CN107363263B - A kind of recovery method of waste and old neodymium iron boron - Google Patents
A kind of recovery method of waste and old neodymium iron boron Download PDFInfo
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- CN107363263B CN107363263B CN201710625061.0A CN201710625061A CN107363263B CN 107363263 B CN107363263 B CN 107363263B CN 201710625061 A CN201710625061 A CN 201710625061A CN 107363263 B CN107363263 B CN 107363263B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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Abstract
The invention discloses a kind of recovery methods of waste and old neodymium iron boron, belong to waste resource utilization technology field.It includes pretreatment, waste and old neodymium iron boron is cleaned up and dried, hydrogen is quick-fried again for first coarse crushing in advance, it is crushed, is sieved under certain temperature and pressure with hydrogen, broken neodymium iron boron waste material is separated with coating, it is broken, fine grain neodymium iron boron is subjected to the regeneration with broken, by further broken neodymium iron boron particle and the freshly prepd molding neodymium iron boron of neodymium iron boron material mixed regeneration.A kind of recovery method of waste and old neodymium iron boron of the invention realizes the complete recycling of waste and old neodymium iron boron, and each rate of recovery is high, and realizes high-end circulation, and obtained waste and old neodymium iron boron material and brand-new neodymium iron boron material proportion >=1, waste water yield is few, and at low cost, low energy consumption.
Description
Technical field
The present invention relates to a kind of recovery methods of waste and old neodymium iron boron, belong to waste resource utilization technology field.
Background technique
Rare earth permanent-magnetic material neodymium iron boron magnetic body from 1985 enter industrialization production since, only used twenties years when
Between, global yield just reaches 120,000 tons, and its use scope constantly expands.Currently, large quantities of productions using the magnet steel component
The automobile-used Nd-Fe-B magnet steel of product, especially electrical salf-walking has had passed over the product service life period, the product magnet steel component
Efficiently, the key subjects that cleaning recovering rare earth Permanent Magnet Material Industry faces.
In process of production, to improve corrosion resistance, one or more layers nickel has mostly been electroplated in surface to Nd-Fe-B magnet steel
Or the protective layer of zinc metal, the magnet steel is recycled, first has to remove electroplated layer, zinc coat can be cleared easily with acid wash, and plates
For nickel layer since its chemical property is stablized, adhesive force is strong, removes rather laborious.
Currently, domestic enterprise recycles nickel plating magnet steel, there are mainly two types of methods: first is that hydrometallurgy recovering rare earth oxide；
Second is that the Nd-Fe-B magnet steel of nickel plating is directly put into mid-frequency melting furnace melting, new production is produced in then powder processed, molding, sintering
Product.First method is time-consuming and laborious, and energy consumption is high, three wastes discharge amount is big, can only be with rare earth oxide low value Product recycling；And second
Kind method forms neodymium ni-b alloy since nickel metal enters iron phase in fusion process, reduce final neodymium iron boron and produce
The comprehensive magnetic energy of product, thus the recycling magnet steel raw material can only produce low-end product, and low-end product can not have to rare earth dysprosium, because
But waste the rare earth metal dysprosium element of high value.
Summary of the invention
In view of this, realizing the complete of waste and old neodymium iron boron the present invention provides a kind of recovery method of waste and old neodymium iron boron
Recycling, each rate of recovery is high, and realizes high-end circulation, and obtained waste and old neodymium iron boron material and brand-new neodymium iron boron material proportion >=1 are given up
Water yield is few, at low cost, and low energy consumption.
The present invention solves above-mentioned technical problem by following technological means:
A kind of recovery method of waste and old neodymium iron boron of the invention, is following steps:
(1) it pre-processes, waste and old neodymium iron boron addition detergent is washed, then detergent is rinsed well and dried with water
It is dry；
(2) hydrogen is quick-fried, and washes clean and the waste and old neodymium iron boron first preparatory coarse crushing of drying place into the quick-fried device of hydrogen, lead to
Enter and continue to be passed through hydrogen after hydrogen catches up with the air in the quick-fried device of hydrogen only completely, Hydrogen Vapor Pressure is in the maintenance quick-fried device of hydrogen
0.11-0.12Mpa, while being warming up to temperature is 450-500 DEG C, heating rate is 5-10 DEG C/min, then maintains this temperature 2-3
Hour, then start to cool down, it is cooled to room temperature, cooling rate is 20-30 DEG C/min；
(3) it sieves, after material of the hydrogen after quick-fried is taken out, is sieved, the neodymium iron boron particle of coating and hydrogen after quick-fried is carried out
Screening separation, for the sieve used for 50-80 mesh, oversize is coating, and screenings is neodymium iron boron particle；
(4) it is crushed, screenings is added in airflow milling and is crushed, air-flow uses stream of nitrogen gas, broken material
It is separated by turbine separator, 4-5 μm of material discharge, the material sinking greater than 5 μm continues to be crushed；
(5) it regenerates, by broken fine powder and produces upper freshly prepared Nd2Fe14B fine powder 1:0.8-1 in mass ratio carries out biradical
Green compact, sintering and surface treatment regeneration are carried out after mixed powder obtains neodymium iron boron material.
Step (1) detergent is water system industrial cleaning agent, and wash time is 1-2 hours, wash temperature 50-60
DEG C, the additional ultrasonic wave of washing process, the mass fraction of detergent is 10-15%.
