CN106995884B - A method of the Extraction of rare earth element from waste phosphor powder - Google Patents
A method of the Extraction of rare earth element from waste phosphor powder Download PDFInfo
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- CN106995884B CN106995884B CN201610052604.XA CN201610052604A CN106995884B CN 106995884 B CN106995884 B CN 106995884B CN 201610052604 A CN201610052604 A CN 201610052604A CN 106995884 B CN106995884 B CN 106995884B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The method of the invention discloses a kind of from waste phosphor powder Extraction of rare earth element, belongs to technical field of resource recovery.The specific steps of the present invention are as follows: (1) aluminium chloride being carried out precise with fluorination lithium powder and be uniformly mixed, obtain mixed halide；(2) waste phosphor powder is sieved, removes large granular impurity therein, obtain the low fluorescent powder scrap of impurity content；(3) mixed halide is heated and is melted, fluorescent powder scrap is then added into halide melts salt, and react 5~10h at 600~1100 DEG C；(4) clarified separation is carried out to gained reaction product after reacting, respectively obtains solid residue and fused salt, solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-lithium fluoride mixture.Aluminium chloride in the present invention can selectively be reacted with waste phosphor powder middle rare earth, and lithium fluoride can improve the physical property of fused salt, and can effectively improve the recovery rate of cerium and terbium.
Description
Technical field
The invention belongs to the recycling of rare earth resources and the clean utilization technical field of secondary resource, more specifically to
A method of the Extraction of rare earth element from waste phosphor powder.
Background technique
Rare earth phosphor is because its light emission luminance and luminous efficiency are high, excitation purity and stability are good, long service life and harmless
Property, it has been widely used in trichromatic energy saving lamp, plasma scope, cathode-ray tube TV, LCD backlight source etc.
Field.With the expansion of rare earth phosphor application field and the continuous development of industry, yield is continuously increased.Meanwhile largely
Waste phosphor powder also comes into being, it is estimated that annual practical about 2000 tons of rare earth phosphor waste material for recycling in China.Fluorescence
Contain the rare earth elements such as a large amount of yttrium and a small amount of europium, cerium and terbium in powder waste material, is a kind of biggish rare earth two of industrial reserves
Secondary resource.Rare earth is that a kind of important strategic resource can not only pollute if such waste phosphor powder is taken as solid refuse processing
Environment will also cause the waste of rare earth resources.Therefore, it extracts from waste phosphor powder, recovering rare earth element, can not only save
Resource reduces industrial refuse, can also reduce from Rare Earth Mine exploitation to production, process brought environmental pollution, to China
Rare earth resources and environmental protection all have significance.
Mainly there is the FLOTATION SEPARATION, acid-hatching of young eggs, compound excellent molten about the extracting method of rare earth element in waste phosphor powder at present
Without ammonia saponification process, Selective oxidation reduction method, supercritical technology extraction, centrifugal separation high pressure digestion etc..
(Hirajima T, Sasaki K, Tsunekawa M, the et al.Feasibility of an such as Hirajima T
efficient recovery of rare earth-activated phosphors from waste fluorescent
lamps through dense-medium centrifugation.Separation&Purification Technology,
2005,44 (3): 197-204.) it is realized close for density centrifugation medium using enuatrol as surfactant using diiodomethane
Spend the separation of lesser calcium halophosphate activated by antimony andmanganese Yu the biggish rare earth phosphor of density；Mei Guangjun etc. (Guangjun Mei, Peng Rao,
Mitsuaki Matsuda,et al.Separation of Red(Y2O3:Eu3+),Blue(BaMgAl10O17:Eu2+)and
Green(CeMgAl10O17:Tb3+)Rare Earth Phosphors by Liquid/Liquid Extraction.Journal
Wuhan university of Technology-Mater.Sci.Ed., 2009,24 (4): 603-607.) use floatation energy
Preferably calcium halophosphate activated by antimony andmanganese and the triphosphor Fluorescent Powder in fluorescent powder scrap are separated, but gained triphosphor Fluorescent Powder
The rate of recovery and purity is not high, can not direct Returning utilization.In addition, separating medium, surfactant or flotation agent should be needed in the process
Deng, higher cost and unstable, pollution is easily caused to environment.
Xie Kefeng (Xie Kefeng discarded fluorescent lamp is innoxious, the Wuhan resource utilization treatment research: Wuhan University of Technology,
2007.) rare earth element in waste and old rare earth phosphor, rare earth are recycled by salt Ore Leaching-ammonia precipitation process-oxalic acid precipitation technique
Leaching rate is up to 93.19%；(Yang Youming, Deng Shenghua, Xie Fanghao wait Extraction of rare earth technique from fluorescent powder scrap to Yang Youming etc.
Study non-ferrous metal: Smelting Part, 2012 (10): 23-26.) first with the rare earth element in hydrochloric acid Ore Leaching fluorescent powder scrap,
The cerium and terbium for being extracted more difficult leaching in slag with sodium carbonate roasting method again, finally neutralize pickle liquor, are cleaned.Using above-mentioned acid
Leaching method technique is simpler, easy to operate, is suitble to industrial mass production, but has that acid consumption is big, the rate of recovery is low, environmental pollution is serious
Problem.
(Gao Zhuo Ganzhou tungsten and rare earth state examine center for country, Ganzhou City tungsten and rare-earth products Quality Supervision and Inspection Center
Help local pillar industry chemical analysis metering, 2010 (3): 6-6.) low-temperature bake pretreatment first is carried out to Waste fluorescent powder,
Then it is decomposed in hydrochloric acid-hydrogen peroxide-glacial acetic acid system, the isolated high-purity yttrium oxide of reduction extraction is saponified with no ammonia
With europium oxide feed liquid, high-purity low silicon ultrafine yttria europium most is prepared through oxalic acid precipitation, high temperature sintering technique afterwards.This method tool
Have the advantages that rare earth resolution ratio height, extraction are also easy to produce emulsification now without saponification, fine and even product grains, but without ammonia saponifiable extraction
As organic phase loss is larger.
