CN104946895B - Rare earth compound recycling method utilizing waste rare earth polishing powder - Google Patents
Rare earth compound recycling method utilizing waste rare earth polishing powder Download PDFInfo
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- CN104946895B CN104946895B CN201510367797.3A CN201510367797A CN104946895B CN 104946895 B CN104946895 B CN 104946895B CN 201510367797 A CN201510367797 A CN 201510367797A CN 104946895 B CN104946895 B CN 104946895B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 182
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 102
- 238000005498 polishing Methods 0.000 title claims abstract description 66
- 239000000843 powder Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 36
- -1 Rare earth compound Chemical class 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 72
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 6
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000004615 ingredient Substances 0.000 claims description 21
- 230000008929 regeneration Effects 0.000 claims description 18
- 238000011069 regeneration method Methods 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- 239000011268 mixed slurry Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000001802 infusion Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 235000012820 baking ingredients and mixes Nutrition 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- 239000010703 silicon Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000004411 aluminium Substances 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000000306 component Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 101710089042 Demethyl-4-deoxygadusol synthase Proteins 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a rare earth compound recycling method utilizing waste rare earth polishing powder, which comprises the following steps: (1) the waste rare earth polishing powder is subjected to enrichment to prepare an enrichment material of a rare earth element; (2) the enrichment material of the rare earth element is roasted with concentrated sulfuric acid under a low temperature and is subjected to water leaching, and ammonium bicarbonate is used to realize double decomposition for neutralization and filtration cleaning, so that crude carbonic acid rare earth is prepared, and a high-purity rare earth compound is prepared by extraction separation. The invention has the advantages that (1) the separation efficiency is greatly improved, and the total rare earth oxide (TREO) is above 95%; (2) the novel technology is capable of realizing the aim of recycling the rare earth compound from the waste rare earth polishing powder in low cost and high efficiency;(3) the method is simple in operation, the manufacturing costs of required apparatuses are low, the product quality can be guaranteed, and industrial production can be realized; and (4) a lot of waste rare earth polishing powder is recycled so as to solve the problems of environment pollution and resource shortage.
Description
Technical field
The present invention relates to circular regeneration rare earth compound method, more particularly to dilute using useless polishing powder from rare earth circular regeneration
Earth compounds method.
Background technology
With worldwide electronic technology and the development of glass industry, the need to the polishing material based on rare earth element
The amount of asking grows with each passing day.Count according to internal authority mechanism, in the rare earth application of global range in 2013, for polishing industry
Rare-earth usage accounts for total consumption more than 20%.And the usage amount of the annual rare-earth polishing material of China is at 25000 tons.Especially with
China's mobile phone, LCDs industry to develop rapidly, rare-earth polishing material demand increasing with the speed in year 15%.Into
For an important application of China's Rare-earth Industry, simultaneously as the special crystal knot that rare-earth polishing material has
Structure, becomes irreplaceable unique fine polishing material in precise polished field, and application is increasingly extensive.
But, the consumption of domestic annual 25000 tons of polishing powder from rare earth can therewith produce the discarded dilute of total amount of rare earth 30wt%
More than 77000 tons of native polishing powder, containing more than 23000 tons of rare earth oxide.And this solid waste is because containing 1.7-1.8wt%'s
Fluorine can cause problem of environmental pollution.Recent domestic polishing powder from rare earth user is anxious for solving this problem.And with me
State's rare earth resources are developed in a large number year by year, it is necessary to reclaimed rare earth waste, regeneration.Have what patent was related at present
The recovery and treatment method of useless polishing powder from rare earth has：
1st, by useless polishing powder from rare earth acid dissolving DDGS, 800 DEG C of high temperature above roastings of Jing are removed greasy dirt, then fine grinding, are reached
To certain particle size, polishing is reused for.Regeneration polishing powder from rare earth after this method process, crystalline structure is bad, actually makes
Low with middle polishing efficiency, service life is short, can only become that simply hand polish is low-level uses, it is impossible to meet extensive,
The use of normal buff industry, so so far nobody is in this way.
2nd, useless polishing powder from rare earth is inserted in high speed dispersor, turns to disperse at a high speed using 3000-5000 per minute, Ran Houfen
From removal of impurities, rare earth polishing agent finished product is finally obtained.This method can only make a try under lab, it is impossible in large-scale industry
Metaplasia is applied in producing.Its reason is the batch mixing dispersion under the running up that 3000-5000 per minute turns, and industrial production is difficult to reality
It is existing, its secondary rare earth polishing agent finished product that concentration can be obtained after four times are disperseed removal of impurities, and quality is not high, can only obtain one
The product of individual mixed type, thus be also worthless in large-scale production.
