CN104388087A - Method for preparing rare-earth fluorescent up-conversion material by use of waste fluorescent powder - Google Patents
Method for preparing rare-earth fluorescent up-conversion material by use of waste fluorescent powder Download PDFInfo
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- CN104388087A CN104388087A CN201410670609.XA CN201410670609A CN104388087A CN 104388087 A CN104388087 A CN 104388087A CN 201410670609 A CN201410670609 A CN 201410670609A CN 104388087 A CN104388087 A CN 104388087A
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Abstract
The invention relates to a method for preparing a rare-earth fluorescent up-conversion material by use of waste fluorescent powder. The method comprises the following steps: weighing process waste fluorescent powder, and leaching the fluorescent powder in a sulfuric acid solution to obtain a solution; performing solid-liquid separation, regulating the pH by use of ammonia water, and then performing primary sedimentation, secondary sedimentation, third sedimentation, fourth sedimentation, aging and filtering to obtain filter residue; firing at a high temperature, cooling until the temperature drops to a room temperature, and then adding MOH solution and performing suction filtration to obtain white powder; adding a hydrochloric acid solution, and drying by distillation to obtain the mixture of anhydrous yttrium chloride and anhydrous europium chloride, MOH solid and MHF2 fine powder and RmF3 or RmCl3 solid, and homogenizing; adding a high boiling point solvent, heating and stirring; centrifuging, performing centrifugal washing on the obtained solid powder by use of normal hexane or acetone, drying and then washing by use of boiling water a plurality of times and drying, thereby obtaining the rare-earth fluorescent up-conversion material. The method for preparing the rare-earth fluorescent up-conversion material by use of the waste fluorescent powder has the advantage and the characteristic that green high-value recycling comprehensive utilization of rare earth elements in rare-earth trichromatic phosphor waste can be realized.
Description
Technical field
The present invention relates to a kind of solid waste resource recovery and utilize new technology, be particularly suitable for the green high level recycling of rare-earth trichromatic fluorescent powder waste material, particularly relate to a kind of method of rare earth secondary resource synthesizing rare-earth fluorescence up-conversion.
Background technology
When rare-earth fluorescent upconverting fluorescent material refers to that material is subject to optical excitation, can based on two-photon or multi-photon mechanism, absorb the long-wave radiation of low photon energy, launch the short-wave radiation of high photon energy, its essence is a kind of anti-Stokes luminescence.In recent years, up-conversion luminescent material is at Solid State Laser, 3-D display, infrared imaging, solar cell, particularly have broad application prospects in biomacromolecule analysis, biomedical clinical field as a kind of novel fluorescence marker, receive and pay close attention to widely.Compared with conventional fluorescent marker, up-conversion luminescence nanomaterial has that toxicity is low, luminous intensity is high, and the advantages such as anti-light bleaching and photodegradation, can realize overdelicate biological detection.Simultaneously because the exciting light of up-conversion luminescence nanomaterial is infrared light, interference and the scattered light phenomenon of biological sample autofluorescence can be avoided, thus reduction detection background, improve signal to noise ratio, and infrared light is also less to the infringement of biological tissue in testing process.
With market to the progressively accreditation of rare-earth fluorescent up-conversion, relevant industries are increasing to its demand.Rare-earth fluorescent up-conversion the most frequently used is at present is substrate material with the fluorochemical of yttrium, in view of the technical limitation of preparation method so need the purity of raw material to reach the yttrium oxide of more than 99% or the crystalline hydrate of Yttrium trichloride or Yttrium trinitrate crystalline hydrate to ensure fluorescent effect in preparation process, and above-mentioned purity reaches the raw material basic source of more than 99% in rare-earth mineral, exploit the rare-earth mineral at substantial energy and resource and bring series of environmental problems, and the rare earth of China strategy reserves reduce day by day, government starts the exploitation progressively limiting rare earth, therefore above-mentioned raw materials price is day by day expensive, the rare-earth fluorescent up-conversion cost prepared finally is caused to remain high, this industrialization for rare-earth fluorescent up-conversion and marketing are critical defects.
