CN106044830A - Method for recycling and preparing rare earth oxide from neodymium iron boron permanent magnetic powder - Google Patents
Method for recycling and preparing rare earth oxide from neodymium iron boron permanent magnetic powder Download PDFInfo
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- CN106044830A CN106044830A CN201610360624.3A CN201610360624A CN106044830A CN 106044830 A CN106044830 A CN 106044830A CN 201610360624 A CN201610360624 A CN 201610360624A CN 106044830 A CN106044830 A CN 106044830A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
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Abstract
The invention discloses a method for recycling and preparing rare earth oxide from neodymium iron boron permanent magnetic powder. The method includes: well mixing the neodymium iron boron permanent magnetic powder with graphite powder according to a mass percentage ratio of 9:1, tabletting, and putting a mixed sample in a vacuum resistance furnace; vacuumizing until air pressure in a hearth is less than 10 Pa; allowing solid-phase reaction at temperature of 1200-1450 DEG C for 60 min; hydrolyzing a sample obtained by reaction in deionized water, and obtaining rare earth hydroxide and iron powder by means of magnetic separation; using a Muffle furnace to calcine the rare earth hydroxide in an air atmosphere at 600 DEG C for 2 h to obtain the rare earth oxide. Purity of the rare earth oxide recycled by the method is greater than 95%. The method is simple in technological process, environment-friendly, low in cost and easy for industrialization.
Description
Technical field
The invention belongs to field of resource recovery technique, relate to a kind of recovering rare earth unit from Nd-Fe-B permanent magnet material
Element, the method preparing rare earth oxide.This technique is with solid state reaction under neodymium iron boron and graphite mixed powder vacuum, aggregate sample hydrolysis system
Standby rare-earth hydroxide, rare-earth hydroxide calcines to obtain rare earth oxide.
Background technology
Nd-Fe-B permanent magnet material is widely applied to as third generation rare earth permanent-magnetic material, the combination property outstanding due to it
Multiple fields of modern industry, its demand is the most increasing.But can produce in the process of manufacture of neodymium iron boron product
Powdery, granular, block, pureed etc. various difform waste materials, constitute about the 30% of total amount.And along with electronics produces
Product aging, part neodymium iron boron product is discarded.Therefore above-mentioned neodymium iron boron waste material is reclaimed, and extract its Rare Earth Elements
Element will produce significant environmental benefit and considerable economic benefit.
Rare earth oxide is because the physicochemical properties of its uniqueness become the object that scholars is widely studied.Rare-earth oxidation
Thing has a wide range of applications at aspects such as optical material, catalysis material and magnetic materials.
From NdFeB material, rare earth oxide is prepared in recovery, not only reclaims rare earth resources, and prepare dilute
Soil oxide has high surcharge.
Summary of the invention
It is an object of the invention to the method that rare earth oxide is prepared in recovery from Nd-Fe-B permanent magnetic powder.
A kind of method that rare earth oxide is prepared in recovery from Nd-Fe-B permanent magnetic powder of the present invention, it is characterised in that have with
Under process and step:
A. Nd-Fe-B permanent magnet material powder and the solid state reaction of powdered graphite: by certain business fast quenching Nd-Fe-B permanent magnetic powder (neodymium
20.20%, praseodymium 4.72%, lanthanum 2.13%, cerium 0.26%, zirconium 5.20%, ferrum 66.35% and boron 1.14%) and powdered graphite press percent mass
Ratio is tabletting after the ratio mix homogeneously of 9:1；Vacuum resistance furnace is evacuated to burner hearth internal gas pressure and is less than 10Pa, then by neodymium iron boron
In described vacuum resistance furnace, it is heated to 1200-1450 DEG C with graphite aggregate sample, and is incubated 60min；Finally, sample furnace cooling
To room temperature, obtain the aggregate sample containing Rare Earth Carbides；
B. the hydrolysis of aggregate sample: above-mentioned aggregate sample is direct plungeed in Enough Dl water and hydrolyze, in hydrolytic process, rare earth carbonization
Thing and water react generation rare-earth hydroxide and depart from iron-based body, and the graphite in sample then floats to the water surface, releases a large amount of simultaneously
Gas；After hydrolysis terminates at room temperature, flotation is fallen to swim in the graphite of the water surface；
C. the magnetic separation separation of hydrolyzate and the calcining of rare-earth hydroxide: hydrolysis prods is carried out magnetic separation, through repeatedly washing magnetic
Choosing, obtains rare-earth hydroxide nano powder and iron powder；Rare-earth hydroxide is used in air atmosphere Muffle furnace 600 DEG C of calcinings
2h, obtains rare earth dioxide；Its purity is more than 95%；Major impurity is that iron sesquioxide can be solid-solution in the unit in ferrum with some
Element zirconium and boron.
