CN102838988B - Method for recovering yttrium and europium in waste fluorescent powder to prepare yttrium europium oxide - Google Patents
Method for recovering yttrium and europium in waste fluorescent powder to prepare yttrium europium oxide Download PDFInfo
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Abstract
The invention discloses a method for recovering yttrium and europium in waste fluorescent powder to prepare yttrium europium oxide, and belongs to the technical field of waste recovery. The method includes following steps: a. mixing the waste fluorescent powder, ammonium chloride and potassium pyrosulfate powder, and moving the mixture into a roasting furnace to be roasted at the temperature of 340-400 DEG C; b. water immersing solid after roasting, and then obtaining solution including the yttrium and the europium; c. adding sodium sulphide into the solution including the yttrium and the europium to refine; and d. the potential of hydrogen (pH) value of the solution after refinement is adjusted to range from 1.5 to 2, and then adding oxalic acid to enable the yttrium and the europium to precipitate to obtain yttrium oxalate hydrate and oxalic acid europium. According to requirements of fluorescent powder of a color television or a three band fluorescent lamp for raw materials, at least one of the yttrium oxalate hydrate or the oxalic acid europium or yttrium oxide or europium oxide is added into the yttrium oxalate hydrate and the oxalic acid europium, and ytterbium europium oxide is obtained after the reaction. The method can reduce production cost, and improves the recovery rate of the yttrium and the europium; and the obtained ytterbium europium oxide can be directly used for preparing the fluorescent powder of the color television or the three band fluorescent lamp.
Description
Technical field
The invention belongs to household electric appliances Waste recovery technical field, be specifically related to a kind of method that yttrium and europium are produced yttrium europium oxide that reclaims from waste phosphor powder.
Background technology
Waste and old CRT TV, waste and old PDP TV, three-color fluorescent lamp all contain a large amount of rare earth elements, and average every waste and old CRT TV approximately approximately approximately contains fluorescent material 3 grams containing fluorescent material 30 grams, every three-color fluorescent lamp containing fluorescent material 8 grams, every waste and old PDP TV.Mainly contain rare earth element yttrium and europium in waste and old fluorescent material, in addition also contain the rare earth elements such as cerium, terbium, dysprosium.From protection rare earth resources, recycle rare earth resources, environmental angle, reclaim fluorescent material middle-weight rare earths resource imperative.
At present, for the recovery of fluorescent material, generally all adopt wet method, long reaction time not only, and also the acid consumption is high.For popularization and the scale production that realizes that fluorescent material reclaims, need to reduce sour consumption, the reduction energy consumption, need to explore how to improve the mixed economy recovery method that fluorescent material leaches dissolved efficiency and main two kinds of rare earth element yttriums and europium especially.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of recovery yttrium from waste phosphor powder of cost recovery and raising yttrium and the europium rate of recovery and method that europium is produced yttrium europium oxide of reducing.
The technical solution adopted for the present invention to solve the technical problems is: reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder, comprise the following steps:
A, waste phosphor powder and ammonium chloride, potassium pyrosulfate powder mixed and move into stoving oven, with the temperature roasting of 340～400 ℃, then using the temperature roasting of 500～550 ℃;
Solid after b, water logging step a roasting, then filter solution and the undissolved phosphor powder obtained containing yttrium and europium;
C, in the solution containing yttrium and europium, add the sodium sulphite removal of impurities;
D, the solution after step c removal of impurities is regulated between pH value to 1.5～2, then added oxalic acid to make yttrium and europium precipitation obtain yttrium oxalate and oxalic acid europium; To the requirement of phosphor raw material, in yttrium oxalate and oxalic acid europium, allocate at least one in yttrium oxalate, oxalic acid europium, yttrium oxide or europium sesquioxide into according to color TV or three-color fluorescent lamp, reaction makes the product yttrium europium oxide.
Wherein, in aforesaid method step a, the quality proportioning of waste phosphor powder and ammonium chloride, potassium pyrosulfate is: Fei abandons Ying Guang Fen ︰ Lvization An ︰ potassium pyrosulfate=1 ︰ 6～10 ︰ 0.05～0.1.
