CN107630143B - Method for extracting rare earth from rare earth fluorescent powder waste and fluorine-containing rare earth electrolysis waste residue - Google Patents

Abstract

The invention provides a method for extracting rare earth from rare earth fluorescent powder waste and fluorine-containing rare earth electrolysis waste residue. First, the rare earth fluorescent powder waste, fluorine-containing rare earth electrolysis waste residue and alkali are mixed, and then roasted; After washing with water and solid-liquid separation, the filter residue is acid-dissolved, and the pH value of the obtained acid-dissolved liquid is adjusted with alkaline solution, and the solid-liquid separation is performed to obtain a feed liquid of rare earth ions. During the roasting process of the present invention, the glass powder in the rare earth fluorescent powder waste reacts with the fluoride in the fluorine-containing rare earth electrolysis waste residue to generate rare earth silicate salt, which promotes the conversion of fluorine, thereby reducing the amount of alkali; Destroy the material structure in the phosphor to generate rare earth oxides and metaaluminates; combine with water washing to realize the dissolution of metaaluminate and fluoride salts in water, which in turn helps in the extraction of rare earths. The results of the examples show that the leaching rate of rare earth elements in the present invention reaches more than 98.5%, and the energy consumption is significantly reduced.

Description

A method for extracting rare earth from rare earth phosphor waste and fluorine-containing rare earth electrolysis waste method

technical field

The invention belongs to the technical field of resource recycling, and in particular relates to a method for extracting rare earth from rare earth fluorescent powder waste and fluorine-containing rare earth electrolysis waste residue.

Background technique

Rare earth is an important strategic resource of the country. Recycling rare earth from rare earth waste is of great significance to improve the utilization rate of rare earth resources and the sustainable development of rare earth industry. Common wastes used for rare earth recycling in the prior art include fluorine-containing rare earth electrolysis waste residues and waste luminescent materials.

As an important luminescent material, rare earth phosphors are widely used in plasma TVs, semiconductor lighting LEDs, rare earth fluorescent lamps, mobile phones and computers. These products are eventually discarded by consumers in the form of solid waste, and the random disposal or improper disposal of solid waste containing rare earth phosphors will result in a waste of rare earth resources.

When the rare earth fluoride molten salt system is used to produce rare earth metal, the solute is rare earth oxide, and the electrolyte is lithium fluoride or a mixture of lithium fluoride and barium fluoride. With the progress of production, various non-rare earth impurities are brought into the electrolytic cell: for example, when rare earth oxides are added, the impurities enter the electrolysis system; when the anode is replaced, non-rare earth impurities are also brought in, resulting in The continuous enrichment of non-rare earth elements makes the electrolyte no longer meet the needs of normal production. At this time, it is necessary to replace the new electrolyte, thus forming the fluorine-containing rare earth electrolysis waste residue. The content of rare earth in the waste residue is relatively high, and the content of rare earth is 10% to 80%, mainly in the form of rare earth fluoride and rare earth oxide.

There are mainly two methods for recovering rare earth from rare earth phosphor waste, acid-soluble and alkali-soluble. For example, Chinese patent CN 201210285746.2 discloses a method for decomposing waste rare earth luminescent materials by two-generation acid hydrolysis. Chinese patent CN200810029417.5 discloses a method for recovering rare earth elements from waste fluorescent lamps by means of alkali dissolution. However, in the rare earth recovery process of these two methods, the leaching rate of rare earth elements is not high, and the leaching rate is far from reaching 80%.

The common methods for recovering rare earth elements from fluorine-containing rare earth electrolysis waste residues mainly include concentrated sulfuric acid high temperature sintering method and alkali burning method, both of which have the problems of low rare earth leaching rate, single treatment object and high comprehensive energy consumption.

SUMMARY OF THE INVENTION

In view of this, the purpose of the present invention is to provide a method for extracting rare earth from rare earth phosphor waste and fluorine-containing rare earth electrolysis waste. When the rare earth is recovered by the method provided by the invention, the leaching rate of the rare earth is over 98.5%.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a method for extracting rare earth from rare earth phosphor waste and fluorine-containing rare earth electrolysis waste residue, comprising the following steps:

(1) after mixing rare earth phosphor waste, fluorine-containing rare earth electrolysis waste residue and alkali, roasting is carried out to obtain roasting material;

(2) the roasting material obtained in the step (1) is washed with water to obtain a roasting turbid liquid;

(3) solid-liquid separation is carried out with the roasting turbid liquid obtained in the step (2) to obtain a filter residue;

(4) acid-dissolving the filter residue obtained in the step (3) to obtain an acid-dissolving solution;

(5) After adjusting the pH value of the acid solution obtained in the step (4) with alkaline solution, carry out solid-liquid separation to obtain a feed liquid containing rare earth ions.

