CN104532006B - Europium oxide and the method for yittrium oxide is extracted from Waste fluorescent powder - Google Patents
Europium oxide and the method for yittrium oxide is extracted from Waste fluorescent powder Download PDFInfo
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Abstract
The invention discloses and a kind of extract europium oxide and the method for yittrium oxide from Waste fluorescent powder, it specifically includes that seven steps such as extraction step of sodium carbonate roasting step, potassium cloride step, calcium phosphate precipitation step, precipitation step of converting, extract and separate yttrium step, the extraction step of high purity yttria and high-purity mangesium oxide europium.Wherein, extract and separate yttrium is by using P507 extraction separation method, it is achieved that rare-earth yttrium separates with the summary high efficiency continuously of europium, and its separation efficiency is high, low cost.The present invention, relative to prior art, has technological process short, and rare earth element extraction ratio is high, the purity of rare-earth products is high, and the beneficial effect such as extraction cost is low.
Description
Technical field
The present invention relates to the extracting method of a kind of rare earth element, particularly relate to a kind of extraction europium oxide and method of yittrium oxide from Waste fluorescent powder, belong to waste material regeneration field.
Background technology
In television set cathode ray tube (CRT) cutting process, panel glass has substantial amounts of fluorescent material, containing rare earth metals such as europium (Eu), yttrium (Y), erbiums (Er) in this fluorescent material.If dealt with improperly, the pollutant such as metal complex in CRT fluorescent material and the lead bearing glass that is mixed in fluorescent material enter in soil, air and river, can cause serious problem.
Therefore, consider from environmental management and the utilization of resources, need the fluorescent material in CRT through going appropriate recycling.
Recycling of WEEE is increasingly paid close attention to by everybody, the electron wastes having nearly million tons every year produces, and television set accounts for wherein significant proportion, when processing television set CRT, owing to television set fluorescent material contains the zinc of the rare earth such as yttrium and europium and very high-load, typically all can focus on after being collected separately, the following is the various different mixed composition of television set fluorescent material:
| Composition | Ca | Zn | Cd | Al | Mg | Y | Eu |
| Content | 0.13 | 45.38 | 1.12 | 0.29 | 0.15 | 21.25 | 1.85 |
Owing to fluorescent material containing rare earth element and zinc, add containing toxic element such as cadmium and a small amount of barium, lead, chromium, so the process of fluorescent material not only has economic benefit, also there is the highest social benefit simultaneously.
Rare earth element is as " industry monosodium glutamate ", being widely used in all trades and professions, and Extraction of rare earth causes serious environmental pollution and ecological disruption from mineral, from secondary resource, Extraction of rare earth has the advantage such as low cost, environmental protection, decrease raw ore exploitation simultaneously, have economic and social benefit.
But red fluorescence powder (Y is mainly included due to Waste fluorescent powder2O3: Eu and Y2O2, green emitting phosphor be mainly silicate, borate S: Eu), phosphate, and some oxides, owing to rare earth element defines some ceramic phases, stable within being present in crystal, the method rare earth element extraction ratio causing routine is low, and the taste of rare earth element is on the low side.
Chinese patent application CN102796872A discloses a kind of method reclaiming cathodic ray-tube fluorescent powder middle rare earth, comprise the following steps: (1) takes cathodic ray-tube fluorescent powder, add the dilute sulfuric acid that concentration is 5%-15% to dissolve, 0.5-2h is stirred at a temperature of 85-90 DEG C, sucking filtration, must contain the filtrate of rare earth ion；(2) taking hydrofluoric acid solution and add the described filtrate containing rare earth ion, reaction generates rare earth fluoride, sucking filtration separating filtrate, and rare earth fluoride remains in filter cake, and washing filter cake 1-5 time must contain the filter cake of pure rare earth fluoride.
But, the method for above-mentioned recovery cathodic ray-tube fluorescent powder middle rare earth, the response rate of its main rare earth metal y and Eu respectively: 89% and 94.5%, the extraction ratio of rare earth composition is the highest.