The content of the invention
It is an object of the invention to provide the efficient, continuous of Rare Earth Production, cleanly production can be realized, and reclaim comprehensively
The useless polishing powder from rare earth circular regeneration rare earth compound method of the utilization of valuable element.
The purpose of the present invention is implemented by following technical scheme, using the side of useless polishing powder from rare earth circular regeneration rare earth compound
Method, it comprises the steps：(1) polishing powder from rare earth that gives up is enriched, produces the enrichment material of rare earth element；(2) by the rare earth
The enrichment material of element in ammonium hydrogen carbonate double decomposition and filtering and impurity removing, prepares thick carbonated rare earth with concentrated sulfuric acid low-temperature bake water logging,
Extract and separate high purity rare earth compound.Useless polishing powder from rare earth is water insoluble with the presence of oxyfluoride form, is slightly soluble in acid,
The organic impurities such as dispersant are removed first in the weak acid solution that pH is 4.It is in secondary dedoping step, silicon, aluminium, iron is cleared,
TREO can be obtained Jing after filtering precipitation>80% useless polishing powder from rare earth material.Then, by TREO>80% useless polishing powder from rare earth
Material enters sulfuric acid decomposition operation.
Specifically, the step (1) is implemented as follows：
A, prepare slip：By the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, water immersion 5-10 is added
Minute makes slip, and the stock quality concentration is 20%, then adds hydrochloric acid in the slip, and the slip pH value is adjusted to
3-4, spiral classifier is entered after then the slurry being stirred into 20-25 minutes in mixing agitator by conduit；Control pH
Value, acidity is too strong, and height is tided in dissolving, will cause material pasty state, is difficult to filter precipitation.
B, slip Jing spiral classifier concentration and separations：Spiral classifier top described in mass flow Jing containing frivolous material 10%
Overflow outlet overflow, the mesh filter screens of Jing 200 are filtered, and the clear water Jing pump lines after filtration are back to mixing agitator circulation and make
With the debris on filter screen are discarded object；Wherein, in the mass flow unit interval, fluid is effective by closed conduct or open channel
The fluid mass in section.Frivolous material includes resin component, calcium, dispersant.
The non-rare earth heavy element isolated is discharged by spiral classifier bottom waste outlet, the non-rare earth weight unit
Have aluminium (Al2O3), silicon (SiO2) also have 2% or so rare earth element mix wherein, the non-rare earth heavy element is used as byproduct
Enrichment storage is pending Jing after quiescent setting；
The enrichment material of the rare earth element isolated is discharged by the major ingredient outlet in the middle part of the spiral classifier, and 60%
The slip of mass percent is reclaimed by major ingredient outlet, the enrichment material Jing of the rare earth element of recovery 24 hours from
After being so filtered dry, in 10-15%, the enrichment material Rare Earth Element Contents of the rare earth element are 60-80% to moisture.
Spiral classifier, using the distinctive proportion of rare earth element, controls the flow of slurries, effectively with spiral gravity shunting
Isolate the impurity such as silicon, aluminium, iron.
Preferably, the hydrochloric acid is technical hydrochloric acid, and the concentration of the technical hydrochloric acid is more than 36wt%.
Preferably, the rotating speed of the mixing agitator is 30-50 rev/min.In stirring mixed process, rotating speed was difficult
Height, reach slurry it is uniform it is not stratified be advisable, be sufficiently mixed, will overflow beneficial to frivolous material such as filtering and impurity removing, the dispersants in feed liquid
Separate in stream, frivolous material includes resin component, calcium, dispersant.
Specifically, the spiral classifier includes agitator, is provided with shaft in the agitator, the one of the shaft
End is extended to outside the agitator up or down by the top or bottom of the agitator, the institute in the agitator
State shaft and be provided with stirring vane, the end of the shaft outside the agitator and motor connection, the stirring
The top of bucket is provided with the overflow outlet, and the major ingredient outlet is provided with the middle part of the agitator, and the bottom of the agitator sets
The top for having the waste outlet, the agitator is provided with charging aperture.
Preferably, the overflow outlet is arranged at and highly locates apart from agitator described in agitator top 20%, described
Major ingredient outlet is arranged at highly to be located apart from agitator described in agitator top 70%, and the waste outlet is along the stirring
Bottom of the barrel is arranged.