Wherein, aforesaid method also comprises step e, in step a during with the temperature roasting of 500～550 ℃, and the ammonium chloride gas that cooling recovery roasting produces, residual gas alkali liquor absorption.
Wherein, in aforesaid method step a, with the time of the temperature roastings of 340～400 ℃ be 20～50 minutes.
Wherein, in aforesaid method step a, with the time of the temperature roastings of 500～550 ℃ be 5～10 minutes.
Wherein, in aforesaid method step b, the solid-to-liquid ratio of water logging is 1g ︰ 5～30ml.
Wherein, in the aforesaid method steps d, by the mode of calcining in 800～900 ℃ of temperature ranges, react and make yttrium europium oxide, calcination time is 3～10 hours.
Wherein, in the aforesaid method steps d, in yttrium oxalate and oxalic acid europium, allocate at least one in yttrium oxalate, oxalic acid europium, yttrium oxide or europium sesquioxide into, make the quality of the Zhi Liang ︰ europium of yttrium=13～18.
Wherein, aforesaid method also comprises step f, in the undissolved phosphor powder of gained in step b, adds at least one acid in nitric acid or hydrochloric acid, reacts 2～5 minutes, filters, and the pH after filtration is 2.5～3.5; In the solution after filtering, add vitriol to reclaim barium, then add sodium sulphite to reclaim zinc, between regulator solution pH value to 1.5～2, add remaining rare earth element in excessive recovery of oxalic acid solution afterwards.
Wherein, the described waste phosphor powder of aforesaid method refers at least one in discarded CRT fluorescent material, discarded PDP fluorescent material or discarded fluorescent lamp fluorescent material.
The invention has the beneficial effects as follows: the present invention is baking mixed by waste phosphor powder and ammonium chloride, potassium pyrosulfate powder, under ammonium chloride and potassium pyrosulfate acting in conjunction and control the temperature of roasting, can effectively destroy the coating layer of phosphor surface, destroy the structure of waste phosphor powder, fully reaction makes the mixture of Yttrium trichloride, Europium trichloride, yttrium sulfate and europium sulfate, make it very easily water-soluble, and can be by (2-5 minute) dissolving fast of residue fluorescent material with a small amount of acid, thereby reduced greatly sour consumption, reduced cost recovery.In addition, thereby the technique of the inventive method by roasting, water logging, removal of impurities, precipitation, calcining just can reclaim yttrium fully and europium makes yttrium europium oxide, and the rate of recovery of yttrium and europium all is greater than 90%.Moreover, the inventive method also fully reclaims residue rare earth element wherein by the undissolved fluorescent material of water logging by the mode of acidleach, and reclaims barium and zinc in this process, and wherein the rate of recovery of zinc can reach more than 95%.The yttrium europium oxide that the inventive method makes, can be directly used in formulating colorful TV or three-color fluorescent lamp fluorescent material, yttrium europium oxide is follow-up can be used for preparing high-end color TV or three-color fluorescent lamp fluorescent material after purification repeatedly, sorting, rinsing, surface treatment, screening.The economic environmental protection of the inventive method, have certain economic benefit and social benefit.
The accompanying drawing explanation
Fig. 1 is the inventive method schematic process flow diagram.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
As shown in Figure 1, the present invention reclaims the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder, comprises the following steps:
A, waste phosphor powder and ammonium chloride, potassium pyrosulfate powder mixed and move into stoving oven, with the temperature roasting of 340～400 ℃, then using the temperature roasting of 500～550 ℃;
Solid after b, water logging step a roasting, then filter solution and the undissolved phosphor powder obtained containing yttrium and europium;
C, in the solution containing yttrium and europium, add the sodium sulphite removal of impurities;
D, the solution after step c removal of impurities is regulated between pH value to 1.5～2, then added oxalic acid to make yttrium and europium precipitation obtain yttrium oxalate and oxalic acid europium; To the requirement of phosphor raw material, in yttrium oxalate and oxalic acid europium, allocate at least one in yttrium oxalate, oxalic acid europium, yttrium oxide or europium sesquioxide into according to color TV or three-color fluorescent lamp, reaction makes the product yttrium europium oxide.