(a kind of preparation method China that high-purity yttrium europium is recycled from fluorescent powder scrap of Yang Jian, Cao Jianming is specially by Yang Jian etc.
Benefit: 101985694A, 2011-03-16.) use Selective oxidation reduction method to recycle yttrium, europium from rare earth phosphor waste material.Its
Technical process are as follows: carry out acidleach after adding water slurrying to rare earth phosphor waste material, add a small amount of sulphur after filtrate ammonium hydroxide tune pH value
Europium preferential precipitation is precipitated in sour ammonium, reduction zinc powder or barium chloride, and rich yttrium filtrate extraction is glimmering except obtaining after the impurity such as de-iron, zinc
Lighting level yttrium chloride solution；Europium slag obtains europium-enriched solution after acid is molten, and zincification powder filters after sufficiently reacting, and filtrate is extracted, washed
Fluorescence Grade feed liquid containing europium is obtained after removal of impurities；Last yttrium, europium solution are converted into yttrium oxide and oxidation after oxalic acid precipitation, high temperature sintering
Europium.Selective oxidation reduction method can obtain good yttrium oxide and europium oxide product, but its production process is many and diverse, cost recovery
It is high.
(Shimizu R, Sawada K, Enokida Y, the et al.Supercritical fluid such as Ryosuke R
extraction of rare earth elements from luminescent material in waste
Fluorescent lamps.The Journal of supercritical fluids, 2005,33 (3): 235-241.) it will
Waste and old rare earth phosphor is dissolved in the mixed solution of TBP, nitric acid and water, in supercritical CO2Under the action of, control pressure, temperature
With extraction time, 99.7% yttrium in fluorescent powder and 99.8% europium is made to be extracted out, and most of cerium and lanthanum are then with phosphate
Form be stored in raffinate.The advantages of above-mentioned supercritical technology extraction is the extraction yield height of yttrium and europium, but operating condition is tight
Lattice, and a large amount of CO need to be consumed2Gas, safety are poor.
Mahmoud M A(Rabah M A.Recyclables recovery of europium and yttrium
metals and some salts from spent fluorescent lamps.Waste management,2008,28
(2): 318-325.) under high temperature (125 DEG C) high pressure (5MPa), using sulfuric acid and nitric acid make yttrium in waste and old rare earth phosphor and
Europium is converted to rhodanate, then using trimethylphenyl ammonium chloride from wherein selective extraction yttrium and europium, and with nitric acid and phosphorus
Sour tributyl by organic phase yttrium and europium extract in nitric acid solution, then heat-treat to obtain rare earth metal by hydrogen.Using
The rare earth metal of the high-pressure digestion method energy high-purity, but height in the process is pressed with certain risk, extractant consumption damage
It loses larger；In addition, process is difficult to control, and there is also certain risk using inflammable and explosive hydrogen as reducing agent.
The various extracting methods of rare earth element are wet underwater welding process in itself in above-mentioned existing waste phosphor powder, i.e.,
It is carried out in aqueous medium or aqueous medium.The above method extract waste phosphor powder in rare earth element during,
Have the advantages that respective, but their common problems are to need to consume water and other reagents, and operational sequence is many and diverse, and processing cost is high,
And a large amount of waste water is generated, easily cause environmental pollution.So far, when being recycled to the rare earth element in waste phosphor powder, not yet
Develop efficient, non-environmental-pollution treatment process.In addition, the extracting method of rare earth element is for glimmering in existing waste phosphor powder
The extraction effect of yttrium and europium is relatively preferable in light powder, but the cerium and terbium less for content, and extraction effect is then poor, this is also
The problem of perplexing the domestic and international researcher long period and suffering from no preferable solution.
Chinese Patent Application No. is 200980119301.3, and invention and created name is recovery method and the recycling of rare earth element
The patent of invention of device discloses a kind of method by non-hydrometallurgical process Extraction of rare earth element, the method packet of this application
It including and rare earth alloy is immersed in the fuse salt of halide salts, the halide of rare earth element dissolves out the step into fuse salt, or
Make the rare earth alloy waste material coexisted at least one party in Fe and Cu and metal chloride gas 1300~1800K at a temperature of
Reaction, the step of with rare earth element in the vaporous form selective extraction rare earth alloy waste material of rare earth element chloride.The Shen
Please case can be avoided to a certain extent using environmental pollution caused by Wet-process metallurgy method, but it is eventually by distillation/separation
Method halide is separated one by one, vapo(u)rizing temperature is higher, treatment process versus busy, the high requirements on the equipment, and gained is dilute
The purity of earth elements is lower, and relatively low to the rate of recovery of rare earth element, needs to be further increased.
Summary of the invention
1. technical problems to be solved by the inivention
It is in the prior art usually to be extracted in waste phosphor powder using hydrometallurgy it is an object of the invention to overcome
Rare earth element, operational sequence is more many and diverse, and processing cost is high, and generates a large amount of waste water, environmental pollution is easily caused, especially to discarded
The poor deficiency of the extraction effect of the less cerium of content and terbium in fluorescent powder provides one kind Extraction of rare earth from waste phosphor powder
The method of element.By using method of the invention, it is possible to the rare earth element in high efficiency extraction fluorescent powder, and mentioned in rare earth element
Inorganic acid, organic solvent and water, no spent acid and sewage discharge are not consumed during taking, and greatly reduce environmental pollution, and can
Improve the recovery rate to cerium in fluorescent powder and terbium.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of method of Extraction of rare earth element from waste phosphor powder of the invention, this method is by making fluorescent powder scrap
With the fuse salt hybrid reaction of halide, the fused salt mixt containing rare earth halide then is obtained through being separated by solid-liquid separation.
Further, the halide is aluminium chloride and the mixture for being fluorinated lithium powder.
Further, specific steps of the invention are as follows:
(1) aluminium chloride is subjected to precise with fluorination lithium powder and be uniformly mixed, obtain mixed halide；
(2) waste phosphor powder is sieved, removes large granular impurity therein, it is useless to obtain the low fluorescent powder of impurity content
Material；
(3) mixed halide obtained in step (1) is heated and is melted, halide fused salt is obtained, to the halide fused salt
The middle fluorescent powder scrap being added after sieving, reacts halide fused salt sufficiently with fluorescent powder scrap；
(4) clarified separation is carried out to gained reaction product in step (3), respectively obtains solid residue and fused salt, solid
Residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-lithium fluoride
Mixture.