Preferably, in the step (1), the mass ratio of the rare earth phosphor waste waste, the fluorine-containing rare earth electrolysis waste residue and the alkali is 1:1:(0.6-1).

Preferably, in the step (1), the alkali includes one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.

Preferably, the roasting temperature in the step (1) is 500-800° C., and the roasting time is 1-5 h.

Preferably, the pH value of the calcined turbid solution obtained in the step (2) is 7-8.

Preferably, after the solid-liquid separation in the step (3), a filtrate is obtained, which further comprises: defluorination treatment of the filtrate with an acidic solution and lime milk.

Preferably, the acid dissolving in the step (4) includes: mixing the filter residue with concentrated hydrochloric acid and hydrogen peroxide.

Preferably, the mass ratio of the filter residue to the volume of concentrated hydrochloric acid is 1 t: (1.2-1.8) m ³ ; the concentration of the concentrated hydrochloric acid is 10 mol/L.

Preferably, the mass ratio of the filter residue to the volume of hydrogen peroxide is (15-20) t: 1 m ³ ; the mass percentage of the hydrogen peroxide is 30%.

The invention provides a method for extracting rare earth from rare earth fluorescent powder waste and fluorine-containing rare earth electrolysis waste residue. The obtained roasting material is washed with water, and the solid-liquid separation is performed to obtain a filter residue; then the filter residue is acid-dissolved, and the pH value of the obtained acid-dissolved solution is adjusted with an alkaline solution, and a feed liquid of rare earth ions is finally obtained after the solid-liquid separation. . During the roasting process of the present invention, the glass powder in the rare earth fluorescent powder waste reacts with the fluoride in the fluorine-containing rare earth electrolysis waste residue to generate rare earth silicate salt, which promotes the conversion of fluorine, thereby reducing the amount of alkali; Destroy the material structure in the phosphor to generate rare earth oxides and metaaluminates; combined with water washing, the soluble metaaluminate and fluoride salts in the roasting material are dissolved in water, which is helpful for the extraction of rare earths. The results of the examples show that the present invention can realize the extraction of rare earth elements, the leaching rate of rare earth elements reaches more than 98.5%, and the energy consumption is significantly reduced.

Description of drawings

The present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments.

FIG. 1 is a schematic flowchart of a method for extracting rare earth from rare earth phosphor waste and fluorine-containing rare earth electrolysis waste residue provided by the present invention.

Detailed ways

The invention provides a method for extracting rare earth from rare earth fluorescent powder waste and fluorine-containing rare earth electrolysis waste residue. The obtained roasting material is washed with water, and the filter residue is obtained by solid-liquid separation, and then the filter residue is acid-dissolved; after the pH value of the obtained acid-dissolved solution is adjusted with alkali solution, the solid-liquid separation is performed to obtain the feed liquid of rare earth ions.

During the roasting process of the present invention, the glass powder in the rare earth fluorescent powder waste reacts with the fluoride in the fluorine-containing rare earth electrolysis waste residue to generate rare earth silicate salt, which promotes the conversion of fluorine, thereby reducing the amount of alkali, and the alkali is at high temperature. The material structure in the phosphor is destroyed to form rare earth oxides and metaaluminates, etc.; rare earth fluorides react with alkali to obtain rare earth oxides, and the roasting material is mixed with water to realize the soluble metaaluminate and metaaluminate in the roasting material. After dissolving fluoride salts in water, a filter residue mainly including rare earth oxides, rare earth silicates and iron oxides is obtained, and then the filter residue is dissolved in hydrochloric acid, and then the pH value is adjusted to remove iron ions, thereby obtaining rare earth containing ionic feed. The results of the examples show that the method of the present invention can realize the extraction of rare earth elements, the extraction rate of rare earth elements reaches more than 98.5%, and the energy consumption is significantly reduced.

In the present invention, the rare earth fluorescent powder waste, the fluorine-containing rare earth electrolysis waste residue and the alkali are mixed, and then roasted to obtain the roasting material.

