CN104532006A - Method for extracting europium oxide and yttrium oxide from waste fluorescent powder - Google Patents
Method for extracting europium oxide and yttrium oxide from waste fluorescent powder Download PDFInfo
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Abstract
The invention discloses a method for extracting europium oxide and yttrium oxide from waste fluorescent powder, which mainly comprises the following seven steps: sodium carbonate roasting, chlorination leaching, phosphate precipitation, precipitation conversion, yttrium extraction separation, high-purity yttrium oxide extraction and high-purity europium oxide extraction, wherein the yttrium extraction separation is performed through a P507 extraction separation method to realize simplified efficient continuous separation of rare earth yttrium and europium, and the method is high in separation efficiency and low in cost. Compared with the prior art, the method has the advantages of short process flow, high rare earth element extraction rate, high rare earth product purity, low extraction cost and the like.
Description
Technical field
The present invention relates to a kind of extracting method of rare earth element, particularly relate to a kind of method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder, belong to waste material regeneration field.
Background technology
In televisor cathode tube (CRT) cutting process, panel glass there is a large amount of fluorescent material, containing rare earth metals such as europium (Eu), yttrium (Y), erbiums (Er) in this fluorescent material.If dealt with improperly, the metal complex in CRT fluorescent material and be mixed in the pollutents such as flint glass in fluorescent material and enter in soil, air and river, can cause serious problem.
Therefore, considering from environmental management and the utilization of resources, needing the fluorescent material in CRT through going appropriate recycling.
Recycling of WEEE more and more receives everybody concern, the electron wastes of nearly 1,000,000 tons is had to produce every year, and televisor accounts for wherein significant proportion, when processing televisor CRT, because televisor fluorescent material contains the zinc of the rare earth such as yttrium and europium and very high-content, focusing on after generally all collecting separately, is below the mixed compositions of various different televisor 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 containing rare earth element and zinc in fluorescent material, add containing cadmium and a small amount of barium, plumbous, the toxic element such as chromium, so the process of fluorescent material not only has economic benefit, also have very high social benefit simultaneously.
Rare earth element is as " industrial monosodium glutamate ", widely use in all trades and professions, and Extraction of rare earth causes serious environmental pollution and ecological damage from mineral, from secondary resource, Extraction of rare earth has the advantages such as cost is low, environmental protection, decrease raw ore exploitation simultaneously, have economic and social benefit.
But because Waste fluorescent powder mainly comprises red fluorescence powder (Y
2o
3: Eu and Y
2o
2, green emitting phosphor mainly silicate, borate S: Eu), phosphoric acid salt, and some oxide compounds, because rare earth element defines some ceramic phases, be stabilized in and be present in crystal, cause conventional method rare earth element extraction yield low, 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-weight rare earths, comprise the following steps: (1) gets cathodic ray-tube fluorescent powder, adding concentration is that the dilute sulphuric acid of 5%-15% dissolves, 0.5-2h is stirred at 85-90 DEG C of temperature, suction filtration, must containing the filtrate of rare earth ion; (2) get hydrofluoric acid solution and add the described filtrate containing rare earth ion, reaction generates rare earth fluorine, suction filtration separating filtrate, and rare earth fluorine remains in filter cake, washing leaching cake 1-5 time, must containing the filter cake of pure rare earth fluorine.
But, the method for above-mentioned recovery cathodic ray-tube fluorescent powder middle-weight rare earths, the rate of recovery of its main rare earth metal y and Eu respectively: 89% and 94.5%, the extraction yield of rare earth composition is not high.
Chinese patent application CN102660688B discloses a kind of method of Separation and Recovery rare earth from waste and old rare earth luminescent material, processing step is: the collection of waste and old rare earth luminescent material, comprises the quick identification of rare-earth fluorescent light and disassembles fragmentation, the fragmentation of CRT monitor, waste and old rare earth luminescent material and glass basis and peel off and collect; The pre-treatment of waste and old rare earth luminescent material, comprises demercuration oxidation precipitation, alkali fusion and acidolysis; The extracting and separating of rare earth element obtains rare earth chloride enriched substance; The purification by liquid extraction of rare earth element obtains high-purity rare-earth muriate; The precipitate and separate of rare earth element obtains rare earth oxalate or carbonated rare earth throw out; Rare earth oxalate or the roasting of carbonated rare earth throw out obtain high-purity grade of rare earth oxide.
