Abstract:
The invention belongs to the field of recycling of resources, in particular to a method for waste rare earth luminescent material by dual hydrochloric acid. First hydrochloric acid was used to dissolve the red phosphor powder (Y 2 O 3 :Eu) priority, and yttrium-rich rare earth chloride solution and residue were obtained after filtered. Residue&#39;s major components were green and blue phosphor powder, and the removal of Ca 2+  in filtrate was conducted by using Na 2 SO 4 , and CaSO 4  precipitation separation was conducted to get rich rare earth chloride solution, europium and yttrium. Residue was mixed with alkali to perform alkaline fusion at high temperature to decompose green and blue powder, then sodium aluminate, magnesium, barium and rare earth oxides were obtained. Alkaline fusion products were washed with water, and filtered, and then sodium aluminate solution and residues containing rare earth oxides were obtained.

Description:
FIELD OF THE INVENTION 
       [0001]    The present invention pertains to resource recycling field, particularly relates to a method for waste rare earth luminescent material by dual hydrochloric acid dissolution. 
       BACKGROUND 
       [0002]    For the recovery of waste rare earth luminescent materials, in order to obtain a high recovery rate, for the blue, green phosphor in rare earth luminescent materials were aluminum and magnesium salts, the method of direct acid hydrolysis failed to leach REE effectively, which greatly affect the recovery of rare earth recycling, development of industrial and result in a waste of valuable rare earth resources. 
         [0003]    Currently, the Chinese patent (application number: 200810029417.5) discloses a method of recover rare earth element from waste fluorescent light. With alkaline fusion, the waste rare earth phosphor was directly mixed with alkali and roasted. After blue and green phosphors were decomposed, acid hydrolysis and extraction were conducted for recycling. This approach allows the leaching rate of the rare earth is improved, but a large number of unnecessary energy losses is caused due to the alkali consumption and recovery method, while the non-rare earth elements such as Ca, Mg, Ba, etc., are not reasonably separated from rare earth element, resulting in low efficiency of extraction solvent afterwards. Through this patented method, Y, Eu, Tb and Y were leached efficiently step by step, and were preliminarily separated and enriched. 
         [0004]    Compared with the prior art, the advantages of dual hydrochloric in the present invention is that: (1) higher rare earth extraction efficiency; (2) the non-rare earth elements and rare earth elements are effectively separated, at the same time preliminary separation and enrichment among are achieved REE, and the method is simple and easy to control, reducing the extraction pressure on later; (3) energy saving effect is obvious, reducing more than 50% alkali and post-extraction drug consumption, which can greatly reduce the recovery cost. 
       Contents 
       [0005]    The invention aims to provide a more efficient and more energy-efficient method for waste rare earth luminescent materials, which is dual hydrochloric acid dissolution. 
         [0000]    First hydrochloric acid was used to dissolve the red phosphor powder (Y 2 O 3 : Eu) priority, and yttrium-rich rare earth chloride solution and residue obtain after being filtered. Residue&#39;s major components were green and blue phosphor powder, and the removal of Ca 2+  in filtrate was conducted by using Na 2 SO 4 , and CaSO 4  precipitation separation was conducted to get rich rare earth chloride solution, europium and yttrium. Residue was mixed with alkali to perform alkaline fusion at high temperature to decompose green and blue powder, then sodium aluminate, magnesium, barium and rare earth oxides were obtained. Alkaline fusion products were washed with water, and filtered, and then sodium aluminate solution and residues containing rare earth oxides were obtained. After using secondary hydrochloric acid solution, Na 2 SO 4  was used to remove Mg 2+  and Ba 2+ , and MgSO 4  and BaSO 4  precipitate was separated to get europium, terbium and cerium rare earth chloride solution. 
         [0006]    The principles of the present invention can be described as the below chemical reactions. 
         [0007]    Red phosphor acid dissolution: 
         [0000]      Y 2 O 3 :Eu+HCl→→YCl 3 +EuCl 3 +H 2 O
 
         [0008]    calcium, magnesium, barium removing reactions: 
         [0000]      Ca 2+ +SO 4   2− →CaSO 4  
 
         [0000]      Mg 2+ +SO 4   2− →MgSO 4  
 
         [0000]      Ba 2+ +SO 4   2− →BaSO 4  
 
         [0009]    Blue phosphor alkaline fusion: 
         [0000]      Ce 0.67 Tb 0.33 MgAl 11 O 10 +NaOH→NaAlO 2 +MgO+CeO 2 +Tb 2 O 3  
 