Rare earth is non-renewable grand strategy resource, because of many-sided characteristics such as its excellent optical, electrical, magnetic, has been widely used in multiple fields such as electronic information, metallurgical machinery, petrochemical complex, energy environment, defence and military.China is the abundantest country of rare earth resources, but along with the domestic rare earth consumers demand of China increase, the impact of the factor such as a large amount of cheap outlets and long-term gopher, China's rare earth reserves fall sharply.And the learies of China's rare-earth products and material is increasing day by day in recent years, as only China's rare-earth trichromatic fluorescent powder waste material generation in 2014 just reaches 8000 tons, but do not obtain rationally recycling.Therefore, the environmentally friendly resource utilization for rare-earth trichromatic fluorescent powder waste material is recycled, can protection of the environment and increase substantially rare earth resources utilization benefit.The electronic product display screens such as waste and old CRT TV, waste and old PDP TV, three-color fluorescent lamp, mobile phone all contain a large amount of rare earth element, and average every platform waste and old CRT TV about about contains fluorescent material 30 grams, every three-color fluorescent lamp about containing 3 grams, fluorescent material containing 8 grams, fluorescent material, every waste and old PDP TV of platform.Main containing rare earth element yttrium and europium in Waste fluorescent powder, in addition also containing rare earth elements such as cerium, terbium, dysprosiums.From protection rare earth resources, recycle rare earth resources, environmental angle, reclaim fluorescent material middle-weight rare earths resource imperative.
Field is reclaimed at present at waste phosphor powder rare earth resources, fluorescence-class yttrium oxide and europium sesquioxide mixture are extracted in success from fluorescent material, because wherein impurity is too many as the oxide compound containing elements such as a certain amount of aluminium, calcium, barium, manganese, magnesium, silicon, rare-earth fluorescent up-conversion is not yet applied in current fluorescent material preparation field, but because it derives from waste phosphor powder, so its output and cost advantage are far away higher than the yttrium oxide that purity is in the market higher.
Summary of the invention
The object of this invention is to provide a kind of method utilizing waste phosphor powder to prepare rare-earth fluorescent up-conversion, thus significantly reduce the raw materials cost of rare-earth fluorescent up-conversion, and reduce the pollution of waste phosphor powder to environment.
The present invention solves the problems of the technologies described above adopted technical scheme: utilize waste phosphor powder to prepare the method for rare-earth fluorescent up-conversion, comprise the following steps:
1) take technique waste phosphor powder, leach fluorescent material by 1.5mol/L-2.5mol/L sulphuric acid soln, using hydrogen peroxide as solubility promoter, obtain solution;
2) by step 1) in solution put into whizzer and carry out solid-liquid separation, gained leach liquor ammoniacal liquor regulates pH 3.5-4, carries out primary sedimentation, filters, obtains filtrate;
3) by step 2) in filtrate add ammoniacal liquor, carry out secondary sedimentation, adjust pH 7-8, filter, obtain filter residue A and retain filtrate;
4) by step 3) in filtrate add ammoniacal liquor, carry out three precipitations, adjust pH 8-9, filter, obtain filter residue B;
5) by step 3) in filter residue A and step 4) in filter residue B add sulphuric acid soln dissolve obtain pregnant solution, add boiling water, stir, slowly add oxalic acid solution, carry out four times precipitation, ageing, filter, obtain filter residue C;
6) by step 5) in filter residue C high temperature sintering, after being cooled to room temperature, adding MOH solution and keep 10h under temperature 80 DEG C of condition, then carry out suction filtration and obtain mainly containing the mixture white powder of yttrium oxide and europium sesquioxide; Then add hydrochloric acid soln it is dissolved completely, treat solution transparent clarification post-heating evaporate to dryness solution, obtain the mixture of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium;
7) take step 6) in the mixture of the anhydrous chlorides of rase yttrium that obtains and anhydrous chlorides of rase europium, MOH solid and MHF
2fine powder and RmF
3or RmCl
3solid, by its Homogeneous phase mixing, obtains solid mixture;
8) to step 7) in add high boiling solvent in the solid mixture that obtains, then under atmosphere of inert gases protection, be rapidly heated, keep temperature of reaction under the condition of 200 DEG C-350 DEG C, magnetic agitation reaction 30min-3h;
9) by step 8) liquid that obtains after completion of the reaction carries out high speed centrifugation, the pressed powder obtained directly by normal hexane or the centrifugal supersound washing repeated drying of acetone, then with boiling water washing repeatedly, dry, obtain rare-earth fluorescent up-conversion.