The quick-fried device of hydrogen is Horizontal enclosed tank in the step (2), is provided with air inlet and air outlet on the quick-fried device of hydrogen, horizontal
Transmission device is provided on hermetically sealed can, transmission device drives the rotation of Horizontal enclosed tank, is provided on Horizontal enclosed tank peripheral wall infrared
Heating device is provided with pressure sensor and temperature sensor on Horizontal enclosed tank.
Step (3) screening process, is passed through inert gas in vibrating screen and is protected.
The bottom of the airflow milling is provided with nozzle, and turbine separator, turbine separation dress are provided at the top of airflow milling
It sets and is provided with discharge port, be provided with variable-frequency motor on the turbine separator, variable-frequency motor is connect with turbine, the discharging
Mouth is connect with dust arrester installation, and the dust arrester installation is connect with air-introduced machine, and the cloth bag that gathers dust is provided on dust arrester installation, is set on air-introduced machine
It is equipped with electrostatic precipitator.
The broken air pressure used of the step (4) is 2-2.5 atmospheric pressure, the revolving speed of turbine in the turbine separator
For 2000-2500r/min.
The coating is put into autoclave, under 3-4 atmospheric pressure, is passed through oxygen, anti-in 150-180 DEG C of stirring
It answers 2-2.5 hours, mixing speed 200-300r/min, reacts to the pH3-3.5 of solution, being subsequently cooled to temperature is 70-80
DEG C, filtering obtains the first filtrate and the first filter residue, and fluoride is added in the first filtrate, temperature be 70-80 DEG C reaction 1-2 hours,
Filtering obtains the second filtrate and the second filter residue, and pure cobalt liquor is added in the second filtrate, deploys cobalt nickel molar ratio in the second filtrate
For 8-8.5:1-1.5, P204 extractant is then added and is extracted, obtains P204 cobalt nickel organic phase, ammonium hydroxide and hydroxide is added
The mixed solution of sodium is stirred, and the molal quantity of ammonium hydroxide and sodium hydroxide is 1:4-5, and cobalt nickel always rubs in P204 cobalt nickel organic phase
The ratio between mixed solution total mole number hydroxy of that number and ammonium hydroxide and sodium hydroxide is 1:2.2-2.3, is mixed at 50-60 DEG C
30-60 minutes, mixing speed 500-600r/min, blender use dispersion impeller blender, end of reaction by centrifuge from
Heart separation, obtained solid obtain the ball-type nickel cobalt hydroxide that partial size is 3-4 μm after acetone washing after drying,
It is prepared as battery material.
First filter residue by 1-2mol/L sulfuric acid solution wash, 70-80 DEG C reaction 3-4 hours, then filter
Pure water is used afterwards, obtains the iron oxide red of purity > 95%, is used as pigment, it is 3-4mol/L that concentration, which is added, in second filter residue
Sodium hydroxide solution, 50-60 DEG C reaction 2-3 hours, filtering, obtained filtrate contains fluorine ion, returns mixed with fluoride
It closes and uses, sulfuric acid dissolution is added in obtained filter residue, and concentration crystallizes to obtain Dineodymium trisulfate crystal.
There is the feature for inhaling hydrogen and dehydrogenation at different temperature using rare earth intermetallic compound, it is broken separable using hydrogen
Main phase neodymium iron boron, Nd-rich phase and nickel coating out, this is because main phase Nd in NdFeB material2Fe14B, it is swollen to inhale hydrogen volume for rich-Nd phase
Swollen coefficient has significant difference and usually rich-Nd phase preferentially inhales hydrogen and coating Ni without hydrogen-absorbing ability, this results in the hydrogen in HD
Change the regional area generation volume expansion and internal stress that hydride is formed when processing, when internal stress is more than Nd2Fe14B material it is strong
Degree generation hydrogen is quick-fried, and rich-Nd phase hydrogenates first, and then main phase hydrogenates, the former causes intercrystalline cracking (grain boundary fracture), and the latter causes to wear
Crystalline substance fracture (intercrystalline fracture), so that reaching removes nickel coating, main phase, the purpose of rich-Nd phase dusting, thus can get granularity compared with
Uniform Nd Fe B alloys fine powder.
The fine powder obtained after HD is handled is screened to flow grinder sequence powder except supplying gas after nickel.Gas is utilized in airflow milling equipment
Stream by powder particle accelerate to supersonic speed be allowed to mutually collide and be crushed, and turbine separator fine powder discharge, coarse powder sinking
Continue to crush, fine powder is made.
Fine powder made from waste and old Nd-Fe-B magnet steel will be recycled and produce upper freshly prepared Nd2Fe14B fine powder according to a certain percentage into
The postorders such as forming and sintering are sent to handle after the biradical mixed powder of row.The neodymium iron boron magnetic materials of middle and high end performance can be prepared under new process.Using this
The recycling problem of the method not only waste and old Nd-Fe-B magnet steel of very good solution, at the same be also greatly saved new product preparation process at
This.
The technic index that the present invention reaches is as follows:
A) rare earth element recovery utilization rate >=98.5% in waste and old magnet steel；
B) energy consumption reduces by 50% than smelting process；
C) waste and old magnet steel and virgin material proportion >=1；
D) product comprehensive magnetic, which is able to satisfy, prepares electronic automobile-used neodymium iron boron technical indicator, that is, is not less than 38M, 38H and 35SH
Trade mark magnet steel comprehensive magnetic energy.