In the present invention, the rare earth phosphor waste includes glass powder and rare earth oxide; the present invention has no special requirements on the source of the rare earth phosphor waste, and the rare earth phosphor waste known to those skilled in the art can be used. In an embodiment of the present invention, the rare earth phosphor waste is specifically from a light-emitting panel, an ion TV display, a semiconductor lighting LED, a rare-earth fluorescent lamp, a mobile phone display or a computer display.

In the present invention, the fluorine-containing rare earth electrolysis waste residue includes rare earth oxides, rare earth fluorides, elemental iron, iron compounds and graphite powder. The present invention has no special requirements on the source of the fluorine-containing rare earth electrolytic waste residue, and can be known to those skilled in the art. The waste residue produced when the system produces rare earth metals.

The invention uses the rare earth phosphor waste and fluorine-containing rare earth electrolysis waste as raw materials, the glass powder in the rare earth phosphor waste, the rare earth fluoride and alkali in the fluorine-containing rare earth electrolysis waste will react during roasting, and some impurities will be changed into It can be converted into a soluble salt, which promotes the subsequent leaching of rare earth ions, and realizes the recycling of waste; and avoids the need to use a large amount of alkaline substances when recycling rare earth phosphor waste or fluorine-containing rare earth electrolysis waste separately. Reduce processes and reduce energy consumption.

In the present invention, the base is a solid base, preferably including one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.

In the present invention, the mass ratio of the rare earth phosphor waste, the fluorine-containing rare earth electrolysis waste residue and the alkali is preferably 1:1:(0.6-1). The present invention has no special requirements on the mixing method of the rare earth phosphor waste, the fluorine-containing rare earth electrolytic waste residue and the alkali, and a solid-phase material mixing method known to those skilled in the art can be used.

After completing the mixing, the present invention calcines the obtained mixture to obtain a calcined material. In the present invention, the roasting temperature is preferably 500-800°C, more preferably 520-780°C, more preferably 580-720°C, most preferably 620-680°C; the roasting time is preferably 1～780°C 5h, more preferably 1.2 to 4.8h, more preferably 1.8 to 4.2h, more preferably 2.2 to 3.2h.

In the present invention, the main reactions in the roasting process are as follows: the glass powder in the rare earth fluorescent powder waste reacts with alkali to promote the reaction of silica in the rare earth fluorescent powder waste to obtain silicate, and the generated silicate reacts with the rare earth fluorescent powder. The silicate in the powder waste reacts with the rare earth fluoride to obtain the rare earth silicate and the fluoride salt; the rare earth fluoride reacts with the alkali to obtain the rare earth oxide and fluoride; the luminescent material in the rare earth phosphor reacts with the alkali to form the rare earth oxide compounds and meta-aluminates, etc. The invention uses rare earth phosphor waste and fluorine-containing rare earth electrolysis waste as raw materials for rare earth recovery, realizes compound decomposition, and improves the recovery efficiency of rare earth. When taking alkali as NaOH, the reaction that takes place in the roasting process is described:

The reaction between fluorine-containing rare earth electrolysis waste residue and alkali is as follows:

Na ₂ SiO ₃ ·CaSiO ₃ ·XSiO ₂ (glass)+x NaOH=(x+1)Na ₂ SiO ₃ ·CaSiO ₃ ;

2REF ₃ +3Na ₂ SiO ₃ =RE ₂ (SiO ₃ ) ₃ +6NaF;

2REF3+6NaOH _{= RE2O3 + 6NaF3} + _H2O .

When the rare earth phosphor waste is terbium activated green powder phosphor waste, the reaction between the rare earth phosphor waste and the alkali is 2MgAl ₁₁ O ₁₉ ·Tb ₂ O ₃ +22NaOH=2MgO+Tb ₂ O ₃ +22NaAlO ₂ +11H ₂ O. The Tb ₂ O ₃ and Ce ₂ O ₃ obtained by the reaction are easily oxidized to Tb ₄ O ₇ and CeO ₂ by oxygen in the air during the calcination.

After completing the calcination, the present invention washes the obtained calcined material with water to obtain a calcined cloudy liquid.

In the present invention, before the water washing, it is preferable to further include: pulverizing the calcined material; the particle size of the pulverized calcined material is 100-200 mesh. The present invention has no special requirements for the pulverizing method, as long as the calcined material with the target particle size can be obtained. In the present invention, the pulverization contributes to the dissolution of the soluble matter in the calcined material during the water washing process.

