CN102745735B - A kind of method reclaiming discarded red fluorescence powder rare earth elements - Google Patents
A kind of method reclaiming discarded red fluorescence powder rare earth elements Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 84
- 239000000843 powder Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 50
- 238000001354 calcination Methods 0.000 claims abstract description 36
- 238000000605 extraction Methods 0.000 claims abstract description 27
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 19
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 16
- 229960000583 acetic acid Drugs 0.000 claims abstract description 15
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000005194 fractionation Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007127 saponification reaction Methods 0.000 claims abstract description 5
- 238000011105 stabilization Methods 0.000 claims abstract description 3
- 238000007614 solvation Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 239000012074 organic phase Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052753 mercury Inorganic materials 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910001940 europium oxide Inorganic materials 0.000 claims description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000005502 peroxidation Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- -1 rare earth chloride Chemical class 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 239000002699 waste material Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000003916 acid precipitation Methods 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 description 2
- VEVHPEZNNXSONM-UHFFFAOYSA-N oxalic acid;yttrium Chemical compound [Y].OC(=O)C(O)=O VEVHPEZNNXSONM-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- WSVPPALNMDLGQB-UHFFFAOYSA-N europium;oxalic acid Chemical compound [Eu].OC(=O)C(O)=O WSVPPALNMDLGQB-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Luminescent Compositions (AREA)
Abstract
A kind of method reclaiming discarded red fluorescence powder rare earth elements.It is characterized in that: the discarded red fluorescence powder collected carries out calcining pretreatment in calcining stove, remove organic substance contained in discarded red fluorescence powder and other easily form the element of volatile gaseses; Pass through the red fluorescence powder of calcining at acid (HCl, HNO
3)-oxygenant (H
2o
2carry out dissolving decomposition in)-stabilization aid (Glacial acetic acid) Compound-acid system, control lower acidity and red fluorescence powder rare earth elements Y, Eu or other rare earth optimum solvation are all entered in solution, other elements are insolubles, filter with crossing.After obtaining rare earth acid solution, adopt and carry out extracting and separating without the fractionation extraction system of ammonia saponification, obtain highly purified single rare earth muriate YCl
3, EuCl
3or other rare earth chloride enriched substance solution, then obtain single rare earth oxide compound Y after precipitation, calcination operation
2o
3, Eu
2o
3or other rareearth enriching material oxide product.
Description
Technical field
The present invention relates to a kind of method of three wastes comprehensive reutilization, particularly a kind of method reclaiming discarded red fluorescence powder rare earth elements.
Background technology
China's rare-earth fluorescent powder yield in 2010 reaches 9398 tons in kind according to statistics, increases by 29.9% than last year.Wherein the phosphor of rare earth 8000 tons (increasing by 33.3% than last year), 500 tons, colour TV fluorescent material, long persistence luminescent powder 450 tons, about 448 tons, other fluorescent material.Expect 2012, China's rare-earth fluorescent powder yield will reach 14000 tons, by consumption 6500 tons of all kinds of rare earths.In the production of fluorescent material, the production of three-color fluorescent lamp and using substitute in, the production of colour TV and using all produces the fluorescent powder scrap of enormous amount in substituting, expect fluorescent RE powder waste material in 2012 and will reach 7000 tons, wherein red fluorescence powder accounts for 30%-40%, and amount of waste will be 2000 tons-3000 tons.Containing Y in lamp red fluorescence powder
2o
3be about 93%, containing Eu
2o
3be about 7%; And colour TV red fluorescence powder is Y mostly
2o
2s:Eu structure, wherein containing Y
2o
3be about 80%, containing Eu
2o
3be about 5.5%; Other red fluorescence powders have the YVO of high voltage mercury lamp
4: Eu etc.
Because rare earth element is widely used in new and high technology; particularly there is very important effect for a national military technical progress; rare earth has been classified as the specific mineral of protective mining by China; country has carried out strict restriction and management to exploiting rare earth from raw ore, and thus from the three wastes of rare earth, recovering rare earth element has very important significance and huge economic benefit.In addition from the angle of environment protection and renewable resource utilization, the recycling of waste phosphor powder also should be strengthened.