Chinese patent application CN102660688B discloses a kind of method separating and recovering rare earth from waste and old rare earth luminescent material, processing step is: the collection of waste and old rare earth luminescent material, and quickly identify and disassemble broken, waste and old rare earth luminescent material broken, CRT monitor including rare-earth fluorescent light are peeled off and collection with glass basis；The pretreatment of waste and old rare earth luminescent material, including demercuration oxidation precipitation, alkali fusion and acidolysis；The extract and separate of rare earth element obtains rare earth chloride enriched substance；The purification by liquid extraction of rare earth element obtains high-purity rare-earth chloride；The precipitate and separate of rare earth element obtains rare earth oxalate or carbonated rare earth precipitate；Rare earth oxalate or carbonated rare earth precipitate roasting obtain high-purity grade of rare earth oxide.
But, this method separating and recovering rare earth from waste and old rare earth luminescent material, there is technological process long, cost recovery is higher waits deficiency.
Summary of the invention
It is an object of the invention to provide a kind of technological process purity short, rare earth element extraction ratio height, rare-earth products high, and extraction europium oxide and the method for yittrium oxide from Waste fluorescent powder that cost recovery is low.
The present invention be employed technical scheme comprise that for achieving the above object, a kind of extraction europium oxide and method of yittrium oxide from Waste fluorescent powder, comprises the steps:
1) sodium carbonate roasting step: weight ratio 0.5-1 by between solid-liquid: 1, adds liquid caustic soda, pelletize fed to boiler roasting in Waste fluorescent powder；
2) potassium cloride step: by the material after roasting, wash with water；
By the slag after washing in the acid solution that pH value is 3, at 50-99 DEG C, carry out potassium cloride with chlorine, soluble chlorine hydrochlorate or solubility hypochlorite, again wash and leachate is separated with slag；
Described chlorine, soluble chlorine hydrochlorate or solubility hypochlorite are to add in the ratio that mass ratio is 0.1-0.5 1 of chlorine element with Waste fluorescent powder；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 1.1-2 1 of phosphate radical Yu rare earth element, the phosphate of solubility is added in above-mentioned leachate, reaction temperature is controlled at 50-99 DEG C, pH value controls at 1.5-6.5, response time controls, at 1-5 hour, to obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 1 0.2-1.0 by weight, adding concentration in the calcium phosphate precipitation of above-mentioned rare earth is the strong base solution of 1-5mol/L, controls reaction temperature and is 50-99 DEG C, prepares the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 0.5-5mol/L, control reaction temperature and be 50-99 DEG C, entered P507 extract line by the flow volume of lysate with P507 than 1 2-5, lysate, obtain pure yttrium chloride solution；
Wherein, the saponification rate 50%-75%, P507 of P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.1-0.2 0.1-0.2, the concentration of acid regurgitation is 1-6mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds ammonium hydrogen carbonate by mol ratio 1 4-8 of Yttrium chloride(Y2Cl6) with ammonium hydrogen carbonate, reaction temperature is controlled at 50-99 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 1-6 hour at 500-900 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, adds reducing agent, controls reduction reaction temperature and is 50-99 DEG C, 1-6 hour reduction reaction time, obtains the europium ion of bivalence；
After adding soluble sulphate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is added potassium carbonate, sodium hydroxide or potassium oxalate and carries out precipitation conversion, obtain the precipitate of the carbonate of divalent europium, hydroxide or oxalates, then this precipitate is calcined 1-6 hour at 500-900 DEG C, obtain high-purity mangesium oxide europium.
Being preferably, above-mentioned acid solution is one or more in sulfuric acid solution, hydrochloric acid solution, salpeter solution or acetum.
Further preferably, one or more during above-mentioned liquid caustic soda is liquified hydrogen sodium oxide, aqueous potassium hydroxide or liquified hydrogen Barium monoxide；
Described strong base solution is one or more in sodium hydroxide solution, potassium hydroxide solution or barium hydroxide solution.
Further preferably, above-mentioned reducing agent is zinc powder, aluminium powder, magnesium powder, oxammonium hydrochloride., hydrazine hydrate or ascorbic acid.
Further preferably, above-mentioned soluble sulphate is sodium sulfate, potassium sulfate or ammonium sulfate.
Further preferably, above-mentioned soluble phosphate is sodium phosphate, ammonium phosphate or potassium phosphate.Further preferably, above-mentioned soluble chlorine hydrochlorate is potassium chlorate, sodium chlorate or ammonium chlorate；Above-mentioned solubility hypochlorite is postassium hypochlorite, sodium hypochlorite or hypochlorous acid ammonium.