The present invention first with normal hexane or acetone centrifuge washing repeatedly, dry, object is the oleic acid ligand of removing reaction product surface attachment; Then wash repeatedly with boiling water, dry, object is the by product such as side product chlorinated potassium, sodium-chlor, Europium trichloride, europium inside removing reactant.
By such scheme, step 6) and step 7) middle MOH, MHF
2in M be any one and two kinds in Na, K, RmF
3or RmCl
3in Rm be any one and multiple mixing in Er, Tm, Ho.
By such scheme, step 7) in mixture, MOH solid, the MHF of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium
2fine powder, RmF
3or RmCl
3the mass ratio 1:(0.1-0.5 of solid): (0.2-2): (0.01-0.3).
By such scheme, step 8) in high boiling solvent be oleic acid, oleyl amine, octadecylene wherein a kind of or wherein two or more mixed solvent; If mixed solvent, wherein each component solvent dose ratio can be determined as required; Temperature of reaction in step (8) corresponding after choosing coordinative solvent requires the minimum boiling point lower than selected solvent composition, as octadecylene 314 DEG C of oleyl amines 340 DEG C of oleic acid 360 DEG C;
Advantage and disadvantage of the present invention:
1, a part of raw material of the present invention is waste material, with low cost, be simple and easy to obtain, this technical process is simple, preparation condition is gentle, without secondary environmental pollution, can realize the green high level comprehensive utilization of resources of rare-earth trichromatic fluorescent powder waste material rare earth elements;
2, the present invention adopts oleic acid to make the wet chemistry method of solvent, with MHF
2(wherein M is any one and two kinds in Na, K) does fluorine source, under the disturbed condition having a certain amount of europium ion, first at KYF
4only be doped with Er ion in substrate material, successfully prepare the KYF that luminous efficiency is excellent
4: Er
3+nanocrystalline; Also success is mixed with sensitized ions Yb in NaYF4 substrate material
3+and Er
3+ion, and obtain six excellent side phase NaYF4:Yb of luminous efficiency
3+, Er
3+micron is brilliant.
3, the rare-earth fluorescent up-conversion luminous efficiency prepared of the present invention is better, raw material sources are extensive, with low cost, technical process is simple, by appropriate change reaction conditions can effectively size controlling to nano level, rare-earth fluorescent up-conversion prepared by present method is effectively applied to biomarker field, thus has very large promotion meaning to the further marketization of rare-earth fluorescent up-conversion.
Accompanying drawing explanation
Fig. 1 is nano level KYF prepared by embodiment 1
4: Er
3+the XRD diffraction peak figure of rare-earth fluorescent up-conversion;
Fig. 2 is nano level KYF prepared by embodiment 1
4: Er
3+the field emission scanning electron microscope figure of rare-earth fluorescent up-conversion;
Fig. 3 is nano level KYF prepared by embodiment 1
4: Er
3+the fluorescence spectrum of rare-earth fluorescent up-conversion luminescent material 400nm mono-800nm wave band under 980nm laser pumping;
Fig. 4 is six side phase NaYF prepared by embodiment 2
4: Yb
3+, Er
3+rare-earth fluorescent up-conversion XRD diffraction peak figure;
Fig. 5 is six side phase NaYF prepared by embodiment 2
4: Yb
3+, Er
3+the scanning electron microscope (SEM) photograph of rare-earth fluorescent up-conversion;
Fig. 6 is six side phase NaYF prepared by embodiment 2
4: Yb
3+, Er
3+the fluorescence spectrum of rare-earth fluorescent up-conversion 400nm mono-800nm wave band under 980nm laser pumping.
Embodiment
In order to understand the present invention better, set forth content of the present invention further below in conjunction with accompanying drawing, embodiment, but the present invention is not only confined to example below.