Waste and old nickel plating neodymium iron boron, metal dysprosium content break method (hydrogen using hydrogen all 2% or more
Decrepitation HD) remove nickel skin new process, can preferable cleared waste and old magnet steel surface attachment nickel metal, do not influence again
The magnetic property of magnetisation steel, and it is pollution-free, at low cost, work efficiency is high.It is compared to hydrometallurgy recovering rare earth oxide, is saved significantly
About cost, reduces the discharge of pollutant；Compared to smelting process, one of highly energy-consuming process is lacked, has taken full advantage of in raw material
Rare earth dysprosium metal, improve product specification.
Without chemical agent, does not have to intermediate frequency furnace and smelt, it is ingenious to utilize its own characteristic, it is removed and is electroplated with simplest method
Layer and broken magnet carry out simultaneously, do not increase enterprise's existing equipment, are being inhaled using main phase, the Nd-rich phase in neodymium iron boron magnetic body
The coefficient of cubical expansion is different when hydrogen and nickel metal and the unresponsive characteristic of hydrogen, keeps electroless nickel layer and Nd Fe B alloys body peeling-off
And disintegration screens out its nickel coating to achieve the effect that crushing, has just obtained pure NdFeB magnetic powder.With simplest side
Method removes electroplated layer and broken magnet carries out simultaneously, shortens process flow, energy conservation, and return expensive nickel metal effectively
It receives.Compared with wet process can only obtain earth oxide product, this technology can directly obtain the much higher Nd-Fe-B permanent magnetic of the output value and produce
Product；Compared with smelting process effectively cannot remove nickel coating, since this method nickel metal enters iron phase i.e. shape in fusion process
At neodymium nickel boron and Nd Fe B alloys, the comprehensive magnetic energy of its final neodymium iron boron product, thus the recycling magnet steel raw material are reduced
Low-end product can only be produced, and low-end product can not have to rare earth dysprosium, thus be to waste high value rare earth gold in waste and old magnet steel
Belong to dysprosium element, and the waste and old magnet steel of this technology does not enter vacuum melting and directly carries out hydrogen and breaks.
The present invention has been handled simultaneously using chemical method containing nickel coating simultaneously, is leached using high pressure oxygen, high-efficient, is leached
Rate is high, and the iron contained simultaneously can directly obtain to obtain iron oxide red, can not only separate iron, but also can adequately utilize iron, obtain
The solution of the pure nickel containing cobalt is obtained, using extraction to high value-added product using fluoride by a small amount of rare-earth precipitation
P204 cobalt nickel organic phase is obtained, the mixture of sodium hydroxide and ammonium hydroxide is added, back extraction and precipitating is realized, obtains nickel cobalt binary hydrogen-oxygen
Compound precipitating, the preparation for anode material for lithium-ion batteries.The fluoride precipitating obtained simultaneously is added alkali and carries out precipitating conversion,
Obtain the hydroxide of rare earth, acid adding, which dissolves to obtain earth solution, carrys out recovering rare earth, and obtained soluble fluoride solution can be with
Fluoride is used for precipitating rare earth together, realizes recycling for fluorine ion, and improves the rate of recovery of rare earth.
Beneficial effects of the present invention:
(1) the complete recycling of the various components of waste and old neodymium iron boron is realized, 95% or more neodymium iron boron component is by broken sieve
After point, it is directly used in the preparation of new neodymium iron boron, realizes high-end circulation, a small amount of neodymium iron boron and nickel coating pass through hyperbaric oxygen
Gas leaches, and directly obtains ferric oxide red colorant and the solution containing rare earth and nickel cobalt, and fluoride is added and obtains rare-earth precipitation, passes through
Precipitating conversion recovering rare earth is crossed, the overall recovery of final rare earth reaches 98.5% or more, and nickel and cobalt solution is after allotment, using anti-
The extraction precipitation method obtain nickel cobalt binary hydroxide, for the preparation of battery material, to realize returning completely for waste and old neodymium iron boron
It receives, and the obtained uniform high added value of regenerant.
(2) using detergent by the greasy dirt of waste and old neodymium iron boron and other it is dirty wash off, then carry out coarse crushing in advance, then adopt
It is handled with the quick-fried method of hydrogen, also protects neodymium iron boron not oxidized while neodymium iron boron can be crushed, screening process realizes neodymium iron boron
The separation of particle and coating also further avoids the oxidation of neodymium iron boron particle using inert gas shielding, using gas mill come into
One step is levigate, and nitrogen protects waste and old neodymium iron boron fines as gas source, at the same be crushed to granularity be 4-5 μm, can preferably with
Freshly prepd neodymium iron boron mixing, simultaneously because the pretreatment and safeguard measure of early period, >=50% recovered material can be added and
The performance of freshly prepd neodymium iron boron is not influenced.
(3) low energy consumption, at low cost, is reduced costs using this technique and energy consumption, quantity of wastewater effluent also friendly to environment
It is few, it is generated substantially without exhaust gas and waste residue.
Detailed description of the invention
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is flow chart of the invention.