What technique scheme was directly brought has the technical effect that, by sodium carbonate roasting step, the in fluorescent material first big component zinc can become the zincate of solubility, zinc is removed the taste being greatly improved rare earth, reduces the difficulty of follow-up remove impurity.
By potassium cloride step, the leaching rate of rare earth can be improved, reduce cost simultaneously.
Use phosphate precipitating rare earth selectively, can further improve the taste of rare earth, other impurity are stayed in aqueous, the purest earth solution is obtained by precipitation conversion-dissolving with hydrochloric acid, again through extract and separate yttrium europium, the yttrium europium solution purity obtained is high, low cost simultaneously, can realize the serialization produced.
In technique scheme, first Waste fluorescent powder is added before roasting the pretreatment of liquid caustic soda pelletize, rather than use aqueous slkali to carry out pretreatment, main reason is that, use liquid caustic soda, both can realize fluorescent material to be sufficiently mixed uniformly and granulating and forming with liquid caustic soda, and be avoided that again the thermal loss too much brought of the additional moisture content of aqueous slkali, and then increase the energy consumption cost of calcining process.
In technique scheme, in potassium cloride step, by rationally selecting chlorine and the mass ratio (0.1-0.5 1) of Waste fluorescent powder and extraction temperature (50-99 DEG C), this primary concern is that, chlorine is too high with the mass ratio of fluorescent material, can waste chlorine, improve cost；Chlorine is too low with the mass ratio of fluorescent material, and the leaching rate of rare earth will be substantially reduced；
And extraction temperature is too low, the extraction ratio of rare earth is low；Extraction temperature is too high, will result in the waste of heat energy, and then rises high cost.
Similarly, the selection gist of the various process parameters in the calcium phosphate precipitation step of technique scheme, primary concern is that: using soluble phosphate selective precipitation rare earth, precipitation temperature is too low, then the sedimentation time is too short, precipitation process pH is too low, phosphate radical is too low with the mol ratio of rare earth element, and the rate of deposition of rare earth is low, and production efficiency is low, otherwise, then cost is greatly improved.
In the precipitation step of converting of technique scheme, why use the strong base solutions such as sodium hydroxide solution, potassium hydroxide solution or barium hydroxide solution, reason is: use the strong base solutions such as sodium hydroxide, potassium hydroxide, barium hydroxide to be used as precipitating transforming agent, the precipitation conversion ratio of rare earth can be improved, to ensure the high-recovery of rare earth.
In the extract and separate yttrium step of technique scheme, the selection gist of each technological parameter mainly, uses dissolving with hydrochloric acid rare-earth hydroxide, can improve the dissolution rate of rare earth；Solution temperature is too low or concentration of hydrochloric acid is too low, then the dissolution rate of rare earth is on the low side, otherwise then cost improves；
More it is essential that in technique scheme, by using P507 extraction separation method, it is achieved that rare-earth yttrium separates with the summary high efficiency continuously of europium, its separation efficiency is high, low cost.
In the extraction step of the high purity yttria of technique scheme, using ammonium bicarbonate precipitation yttrium, can improve the rate of deposition of yttrium, reduce zinc, barium, the isoionic precipitation of calcium simultaneously, ammonium hydrogen carbonate is cheap simultaneously, and cost can reduce.
Calcine 1-6 hour through relatively low calcining heat (500-900 DEG C) again, i.e. can get high purity yttria.
In the extraction step of the high-purity mangesium oxide europium of technique scheme,
Use the reducing agents such as zinc powder, aluminium powder, magnesium powder, oxammonium hydrochloride. or ascorbic acid that trivalent europium is reduced into divalent europium, sulfate radical precipitation divalent europium is used to obtain being not dissolved in the europous sulfate of water, convert and obtain the carbonate of divalent europium, hydroxide, oxalates through percarbonate, hydroxide, oxalate precipitation, then obtain europium oxide through calcining again.
To sum up, it can be seen that zinc, by using sodium carbonate roasting, is changed into the zincate being dissolvable in water water, improves the taste of rare earth, decrease the trouble of follow-up remove impurity, reduce cost by the present invention；By using calcium phosphate precipitation rare earth, alternative precipitating rare earth, improve the taste of rare earth further, deep impurity-removing for follow-up rare earth does basis simultaneously, take the series technique means such as extract and separate, final rare earth composition extraction ratio is made to be up to more than 99.75%, the yttrium that extracted, the high purity more than 99.96% of europium；It is simultaneously achieved the summary high efficiency separation of yttrium, europium rare earth.