Specifically, the step (2) is implemented as follows：
A, prepare concentrated sulfuric acid mixed slurry：Add in the enrichment material of the rare earth element obtained in the step (1)
The concentrated sulfuric acid to improve slurry dispersiveness and mobility, the enrichment material of the rare earth element is with the concentrated sulfuric acid by weight
For 1：0.6-1：0.7 ratio is well mixed, and concentrated sulfuric acid mixed slurry is obtained；
B, roasting：By the concentrated sulfuric acid mixed slurry in 350 DEG C of -400 DEG C of roasting 1-1.5 hours, baking mixes are obtained,
By baking mixes normal temperature water logging, the concentrated sulfuric acid is washed off, infusion is obtained；
C, prepare rare earth oxide：Routinely extracting process prepares mischmetal oxidation after the neutralized filtration of the infusion
Thing or single rare earth oxide.
Preferably, the concentrated sulfuric acid is technical grade, and concentration is not less than 90wt%, described to be roasted to dynamic roasting, dynamic roasting
Burning refers to that material is in flow regime in roasting process.
Preferably, the optimum calcination temperature in the calcination stepses is 360 DEG C, and optimal roasting time is 1.2 hours.
Using the policy of subsection harnessing, circulation, efficient, the continuous, process conditions of cleanly production rare-earth products are made
And parameter, and the product such as various salts and valuable element of generation during recovery process comprehensively, clean manufacturing is realized, energy-conservation subtracts
Row and the purpose of comprehensive utilization of resources；Most at last the circulation and stress technology is applied to whole industry, and optimization and raising rare earth give up
The level of the secondary resources such as material comprehensive utilization, lifts Industry Innovation level and building capability.
It is an advantage of the current invention that (1) is enriched with by spiral classifier to material, the enriched substance of rare earth element is formed
Material Rare Earth Element Contents are 60-80%, and moisture is carried out to the enrichment material of rare earth element again point in 10-15%, then
From mixed rare-earth oxide or single rare earth oxide is prepared, separative efficiency is greatly improved, and rare earth (TREO) total recovery is 95%
More than；(2) new technology realizes low cost, high efficiency from the purpose of recovering rare earth compound in useless polishing powder from rare earth, one side
Solve discarded polishing powder from rare earth and cause problem of environmental pollution, on the other hand, discarded polishing powder from rare earth is recycled, greatly reduced
Exploitation to China's rare earth resources, reduces resource loss and waste；(3) the inventive method is simple to operate, and equipment needed thereby is manufactured into
This is low, and product quality is secure, it is possible to achieve industrialized production；(4) at present 25000 tons of total consumption of China's polishing powder from rare earth/
Year or so, and with the speedup in year 15% in cumulative year after year, corresponding with this is that the annual discarded polishing powder from rare earth for producing exists
70000-80000 tons or so.Due to, containing impurity such as fluorine, aluminium, silicon, all there is pollution to surface soil in discarded polishing powder from rare earth
Property, bad environments are caused, it is typical trade waste.Substantial amounts of recovery is carried out to this waste, is had to improving environment
Obvious effect；(5) rare earth is used as non-renewable resource, and reserves are limited, realizes a large amount of recovery of industrially scalable, effectively
Economize on resources, reuse, it will have a tremendous social and economic benefits.Thrown with 6000 tons of discarded rare earths of year treating capacity
Light powder is calculated：Recoverable material by 35% rare earth grade, the rate of recovery up to 96%, 2000 tons of recyclable single rare earth product
(TREO>99%), by the calculation of price of existing lanthanum cerium single rare earth oxide：2000 tons × 12000 yuan/ton=24000000
Unit, economic benefit and social benefit it is notable.
Description of the drawings
Fig. 1 is spiral classifier structural representation.
Agitator 1, shaft 2, stirring vane 3, motor 4, overflow outlet 5, major ingredient outlet 6, waste outlet 7, charging
Mouth 8.
