A
Authority
CN
China
Prior art keywords
neodymium
permanent magnet
leaching
naoh solution
oxidizing roasting
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.)
Granted
Application number
CN201510059269.1A
Other languages
Chinese (zh)
Other versions
CN104878204B (en
Inventor
郑景友
尹虎成
金哲主
金圣敦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Korea Institute of Geoscience and Mineral Resources KIGAM
Original Assignee
Korea Institute of Geoscience and Mineral Resources KIGAM
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Korea Institute of Geoscience and Mineral Resources KIGAM filed Critical Korea Institute of Geoscience and Mineral Resources KIGAM
Publication of CN104878204A publication Critical patent/CN104878204A/en
Application granted granted Critical
Publication of CN104878204B publication Critical patent/CN104878204B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • 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

Abstract

The present invention relates to a method for selectively leaching neodymium from a permanent magnet containing neodymium which comprises the steps of: immersing the permanent magnet containing neodymium in a NaOH solution; oxidizing and roasting the immersed permanent magnet; and leaching the oxidized and roasted permanent magnet with acid.

Description

The method of neodymium is optionally leached from the permanent magnet comprising neodymium
Technical field
The present invention relates to a kind of method optionally only leaching neodymium from the permanent magnet comprising neodymium.
Background technology
NdFeB system permanent magnet requires to widely use in the parts of high magnetic force magnet at the rocking-turn motor (cranking motor) of automobile, computer, A/V part (audio-visual components), magnet separator, aerospace systems, miscellaneous equipment etc.
The rush of demand of this NdFeB system permanent magnet, the average growth rate per annum in 10 NdFeB system permanent magnet markets, the Nian Jian world is 30 ~ 70% according to magnet kind in the past, sweeps across permanent magnet market.Therefore, infer because the give up generation of chip of NdFeB system permanent magnet increase in demand also can increase sharply.
In general, containing the neodymium (Nd) of about 20 ~ 30% in useless crumb powder that is NdFeB system permanent magnet is broken and that pulverize and obtain, from this NdFeB system permanent magnet, reclaim the degree that Nd has reached one of the 3 large raw material supply sources being Nd metal.
Therefore, the research being intended to recycle the useless permanent magnet abandoned after use is being carried out in recent years actively.In general, can acid leaching process be utilized during Separation and Recovery neodymium from useless crumb powder, when not to useless crumb powder carry out oxidizing roasting just leach, effectively neodymium can be extracted under low sulfuric acid concentration, but, the leaching yield of iron is also relatively high in this case, therefore, there is the problem that later separation circuit becomes complicated.
Therefore, be badly in need of reducing the leaching yield of iron and optionally improve the scheme of the leaching yield of neodymium.
No. 10-1047838, Ebrean Registered Patent (2011.07.08 bulletin) is had as relevant prior art document, the method reclaiming residual actinides from muriate melting salt is only disclosed in described document, and the unexposed technology leaching neodymium from NdFeB system permanent magnet.
Summary of the invention
The problem that invention will solve
Therefore, the object of the invention is to, a kind of method only leaching neodymium from the permanent magnet comprising neodymium is provided.
The problem that the present invention will solve is not limited to above-mentioned problem, and according to following record, those skilled in the art can be expressly understood other problem not yet mentioned of the present invention.
For solving the scheme of problem
In order to solve above-mentioned problem, the invention provides a kind of method optionally leaching neodymium from the permanent magnet comprising neodymium, it comprises: make the permanent magnet comprising neodymium impregnated in the step of NaOH solution; Permanent magnet through described dipping is carried out to the step of oxidizing roasting process; And with acid the permanent magnet through described oxidizing roasting process is leached step.
The invention is characterized in, the described permanent magnet comprising neodymium can be NdFeB system permanent magnet, described NdFeB system permanent magnet can be the chip or useless permanent magnet discarded after using that produce in permanent magnet manufacturing step, and performs broken process to make described use useless permanent magnet discarded afterwards have powder morphology.
The invention is characterized in, the concentration of described NaOH solution is 10 ~ 60%.
The invention is characterized in, comprise described NaOH solution to make the mode that the volume of described NaOH solution (ml) and the ratio of weight (g) of the permanent magnet comprising neodymium are 1 ~ 10.
The invention is characterized in, described in be immersed in 50 ~ 110 DEG C perform 1 ~ 6 hour.
The invention is characterized in, described oxidizing roasting performs 1 ~ 5 hour more than 200 DEG C, less than 600 DEG C.
Now, the invention is characterized in, after described oxidizing roasting, neodymium is with Nd (OH) 3or Nd 2o 3exist.
The invention is characterized in, described acid can be sulfuric acid or hydrochloric acid, is more than 3.00, mode less than 3.15 comprises described acid to make hydrionic mole number relative to neodymium.
The invention is characterized in, described leaching performs 5 ~ 25 minutes at normal temperature.
Invention effect
According to the present invention, impregnated in NaOH solution and leaching after oxidizing roasting process, therefore, can not be formed as NdFeO 3such mixed oxide, only can leach Nd.
In addition, the present invention can apply for the chip produced in permanent magnet manufacturing step and from the useless permanent magnet that household appliances and automobile etc. are discarded, operation is simple, can process a large amount of permanent magnets, thus only can reclaim with high leaching yield neodymium with low expense.
Accompanying drawing explanation
Fig. 1 illustrates the precedence diagram optionally leaching the method for neodymium from the permanent magnet comprising neodymium of the present invention.
Fig. 2 be of the present invention optionally leach from the permanent magnet comprising neodymium impregnated in NaOH solution in the method for neodymium after the XRD result of resultant that formed.