Compared with the conventional method, the inventive method has the following characteristics that the rare earth dioxide purity 1. reclaiming preparation is big
In 95%.2. both at home and abroad the wet processing of report would generally produce a large amount of waste water, and the not only environmental protection of this technique but also low cost, former
Material only needs cheap graphite powder, and this technique not only achieves the recovery of rare earth element, and reclaims the surcharge of product
High.3. hydrolyzate hydrocarbon gas can reclaim as fuel gas, further increases the surcharge of the method.4. iron powder
Iron and steel enterprise's raw material as steel-making can be supplied to as reclaiming side-product.5. this technological process is short, by reasonably setting
Meter reactor, it is possible to achieve industrialized production.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of rare earth oxide.
Fig. 2 is the back-scattered scanning electron microphotograph of iron powder after hydrolysis.
Detailed description of the invention
In order to preferably describe the present invention, the method provided the present invention below in conjunction with embodiment is made to retouch the most in detail
State.
Embodiment 1
Certain business fast quenching Nd-Fe-B permanent magnetic powder is respectively as follows: neodymium 20.20%, praseodymium 4.72%, lanthanum containing different element mass percents
2.13%, cerium 0.26%, zirconium 5.20%, ferrum 66.35% and boron 1.14%.The condition of rare earth oxide is prepared in recovery: by Nd-Fe-B powder
End and powdered graphite be by mass percentage 9:1 ratio mix homogeneously after tabletting, vacuum resistance furnace is evacuated to gas in burner hearth
Pressure, less than 10Pa, is incubated 60min at a temperature of 1450 DEG C.Sample solid state reaction obtained and deionized water are with 1g/20ml's
Ratio mixes, and is hydrolyzed in room temperature, and hydrolysis time is 6h.By the rare-earth hydroxide of gained in atmosphere in 600 DEG C of calcinings
Process 2h, obtain rare earth oxide.The mass percent finally giving rare earth oxide and major impurity thereof is respectively as follows: titanium dioxide
Neodymium 69.89%, titanium dioxide praseodymium 16.45%, titanium dioxide lanthanum 7.96%, ceria 0.93%, boron 0.06%, zirconium carbide 1.30% and three oxygen
Change two ferrum 3.41%.After hydrolysis magnetic separation, gained iron powder Rare Earth Element Contents (quality %) is: neodymium 7.05%, praseodymium 1.39%, lanthanum 0.71%
With cerium 0.09%.By above-mentioned iron powder mechanical activation comminution, whole mistake 400 mesh sieves, particle diameter is less than 37 μm, then hydrolyzes magnetic separation gained rare earth unit
Cellulose content (quality %) is: neodymium 5.91%, praseodymium 1.30%, lanthanum 0.60% and cerium 0.09%.From the foregoing, the final rare earth oxygen reclaimed
The purity of compound is higher than 95.23%, and the response rate is higher than 77%.
Embodiment 2
Certain business fast quenching Nd-Fe-B permanent magnetic powder is respectively as follows: neodymium 20.20%, praseodymium 4.72%, lanthanum containing different element mass percents
2.13%, cerium 0.26%, zirconium 5.20%, ferrum 66.35% and boron 1.14%.The condition of rare earth oxide is prepared in recovery: by Nd-Fe-B powder
End and powdered graphite be by mass percentage 9:1 ratio mix homogeneously after tabletting, vacuum resistance furnace is evacuated to gas in burner hearth
Pressure, less than 10Pa, is incubated 60min at a temperature of 1200 DEG C.Sample solid state reaction obtained and deionized water are with 1g/20ml's
Ratio mixes, and is hydrolyzed in room temperature, and hydrolysis time is 6h.By the rare-earth hydroxide of gained in atmosphere in 600 DEG C of calcinings
Process 2h, obtain rare earth oxide.The mass percent finally giving rare earth oxide and major impurity thereof is respectively as follows: titanium dioxide
Neodymium 66.27%, titanium dioxide praseodymium 15.44%, titanium dioxide lanthanum 6.98%, ceria 0.74%, boron 1.09%, zirconium carbide 1.80% and three oxygen
Change two ferrum 8.68%.After hydrolysis magnetic separation, gained iron powder Rare Earth Element Contents (quality %) is: neodymium 8.12%, praseodymium 1.84%, lanthanum 0.81%
With cerium 0.09%.From the foregoing, the purity of the final rare earth oxide reclaimed is higher than 89.43%, the response rate is higher than 67%.
Fig. 1 show the X ray diffracting spectrum of rare earth oxide, collection of illustrative plates can be seen that the thing phase except rare earth oxide
Outward, the also peak of iron sesquioxide, the metallic iron being mixed into during magnetic separation separates can be presumably due to.
Fig. 2 show the back-scattered scanning electron microphotograph of iron powder after hydrolysis, it can be seen that after hydrolysis iron powder surface in
Flakey indenture, can be seen that from the size of indenture the Rare Earth Carbides particle diameter of generation is more much smaller than iron powder particle diameter, therefore should
Iron powder smashes into the chance that when more tiny granule can increase hydrolysis, Rare Earth Carbides contacts with water, thus improves the response rate.