Embodiment 1
The concrete steps preparing rare-earth fluorescent up-conversion with waste phosphor powder are as follows:
(1) take a certain amount of technique waste phosphor powder, leach fluorescent material by 2mol/L sulphuric acid soln, and add appropriate hydrogen peroxide as solubility promoter, temperature 70 C, leach 4h, obtain solution;
(2) solution in step (1) is put into whizzer and carry out solid-liquid separation, gained leach liquor at 3.5-4, carries out primary sedimentation by ammoniacal liquor adjust ph, filters, obtains filtrate;
(3) filtrate in step (2) is added ammoniacal liquor, carry out secondary sedimentation, pH value is transferred to 7-8, filters, obtains filter residue A and retain filtrate;
(4) filtrate in step (3) is added ammoniacal liquor, carry out three precipitations, pH value is transferred to 8-9, filters, obtains filter residue B;
(5) the filter residue B in the filter residue A in step (3) and step (4) is added sulphuric acid soln dissolving and obtain pregnant solution, add boiling water, stir, under the condition of temperature 80 DEG C, slowly add oxalic acid solution, carry out four precipitations, ageing 4h, filters, obtains filter residue C;
(6) by the calcination 2h at high temperature 1000 DEG C of the filter residue C in step (5), after being cooled to room temperature, add certain density KOH solution and keep 10h under temperature 80 DEG C of conditions, then carry out suction filtration and obtain white powder, obtain the mixture mainly containing yttrium oxide and europium sesquioxide; Then add hydrochloric acid soln it is dissolved completely, treat solution transparent clarification post-heating evaporate to dryness solution, obtain the white mixture (wherein the mass ratio of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium is about 13:1) of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium.
(7) take the white mixture 0.2g of anhydrous chlorides of rase yttrium and the anhydrous chlorides of rase europium obtained in step (6), take KOH solid and KHF respectively
2fine powder 0.05g, 0.2g, take ErF_3 films 0.008g again, weigh up four parts of solids mixings are evenly joined in 100ml there-necked flask, then in 100ml there-necked flask, add 25ml oleic acid and a stirring magnetic seed, reaction is carried out and stirs magnetic seed being from start to finish in whipped state (stir speed (S.S.) 3000 ~ 5000rpm/min is optionally adjustable) under closed system, after vacuumizing under normal temperature, close vacuum valve, then in reactor, argon gas or nitrogen is passed into, be rapidly heated to 330 DEG C with the temperature rise rate of 10 ~ 20 DEG C/min, temperature maintains about 330 DEG C 70min, stop heating, question response thing cool to room temperature.
(8) reaction soln that step (7) obtains is poured in centrifuge tube carry out centrifugation, obtain the acetone that white solid adds 10ml, ultrasonic vibration 5 ~ 10min, rejoin acetone centrifuge washing 3 times, then wash repeatedly with boiling water, dry, object is the by product such as side product chlorinated potassium, Potassium monofluoride, Europium trichloride, europium inside removing reactant, obtains micron order rare-earth fluorescent up-conversion KYF of the present invention
4: Er
3+; 60 DEG C of oven dry, vacuum is preserved.
Final product XRD, TEM and fluorescence spectrophotometer are carried out to the sign of thing phase, pattern and fluorescence property etc.See that Fig. 1 is XRD diffracting spectrum, interpretation of result shows that the nano particle synthesized is KYF
4: Er
3+, inclusion-free peak; KYF
4: Er
3+transmission electron microscope photo and High-Resolution Map see Fig. 2, it is irregular particulate state that Fig. 2 shows crystal grain, and crystal edge is fuzzyyer, and crystal grain median size is about 150nm; With 980nm laser excitation KYF
4: Er
3+upper conversion rare earth nano fluorescent material measures fluorescence spectrum, has the spectrum peak of green glow and ruddiness to occur, see Fig. 3 at 500 1 550nm and 650 1 675nm regions.