Specific embodiment
Below with reference to attached drawing, the present invention is described in detail, as shown in Figure 1: a kind of waste and old neodymium iron boron of the present embodiment
Recovery method, be following steps:
(1) it pre-processes, waste and old neodymium iron boron addition detergent is washed, then detergent is rinsed well and dried with water
It is dry；
(2) hydrogen is quick-fried, and washes clean and the waste and old neodymium iron boron first preparatory coarse crushing of drying place into the quick-fried device of hydrogen, lead to
Enter and continue to be passed through hydrogen after hydrogen catches up with the air in the quick-fried device of hydrogen only completely, Hydrogen Vapor Pressure is in the maintenance quick-fried device of hydrogen
0.11-0.12Mpa, while being warming up to temperature is 450-500 DEG C, heating rate is 5-10 DEG C/min, then maintains this temperature 2-3
Hour, then start to cool down, it is cooled to room temperature, cooling rate is 20-30 DEG C/min；
(3) it sieves, after material of the hydrogen after quick-fried is taken out, is sieved, the neodymium iron boron particle of coating and hydrogen after quick-fried is carried out
Screening separation, for the sieve used for 50-80 mesh, oversize is coating, and screenings is neodymium iron boron particle；
(4) it is crushed, screenings is added in airflow milling and is crushed, air-flow uses stream of nitrogen gas, broken material
It is separated by turbine separator, 4-5 μm of material discharge, the material sinking greater than 5 μm continues to be crushed；
(5) it regenerates, by broken fine powder and produces upper freshly prepared Nd2Fe14B fine powder 1:0.8-1 in mass ratio carries out biradical
Green compact, sintering and surface treatment regeneration are carried out after mixed powder obtains neodymium iron boron material.
Step (1) detergent is water system industrial cleaning agent, and wash time is 1-2 hours, wash temperature 50-60
DEG C, the additional ultrasonic wave of washing process, the mass fraction of detergent is 10-15%.
The quick-fried device of hydrogen is Horizontal enclosed tank in the step (2), is provided with air inlet and air outlet on the quick-fried device of hydrogen, horizontal
Transmission device is provided on hermetically sealed can, transmission device drives the rotation of Horizontal enclosed tank, is provided on Horizontal enclosed tank peripheral wall infrared
Heating device is provided with pressure sensor and temperature sensor on Horizontal enclosed tank.
Step (3) screening process, is passed through inert gas in vibrating screen and is protected.
The bottom of the airflow milling is provided with nozzle, and turbine separator, turbine separation dress are provided at the top of airflow milling
It sets and is provided with discharge port, be provided with variable-frequency motor on the turbine separator, variable-frequency motor is connect with turbine, the discharging
Mouth is connect with dust arrester installation, and the dust arrester installation is connect with air-introduced machine, and the cloth bag that gathers dust is provided on dust arrester installation, is set on air-introduced machine
It is equipped with electrostatic precipitator.
The broken air pressure used of the step (4) is 2-2.5 atmospheric pressure, the revolving speed of turbine in the turbine separator
For 2000-2500r/min.
The coating is put into autoclave, under 3-4 atmospheric pressure, is passed through oxygen, anti-in 150-180 DEG C of stirring
It answers 2-2.5 hours, mixing speed 200-300r/min, reacts to the pH3-3.5 of solution, being subsequently cooled to temperature is 70-80
DEG C, filtering obtains the first filtrate and the first filter residue, and fluoride is added in the first filtrate, temperature be 70-80 DEG C reaction 1-2 hours,
Filtering obtains the second filtrate and the second filter residue, and pure cobalt liquor is added in the second filtrate, deploys cobalt nickel molar ratio in the second filtrate
For 8-8.5:1-1.5, P204 extractant is then added and is extracted, obtains P204 cobalt nickel organic phase, ammonium hydroxide and hydroxide is added
The mixed solution of sodium is stirred, and the molal quantity of ammonium hydroxide and sodium hydroxide is 1:4-5, and cobalt nickel always rubs in P204 cobalt nickel organic phase
The ratio between mixed solution total mole number hydroxy of that number and ammonium hydroxide and sodium hydroxide is 1:2.2-2.3, is mixed at 50-60 DEG C
30-60 minutes, mixing speed 500-600r/min, blender use dispersion impeller blender, end of reaction by centrifuge from
Heart separation, obtained solid obtain the ball-type nickel cobalt hydroxide that partial size is 3-4 μm after acetone washing after drying,
It is prepared as battery material.
First filter residue by 1-2mol/L sulfuric acid solution wash, 70-80 DEG C reaction 3-4 hours, then filter
Pure water is used afterwards, obtains the iron oxide red of purity > 95%, is used as pigment, it is 3-4mol/L that concentration, which is added, in second filter residue
Sodium hydroxide solution, 50-60 DEG C reaction 2-3 hours, filtering, obtained filtrate contains fluorine ion, returns mixed with fluoride
It closes and uses, sulfuric acid dissolution is added in obtained filter residue, and concentration crystallizes to obtain Dineodymium trisulfate crystal.
