WO2013166781A1

WO2013166781A1 - Method for recovering rare earth from waste rare-earth-containing light-emitting material

Info

Publication number: WO2013166781A1
Application number: PCT/CN2012/078960
Authority: WO
Inventors: 张深根; 刘虎; 潘德安; 田建军
Original assignee: 北京科技大学
Priority date: 2012-05-10
Filing date: 2012-07-20
Publication date: 2013-11-14
Also published as: CN102660688A; CN102660688B

Abstract

A method for separating and recovering rare earth from a waste rare-earth-containing light-emitting material comprises the following process steps: collecting of a waste rare-earth-containing light-emitting material, comprising quick identification and dismantling and breaking of rare-earth containing fluorescent lamps, breaking of CRT displays, separating of the waste rare-earth-containing light-emitting material from glass substrates and collecting of same; pretreatment of the waste rare-earth-containing light-emitting material, comprising removal of mercury, oxidation, precipitation, alkali-based fusion, and acidolysis; extraction-based separation of the rare earth elements to obtain a rare earth chloride concentrate; extraction-based purification of the rare earth elements to obtain highly pure rare earth chlorides; precipitation-based separation of the rare earth elements to obtain a precipitate of rare earth oxalate or rare earth carbonate; baking of the precipitate of rare earth oxalate or rare earth carbonate to obtain highly pure rare earth oxides. The method separates the rare earth elements Ce, Eu, Tb and Y from impurity elements such as Mg, Ba, and Ca, completely separates and recovers light, medium, and heavy rare earth elements, and obtains highly pure rare earth oxides through purification, so as to comprehensively recover and use resources. The process is reasonable, economical, and practical, the recovery rate of the rare earth is high, and the product has a high added value.

Description

Method for recovering rare earth from waste rare earth luminescent material

The invention belongs to the field of resource recycling, and particularly relates to a method for comprehensively recovering rare earth from waste rare earth luminescent materials.

Background technique

The increasing use of rare earths and its strategic position have become increasingly prominent. It is known as "industrial MSG" and "industrial vitamins". It is an indispensable industrial raw material for high-tech, and is widely used in electronic information, national defense, metallurgical machinery, petrochemicals, Farming and animal husbandry and other fields. China is the country with the richest rare earths in the world, providing more than 90% of the world's rare earth demand for a long time. As a result, China has fallen from 74% of the world's total in the 1970s to 33%, and environmental pollution is serious, and ecological damage is intensified.

China's rare earth secondary resources recycling development space and potential is huge. At present, the output and dosage of fluorescent lamps in China ranks first in the world. In 2010, the total output of electric light sources in China was 8 billion, including 1.5 billion rare earth fluorescent lamps and about 6,000 tons of rare earth fluorescent powder. The picture tube is a key component of a cathode ray tube (CRT) TV set, accounting for approximately 60% of the total mass of a CRT TV. According to statistics, in 2008, the number of TV households in China was 504.19 million. Since 2005, China has ushered in the peak of TV replacement. It is estimated that at least 5 million TV sets will be scrapped every year. The phosphor coating on CRT tube glass contains metal complexes, rare earth metals such as lanthanum and cerium. , rare earth phosphor content of 10-60g / only.

At present, there are few studies on the recovery of rare earth resources for waste fluorescent lamps in China, which are basically in the initial stage. Most of the waste fluorescent lamps are incinerated or buried with domestic garbage, and the environmental accumulation, bioabsorption and enrichment of rare earth metals and small amounts of mercury in fluorescent lamps. The accumulation of the food in the food chain and its possible biotoxic effects cause great harm to the human body and the environment. Foreign countries are dealing with waste fluorescent lamps, only dealing with mercury in the lamps, and most of the used CRT monitors are only recycled. The glass fractions do not efficiently separate, purify and recover the rare earth elements Ce, Eu, Tb and Y for valuable trichromatic phosphors.

There are two differences between the recycling of secondary rare earth luminescent materials and the secondary resources of primary rare earth minerals: First, the ceramic phase synthesized by high-temperature calcination of waste rare earth luminescent materials, generally cubic iron-manganese cubic crystal system, magnetic lead ore hexagonal crystal System, monazite monoclinic system, monoclinic system Si0 ₄ tetrahedral β-alumina hexagonal system, apatite hexagonal system, etc., crystal structure is complex, structure is stable, rare earth ions are difficult to separate; second, waste rare earth The luminescent material contains a large amount of A1 element, which seriously affects the recovery of rare earth, especially the recovery rate of rare earth.