Specific embodiment：
Embodiment 1：Using the method for useless polishing powder from rare earth circular regeneration rare earth compound, it comprises the steps：(1) give up
Polishing powder from rare earth is enriched, produces the enrichment material of rare earth element；
A, prepare slip：By the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, water is added to soak 5 minutes
Slip is made, stock quality concentration is 20%, then technical hydrochloric acid is added in slip, the concentration of technical hydrochloric acid is more than 36wt%,
Slip pH value is adjusted to into 3, pH value is controlled, acidity is too strong, height is tided in dissolving, will cause material pasty state, be difficult to filter precipitation.So
Spiral classifier is entered by conduit after afterwards is stirred 20 minutes in mixing agitator slurry, the rotating speed of mixing agitator is 30
Rev/min；In stirring mixed process, rotating speed be difficult it is too high, reach slurry it is uniform it is not stratified be advisable, be sufficiently mixed, be beneficial to
Filter miscellaneous.
B, slip Jing spiral classifier concentration and separations：Mass flow Jing spiral classifier top containing frivolous material 10% overflow
Flow export 5 overflows, and the mesh filter screens of Jing 200 are filtered, and the clear water Jing pump lines after filtration are back to mixing agitator recycling, on filter screen
Debris be discarded object；Wherein, in the mass flow unit interval, fluid is by closed conduct or the fluid of open channel effective cross-section
Quality.Frivolous material includes resin component, calcium, dispersant.
The non-rare earth heavy element isolated is discharged by spiral classifier bottom waste outlet 7, and non-rare earth heavy element has aluminium
(Al2O3), silicon (SiO2) also have 2% or so rare earth element mix wherein, non-rare earth heavy element is used as byproduct Jing quiescent settings
Afterwards enrichment storage is pending；
The enrichment material of the rare earth element isolated is discharged by the major ingredient outlet 6 in the middle part of spiral classifier, 60% mass hundred
The slip for dividing ratio is reclaimed by major ingredient outlet 6, after the enrichment material of the rare earth element of recovery was filtered dry naturally Jing 24 hours, moisture
In 10-15%, the enrichment material Rare Earth Element Contents of rare earth element are 60%.
Spiral classifier, using the distinctive proportion of rare earth element, controls the flow of slurries, effectively with spiral gravity shunting
Isolate the impurity such as silicon, aluminium, iron.
Spiral classifier includes agitator 1, is provided with shaft 2 in agitator 1, one end of shaft 2 up or down by
The top or bottom of agitator 1 is extended to outside agitator 1, and the shaft 2 in agitator 1 is provided with stirring vane 3, position
The end of the shaft 2 outside agitator 1 is connected with motor 4, and the top of agitator 1 is provided with overflow outlet 5, and overflow outlet 5 sets
It is placed at the height of 20% agitator of the top of agitator 11；The middle part of agitator 1 is provided with major ingredient outlet 6, and major ingredient outlet 6 is arranged
In at the height of 70% agitator of the top of agitator 11；The bottom of agitator 1 is provided with waste outlet 7, the edge of waste outlet 7
The bottom of agitator 1 is arranged；The top of agitator 1 is provided with charging aperture 8.
(2) by the enrichment material of rare earth element with concentrated sulfuric acid low-temperature bake water logging, filter with crossing in ammonium hydrogen carbonate double decomposition
It is miscellaneous, prepare thick carbonated rare earth, extract and separate high purity rare earth compound.Useless polishing powder from rare earth exists with oxyfluoride form,
It is water insoluble, acid is slightly soluble in, the organic impurities such as dispersant are removed first in the weak acid solution that pH is 3.In secondary dedoping step
In, silicon, aluminium, iron is cleared, can obtain TREO Jing after drainage precipitation>80% useless polishing powder from rare earth material.Then, by TREO>
80% useless polishing powder from rare earth material enters sulfuric acid decomposition operation.
Step (2) is implemented as follows：
A, prepare concentrated sulfuric acid mixed slurry：The concentrated sulfuric acid is added to use in the enrichment material of rare earth element obtained in step (1)
To improve the dispersiveness and mobility of slurry, enrichment material and the concentrated sulfuric acid of rare earth element are 1 by weight：0.6 ratio is mixed
Close uniform, concentrated sulfuric acid mixed slurry is obtained, the concentrated sulfuric acid is technical grade, and concentration is not less than 90wt%；
B, roasting：By concentrated sulfuric acid mixed slurry in 350 DEG C of dynamic roastings 1.5 hours, baking mixes are obtained, roasting is mixed
Compound normal temperature water logging, the concentrated sulfuric acid is washed off, and infusion is obtained；
C, prepare rare earth oxide：After the neutralized filtration of infusion routinely extracting process prepare mixed rare-earth oxide or
Single rare earth oxide.