At present, the technical study work carrying out recovering rare earth element from discarded red fluorescence powder is both at home and abroad considerably less, and the patent relating to the recycling of lamp phosphor is as follows:
CN101150032 discloses a kind of method recycling all kinds of discarded fluorescent lamp, and this method comprises gaseous mercury in recovery; The recovery of metal recovery and attachment mercury; In fluorescent material, the recovery of mercury and the fire concentrate of fluorescent material rare earth elements and other valuable elements reclaim.This method is by pyrogenic process chlorination breakdown fluorescent material, and formation muriate, exists problem of environmental pollution and cost is high, industrially can not realize, and the rare earth do not related in colour TV red fluorescence powder and other red fluorescence powders reclaims.
CN101307391A discloses a kind of method reclaiming rare earth element in waste florescent lamps, this method adds highly basic (NaOH) in fluorescent material, be heated to 320 DEG C-600 DEG C melting 2-10 hour, water logging obtains re chloride with dissolving with hydrochloric acid insolubles after filtering, then obtains single rare earth oxide through extracting and separating, precipitation, calcination.The rare earth that this method does not relate in colour TV red fluorescence powder and other red fluorescence powders yet reclaims.
Summary of the invention
The object of this invention is to provide a kind of method that low stain reclaims discarded red fluorescence powder (comprising lamp red fluorescence powder, colour TV red fluorescence powder and other red fluorescence powders) rare earth elements Y, Eu.
Method of the present invention comprises following step:
1. calcining pretreatment: red fluorescence powder will be discarded at 550 DEG C-850 DEG C calcining 0.5-3 hour, and make the gas chromatography in fluorescent material and the fully oxidized rear volatilization of nonmetallic impurity, thus obtain purer metal oxide.
2. acid-soluble: by excellent molten in Compound-acid system for the red fluorescence powder waste material after calcining, acid-soluble temperature is at 90 DEG C-110 DEG C, and acidity is at 0.5N-1.0N, and dissolution time is at 3-6 hour, and Compound-acid consists of: acid (HCl, HNO
3) (89%-92%)-oxygenant (H
2o
2) (3%-5%)-stabilization aid (Glacial acetic acid) (3%-8%), rare earth metal amount: Compound-acid volume=1: 3, dissolved by the rare earth of more than 98% by acid-soluble, but the impurity such as Fe, Zn, V are only had an appointment, 1%-5% is dissolved.Also can effectively control in this step H simultaneously
2the generation of S waste gas and the speed of generation, guarantee the H produced
2s waste gas can be absorbed completely by the NaOH solution in absorption tower.
3. filter: by filtering, earth solution is separated with solid impurity, main containing rare earth element and a small amount of Fe, Zn, V impurity elements such as Y, Eu in earth solution.
4. naphthenic acid extracting rare-earth yttrium (Y): by filter after earth solution concentration adjusts to 0.8-1.0mol/L, pH value adjusts to 2-3, entering organic phase is 22% naphthenic acid+18% alcohol mixture+60% sulfonated kerosene, use the fractionation extraction system of NaOH alkali lye saponification, after 75 grades of extractions and 15 grades of washings, obtain highly purified yttrium (Y) solution in aqueous phase outlet, this solution just obtains high-purity yttrium oxide finished product through precipitation, calcination; Other rare earths such as Eu then enters organic phase, with acid, rare earth back extraction from organic phase is out used for lower step operation.
5. zinc reduction extraction Eu: by the strip liquor 4. walked concentration adjusts to 0.6-0.8mol/L, pH value adjusts to 2-3, add zinc powder and make Eu
3+be reduced into Eu
2+, reduction ratio can reach 99%, and the earth solution after reduction enters P507-sulfonated kerosene-HCl extraction system under argon shield condition, adopts three outlet fractionation extraction modes by after 30 grades of extractions, obtains high-purity Eu in aqueous phase
2+, the Eu in aqueous phase
2+eu is become after peroxidation
3+, more just obtain high-purity europium oxide finished product through precipitation, calcination.And other a small amount of rare earth RE
3+then enter organic phase, with acid by rare earth from organic phase after back extraction out, more just obtain other rareearth enriching material products through precipitation, calcination.