The technological process of the present invention is short, process conditions are relatively easy easily-controllable, and the less energy consumption of whole technical process, raw material are easily obtained and with low cost.
In sum, the present invention, relative to prior art, has technological process short, and rare earth element extraction ratio is high, the purity of rare-earth products is high, and the beneficial effect such as extraction cost is low.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the present invention is described in detail.
As shown in Figure 1, the present invention extracts europium oxide and the method for yittrium oxide, including following 7 steps: 1 from Waste fluorescent powder) sodium carbonate roasting step, 2) potassium cloride step, 3) calcium phosphate precipitation step, 4) precipitation step of converting, 5) extract and separate yttrium step, 6) extraction step of high purity yttria, 7) extraction step of high-purity mangesium oxide europium.
Embodiment 1:
Europium oxide and the method for yittrium oxide is extracted, including following 7 steps from Waste fluorescent powder:
1) sodium carbonate roasting step: by the weight ratio 0.75: 1 between solid-liquid, adds liquified hydrogen sodium oxide, pelletize fed to boiler roasting in Waste fluorescent powder；
2) potassium cloride step: by the material after roasting, wash with water；By the slag after washing in the hydrochloric acid solution that pH value is 3, at 85 DEG C, carry out potassium cloride with chlorine, again wash and leachate is separated with slag；
Described chlorine is to add in the ratio that mass ratio is 0.1 1 of chlorine element with Waste fluorescent powder；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 1.1-2 1 of phosphate radical Yu rare earth element, adding sodium phosphate in above-mentioned leachate, reaction temperature controlled at 90 DEG C, pH value controls 6.5, response time controls, at 6 hours, to obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 1 0.2 by weight, adding concentration in the calcium phosphate precipitation of above-mentioned rare earth is the sodium hydroxide solution of 1mol/L, and controlling reaction temperature is 50 DEG C, prepares the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 0.5-5mol/L, controlling reaction temperature is 50 DEG C, by the flow volume ratio 12 of lysate with P507, lysate enters P507 and extracts line, obtains pure yttrium chloride solution；
Wherein, the saponification rate 50% of P507, P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.1 0.1, the concentration of acid regurgitation is 1mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds ammonium hydrogen carbonate by the mol ratio 14 of Yttrium chloride(Y2Cl6) with ammonium hydrogen carbonate, reaction temperature is controlled at 50 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 6 hours at 500 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, addition zinc powder is as reducing agent, and controlling reduction reaction temperature is 50 DEG C, 6 hours reduction reaction time, obtains the europium ion of bivalence；
After adding sodium sulfate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is added potassium carbonate and carries out precipitation conversion, obtain the precipitate of the carbonate of divalent europium, then this precipitate is calcined 6 hours at 500 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction ratio of final rare earth is 99.75%, and the purity of the yittrium oxide obtained is 99.98%, and the purity of the europium oxide obtained is 99.97%.
Embodiment 2
Europium oxide and the method for yittrium oxide is extracted, including following 7 steps from Waste fluorescent powder:
1) sodium carbonate roasting step: by the weight ratio 0.75: 1 between solid-liquid, adds aqueous potassium hydroxide, pelletize fed to boiler roasting in Waste fluorescent powder；
2) potassium cloride step: by the material after roasting, wash with water；
By the slag after washing in the sulfuric acid solution that pH value is 3, at 75 DEG C, carry out potassium cloride with sodium chlorate, again wash and leachate is separated with slag；
Described sodium chlorate is to add in the ratio that mass ratio is 0.2.5 1 of chlorine element with Waste fluorescent powder；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 1.5 1 of phosphate radical Yu rare earth element, adding ammonium phosphate in above-mentioned leachate, reaction temperature controlled at 75 DEG C, pH value controls 3.5, response time controls, at 2.5 hours, to obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 1 0.5 by weight, adding concentration in the calcium phosphate precipitation of above-mentioned rare earth is the potassium hydroxide solution of 2.5mol/L, and controlling reaction temperature is 75 DEG C, prepares the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 2.5mol/L, controlling reaction temperature is 75 DEG C, by the flow volume ratio 1 3.5 of lysate with P507, lysate enters P507 and extracts line, obtains pure yttrium chloride solution；
Wherein, the saponification rate 60% of P507, P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.15 0.15, the concentration of acid regurgitation is 3mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds ammonium hydrogen carbonate by the mol ratio 16 of Yttrium chloride(Y2Cl6) with ammonium hydrogen carbonate, reaction temperature is controlled at 75 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 3.5 hours at 700 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, adds reducing agent aluminium powder, and controlling reduction reaction temperature is 75 DEG C, 3 hours reduction reaction time, obtains the europium ion of bivalence；
After adding potassium sulfate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is added sodium hydroxide and carries out precipitation conversion, obtain the precipitate of the hydroxide of divalent europium, then this mixed sediment is calcined 3.5 hours at 700 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction ratio of final rare earth is 99.75%, and the purity of the yittrium oxide obtained is 99.96%, and the purity of the europium oxide obtained is 99.96%.