But the method for this Separation and Recovery rare earth from waste and old rare earth luminescent material, exists technical process long, cost recovery is higher waits deficiency.
Summary of the invention
The object of this invention is to provide that a kind of technical process is short, rare earth element extraction yield is high, purity that is rare-earth products is high, and the method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder that cost recovery is low.
The technical scheme that the present invention is adopted for achieving the above object is, a kind of method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder, comprises the steps:
1) sodium carbonate roasting step: by weight ratio 0.5-1: 1 between solid-liquid, add liquid caustic soda in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water;
Be in the acid solution of 3 in pH value by the slag after washing, at 50-99 DEG C, carry out potassium cloride with chlorine, soluble chlorine hydrochlorate or solubility hypochlorite, again wash and leach liquor is separated with slag;
Described chlorine, oxymuriate or hypochlorite are that the ratio being 0.1-0.5 ︰ 1 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 1.1-2 ︰ 1, the phosphoric acid salt of solubility is added in above-mentioned leach liquor, temperature of reaction is controlled at 50-99 DEG C, pH value controls at 1.5-6.5, reaction times controls at 1-5 hour, obtains the calcium phosphate precipitation of rare earth;
4) step of converting is precipitated: be 1 ︰ 0.2-1.0 by weight, add the strong base solution that concentration is 1-5mol/l in the calcium phosphate precipitation of above-mentioned rare earth, control temperature of reaction is 50-99 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 0.5-5mol/l, control temperature of reaction is 50-99 DEG C, by the flow volume of lysate and P507 than 1 ︰ 2-5, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 50%-75% of P507, P507 with wash acid and the flow volume ratio of sour regurgitation is 1 ︰ 0.1-0.2 ︰ 0.1-0.2, the concentration of sour regurgitation is 1-6mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by the mol ratio 1 ︰ 4-8 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 50-99 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, add reductive agent, control reduction reaction temperature is 50-99 DEG C, and reduction reaction time 1-6 hour, obtains the europium ion of divalence;
After adding soluble sulphate again, obtain europous sulfate precipitation;
Above-mentioned europous sulfate precipitation is added salt of wormwood, sodium hydroxide or potassium oxalate and carries out precipitation conversion, obtain the throw out of the carbonate of divalent europium, oxyhydroxide or oxalate, then this throw out is calcined 1-6 hour at 500-900 DEG C, obtain high-purity mangesium oxide europium.
Be preferably, above-mentioned acid solution is one or more in sulphuric acid soln, hydrochloric acid soln, salpeter solution or acetum.
Further preferably, above-mentioned liquid caustic soda is one or more in liquid hydrogen sodium oxide, aqueous potassium hydroxide or liquid hydrogen barium oxide;
Described strong base solution is one or more in sodium hydroxide solution, potassium hydroxide solution or barium hydroxide solution.
Further preferably, above-mentioned reductive agent is zinc powder, aluminium powder, magnesium powder, oxammonium hydrochloride, hydrazine hydrate or xitix.
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 potassiumphosphate.Further preferably, above-mentioned soluble chlorine hydrochlorate is Potcrate, sodium chlorate or ammonium chlorate; Above-mentioned solubility hypochlorite is potassium hypochlorite, clorox or hypochlorous acid ammonium.。
The technique effect that technique scheme is directly brought is, by sodium carbonate roasting step, component zinc first in fluorescent material can be become the zincate of solubility, zinc be removed the taste that greatly can improve rare earth, reduce the difficulty of follow-up removal of impurities.
By potassium cloride step, the leaching yield of rare earth can be improved, reduce cost simultaneously.
Adopt phosphoric acid salt precipitating rare earth selectively, can further improve the taste of rare earth, other impurity are stayed in aqueous, comparatively pure earth solution is obtained by precipitation conversion-dissolving with hydrochloric acid, again through extracting and separating yttrium europium, the yttrium europium solution purity obtained is high, and cost is low simultaneously, can realize the serialization of producing.
In technique scheme, first Waste fluorescent powder is added the pre-treatment of liquid caustic soda granulation before roasting, instead of adopt alkaline solution to carry out pre-treatment, major cause is, adopt liquid caustic soda, both can realize fluorescent material fully to mix and granulating and forming with liquid caustic soda, too much the brought calorific loss of the additional moisture content of alkaline solution can have been avoided again, and then increase the energy consumption cost of calcining process.