Embodiment 2：Using the method for useless polishing powder from rare earth circular regeneration rare earth compound, it comprises the steps：(1) give up
Polishing powder from rare earth is enriched, produces the enrichment material of rare earth element；
A, prepare slip：By the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, water is added to soak 10 points
Clock makes slip, and stock quality concentration is 20%, then adds the concentration of technical hydrochloric acid, technical hydrochloric acid to be more than in slip
36wt%, by slip pH value 4 are adjusted to, and control pH value, and acidity is too strong, and height is tided in dissolving, will cause material pasty state, are difficult to filter
Precipitation.Then spiral classifier is entered by conduit after is stirred 25 minutes in mixing agitator slurry, mixing agitator turns
Speed is 50 revs/min；In stirring mixed process, rotating speed be difficult it is too high, reach slurry it is uniform it is not stratified be advisable, be sufficiently mixed,
Beneficial to filtering and impurity removing.
B, slip Jing spiral classifier concentration and separations：Mass flow Jing spiral classifier top containing frivolous material 10% overflow
Flow export 5 overflows, and the mesh filter screens of Jing 200 are filtered, and the clear water Jing pump lines after filtration are back to mixing agitator recycling, on filter screen
Debris be discarded object；Wherein, in the mass flow unit interval, fluid is by closed conduct or the fluid of open channel effective cross-section
Quality.Frivolous material includes resin component, calcium, dispersant.
The non-rare earth heavy element isolated is discharged by spiral classifier bottom waste outlet 7, and non-rare earth heavy element has aluminium
(Al2O3), silicon (SiO2) also have 2% or so rare earth element mix wherein, non-rare earth heavy element is used as byproduct Jing quiescent settings
Afterwards enrichment storage is pending；
The enrichment material of the rare earth element isolated is discharged by the major ingredient outlet 6 in the middle part of spiral classifier, 60% mass hundred
The slip for dividing ratio is reclaimed by major ingredient outlet 6, after the enrichment material of the rare earth element of recovery was filtered dry naturally Jing 24 hours, moisture
In 10-15%, the enrichment material Rare Earth Element Contents of rare earth element are 80%.
Spiral classifier, using the distinctive proportion of rare earth element, controls the flow of slurries, effectively with spiral gravity shunting
Isolate the impurity such as silicon, aluminium, iron.
Spiral classifier includes agitator 1, is provided with shaft 2 in agitator 1, one end of shaft 2 up or down by
The top or bottom of agitator 1 is extended to outside agitator 1, and the shaft 2 in agitator 1 is provided with stirring vane 3, position
The end of the shaft 2 outside agitator 1 is connected with motor 4, and the top of agitator 1 is provided with overflow outlet 5, and overflow outlet 5 sets
It is placed at the height of 20% agitator of the top of agitator 11；The middle part of agitator 1 is provided with major ingredient outlet 6, and major ingredient outlet 6 is arranged
In at the height of 70% agitator of the top of agitator 11；The bottom of agitator 1 is provided with waste outlet 7, the edge of waste outlet 7
The bottom of agitator 1 is arranged；The top of agitator 1 is provided with charging aperture 8.
(2) by the enrichment material of rare earth element with concentrated sulfuric acid low-temperature bake water logging, filter with crossing in ammonium hydrogen carbonate double decomposition
It is miscellaneous, prepare thick carbonated rare earth, extract and separate high purity rare earth compound.Useless polishing powder from rare earth exists with oxyfluoride form,
It is water insoluble, acid is slightly soluble in, the organic impurities such as dispersant are removed first in the weak acid solution that pH is 4.In secondary dedoping step
In, silicon, aluminium, iron is cleared, can obtain TREO Jing after drainage precipitation>80% useless polishing powder from rare earth material.Then, by TREO>
80% useless polishing powder from rare earth material enters sulfuric acid decomposition operation.
Step (2) is implemented as follows：
A, prepare concentrated sulfuric acid mixed slurry：The concentrated sulfuric acid is added to use in the enrichment material of rare earth element obtained in step (1)
To improve the dispersiveness and mobility of slurry, enrichment material and the concentrated sulfuric acid of rare earth element are 1 by weight：0.7 ratio is mixed
Close uniform, concentrated sulfuric acid mixed slurry is obtained, the concentrated sulfuric acid is technical grade, and concentration is not less than 90wt%；
B, roasting：By concentrated sulfuric acid mixed slurry in 400 DEG C of dynamic roastings 1 hour, baking mixes are obtained, roasting is mixed
Thing normal temperature water logging, the concentrated sulfuric acid is washed off, and infusion is obtained；
C, prepare rare earth oxide：After the neutralized filtration of infusion routinely extracting process prepare mixed rare-earth oxide or
Single rare earth oxide.