Embodiment 2
The concrete steps preparing rare-earth fluorescent up-conversion with waste phosphor powder are as follows:
(1) take a certain amount of technique waste phosphor powder, leach fluorescent material by 2mol/L sulphuric acid soln, and add appropriate hydrogen peroxide as solubility promoter, temperature 70 C, leach 4h, obtain solution;
(2) solution in step (1) is put into whizzer and carry out solid-liquid separation, gained leach liquor at 3.5-4, carries out primary sedimentation by ammoniacal liquor adjust ph, filters, obtains filtrate;
(3) filtrate in step (2) is added ammoniacal liquor, carry out secondary sedimentation, pH value is transferred to 7-8, filters, obtains filter residue A and retain filtrate;
(4) filtrate in step (3) is added ammoniacal liquor, carry out three precipitations, pH value is transferred to 8-9, filters, obtains filter residue B;
(5) by step 3) in filter residue A and filter residue B in step (4) add sulphuric acid soln and dissolve and obtain pregnant solution, add boiling water, stir, under the condition of temperature 80 DEG C, slowly add oxalic acid solution, carry out four precipitations, ageing 4h, filters, obtains filter residue C;
(6) by the calcination 2h at high temperature 1000 DEG C of the filter residue C in step (5), after being cooled to room temperature, add certain density NaOH solution and keep 10h under temperature 80 DEG C of conditions, then carry out suction filtration and obtain white powder, obtain the mixture mainly containing yttrium oxide and europium sesquioxide; Then add hydrochloric acid soln it is dissolved completely, treat solution transparent clarification post-heating evaporate to dryness solution, obtain the white mixture (wherein the mass ratio of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium is about 13:1) of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium.
(7) the white mixture 0.2g of anhydrous chlorides of rase yttrium and the anhydrous chlorides of rase europium obtained in step (6) is taken, respectively weighing sodium hydroxide solid and NaHF
2fine powder 0.04g, 0.16g, take ErF_3 films 0.01g again, (ytterbium ion enters in NaYF4 matrix as sensitizing agent doping to fluoridize ytterbium, can the fluorescent effect of strongthener) 0.08g, weigh up four parts of solids mixings are evenly joined in 100ml there-necked flask, then in 100ml there-necked flask, add 25ml oleic acid and a stirring magnetic seed, reaction is carried out and stirs magnetic seed being from start to finish in whipped state (stir speed (S.S.) 3000 ~ 5000rpm/min is optionally adjustable) under closed system, after vacuumizing under normal temperature, close vacuum valve, then in reactor, argon gas or nitrogen is passed into, be rapidly heated to 330 DEG C with the temperature rise rate of 10 ~ 20 DEG C/min, temperature maintains about 330 DEG C 80min, stop heating, question response thing cool to room temperature.
(8) reaction soln that step (7) obtains is poured in centrifuge tube carry out centrifugation, obtain the acetone that white solid adds 10ml, ultrasonic vibration 5 ~ 10min, rejoin acetone centrifuge washing 3 times, then wash repeatedly with boiling water, dry, object is the by product such as by product Sodium Fluoride, sodium-chlor, Europium trichloride, europium inside removing reactant; Obtain micron order rare-earth fluorescent up-conversion NaYF of the present invention
4: Yb
3+, Er
3+.
Final product XRD, TEM and fluorescence spectrophotometer are carried out to the sign of thing phase, pattern and fluorescence property etc.See that Fig. 4 is XRD diffracting spectrum, interpretation of result shows that the micron particle synthesized is NaYF
4: Yb
3+, Er
3+, inclusion-free peak; NaYF
4: Yb
3+, Er
3+transmission electron microscope photo and High-Resolution Map see Fig. 5, Fig. 5 shows six side's phases that crystal grain is rule, and crystal edge is clear, and crystal grain distribution is comparatively even, and median size is about 1 μm; With 980nm laser excitation NaYF
4: Yb
3+, Er
3+upper conversion rare earth micrometer fluorescent material measures fluorescence spectrum, has the spectrum peak of green glow and ruddiness to occur, see Fig. 6 at 500 1 550nm and 650 1 675nm regions.
Embodiment 3
The concrete steps preparing rare-earth fluorescent up-conversion with waste phosphor powder are as follows:
(1) take a certain amount of technique waste phosphor powder, leach fluorescent material by 2mol/L sulphuric acid soln, and add appropriate hydrogen peroxide as solubility promoter, temperature 70 C, leach 4h, obtain solution;
(2) solution in step (1) is put into whizzer and carry out solid-liquid separation, gained leach liquor at 3.5-4, carries out primary sedimentation by ammoniacal liquor adjust ph, filters, obtains filtrate;
(3) filtrate in step (2) is added ammoniacal liquor, carry out secondary sedimentation, pH value is transferred to 7-8, filters, obtains filter residue A and retain filtrate;
(4) filtrate in step (3) is added ammoniacal liquor, carry out three precipitations, pH value is transferred to 8-9, filters, obtains filter residue B;
(5) by step 3) in filter residue A and filter residue B in step (4) add sulphuric acid soln and dissolve and obtain pregnant solution, add boiling water, stir, under the condition of temperature 80 DEG C, slowly add oxalic acid solution, carry out four precipitations, ageing 4h, filters, obtains filter residue C;
(6) by the calcination 2h at high temperature 1000 DEG C of the filter residue C in step (5), after being cooled to room temperature, add certain density KOH solution and keep 10h under temperature 80 DEG C of conditions, then carry out suction filtration and obtain white powder, obtain the mixture mainly containing yttrium oxide and europium sesquioxide; Then add hydrochloric acid soln it is dissolved completely, treat solution transparent clarification post-heating evaporate to dryness solution, obtain the white mixture (wherein the mass ratio of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium is about 13:1) of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium.