Fig. 3 is in the XRD result optionally leached from the permanent magnet comprising neodymium according to the resultant of the ratio of mixture of give up permanent magnet powder and NaOH in the method for neodymium of the present invention.
Fig. 4 is in the XRD result optionally leached according to the resultant of NaOH dipping time formation in the method for neodymium of the present invention.
Fig. 5 carries out oxidizing roasting process in 2 hours and the XRD result of the resultant formed of the present invention optionally leaching in the method for neodymium at 200 DEG C.
Fig. 6 carries out oxidizing roasting process in 2 hours 350 DEG C and 450 DEG C in the method for neodymium and the XRD result of the resultant formed respectively of the present invention optionally leaching.
Fig. 7 carries out oxidizing roasting process in 2 hours and the XRD result of the resultant formed of the present invention optionally leaching in the method for neodymium at 600 DEG C.
Fig. 8 a illustrates at the graphic representation optionally leaching the leaching yield of metal in the method for neodymium after following process of the present invention, this process is, after the NaOH solution being 50% with the useless permanent magnet powder of 1 ︰ 10 (20g ︰ 200ml) interpolation and concentration is flooded 5 hours, carry out oxidizing roasting process in 2 hours at 200 DEG C, with hydrochloric acid make ore deposit liquid concentration be 1% carry out 20 minutes leach.
Fig. 8 b illustrates at the graphic representation optionally leaching the leaching yield of metal in the method for neodymium after following process of the present invention, this process is, after flooding 5 hours adding the NaOH solution of useless permanent magnet powder and 50% with 1 ︰ 10 (20g ︰ 200ml), carry out oxidizing roasting process in 2 hours at 200 DEG C, with hydrochloric acid make ore deposit liquid concentration be 10% carry out 20 minutes leach.
Fig. 9 a illustrates at the graphic representation optionally leaching the leaching yield of metal in the method for neodymium after following process of the present invention, this process is, after flooding 5 hours adding the NaOH solution of useless permanent magnet powder and 50% with 1 ︰ 10 (20g ︰ 200ml), carry out oxidizing roasting process in 2 hours at 350 DEG C, with sulfuric acid make ore deposit liquid concentration be 1% carry out 20 minutes leach.
Fig. 9 b illustrates at the graphic representation optionally leaching the leaching yield of metal in the method for neodymium after following process of the present invention, this process is, after flooding 5 hours adding the NaOH solution of useless permanent magnet powder and 50% with 1 ︰ 10 (20g ︰ 200ml), carry out oxidizing roasting process in 2 hours at 350 DEG C, with sulfuric acid make ore deposit liquid concentration be 10% carry out 20 minutes leach.
Figure 10 a illustrates that hydrochloric acid makes ore deposit liquid concentration be 1% graphic representation carrying out the leaching yield of the metal after leaching for 20 minutes when to carry out Ore Leaching under the leaching condition of Fig. 9 a.
Figure 10 b illustrates that hydrochloric acid makes ore deposit liquid concentration be 10% graphic representation carrying out the leaching yield of the metal after leaching for 20 minutes when to carry out Ore Leaching under the leaching condition of Fig. 9 b.
Figure 11 a illustrates at the graphic representation optionally leaching the leaching yield of metal in the method for neodymium after following process of the present invention, this process is, after flooding 5 hours adding the NaOH solution of useless permanent magnet powder and 50% with 1 ︰ 10 (20g ︰ 200ml), carry out oxidizing roasting process in 2 hours at 450 DEG C, with hydrochloric acid make ore deposit liquid concentration be 1% carry out 20 minutes leach.
Figure 11 b illustrates at the graphic representation optionally leaching the leaching yield of metal in the method for neodymium after following process of the present invention, this process is, after flooding 5 hours adding the NaOH solution of useless permanent magnet powder and 50% with 1 ︰ 10 (20g ︰ 200ml), carry out oxidizing roasting process in 2 hours at 450 DEG C, with hydrochloric acid make ore deposit liquid concentration be 10% carry out 20 minutes leach.
Figure 12 a illustrates at the graphic representation optionally leaching the leaching yield of metal in the method for neodymium after following process of the present invention, this process is, after flooding 1 hour adding the NaOH solution of useless permanent magnet powder and 50% with 1 ︰ 1 (200g ︰ 200ml), carry out oxidizing roasting process in 2 hours at 450 DEG C, with hydrochloric acid make ore deposit liquid concentration be 1% carry out 20 minutes leach.
Figure 12 b illustrates at the graphic representation optionally leaching the leaching yield of metal in the method for neodymium after following process of the present invention, this process is, after flooding 1 hour adding the NaOH solution of useless permanent magnet powder and 50% with 1 ︰ 1 (200g ︰ 200ml), carry out oxidizing roasting process in 2 hours at 450 DEG C, with hydrochloric acid make ore deposit liquid concentration be 10% carry out 20 minutes leach.
Figure 13 illustrates at the graphic representation optionally leaching the leaching content of metal in the method for neodymium after following process of the present invention, this process is, after flooding 5 hours adding the NaOH solution of useless permanent magnet powder and 50% with 1 ︰ 10 (20g ︰ 200ml), carry out oxidizing roasting process in 2 hours 450 DEG C and 600 DEG C, with hydrochloric acid make ore deposit liquid concentration be 10% carry out 20 minutes leach.
Embodiment
Below, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
When by reference to the accompanying drawings with reference to the embodiment described in detail below, advantages and features of the invention and the method for reaching these advantages and feature will become clear.
But, the invention is not restricted to the embodiment of following discloses, to realize with mutually different various ways, these embodiments are only in order to disclose the present invention fully, inform that the category of invention provides fully to those skilled in the art, and the present invention is only defined by claims.
In addition, when the present invention will be described, when judge related known technology etc. likely fuzzy main idea of the present invention, detailed description thereof will be omitted.