In technique scheme, in potassium cloride step, by mass ratio (0.1-0.5 ︰ 1) and the extraction temperature (50-99 DEG C) of choose reasonable chlorine and Waste fluorescent powder, this main it is considered that, the mass ratio of chlorine and fluorescent material is too high, can waste chlorine, improve cost; The mass ratio of chlorine and fluorescent material is too low, and the leaching yield of rare earth will reduce greatly;
And extraction temperature is too low, the extraction yield of rare earth is low; Extraction temperature is too high, will cause the waste of heat energy, and then raises cost.
Similarly, the selection gist of the various process parameters in the calcium phosphate precipitation step of technique scheme, main it is considered that adopt soluble phosphate selective precipitation rare earth, precipitation temperature is too low, then sedimentation time is too short, precipitation process pH is too low, the mol ratio of phosphate radical and rare earth element is too low, and the deposition rate of rare earth is low, and production efficiency is low, otherwise then cost improves greatly.
In the precipitation step of converting of technique scheme, why adopt the strong base solutions such as sodium hydroxide solution, potassium hydroxide solution or barium hydroxide solution, reason is: adopt the strong base solutions such as sodium hydroxide, potassium hydroxide, hydrated barta to be used as precipitating transforming agent, the precipitation transformation efficiency of rare earth can be improved, to ensure the high-recovery of rare earth.
In the extracting and separating yttrium step of technique scheme, the selection gist of each processing parameter mainly, adopts dissolving with hydrochloric acid rare-earth hydroxide, can improve the dissolution rate of rare earth; Solvent 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 crucially, in technique scheme, by adopting P507 extraction separation method, achieve rare-earth yttrium and be separated with the summary high efficiency continuously of europium, its separation efficiency is high, cost is low.
In the extraction step of the high purity yttria of technique scheme, adopt ammonium bicarbonate precipitation yttrium, can improve the deposition rate of yttrium, reduce zinc, barium, the isoionic precipitation of calcium simultaneously, bicarbonate of ammonia is cheap simultaneously, and cost can reduce.
Again through lower calcining temperature (500-900 DEG C) calcining 1-6 hour, high purity yttria can be obtained.
In the extraction step of the high-purity mangesium oxide europium of technique scheme,
The reductive agents such as zinc powder, aluminium powder, magnesium powder, oxammonium hydrochloride or xitix are adopted trivalent europium to be reduced into divalent europium, sulfate radical precipitation divalent europium is adopted to obtain the europous sulfate being not dissolved in water, transform the carbonate, oxyhydroxide, the oxalate that obtain divalent europium through percarbonate, oxyhydroxide, oxalate precipitation, then obtain europium sesquioxide through calcining again.
To sum up, can find out, zinc, by adopting 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 removal of impurities, reduce cost by the present invention; By adopting calcium phosphate precipitation rare earth, alternative precipitating rare earth, the taste of further raising rare earth, simultaneously for the deep impurity-removing of follow-up rare earth does basis, take the series technique means such as extracting and separating, make final rare earth composition extraction yield up to more than 99.75%, the high purity more than 99.96% of the yttrium extracted, europium; Achieve the summary high efficiency separation of yttrium, europium rare earth simultaneously.
Technical process of the present invention is short, processing condition are relatively simple and easy to control, the less energy consumption of whole technological process, raw material be easy to obtain and with low cost.
In sum, the present invention, relative to prior art, has technical process short, and rare earth element extraction yield 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 process flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
As shown in Figure 1, the method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder of the present invention, comprises following 7 steps: 1) sodium carbonate roasting step, 2) potassium cloride step, 3) calcium phosphate precipitation step, 4) precipitation step of converting, 5) extracting and separating yttrium step, 6) extraction step, 7 of high purity yttria) extraction step of high-purity mangesium oxide europium.