Further, the mass percentage content of aluminium chloride is 40%~80% in the halide mixed-powder.
Further, the aluminium chloride and fluorination lithium powder are the anhydrous halide without the crystallization water, and are made
It is dried at 100-200 DEG C with preceding, to remove absorption water therein.
Further, waste phosphor powder is sieved using 100 the polished standard screens in step (2).
Further, the mass ratio of the halide fused salt in step (3) and fluorescent powder scrap is 3:1~10:1, and halogen
Compound fused salt carries out reacting 5~10h at 600~1100 DEG C with fluorescent powder scrap.
Further, the lithium fluoride using potassium fluoride, magnesium fluoride, calcirm-fluoride, barium fluoride, sodium fluoride, sodium chloride,
Potassium chloride, lithium chloride, magnesium chloride, calcium chloride, barium chloride, sodium bromide, potassium bromide, sodium iodide, a kind or a kind in potassium iodide with
The mixture of upper material composition replaces.
Further, the lithium fluoride is using lithium fluoride and potassium fluoride, magnesium fluoride, calcirm-fluoride, barium fluoride, fluorination
Sodium, sodium chloride, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, barium chloride, sodium bromide, potassium bromide, sodium iodide, 1 in potassium iodide
It plants or the mixture of a kind or more material composition replaces.
Further, the aluminium chloride is replaced using frerrous chloride, zinc chloride, aluminium bromide or zinc iodide.
3. beneficial effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result:
(1) method of a kind of Extraction of rare earth element from waste phosphor powder of the invention, is impregnated in halogen for waste phosphor powder
In the fuse salt of compound, the fuse salt of above-mentioned halide can selectively occur with the rare earth oxide in waste phosphor powder anti-
Rare earth halide should be formed and enter fused salt, so as to effectively avoid the impurity element in fluorescent powder to gained rare earth element purity
Influence, and generate rare earth halide fused salt can also dissolve the rare earth oxide in fluorescent powder, to substantially increase glimmering
The recovery rate of rare earth element in light powder, ensure that the high efficiency extraction of rare earth element.
(2) method of a kind of Extraction of rare earth element from waste phosphor powder of the invention, by selecting suitable halide
Type and proportion, and control is optimized to the ratio etc. of reaction temperature, reaction time, waste phosphor powder and fused salt, so as to
To further increase the extraction effect of rare earth element in fluorescent powder scrap, especially by the addition of aluminium chloride and to mixing halogenation
The content of aluminium chloride, which carries out control, in object can guarantee the recovery rate of rare earth element in fluorescent powder scrap.In addition, passing through lithium fluoride
Addition can not only advantageously reduce the fusion temperature and viscosity of fused salt as reaction promoter, accelerate reaction progress, improve
The recovery rate of rare earth element, while the extraction effect to cerium in fluorescent powder and terbium can also be improved, it is right in the prior art to overcome
The poor deficiency of the extraction effect of cerium and terbium in fluorescent powder.
(3) method of a kind of Extraction of rare earth element from waste phosphor powder of the invention, rare earth element in fluorescent powder
Entire extraction process carries out in non-aqueous molten salt system, overcomes and uses existing for existing hydrometallurgical recovery technology not
Foot is not necessarily to consumption acids, organic solvent and water during recovering rare earth, and no spent acid and discharge of wastewater, environmental benefit are preferable.
(4) method of a kind of Extraction of rare earth element from waste phosphor powder of the invention, the rare earth in waste phosphor powder
First procatarxis dissolution or reaction form rare earth halide and enter in fused salt, ensure that rare earth element can all be entered with ionic state
Into fused salt, the recovery rate of rare earth reaches as high as 93% or more, and the finally obtained halide dissolved with rare earth oxide is molten
Salt can be used as the electrolyte system of electrolysis production rare earth alloy.
(5) method of a kind of Extraction of rare earth element from waste phosphor powder of the invention, process flow is brief, is easy to grasp
Make, removal process is at low cost, non-environmental-pollution and Extraction of rare eart rate are high.
Specific embodiment
To further appreciate that the contents of the present invention, the present invention will be further described with reference to the examples below.
Embodiment 1
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is aluminium chloride and the mixture for being fluorinated lithium powder.This method specifically includes the following steps:
(1) aluminium chloride and lithium fluoride are subjected to precise according to mass ratio 2:1, are then added to graphite after mixing
In crucible, mixed halide is obtained.Specifically in the present embodiment, aluminium chloride and fluorination lithium powder are without the anhydrous of the crystallization water
Halide and be that analysis is pure, weighs 40.0g aluminum chloride powder and 20.0g fluorination lithium powder and is uniformly mixed, use it is preposition in
It is dried at a temperature of 100 DEG C, avoids deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 10.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, terbium
Content 1.08wt%.The present embodiment reduces the impurity content in fluorescent powder scrap by screening, to a certain extent may be used
It to improve the purity of the rare earth element finally extracted, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder can be promoted useless
Material is sufficiently reacted with halide fused salt, is accelerated reaction rate, is further improved the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, halide fused salt and fluorescent powder scrap is made to exist
6h is reacted at 1000 DEG C, whole process carries out under inert gas protection.