The invention provides a kind of method optionally leaching neodymium from the permanent magnet comprising neodymium, it comprises: make the permanent magnet comprising neodymium impregnated in the step of NaOH solution; Permanent magnet is carried out to the step of oxidizing roasting process after described dipping process; And with acid the permanent magnet through described oxidizing roasting process is leached step.
The method optionally leaching neodymium from the permanent magnet comprising neodymium of the present invention makes neodymium be formed as oxyhydroxide (Nd (OH) by making the permanent magnet comprising neodymium impregnated in NaOH solution 3), make iron be formed as oxide compound (Fe 3o 4), by can not NdFeO be being formed 3condition under carry out oxidizing roasting process, make Fe 3o 4to Fe 2o 3carry out phase transformation, thus suppress a Fe just leached at below pH3 2o 3dissolving and optionally only dissolve Nd (OH) 3or Nd 2o 3(leaching at below pH6.8), optionally only can leach neodymium thus.In addition, the present invention can apply for the chip produced in permanent magnet manufacturing step and from the useless permanent magnet that household appliances and automobile etc. are discarded, and operation is simple, can process a large amount of permanent magnets, therefore, can only make Nd leach with high leaching yield with low expense and reclaim.
Fig. 1 illustrates the precedence diagram optionally leaching the method for neodymium from the permanent magnet comprising neodymium of the present invention.Below, be described in more detail with reference to figure 1 couple of the present invention.
The method optionally leaching neodymium from the permanent magnet comprising neodymium of the present invention comprises the step S100 making the permanent magnet comprising neodymium impregnated in NaOH solution.
Now, described in comprise neodymium permanent magnet can be NdFeB system permanent magnet, specifically, can be Nd 2fe 14b permanent magnet can be the chip or useless permanent magnet discarded after using that produce in permanent magnet manufacturing step.The chip produced in permanent magnet manufacturing step is powder morphology, therefore can use chip itself, uses rear discarded permanent magnet then can perform broken process to make it have powder morphology.
When the described permanent magnet comprising neodymium be impregnated in NaOH solution, the neodymium comprised in permanent magnet and iron can generate Nd (OH) as following reaction formula 1 3and Fe 3o 4(with reference to figure 2).
[reaction formula 1]
The situation of Nd: 2Nd+6H 2o → 2Nd (OH) 3+ 3H 2
The situation of Fe: 3Fe+4H 2o → Fe 3o 4+ 8H +
Preferably when the described permanent magnet comprising neodymium being impregnated in NaOH solution, the concentration of NaOH solution is 10 ~ 60%.When the concentration of described NaOH solution is less than 10%, exist because Nd can not change Nd (OH) into 3and the problem of the leaching yield reduction of neodymium when leaching afterwards, the leaching yield rising of Fe, when more than 60%, neodymium is to Nd (OH) 3transformation can not increase further, therefore, from the viewpoint of efficiency, be preferably less than 60%.
In addition, preferably to make the mode that the volume of described NaOH solution (ml) and the ratio (volume ratio) of weight (g) of the permanent magnet comprising neodymium are 1 ~ 10 comprise described NaOH solution.When the volume ratio of described NaOH solution is less than 1, existence comprises the neodymium comprised in the permanent magnet of neodymium and can not fully react with NaOH and not form Nd (OH) 3problem, when volume ratio is more than 10, neodymium is to Nd (OH) 3transformation can not increase further, therefore, preferred volume ratio is less than 10.
Preferred described NaOH solution be immersed in 50 ~ 110 DEG C perform 1 ~ 6 hour.When described temperature is less than 50 DEG C, there is the problem that the reaction required time of permanent magnet and NaOH is long, when more than 110 DEG C, neodymium is to Nd (OH) 3or Nd 2o 3transformation can not increase further, therefore, from the viewpoint of efficiency, be preferably less than 110 DEG C.The restriction reason of described dipping time is identical with the restriction reason of temperature.
Then, the method optionally leaching neodymium from the permanent magnet comprising neodymium of the present invention to carry out the step S200 of oxidizing roasting process to permanent magnet after being included in and impregnated in described NaOH solution.
The temperature of permanent magnet more than 200 DEG C, less than 600 DEG C through NaOH solution dipping is carried out the following reaction formula 2 of oxidizing roasting process after image and is formed Nd like that 2o 3and Fe 2o 3.Now, when carrying out oxidizing roasting for 200 DEG C, only carry out Fe 3o 4change Fe into 2o 3reaction, Nd (OH) 3can not undergo phase transition.That is, as shown in Figure 5, the known oxidizing roasting temperature Nd (OH) at 200 DEG C 3maintain former state, as shown in Figure 6, known 350 DEG C of Nd (OH) 3change Nd into 2o 3.
[reaction formula 2]
The situation of Nd: 2Nd (OH) 3→ Nd 2o 3+ 3H 2o
The situation of Fe: 2Fe 3o 4+ 1/2O 2→ 3Fe 2o 3
Oxidizing roasting process is carried out, thereby, it is possible to prevent NdFeO after the method optionally leaching neodymium from the permanent magnet comprising neodymium of the present invention formerly impregnated in NaOH solution 3formation (can be formed when carrying out oxidizing roasting process without the operation that impregnated in NaOH solution), can prevent from needing to only leach neodymium performing for making NdFeO 3be formed as Nd 2o 3the problem of operation, therefore, it is possible to only leach neodymium with simple operation.
Now, preferred described oxidizing roasting performs 1 ~ 5 hour more than 200 DEG C, less than 600 DEG C.When performing described oxidizing roasting less than 200 DEG C, because of Fe 3o 4change Fe into 2o 3time long and there is the problem of engineering, can be formed as NdFeO more than 600 DEG C 3such phase and Fe is leached increase, there is the problem that only can not leach Nd.
The method optionally leaching neodymium from the permanent magnet comprising neodymium of the present invention comprises the step S300 permanent magnet through described oxidizing roasting process being leached with acid.
When with acid to when leaching through the permanent magnet of described oxidizing roasting process, be only included in neodymium in permanent magnet and leach, iron major part all can not leach.