Embodiment 3：Using the method for useless polishing powder from rare earth circular regeneration rare earth compound, it comprises the steps：(1) give up
Polishing powder from rare earth is enriched, produces the enrichment material of rare earth element；
A, prepare slip：By the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, water is added to soak 8 minutes
Slip is made, stock quality concentration is 20%, then technical hydrochloric acid is added in slip, the concentration of technical hydrochloric acid is more than 36wt%,
Slip pH value is adjusted to into 3, pH value is controlled, acidity is too strong, height is tided in dissolving, will cause material pasty state, be difficult to filter precipitation.So
Spiral classifier is entered by conduit after afterwards is stirred 22 minutes in mixing agitator slurry, the rotating speed of mixing agitator is 40
Rev/min；In stirring mixed process, rotating speed be difficult it is too high, reach slurry it is uniform it is not stratified be advisable, be sufficiently mixed, be beneficial to
Filter miscellaneous.
B, slip Jing spiral classifier concentration and separations：Mass flow Jing spiral classifier top containing frivolous material 10% overflow
Flow export 5 overflows, and the mesh filter screens of Jing 200 are filtered, and the clear water Jing pump lines after filtration are back to mixing agitator recycling, on filter screen
Debris be discarded object；Wherein, in the mass flow unit interval, fluid is by closed conduct or the fluid of open channel effective cross-section
Quality.Frivolous material includes resin component, calcium, dispersant.
The non-rare earth heavy element isolated is discharged by spiral classifier bottom waste outlet 7, and non-rare earth heavy element has aluminium
(Al2O3), silicon (SiO2) also have 2% or so rare earth element mix wherein, non-rare earth heavy element is used as byproduct Jing quiescent settings
Afterwards enrichment storage is pending；
The enrichment material of the rare earth element isolated is discharged by the major ingredient outlet 6 in the middle part of spiral classifier, 60% mass hundred
The slip for dividing ratio is reclaimed by major ingredient outlet 6, after the enrichment material of the rare earth element of recovery was filtered dry naturally Jing 24 hours, moisture
In 10-15%, the enrichment material Rare Earth Element Contents of rare earth element are 68%.
Spiral classifier, using the distinctive proportion of rare earth element, controls the flow of slurries, effectively with spiral gravity shunting
Isolate the impurity such as silicon, aluminium, iron.
Spiral classifier includes agitator 1, is provided with shaft 2 in agitator 1, one end of shaft 2 up or down by
The top or bottom of agitator 1 is extended to outside agitator 1, and the shaft 2 in agitator 1 is provided with stirring vane 3, position
The end of the shaft 2 outside agitator 1 is connected with motor 4, and the top of agitator 1 is provided with overflow outlet 5, and overflow outlet 5 sets
It is placed at the height of 20% agitator of the top of agitator 11；The middle part of agitator 1 is provided with major ingredient outlet 6, and major ingredient outlet 6 is arranged
In at the height of 70% agitator of the top of agitator 11；The bottom of agitator 1 is provided with waste outlet 7, the edge of waste outlet 7
The bottom of agitator 1 is arranged；The top of agitator 1 is provided with charging aperture 8.
(2) by the enrichment material of rare earth element with concentrated sulfuric acid low-temperature bake water logging, filter with crossing in ammonium hydrogen carbonate double decomposition
It is miscellaneous, prepare thick carbonated rare earth, extract and separate high purity rare earth compound.Useless polishing powder from rare earth exists with oxyfluoride form,
It is water insoluble, acid is slightly soluble in, the organic impurities such as dispersant are removed first in the weak acid solution that pH is 4.In secondary dedoping step
In, silicon, aluminium, iron is cleared, can obtain TREO Jing after drainage precipitation>80% useless polishing powder from rare earth material.Then, by TREO>
80% useless polishing powder from rare earth material enters sulfuric acid decomposition operation.