Embodiment 1:
From Waste fluorescent powder, extract the method for europium sesquioxide and yttrium oxide, comprise following 7 steps:
1) sodium carbonate roasting step: by the weight ratio 0.75: 1 between solid-liquid, add liquid hydrogen sodium oxide in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water; Be in the hydrochloric acid soln of 3 in pH value by the slag after washing, at 85 DEG C, carry out potassium cloride with chlorine, again wash and leach liquor is separated with slag;
Described chlorine is that the ratio being 0.1 ︰ 1 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 1.1-2 ︰ 1, in above-mentioned leach liquor, add sodium phosphate, temperature of reaction controlled at 90 DEG C, pH value controls 6.5, reaction times controls, at 6 hours, to obtain the calcium phosphate precipitation of rare earth;
4) precipitate step of converting: be 1 ︰ 0.2 by weight, add the sodium hydroxide solution that concentration is 1mol/l in the calcium phosphate precipitation of above-mentioned rare earth, controlling temperature of reaction is 50 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 0.5-5mol/l, controlling temperature of reaction is 50 DEG C, by the flow volume of lysate and P507 than 1 ︰ 2, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 50%, P507 of P507 is 1 ︰ 0.1 ︰ 0.1 with the flow volume ratio washing acid and sour regurgitation, and the concentration of sour regurgitation is 1mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by mol ratio 1 ︰ 4 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 50 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, adds zinc powder as reductive agent, and controlling reduction reaction temperature is 50 DEG C, 6 hours reduction reaction time, obtains the europium ion of divalence;
After adding sodium sulfate again, obtain europous sulfate precipitation;
Above-mentioned europous sulfate precipitation is added salt of wormwood and carries out precipitation conversion, obtain the throw out of the carbonate of divalent europium, then this throw out is calcined 6 hours at 500 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction yield of final rare earth is 99.75%, and the purity of the yttrium oxide obtained is 99.98%, and the purity of the europium sesquioxide obtained is 99.97%.
Embodiment 2
From Waste fluorescent powder, extract the method for europium sesquioxide and yttrium oxide, comprise following 7 steps:
1) sodium carbonate roasting step: by the weight ratio 0.75: 1 between solid-liquid, add aqueous potassium hydroxide in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water;
Be in the sulphuric acid soln of 3 in pH value by the slag after washing, at 75 DEG C, carry out potassium cloride by sodium chlorate, again wash and leach liquor is separated with slag;
Described sodium chlorate is that the ratio being 0.2.5 ︰ 1 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 1.5 ︰ 1, in above-mentioned leach liquor, add ammonium phosphate, temperature of reaction controlled at 75 DEG C, pH value controls 3.5, reaction times controls, at 2.5 hours, to obtain the calcium phosphate precipitation of rare earth;
4) precipitate step of converting: be 1 ︰ 0.5 by weight, add the potassium hydroxide solution that concentration is 2.5mol/l in the calcium phosphate precipitation of above-mentioned rare earth, controlling temperature of reaction is 75 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 2.5mol/l, controlling temperature of reaction is 75 DEG C, by the flow volume of lysate and P507 than 1 ︰ 3.5, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 60%, P507 of P507 is 1 ︰ 0.15 ︰ 0.15 with the flow volume ratio washing acid and sour regurgitation, and the concentration of sour regurgitation is 3mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by mol ratio 1 ︰ 6 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 75 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, adds reductive agent aluminium powder, and controlling reduction reaction temperature is 75 DEG C, 3 hours reduction reaction time, obtains the europium ion of divalence;
After adding potassium sulfate again, obtain europous sulfate precipitation;
Above-mentioned europous sulfate precipitation is added sodium hydroxide and carries out precipitation conversion, obtain the throw out of the oxyhydroxide 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 yield of final rare earth is 99.75%, and the purity of the yttrium oxide obtained is 99.96%, and the purity of the europium sesquioxide obtained is 99.96%.