Now, described acid can use sulfuric acid and hydrochloric acid etc., mode preferably to make hydrionic mole number be more than 3.00 relative to neodymium, less than 3.15 comprises described acid solution, preferably with make ore deposit liquid concentration (percentage relative to the weight (w) of the permanent magnet particle of the volume (v) of acid) be 1 ~ 50% mode add.When described mole number is less than 3.00, the problem that the leaching yield that there is Nd reduces, more than 3.15, the problem that the leaching that there is iron increases.
In addition, preferred described leaching performs 5 ~ 25 minutes at normal temperature.When described leaching performed less than 5 minutes, there is the problem that Nd can not fully leach, when more than 25 minutes, there is the problem that can not produce the leaching of Nd further.
Embodiment 1: leach Nd 1 from useless permanent magnet
The Nd of mixing 20g 2fe 14b powder and 50% NaOH solution 200ml, in NaOH solution 100 DEG C dipping 5 hours, then carry out oxidizing roasting process in 2 hours at 200 DEG C, make ore deposit liquid concentration (Nd with the HCl of 0.05M 2fe 14volume × 100 of the weight/HCl of B) be 1% carry out 20 minutes leach.
Embodiment 2: leach Nd 2 from useless permanent magnet
Except using the HCl of 0.5M, making ore deposit liquid concentration be except 10%, from useless permanent magnet, leach Nd with the method identical with described embodiment 1.
Embodiment 3: leach Nd 3 from useless permanent magnet
The Nd of mixing 20g 2fe 14b powder and 50% NaOH solution 200ml, in NaOH solution 100 DEG C dipping 5 hours, then carry out oxidizing roasting process in 2 hours at 350 DEG C, with the HCl of 0.05M make ore deposit liquid concentration be 1% and normal temperature carry out 20 minutes leach.
Embodiment 4: leach Nd 4 from useless permanent magnet
Except using the HCl of 0.5M, making ore deposit liquid concentration be except 10%, from useless permanent magnet, leach Nd with the method identical with described embodiment 3.
Embodiment 5: leach Nd 5 from useless permanent magnet
Except using the H of 0.05M 2sO 4in addition, from useless permanent magnet, Nd is leached with the method identical with described embodiment 3.
Embodiment 6: leach Nd 6 from useless permanent magnet
Except using the H of 0.5M 2sO 4in addition, from useless permanent magnet, Nd is leached with the method identical with described embodiment 4.
Embodiment 7: leach Nd 7 from useless permanent magnet
Except performing except oxidizing roasting at 450 DEG C, from useless permanent magnet, leach Nd with the method identical with described embodiment 3.
Embodiment 8: leach Nd 8 from useless permanent magnet
Being 10% except making ore deposit liquid concentration, using except the HCl of 0.5M, from useless permanent magnet, leach Nd with the method identical with described embodiment 7.
Embodiment 9: leach Nd 9 from useless permanent magnet
Except mixing the Nd of 200g 2fe 14b powder and 50% NaOH solution 200ml and perform beyond 1 hour NaOH dipping, from useless permanent magnet, leach Nd with the method identical with described embodiment 7.
Embodiment 10: leach Nd 10 from useless permanent magnet
Except using the HCl of 0.5M, making ore deposit liquid concentration be except 10%, from useless permanent magnet, leach Nd with the method identical with described embodiment 9.
Experimental example 1: according to NaOH and Nd 2fe 14the resultant analysis of the ratio of mixture of B powder and the dipping time in NaOH solution
Analyze at the resultant formed according to the ratio of mixture of give up permanent magnet powder and NaOH in the method for neodymium that optionally leaches of the present invention, the results are shown in Fig. 3.
NaOH solution (ml) ︰ Nd with 50% 2fe 14b powder (g)=200 ︰ 20,200 ︰ 100,200 ︰ 200 analyzes resultant after carrying out mixing and impregnated in NaOH solution.As shown in Figure 3, can confirm that dipping defined Nd (OH) after 5 hours in NaOH solution 3and Fe 3o 4.
In addition, analyze at the resultant formed according to NaOH dipping time in the method for neodymium that optionally leaches from the permanent magnet comprising neodymium of the present invention, the results are shown in Fig. 4.As shown in Figure 4, can confirm that the result of flooding 1 hour, 3 hours and 5 hours in NaOH solution defines Nd (OH) 3and Fe 3o 4.
Experimental example 2: according to the resultant analysis of oxidizing roasting treatment temp
Analyze at the resultant formed according to the oxidizing roasting treatment temp of useless permanent magnet powder in the method for neodymium that optionally leaches of the present invention, the results are shown in Fig. 5, Fig. 6 and Fig. 7.
Fig. 5 carries out mixing at permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up of the NaOH Rong Ye ︰ with 50% and floods in NaOH solution after 5 hours and carry out oxidizing roasting process in 2 hours and the XRD result of resultant that formed at 200 DEG C.As shown in Figure 5, known Fe 3o 4define γ-Fe 2o 3, the Nd (OH) that known existence is formed by the dipping of NaOH solution 3.
Fig. 6 carries out mixing at permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up of the NaOH Rong Ye ︰ with 50% and floods in NaOH solution and carry out oxidizing roasting process in 2 hours respectively 350 DEG C and 450 DEG C after 5 hours and the XRD result of material that generates.As shown in Figure 6, when carrying out oxidizing roasting process in 2 hours respectively 350 DEG C and 450 DEG C, Fe 3o 4be formed as γ-Fe 2o 3be formed as α-Fe afterwards 2o 3, 2Nd (OH) 3become Nd mutually 2o 3.
Fig. 7 carries out mixing at permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up of the NaOH Rong Ye ︰ with 50% and floods in NaOH solution after 5 hours and carry out oxidizing roasting process in 2 hours and the XRD result of material that generates at 600 DEG C.As shown in Figure 7, after carrying out oxidizing roasting process in 2 hours at 600 DEG C, Fe 3o 4be formed as γ-Fe 2o 3be formed as α-Fe afterwards 2o 3, 2Nd (OH) 3become Nd mutually 2o 3, but meanwhile define 2FeNdO 3.Therefore, known preferential oxidation calcination process is less than 600 DEG C of execution.
Experimental example 3: according to the leaching yield analysis of Ore Leaching
Optionally leach the leaching yield of the Ore Leaching of the useless permanent magnet powder of basis in the method for neodymium to of the present invention and leach analyzing mutually of rear permanent magnet, the results are shown in Fig. 8 a, Fig. 8 b, Fig. 9 a, Fig. 9 b, Figure 10 a, Figure 10 b, Figure 11 a, Figure 11 b, Figure 12 a, Figure 12 b and Figure 13.