Embodiment 1
(1) it pre-processes, waste and old neodymium iron boron addition detergent is washed, then detergent is rinsed well and dried with water
It is dry；
(2) hydrogen is quick-fried, and washes clean and the waste and old neodymium iron boron first preparatory coarse crushing of drying place into the quick-fried device of hydrogen, lead to
Enter and continue to be passed through hydrogen after hydrogen catches up with the air in the quick-fried device of hydrogen only completely, Hydrogen Vapor Pressure is in the maintenance quick-fried device of hydrogen
0.115Mpa, while being warming up to temperature is 476 DEG C, heating rate is 8.2 DEG C/min, then maintains this temperature 2.5 hours, then open
Begin to cool down, be cooled to room temperature, cooling rate is 25 DEG C/min；
(3) it sieves, after material of the hydrogen after quick-fried is taken out, is sieved, the neodymium iron boron particle of coating and hydrogen after quick-fried is carried out
Screening separation, for the sieve used for 50 mesh, oversize is coating, and screenings is neodymium iron boron particle；
(4) it is crushed, screenings is added in airflow milling and is crushed, air-flow uses stream of nitrogen gas, broken material
It is separated by turbine separator, 4-5 μm of material discharge, the material sinking greater than 5 μm continues to be crushed；
(5) it regenerates, by broken fine powder and produces upper freshly prepared Nd2Fe14B fine powder 1:0.95 in mass ratio carries out biradical mixed
Green compact, sintering and surface treatment regeneration are carried out after powder obtains neodymium iron boron material.
Step (1) detergent is water system industrial cleaning agent, and wash time is 1.5 hours, and wash temperature is 55 DEG C, is washed
The additional ultrasonic wave of process is washed, the mass fraction of detergent is 12.5%.
The quick-fried device of hydrogen is Horizontal enclosed tank in the step (2), is provided with air inlet and air outlet on the quick-fried device of hydrogen, horizontal
Transmission device is provided on hermetically sealed can, transmission device drives the rotation of Horizontal enclosed tank, is provided on Horizontal enclosed tank peripheral wall infrared
Heating device is provided with pressure sensor and temperature sensor on Horizontal enclosed tank.
Step (3) screening process, is passed through inert gas in vibrating screen and is protected.
The bottom of the airflow milling is provided with nozzle, and turbine separator, turbine separation dress are provided at the top of airflow milling
It sets and is provided with discharge port, be provided with variable-frequency motor on the turbine separator, variable-frequency motor is connect with turbine, the discharging
Mouth is connect with dust arrester installation, and the dust arrester installation is connect with air-introduced machine, and the cloth bag that gathers dust is provided on dust arrester installation, is set on air-introduced machine
It is equipped with electrostatic precipitator.
The broken air pressure used of the step (4) is 2.3 atmospheric pressure, and the revolving speed of turbine is in the turbine separator
2450r/min。
The coating is put into autoclave, under 3.5 atmospheric pressures, is passed through oxygen, is stirred to react at 170 DEG C
It 2.35 hours, mixing speed 250r/min, reacts to the pH3.35 of solution, being subsequently cooled to temperature is 75 DEG C, and filtering obtains
Fluoride is added in first filtrate and the first filter residue, the first filtrate, is 75 DEG C in temperature and reacts 1.3 hours, and filtering obtains the second filter
Pure cobalt liquor is added in liquid and the second filter residue, the second filtrate, and deploying cobalt nickel molar ratio in the second filtrate is 8.4:1.3, then
P204 extractant is added to be extracted, P204 cobalt nickel organic phase is obtained, the mixed solution stirring that ammonium hydroxide and sodium hydroxide is added is mixed
It closes, the molal quantity of ammonium hydroxide and sodium hydroxide is 1:4.8, the total mole number and ammonium hydroxide and hydroxide of cobalt nickel in P204 cobalt nickel organic phase
The ratio between the mixed solution of sodium total mole number hydroxy is 1:2.25, is mixed 50 minutes, mixing speed 550r/min at 58 DEG C,
Blender uses dispersion impeller blender, and end of reaction is centrifugated by centrifuge, and obtained solid is after acetone washing, warp
The ball-type nickel cobalt hydroxide that partial size is 3.5 μm is obtained after crossing drying, is used as battery material and prepares.
First filter residue is washed by the sulfuric acid solution of 1.8mol/L, is reacted at 75 DEG C 3.5 hours, is used after then filtering
Pure water obtains the iron oxide red of purity > 95%, is used as pigment, and the hydrogen that concentration is 3.5mol/L is added in second filter residue
Sodium hydroxide solution is reacted 2.8 hours at 55 DEG C, filtering, and obtained filtrate contains fluorine ion, and return is used in mixed way with fluoride,
Sulfuric acid dissolution is added in obtained filter residue, and concentration crystallizes to obtain Dineodymium trisulfate crystal.
It is final:
Rare earth total recovery: 98.9%；The total recovery of iron: 99.2%；The total recovery of nickel cobalt: 99.1%
The index of iron oxide red meets the requirement of GB/T1863-2008
The index of obtained nickel cobalt binary hydroxide is as follows:
| Index | Jolt ramming | Specific surface | D10 | D50 | D90 |
| Numerical value | 2.2g/mL | 12m2/g | 4.7μm | 3.5μm | 6.5μm |
| Magnetic foreign body | Fe | Cu | Ca | Mg | Sulfate radical |
| 0.02ppm | 1ppm | 0.2ppm | 5ppm | 4ppm | 30ppm |
The performance of the neodymium iron boron of finally obtained brand-new is as follows:
Embodiment 2
(1) it pre-processes, waste and old neodymium iron boron addition detergent is washed, then detergent is rinsed well and dried with water
It is dry；
(2) hydrogen is quick-fried, and washes clean and the waste and old neodymium iron boron first preparatory coarse crushing of drying place into the quick-fried device of hydrogen, lead to
Enter and continue to be passed through hydrogen after hydrogen catches up with the air in the quick-fried device of hydrogen only completely, Hydrogen Vapor Pressure is in the maintenance quick-fried device of hydrogen
0.116Mpa, while being warming up to temperature is 495 DEG C, heating rate is 8.5 DEG C/min, then maintains this temperature 2.7 hours, then open
Begin to cool down, be cooled to room temperature, cooling rate is 29 DEG C/min；
(3) it sieves, after material of the hydrogen after quick-fried is taken out, is sieved, the neodymium iron boron particle of coating and hydrogen after quick-fried is carried out
Screening separation, for the sieve used for 80 mesh, oversize is coating, and screenings is neodymium iron boron particle；
(4) it is crushed, screenings is added in airflow milling and is crushed, air-flow uses stream of nitrogen gas, broken material
It is separated by turbine separator, 4-5 μm of material discharge, the material sinking greater than 5 μm continues to be crushed；
(5) it regenerates, by broken fine powder and produces upper freshly prepared Nd2Fe14B fine powder 1:0.94 in mass ratio carries out biradical mixed
Green compact, sintering and surface treatment regeneration are carried out after powder obtains neodymium iron boron material.