Embodiment 3
From Waste fluorescent powder, extract the method for europium sesquioxide and yttrium oxide, comprise following 7 steps:
1) sodium carbonate roasting step: by the weight ratio 0.85: 1 between solid-liquid, add liquid hydrogen barium oxide in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water;
Be in the acetum of 3 in pH value by the slag after washing, at 80 DEG C, carry out potassium cloride with clorox, again wash and leach liquor is separated with slag;
Described clorox is that the ratio being 0.35 ︰ 1 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 1.6 ︰ 1, in above-mentioned leach liquor, add potassiumphosphate, temperature of reaction controlled at 80 DEG C, pH value controls 3.5, reaction times controls, at 4 hours, to obtain the calcium phosphate precipitation of rare earth;
4) precipitate step of converting: be 1 ︰ 0.8 by weight, add the barium hydroxide solution that concentration is 3.5mol/l in the calcium phosphate precipitation of above-mentioned rare earth, controlling temperature of reaction is 80 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 3.5mol/l, controlling temperature of reaction is 80 DEG C, by the flow volume of lysate and P507 than 1 ︰ 4, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 65%, P507 of P507 is 1 ︰ 0.2 ︰ 0.2 with the flow volume ratio washing acid and sour regurgitation, and the concentration of sour regurgitation is 4mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by mol ratio 1 ︰ 7 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 80 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, adds magnesium powder as reductive agent, and controlling reduction reaction temperature is 80 DEG C, 4 hours reduction reaction time, obtains the europium ion of divalence;
After adding vitriol again, obtain europous sulfate precipitation;
Above-mentioned europous sulfate precipitation is added potassium oxalate and carries out precipitation conversion, obtain the throw out of the oxalate of divalent europium, then this throw out is calcined 2 hours at 800 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction yield of final rare earth is 99.78%, and the purity of the yttrium oxide obtained is 99.96%, and the purity of the europium sesquioxide obtained is 99.97%.
Embodiment 4
From Waste fluorescent powder, extract the method for europium sesquioxide and yttrium oxide, comprise following 7 steps:
1) sodium carbonate roasting step: by the weight ratio 1: 1 between solid-liquid, add aqueous potassium hydroxide in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water;
Be in the salpeter solution of 3 in pH value by the slag after washing, at 99 DEG C, carry out potassium cloride with potassium hypochlorite, again wash and leach liquor is separated with slag;
Described potassium hypochlorite is that the ratio being 0.5 ︰ 1 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 2 ︰ 1, in above-mentioned leach liquor, add ammonium phosphate, temperature of reaction controlled at 99 DEG C, pH value controls 1.5, reaction times controls, at 1 hour, to obtain the calcium phosphate precipitation of rare earth;
4) precipitate step of converting: be 1 ︰ 1 by weight, add the potassium hydroxide solution that concentration is 1mol/l in the calcium phosphate precipitation of above-mentioned rare earth, controlling temperature of reaction is 99 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 5mol/l, controlling temperature of reaction is 99 DEG C, by the flow volume of lysate and P507 than 1 ︰ 5, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 75%, P507 of P507 is 1 ︰ 0.2 ︰ 0.2 with the flow volume ratio washing acid and sour regurgitation, and the concentration of sour regurgitation is 6mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by mol ratio 1 ︰ 8 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 99 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, adds oxammonium hydrochloride as reductive agent, and controlling reduction reaction temperature is 99 DEG C, 6 hours reduction reaction time, obtains the europium ion of divalence;
After adding ammonium sulfate again, obtain europous sulfate precipitation;
Above-mentioned europous sulfate precipitation is successively added salt of wormwood and carries out precipitation conversion, obtain the throw out of the carbonate of divalent europium, oxyhydroxide 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 yield of final rare earth is 99.81%, and the purity of the yttrium oxide obtained is 99.98%, and the purity of the europium sesquioxide obtained is 99.97%.
Embodiment 5
1) sodium carbonate roasting step: by the weight ratio 1: 1 between solid-liquid, add liquid hydrogen sodium oxide in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water;
Be in the acid solution of 3 in pH value by the slag after washing, at 85 DEG C, carry out potassium cloride with the mixture of sodium chlorate and clorox, again wash and leach liquor is separated with slag;
The mixture of described sodium chlorate and clorox is that the ratio being 0.85 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 2 ︰ 1, in above-mentioned leach liquor, add potassiumphosphate, temperature of reaction controlled at 85 DEG C, pH value controls 4.5, reaction times controls, at 5 hours, to obtain the calcium phosphate precipitation of rare earth;
4) precipitate step of converting: be 1 ︰ 0.8 by weight, add the sodium hydroxide solution that concentration is 5mol/l in the calcium phosphate precipitation of above-mentioned rare earth, controlling temperature of reaction is 85 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 4.5mol/l, controlling temperature of reaction is 85 DEG C, by the flow volume of lysate and P507 than 1 ︰ 5, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 75%, P507 of P507 is 1 ︰ 0.2 ︰ 0.2 with the flow volume ratio washing acid and sour regurgitation, and the concentration of sour regurgitation is 6mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by mol ratio 1 ︰ 8 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 85 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, adds oxammonium hydrochloride as reductive agent, and controlling reduction reaction temperature is 85 DEG C, 3 hours reduction reaction time, obtains the europium ion of divalence;
After adding sodium sulfate again, obtain europous sulfate precipitation;
Above-mentioned europous sulfate precipitation is successively added sodium hydroxide and carries out precipitation conversion, obtain the throw out of the oxyhydroxide of divalent europium, then this throw out is calcined 5 hours at 850 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction yield of final rare earth is 99.81%, and the purity of the yttrium oxide obtained is 99.97%, and the purity of the europium sesquioxide obtained is 99.96%.