Fig. 8 a is the graphic representation of the leaching yield that the metal after being handled as follows is shown, this process is, carry out mixing at permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up of the NaOH Rong Ye ︰ with 50% and flood after 5 hours in NaOH solution, oxidizing roasting process in 2 hours is carried out at 200 DEG C, ore deposit liquid concentration is made to be 1% (w/v with hydrochloric acid, useless permanent magnet powder 10g, hydrochloric acid soln 1000ml) and carry out leaching for 20 minutes, Fig. 8 b is the graphic representation of the leaching yield that the metal after being handled as follows is shown, this process is, NaOH Rong Ye ︰ with 50% permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up mixes, ore deposit liquid concentration is made to be 10% (w/v with hydrochloric acid, useless permanent magnet 100g, hydrochloric acid soln 1000ml) and leach.As shown in figs. 8 a and 8b, 1% ore deposit liquid concentration and 10% ore deposit liquid concentration under the leaching yield of the Nd leaching yield that is all shown as more than 90%, Fe be less than 2%.
Fig. 9 a is the graphic representation of the leaching yield that the metal after being handled as follows is shown, this process is, carry out mixing at permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up of the NaOH Rong Ye ︰ with 50% and flood after 5 hours in NaOH solution, oxidizing roasting process in 2 hours is carried out at 350 DEG C, ore deposit liquid concentration is made to be 1% (w/v with sulfuric acid, useless permanent magnet powder 10g, sulphuric acid soln 1000ml) and carry out leaching for 20 minutes, Fig. 9 b is the graphic representation of the leaching yield that the metal after being handled as follows is shown, this process is, NaOH Rong Ye ︰ with 50% permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up mixes, ore deposit liquid concentration is made to be 10% (w/v with sulfuric acid, useless permanent magnet 100g, sulphuric acid soln 1000ml) and leach.As illustrated in figures 9 a and 9b, 1% ore deposit liquid concentration and 10% ore deposit liquid concentration under the leaching yield of the Nd leaching yield that is all shown as more than 90%, Fe be less than 2%.
Figure 10 illustrates the graphic representation using hydrochloric acid to carry out the leaching yield of the metal after Ore Leaching under the leaching condition of Fig. 9.As shown in figures 10 a and 10b, 1% ore deposit liquid concentration (leaching yield that under the ore deposit liquid concentration (Figure 10 b) of Figure 10 a) He 10%, the leaching yield of Nd is all shown as more than 90%, Fe is less than 2%.
Figure 11 a is the graphic representation of the leaching yield that the metal after being handled as follows is shown, this process is, carry out mixing at permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up of the NaOH Rong Ye ︰ with 50% and flood after 5 hours in NaOH solution, oxidizing roasting process in 2 hours is carried out at 450 DEG C, ore deposit liquid concentration is made to be 1% (w/v with hydrochloric acid, useless permanent magnet 10g, hydrochloric acid soln 1000ml) and carry out leaching for 20 minutes, Figure 11 b is the graphic representation of the leaching yield that the metal after being handled as follows is shown, this process is, NaOH Rong Ye ︰ with 50% permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up mixes, ore deposit liquid concentration is made to be 10% (w/v with hydrochloric acid, useless permanent magnet 100g, hydrochloric acid soln 1000ml) and leach.As shown in figures 1 la and 1 lb, 1% ore deposit liquid concentration and 10% ore deposit liquid concentration under the leaching yield of the Nd leaching yield that is all shown as more than 90%, Fe be less than 2%.
Figure 12 a is the graphic representation of the leaching yield that the metal after being handled as follows is shown, this process is, carry out mixing at permanent magnet powder=1 ︰ 1 (200ml ︰ 200g) that gives up of the NaOH Rong Ye ︰ with 50% and flood after 1 hour in NaOH solution, oxidizing roasting process in 2 hours is carried out at 450 DEG C, ore deposit liquid concentration is made to be 1% (w/v with hydrochloric acid, useless permanent magnet 10g, hydrochloric acid soln 1000ml) and carry out leaching for 20 minutes, Figure 12 b is the graphic representation of the leaching yield that the metal after being handled as follows is shown, this process is, NaOH Rong Ye ︰ with 50% permanent magnet powder=1 ︰ 1 (200ml ︰ 200g) that gives up mixes, ore deposit liquid concentration is made to be 10% (w/v with hydrochloric acid, useless permanent magnet 100g, hydrochloric acid soln 1000ml) and leach.As shown in figures 12 a and 12b, 1% ore deposit liquid concentration and 10% ore deposit liquid concentration under the leaching yield of the Nd leaching yield that is all shown as more than 90%, Fe be less than 2%.
The graphic representation of the leaching content of the metal after Figure 13 illustrates and is handled as follows, this process is, carry out mixing at permanent magnet powder=10 ︰ 1 (200ml ︰ 20g) that gives up of the NaOH Rong Ye ︰ with 50% and flood after 5 hours in NaOH solution, oxidizing roasting process in 2 hours is carried out at 600 DEG C, ore deposit liquid concentration is made to be 10% (w/v with hydrochloric acid, useless permanent magnet 100g, hydrochloric acid soln 1000ml) and carry out leaching for 20 minutes.As shown in figure 13, NdFeO can be generated when carrying out oxidizing roasting for 600 DEG C 3inhibit the leaching of Nd and Dy rare earth element mutually, on the contrary, the leaching of Fe but adds.Therefore, known in order to suppress NdFeO 3the generation of phase needs performing oxidizing roasting less than 600 DEG C.
Be illustrated about the specific embodiment optionally leaching the method for neodymium from the permanent magnet comprising neodymium of the present invention so far, but, multiple enforcement distortion obviously can be carried out in the limit do not departed from the scope of the present invention.
Therefore, the embodiment that scope of the present invention should not be limited to be described is determined, should determine by appended claims and with the scope of this claims equalization.
Namely, being interpreted as aforesaid embodiment is all exemplary in all respects, instead of it is determinate, compare detailed description, scope of the present invention is more shown by appended claims, and all changes of being derived by the meaning of these claims and scope and equivalent concepts thereof or the mode of distortion all should be interpreted as being contained in scope of the present invention.