Embodiment 3
Europium oxide and the method for yittrium oxide is extracted, including following 7 steps from Waste fluorescent powder:
1) sodium carbonate roasting step: by the weight ratio 0.85: 1 between solid-liquid, adds liquified hydrogen Barium monoxide, pelletize fed to boiler roasting in Waste fluorescent powder；
2) potassium cloride step: by the material after roasting, wash with water；
By the slag after washing in the acetum that pH value is 3, at 80 DEG C, carry out potassium cloride with sodium hypochlorite, again wash and leachate is separated with slag；
Described sodium hypochlorite is to add in the ratio that mass ratio is 0.35 1 of chlorine element with Waste fluorescent powder；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 1.6 1 of phosphate radical Yu rare earth element, adding potassium phosphate in above-mentioned leachate, reaction temperature controlled at 80 DEG C, pH value controls 3.5, response time controls, at 4 hours, to obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 1 0.8 by weight, adding concentration in the calcium phosphate precipitation of above-mentioned rare earth is the barium hydroxide solution of 3.5mol/L, and controlling reaction temperature is 80 DEG C, prepares the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 3.5mol/L, controlling reaction temperature is 80 DEG C, by the flow volume ratio 14 of lysate with P507, lysate enters P507 and extracts line, obtains pure yttrium chloride solution；
Wherein, the saponification rate 65% of P507, P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.2 0.2, the concentration of acid regurgitation is 4mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds ammonium hydrogen carbonate by the mol ratio 17 of Yttrium chloride(Y2Cl6) with ammonium hydrogen carbonate, reaction temperature is controlled at 80 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 2 hours at 800 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, addition magnesium powder is as reducing agent, and controlling reduction reaction temperature is 80 DEG C, 4 hours reduction reaction time, obtains the europium ion of bivalence；
After adding sulfate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is added potassium oxalate and carries out precipitation conversion, obtain the precipitate of the oxalates of divalent europium, then this precipitate is calcined 2 hours at 800 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction ratio of final rare earth is 99.78%, and the purity of the yittrium oxide obtained is 99.96%, and the purity of the europium oxide obtained is 99.97%.
Embodiment 4
Europium oxide and the method for yittrium oxide is extracted, including following 7 steps from Waste fluorescent powder:
1) sodium carbonate roasting step: by the weight ratio 1: 1 between solid-liquid, adds aqueous potassium hydroxide, pelletize fed to boiler roasting in Waste fluorescent powder；
2) potassium cloride step: by the material after roasting, wash with water；
By the slag after washing in the salpeter solution that pH value is 3, at 99 DEG C, carry out potassium cloride with postassium hypochlorite, again wash and leachate is separated with slag；
Described postassium hypochlorite is to add in the ratio that mass ratio is 0.5 1 of chlorine element with Waste fluorescent powder；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 21 of phosphate radical Yu rare earth element, adding ammonium phosphate in above-mentioned leachate, reaction temperature controlled at 99 DEG C, pH value controls 1.5, response time controls, at 1 hour, to obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 11 by weight, adding concentration in the calcium phosphate precipitation of above-mentioned rare earth is the potassium hydroxide solution of 1mol/L, and controlling reaction temperature is 99 DEG C, prepares the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 5mol/L, controlling reaction temperature is 99 DEG C, by the flow volume ratio 15 of lysate with P507, lysate enters P507 and extracts line, obtains pure yttrium chloride solution；
Wherein, the saponification rate 75% of P507, P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.2 0.2, the concentration of acid regurgitation is 6mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds ammonium hydrogen carbonate by the mol ratio 18 of Yttrium chloride(Y2Cl6) with ammonium hydrogen carbonate, reaction temperature is controlled at 99 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 1 hour at 900 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, addition oxammonium hydrochloride. is as reducing agent, and controlling reduction reaction temperature is 99 DEG C, 6 hours reduction reaction time, obtains the europium ion of bivalence；
After adding ammonium sulfate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is successively added potassium carbonate and carries out precipitation conversion, obtain the precipitate of the carbonate of divalent europium, hydroxide and carbonic acid, then this mixed sediment is calcined 1 hour at 900 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction ratio of final rare earth is 99.81%, and the purity of the yittrium oxide obtained is 99.98%, and the purity of the europium oxide obtained is 99.97%.