The yttrium europium oxide that the present invention makes, can be directly used in formulating colorful TV or three-color fluorescent lamp fluorescent material.
Because electrical and chemical mobility of the surface can cause the fluorescent material degradation, so the surface of fluorescent material often is coated with the chemical substances such as aluminum oxide, titanium oxide to guarantee its chemical stability, particularly Alpha-alumina resistance to acids and bases wherein is strong, the present invention adds the roasting of potassium pyrosulfate powder can effectively destroy coating layer, and the principal reaction equation is as follows:
3K
2S
2O
7+Al
2O
3=Al
2(SO
4)
3+3K
2SO
4
Because the fluorescent material containing yttrium and europium often generates by pyroreaction, crystalline structure is tight, so waste phosphor powder is difficult to be dissolved at short notice acid.The present invention is baking mixed by waste phosphor powder and ammonium chloride, potassium pyrosulfate powder, and the final mixture that generates Yttrium trichloride, Europium trichloride, yttrium sulfate and europium sulfate of reaction is very easily water-soluble.
In step a, at first the present invention controls maturing temperature at 340～400 ℃, in order to impel the fluorescent material containing yttrium and europium fully to react generation Yttrium trichloride, Europium trichloride, yttrium sulfate and europium sulfate, if temperature of reaction all can reduce reaction efficiency lower than 340 ℃ or higher than 400 ℃; Be warming up to again 500～550 ℃ of roastings, be in order rapidly and efficiently to reclaim the excess chlorination ammonium, and do not affect the chemical property of Yttrium trichloride, Europium trichloride, yttrium sulfate and the europium sulfate of generation.In step c, add sodium sulphite can remove the impurity such as iron a small amount of in solution, zinc, cadmium, lead, it will be appreciated by persons skilled in the art that the amount that adds sodium sulphite should come according to foreign matter content fixed.
Preferably, for fully being reacted, waste phosphor powder generates Yttrium trichloride, Europium trichloride, yttrium sulfate and europium sulfate, and raising speed of reaction, in aforesaid method step a, the quality proportioning of waste phosphor powder and ammonium chloride, potassium pyrosulfate is: Fei abandons Ying Guang Fen ︰ Lvization An ︰ potassium pyrosulfate=1 ︰ 6～10 ︰ 0.05～0.1.
Preferably, aforesaid method also comprises step e, in step a during with the temperature roasting of 500～550 ℃, and the ammonium chloride gas that cooling recovery roasting produces, residual gas alkali liquor absorption.
Preferably, in aforesaid method step a, with the time of the temperature roastings of 340～400 ℃ be 20～50 minutes.
Preferably, in aforesaid method step a, with the time of the temperature roastings of 500～550 ℃ be 5～10 minutes.
Preferably, in aforesaid method step b, the solid-to-liquid ratio of water logging is 1g ︰ 5～30ml.
Preferably, for the color TV that obtains better quality or the raw material of three-color fluorescent lamp fluorescent material, in the aforesaid method steps d, by the mode of calcining in 800～900 ℃ of temperature ranges, react and make yttrium europium oxide, calcination time is 3～10 hours.
Preferably, for the color TV that obtains better quality or the raw material of three-color fluorescent lamp fluorescent material, in the aforesaid method steps d, in yttrium oxalate and oxalic acid europium, allocate at least one in yttrium oxalate, oxalic acid europium, yttrium oxide or europium sesquioxide into, make the quality of the Zhi Liang ︰ europium of yttrium=13～18.