Using the technical solution of the present embodiment, make the extraction process of rare earth element in fluorescent powder in non-aqueous molten salt system
It carries out, does not consume inorganic acid, organic solvent and water during recovering rare earth to reach, the mesh of no spent acid and sewage discharge
's.In the present embodiment, aluminium chloride can selectively react with the rare earth oxide in waste phosphor powder, hence it is evident that reduce fluorescence
The influence of impurity element in powder improves the purity of gained rare earth element, and the rare earth halide generated also can preferably dissolve fluorescence
Rare earth oxide in powder, and to the content and reaction temperature of aluminium chloride in the proportion of halide and fluorescent powder scrap, halide
It is controlled with the reaction time, to ensure that the recovery rate of rare earth element in fluorescent powder.Lithium fluoride in above-mentioned halide is done
For reaction promoter, the fusion temperature and viscosity of fused salt can reduce, accelerate the progress of reaction, improve the recovery rate of rare earth element,
More particularly to significantly improving the extraction effect to cerium in fluorescent powder and terbium, overcome in the prior art to cerium in fluorescent powder and terbium
The poor deficiency of extraction effect.The finally obtained fused salt mixt containing rare earth halide of the present embodiment, can be by being electrolysed come straight
It connects and prepares rare earth alloy, preparation method is simpler, and the purity of the rare earth alloy as obtained by being electrolysed and can further increase, and improves
The grade of rare earth alloy.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-fluorination
The mixture of lithium.
It is worth noting that for deficiency existing for existing hydrometallurgical recovery technology, inventor is devoted for years in various
The extraction research of rare earth element in waste material, inventor is first using neodymium iron boron waste material as research object, by a large amount of experimental study
It was found that aluminum fluoride powder can be reacted with the fuse salt of ice crystal powder with the rare earth oxide in neodymium iron boron waste material, lead to
It crosses and selects suitable powder with when reaction process parameter, the rare earth element that can effectively extract in neodymium iron boron waste material (are specifically shown in
Filed in inventor on 07 23rd, 2014, application No. is: 201410353173.1, a kind of invention and created name are as follows: neodymium iron
The patent document of the recovery method of rare earth element in boron waste material).For the effect obtained above, inventor feels more joyful and abnormal
Excitement, but when the method in above-mentioned patent is gamely directly applied to rare earth element in fluorescent powder scrap system by inventor
Extraction when have been found that, the method in above-mentioned patent is unsatisfactory to the extraction effect of rare earth element in fluorescent powder scrap, to glimmering
The recovery rate of rare earth element is lower in light powder waste material, and the impurity in final gained rare earth element is more, the purity of rare earth element compared with
It is low, it is difficult to meet the higher requirement using standard.For this purpose, inventor feels to get screwed, inventor summarized through self-examination think by
Different from the component system of neodymium iron boron waste material system in fluorescent powder scrap system, different component systems causes the property of the two to be deposited
In larger difference, therefore the method in above-mentioned patent cannot directly be brought to the extraction for being used for rare earth element in fluorescent powder scrap,
And the component system of fluorescent powder scrap is more complicated compared to neodymium iron boron waste material, dopant species and content are more, therefore how
Guarantee that the recovery rate from gained rare earth element in fluorescent powder scrap (especially guarantees the lower cerium of content and terbium in fluorescent powder scrap
Extraction effect) and purity be perplex inventor greatest problem.
In the next time more than a year, inventor has daily and nightly in the thoughts, in conjunction with the composition characteristic and property of fluorescent powder scrap,
By largely attempting surprisingly to find with experimental study, select in the present embodiment the fuse salt of aluminium chloride and fluorination lithium powder with
Fluorescent powder scrap is reacted, and to the proportion of aluminium chloride and lithium fluoride, halide total amount and fluorescent powder scrap with when anti-
It answers technological parameter to optimize, the extraction effect of rare earth element in fluorescent powder scrap, chlorination therein can be effectively improved
Reacted with the rare earth element in fluorescent powder scrap to the aluminium property of can choose, it is miscellaneous in fluorescent powder scrap so as to effectively avoid
The influence of prime element improves the purity of gained rare earth element.In addition, inventor has found under study for action, chlorination in mixed halide
The content of aluminium is most important to the recovery rate of rare earth element in fluorescent powder scrap, when the mass fraction of aluminium chloride is lower than 40%,
The recovery rate of final gained rare earth element is then undesirable, to cause a large amount of wastes of rare earth element.It is particularly noteworthy that
Inventor surprisingly has found in the course of the research, can not only reduce the fusion temperature of fused salt by adding a certain amount of lithium fluoride
And viscosity, accelerate the progress of reaction, further increases the recovery rate of rare earth element, and have to the extraction of cerium in fluorescent powder and terbium
Facilitation be better extracted the cerium that content is less in fluorescent powder scrap also can with terbium.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Crossing and calculating the recovery rate of rare earth is 93.5%, and it also increases to the extraction effect of cerium, terbium.The present embodiment passes through construction chlorine
Change aluminium-lithium fluoride molten salt system, and control the proportion relation of each substance, make rare earth oxide in waste phosphor powder because of reaction and
Dissolution and be converted into rare earth halide and enter fused salt in, it is molten to ensure that rare earth element can be entered all with ionic state
In salt, to effectively increase the recovery rate of rare earth.
Embodiment 2
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is aluminium chloride and the mixture for being fluorinated lithium powder.This method specifically includes the following steps:
(1) aluminium chloride and lithium fluoride are subjected to precise according to mass ratio 3:1, are then added to graphite after mixing
In crucible, mixed halide is obtained.Specifically in the present embodiment, aluminium chloride and fluorination lithium powder are without the anhydrous of the crystallization water
Halide and be that analysis is pure, weighs 45.0g aluminum chloride powder and 15.0g fluorination lithium powder and is uniformly mixed, use it is preposition in
It is dried at a temperature of 140 DEG C, avoids deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 10.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, terbium
Content 1.08wt%.The present embodiment reduces the impurity content in fluorescent powder scrap by screening, to a certain extent may be used
It to improve the purity of the rare earth element finally extracted, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder can be promoted useless
Material is sufficiently reacted with halide fused salt, is accelerated reaction rate, is further improved the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
Obtained fluorescent powder scrap after sieving is added in step (2) into the fuse salt, make in halide fused salt and fluorescent powder scrap
8h is reacted at 1050 DEG C, whole process carries out under inert gas protection.