The three key technologies for the recycling and recycling of waste rare earth fluorescent lamps and their waste rare earth luminescent materials, namely mercury pollution, disintegration of ceramic phase crystal structure and removal of A1 impurity elements, have no relevant complete sets of technologies and processes at home and abroad. With the increasing scarcity of rare earths, especially strategic medium-heavy rare earth resources, there is an urgent need to continue to develop a complete set of key technologies and processes for the recycling and recycling of used rare earth luminescent materials.

Summary of the invention

The object of the present invention is to provide a method for recovering rare earth from waste rare earth luminescent materials, which solves waste rare earth by collecting, pretreating, extracting, extracting, purifying, precipitating and roasting of waste rare earth luminescent materials. The mercury pollution of the fluorescent lamp and its waste rare earth luminescent materials, the disintegration of the crystal phase of the ceramic phase and the removal of the A1 impurity element minimize the secondary pollution of the recycling process, improve the recovery rate of rare earth, and facilitate industrial production. .

The main steps of the invention are as follows:

1) Collection of waste rare earth luminescent materials, including rapid identification of rare earth fluorescent lamps and their disassembly and disassembly, crushing of CRT displays, stripping and collection of waste rare earth luminescent materials and glass substrates;

2) Pretreatment of waste rare earth luminescent materials, including mercury removal oxidative precipitation, alkali fusion and acid hydrolysis;

3) extraction and separation of rare earth elements to obtain rare earth chloride enrichment;

4) extraction and purification of rare earth elements, obtaining 99.9%-99.9999% rare earth chloride;

5) precipitation separation of rare earth elements, obtaining 99.9%-99.9999% rare earth oxalate or rare earth carbonate precipitate;

6) Calcination of oxalic acid rare earth or rare earth carbonate precipitate to obtain 99.9%-99.9999% rare earth oxide. The rare earth elements are mainly lanthanum, cerium, lanthanum and cerium.

The main steps described above specifically include:

1) Collection of waste rare earth luminescent materials:

(a) Using artificial assistance to quickly identify used rare earth fluorescent lamps, using fully enclosed crushing, collecting mercury vapor under negative pressure, and recovering mercury by means of sulfide precipitation and activated carbon adsorption; phosphors, glass and lamp holders are collected by gravity sorting .

(b) CRT tube screen cone separation, negative pressure collection of rare earth phosphors, lead glass is concentrated in professional institutions;

2) Pretreatment of waste rare earth luminescent materials:

(a) Mercury removal: Dispose of fluorescent lamps and CRT monitors, disassemble and crush, and collect mercury vapor under negative pressure. The waste fluorescent powder is washed with acetone solution with a concentration of 10~30%, and the oxidation reaction is carried out with a concentration of 0.2~lg/L potassium permanganate. The zinc sulfide is added 0.3-0.8g/L, and the Hg ^{2+ is} precipitated by the sulfurization reaction. The mercury time is 0.5~5h, and finally the residual mercury in the phosphor is removed by activated carbon.

(b) Alkali melting: According to the cleaned rare earth luminescent material and alkali mixed and stirred uniformly, (by mass ratio) waste rare earth luminescent materials: NaOH or KOH is 1:1~10, alkali at 600~1200°C After melting for l~10h, the alkali fusion product is washed twice by the second deionization and then enters the next acid hydrolysis process.

(c) Acid hydrolysis: After washing, the alkali fusion product is prepared by using 3~8mol/L hydrochloric acid to prepare an acid hydrolysis solution with a solid-liquid ratio of 1:3~10, and adjusting the pH to a range of 3~5 with ammonia water. 2~5^% of 1^. The flocculant is acid-decomposed at 20~80 °C for 1~8h to remove Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

3) Extraction and separation of rare earth elements:

The rare earth chloride solution is adjusted in the range of 3.5~4.5, and the REC1 ₃ content is 0.5~1.5mol/L, and the extractant is 0.5~1.5mol/L P204-sulfonated kerosene for the extraction and separation of rare earth. First, the light rare earth group is grouped, and the rare earths (Ce, Eu, Tb, and Y) are extracted into the organic phase, and the light rare earth Ce entering the organic phase is washed with a concentration of 0.6 to 1 mol/L hydrochloric acid as the washing liquid 1 and represented by V. The volume of the organic extractant, V ₄ represents the volume of the liquid, V i* represents the volume of the washing liquid, and the flow ratio is V _: V , ₄ : V _ffi = 2~3: 1:0.2-0.3, and the CeCl ₃ solution is obtained. The light rare earth group is exported to the organic phase 1 by stripping the rare earth with 1.5~2.5mol/L hydrochloric acid, using V «τ for the volume of the new organic phase, V for the volume of the organic phase in the solution, and V * for the volume of the aqueous phase. The flow ratio is V new: V material: V water = 0.1~0.15: 1:0.1~0.15, the middle rare earth group is divided, and finally P204-sulfonated kerosene is used as the organic phase to extract the heavy rare earth, and the outlet water phase 2 is respectively obtained to contain the strontium. , 铽 rich collection, the organic phase 2 after the combination of rare earths is back-extracted with rare earth with 3.5~4.5mol/L hydrochloric acid, V has the volume of organic phase, and V water represents the volume of water phase, compared with V:V ₇ K = 1: 0.1 ~ 0.2, after multi-stage extraction, the ruthenium enrichment is obtained, wherein the ruthenium content is about 75%.

4) Extraction and purification of rare earth elements:

(a) Purification of cockroaches:

The cerium-rich concentrate is precipitated by oxalic acid and calcined, and then dissolved in sulfuric acid. The compounding solution contains REC1 _{3 to} be 0.5-1.5 mol/L, and potassium permanganate 10 to 50 g/L is added to mix with the liquid, and the extracting agent is 0.5. ~1.5mol/L P507-sulfonated kerosene, extracting light rare earth (Ce) into organic phase 4, using 0.2~lmol/L hydrochloric acid as pickling solution 2, washing the medium heavy rare earth entering organic phase 5, using V Indicates the organic extractant, “represents the volume of the liquid, V wash represents the volume of the washing liquid, and the flow ratio is V: V _fi: V _ffi = 1.5~2.5: l: 0.4~0.8, and a light rare earth liquid (CeCl ₄ ) is obtained. The light rare earth is back-extracted with 1.5~2.5mol/L hydrochloric acid, and the volume of the organic phase is represented by V. The volume of the aqueous phase is V _7K , which is V: V *=l: 0.1~0.2, and the purity is obtained after multi-stage extraction. 99.99% cerium chloride solution.

(b) Purification of cockroaches:

Using cesium-rich concentrate as raw material, using fractional fractionation extraction, the blending solution contains P-sulfonated kerosene with REC1 ₃ of 0.5~1.5mol/L and extractant of 0.5~1.5mol/L mol/L. Fractionation extraction: The saponification degree of 25%~40% of the extractant and the rare earth liquid simultaneously enter the tank and flow to the 10th stage to form a rare earth saponification form into the tank. After the extraction, the organic phase 7 is washed with 3~5.5mol/L hydrochloric acid, using V Indicates the organic extractant, ₄ indicates the volume of the feed solution, V _ffi indicates the volume of the wash solution, and the flow ratio V has: V | ₄ : V _ffi = 6~20: l: 0.3-1.8, enters the second stage fractionation extraction: first The organic phase 8 from the extraction section is the feed liquid. The second stage uses the same organic phase and washing liquid as the first stage, V is the organic extractant, V _fi is the volume of the liquid, and V _ffi is the volume of the washing liquid. _: V | ₄ : V _ffi =6.5~18:1:0.35~2.0. After multiple extractions, a cerium chloride solution having a purity of 99.99% was finally obtained.

(c) Purification of cockroaches:

The ruthenium-rich concentrate is used as a raw material, and the dosage solution contains REC1 ₃ of 0.5~1.5mol/L, pH value of 1-4, and it flows through the reduction column containing zinc particles and the P507 extracted in series with it. The extraction chromatography column of the resin controls the feed amount to be 5~30g/100g resin, the flow rate is 0.5 1.5 ml /min · cm ² , and the effluent is pure bismuth solution. Then, the pure ruthenium solution is oxidized with H ₂ O _{2 to} form a trivalent ruthenium, and the acidity is adjusted to 0.5 with hydrochloric acid, and the P507 extraction color layer column is passed to control the flow rate and the feed amount of the rare earth material, and the impurity ions such as zinc and calcium are used. The effluent flows out, and the ruthenium is adsorbed on the extraction chromatography column. The concentration of 0.3~1.5 mol/L hydrochloric acid is used as the pickling solution 5 and flows through the P507 extraction chromatography column. The feed amount is 5-20 g/100 g resin, and the flow rate is A purity of 99.99% cerium chloride solution was obtained at 1.5 to 2.2 ml/min * _C m ² .