(7) take the white mixture 0.2g of anhydrous chlorides of rase yttrium and the anhydrous chlorides of rase europium obtained in step (6), take NaOH solid and KHF respectively
2fine powder 0.1g, 0.2g, take ErF_3 films 0.008g again, weigh up four parts of solids mixings are evenly joined in 100ml there-necked flask, then in 100ml there-necked flask, add 25ml oleic acid and a stirring magnetic seed, reaction is carried out and stirs magnetic seed being from start to finish in whipped state (stir speed (S.S.) 3000 ~ 5000rpm/min is optionally adjustable) under closed system, after vacuumizing under normal temperature, close vacuum valve, then in reactor, argon gas or nitrogen is passed into, be rapidly heated to 330 DEG C with the temperature rise rate of 10 ~ 20 DEG C/min, temperature maintains about 330 DEG C 70min, stop heating, question response thing cool to room temperature.
(8) reaction soln that step (7) obtains is poured in centrifuge tube carry out centrifugation, obtain the acetone that white solid adds 10ml, ultrasonic vibration 5 ~ 10min, rejoin acetone centrifuge washing 3 times, then wash repeatedly with boiling water, dry, object is the by product such as side product chlorinated potassium, Potassium monofluoride, Sodium Fluoride, sodium-chlor, Europium trichloride, europium inside removing reactant; Obtain nano-scale rare earth fluorescence up-conversion K of the present invention
2naYF
6: Er
3+.
Embodiment 4
The concrete steps preparing rare-earth fluorescent up-conversion with waste phosphor powder are as follows:
(1) take a certain amount of technique waste phosphor powder, leach fluorescent material by 2mol/L sulphuric acid soln, and add appropriate hydrogen peroxide as solubility promoter, temperature 70 C, leach 4h, obtain solution;
(2) solution in step (1) is put into whizzer and carry out solid-liquid separation, gained leach liquor at 3.5-4, carries out primary sedimentation by ammoniacal liquor adjust ph, filters, obtains filtrate;
(3) filtrate in step (2) is added ammoniacal liquor, carry out secondary sedimentation, pH value is transferred to 7-8, filters, obtains filter residue A and retain filtrate;
(4) filtrate in step (3) is added ammoniacal liquor, carry out three precipitations, pH value is transferred to 8-9, filters, obtains filter residue B;
(5) by step 3) in filter residue A and filter residue B in step (4) add sulphuric acid soln and dissolve and obtain pregnant solution, add boiling water, stir, under the condition of temperature 80 DEG C, slowly add oxalic acid solution, carry out four precipitations, ageing 4h, filters, obtains filter residue C;
(6) by the calcination 2h at high temperature 1000 DEG C of the filter residue C in step (5), after being cooled to room temperature, add certain density NaOH solution and keep 10h under temperature 80 DEG C of conditions, then carry out suction filtration and obtain white powder, obtain the mixture mainly containing yttrium oxide and europium sesquioxide; Then add hydrochloric acid soln it is dissolved completely, treat solution transparent clarification post-heating evaporate to dryness solution, obtain the white mixture (wherein the mass ratio of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium is about 13:1) of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium.