Step (2) is implemented as follows：
A, prepare concentrated sulfuric acid mixed slurry：The concentrated sulfuric acid is added to use in the enrichment material of rare earth element obtained in step (1)
To improve the dispersiveness and mobility of slurry, enrichment material and the concentrated sulfuric acid of rare earth element are 1 by weight：0.6 ratio is mixed
Close uniform, concentrated sulfuric acid mixed slurry is obtained, the concentrated sulfuric acid is technical grade, and concentration is not less than 90wt%；
B, roasting：By concentrated sulfuric acid mixed slurry in 360 DEG C of dynamic roastings 1.2 hours, baking mixes are obtained, roasting is mixed
Compound normal temperature water logging, the concentrated sulfuric acid is washed off, and infusion is obtained；
C, prepare rare earth oxide：After the neutralized filtration of infusion routinely extracting process prepare mixed rare-earth oxide or
Single rare earth oxide.
Embodiment 4：Using the rare-earth products of embodiment 1-3 method reclaiming, rare-earth yield is more than 95%, efficiency high,
Yield is big, earth solution Jing precipitations can output carbonated rare earth or rare earth oxalate, can be directly used as preparing rare-earth polishing material.
Claims (8)
1. using the method for useless polishing powder from rare earth circular regeneration rare earth compound, it is characterised in that it comprises the steps：(1)
Useless polishing powder from rare earth is enriched, produces the enrichment material of rare earth element；(2) by the enrichment material of the rare earth element with the concentrated sulfuric acid
Low-temperature bake water logging, in ammonium hydrogen carbonate double decomposition and filtering and impurity removing, prepares thick carbonated rare earth, extract and separate high purity rare earth
Compound；
The step (1) is implemented as follows：
A, prepare slip：By the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, water immersion 5-10 minutes are added
Slurry is made, the stock quality concentration is 20%, then adds hydrochloric acid in the slip, and the slip pH value is adjusted to into 3-4,
Then spiral classifier is entered by conduit after the slurry being stirred into 20-25 minutes in mixing agitator；
B, slip Jing spiral classifier concentration and separations：Spiral classifier top described in mass flow Jing containing frivolous material 10% overflow
Flow export overflows, and the mesh filter screens of Jing 200 are filtered, and the clear water Jing pump lines after filtration are back to the mixing agitator and recycle, filter
Online debris are discarded object；
The non-rare earth heavy element isolated is discharged by spiral classifier bottom waste outlet, and the non-rare earth heavy element is made
Storage is enriched with Jing after quiescent setting for byproduct pending；
The enrichment material of the rare earth element isolated is discharged by the major ingredient outlet in the middle part of the spiral classifier, 60% mass
The slip of percentage is reclaimed by major ingredient outlet, and the enrichment material Jing of the rare earth element of recovery is filtered for 24 hours naturally
After dry, in 10-15%, the enrichment material Rare Earth Element Contents of the rare earth element are 60-80% to moisture.
2. it is according to claim 1 using useless polishing powder from rare earth circular regeneration rare earth compound method, it is characterised in that institute
It is technical hydrochloric acid to state hydrochloric acid, and the concentration of the technical hydrochloric acid is more than 36wt%.
3. it is according to claim 1 using useless polishing powder from rare earth circular regeneration rare earth compound method, it is characterised in that institute
The rotating speed for stating mixing agitator is 30-50 rev/min.
4. it is according to claim 1 using useless polishing powder from rare earth circular regeneration rare earth compound method, it is characterised in that institute
Spiral classifier is stated including agitator, shaft is provided with the agitator, one end of the shaft is up or down by institute
The top or bottom for stating agitator is extended to outside the agitator, and the shaft in the agitator is provided with and stirs
Blade is mixed, the end of the shaft outside the agitator and motor connection, the top of the agitator is provided with described
Overflow is exported, and the major ingredient outlet is provided with the middle part of the agitator, and the bottom of the agitator is provided with the waste outlet,
The top of the agitator is provided with charging aperture.
5. it is according to claim 4 using useless polishing powder from rare earth circular regeneration rare earth compound method, it is characterised in that institute
State overflow outlet and be arranged at and highly locate apart from agitator described in agitator top 20%, the major ingredient outlet is arranged at distance
Agitator described in the agitator top 70% is highly located, and the waste outlet is arranged along the stirring bottom of the barrel.