Claims (12)

1. from the permanent magnet comprising neodymium, optionally leach a method for neodymium, comprise:
The permanent magnet comprising neodymium is made to impregnated in the step of NaOH solution;
Permanent magnet through described dipping is carried out to the step of oxidizing roasting process; And
By the step that acid makes the permanent magnet through described oxidizing roasting process leach.
2. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
The described permanent magnet comprising neodymium is NdFeB system permanent magnet.
3. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 2, is characterized in that,
Described NdFeB system permanent magnet is the chip or useless permanent magnet discarded after using that produce in permanent magnet manufacturing step.
4. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 3, is characterized in that,
Broken process is performed in order to make described use useless permanent magnet discarded afterwards have powder morphology.
5. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
The concentration of described NaOH solution is 10 ~ 60%.
6. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
Described NaOH solution is comprised to make the mode that the volume of described NaOH solution (ml) and the ratio of weight (g) of the permanent magnet comprising neodymium are 1 ~ 10.
7. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
Described be immersed in 50 ~ 110 DEG C perform 1 ~ 6 hour.
8. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
Described oxidizing roasting performs 1 ~ 5 hour more than 200 DEG C, less than 600 DEG C.
9. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
After described oxidizing roasting, neodymium is with Nd (OH) 3or Nd 2o 3exist.
10. the method optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
Described acid is sulfuric acid or hydrochloric acid.
11. methods optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
Be more than 3.00 to make hydrogen ion mole number relative to neodymium, mode less than 3.15 comprises described acid.
12. methods optionally leaching neodymium from the permanent magnet comprising neodymium according to claim 1, is characterized in that,
Described leaching performs 5 ~ 25 minutes at normal temperature.
CN201510059269.1A 2014-02-28 2015-02-04 The method that neodymium is optionally leached from the permanent magnet comprising neodymium Active CN104878204B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0024237 2014-02-28
KR1020140024237A KR101427158B1 (en) 2014-02-28 2014-02-28 Leaching method of neodymium from permanent magnet containing neodymium