Using the technical solution of the present embodiment, make the extraction process of rare earth element in fluorescent powder in non-aqueous molten salt system
It carries out, does not consume inorganic acid, organic solvent and water during recovering rare earth to reach, the mesh of no spent acid and sewage discharge
's.In the present embodiment, aluminium chloride can selectively react with the rare earth oxide in waste phosphor powder, reduce in fluorescent powder
The influence of impurity element improves the purity of gained rare earth element, and the rare earth halide generated also can preferably dissolve in fluorescent powder
Rare earth oxide, and content and reaction temperature to aluminium chloride in the proportion of halide and fluorescent powder scrap, halide and anti-
It is controlled between seasonable, to ensure that the recovery rate of rare earth element in fluorescent powder.Lithium fluoride in above-mentioned halide is as anti-
Auxiliary agent is answered, can reduce the fusion temperature and viscosity of fused salt, accelerates the progress of reaction, improves the recovery rate of rare earth element, especially
The extraction effect to cerium in fluorescent powder and terbium can be significantly improved, the extraction in the prior art to cerium in fluorescent powder and terbium is overcome
The poor deficiency of effect.The finally obtained fused salt mixt containing rare earth halide of the present embodiment, can directly be made by being electrolysed
Standby rare earth alloy, preparation method is simpler, and the purity of the rare earth alloy as obtained by being electrolysed and can further increase, and improves rare earth
The grade of alloy.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-fluorination
The mixture of lithium.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Crossing and calculating the recovery rate of rare earth is 94.1%, and it also increases to the extraction effect of cerium, terbium.The present embodiment passes through construction chlorine
Change aluminium-lithium fluoride molten salt system, and control the proportion relation of each substance, make rare earth oxide in waste phosphor powder because of reaction and
Dissolution and be converted into rare earth halide and enter fused salt in, ensure that rare earth element can as far as possible completely with ionic state into
Enter into fused salt, to effectively increase the recovery rate of rare earth.
Embodiment 3
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is aluminium chloride and the mixture for being fluorinated lithium powder.This method specifically includes the following steps:
(1) aluminium chloride and lithium fluoride are subjected to precise according to mass ratio 4:1, are then added to graphite after mixing
In crucible, mixed halide is obtained.Specifically in the present embodiment, aluminium chloride and fluorination lithium powder are without the anhydrous of the crystallization water
Halide and be that analysis is pure, weighs 48.0g aluminum chloride powder and 12.0g fluorination lithium powder and is uniformly mixed, use it is preposition in
It is dried at a temperature of 200 DEG C, avoids deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 20.0g sieve is therefrom weighed, in which: the fluorescence of the present embodiment
Powder waste material: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, terbium content
1.08wt%.The present embodiment reduces the impurity content in fluorescent powder scrap by screening, to can mention to a certain extent
The purity of rare earth element that height finally extracts, and being controlled by the granularity to fluorescent powder scrap, can promote fluorescent powder scrap with
The abundant reaction of halide fused salt, accelerates reaction rate, further improves the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, halide fused salt and fluorescent powder scrap is made to exist
5h is reacted at 1100 DEG C, whole process carries out under inert gas protection.
Using the technical solution of the present embodiment, make the extraction process of rare earth element in fluorescent powder in non-aqueous molten salt system
It carries out, does not consume inorganic acid, organic solvent and water during recovering rare earth to reach, the mesh of no spent acid and sewage discharge
's.In the present embodiment, aluminium chloride can selectively react with the rare earth oxide in waste phosphor powder, hence it is evident that reduce fluorescence
The influence of impurity element in powder improves the purity of gained rare earth element, and the rare earth halide generated also can preferably dissolve fluorescence
Rare earth oxide in powder, and to the content and reaction temperature of aluminium chloride in the proportion of halide and fluorescent powder scrap, halide
It is controlled with the reaction time, to ensure that the recovery rate of rare earth element in fluorescent powder.Lithium fluoride in above-mentioned halide is done
For reaction promoter, the fusion temperature and viscosity of fused salt can reduce, accelerate the progress of reaction, improve the recovery rate of rare earth element,
More particularly to effectively improving the extraction effect to cerium in fluorescent powder and terbium, overcome in the prior art to cerium in fluorescent powder and terbium
The poor deficiency of extraction effect.The finally obtained fused salt mixt containing rare earth halide of the present embodiment, can be by being electrolysed come straight
It connects and prepares rare earth alloy, preparation method is simpler, and the purity of the rare earth alloy as obtained by being electrolysed and can further increase, and improves
The grade of rare earth alloy.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-fluorination
The mixture of lithium.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Crossing and calculating the recovery rate of rare earth is 94.2%, and it is remarkably improved the extraction effect of cerium, terbium.The present embodiment passes through structure
Aluminium chloride-lithium fluoride molten salt system is made, and controls the proportion relation of each substance, makes the rare earth oxide in waste phosphor powder because anti-
Should with dissolution and be converted into rare earth halide and enter fused salt in, ensure that rare earth element can all be entered with ionic state
Into fused salt, to effectively increase the recovery rate of rare earth.
Embodiment 4
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is aluminium chloride and the mixture for being fluorinated lithium powder.This method specifically includes the following steps:
(1) aluminium chloride and lithium fluoride are subjected to precise according to mass ratio 2:3, are then added to graphite after mixing
In crucible, mixed halide is obtained.Specifically in the present embodiment, aluminium chloride and fluorination lithium powder are without the anhydrous of the crystallization water
Halide and be that analysis is pure, weighs 24.0g aluminum chloride powder and 36.0g fluorination lithium powder and is uniformly mixed, use it is preposition in
It is dried at a temperature of 150 DEG C, avoids deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 6.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, and terbium contains
Measure 1.08wt%.The present embodiment reduces impurity content in fluorescent powder scrap by screening, thus to a certain extent can be with
The purity of the rare earth element finally extracted is improved, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder scrap can be promoted
With sufficiently reacting for halide fused salt, reaction rate is accelerated, further improves the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, makes halide fused salt and fluorescent powder scrap 600
10h is reacted at DEG C, whole process carries out under inert gas protection.