Claims (1)
1. the method that rare earth oxide is prepared in recovery from Nd-Fe-B permanent magnetic powder, it is characterised in that there is following process
And step:
A. Nd-Fe-B permanent magnet material powder and the solid state reaction of powdered graphite: by certain business fast quenching Nd-Fe-B permanent magnetic powder (neodymium
20.20%, praseodymium 4.72%, lanthanum 2.13%, cerium 0.26%, zirconium 5.20%, ferrum 66.35% and boron 1.14%) and powdered graphite press percent mass
Ratio is tabletting after the ratio mix homogeneously of 9:1；Vacuum resistance furnace is evacuated to burner hearth internal gas pressure and is less than 10Pa, then by neodymium iron boron
In described vacuum resistance furnace, it is heated to 1200-1450 DEG C with graphite aggregate sample, and is incubated 60min；Finally, sample furnace cooling
To room temperature, obtain the aggregate sample containing Rare Earth Carbides；
B. the hydrolysis of aggregate sample: above-mentioned aggregate sample is direct plungeed in Enough Dl water and hydrolyze；In hydrolytic process, rare earth carbonization
Thing and water react generation rare-earth hydroxide and depart from iron-based body, and the graphite in sample then floats to the water surface, releases a large amount of simultaneously
Gas；After hydrolysis terminates at room temperature, flotation is fallen to swim in the graphite of the water surface；
C. the magnetic separation separation of hydrolyzate and the calcining of rare-earth hydroxide: hydrolysis prods is carried out magnetic separation；Through repeatedly washing magnetic
Choosing, obtains rare-earth hydroxide nano powder and iron powder；Rare-earth hydroxide is used in air atmosphere Muffle furnace 600 DEG C of calcinings
2h, obtains rare earth dioxide；Its purity is more than 95%；Major impurity is that iron sesquioxide can be solid-solution in the unit in ferrum with some
Element zirconium and boron.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610360624.3A CN106044830A (en) | 2016-05-28 | 2016-05-28 | Method for recycling and preparing rare earth oxide from neodymium iron boron permanent magnetic powder |
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| CN201610360624.3A CN106044830A (en) | 2016-05-28 | 2016-05-28 | Method for recycling and preparing rare earth oxide from neodymium iron boron permanent magnetic powder |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108866357A (en) * | 2018-06-07 | 2018-11-23 | 福建省华裕天恒科技有限公司 | A kind of method of low-grade NFB waste recovery rare earth |
| CN109385528A (en) * | 2018-11-01 | 2019-02-26 | 华南理工大学 | The recovery method of rare earth in a kind of useless permanent magnet |
| CN117684006A (en) * | 2023-08-02 | 2024-03-12 | 江西省科学院应用物理研究所 | Recovery method of NdFeB waste material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016399A (en) * | 2014-06-10 | 2014-09-03 | 上海大学 | Method for recovering and preparing nano rare earth hydroxide from neodymium iron boron permanent magnet material |
| CN104036940A (en) * | 2013-03-08 | 2014-09-10 | 三环瓦克华（北京）磁性器件有限公司 | Method for preparing sintered NdFeB magnet |
| CN104681225A (en) * | 2013-12-03 | 2015-06-03 | 湖南稀土金属材料研究院 | Treating method for improving performance of sintered NdFeB (neodymium iron boron) materials |
| CN105316485A (en) * | 2014-08-05 | 2016-02-10 | 阳泉市林兴磁性材料有限责任公司 | Recovery method for neodymium iron boron waste free of wastewater discharge |
-
2016
- 2016-05-28 CN CN201610360624.3A patent/CN106044830A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104036940A (en) * | 2013-03-08 | 2014-09-10 | 三环瓦克华（北京）磁性器件有限公司 | Method for preparing sintered NdFeB magnet |
| CN104681225A (en) * | 2013-12-03 | 2015-06-03 | 湖南稀土金属材料研究院 | Treating method for improving performance of sintered NdFeB (neodymium iron boron) materials |
| CN104016399A (en) * | 2014-06-10 | 2014-09-03 | 上海大学 | Method for recovering and preparing nano rare earth hydroxide from neodymium iron boron permanent magnet material |
| CN105316485A (en) * | 2014-08-05 | 2016-02-10 | 阳泉市林兴磁性材料有限责任公司 | Recovery method for neodymium iron boron waste free of wastewater discharge |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108866357A (en) * | 2018-06-07 | 2018-11-23 | 福建省华裕天恒科技有限公司 | A kind of method of low-grade NFB waste recovery rare earth |
| CN109385528A (en) * | 2018-11-01 | 2019-02-26 | 华南理工大学 | The recovery method of rare earth in a kind of useless permanent magnet |
| CN117684006A (en) * | 2023-08-02 | 2024-03-12 | 江西省科学院应用物理研究所 | Recovery method of NdFeB waste material |
| CN117684006B (en) * | 2023-08-02 | 2024-06-28 | 江西省科学院应用物理研究所 | Recovery method of NdFeB waste material |
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Application publication date: 20161026 |