6. it is according to claim 1 using useless polishing powder from rare earth circular regeneration rare earth compound method, it is characterised in that institute
State step (2) to implement as follows：
A, prepare concentrated sulfuric acid mixed slurry：Dense sulphur is added in the enrichment material of the rare earth element obtained in the step (1)
Acid, enrichment material and the concentrated sulfuric acid of the rare earth element are 1 by weight：0.6-1：0.7 ratio is well mixed, and is obtained
Concentrated sulfuric acid mixed slurry；
B, roasting：By the concentrated sulfuric acid mixed slurry in 350 DEG C of -400 DEG C of roasting 1-1.5 hours, baking mixes are obtained, by institute
State baking mixes normal temperature water logging；
C, prepare rare earth oxide：After the neutralized filtration of the infusion routinely extracting process prepare mixed rare-earth oxide or
Single rare earth oxide.
7. it is according to claim 6 using useless polishing powder from rare earth circular regeneration rare earth compound method, it is characterised in that institute
It is technical grade to state the concentrated sulfuric acid, and concentration is not less than 90wt%, described to be roasted to dynamic roasting.
8. it is according to claim 6 using useless polishing powder from rare earth circular regeneration rare earth compound method, it is characterised in that institute
It is 360 DEG C to state the optimum calcination temperature in calcination stepses, and optimal roasting time is 1.2 hours.
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| CN105489332B (en) * | 2016-01-05 | 2018-01-12 | 江苏南方永磁科技有限公司 | More rare-earth phase permanent-magnet materials and preparation method |
| CN108396140A (en) * | 2016-12-18 | 2018-08-14 | 常州爱上学教育科技有限公司 | Rare earth oxide extraction equipment and its working method |
| CN106498173B (en) * | 2016-12-18 | 2017-12-26 | 盐城市兰丰环境工程科技有限公司 | A kind of rare earth waste recovery use can improve the device of rare earth waste utilization rate |
| CN106916941B (en) * | 2017-03-13 | 2018-06-05 | 北京科技大学 | A kind of method that production rare earth is separated using iron content rare-earth original ore |
| CN107188215A (en) * | 2017-05-24 | 2017-09-22 | 中国北方稀土（集团）高科技股份有限公司 | The method that reaction end is automatically adjusted in carbonated rare earth continuous precipitation production process |
| CN107555799B (en) * | 2017-09-26 | 2020-10-23 | 东北大学 | Method for preparing glass ceramic by using waste rare earth polishing powder |
| CN108372179A (en) * | 2017-12-28 | 2018-08-07 | 龙南县中利再生资源开发有限公司 | A kind of regeneration method of rare earth permanent-magnetic material |
| CN108559851B (en) * | 2018-06-22 | 2023-11-17 | 长沙中硅环保科技有限公司 | System and method for cooperatively disposing rare earth polishing powder waste by cement kiln |
| CN112725622B (en) * | 2020-12-02 | 2022-09-09 | 北京工业大学 | Method for recovering rare earth in waste cerium-based rare earth polishing powder by two-step acid leaching gradient separation |
| CN114381206B (en) * | 2022-01-07 | 2023-04-14 | 甘肃金阳高科技材料有限公司 | Method for preparing rare earth polishing powder by regenerating glass polishing waste residues |
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| EP2444507B1 (en) * | 2010-10-20 | 2015-03-04 | Montanuniversität Leoben | Recovery of rare earth metals from waste material by leaching in non-oxidizing acid and by precipitating using sulphates |
| CN102251117B (en) * | 2011-06-17 | 2013-01-16 | 金华冠华水晶有限公司 | Method for extracting rare earth component from crystal waste slag |
| CN102296182A (en) * | 2011-07-28 | 2011-12-28 | 包头市新源稀土高新材料有限公司 | Method for recovering rare earth elements from waste rare earth element grinding materials |
| CN104060111B (en) * | 2014-07-12 | 2015-09-02 | 连云港健发磁性材料有限公司 | A kind of method of sharpening segmentation recovering rare earth element from polishing powder from rare earth waste residue |
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Effective date of registration: 20200422 Address after: 014060 west side of Baofu railway bridge, Baotou City, Inner Mongolia Autonomous Region Patentee after: Baotou Haorui rare earth Co.,Ltd. Address before: 014010, the Inner Mongolia Autonomous Region C rare earth hi tech Zone Pioneering Center Software Park, block 506, Baotou Patentee before: BAOTOU NEW CENTURY RARE EARTH LTD. |
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Denomination of invention: Method for recycling rare earth compound using waste rare earth polishing powder Effective date of registration: 20220909 Granted publication date: 20170426 Pledgee: Shanghai Pudong Development Bank Co.,Ltd. Baotou Branch Pledgor: Baotou Haorui rare earth Co.,Ltd. Registration number: Y2022150000098 |
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