Using the technical solution of the present embodiment, make the extraction process of rare earth element in fluorescent powder in non-aqueous molten salt system
It carries out, does not consume inorganic acid, organic solvent and water during recovering rare earth to reach, the mesh of no spent acid and sewage discharge
's.In the present embodiment, aluminium chloride can selectively react with the rare earth oxide in waste phosphor powder, hence it is evident that reduce fluorescence
The influence of impurity element in powder improves the purity of gained rare earth element, and the rare earth halide generated also can preferably dissolve fluorescence
Rare earth oxide in powder, and to the content and reaction temperature of aluminium chloride in the proportion of halide and fluorescent powder scrap, halide
It is controlled with the reaction time, to ensure that the recovery rate of rare earth element in fluorescent powder.Lithium fluoride in above-mentioned halide is done
For reaction promoter, the fusion temperature and viscosity of fused salt can reduce, accelerate the progress of reaction, improve the recovery rate of rare earth element,
More particularly to improve the extraction effect to cerium in fluorescent powder and terbium, the extraction in the prior art to cerium in fluorescent powder and terbium is overcome
The poor deficiency of effect.The finally obtained fused salt mixt containing rare earth halide of the present embodiment, can directly be made by being electrolysed
Standby rare earth alloy, preparation method is simpler, and the purity of the rare earth alloy as obtained by being electrolysed and can further increase, and improves rare earth
The grade of alloy.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-fluorination
The mixture of lithium.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Crossing and calculating the recovery rate of rare earth is 92.5%, and it is remarkably improved the extraction effect of cerium, terbium.The present embodiment passes through structure
Aluminium chloride-lithium fluoride molten salt system is made, and controls the proportion relation of each substance, makes the rare earth oxide in waste phosphor powder because anti-
Should with dissolution and be converted into rare earth halide and enter fused salt in, ensure that most of rare earth element is entered with ionic state
In fused salt, to effectively increase the recovery rate of rare earth.
Embodiment 5
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is the mixture of aluminium chloride and lithium fluoride, calcirm-fluoride powder.This method specifically includes the following steps:
(1) aluminium chloride and lithium fluoride, calcirm-fluoride are subjected to precise according to mass ratio 3:2:1, then after mixing
It is added in graphite crucible, obtains mixed halide.Specifically in the present embodiment, aluminium chloride and lithium fluoride, calcirm-fluoride powder are equal
For the anhydrous halide without the crystallization water and it is that analysis is pure, weighs 30.0g aluminum chloride powder and 20.0g is fluorinated lithium powder, 10g
Calcirm-fluoride powder be uniformly mixed, using it is preposition in 170 DEG C at a temperature of dry, avoid deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 12.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, terbium
Content 1.08wt%.The present embodiment reduces the impurity content in fluorescent powder scrap by screening, to a certain extent may be used
It to improve the purity of the rare earth element finally extracted, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder can be promoted useless
Material is sufficiently reacted with halide fused salt, is accelerated reaction rate, is further improved the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, makes halide fused salt and fluorescent powder scrap 700
7h is reacted at DEG C, whole process carries out under inert gas protection.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-fluorination
Lithium-calcirm-fluoride mixture.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Crossing and calculating the recovery rate of rare earth is 93.5%, and it is also preferable to the extraction effect of cerium, terbium.
Embodiment 6
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is the mixture of aluminium chloride and lithium fluoride, potassium bromide powder.This method specifically includes the following steps:
(1) aluminium chloride and lithium fluoride, potassium bromide are subjected to precise according to mass ratio 4:1:1, then after mixing
It is added in graphite crucible, obtains mixed halide.Specifically in the present embodiment, aluminium chloride and lithium fluoride, potassium bromide powder are equal
For the anhydrous halide without the crystallization water and be analysis it is pure, weigh 40.0g aluminum chloride powder and 10.0g fluorination lithium powder,
10.0g potassium bromide powder be uniformly mixed, using it is preposition in 185 DEG C at a temperature of dry, avoid deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 15.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, terbium
Content 1.08wt%.The present embodiment reduces the impurity content in fluorescent powder scrap by screening, to a certain extent may be used
It to improve the purity of the rare earth element finally extracted, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder can be promoted useless
Material is sufficiently reacted with halide fused salt, is accelerated reaction rate, is further improved the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, makes halide fused salt and fluorescent powder scrap 700
7h is reacted at DEG C, whole process carries out under inert gas protection.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-fluorination
Lithium-potassium bromide mixture.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
The recovery rate for crossing calculating rare earth is closer to embodiment 3, is slightly below embodiment 3 to the extraction effect of cerium, terbium.
Embodiment 7
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is frerrous chloride and the mixture for being fluorinated lithium powder.This method specifically includes the following steps:
(1) frerrous chloride and lithium fluoride are subjected to precise according to mass ratio 4:1, are then added to stone after mixing
In black crucible, mixed halide is obtained.Specifically in the present embodiment, frerrous chloride and fluorination lithium powder are without the crystallization water
Anhydrous halide and be that analysis is pure, weighs 48.0g frerrous chloride powder and 12.0g and is fluorinated lithium powder and be uniformly mixed, and is using
It is preposition to be dried at a temperature of 100 DEG C, it avoids deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 6.5g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, and terbium contains
Measure 1.08wt%.The present embodiment reduces impurity content in fluorescent powder scrap by screening, thus to a certain extent can be with
The purity of the rare earth element finally extracted is improved, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder scrap can be promoted
With sufficiently reacting for halide fused salt, reaction rate is accelerated, further improves the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, makes halide fused salt and fluorescent powder scrap 700
8h is reacted at DEG C, whole process carries out under inert gas protection.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-frerrous chloride-fluorine
Change the mixture of lithium.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
It crosses and calculates preferable to the extraction effect of rare earth element in the present embodiment, but be lower than embodiment 1-6, and it imitates the extraction of cerium, terbium
Fruit is then closer to embodiment 3.