(d) Purification of cockroaches:

The eutrophic material is used as raw material, and the dosage solution contains REC1 ₃ of 0.5~1.5 mol/L, pH=2~3, and the saponification degree is 70% by using the extractant as naphthenic acid-long-chain alcohol-kerosene and NaOH. ~90%, after split extraction, the organic phase is washed with a concentration of 2~3mol/L hydrochloric acid, with V as the organic extractant, "representing the volume of the liquid, V _ffi means the volume of the washing liquid, the flow ratio is V : V 4: V _ffi =6~8:l:l~2, after multi-stage extraction and washing, the outlet aqueous phase 11 is a 99.995% cerium chloride solution. Washed organic with non-rhenium rare earth and a small amount of antimony Phase 11 is subjected to secondary extraction. The organic phase is stripped with acid I, the concentration is 1-2 mol/L hydrochloric acid, and the stripping acid II is at a concentration of 0.1-0.5 mol/L hydrochloric acid for stripping. V ₄ indicates newly added The volume of the liquid, V _fi3⁄4£ei represents the volume of the stripping acid I, V stripping acid π means the volume of the stripping acid II, the flow ratio is V: V «4: V stripping acid _{I :} V anti-stability π=6~ 8:1:1~2:8~9 ο The second stripping solution has an outlet. The first stripping solution has a high content of cerium and a purity of about 99%. The second stripping solution mainly contains Heavy rare earth element, the organic phase 13 after stripping is washed with pure water and then de-acidized. After sodium saponification, it can be returned to use. After multiple extractions, a purity of 99.999% cerium chloride solution is obtained.

5) Separation of rare earth precipitates:

After the sediment liquid is adjusted, the ρΗ value is removed by impurities, and then precipitated by CP-oxalic acid or soda ash for 1~5h, and then washed thoroughly with secondary ionized water and then sent to roasting.

6) High temperature roasting:

After the precipitate is calcined at a high temperature, dehydrated, carbonized, oxidized, etc., 4N~6N rare earth oxide is obtained, wherein the baking temperature is 600~1200 °C, and the baking time is l~10h.

Advantages of the invention:

The invention adopts a full-wet green process to recover rare earth elements in waste rare earth luminescent materials, and realizes complete separation and purification of lanthanum, cerium, lanthanum, cerium, light, medium and heavy rare earth elements in waste rare earth luminescent materials, and recovery rate of rare earth elements high. The recovery of rare earth from waste rare earth luminescent materials not only protects China's valuable medium and heavy rare earth strategic resources, but also protects the environment. On the one hand, it avoids the pollution caused by the waste rare earth products itself; on the other hand, it reduces the consumption of the ion-type rare earth mineral resources in the south, and greatly reduces the serious environmental burden brought by the mining, selection and smelting of rare earth minerals. The main advantages of the invention are:

1. The invention can collect and remove mercury from waste rare earth fluorescent lamps and solve the environmental pollution problem of mercury;

2. The invention can disintegrate the crystal structure of the ceramic phase of the waste rare earth luminescent material, thereby separating the rare earth ions for further extraction and purification;

3. The invention can remove A1 impurity element efficiently and improve the recovery rate of rare earth. At present, there are no related complete sets of technology and process solutions at home and abroad;

4. The invention solves the problem of recycling and recycling of the extraction tail liquid in the process of recycling and recycling waste rare earth luminescent materials, reduces raw material input and waste discharge, and realizes energy saving and emission reduction.

In short, the invention solves the three key technologies of mercury pollution, ceramic phase crystal structure dissociation and A1 impurity element removal of waste rare earth fluorescent lamp and its waste rare earth luminescent material, and eliminates the secondary pollution problem of the recycling process to the utmost extent, The rare earth has high recovery rate and does not cause secondary pollution. The equipment is simple and easy to industrialize. DRAWINGS

1 is a flow chart of an overall implementation process of a method for recovering rare earth from waste rare earth luminescent materials according to the present invention, which is divided into six parts: (1) collection of waste rare earth luminescent materials; (2) pretreatment of waste rare earth luminescent materials; 3) extraction and separation of rare earth elements; (4) extraction and purification of rare earth elements; (5) precipitation of rare earth elements; (6) roasting of rare earth element precipitates.