Embodiment 5
1) sodium carbonate roasting step: by the weight ratio 1: 1 between solid-liquid, adds liquified hydrogen sodium oxide, pelletize fed to boiler roasting in Waste fluorescent powder；
2) potassium cloride step: by the material after roasting, wash with water；
By the slag after washing in the acid solution that pH value is 3, at 85 DEG C, carry out potassium cloride with the mixture of sodium chlorate and sodium hypochlorite, again wash and leachate is separated with slag；
The mixture of described sodium chlorate and sodium hypochlorite is to add in the ratio that mass ratio is 0.85 of chlorine element with Waste fluorescent powder；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 21 of phosphate radical Yu rare earth element, adding potassium phosphate in above-mentioned leachate, reaction temperature controlled at 85 DEG C, pH value controls 4.5, response time controls, at 5 hours, to obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 1 0.8 by weight, adding concentration in the calcium phosphate precipitation of above-mentioned rare earth is the sodium hydroxide solution of 5mol/L, and controlling reaction temperature is 85 DEG C, prepares the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 4.5mol/L, controlling reaction temperature is 85 DEG C, by the flow volume ratio 15 of lysate with P507, lysate enters P507 and extracts line, obtains pure yttrium chloride solution；
Wherein, the saponification rate 75% of P507, P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.2 0.2, the concentration of acid regurgitation is 6mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds ammonium hydrogen carbonate by the mol ratio 18 of Yttrium chloride(Y2Cl6) with ammonium hydrogen carbonate, reaction temperature is controlled at 85 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 5 hours at 850 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, addition oxammonium hydrochloride. is as reducing agent, and controlling reduction reaction temperature is 85 DEG C, 3 hours reduction reaction time, obtains the europium ion of bivalence；
After adding sodium sulfate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is successively added sodium hydroxide and carries out precipitation conversion, obtain the precipitate of the hydroxide of divalent europium, then this precipitate is calcined 5 hours at 850 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction ratio of final rare earth is 99.81%, and the purity of the yittrium oxide obtained is 99.97%, and the purity of the europium oxide obtained is 99.96%.
Embodiment 6
1) sodium carbonate roasting step: by the weight ratio 1: 1 between solid-liquid, adds liquified hydrogen Barium monoxide, pelletize fed to boiler roasting in Waste fluorescent powder；
2) potassium cloride step: by the material after roasting, wash with water；
By the slag after washing in the salpeter solution that pH value is 3, at 80 DEG C, with potassium chlorate and the mixture of postassium hypochlorite, and it is passed through chlorine, carries out potassium cloride, again washing leachate is separated with slag；
Above-mentioned potassium chlorate and the mixture of postassium hypochlorite, and it is passed through chlorine, it is to add in the ratio that mass ratio is 0.45 1 of chlorine element with Waste fluorescent powder；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 1.1-2 1 of phosphate radical Yu rare earth element, adding the potassium phosphate of solubility in above-mentioned leachate, reaction temperature controlled at 80 DEG C, pH value controls 5.5, response time controls, at 4 hours, to obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 1 0.6 by weight, adding concentration in the calcium phosphate precipitation of above-mentioned rare earth is the barium hydroxide solution of 4mol/L, and controlling reaction temperature is 80 DEG C, prepares the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 4mol/L, controlling reaction temperature is 80 DEG C, by the flow volume ratio 14 of lysate with P507, lysate enters P507 and extracts line, obtains pure yttrium chloride solution；
Wherein, the saponification rate 70% of P507, P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.1 0.1, the concentration of acid regurgitation is 4.5mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds ammonium hydrogen carbonate by the mol ratio 16 of Yttrium chloride(Y2Cl6) with ammonium hydrogen carbonate, reaction temperature is controlled at 80 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 4 hours at 800 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, adds aluminium powder and is 50-99 DEG C as reducing agent, control reduction reaction temperature, 1-6 hour reduction reaction time, obtains the europium ion of bivalence；
After adding ammonium sulfate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is successively added potassium oxalate and carries out precipitation conversion, obtain the oxalate precipitation thing of divalent europium, then this precipitate is calcined 4 hours at 800 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction ratio of final rare earth is 99.8%, and the purity of the yittrium oxide obtained is 99.97%, and the purity of the europium oxide obtained is 99.97%.