(7) take the white mixture 0.2g of anhydrous chlorides of rase yttrium and the anhydrous chlorides of rase europium obtained in step (6), take NaOH solid and NaHF respectively
2fine powder 0.04g, 0.16g, take again and fluoridize thulium 0.01g, (ytterbium ion enters in NaYF4 matrix as sensitizing agent doping to fluoridize ytterbium, can the fluorescent effect of strongthener) 0.08g, weigh up four parts of solids mixings are evenly joined in 100ml there-necked flask, then in 100ml there-necked flask, add 25ml oleic acid and 5ml oleyl amine and one stir magnetic seed, reaction is carried out and stirs magnetic seed being from start to finish in whipped state (stir speed (S.S.) 3000 ~ 5000rpm/min is optionally adjustable) under closed system, after vacuumizing under normal temperature, close vacuum valve, then in reactor, argon gas or nitrogen is passed into, be rapidly heated to 320 DEG C with the temperature rise rate of 10 ~ 20 DEG C/min, temperature maintains about 320 DEG C 80min, stop heating, question response thing cool to room temperature.
(8) reaction soln that step (7) obtains is poured in centrifuge tube carry out centrifugation, obtain the acetone that white solid adds 10ml, ultrasonic vibration 5 ~ 10min, rejoin acetone centrifuge washing 3 times, then wash repeatedly with boiling water, dry, object is the by product such as by product Sodium Fluoride, sodium-chlor, Europium trichloride, europium inside removing reactant; Obtain rare-earth fluorescent of the present invention turns material NaYF
4: Yb
3+, Tm
3+.
Embodiment 5
The concrete steps preparing rare-earth fluorescent up-conversion with waste phosphor powder are as follows:
(1) take a certain amount of technique waste phosphor powder, leach fluorescent material by 2mol/L sulphuric acid soln, and add appropriate hydrogen peroxide as solubility promoter, temperature 70 C, leach 4h, obtain solution;
(2) solution in step (1) is put into whizzer and carry out solid-liquid separation, gained leach liquor at 3.5-4, carries out primary sedimentation by ammoniacal liquor adjust ph, filters, obtains filtrate;
(3) filtrate in step (2) is added ammoniacal liquor, carry out secondary sedimentation, pH value is transferred to 7-8, filters, obtains filter residue A and retain filtrate;
(4) filtrate in step (3) is added ammoniacal liquor, carry out three precipitations, pH value is transferred to 8-9, filters, obtains filter residue B;
(5) by step 3) in filter residue A and filter residue B in step (4) add sulphuric acid soln and dissolve and obtain pregnant solution, add boiling water, stir, under the condition of temperature 80 DEG C, slowly add oxalic acid solution, carry out four precipitations, ageing 4h, filters, obtains filter residue C;
(6) by the calcination 2h at high temperature 1000 DEG C of the filter residue C in step (5), after being cooled to room temperature, add certain density KOH solution and keep 10h under temperature 80 DEG C of conditions, then carry out suction filtration and obtain white powder, obtain the mixture mainly containing yttrium oxide and europium sesquioxide; Then add hydrochloric acid soln it is dissolved completely, treat solution transparent clarification post-heating evaporate to dryness solution, obtain the white mixture (wherein the mass ratio of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium is about 13:1) of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium.
(7) take the white mixture 0.2g of anhydrous chlorides of rase yttrium and the anhydrous chlorides of rase europium obtained in step (6), take KOH solid and KHF respectively
2fine powder 0.05g, 0.2g, take holmium fluoride 0.01g again, weigh up four parts of solids mixings are evenly joined in 100ml there-necked flask, then in 100ml there-necked flask, add 25ml oleic acid and 5ml octadecylene and one stir magnetic seed, reaction is carried out and stirs magnetic seed being from start to finish in whipped state (stir speed (S.S.) 3000 ~ 5000rpm/min is optionally adjustable) under closed system, after vacuumizing under normal temperature, close vacuum valve, then in reactor, argon gas or nitrogen is passed into, be rapidly heated to 310 DEG C with the temperature rise rate of 10 ~ 20 DEG C/min, temperature maintains about 310 DEG C 70min, stop heating, question response thing cool to room temperature.
(8) reaction soln that step (7) obtains is poured in centrifuge tube carry out centrifugation, obtain the acetone that white solid adds 10ml, ultrasonic vibration 5 ~ 10min, rejoin acetone centrifuge washing 3 times, then wash repeatedly with boiling water, dry, object is the by product such as side product chlorinated potassium, Potassium monofluoride, Europium trichloride, europium inside removing reactant; Obtain rare-earth fluorescent of the present invention turns material KYF
4: Ho
3+.