6. reclaim Zn: in the fractionation extraction system 4. walked, be provided with the 3rd outlet, the 3rd outlet is enriched with certain flow and the higher zinc chloride (ZnCl of purity
2) solution, this solution can be made into zinc product through sedimentation and filtration washing or Direct Electrolysis.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention
Embodiment
Embodiment 1
Get the discarded red fluorescence powder of 1000g three-color fluorescent lamp, total amount of rare earth (TREO): 81.56%, Eu
2o
3/ TREO:7.25%, Y
2o
3/ TREO:92.73%, other rare earths < 0.02%, 550 DEG C of calcinings 3 hours, then in the Compound-acid system of 2.45L acid-soluble 6 hours, Compound-acid consisted of: hydrochloric acid (HCl) (89%)-oxygenant (H
2o
2) (3%)-Glacial acetic acid (CH
3cOOH) (8%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 90 DEG C, acid-soluble rear mistake filters insolubles and obtains the re chloride that 2.4L concentration is 338.1g/l, and calculating rare earth dissolving yield is 99.5%.Re chloride be diluted to concentration 120 ± 5g/l and adjust PH2.5 ± 0.3, entering by the organic phase of NaOH saponification is carry out extracting and separating in the fractionation extraction system of 22% naphthenic acid+18% alcohol mixture+60% sulfonated kerosene, after 75 grades of extractions and 15 grades of washings, obtain highly purified Yttrium trichloride (YCl in aqueous phase outlet
3) solution, this solution filters with premium grade oxalic acid precipitation and obtains solid oxalic acid yttrium, and calcination yttrium oxalate just obtains high-purity yttrium oxide finished product.Eu
3+then enter organic phase, use high purity hydrochloric acid (HCl) the back extraction organic phase of 4N ± 0.5N concentration, obtain with Europium trichloride (EuCl
3) be the solution of main component, this solution dilution is adjusted PH2.5 ± 0.3 to concentration 120 ± 5g/l, in this solution, adds zinc powder make Eu
3+be reduced to Eu
2+, the Europium trichloride solution after reduction enters P507-sulfonated kerosene-HCl extraction system under argon shield, adopts three outlet fractionation extraction modes by after 30 grades of extractions, obtains high-purity Eu in aqueous phase
2+solution, the Eu in aqueous phase
2+eu is become after hydrogen peroxide oxidation
3+, more just obtain high-purity europium oxide finished product through oxalic acid precipitation, filtration, calcination oxalic acid europium.Other a small amount of rare earth then enters organic phase, uses hydrochloric acid (HCl) the back extraction organic phase of 4N ± 0.5N concentration, obtains rare earth chloride enriched substance solution, more just obtains rare earth oxide enriched substance product through oxalic acid precipitation, filtration, calcination.In the 3rd outlet, obtain liquor zinci chloridi, through volatile salt precipitation, filter the calcination zinc oxide product that just acquisition purity is higher.
Embodiment 2
Get the discarded red fluorescence powder of 1000g three-color fluorescent lamp, total amount of rare earth (TREO): 81.56%, EU
2o
3/ TREO:7.25%, Y
2o
3/ TREO:92.73%, other rare earths < 0.02%, 850 DEG C of calcinings 0.5 hour, then in the Compound-acid system of 2.45L acid-soluble 3 hours, Compound-acid consisted of: hydrochloric acid (HCl) (92%)-oxygenant (H
2o
2) (5%)-Glacial acetic acid (CH
3cOOH) (3%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 110 DEG C, acid-soluble rear mistake filters insolubles and obtains the re chloride that 2.41L concentration is 337.0g/l, and calculating rare earth dissolving yield is 99.6%.Subsequent process steps is with embodiment 1.