Embodiment 7
1) sodium carbonate roasting step: by the weight ratio 0.6: 1 between solid-liquid, adds aqueous potassium hydroxide and the mixed liquor of liquified hydrogen sodium oxide, pelletize fed to boiler roasting in Waste fluorescent powder；
2) potassium cloride step: by the material after roasting, wash with water；
By the slag after washing in the sulfuric acid solution that pH value is 3, at 65 DEG C, carry out potassium cloride with ammonium chlorate, again wash and leachate is separated with slag；
Described ammonium chlorate is to add in the ratio that mass ratio is 0.4 1 of chlorine element with Waste fluorescent powder；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 1.8 1 of phosphate radical Yu rare earth element, adding potassium phosphate in above-mentioned leachate, reaction temperature controlled at 65 DEG C, pH value controls 3.5, response time controls, at 3.5 hours, to obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 1 0.8 by weight, adds sodium hydroxide and the mixed solution of potassium hydroxide that concentration is 3.5mol/L in the calcium phosphate precipitation of above-mentioned rare earth, and controlling reaction temperature is 65 DEG C, prepares the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 3.5mol/L, controlling reaction temperature is 65 DEG C, by the flow volume ratio 14 of lysate with P507, lysate enters P507 and extracts line, obtains pure yttrium chloride solution；
Wherein, the saponification rate 65% of P507, P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.15 0.15, the concentration of acid regurgitation is 4mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds ammonium hydrogen carbonate by the mol ratio 17 of Yttrium chloride(Y2Cl6) with ammonium hydrogen carbonate, reaction temperature is controlled at 65 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 1-6 hour at 500-900 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, addition hydrazine hydrate is as reducing agent, and controlling reduction reaction temperature is 65 DEG C, 5 hours reduction reaction time, obtains the europium ion of bivalence；
After adding sodium sulfate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is successively added potassium carbonate and carries out precipitation conversion, obtain the carbonate sediment of divalent europium, then this precipitate is calcined 4 hours at 850 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction ratio of final rare earth is 99.83%, and the purity of the yittrium oxide obtained is 99.97%, and the purity of the europium oxide obtained is 99.97%.
Claims (7)
1. from Waste fluorescent powder, extract europium oxide and a method for yittrium oxide, comprise the steps:
1) sodium carbonate roasting step: weight ratio 0.5-1 by between solid-liquid: 1, adds liquid caustic soda in Waste fluorescent powder, enters after pelletize
Stove roasting；
2) potassium cloride step: by the material after roasting, wash with water；
By the slag after washing in the acid solution that pH value is 3, at 50-99 DEG C, by chlorine, soluble chlorine hydrochlorate or solubility
Hypochlorite carries out potassium cloride, again washs and is separated with slag by leachate；
Described chlorine, soluble chlorine hydrochlorate or solubility hypochlorite are to be 0.1-0.5 by the mass ratio of chlorine element Yu Waste fluorescent powder
The ratio of 1 adds；
3) calcium phosphate precipitation step: in the ratio that mol ratio is 1.1-2 1 of phosphate radical Yu rare earth element, in above-mentioned leachate
Adding the phosphate of solubility, reaction temperature controlled at 50-99 DEG C, pH value controls at 1.5-6.5, and the response time controls at 1-5
Hour, obtain the calcium phosphate precipitation of rare earth；
4) precipitation step of converting: be 1 0.2-1.0 by weight, adding concentration in the calcium phosphate precipitation of above-mentioned rare earth is
The strong base solution of 1-5mol/L, controls reaction temperature and is 50-99 DEG C, prepare the hydroxide of rare earth；
5) extract and separate yttrium step: after the hydroxide of above-mentioned rare earth is added the dissolving with hydrochloric acid that concentration is 0.5-5mol/L, control