         [0010]    Green phosphor alkaline fusion: 
         [0000]      BaMgAl 10 O 17 :Eu+NaOH→NaAlO 2 +MgO+BaCO 3 +Eu 2 O 3  
 
         [0000]      CeO 2 +HCl→CeCl 4 +H 2 O
 
         [0000]      Tb 2 O 3 +HCl→TbCl 3 +H 2 O
 
         [0011]    The method of the present invention comprises the following steps of: 
         [0012]    1. A method for waste rare earth luminescent material by dual hydrochloric acid dissolution, characterized by comprising the steps of: 
         [0013]    (1) First acid dissolution was performed for waste rare earth luminescent material with HCL solution was used firstly to dissolve the red phosphor powder (Y 2 O 3 :Eu) contained in waste rare earth luminescent material, after filtering, rare earth chloride solution and residue was obtained; 
         [0014]    (2) Na 2 SO 4  was added to rare earth filtrate, Ca 2+  was transformed to CaSO 4  precipitation for recycling, and the obtained rich rare earth yttrium-europium filtrate was continued to be extracted, separated and purified successively to obtain high purity rare earth products; 
         [0015]    The residue was mixed with alkali for alkaline fusion at high temperature: residues and alkali was uniformly mixed under mass mixing ratio of 1:1 to 1:4, and the alkali was one or a few sorts of NaOH and KOH, alkaline fusion was performed at 400˜800° C. for 1˜8 h, and alkaline fusion products were obtained; 
         [0016]    (3) The alkaline fusion products were washed with deionized water for 5 to 8 times, mass ratio of the deionized water and the alkaline fusion products is 10:1, after that, rare earth-containing washed subjects and cleaning solution containing NaAlO 2  were obtained by solid-liquid separating, to achieve the efficient separation of REE and non-REE Al; 
         [0017]    (4) Secondary acid dissolution was performed by dissolving the washing of step (3) with HCl solution, after that, secondary residue and secondary filtrate were obtained; for improving overall recovery of rare earth, the secondary residue was processed again by alkaline fusion technology; 
         [0018]    After adding Na 2 SO 4  to the secondary filtrate, impurity ions Mg 2+ , Ba 2+  were removed, and terbium Tb, cerium Ce enrichment liquid was obtained, which would be extracted, separated and purified successively to obtain high-purity rare earth products. 
         [0019]    Further, in the step (1), the concentration of HCl solution mentioned is 3˜10 mol/L, and the solid-liquid mass ratio (the waste rare earth luminescent material to the HCl solution) is 1:3 to 1:10, and the mixture was acid hydrolyzed and stirred for at 20˜80° C. for 1˜10 h to get rare earth filtrate. 
         [0020]    Further, the concentration of Na 2 SO 4  mentioned in step (2) is 0.5 to 2 mol/L. 
         [0021]    Further, the concentration of HCl solution mentioned in step (4) is 3˜10 mol/L, the mixture of washed subjects and acid dissolution was stirred at 20˜80° C. for 1˜10 h, where the solid-liquid mass ratio of washed subjects to HCl solution was 1:10˜1:20, and the secondary filtrate and the secondary residue were obtained. 
         [0022]    Further, the concentration of Na 2 SO 4  mentioned step in (4) is 0.5 to 2 mol/L. 
         [0023]    To ensure the decomposition of waste rare earth luminescent materials and improve the rare earth recovery rate, this invention of dual hydrochloric acid dissolution method, firstly the contained red phosphor was dissolved, and then blue and green phosphor were dissolved by alkaline fusion, finally secondary acid dissolution was performed. This method effectively improved the decomposition rate of waste rare earth luminescent materials, further increased the rare earth leaching rate, and Ca, Al, Mg, Ba impurity elements and REE were separated effectively, the simple separation and enrichment between rare earths were achieved. Ultimately, less rich europium and yttrium filtrate and terbium Tb, cerium Ce enrichment liquid was obtained. 
         [0024]    The invention reduced the amount of caustic alkali in alkaline fusion and rare earth chloride extraction greatly and relieve the pressure of separation and purification on later and the energy saving effect is remarkable, at the same time this method shares low production cost. 
     