Publications (2)

Publication Number Publication Date
CN104878204A true CN104878204A (en) 2015-09-02
CN104878204B CN104878204B (en) 2017-06-16

Family

ID=51749704

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510059269.1A Active CN104878204B (en) 2014-02-28 2015-02-04 The method that neodymium is optionally leached from the permanent magnet comprising neodymium

Country Status (2)

Country Link
KR (1) KR101427158B1 (en)
CN (1) CN104878204B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113652539A (en) * 2021-07-15 2021-11-16 江西理工大学 Method for comprehensively recycling neodymium iron boron waste by calcification roasting

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101562007B1 (en) 2015-02-26 2015-10-20 한국지질자원연구원 Leaching method of neodymium from permanent magnet scrap
KR101662445B1 (en) * 2015-05-07 2016-10-04 주식회사 에이.엠.씨 The selective leaching method of only the rare earth elements in the NdFeB magnet scrap
KR101792352B1 (en) 2015-11-16 2017-11-02 주식회사 에이.엠.씨 The Selective Dissolving Method of Rare Earth Elements by Hydrochloric acid in the Scrapped permanent magnet NdFeB
KR101935826B1 (en) * 2017-09-28 2019-01-07 한국지질자원연구원 Method for the separation of Nd and Dy by use of REE-sulfate double salt precipitation
KR102289085B1 (en) 2019-11-29 2021-08-12 한국생산기술연구원 Highly efficient leaching method of waste Nd permanent magnets by selective oxidation heat treatment and a powder produced thereby
KR102571774B1 (en) 2021-08-11 2023-08-28 성림희토금속 주식회사 Recovery of rare earth metal using phase decomposition with hydrogen and acid leaching
KR102577316B1 (en) 2021-10-14 2023-09-12 한국생산기술연구원 Selective Oxidation Heat Treatment Apparatus For Waste NdFeB Magnet Recycling And Method Thereof
KR102553034B1 (en) 2021-10-26 2023-07-10 성림희토금속 주식회사 Recovery of rare earth metal using phase decomposition with hydrogen environment, oxidizing roasting, and acid leaching
KR102632183B1 (en) 2021-12-21 2024-02-02 성림희토금속 주식회사 Recovery of rare earth metal using double step acid leaching