Embodiment 6
1) sodium carbonate roasting step: by the weight ratio 1: 1 between solid-liquid, add liquid hydrogen barium oxide in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water;
By the slag after washing be in the salpeter solution of 3 in pH value, at 80 DEG C, with the mixture of Potcrate and potassium hypochlorite, and pass into chlorine, carry out potassium cloride, again washing leach liquor is separated with slag;
The mixture of above-mentioned Potcrate and potassium hypochlorite, and pass into chlorine is that the ratio being 0.45 ︰ 1 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 1.1-2 ︰ 1, in above-mentioned leach liquor, add the potassiumphosphate of solubility, temperature of reaction controlled at 80 DEG C, pH value controls 5.5, reaction times controls, at 4 hours, to obtain the calcium phosphate precipitation of rare earth;
4) precipitate step of converting: be 1 ︰ 0.6 by weight, add the barium hydroxide solution that concentration is 4mol/l in the calcium phosphate precipitation of above-mentioned rare earth, controlling temperature of reaction is 80 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 4mol/l, controlling temperature of reaction is 80 DEG C, by the flow volume of lysate and P507 than 1 ︰ 4, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 70%, P507 of P507 is 1 ︰ 0.1 ︰ 0.1 with the flow volume ratio washing acid and sour regurgitation, and the concentration of sour regurgitation is 4.5mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by mol ratio 1 ︰ 6 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 80 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, adds aluminium powder as reductive agent, and control reduction reaction temperature is 50-99 DEG C, and reduction reaction time 1-6 hour, obtains the europium ion of divalence;
After adding ammonium sulfate again, 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 throw out is calcined 4 hours at 800 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction yield of final rare earth is 99.8%, and the purity of the yttrium oxide obtained is 99.97%, and the purity of the europium sesquioxide obtained is 99.97%.
Embodiment 7
1) sodium carbonate roasting step: by the weight ratio 0.6: 1 between solid-liquid, add the mixed solution of aqueous potassium hydroxide and liquid hydrogen sodium oxide in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water;
Be in the sulphuric acid soln of 3 in pH value by the slag after washing, at 65 DEG C, carry out potassium cloride with ammonium chlorate, again wash and leach liquor is separated with slag;
Described ammonium chlorate is that the ratio being 0.4 ︰ 1 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 1.8 ︰ 1, in above-mentioned leach liquor, add potassiumphosphate, temperature of reaction controlled at 65 DEG C, pH value controls 3.5, reaction times controls, at 3.5 hours, to obtain the calcium phosphate precipitation of rare earth;
4) precipitate step of converting: be 1 ︰ 0.8 by weight, in the calcium phosphate precipitation of above-mentioned rare earth, add concentration is the sodium hydroxide of 3.5mol/l and the mixing solutions of potassium hydroxide, controlling temperature of reaction is 65 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 3.5mol/l, controlling temperature of reaction is 65 DEG C, by the flow volume of lysate and P507 than 1 ︰ 4, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 65%, P507 of P507 is 1 ︰ 0.15 ︰ 0.15 with the flow volume ratio washing acid and sour regurgitation, and the concentration of sour regurgitation is 4mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by mol ratio 1 ︰ 7 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 65 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, adds hydrazine hydrate as reductive agent, and controlling reduction reaction temperature is 65 DEG C, 5 hours reduction reaction time, obtains the europium ion of divalence;
After adding sodium sulfate again, obtain europous sulfate precipitation;
Above-mentioned europous sulfate precipitation is successively added salt of wormwood and carries out precipitation conversion, obtain the carbonate sediment of divalent europium, then this throw out is calcined 4 hours at 850 DEG C, obtain high-purity mangesium oxide europium.
After testing, the extraction yield of final rare earth is 99.83%, and the purity of the yttrium oxide obtained is 99.97%, and the purity of the europium sesquioxide obtained is 99.97%.