Embodiment 3
Get the discarded red fluorescence powder of 1000g three-color fluorescent lamp, total amount of rare earth (TREO): 81.56%, Eu
2o
3/ TREO:7.25%, Y
2o
3/ TREO:92.73%, other rare earths < 0.02%, 550 DEG C of calcinings 3 hours, then in the Compound-acid system of 2.45L acid-soluble 6 hours, Compound-acid consisted of: nitric acid (HNO
3) (89%)-oxygenant (H
2o
2) (3%)-Glacial acetic acid (CH
3cOOH) (8%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 90 DEG C, acid-soluble rear mistake filters insolubles and obtains the rare earth nitrate solution that 2.41L concentration is 337.0g/l, and calculating rare earth dissolving yield is 99.6%.Rare earth nitrate solution be diluted to concentration 120 ± 5g/l and adjust PH2.5 ± 0.3, entering by the organic phase of NaOH saponification is carry out extracting and separating in the fractionation extraction system of 22% naphthenic acid+18% alcohol mixture+60% sulfonated kerosene, after 75 grades of extractions and 15 grades of washings, obtain highly purified Yttrium trinitrate (Y (NO in aqueous phase outlet
3)
3) solution, this solution filters with premium grade oxalic acid precipitation and obtains solid oxalic acid yttrium, and calcination yttrium oxalate just obtains high-purity yttrium oxide finished product.Eu
3+then enter organic phase, use high purity hydrochloric acid (HCl) the back extraction organic phase of 4N ± 0.5N concentration, obtain with Europium trichloride (EuCl
3) be the solution of main component.Subsequent process steps is with embodiment 1.
Embodiment 4
Get the discarded red fluorescence powder of 1000g three-color fluorescent lamp, total amount of rare earth (TREO): 81.56%, Eu
2o
3/ TREO:7.25%, Y
2o
3/ TREO:92.73%, other rare earths < 0.02%, 850 DEG C of calcinings 0.5 hour, then in the Compound-acid system of 2.45L acid-soluble 3 hours, Compound-acid consisted of: nitric acid (HNO
3) (92%)-oxygenant (H
2o
2) (5%)-Glacial acetic acid (CH
3cOOH) (3%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 110 DEG C, acid-soluble rear mistake filters insolubles and obtains the rare earth nitrate solution that 2.41L concentration is 336.5g/l, and calculating rare earth dissolving yield is 99.4%.Subsequent process steps is with embodiment 3.
Embodiment 5
Get the discarded red fluorescence powder of 1000g colour TV, total amount of rare earth (TREO): 71.74%, Eu
2o
3/ TREO:6.31%, Y
2o
3/ TREO:92.96%, other rare earths: 0.73%, 550 DEG C of calcinings 3 hours, then in the Compound-acid system of 2.2L acid-soluble 6 hours, Compound-acid consisted of: hydrochloric acid (HCl) (89%)-oxygenant (H
2o
2) (3%)-Glacial acetic acid (CH
3cOOH) (8%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 90 DEG C, acid-soluble rear mistake filters insolubles and obtains the re chloride that 2.18L concentration is 326.5g/l, and calculating rare earth dissolving yield is 99.2%.Subsequent process steps is with embodiment 1.
Embodiment 6
Get the discarded red fluorescence powder of 1000g colour TV, total amount of rare earth (TREO): 71.74%, Eu
2o
3/ TREO:6.04%, Y
2o
3/ TREO:92.96%, other rare earths: 0.73%, 850 DEG C of calcinings 0.5 hour, then in the Compound-acid system of 2.2L acid-soluble 3 hours, Compound-acid consisted of: hydrochloric acid (HCl) (92%)-oxygenant (H
2o
2) (5%)-Glacial acetic acid (CH
3cOOH) (3%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 110 DEG C, acid-soluble rear mistake filters insolubles and obtains the re chloride that 2.19L concentration is 326.2g/l, and calculating rare earth dissolving yield is 99.5%.Subsequent process steps is with embodiment 1.
Embodiment 7
Get the discarded red fluorescence powder of 1000g colour TV, total amount of rare earth (TREO): 71.74%, Eu
2o
3/ TREO:6.31%, Y
2o
3/ TREO:92.96%, other rare earths: 0.73%, 550 DEG C of calcinings 3 hours, then in the Compound-acid system of 2.2L acid-soluble 6 hours, Compound-acid consisted of: nitric acid (HNO
3) (89%)-oxygenant (H
2o
2) (3%)-Glacial acetic acid (CH
3cOOH) (8%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 90 DEG C, acid-soluble rear mistake filters insolubles and obtains the rare earth nitrate solution that 2.17L concentration is 326.8g/l, and calculating rare earth dissolving yield is 98.9%.Subsequent process steps is with embodiment 3.