The present invention has no special requirements for the water washing method, and the material water washing method well known to those skilled in the art can be used. In the present invention, the washing with water preferably includes: mixing the calcined material with clean water to realize the dissolution of soluble fluoride salts, meta-aluminates, silicates and remaining alkalis in the calcined material in water. In the present invention, the number of times of washing with water is preferably 3 to 5 times; when washing with water for multiple times, the present invention preferably mixes the calcined material with clean water, and then performs solid-liquid separation to obtain insoluble solid rare earth oxides; The described insoluble solids are mixed with clear water, washed again, and repeated; the present invention monitors the pH value of the obtained washing mixture in real time, and when the pH value of the washing mixture reaches 7 to 8, the washing is stopped to obtain roasting. turbid liquid.

After obtaining the calcined cloudy liquid, the present invention performs solid-liquid separation on the obtained calcined cloudy liquid to obtain a filter residue. The present invention has no special requirements on the method of solid-liquid separation, and a solid-liquid separation method known to those skilled in the art can be adopted; in the embodiment of the present invention, the method of solid-liquid separation is specifically pressing. In the present invention, the filter residue preferably includes oxides of rare earth oxides, rare earth silicates, graphite powder, silica and iron.

After the solid-liquid separation, in the present invention, the obtained filter residue is acid-dissolved to obtain an acid-dissolved solution. In the present invention, the acid dissolving preferably comprises: mixing the filter residue with concentrated hydrochloric acid and hydrogen peroxide. In the present invention, the mixing is preferably performed under stirring conditions, and the stirring temperature is preferably 70-90° C., more preferably 72-78° C., and more preferably 75° C. The stirring time is preferably 1～90° C. 2h, more preferably 1.2 to 1.5h. In the present invention, the hydrogen peroxide helps to promote the dissolution of the filter residue when the acid is dissolved. In the present invention, the mixing of the filter residue with concentrated hydrochloric acid and hydrogen peroxide is preferably as follows: the filter residue and concentrated hydrochloric acid are mixed, stirred for 1 hour, and then mixed with hydrogen peroxide.

In the present invention, the main equation for the reaction between hydrochloric acid and rare earth oxides, rare earth silicates and iron oxides in the filter residue in the acid dissolution process is: RE ₂ O ₃ +6H ⁺ =2RE ³⁺ +3H ₂ O, RE ₂ (SiO ₃ ) ₃ +6H ⁺ =2RE ³⁺ +3H ₂ SiO ₃ and Fe ₂ O ₃ +6H ⁺ =2Fe ³⁺ +3H ₂ O. In the present invention, the mass ratio of the filter residue to the volume of concentrated hydrochloric acid is preferably 1t:(1.2～1.8)m ³ , more preferably 1t:1.5m ³ ; the concentration of the concentrated hydrochloric acid is preferably 10mol/L. The present invention adopts high-concentration hydrochloric acid to avoid introducing a large amount of water, thereby increasing the concentration of rare earth ions in the subsequent feed liquid containing rare earth ions.

In the present invention, the mass ratio of the filter residue and the volume of hydrogen peroxide is preferably (15-25)t:1m ³ , more preferably 20t:1m ³ ; the mass percentage of the hydrogen peroxide is 30%. The present invention adopts high-concentration hydrogen peroxide to avoid introducing a large amount of water, thereby increasing the concentration of rare earth ions in the subsequent feed liquid containing rare earth ions. In the present invention, the hydrogen peroxide helps to dissolve insoluble ceria and terbium oxide, such as 2CeO ₂ +H ₂ O ₂ +6H ⁺ =2Ce ³⁺ +4H ₂ O+O ₂ .

In the present invention, the filtrate is obtained after the solid-liquid separation of the roasted turbid liquid, and further comprises: defluorination treatment of the filtrate with an acidic solution and lime milk. In the present invention, the milk of lime can react with fluoride ions in the filtrate under the action of the acidic solution to adjust the pH value of the filtrate to generate calcium fluoride precipitation, which is removed from the filtrate to avoid pollution when the filtrate is discharged , to achieve harmless discharge. The present invention has no special requirements on the source and consumption of the acidic solution and lime milk, so long as the pH value of the filtrate reaches about 7 and meets the environmental protection discharge standard.