Preferably, aforesaid method also comprises step f, in the undissolved phosphor powder of gained in step b, adds at least one acid in nitric acid or hydrochloric acid, reacts 2～5 minutes, filters, and the pH after filtration is 2.5～3.5; In the solution after filtering, add vitriol to reclaim barium, then add sodium sulphite to reclaim zinc, between regulator solution pH value to 1.5～2, add remaining rare earth element in excessive recovery of oxalic acid solution afterwards.It will be appreciated by persons skilled in the art that generally to waste phosphor powder processed for be all the mixture that contains dissimilar fluorescent material mixed, the amount of the fluorescent material of single type is fewer after all, as discarded fluorescent lamp fluorescent material.For step f, composition difference according to all kinds fluorescent material, can adopt slightly different processing mode: if just processed for discarded CRT fluorescent material, can be after acid be dissolved, first add sodium sulphite to be reclaimed zinc sulphide, then pH is adjusted to 1.5～2, then add oxalic acid, oxalic acid is excessive 10～20%, then reclaims the rare earth element such as remaining a small amount of yttrium in solution; If just for discarded PDP fluorescent material, can, after acid is dissolved, first add vitriol reclaim(ed) sulfuric acid barium, add again sodium sulphite to reclaim zinc sulphide, then pH is adjusted to 1.5～2, then add oxalic acid, oxalic acid is excessive 10～20%, reclaims the rare earth elements such as remaining a small amount of yttrium, europium in solution; If just for discarded fluorescent lamp fluorescent material, can after dissolve, acid first add vitriol reclaim(ed) sulfuric acid barium, then pH is adjusted to 1.5～2, then add oxalic acid, and oxalic acid is excessive 10～20%, reclaims in solution the rare earth elements such as remaining cerium.
Wherein, the described waste phosphor powder of aforesaid method refers at least one in discarded CRT fluorescent material, discarded PDP fluorescent material or discarded fluorescent lamp fluorescent material.
Below by embodiment, the specific embodiment of the present invention is further described, but therefore protection scope of the present invention is not limited among embodiment.
In embodiment, handled waste phosphor powder is the mixture of discarded CRT fluorescent material, discarded PDP fluorescent material and discarded fluorescent lamp fluorescent material, and discarded CRT fluorescent material is mainly by rouge and powder Y
2o
3: Eu
3+, green powder Y
2o
2s:Tb
3+, blue powder ZnS:Ag forms; Discarded PDP fluorescent material is mainly by rouge and powder Y (V, P) O
4: Eu
3+, green powder Zn
2siO
4: Mn
2+, blue powder BaMgAl
10o
17: Eu
2+form; Discarded fluorescent lamp fluorescent material is mainly by rouge and powder Y
2o
3: Eu
3+, green powder Ce
0.67mg
0.33al
11o
19: Tb
3+, blue powder BaMgAl
16o
27: Eu
2+form.
Embodiment mono-
A, weighing waste phosphor powder 50.0g, wherein, by weight containing yttrium 9.60g, containing europium 0.75g, containing zinc 14.0g.Ammonium chloride and potassium pyrosulfate are by waste phosphor powder: ammonium chloride: potassium pyrosulfate=1:6:0.1 quality proportioning mixes in the powder mixing tank with waste phosphor powder, then is placed in stoving oven, and 350 ℃ of insulations 20 minutes, allow fluorescent material fully react.By roasting furnace temperature elevation to 500 ℃, and then after reacting, solid is put into stoving oven, and 500 ℃ are incubated 10 minutes.
B, by solid-to-liquid ratio, be that 1g:5ml adds deionized water, solid after water logging step a end reaction, filter and obtain containing yttrium and europium solution and undissolved phosphor powder 18.30g.
C, lysate pH is adjusted to 2.5, then adds sodium sulphite 3.11g, remove the impurity such as a small amount of iron, zinc, cadmium, lead.
D, will be adjusted to 1.5 containing the pH of yttrium and europium, add again oxalic acid, oxalic acid is excessive 10%, and yttrium and europium are precipitated fully, dry yttrium oxalate 10.29g and oxalic acid europium 1.28g, allocate yttrium oxalate 2.10g into, the mass ratio that makes yttrium and europium is 14.1,800 ℃ of reactions, within 10 hours, obtains yttrium europium oxide 12.93g, can be directly used in formulating colorful TV or three-color fluorescent lamp fluorescent material, the yttrium rate of recovery 91.2%, the europium rate of recovery 91.0%.
The ammonium chloride gas that e, cooling recycling step a reaction produces, the residual gas alkali liquor absorption.