    
     
       BRIEF DESCRIPTION 
         [0025]      FIG. 1  is the flow chart of the present invention. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0026]    With reference to embodiments below, the present invention will be further described, but the present invention is not limited to the following examples. 
       Example 1 
       [0027]    Using HCl solution of 3 mol/L to dissolve waste rare earth luminescent material, in which the solid-liquid ratio was 1:10, the mixture was acid hydrolyzed and stirred for 3 h at 60° C. before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 0.5 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 94.04% of total rare earths, europium Eu accounted for 5.14% of total rare earths. After HCl solution preferentially dissolved the residue, residue and NaOH were evenly mixed as the mass ratio of residue to NaOH of 1 to 4, and alkaline fusion was performed at 500° C. for 6 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 7 mol/L, acid solution of waste rare earth luminescent materials was stirred for 4 h at 70° C., in which the solid-liquid ratio is 1:10, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount Na 2 SO 4 , concentration of 1 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium content accounted for 49.78% of the total rare earth, terbium Tb content accounted for 29.83% of the total rare earths, yttrium Y content accounted for 10.34% of the total rare earths, Eu content accounted for 5.61% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 93.6%, in which yttrium Y leaching rate was 99.1%, europium Eu leaching rate was 98.4%, cerium Ce leaching rate was 74.1%, terbium Tb leaching rate was 70.3%. 
       Example 2 
       [0028]    Using HCl solution of 4 mol/L to dissolve waste luminescent material, in which a solid-liquid ratio was 1:9, the mixture was acid hydrolyzed and stirred for 4 h at 70° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 1 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 93.38% of total rare earths, europium Eu accounted for 5.02% of total rare earths. After HCl solution preferentially dissolved the residue, residue and KOH were evenly mixed as the mass ratio of residue to KOH of 1 to 3, and alkaline fusion was performed at 600° C. for 7 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 8 mol/L, acid solution of waste rare earth luminescent materials was stirred for 5 h at 80° C., in which the solid-liquid ratio is 1:12, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount Na 2 SO 4 , concentration of 1.5 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba) SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium content accounted for 48.46% of the total rare earths, terbium Tb content accounted for 29.43% of the total rare earths, yttrium Y content accounted for 10.67% of the total rare earths, Eu content accounted for 5.26% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 93.6%, in which yttrium Y leaching rate was 99.1%, europium Eu leaching rate was 98.4%, cerium Ce leaching rate was 74.1%, terbium Tb leaching rate was 70.3%. 
       Example 3 
       [0029]    Using HCl solution of 5 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:8, the mixture was acid hydrolyzed and stirred for 5 h at 80° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 1.5 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 92.98% of total rare earths, europium Eu accounted for 5.08% of total rare earths. After HCl solution preferentially dissolved the residue, residue and NaOH were evenly mixed as the mass ratio of residue to NaOH of 1 to 2, and alkaline fusion was performed at 700° C. for 8 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 9 mol/L, solution of waste rare earth luminescent materials was stirred for 6 h at 20° C. in which the solid-liquid ratio is 1:14, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 2 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium content accounted for 48.74% of the total rare earths, terbium Tb content accounted for 28.94% of the total rare earths, yttrium Y content accounted for 10.56% of the total rare earths, Eu content accounted for 5.48% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate is 94.0%, in which yttrium Y leaching was 99.2%, europium Eu leaching rate was 98.1%, cerium Ce leaching rate was 73.2%, terbium Tb leaching rate was 71.6%. 
       Example 4 
       [0030]    Using HCl solution of 6 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:7, the mixture was acid hydrolyzed and stirred for 6 h at 20° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 2 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 94.32% of total rare earths, europium Eu accounted for 5.21% of total rare earths. After HCl solution preferentially dissolved the residue, residue and NaOH were evenly mixed as the mass ratio of residue to NaOH of 1 to 1, and alkaline fusion was performed at 800° C. for 1 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 10 mol/L, acid solution of waste rare earth luminescent materials was stirred for 7 h at 30° C. in which the solid-liquid ratio of 1:16, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 0.5 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 49.54% of the total rare earths, terbium Tb content accounted for 29.43% of the total rare earths, yttrium Y content accounted for 10.16% of the total rare earths, Eu content accounted for 5.40% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 91.7%, in which yttrium Y leaching was 96.8%, europium Eu leaching rate was 96.1%, cerium Ce leaching rate was 70.5%, terbium Tb leaching rate was 71.3%. 