Embodiment 8
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is the mixture of aluminium bromide and lithium fluoride, magnesium chloride powder.This method specifically includes the following steps:
(1) aluminium bromide and lithium fluoride, magnesium chloride powder are subjected to precise according to mass ratio 4:1:1, then mixing is equal
It is added in graphite crucible after even, obtains mixed halide.Specifically in the present embodiment, aluminium bromide and lithium fluoride, magnesium chloride powder
End is the anhydrous halide without the crystallization water and is that analysis is pure, weigh 40.0g bromination aluminium powder and 10.0g lithium fluoride,
10.0g magnesium chloride powder be uniformly mixed, using it is preposition in 150 DEG C at a temperature of dry, avoid deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 8.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, and terbium contains
Measure 1.08wt%.The present embodiment reduces impurity content in fluorescent powder scrap by screening, thus to a certain extent can be with
The purity of the rare earth element finally extracted is improved, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder scrap can be promoted
With sufficiently reacting for halide fused salt, reaction rate is accelerated, further improves the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, makes halide fused salt and fluorescent powder scrap 900
7.5h is reacted at DEG C, whole process carries out under inert gas protection.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium bromide-fluorination
Lithium-magnesium chloride mixture.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Cross calculating, it is preferable to the extraction effect of overall rare earth element and cerium, terbium in the present embodiment, but it is lower than embodiment 1-6.
Embodiment 9
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is the mixture of aluminium chloride and potassium chloride powder.This method specifically includes the following steps:
(1) aluminium chloride and potassium chloride powder are subjected to precise according to mass ratio 2:1, are then added to after mixing
In graphite crucible, mixed halide is obtained.Specifically in the present embodiment, aluminium chloride and potassium chloride powder are without the crystallization water
Anhydrous halide and be analysis it is pure, weigh 50.0g aluminum chloride powder and be uniformly mixed with 25.0g potassium chloride powder, before use
It is dried at a temperature of being placed in 200 DEG C, avoids deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 10.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, terbium
Content 1.08wt%.The present embodiment reduces the impurity content in fluorescent powder scrap by screening, to a certain extent may be used
It to improve the purity of the rare earth element finally extracted, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder can be promoted useless
Material is sufficiently reacted with halide fused salt, is accelerated reaction rate, is further improved the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, makes halide fused salt and fluorescent powder at 800 DEG C
8h is reacted, whole process carries out under inert gas protection.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with molten chloride in fluorescent powder, and fused salt is rare earth-iron-boron-aluminium chloride-chlorination
The mixture of potassium.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Crossing and calculating the recovery rate of rare earth is 90.8%.The present invention controls matching for each substance by structure aluminium chloride-potassium chloride molten salt system
Than relationship, so that the rare earth oxide in waste phosphor powder is converted into rare earth-iron-boron because of reaction and dissolution and enter fused salt
In, to effectively increase the recovery rate of rare earth, but relatively poor to the extraction effect of cerium and terbium in the present embodiment.
Embodiment 10
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogenation of the present embodiment through being separated by solid-liquid separation
Object is the mixture of aluminium chloride and sodium fluoride powder.This method specifically includes the following steps:
(1) aluminium chloride and sodium fluoride powder are subjected to precise according to mass ratio 3:2, are then added to after mixing
In graphite crucible, mixed halide is obtained.Specifically in the present embodiment, aluminium chloride and sodium fluoride powder are without the crystallization water
Anhydrous halide and be analysis it is pure, weigh 36.0g aluminum chloride powder and be uniformly mixed with 24.0g potassium chloride powder, before use
It is dried at a temperature of being placed in 180 DEG C, avoids deliquescing because of water suction.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 10.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, terbium
Content 1.08wt%.The present embodiment reduces the impurity content in fluorescent powder scrap by screening, to a certain extent may be used
It to improve the purity of the rare earth element finally extracted, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder can be promoted useless
Material is sufficiently reacted with halide fused salt, is accelerated reaction rate, is further improved the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
The fluorescent powder scrap obtained after sieving in step (2) is added into the fuse salt, makes halide fused salt and fluorescent powder scrap 800
9h is reacted at DEG C, whole process carries out under inert gas protection.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with molten chloride in fluorescent powder, and fused salt is rare earth-iron-boron-aluminium chloride-fluorination
The mixture of sodium.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Calculating is crossed, the recovery rate of rare earth is 90.5%.The present invention controls each substance by structure aluminium chloride-sodium fluoride molten salt system
Proportion relation makes the rare earth oxide in waste phosphor powder be converted into rare earth-iron-boron because of reaction and dissolution and enters molten
In salt, to effectively increase the recovery rate of rare earth, but then relatively poor to the extraction effect of cerium and terbium in the present embodiment.
Embodiment 11
A kind of method of Extraction of rare earth element from waste phosphor powder of the present embodiment, is by making fluorescent powder scrap and halogen
Then the fuse salt hybrid reaction of compound obtains the fused salt mixt containing rare earth halide, the halogen of the present embodiment through being separated by solid-liquid separation
Compound is the mixture of aluminium chloride and magnesium fluoride, chlorination barium dust.This method specifically includes the following steps:
(1) aluminium chloride, magnesium fluoride and barium chloride are subjected to precise according to mass ratio 3:2:2, then after mixing
It is added in graphite crucible, obtains mixed halide.Specifically in the present embodiment, aluminium chloride, magnesium fluoride and chlorination barium dust are equal
For the anhydrous halide without the crystallization water and be analysis it is pure, weigh 30.0g aluminum chloride powder, 20.0g magnesium fluoride powder with
20.0g chlorination barium dust is uniformly mixed, and is dried at a temperature of before in 120 DEG C, avoids absorbing water and deliquescing.
(2) waste phosphor powder is sieved using 100 the polished standard screens, to remove large granular impurity therein, is obtained
To the lower fluorescent powder scrap of impurity content, the fluorescent powder scrap under 12.0g sieve is therefrom weighed, in which: after the present embodiment sieving
Fluorescent powder scrap: 149 microns of partial size is hereinafter, yttrium content 18.5wt%, europium content 1.58wt%, cerium content 2.02wt%, terbium
Content 1.08wt%.The present embodiment reduces the impurity content in fluorescent powder scrap by screening, to a certain extent may be used
It to improve the purity of the rare earth element finally extracted, and is controlled by the granularity to fluorescent powder scrap, fluorescent powder can be promoted useless
Material is sufficiently reacted with halide fused salt, is accelerated reaction rate, is further improved the recovery rate of rare earth element.