Embodiment 8
Get the discarded red fluorescence powder of 1000g colour TV, total amount of rare earth (TREO): 71.74%, Eu
2o
3/ TREO:6.31%, Y
2o
3/ TREO:92.96%, other rare earths: 0.73%, 850 DEG C of calcinings 0.5 hour, then in the Compound-acid system of 2.2L acid-soluble 3 hours, Compound-acid consisted of: nitric acid (HNO
3) (89%)-oxygenant (H
2o
2) (3%)-Glacial acetic acid (CH
3cOOH) (8%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 110 DEG C, acid-soluble rear mistake filters insolubles and obtains the rare earth nitrate solution that 2.18L concentration is 327.0g/l, and calculating rare earth dissolving yield is 99.4%.Subsequent process steps is with embodiment 3.
Embodiment 9
Get the discarded red fluorescence powder of 2000g high voltage mercury lamp, total amount of rare earth (TREO): 50.10%, Eu
2o
3/ TREO:8.55%, Y
2o
3/ TREO:91.40%, other rare earths < 0.05%, 550 DEG C of calcinings 3 hours, then in the Compound-acid system of 3.1L acid-soluble 6 hours, Compound-acid consisted of: hydrochloric acid (HCl) (89%)-oxygenant (H
2o
2) (3%)-Glacial acetic acid (CH
3cOOH) (8%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 90 DEG C, acid-soluble rear mistake filters insolubles and obtains the re chloride that 2.95L concentration is 335.3g/l, and calculating rare earth dissolving yield is 98.7%.Subsequent process steps is with embodiment 1.
Embodiment 10
Get the discarded red fluorescence powder of 2000g high voltage mercury lamp, total amount of rare earth (TREO): 50.10%, Eu
2o
3/ TREO:8.55%, Y
2o
3/ TREO:91.40%, other rare earths < 0.05%, 850 DEG C of calcinings 0.5 hour, then in the Compound-acid system of 3.1L acid-soluble 3 hours, Compound-acid consisted of: hydrochloric acid (HCl) (92%)-oxygenant (H
2o
2) (5%)-Glacial acetic acid (CH
3cOOH) (3%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 110 DEG C, acid-soluble rear mistake filters insolubles and obtains the re chloride that 2.98L concentration is 335.2g/l, and calculating rare earth dissolving yield is 98.7%.Subsequent process steps is with embodiment 1.
Embodiment 11
Get the discarded red fluorescence powder of 2000g high voltage mercury lamp, total amount of rare earth (TREO): 50.10%, Eu
2o
3/ TREO:8.55%, Y
2o
3/ TREO:91.40%, other rare earths < 0.05%, 550 DEG C of calcinings 3 hours, then in the Compound-acid system of 3.1L acid-soluble 6 hours, Compound-acid consisted of: nitric acid (HNO
3) (89%)-oxygenant (H
2o
2) (3%)-Glacial acetic acid (CH
3cOOH) (8%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 90 DEG C, acid-soluble rear mistake filters insolubles and obtains the rare earth nitrate solution that 2.96L concentration is 332.1g/l, and calculating rare earth dissolving yield is 98.1%.Subsequent process steps is with embodiment 3.
Embodiment 12
Get the discarded red fluorescence powder of 2000g high voltage mercury lamp, total amount of rare earth (TREO): 50.10%, Eu
2o
3/ TREO:8.55%, Y
2o
3/ TREO:91.40%, other rare earths < 0.05%, 850 DEG C of calcinings 0.5 hour, then in the Compound-acid system of 3.1L acid-soluble 3 hours, Compound-acid consisted of: nitric acid (HNO
3) (89%)-oxygenant (H
2o
2) (3%)-Glacial acetic acid (CH
3cOOH) (8%), rare earth metal amount: Compound-acid volume=1: 3, acid-soluble condition is: acidity 0.5N, acid-soluble temperature 110 DEG C, acid-soluble rear mistake filters insolubles and obtains the re chloride that 2.99L concentration is 330.2g/l, and calculating rare earth dissolving yield is 98.5%.Subsequent process steps is with embodiment 3.