Claims (7)
1. from Waste fluorescent powder, extract a method for europium sesquioxide and yttrium oxide, comprise the steps:
1) sodium carbonate roasting step: by weight ratio 0.5-1: 1 between solid-liquid, add liquid caustic soda in Waste fluorescent powder, the roasting of granulation fed to boiler;
2) potassium cloride step: by the material after roasting, wash with water;
Be in the acid solution of 3 in pH value by the slag after washing, at 50-99 DEG C, carry out potassium cloride with chlorine, soluble chlorine hydrochlorate or solubility hypochlorite, again wash and leach liquor is separated with slag;
Described chlorine, oxymuriate or hypochlorite are that the ratio being 0.1-0.5 ︰ 1 in the mass ratio of chlorine element and Waste fluorescent powder adds;
3) calcium phosphate precipitation step: the ratio in the mol ratio of phosphate radical and rare earth element being 1.1-2 ︰ 1, the phosphoric acid salt of solubility is added in above-mentioned leach liquor, temperature of reaction is controlled at 50-99 DEG C, pH value controls at 1.5-6.5, reaction times controls at 1-5 hour, obtains the calcium phosphate precipitation of rare earth;
4) step of converting is precipitated: be 1 ︰ 0.2-1.0 by weight, add the strong base solution that concentration is 1-5mol/l in the calcium phosphate precipitation of above-mentioned rare earth, control temperature of reaction is 50-99 DEG C, the oxyhydroxide of obtained rare earth;
5) extracting and separating yttrium step: the oxyhydroxide of above-mentioned rare earth being added concentration is after the dissolving with hydrochloric acid of 0.5-5mol/l, control temperature of reaction is 50-99 DEG C, by the flow volume of lysate and P507 than 1 ︰ 2-5, lysate enters P507 and extracts line, obtains pure yttrium chloride solution;
Wherein, the saponification degree 50%-75% of P507, P507 with wash acid and the flow volume ratio of sour regurgitation is 1 ︰ 0.1-0.2 ︰ 0.1-0.2, the concentration of sour regurgitation is 1-6mol/L;
6) extraction step of high purity yttria: in above-mentioned yttrium chloride solution, adds bicarbonate of ammonia by the mol ratio 1 ︰ 4-8 of Yttrium trichloride and bicarbonate of ammonia, temperature of reaction is controlled at 50-99 DEG C, obtains yttrium carbonate precipitation;
By this yttrium carbonate 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 extracting and separating yttrium, add reductive agent, control reduction reaction temperature is 50-99 DEG C, and reduction reaction time 1-6 hour, obtains the europium ion of divalence;
After adding soluble sulphate again, obtain europous sulfate precipitation;
Above-mentioned europous sulfate precipitation is added salt of wormwood, sodium hydroxide or potassium oxalate and carries out precipitation conversion, obtain the throw out of the carbonate of divalent europium, oxyhydroxide or oxalate, then this throw out is calcined 1-6 hour at 500-900 DEG C, obtain high-purity mangesium oxide europium.
2. the method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder according to claim 1, is characterized in that, described acid solution is one or more in sulphuric acid soln, hydrochloric acid soln, salpeter solution or acetum.
3. the method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder according to claim 1, is characterized in that, described liquid caustic soda is one or more in liquid hydrogen sodium oxide, aqueous potassium hydroxide or liquid hydrogen barium oxide;
Described strong base solution is one or more in sodium hydroxide solution, potassium hydroxide solution or barium hydroxide solution.
4. the method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder according to claim 1, is characterized in that, described reductive agent is zinc powder, aluminium powder, magnesium powder, oxammonium hydrochloride, hydrazine hydrate or xitix.
5. the method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder according to claim 1, is characterized in that, described soluble sulphate is sodium sulfate, potassium sulfate or ammonium sulfate.
6. the method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder according to claim 1, is characterized in that, described soluble phosphate is sodium phosphate, ammonium phosphate or potassiumphosphate.
7. the method extracting europium sesquioxide and yttrium oxide from Waste fluorescent powder according to claim 1, is characterized in that, described soluble chlorine hydrochlorate is Potcrate, sodium chlorate or ammonium chlorate;
Described solubility hypochlorite is potassium hypochlorite, clorox or hypochlorous acid ammonium.
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