Step (1) detergent is water system industrial cleaning agent, and wash time is 1.5 hours, and wash temperature is 50 DEG C, is washed
The additional ultrasonic wave of process is washed, the mass fraction of detergent is 13.8%.
The quick-fried device of hydrogen is Horizontal enclosed tank in the step (2), is provided with air inlet and air outlet on the quick-fried device of hydrogen, horizontal
Transmission device is provided on hermetically sealed can, transmission device drives the rotation of Horizontal enclosed tank, is provided on Horizontal enclosed tank peripheral wall infrared
Heating device is provided with pressure sensor and temperature sensor on Horizontal enclosed tank.
Step (3) screening process, is passed through inert gas in vibrating screen and is protected.
The bottom of the airflow milling is provided with nozzle, and turbine separator, turbine separation dress are provided at the top of airflow milling
It sets and is provided with discharge port, be provided with variable-frequency motor on the turbine separator, variable-frequency motor is connect with turbine, the discharging
Mouth is connect with dust arrester installation, and the dust arrester installation is connect with air-introduced machine, and the cloth bag that gathers dust is provided on dust arrester installation, is set on air-introduced machine
It is equipped with electrostatic precipitator.
The broken air pressure used of the step (4) is 2.43 atmospheric pressure, the revolving speed of turbine in the turbine separator
For 2300r/min.
The coating is put into autoclave, under 3.5 atmospheric pressures, is passed through oxygen, is stirred to react at 175 DEG C
It 2.42 hours, mixing speed 280r/min, reacts to the pH3.4 of solution, being subsequently cooled to temperature is 71 DEG C, and filtering obtains
Fluoride is added in first filtrate and the first filter residue, the first filtrate, is 72 DEG C in temperature and reacts 1.7 hours, and filtering obtains the second filter
Pure cobalt liquor is added in liquid and the second filter residue, the second filtrate, and deploying cobalt nickel molar ratio in the second filtrate is 8.2:1.4, then
P204 extractant is added to be extracted, P204 cobalt nickel organic phase is obtained, the mixed solution stirring that ammonium hydroxide and sodium hydroxide is added is mixed
It closes, the molal quantity of ammonium hydroxide and sodium hydroxide is 1:4.2, the total mole number and ammonium hydroxide and hydroxide of cobalt nickel in P204 cobalt nickel organic phase
The ratio between the mixed solution of sodium total mole number hydroxy is 1:2.27, is mixed 50 minutes, mixing speed 550r/min at 58 DEG C,
Blender uses dispersion impeller blender, and end of reaction is centrifugated by centrifuge, and obtained solid is after acetone washing, warp
The ball-type nickel cobalt hydroxide that partial size is 3.85 μm is obtained after crossing drying, is used as battery material and prepares.
First filter residue is washed by the sulfuric acid solution of 1.8mol/L, is reacted at 78 DEG C 3.6 hours, is used after then filtering
Pure water obtains the iron oxide red of purity > 95%, is used as pigment, and the hydrogen that concentration is 3.5mol/L is added in second filter residue
Sodium hydroxide solution is reacted 2.8 hours at 57 DEG C, filtering, and obtained filtrate contains fluorine ion, and return is used in mixed way with fluoride,
Sulfuric acid dissolution is added in obtained filter residue, and concentration crystallizes to obtain Dineodymium trisulfate crystal.
It is final:
Rare earth total recovery: 99.1%；The total recovery of iron: 99.2%；The total recovery of nickel cobalt: 99.2%
The index of iron oxide red meets the requirement of GB/T1863-2008
The index of obtained nickel cobalt binary hydroxide is as follows:
The performance of the neodymium iron boron of finally obtained brand-new is as follows:
| Maximum operating temperature | Curie temperature | Remanence strength | Coercivity | Maximum magnetic energy product |
| 150 DEG C of > | > 585K | 1390br mT | 13.9K Oe | 360MG Oe |
Embodiment 3
(1) it pre-processes, waste and old neodymium iron boron addition detergent is washed, then detergent is rinsed well and dried with water
It is dry；
(2) hydrogen is quick-fried, and washes clean and the waste and old neodymium iron boron first preparatory coarse crushing of drying place into the quick-fried device of hydrogen, lead to
Enter and continue to be passed through hydrogen after hydrogen catches up with the air in the quick-fried device of hydrogen only completely, Hydrogen Vapor Pressure is in the maintenance quick-fried device of hydrogen
0.117Mpa, while being warming up to temperature is 475 DEG C, heating rate is 6.9 DEG C/min, then maintains this temperature 2.8 hours, then open
Begin to cool down, be cooled to room temperature, cooling rate is 21 DEG C/min；
(3) it sieves, after material of the hydrogen after quick-fried is taken out, is sieved, the neodymium iron boron particle of coating and hydrogen after quick-fried is carried out
Screening separation, for the sieve used for 65 mesh, oversize is coating, and screenings is neodymium iron boron particle；
(4) it is crushed, screenings is added in airflow milling and is crushed, air-flow uses stream of nitrogen gas, broken material
It is separated by turbine separator, 4-5 μm of material discharge, the material sinking greater than 5 μm continues to be crushed；
(5) it regenerates, by broken fine powder and produces upper freshly prepared Nd2Fe14B fine powder 1:0.85 in mass ratio carries out biradical mixed
Green compact, sintering and surface treatment regeneration are carried out after powder obtains neodymium iron boron material.