Claims (4)
1. utilize waste phosphor powder to prepare the method for rare-earth fluorescent up-conversion, comprise the following steps:
1) take technique waste phosphor powder, leach fluorescent material by 1.5mol/L-2.5mol/L sulphuric acid soln, using hydrogen peroxide as solubility promoter, obtain solution;
2) by step 1) in solution put into whizzer and carry out solid-liquid separation, gained leach liquor ammoniacal liquor regulates pH 3.5-4, carries out primary sedimentation, filters, obtains filtrate;
3) by step 2) in filtrate add ammoniacal liquor, carry out secondary sedimentation, adjust pH 7-8, filter, obtain filter residue A and retain filtrate;
4) by step 3) in filtrate add ammoniacal liquor, carry out three precipitations, adjust pH 8-9, filter, obtain filter residue B;
5) by step 3) in filter residue A and step 4) in filter residue B add sulphuric acid soln dissolve obtain pregnant solution, add boiling water, stir, slowly add oxalic acid solution, carry out four times precipitation, ageing, filter, obtain filter residue C;
6) by step 5) in filter residue C high temperature sintering, after being cooled to room temperature, adding MOH solution and keep 10h under temperature 80 DEG C of condition, then carry out suction filtration and obtain mainly containing the mixture white powder of yttrium oxide and europium sesquioxide; Then add hydrochloric acid soln it is dissolved completely, treat solution transparent clarification post-heating evaporate to dryness solution, obtain the mixture of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium;
7) take step 6) in the mixture of the anhydrous chlorides of rase yttrium that obtains and anhydrous chlorides of rase europium, MOH solid and MHF
2fine powder and RmF
3or RmCl
3solid, by its Homogeneous phase mixing, obtains solid mixture;
8) to step 7) in add high boiling solvent in the solid mixture that obtains, then under atmosphere of inert gases protection, be rapidly heated, keep temperature of reaction under the condition of 200 DEG C-350 DEG C, magnetic agitation reaction 30min-3h;
9) by step 8) liquid that obtains after completion of the reaction carries out high speed centrifugation, the pressed powder obtained directly by normal hexane or the centrifugal supersound washing repeated drying of acetone, then with boiling water washing repeatedly, dry, obtain rare-earth fluorescent up-conversion.
2. the method utilizing waste phosphor powder to prepare rare-earth fluorescent up-conversion according to claim 1, is characterized in that, step 6) and step 7) middle MOH, MHF
2in M be any one and two kinds in Na, K, RmF
3or RmCl
3in Rm be any one and multiple mixing in Er, Tm, Ho.
3. the method utilizing waste phosphor powder to prepare rare-earth fluorescent up-conversion according to claim 1 and 2, is characterized in that, step 7) in mixture, MOH solid, the MHF of anhydrous chlorides of rase yttrium and anhydrous chlorides of rase europium
2fine powder, RmF
3or RmCl
3the mass ratio 1:(0.25-0.5 of solid): (1-2): (0.01-0.1).
4. the method utilizing waste phosphor powder to prepare rare-earth fluorescent up-conversion according to claim 1, is characterized in that, step 8) in high boiling solvent be wherein one or more the mixing of oleic acid, oleyl amine, octadecylene.
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| CN108300477A (en) * | 2018-01-31 | 2018-07-20 | 武汉理工大学 | A method of it recycling yttrium from waste phosphor powder and prepares rare earth up-conversion |
| CN110452682A (en) * | 2018-05-08 | 2019-11-15 | 中国科学院福建物质结构研究所 | A kind of method that one kettle way is prepared on a large scale rare-earth doping fluoride nano crystalline substance |
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| CN104927863A (en) * | 2015-06-05 | 2015-09-23 | 武汉理工大学 | Method for preparing rare earth metal co-doped hexagonal NaYF4 nanocrystalline by use of discarded fluorescent powder |
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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 |
| CN108300477A (en) * | 2018-01-31 | 2018-07-20 | 武汉理工大学 | A method of it recycling yttrium from waste phosphor powder and prepares rare earth up-conversion |
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| CN115094238B (en) * | 2022-05-09 | 2023-10-20 | 中南大学 | Device and method for recycling rare earth elements from zinc sulfide-based fluorescent powder |
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