       Example 5 
       [0031]    Using HCl solution of 7 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:6, the mixture was acid hydrolyzed and stirred for 7 h at 30° C. before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 0.5 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 92.14% of total rare earths, europium Eu accounted for 4.96% of total rare earths. After HCl solution preferentially dissolved the residue, residue and KOH were evenly mixed as the mass ratio of residue to KOH of 1 to 4, and alkaline fusion was performed at 400° C. for 2 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 3 mol/L, acid solution of waste rare earth luminescent materials was stirred for 8 h at 40° C. in which the solid liquid was 1:18, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 1 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 47.35% of the total rare earths, terbium Tb content accounted for 29.45% of the total rare earths, yttrium Y content accounted for 10.46% of the total rare earths, Eu content accounted for 5.24% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 93.1%, in which yttrium Y leaching rate was 98.3%, europium Eu leaching rate was 97.6%, cerium Ce leaching rate was 73.5%, terbium Tb leaching rate was 70.1%. 
       Example 6 
       [0032]    Using HCl solution of 8 mol/L to dissolve waste luminescent material, in which a solid-liquid ratio was 1:5, the mixture was acid hydrolyzed and stirred for 8 h at 40° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 1 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 94.21% of total rare earths, europium Eu accounted for 5.17% of total rare earths. After HCl solution preferentially dissolved the residue, residue and the mixed alkali of NaOH and KOH were evenly mixed as the mass ratio of residue to mixed alkali of 1 to 3 and alkaline fusion was performed at 500° C. for 3 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 4 mol/L, acid solution of waste rare earth luminescent materials was stirred for 9 h at 50° C. in which the solid-liquid ratio of 1:20, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 1.5 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 49.32% of the total rare earths, terbium Tb content accounted for 29.95% of the total rare earths, yttrium Y content accounted for 10.56% of the total rare earths, Eu content accounted for 5.79% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 94.2%, in which yttrium Y leaching rate was 99.1%, europium Eu leaching rate was 98.2%, cerium Ce leaching rate was 74.3%, terbium Tb leaching rate was 71.3%. 
       Example 7 
       [0033]    Using HCl solution of 9 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:4, the mixture was acid hydrolyzed and stirred for 9 h at 50° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 1.5 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 93.76% of total rare earths, europium Eu accounted for 5.02% of total rare earths. After HCl solution preferentially dissolved the residue, residue and NaOH were evenly mixed as the mass ratio of residue to NaOH of 1 to 2 and alkaline fusion was performed at 600° C. for 4 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 5 mol/L, acid solution of waste rare earth luminescent materials was stirred for 10 h at 60° C. in which the solid-liquid ratio of 1:10, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 2 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba) SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 50.12% of the total rare earths, terbium Tb content accounted for 30.73% of the total rare earths, yttrium Y content accounted for 9.55% of the total rare earths, Eu content accounted for 5.13% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 94.1%, in which yttrium Y leaching rate was 98.7%, europium Eu leaching rate was 98.2%, cerium Ce leaching rate was 75.2%, terbium Tb leaching rate was 71.8%. 
       Example 8 
       [0034]    Using HCl solution of 10 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:3, the mixture was acid hydrolyzed and stirred for 10 h at 60° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 2 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 91.98% of total rare earths, europium Eu accounted for 4.95% of total rare earths. After HCl solution preferentially dissolved the residue, residue and KOH were evenly mixed as the mass ratio of residue to KOH of 1 to 1 and alkaline fusion was performed at 700° C. for 5 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 6 mol/L, in which the solid-liquid ratio was 1:12, acid solution of waste rare earth luminescent materials was stirred for 1 h at 70° C., to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 0.5 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 50.85% of the total rare earth, terbium Tb content accounted for 31.45% of the total rare earths, yttrium Y content accounted for 8.43% of the total rare earths, Eu content accounted for 4.65% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 92.4%, in which yttrium Y leaching rate was 97.2%, europium Eu leaching rate was 96.3%, cerium Ce leaching rate was 70.3%, terbium Tb leaching rate was 68.5%. 
       Example 9 