Step (1) detergent is water system industrial cleaning agent, and wash time is 1.8 hours, and wash temperature is 55 DEG C, is washed
The additional ultrasonic wave of process is washed, the mass fraction of detergent is 14.5%.
The quick-fried device of hydrogen is Horizontal enclosed tank in the step (2), is provided with air inlet and air outlet on the quick-fried device of hydrogen, horizontal
Transmission device is provided on hermetically sealed can, transmission device drives the rotation of Horizontal enclosed tank, is provided on Horizontal enclosed tank peripheral wall infrared
Heating device is provided with pressure sensor and temperature sensor on Horizontal enclosed tank.
Step (3) screening process, is passed through inert gas in vibrating screen and is protected.
The bottom of the airflow milling is provided with nozzle, and turbine separator, turbine separation dress are provided at the top of airflow milling
It sets and is provided with discharge port, be provided with variable-frequency motor on the turbine separator, variable-frequency motor is connect with turbine, the discharging
Mouth is connect with dust arrester installation, and the dust arrester installation is connect with air-introduced machine, and the cloth bag that gathers dust is provided on dust arrester installation, is set on air-introduced machine
It is equipped with electrostatic precipitator.
The broken air pressure used of the step (4) is 2.45 atmospheric pressure, the revolving speed of turbine in the turbine separator
For 2400r/min.
The coating is put into autoclave, under 3.8 atmospheric pressures, is passed through oxygen, is stirred to react at 170 DEG C
It 2.45 hours, mixing speed 280r/min, reacts to the pH3.41 of solution, being subsequently cooled to temperature is 74 DEG C, and filtering obtains
Fluoride is added in first filtrate and the first filter residue, the first filtrate, is 78 DEG C in temperature and reacts 1.2 hours, and filtering obtains the second filter
Pure cobalt liquor is added in liquid and the second filter residue, the second filtrate, and deploying cobalt nickel molar ratio in the second filtrate is 8.2:1.35, then
P204 extractant is added to be extracted, P204 cobalt nickel organic phase is obtained, the mixed solution stirring that ammonium hydroxide and sodium hydroxide is added is mixed
It closes, the molal quantity of ammonium hydroxide and sodium hydroxide is 1:4.5, the total mole number and ammonium hydroxide and hydroxide of cobalt nickel in P204 cobalt nickel organic phase
The ratio between the mixed solution of sodium total mole number hydroxy is 1:2.25, is mixed 50 minutes, mixing speed 560r/min at 54 DEG C,
Blender uses dispersion impeller blender, and end of reaction is centrifugated by centrifuge, and obtained solid is after acetone washing, warp
The ball-type nickel cobalt hydroxide that partial size is 3.3 μm is obtained after crossing drying, is used as battery material and prepares.
First filter residue is washed by the sulfuric acid solution of 1.8mol/L, is reacted at 73 DEG C 3.5 hours, is used after then filtering
Pure water obtains the iron oxide red of purity > 95%, is used as pigment, and the hydrogen that concentration is 3.5mol/L is added in second filter residue
Sodium hydroxide solution is reacted 2.5 hours at 52 DEG C, filtering, and obtained filtrate contains fluorine ion, and return is used in mixed way with fluoride,
Sulfuric acid dissolution is added in obtained filter residue, and concentration crystallizes to obtain Dineodymium trisulfate crystal.