F, in the undissolved phosphor powder of gained in step b, add nitric acid, dissolve 2 minutes, filtration, to filtering in the solution that rear pH value is 3, add vitriol to reclaim barium, add again sodium sulphite to reclaim zinc sulphide 19.89g, zinc recovery 95.20%, regulator solution pH value to 1.8, add the rare earth elements such as remaining cerium, yttrium, europium in excessive recovery of oxalic acid solution afterwards.
Embodiment bis-
A, weighing waste phosphor powder 75.0g, wherein, by weight containing yttrium 14.25g, containing europium 1.16g, containing zinc 21.75g.Ammonium chloride and potassium pyrosulfate are by waste phosphor powder: ammonium chloride: potassium pyrosulfate=1:8:0.08 quality proportioning mixes in the powder mixing tank with waste phosphor powder, then is placed in stoving oven, and 370 ℃ of insulations 30 minutes, allow fluorescent material fully react.By roasting furnace temperature elevation to 525 ℃, and then after reacting, solid is put into stoving oven, and 525 ℃ are incubated 5 minutes.
B, by solid-to-liquid ratio, be that 1g:15ml adds deionized water, solid after water logging step a end reaction, filter and obtain containing yttrium and europium solution and undissolved phosphor powder 28.33g.
C, lysate pH is adjusted to 2.2, then adds sodium sulphite 3.89g, remove the impurity such as a small amount of iron, zinc, cadmium, lead.
D, will be adjusted to 1.8 containing the pH of yttrium and europium, add again oxalic acid, oxalic acid is excessive 15%, and yttrium and europium are precipitated fully, dry yttrium oxalate 14.48g and oxalic acid europium 1.96g, allocate yttrium oxide 2.20g into, the mass ratio that makes yttrium and europium is 13.8,850 ℃ of reactions, within 6 hours, obtains yttrium europium oxide 19.66g, can be directly used in formulating colorful TV or three-color fluorescent lamp fluorescent material, the yttrium rate of recovery 90.7%, the europium rate of recovery 90.5%.
The ammonium chloride gas that e, cooling recycling step a reaction produces, the residual gas alkali liquor absorption.
F, in the undissolved phosphor powder of gained in step b, add hydrochloric acid, dissolve 3 minutes, filtration, to filtering in the solution that rear pH value is 3, add vitriol to reclaim barium, add again sodium sulphite to reclaim zinc sulphide 31.58g, zinc recovery 97.83%, regulator solution pH value to 1.5, add the rare earth elements such as remaining cerium, yttrium, europium in excessive recovery of oxalic acid solution afterwards.
Embodiment tri-
A, weighing waste phosphor powder 100.0g, wherein, by weight containing yttrium 23.15g, containing europium 1.23g, containing zinc 11.38g.Ammonium chloride and potassium pyrosulfate are by waste phosphor powder: ammonium chloride: potassium pyrosulfate=1:10:0.1 quality proportioning mixes in the powder mixing tank with waste phosphor powder, then is placed in stoving oven, and 390 ℃ of insulations 45 minutes, allow fluorescent material fully react.By roasting furnace temperature elevation to 550 ℃, and then after reacting, solid is put into stoving oven, and 550 ℃ are incubated 5 minutes.
B, by solid-to-liquid ratio, be that 1g:25ml adds deionized water, solid after water logging step a end reaction, filter and obtain containing yttrium and europium solution and undissolved phosphor powder 19.89g.
C, lysate pH is adjusted to 2.8, then adds sodium sulphite 6.17g, remove the impurity such as a small amount of iron, zinc, cadmium, lead.
D, will be adjusted to 1.7 containing the pH of yttrium and europium, add again oxalic acid, oxalic acid is excessive 20%, and yttrium and europium are precipitated fully, dry yttrium oxalate 22.62g and oxalic acid europium 2.10g, allocate oxalic acid europium 0.51g into, the mass ratio that makes yttrium and europium is 15.4,900 ℃ of reactions, within 3 hours, obtains yttrium europium oxide 28.08g, can be directly used in formulating colorful TV or three-color fluorescent lamp fluorescent material, the yttrium rate of recovery 90.8%, the europium rate of recovery 90.9%.