Claims (1)
1. reclaim a method for discarded red fluorescence powder rare earth elements, concrete steps are:
1. by the calcining of discarded red fluorescence powder raw material;
2. the raw material after calcining dissolves in Compound-acid solution, makes rare earth element reach optimum solvation;
3. filter and earth solution is separated with solid impurity;
4. using naphthenic acid to make extraction agent adopts fractionation extraction system to be purified from earth solution by yttrium, obtains high-purity yttrium solution, then obtains high-purity yttrium oxide product through precipitation, calcination;
5. with hydrochloric acid by the 4. the rare earth back extraction walked in organic phase get off, become the main re chloride containing europium element, in this solution, add metallic zinc by Eu
3+be reduced into Eu
2+, the re chloride after reduction by P507-sulfonated kerosene-HCl extraction system, adopts three outlet fractionation extraction modes to be purified by europium, and in aqueous phase, obtains high-purity Eu under argon shield
2+, Eu
2+eu is become after peroxidation
3+, then obtain high-purity europium oxide product through precipitation, calcination; And other a small amount of rare earth RE
3+then enter organic phase, with acid by rare earth from organic phase after back extraction out, then obtain other rareearth enriching material products through precipitation, calcination; Zinc chloride then in the 3rd outlet enrichment, obtains high-purity zinc oxide product through precipitation, calcination;
Described step 1. in red fluorescence powder raw material be three-color fluorescent lamp red fluorescence powder, colour TV cathode-ray picture tube red fluorescence powder, red phosphor powder for high pressure mercury lamp or other contain the red fluorescence powder of rare earth element; Calcining temperature: 550 DEG C-850 DEG C, calcination time: 0.5-3 hour;
Described step 2. in Compound-acid solution be configured to: acid is for HCl or HNO
3, content 89%-92%, oxygenant is H
2o
2, content 3%-5%, stabilization aid is Glacial acetic acid, content 3%-8%; Acid-soluble condition is: temperature is at 90 DEG C-110 DEG C, and acidity is at 0.5N-1.0N, and dissolution time is at 3-6 hour; Consumption is: rare earth metal amount: Compound-acid liquor capacity=1: 3;
Described step 4. in the organic phase of fractionation extraction system be configured to: 22% naphthenic acid+18% alcohol mixture+60% sulfonated kerosene, and use the saponification of NaOH alkali lye.
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| CN103521500A (en) * | 2013-10-22 | 2014-01-22 | 吉林化工学院 | Method for recovering europium hydroxide from discarded displays |
| CN103627906B (en) * | 2013-12-09 | 2016-03-23 | 湖南稀土金属材料研究院 | The synthetical recovery treatment process of useless rare-earth fluorescent light |
| CN105755288B (en) * | 2016-04-01 | 2017-08-25 | 北京工业大学 | A kind of method that zinc in discarded cathodic ray-tube fluorescent powder is reclaimed based on self-propagating reaction and rare earth is enriched with |
| CN106191446B (en) * | 2016-07-05 | 2018-04-17 | 北京工业大学 | A kind of recovering rare earth yttrium from waste phosphor powder and the method for preparing resin surface composite deposite |
| CN109735719B (en) * | 2019-03-19 | 2020-07-14 | 王柯娜 | Method for processing waste television fluorescent powder |
| CN111392756A (en) * | 2020-05-06 | 2020-07-10 | 龙南县中利再生资源开发有限公司 | Process for extracting high-purity rare earth oxide from fluorescent powder waste |
| CN115092953A (en) * | 2022-05-05 | 2022-09-23 | 龙南京利有色金属有限责任公司 | Method for extracting rare earth oxide from rare earth fluorescent powder waste |
| CN115072759B (en) * | 2022-05-05 | 2024-11-29 | 龙南京利有色金属有限责任公司 | A method for recovering high-purity europium oxide from rare earth phosphor waste |
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