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362459A (en) * 1993-05-17 1994-11-08 Pure-Etch Co. Neodymium recovery process
JP2000144275A (en) * 1998-11-10 2000-05-26 Agency Of Ind Science & Technol Method for recovering rare earth element
CN1605638A (en) * 2004-06-28 2005-04-13 辽宁美宝稀土材料有限公司 Process for recovering rare earth from neodymium-ion-boron waste materials
KR20060040162A (en) * 2004-11-04 2006-05-10 한국지질자원연구원 Recovery of neodymium from ndfeb oxidation-roasted scrap by acetic acid leaching
KR101147643B1 (en) * 2012-02-17 2012-05-23 한국지질자원연구원 Neodymium leaching method using immersion method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362459A (en) * 1993-05-17 1994-11-08 Pure-Etch Co. Neodymium recovery process
JP2000144275A (en) * 1998-11-10 2000-05-26 Agency Of Ind Science & Technol Method for recovering rare earth element
CN1605638A (en) * 2004-06-28 2005-04-13 辽宁美宝稀土材料有限公司 Process for recovering rare earth from neodymium-ion-boron waste materials
KR20060040162A (en) * 2004-11-04 2006-05-10 한국지질자원연구원 Recovery of neodymium from ndfeb oxidation-roasted scrap by acetic acid leaching
KR101147643B1 (en) * 2012-02-17 2012-05-23 한국지질자원연구원 Neodymium leaching method using immersion method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王毅军等: "用盐酸优溶法从NdFeB废料中回收稀土", 《湿法冶金》 *
王素玲等: "从废铁合金中回收稀土的研究与生产", 《稀有金属与硬质合金》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113652539A (en) * 2021-07-15 2021-11-16 江西理工大学 Method for comprehensively recycling neodymium iron boron waste by calcification roasting

Also Published As

Publication number Publication date
CN104878204B (en) 2017-06-16
KR101427158B1 (en) 2014-08-07

Similar Documents

Publication Publication Date Title
CN104878204A (en) Leaching Method Of Neodymium From Permanent Magnet Containing Neodymium
JP5647750B2 (en) Rare earth recovery method from rare earth element containing alloys
Venkatesan et al. Selective extraction of rare-earth elements from NdFeB magnets by a room-temperature electrolysis pretreatment step
Liu et al. High-efficiency simultaneous extraction of rare earth elements and iron from NdFeB waste by oxalic acid leaching
KR101392307B1 (en) Recovery method of rare earth elements from waste permanent magnet
KR101147643B1 (en) Neodymium leaching method using immersion method
CN103509952B (en) The technique of recovering rare earth in a kind of electron wastes permanent magnet spent material
CN106498169B (en) A kind of neodymium iron boron waste material recovery process
US10648063B2 (en) Dissolution and separation of rare earth metals
Lai et al. Recovery of a composite powder from NdFeB slurry by co-precipitation
CN103146925B (en) Method of recycling rear earth from neodymium iron boron waste
JP5852478B2 (en) Rare earth recovery method from rare earth containing scrap
KR102289085B1 (en) Highly efficient leaching method of waste Nd permanent magnets by selective oxidation heat treatment and a powder produced thereby
CN113652550B (en) Method for comprehensively recovering rare earth and iron from neodymium iron boron oil sludge
CN104388684A (en) Method for preparing rare earth oxide slag from composite rare earth waste and method for leaching rare earth from slag
CN113652538A (en) Method for separating and recycling rare earth and iron from neodymium iron boron oil sludge
KR101193454B1 (en) Iron powder recovery method from waste permanent magnet
CN105886801B (en) A kind of method for recycling valuable dysprosium doping from discarded plating dysprosium molybdenum plate
Tran et al. Use of ferric salt solutions as leaching agents of Co, Ni, Cu, Fe, and Mn from metallic alloys of spent lithium-ion batteries and separation of iron from the leaching solution
CN113667819A (en) Method for separating and recycling neodymium iron boron waste materials through zinc roasting
KR102576614B1 (en) Method for recovering valuable metals from waste lithium ion batteries
Hua Rare earth recycling from NdFeB
CN114075626B (en) Method for integrally recovering rare earth metals in rare earth permanent magnet waste by utilizing hydrothermal method
CN113667823A (en) Method for comprehensively recovering rare earth and iron from neodymium iron boron waste
Isomura Development of chemical process for recovering high-quality rare-earth oxides from HV motor magnets

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