The ammonium chloride gas that e, cooling recycling step a reaction produces, the residual gas alkali liquor absorption.
F, in the undissolved phosphor powder of gained in step b, add nitric acid, dissolve 4 minutes, filtration, to filtering in the solution that rear pH value is 3, add vitriol to reclaim barium, add again sodium sulphite to reclaim zinc sulphide 16.40g, zinc recovery 96.59%, regulator solution pH value to 1.6, add the rare earth elements such as remaining cerium, yttrium, europium in excessive recovery of oxalic acid solution afterwards.
From embodiment, can find out, the present invention is by baking mixed by waste phosphor powder and ammonium chloride, potassium pyrosulfate powder, fully reaction makes the mixture of Yttrium trichloride, Europium trichloride, yttrium sulfate and europium sulfate, make it very easily water-soluble, and residue fluorescent material can be dissolved fast with a small amount of acid, thereby reduced greatly sour consumption, reduced production cost.In addition, the inventive method just can make the rate of recovery of yttrium and europium all be greater than 90% by the technique of roasting, water logging, removal of impurities, precipitation, calcining, and simultaneously, also the undissolved fluorescent material of water logging is fully reclaimed to residue rare earth element wherein by the mode of acidleach, and the rate of recovery of zinc can reach more than 95% in this process.The yttrium europium oxide that the inventive method makes, can be directly used in formulating colorful TV or three-color fluorescent lamp fluorescent material, and the process economy environmental protection, have certain economic benefit and social benefit.
Claims (9)
1. reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder, it is characterized in that comprising the following steps:
A, waste phosphor powder and ammonium chloride, potassium pyrosulfate powder mixed and move into stoving oven, with the temperature roasting of 340～400 ℃, then using the temperature roasting of 500～550 ℃;
Described waste phosphor powder refers at least one in discarded CRT fluorescent material, discarded PDP fluorescent material or discarded fluorescent lamp fluorescent material; Discarded CRT fluorescent material is mainly by rouge and powder Y
2o
3: Eu
3+, green powder Y
2o
2s:Tb
3+, blue powder ZnS:Ag forms; Discarded PDP fluorescent material is mainly by rouge and powder Y (V, P) O
4: Eu
3+, green powder Zn
2siO
4: Mn
2+, blue powder BaMgAl
10o
17: Eu
2+form; Discarded fluorescent lamp fluorescent material is mainly by rouge and powder Y
2o
3: Eu
3+, green powder Ce
0.67mg
0.33al
11o
19: Tb
3+, blue powder BaMgAl
16o
27: Eu
2+form;
Solid after b, water logging step a roasting, then filter solution and the undissolved phosphor powder obtained containing yttrium and europium;
C, in the solution containing yttrium and europium, add the sodium sulphite removal of impurities;
D, the solution after step c removal of impurities is regulated between pH value to 1.5～2, then added oxalic acid that yttrium and europium are precipitated to obtain yttrium oxalate and oxalic acid europium; To the requirement of phosphor raw material, in yttrium oxalate and oxalic acid europium, allocate at least one in yttrium oxalate, oxalic acid europium, yttrium oxide or europium sesquioxide into according to color TV or three-color fluorescent lamp, reaction makes the product yttrium europium oxide.
2. according to claim 1ly reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder, it is characterized in that: in step a, the quality proportioning of waste phosphor powder and ammonium chloride, potassium pyrosulfate is: waste phosphor powder: ammonium chloride: potassium pyrosulfate=1: 6～10: 0.05～0.1.
3. according to claim 1ly reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder, it is characterized in that: also comprise step e, be in step a during with the temperature roasting of 500～550 ℃, the ammonium chloride gas that cooling recovery roasting produces, residual gas alkali liquor absorption.
4. describedly reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder according to claim 1,2 or 3, it is characterized in that: in step a, with the time of the temperature roastings of 340～400 ℃ be 20～50 minutes.
5. describedly reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder according to claim 1,2 or 3, it is characterized in that: in step a, with the time of the temperature roastings of 500～550 ℃ be 5～10 minutes.