It is final:
Rare earth total recovery: 99.3%；The total recovery of iron: 99.1%；The total recovery of nickel cobalt: 99.3%
The index of iron oxide red meets the requirement of GB/T1863-2008
The index of obtained nickel cobalt binary hydroxide is as follows:
| Index | Jolt ramming | Specific surface | D10 | D50 | D90 |
| Numerical value | 2.15g/mL | 10.8m2/g | 4.6μm | 3.3μm | 5.5μm |
| Magnetic foreign body | Fe | Cu | Ca | Mg | Sulfate radical |
| 0.03ppm | 1.2ppm | 0.2ppm | 5ppm | 5ppm | 35ppm |
The performance of the neodymium iron boron of finally obtained brand-new is as follows:
| Maximum operating temperature | Curie temperature | Remanence strength | Coercivity | Maximum magnetic energy product |
| 150 DEG C of > | > 585K | 1410br mT | 14.1K Oe | 360MG Oe |
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (7)
1. a kind of recovery method of waste and old neodymium iron boron, which is characterized in that be following steps:
(1) it pre-processes, waste and old neodymium iron boron addition detergent is washed, then detergent is rinsed well and dried with water；
(2) hydrogen is quick-fried, by washes clean and the waste and old neodymium iron boron first preparatory coarse crushing of drying, places into the quick-fried device of hydrogen, is passed through hydrogen
Gas continues to be passed through hydrogen after catching up with the air in the quick-fried device of hydrogen only completely, and maintaining Hydrogen Vapor Pressure in the quick-fried device of hydrogen is 0.11-
0.12Mpa, while being warming up to temperature is 450-500 DEG C, heating rate is 5-10 DEG C/min, then maintain this temperature 2-3 hours,
Start to cool down again, be cooled to room temperature, cooling rate is 20-30 DEG C/min；
(3) it sieves, after material of the hydrogen after quick-fried is taken out, is sieved, coating and neodymium iron boron particle of the hydrogen after quick-fried are sieved
Separation, for the sieve used for 50-80 mesh, oversize is coating, and screenings is neodymium iron boron particle；
(4) it is crushed, screenings is added in airflow milling and is crushed, air-flow uses stream of nitrogen gas, and broken material passes through
The separation of turbine separator, 4-5 μm of material discharge, the material sinking greater than 5 μm continue to be crushed；
(5) it regenerates, by broken fine powder and produces upper freshly prepared Nd2Fe14B fine powder 1:0.8-1 in mass ratio carries out biradical mixed powder
Green compact, sintering and surface treatment regeneration are carried out afterwards obtains neodymium iron boron material；
The coating is put into autoclave, under 3-4 atmospheric pressure, is passed through oxygen, is stirred to react 2- at 150-180 DEG C
It 2.5 hours, mixing speed 200-300r/min, reacts to the pH3-3.5 of solution, being subsequently cooled to temperature is 70-80 DEG C, mistake
Filter, obtains the first filtrate and the first filter residue, and fluoride is added in the first filtrate, temperature be 70-80 DEG C reaction 1-2 hours, filter,
The second filtrate and the second filter residue are obtained, pure cobalt liquor is added in the second filtrate, and deploying cobalt nickel molar ratio in the second filtrate is 8-
Then 8.5:1-1.5 is added P204 extractant and is extracted, obtains P204 cobalt nickel organic phase, ammonium hydroxide and sodium hydroxide is added
Mixed solution is stirred, and the molal quantity of ammonium hydroxide and sodium hydroxide is 1:4-5, the total mole number of cobalt nickel in P204 cobalt nickel organic phase
It is 1:2.2-2.3 with the ratio between the mixed solution total mole number hydroxy of ammonium hydroxide and sodium hydroxide, in 50-60 DEG C of mixing 30-60
Minute, mixing speed 500-600r/min, blender uses dispersion impeller blender, and end of reaction is by centrifuge centrifugation point
From obtained solid obtains the ball-type nickel cobalt hydroxide that partial size is 3-4 μm after drying, be used as after acetone washing
Battery material preparation.
2. a kind of recovery method of waste and old neodymium iron boron according to claim 1, it is characterised in that: step (1) washing
Agent is water system industrial cleaning agent, and wash time is 1-2 hours, and wash temperature is 50-60 DEG C, and the additional ultrasonic wave of washing process is washed
The mass fraction for washing agent is 10-15%.
3. a kind of recovery method of waste and old neodymium iron boron according to claim 1, it is characterised in that: hydrogen in the step (2)
Quick-fried device is Horizontal enclosed tank, is provided with air inlet and air outlet on the quick-fried device of hydrogen, is provided with transmission device on Horizontal enclosed tank,
Transmission device drives the rotation of Horizontal enclosed tank, is provided with infrared heating device on Horizontal enclosed tank peripheral wall, sets on Horizontal enclosed tank
It is equipped with pressure sensor and temperature sensor.
4. a kind of recovery method of waste and old neodymium iron boron according to claim 1, it is characterised in that: step (3) screening
Process is passed through inert gas in vibrating screen and is protected.
5. a kind of recovery method of waste and old neodymium iron boron according to claim 1, it is characterised in that: the bottom of the airflow milling
It is provided with nozzle, turbine separator is provided at the top of airflow milling, discharge port, the turbine are provided on turbine separator
Variable-frequency motor is provided on separator, variable-frequency motor is connect with turbine, and the discharge port is connect with dust arrester installation, described to gather dust
Device is connect with air-introduced machine, and the cloth bag that gathers dust is provided on dust arrester installation, is provided with electrostatic precipitator on air-introduced machine.
6. a kind of recovery method of waste and old neodymium iron boron according to claim 1, it is characterised in that: the step (4) is broken
The air pressure used is 2-2.5 atmospheric pressure, and the revolving speed of turbine is 2000-2500r/min in the turbine separator.
7. a kind of recovery method of waste and old neodymium iron boron according to claim 1, it is characterised in that: first filter residue passes through
The sulfuric acid solution of 1-2mol/L washs, 70-80 DEG C reaction 3-4 hour, then obtain purity > with pure water after filtering
95% iron oxide red is used as pigment, and the sodium hydroxide solution that concentration is 3-4mol/L is added in second filter residue, in 50-60
DEG C reaction 2-3 hour, filtering, obtained filtrate contained fluorine ion, and return is used in mixed way with fluoride, obtained filter residue addition sulphur
Acid dissolution, concentration crystallize to obtain Dineodymium trisulfate crystal.
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