After the acid dissolving, the present invention adopts the alkaline solution to adjust the pH value of the acid dissolving solution, and then performs solid-liquid separation to obtain a feed solution containing rare earth ions. In the present invention, the pH value of the acid dissolving solution after the pH value adjustment is preferably 3.5. In the present invention, the alkali solution is preferably sodium hydroxide solution or sodium carbonate solution or the like. The present invention has no special requirements on the amount of the alkali solution, so long as the pH value of the slag solution can be adjusted to the target range. In the present invention, the adjustment of the pH value can make the iron ions form iron hydroxide precipitates, and then separate from the rare earth ions, thereby improving the purity in the rare earth recovery process.

After the pH adjustment, the present invention preferably performs solid-liquid separation on the pH adjusted feed liquid to obtain a rare earth ion-containing feed liquid. The present invention has no special requirements for the specific implementation of the solid-liquid separation, and a method well known to those skilled in the art can be used.

After the rare earth ion-containing feed liquid is obtained, the present invention preferably extracts and separates the rare earth ion-containing feed liquid to obtain a rare earth metal-containing solid. The present invention has no special requirements on the method of extraction and separation, and the method of extraction and separation well known to those skilled in the art can be adopted.

The method for extracting rare earth from rare earth phosphor waste and fluorine-containing rare earth electrolysis waste provided by the present invention will be described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present invention.

Example 1

Provide 100Kg of phosphor waste, which contains 27.2Kg of rare earth REO (mainly contains 7.35% of cerium, 5.94% of europium, 3.70% of terbium, 81.39% of yttrium) and 25.8Kg of aluminum oxide. 100Kg of rare earth molten salt waste slag, which contains 42.3Kg of rare earth REO (which mainly contains 16.06% of praseodymium and 82.14% of neodymium) and 17.6Kg of fluorine.

According to the flow chart shown in FIG. 1 , the rare earth phosphor waste and the fluorine-containing rare earth electrolysis waste residue are extracted from rare earth. The rare earth phosphor waste, the fluorine-containing rare earth electrolysis waste and the sodium hydroxide are uniformly mixed in a mass ratio of 1:1:0.6. It was calcined at 500° C. for 2 hours and cooled to obtain a lumpy calcined material which was crushed to 200 mesh with a Raymond machine.

Put the burning material in the washing bucket, add about 2 tons of water to the washing bucket and wash it three times until the pH value is about 7, press and separate, and obtain about 186Kg of filter residue. Wash the slag with about 0.27 cubic meters of concentrated hydrochloric acid with a concentration of 10 mol/L in an acid-dissolving bucket, stir at 80 ° C for 2 hours, add 10 L of hydrogen peroxide while stirring, and then adjust the pH value to 3.5 with lye, then press and separate. , to obtain rare earth chloride feed liquid.

The dissolution rate of rare earth in the obtained feed liquid is measured, and the dissolution rate of rare earth can be obtained as 98.54%, among which the dissolution rate of insoluble cerium is 78.2% and that of terbium is 80.1%.

The filtrate obtained after washing with water is subjected to defluorination treatment: lime milk and acid solution are added to the filtrate to remove fluorine in the form of calcium fluoride precipitation, so as to avoid the harm of the discharged filtrate to the environment.

Example 2

Provide 100Kg of phosphor waste, which contains 27.2Kg of rare earth REO (mainly contains 7.35% of cerium, 5.94% of europium, 3.70% of terbium, 81.39% of yttrium) and 25.8Kg of aluminum. 100Kg of rare earth molten salt waste slag, which contains 42.3Kg of rare earth REO (mainly contains 16.06% of praseodymium and 82.14% of neodymium) and 17.6Kg of fluorine.

The rare earth phosphor waste, the fluorine-containing rare earth electrolysis waste and the sodium hydroxide are uniformly mixed in a mass ratio of 1:1:1. It was calcined at 800° C. for 4 hours, and cooled to obtain a lumpy calcined material, which was crushed to 200 mesh with a Raymond machine.

Put the burning material in the washing bucket, add about 2 tons of water to the washing bucket and wash it three times until the pH value is about 7, press and separate, and obtain about 179Kg of filter residue. Wash the slag in an acid-dissolving bucket with about 0.27 cubic meters of concentrated hydrochloric acid with a concentration of 10 mol/L, and stir at 90 ° C for 2 hours, add 10 L of hydrogen peroxide while stirring, and then adjust the pH value to 3.5 with lye, then press and separate. , to obtain rare earth chloride feed liquid.