Reaction temperature is 50-99 DEG C, is entered P507 by the flow volume of lysate with P507 extract line than 1 2-5, lysate,
To pure yttrium chloride solution；
Wherein, the saponification rate 50%-75%, P507 of P507 with wash acid and the flow volume ratio of acid regurgitation is 1 0.1-0.2 0.1-0.2,
The concentration of acid regurgitation is 1-6mol/L；
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, by the mol ratio 1 of Yttrium chloride(Y2Cl6) Yu ammonium hydrogen carbonate
4-8 adds ammonium hydrogen carbonate, reaction temperature is controlled at 50-99 DEG C, obtains Yttrium carbonate (Y2(CO3)3) precipitation；
By this Yttrium carbonate (Y2(CO3)3) precipitation after calcining 1-6 hour at 500-900 DEG C, obtain high purity yttria；
7) extraction step of high-purity mangesium oxide europium: in the raffinate after extract and separate yttrium, adds reducing agent, controls reduction reaction
Temperature is 50-99 DEG C, 1-6 hour reduction reaction time, obtains the europium ion of bivalence；
After adding soluble sulphate, obtain europous sulfate precipitation；
Above-mentioned europous sulfate precipitation is added potassium carbonate, sodium hydroxide or potassium oxalate and carries out precipitation conversion, obtain the carbonic acid of divalent europium
The precipitate of salt, hydroxide or oxalates, then this precipitate is calcined 1-6 hour at 500-900 DEG C, obtain high purity oxygen
Change europium.
Extraction europium oxide and the method for yittrium oxide from Waste fluorescent powder the most according to claim 1, it is characterised in that described
Acid solution is one or more in sulfuric acid solution, hydrochloric acid solution, salpeter solution or acetum.
Extraction europium oxide and the method for yittrium oxide from Waste fluorescent powder the most according to claim 1, it is characterised in that described
Liquid caustic soda is one or more in liquified hydrogen sodium oxide, aqueous potassium hydroxide or liquified hydrogen Barium monoxide；
Described strong base solution is one or more in sodium hydroxide solution, potassium hydroxide solution or barium hydroxide solution.
Extraction europium oxide and the method for yittrium oxide from Waste fluorescent powder the most according to claim 1, it is characterised in that described
Reducing agent is zinc powder, aluminium powder, magnesium powder, oxammonium hydrochloride., hydrazine hydrate or ascorbic acid.
Extraction europium oxide and the method for yittrium oxide from Waste fluorescent powder the most according to claim 1, it is characterised in that described
Soluble sulphate is sodium sulfate, potassium sulfate or ammonium sulfate.
Extraction europium oxide and the method for yittrium oxide from Waste fluorescent powder the most according to claim 1, it is characterised in that described
Soluble phosphate is sodium phosphate, ammonium phosphate or potassium phosphate.
Extraction europium oxide and the method for yittrium oxide from Waste fluorescent powder the most according to claim 1, it is characterised in that described
Soluble chlorine hydrochlorate is potassium chlorate, sodium chlorate or ammonium chlorate；
Described solubility hypochlorite is postassium hypochlorite, sodium hypochlorite or hypochlorous acid ammonium.
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| CN104946896B (en) * | 2015-07-15 | 2017-07-14 | 江西理工大学 | A kind of method of the Extraction of rare earth from useless fluorescent RE powder |
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| CN111485124A (en) * | 2020-04-13 | 2020-08-04 | 中稀(宜兴)稀土新材料有限公司 | High-purity europium oxide production process adopting linkage extraction |
| CN114507785A (en) * | 2021-11-04 | 2022-05-17 | 赣州齐畅新材料有限公司 | Treatment method for treating rare earth fluorescent powder by using caustic soda flakes |
| CN115072759A (en) * | 2022-05-05 | 2022-09-20 | 龙南京利有色金属有限责任公司 | Method for recovering high-purity europium oxide from rare earth fluorescent powder waste |
| CN114990366B (en) * | 2022-07-11 | 2023-03-21 | 重庆上甲电子股份有限公司 | Method for recycling rare earth elements by utilizing alkali fusion pretreatment waste fluorescent powder and fluxing agent |
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