       [0035]    Using HCl solution of 3 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:10, the mixture was acid hydrolyzed and stirred for 8 h at 70° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 0.5 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 94.06% of total rare earths, europium Eu accounted for 5.12% of total rare earths. After HCl solution preferentially dissolved the residue, residue and NaOH were evenly mixed as the mass ratio of residue to NaOH of 1 to 4, and alkaline fusion was performed at 800° C. for 6 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 7 mol/L, acid solution of waste rare earth luminescent materials was stirred 2 h at 80° C. in which the solid-liquid ratio was 1:14, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 1 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba) SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 49.53% of the total rare earths, terbium Tb content accounted for 29.43% of the total rare earths, yttrium Y content accounted for 10.54% of the total rare earths, Eu content accounted for 5.62% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 93.6%, in which yttrium Y leaching rate was 98.8%, europium Eu leaching rate was 98.1%, cerium Ce leaching rate was 73.7%, terbium Tb leaching rate of 71.6%. 
       Example 10 
       [0036]    Using HCl solution of 4 mol/L to dissolve waste luminescent material, in which a solid-liquid ratio was 1:9, the mixture was acid hydrolyzed and stirred for 6 h at 80° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 1 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 94.60% of total rare earths, europium Eu accounted for 5.18% of total rare earths. After HCl solution preferentially dissolved the residue, residue and NaOH were evenly mixed as the mass ratio of residue to NaOH of 1 to 3, and alkaline fusion was performed at 400° C. for 7 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 8 mol/L, acid solution of waste rare earth luminescent materials was stirred for 3 h at 20° C. in which the solid-liquid ratio of 1:16, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 1.5 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 51.36% of the total rare earths, terbium Tb content accounted for 30.38% of the total rare earths, yttrium Y content accounted for 10.03% of the total rare earths, Eu content accounted for 5.36% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 92.5%, in which yttrium Y leaching rate was 96.2%, europium Eu leaching rate was 95.4%, cerium Ce leaching rate was 74.5%, terbium Tb leaching rate was 73.0%. 
       Example 11 
       [0037]    Using HCl solution of 5 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:8, the mixture was acid hydrolyzed and stirred for 4 h at 20° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 1.5 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 93.93% of total rare earths, europium Eu accounted for 5.06% of total rare earths. After HCl solution preferentially dissolving the residue, residue and KOH were evenly mixed at the mass ratio of residue to KOH of 1 to 2, and alkaline fusion was performed at 500° C. for 8 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 9 mol/L, acid solution of waste rare earth luminescent materials was stirred 4 h at 30° C. in which the solid-liquid ratio was 1:18, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 2 mol/L, to rare earth secondary filtrate, impurity ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 50.75% of the total rare earths, terbium Tb content accounted for 29.54% of the total rare earths, yttrium Y content accounted for 10.48 of the total rare earths, Eu content accounted for 5.66% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 93.2%, in which yttrium Y leaching rate was 98.5%, europium Eu leaching rate of 98.3%, cerium Ce leaching rate was 73.5%, terbium Tb leaching rate was 70.6%. 
       Example 12 
       [0038]    Using HCl solution of 6 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:7, the mixture was acid hydrolyzed and stirred for 2 h at 30° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 2 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 93.84% of total rare earths europium Eu accounted for 5.03% of total rare earths. After HCl solution preferentially dissolved the residue, residue and the mixed alkali of NaOH and KOH were evenly mixed as the mass ratio of residue to the mixed alkali of 1 to 1, and alkaline fusion was performed at 600° C. for 1 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 10 mol/L, acid solution of waste rare earth luminescent materials was stirred 5 h at 40° C., in which the solid-liquid ratio of 1:20, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 0.5 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 51.57% of the total rare earths, terbium Tb content accounted for 30.93% of the total rare earths, yttrium Y content accounted for 10.46% of the total rare earths, Eu content accounted for 5.28% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 91.8%, in which yttrium Y leaching rate was 97.3%, europium Eu leaching rate was 96.2%, cerium Ce leaching rate was 74.5%, terbium Tb leaching rate was 70.1%. 
       Example 13 