The dissolution rate of rare earth in the obtained feed liquid is measured, and the dissolution rate of rare earth can be obtained as 99.24%, among which the dissolution rate of insoluble cerium is 84.1% and that of terbium is 89.2%.

The filtrate obtained after washing with water is subjected to defluorination treatment: lime milk and acid solution are added to the filtrate to remove fluorine in the form of calcium fluoride precipitation, so as to avoid the harm of the discharged filtrate to the environment.

Example 3

Provide 100Kg of phosphor waste, which contains 22.4Kg of rare earth REO (mainly contains 8.26% of cerium, 7.34% of europium, 4.00% of terbium, 79.30% of yttrium) and 25.8Kg of aluminum. The rare earth molten salt waste slag is 100Kg, which contains 47.5Kg of rare earth REO (mainly contains 16.06% of praseodymium and 82.14% of neodymium) and 21.23Kg of fluorine.

The rare earth phosphor waste, the fluorine-containing rare earth electrolysis waste and the sodium hydroxide are uniformly mixed in a mass ratio of 1:1:0.8. It was calcined at 700° C. for 3 hours and cooled to obtain a lumpy calcined material which was crushed to 200 mesh with a Raymond machine.

Put the burning material in a water washing bucket, add about 2 tons of water to the water washing bucket and wash it three times until the pH value is about 7, press and separate, and obtain about 193Kg of filter residue. Wash the residue with about 0.28 cubic meters of concentrated hydrochloric acid with a concentration of 10 mol/L in an acid-dissolving bucket, stir at 90 ° C for 2 hours, add 10Kg of hydrogen peroxide while stirring, and then adjust the pH value to 3.5 with lye, then press and separate. , to obtain rare earth chloride feed liquid.

The dissolution rate of rare earth in the obtained feed solution was measured, and the dissolution rate of rare earth was 98.97%, among which the dissolution rate of insoluble cerium was 82.1% and that of terbium was 88.3%.

The filtrate obtained after washing with water is subjected to defluorination treatment: lime milk and acid solution are added to the filtrate to remove fluorine in the form of calcium fluoride precipitation, so as to avoid the harm of the discharged filtrate to the environment.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (6)

1. a kind of method of the Extraction of rare earth from rare earth phosphor waste material and fluorine-containing Rare Earth Electrolysis waste residue, comprising the following steps:

(1) it after mixing rare earth phosphor waste material, fluorine-containing Rare Earth Electrolysis waste residue and alkali, is roasted, obtains roasting material；The step Suddenly the mass ratio of rare earth phosphor waste material, fluorine-containing Rare Earth Electrolysis waste residue and alkali is 1:1:(0.6~1 in (1))；

(2) roasting material obtained to the step (1) is washed, and obtains roasting turbid；

(3) the roasting turbid that the step (2) obtains is separated by solid-liquid separation, obtains filter residue；

(4) filter residue for obtaining the step (3) carries out sour molten, obtains acid dissoluting liquid；

(5) it after carrying out pH value adjusting to the acid dissoluting liquid that the step (4) obtains using lye, is separated by solid-liquid separation, is contained The feed liquid of rare earth ion；

In the step (4) acid it is molten include: to mix the filter residue with concentrated hydrochloric acid and hydrogen peroxide；The quality of the filter residue and The volume ratio of hydrogen peroxide is (15~25) t:1m³；The mass percentage of the hydrogen peroxide is 30%；

It include glass powder and rare earth oxide in the rare earth phosphor waste material；Contain cerium and terbium in the rare earth oxide；

It include the compound and graphite of rare earth oxide, rare earth fluoride, iron simple substance, iron in the fluorine-containing Rare Earth Electrolysis waste residue Powder.

2. the method according to claim 1, wherein alkali includes sodium hydroxide, potassium hydroxide in the step (1) With one of sodium carbonate or a variety of.

3. the method according to claim 1, wherein the step (1) in roast temperature be 500~800 DEG C, The time of the roasting is 1~5h.

4. the method according to claim 1, wherein the pH value for the roasting turbid that the step (2) obtains be 7~ 8。

5. the method according to claim 1, wherein also obtaining filtrate after the separation of solid and liquid of the step (3), also It include: that fluorine removal processing is carried out to the filtrate using acid solution and milk of lime.

6. the method according to claim 1, wherein the quality of the filter residue and the volume ratio of concentrated hydrochloric acid are 1t: (1.2~1.8) m³；The concentration of the concentrated hydrochloric acid is 10mol/L.