2 is a flow chart of the complete separation process of light, medium and heavy rare earths in the waste rare earth luminescent materials of the present invention 3 is a flow chart of the purification process of rare earth element cerium in the present invention

4 is a flow chart of the purification process of rare earth element cerium in the present invention

Figure 5 is a flow chart of the purification process of rare earth element cerium in the present invention

6 is a flow chart of the purification process of rare earth element cerium in the present invention

detailed description

Hereinafter, the method for recovering rare earth from waste rare earth luminescent materials of the present invention will be further described by way of examples with reference to the accompanying drawings.

Example 1

Disused fluorescent lamps and CRT monitors are disassembled and crushed, and mercury vapor is collected under negative pressure. The waste phosphor is washed with a 20% acetone solution, and the concentration of 0.8g/L potassium permanganate is used for oxidative mercury removal for 4h. The zinc sulfide addition amount is 0.8g/L cleaning solution, and Hg ^{2+ is} precipitated by sulfurization. Activated carbon removes residual mercury from the phosphor.

The cleaned rare earth luminescent material and the alkali (NaOH) are mixed and stirred uniformly, and the alkali fusion product obtained after alkali fusion at 80 CTC for 1 hour at a mass ratio of 1:6 is uniformly washed with secondary deionized water. The remaining NaOH and part of NaA10 are added to the rare earth-containing insolubles. 6 mol/L hydrochloric acid was used for acid hydrolysis at 70 ° C for 2 h. The solid-liquid ratio of insoluble matter to hydrochloric acid was 1:10, and the acid hydrolysis solution was adjusted to pH 3 with ammonia water to add 4% by weight. The flocculating agent removes Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

The rare earth chloride solution was adjusted to a pH of 4, and the REC1 ₃ content was 0.5 mol/L, and the extractant was subjected to extraction and separation of rare earth by using 0.5 mol/L of P204-sulfonated kerosene. First, the light rare earth group is grouped, and the rare earth (Ce Eu Tb and BY) is extracted into the organic phase, and the light rare earth Ce entering the organic phase is washed with a concentration of 0.9 mol/L hydrochloric acid as the washing liquid 1. The flow ratio is VV _l4 : V _Ffi = 2: l: 0.2, a solution of CeCl ₃ was obtained. The light rare earth is grouped out of the organic phase. The rare earth is stripped with 2.5 mol/L hydrochloric acid. The flow ratio is VVV _7K = 0.1 _: 1:0.1. The middle rare earth is grouped. Finally, the P204-sulfonated kerosene is used as the organic phase to extract the heavy rare earth. The aqueous phase 2 is obtained with cerium and lanthanum-rich concentrates respectively. The organic phase 2 of the intermediate rare earth group is back-extracted with 3.5 mol/L hydrochloric acid, and the flow ratio is V _: V _7X = 2: 0.5. After multi-stage extraction, Obtaining a rich enrichment, wherein the antimony content is about 75%

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1.5mol/L, adding potassium permanganate 30g/L and mixing with the liquid, extracting agent is 1mol/L P507-sulfonated kerosene, extracting light rare earth (Ce) The organic phase 4, with 0.7 mol/L hydrochloric acid as the pickling solution 2, is washed into the medium-heavy rare earth entering the organic phase 5, and the flow ratio is V: V _fi: V _ffi = 1.5 _: l: 0.4 to obtain a light rare earth liquid (CeCl ₄ ). The light rare earth was back-extracted with 2 mol/L hydrochloric acid, and compared with V _: V*=l:0.1, a cerium chloride solution having a purity of 99.99% was obtained after multistage extraction.