(3) mixed halide obtained in step (1) is placed in heat in vacuum electric furnace and is melted, obtain halide fused salt,
Fluorescent powder scrap obtained in step (2) is added into the fuse salt, makes halide fused salt and fluorescent powder scrap at 1000 DEG C
6h is reacted, whole process carries out under inert gas protection.
(4) gained reaction product in step (3) is subjected to solid-liquid clarified separation, respectively obtains solid residue and fused salt,
Solid residue is the component that do not react with fluoride molten salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-fluorination
Magnesium-barium chloride mixture.
Using the recovery method of the present embodiment, x ray fluorescence spectrometry and inductively coupled plasma body atomic emissions are utilized
Spectroscopic methodology to final gained fused salt in solid residue yttrium, europium, cerium, four kinds of rare earth elements of terbium content detect, lead to
Calculating is crossed, the recovery rate of rare earth is 93.9%.The present invention is controlled each by structure aluminum fluoride-magnesium fluoride-barium chloride molten salt system
The proportion relation of substance makes the rare earth oxide in waste phosphor powder be converted into rare earth fluoride simultaneously because of reaction and dissolution
Into in fused salt, to effectively increase the recovery rate of rare earth, but it is to the extraction effect of cerium in fluorescent powder scrap and terbium then phase
To poor.
Comparative example 1
This comparative example is identical as the method for Extraction of rare earth element in the slave fluorescent powder of embodiment 1, and difference is only that this is right
The mass ratio of aluminium chloride and lithium fluoride in ratio is 7:15.
Comparative example 2
This comparative example is identical as the method for Extraction of rare earth element in the slave fluorescent powder of embodiment 1, and difference is only that this is right
The mass ratio of aluminium chloride and lithium fluoride in ratio is 1:3.
Comparative example 3
This comparative example is identical as the method for Extraction of rare earth element in the slave fluorescent powder of embodiment 5, and difference is only that this is right
The mass ratio of aluminium chloride and lithium fluoride, calcirm-fluoride is 1:3:1 in ratio.
The rare earth element in fluorescent powder scrap is extracted using the recovery method of comparative example 1-3, utilizes x-ray fluorescence
Spectroscopic methodology and inductively coupled plasma atomic emission spectrometry in final gained fused salt and solid residue yttrium, europium, cerium,
The content of four kinds of rare earth elements of terbium is detected, the results showed that, using the method in comparative example 1-3 to rare earth in fluorescent powder scrap
The extraction effect of element is relatively poor, and recovery rate is lower, cannot meet the requirements, and easily causes a large amount of wastes of resource.
Lithium fluoride in the present invention can use potassium fluoride, magnesium fluoride, calcirm-fluoride, barium fluoride, sodium fluoride, sodium chloride, chlorine
Change potassium, lithium chloride, magnesium chloride, calcium chloride, barium chloride, sodium bromide, potassium bromide, sodium iodide, a kind or a kind or more in potassium iodide
The mixture of material composition replaces, can also be using lithium fluoride and potassium fluoride, magnesium fluoride, calcirm-fluoride, barium fluoride, sodium fluoride, chlorine
Change sodium, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, barium chloride, sodium bromide, potassium bromide, sodium iodide, a kind or 1 in potassium iodide
Kind or more material composition mixture replace.Aluminium chloride in the present invention can use frerrous chloride, zinc chloride, aluminium bromide or iodine
Change zinc to be replaced, but because length is limited, inconvenience is arranged one by one here to be taken.
1-10 and comparative example 1-3 is it is found that can be in fluorescent powder scrap using method of the invention based on the above embodiments
Rare earth element effectively extracted, wherein best with extraction effect of the aluminium chloride to rare earth element, but control chlorine must be passed through
The content and reaction process parameter for changing aluminium, can just guarantee to obtain higher rare earth element recovery rate.In addition, the present invention passes through fluorine
The addition for changing lithium can effectively improve the recovery rate of cerium and terbium in fluorescent powder scrap, and overcoming in the prior art cannot be to cerium and terbium
The deficiency effectively extracted.
Claims (5)
1. a kind of method of the Extraction of rare earth element from waste phosphor powder, it is characterised in that: this method is by keeping fluorescent powder useless
The fuse salt of material and halide 5~10h of hybrid reaction at 600~1100 DEG C, then obtains through being separated by solid-liquid separation containing rare earth halide
The fused salt mixt of object；The mass ratio of the halide fused salt and fluorescent powder scrap is 3:1~10:1, which is aluminium chloride
With fluorination lithium powder mixture, and in halide mixed-powder aluminium chloride mass percentage content be 40%~80%.
2. a kind of method of Extraction of rare earth element from waste phosphor powder according to claim 1, it is characterised in that: it has
Body step are as follows:
(1) aluminium chloride is subjected to precise with fluorination lithium powder and be uniformly mixed, obtain mixed halide；
(2) waste phosphor powder is sieved, removes large granular impurity therein, obtain the low fluorescent powder scrap of impurity content；
(3) mixed halide obtained in step (1) is heated and is melted, obtain halide fused salt, added into the halide fused salt
Fluorescent powder scrap after entering sieving, reacts halide fused salt sufficiently with fluorescent powder scrap；
(4) clarified separation is carried out to gained reaction product in step (3), respectively obtains solid residue and fused salt, solid residues
Object is the component that do not react with halide fused salt in fluorescent powder, and fused salt is rare earth halide-aluminium chloride-lithium fluoride mixing
Object.
3. a kind of method of Extraction of rare earth element from waste phosphor powder according to claim 1 or 2, it is characterised in that:
The aluminium chloride and fluorination lithium powder is the anhydrous halide without the crystallization water, and using preceding at 100-200 DEG C
It is dried, to remove absorption water therein.
4. a kind of method of Extraction of rare earth element from waste phosphor powder according to claim 2, it is characterised in that: step
(2) waste phosphor powder is sieved using 100 the polished standard screens in.
5. a kind of according to claim 1, method of the Extraction of rare earth element from waste phosphor powder described in any one of 2,4,
Be characterized in that: the aluminium chloride is replaced using frerrous chloride, zinc chloride, aluminium bromide or zinc iodide.
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