6. describedly reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder according to claim 1,2 or 3, it is characterized in that: in step b, the solid-to-liquid ratio of water logging is 1g: 5～30ml.
7. describedly reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder according to claim 1,2 or 3, it is characterized in that: in steps d, react and make yttrium europium oxide by the mode of calcining in 800～900 ℃ of temperature ranges, calcination time is 3～10 hours.
8. describedly reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder according to claim 1,2 or 3, it is characterized in that: in steps d, allocate at least one in yttrium oxalate, oxalic acid europium, yttrium oxide or europium sesquioxide in yttrium oxalate and oxalic acid europium, make the quality of yttrium: the quality of europium=13～18.
9. describedly reclaim the method that yttrium and europium are produced yttrium europium oxide from waste phosphor powder according to claim 1,2 or 3, it is characterized in that: also comprise step f, add at least one acid in nitric acid or hydrochloric acid in the undissolved phosphor powder of gained in step b, react 2～5 minutes, filter, the pH after filtration is 2.5～3.5; In the solution after filtering, add vitriol to reclaim barium, then add sodium sulphite to reclaim zinc, between regulator solution pH value to 1.5～2, add remaining rare earth element in excessive recovery of oxalic acid solution afterwards.
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| DE102014206223A1 (en) | 2014-04-01 | 2015-10-01 | Fme Freiberger Metallrecycling Und Entwicklungsdienstleistungen Gmbh | Process for the recovery of rare earths from rare earth-containing compositions |
| DE102014224015A1 (en) | 2014-11-25 | 2016-05-25 | Fme Freiberger Metallrecycling Und Entwicklungsdienstleistungen Gmbh | Process for the recovery of rare earths from rare earth-containing phosphors |
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| CN104927863B (en) * | 2015-06-05 | 2017-06-13 | 武汉理工大学 | The nanocrystalline method of hexagonal phase sodium yttrium tetrafluoride that rare earth metal is co-doped with is prepared using waste phosphor powder |
| CN113413948B (en) * | 2021-06-24 | 2022-06-07 | 福建省华裕天恒科技有限公司 | Classified fluorescent powder waste recovery device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5160663A (en) * | 1991-12-09 | 1992-11-03 | Gte Products Corporation | Method of reclaiming lamp phosphor |
| CN101985694A (en) * | 2010-10-26 | 2011-03-16 | 赣县金鹰稀土实业有限公司 | Preparation method for recovering high-purity yttrium europium from fluorescent powder scrap |
| CN102312098A (en) * | 2011-09-28 | 2012-01-11 | 武汉理工大学 | Method for separation and purification of fluorescent grade yttrium oxide and europium oxide from waste phosphor powder |
| CN102312095A (en) * | 2011-05-24 | 2012-01-11 | 深圳市格林美高新技术股份有限公司 | CRT (cathode ray tube) fluorescent powder processing method |
-
2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5160663A (en) * | 1991-12-09 | 1992-11-03 | Gte Products Corporation | Method of reclaiming lamp phosphor |
| CN101985694A (en) * | 2010-10-26 | 2011-03-16 | 赣县金鹰稀土实业有限公司 | Preparation method for recovering high-purity yttrium europium from fluorescent powder scrap |
| CN102312095A (en) * | 2011-05-24 | 2012-01-11 | 深圳市格林美高新技术股份有限公司 | CRT (cathode ray tube) fluorescent powder processing method |
| CN102312098A (en) * | 2011-09-28 | 2012-01-11 | 武汉理工大学 | Method for separation and purification of fluorescent grade yttrium oxide and europium oxide from waste phosphor powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014206223A1 (en) | 2014-04-01 | 2015-10-01 | Fme Freiberger Metallrecycling Und Entwicklungsdienstleistungen Gmbh | Process for the recovery of rare earths from rare earth-containing compositions |
| DE102014224015A1 (en) | 2014-11-25 | 2016-05-25 | Fme Freiberger Metallrecycling Und Entwicklungsdienstleistungen Gmbh | Process for the recovery of rare earths from rare earth-containing phosphors |
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