       [0039]    Using HCl solution of 7 mol/L to dissolve waste luminescent material, in which a solid-liquid ratio was 1:6, the mixture was acid hydrolyzed and stirred for 1 h at 40° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 0.5 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 93.75% of total rare earths, europium Eu accounted for 5.01% of total rare earth. After HCl solution preferentially dissolving the residue, residue and NaOH were evenly mixed at the mass ratio of residue to NaOH of 1 to 4 and alkaline fusion was performed at 700° C. for 2 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 3 mol/L, acid solution of waste rare earth luminescent materials was stirred 6 h at 50° C., in which the solid-liquid ratio of 1:10, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 1 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 50.78% of the total rare earths, terbium Tb content accounted for 30.36% of the total rare earths, yttrium Y content accounted for 10.54% of the total rare earths, Eu content accounted for 5.73% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 93.9%, in which yttrium Y leaching rate was 99.2%, europium Eu leaching rate was 98.3%, cerium Ce leaching rate was 74.2%, terbium Tb leaching rate was 71.4%. 
       Example 14 
       [0040]    Using HCl solution of 8 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:5, the mixture was acid hydrolyzed and stirred for 1 h at 50° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 1 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 93.63% of total rare earths, europium Eu accounted for 4.99% of total rare earths. After HCl solution preferentially dissolved the residue, residue and KOH were evenly mixed as the mass ratio of residue to KOH of 1 to 3, and alkaline fusion was performed at 800° C. for 3 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 4 mol/L, acid solution of waste rare earth luminescent materials was stirred 7 h at 60° C., in which the solid-liquid ratio was 1:12, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount Na 2 SO 4 , concentration of 1.5 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 48.18% of the total rare earths, terbium Tb content accounted for 28.45% of the total rare earths, yttrium Y content accounted for 12.54% of the total rare earths, Eu content accounted for 5.97% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 92.5%, in which yttrium Y leaching rate was 98.2%, europium Eu leaching rate was 97.4%, cerium Ce leaching rate was 73.8%, terbium Tb leaching rate of 69.5%. 
       Example 15 
       [0041]    Using HCl solution of 9 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:4, the mixture was acid hydrolyzed and stirred for 5 h at 60° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 1.5 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 94.20% of total rare earths, europium Eu accounted for 5.16% of total rare earths. After HCl solution preferentially dissolved the residue, residue and the mixed alkali were evenly mixed as the mass ratio of residue to the mixed alkali of 1 to 2, and alkaline fusion was performed at 500° C. for 4 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 5 mol/L, acid solution of waste rare earth luminescent materials was stirred for 8 h at 70° C., in which the solid-liquid ratio was 1:14, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 2 mol/L, to rare earth secondary filtrate, impure ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 50.75% of the total rare earth, terbium Tb content accounted for 30.32% of the total rare earths, yttrium Y content accounted for 9.53% of the total rare earths, Eu content accounted for 5.26% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 92.9%, in which yttrium Y leaching rate was 97.4%, europium Eu leaching rate was 96.7%, cerium Ce leaching rate was 73.4%, terbium Tb leaching rate was 71.8%. 
       Example 16 
       [0042]    Using HCl solution of 10 mol/L to dissolve waste luminescent material, in which the solid-liquid ratio was 1:3, the mixture was acid hydrolyzed and stirred for 7 h at 70° C., before the rare earth filtrate 1 was obtained. Adding an appropriate amount of Na 2 SO 4 , concentration of 2 mol/L, to rare earth filtrate 1, Ca 2+  was transformed to CaSO 4  precipitation for recycling, while the rich rare earth yttrium-europium filtrate was got, in which yttrium Y accounted for 93.82% of total rare earths, europium Eu accounted for 5.03% of total rare earths. After HCl solution preferentially dissolved the residue, residue and NaOH were evenly mixed as the mass ratio of residue to NaOH of 1 to 1, and alkaline fusion was performed at 600° C. for 5 h, getting alkaline fusion products. Alkaline fusion products were washed several times with deionized water to wash away the NaAlO 2 . Using HCl solution of 6 mol/L, acid solution of waste rare earth luminescent materials was stirred for 9 h at 80° C., in which the solid-liquid ratio was 1:16, to get rare earth secondary filtrate and secondary residue, then the secondary residue was return back to alkaline fusion method. Adding an appropriate amount of Na 2 SO 4 , concentration of 0.5 mol/L, to rare earth secondary filtrate, impurity ions Mg 2+ , Ba 2+  were transformed to (Mg, Ba)SO 4  precipitation, ultimately getting terbium Tb, cerium Ce enrichment liquor, wherein the cerium Ce content accounted for 50.47% of the total rare earths, terbium Tb content accounted for 30.57% of the total rare earths, yttrium Y content accounted for 9.54% of the total rare earths, Eu content accounted for 5.26% of the total rare earths. Extraction, separation and purification were performed successively in order to obtain high purity rare earth products. The total rare earth leaching rate was 94.3%, in which yttrium Y leaching rate was 98.7%, europium Eu leaching rate was 98.2%, cerium Ce leaching rate was 74.4%, terbium Tb leaching rate was 70.7%.