Purification of hydrazine, using fractional fractionation extraction, the formulation liquid containing REC1 ₃ is 0.5mol/L, the extracting agent is 1mol/L P204-sulfonated kerosene, the first stage fractionation extraction: 35% saponification degree extractant and rare earth The feed liquid enters the tank at the same time and flows into the tank after 10 stages of saponification. After extraction, the organic phase 7 is washed with 5.5 mol/L hydrochloric acid, and the flow ratio V _: V | ₄ : V _ffi = 6: l: 0.3, enters the first Two-stage fractional extraction: the organic phase 8 flowing out of the first extraction section is used as the feed liquid, and the second phase is the same organic phase and washing liquid as the first stage, V: VV _ffi = 6.5:1:0.35, after multiple times Extraction, finally obtaining a cerium chloride solution having a purity of 99.99%.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 0.5 mol/L pH value 1, allowing it to flow through the zinc particles The reduction column and the extraction chromatography column with P507 extraction resin connected in series control the feed amount to 10 g/100 g resin, the flow rate is 0.5 ml/min · cm ² , and the effluent is a pure ruthenium solution. Then, the pure ruthenium solution is oxidized with H ₂ O _{2 to} form a trivalent ruthenium, and the acidity is adjusted to 0.5 with hydrochloric acid, and the P507 extraction color layer column is passed to control the flow rate and the feed amount of the rare earth material, and the impurity ions such as zinc and calcium are used. The effluent flows out, and the ruthenium is adsorbed on the extraction chromatography column. The concentration of 0.8 mol/L hydrochloric acid is used as the pickling solution 5 and flows through the P507 extraction chromatography column. The feed amount is 15 g/100 g of resin, and the flow rate is 2 ml/min. · cm ² to obtain a yttrium chloride solution with a purity of 99.99%.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 0.5 mol/L, pH=2.5, using an extractant for naphthenic acid-long-chain alcohol-kerosene, NaOH for saponification, saponification degree of 80%, and organic phase after split extraction The concentration was 3 mol/L hydrochloric acid washing, and the flow ratio was V:V | ₄ : V _ffi = 6:1:1. After multistage extraction and washing, the outlet aqueous phase 11 was a 99.995% cerium chloride solution. The washed organic phase 11 containing non-antimony rare earth and a small amount of cerium is subjected to secondary extraction, and the organic phase is subjected to stripping acid I, a concentration of 1 mol/L hydrochloric acid, and a stripping acid II at a concentration of 0.3 mol/L hydrochloric acid. For stripping, the flow ratio is VVV _{I :} V _π =6:1:1:8. The second stripping solution has an outlet. The first stripping solution has a high content of cerium and a purity of about 99%. The second stripping solution mainly contains non-heavy rare earth elements, and the organic phase 13 after stripping. After washing with pure water and removing the free acid, it can be returned to sodium saponification. After multiple extractions, a solution of 99.999% ruthenium chloride is obtained.

The obtained high-purity rare earth chloride is precipitated by oxalic acid, and the precipitation reaction time is lh. After washing with secondary ionized water, it is calcined at 100CTC for 1 hour to prepare 4N~6N rare earth oxides.

Example 2

Disused fluorescent lamps and CRT monitors are disassembled and broken, and mercury vapor is collected under negative pressure. The waste phosphor was washed with a 30% acetone solution, and oxidized and dehydrated for 5 h at a concentration of lg/L potassium permanganate to remove residual mercury from the phosphor.

The cleaned rare earth luminescent material and the alkali (KOH) are mixed and stirred uniformly, and the alkali fusion product obtained after alkali fusion at 100 CTC for 3 hours is uniformly removed by mass ratio 1:10 with water, and then washed with secondary deionized water. Remaining KOH and part of KA10 to insoluble matter containing rare earth. Acid hydrolysis was carried out at 8 °C with 8 mol/L hydrochloric acid for 4 h. The solid-liquid ratio of insoluble matter to hydrochloric acid was 1:3, and the acid hydrolysis solution was adjusted to pH 4 with aqueous ammonia, and 5^% of 1^ was added. The flocculating agent removes Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

The rare earth chloride solution was adjusted to a pH of 3.5, and the REC1 ₃ content was 1 mol/L, and the extractant was subjected to extraction and separation of rare earth by using 1.5 mol/L of P204-sulfonated kerosene. First, the light rare earth group is grouped, and the rare earth (Ce, Eu, Tb, and BY) is extracted into the organic phase, and the light rare earth Ce entering the organic phase is washed with a concentration of 0.6 mol/L hydrochloric acid as the washing liquid 1, and the flow ratio is V _: V _|4 : V _ffi =2.5: 1:0.25, a solution of CeCl ₃ was obtained. The organic phase 1 of the light rare earth group is stripped with 1.5 mol/L hydrochloric acid, and the flow ratio is VVV = 0.15:1:0.15. The middle rare earth is grouped. Finally, the P204-sulfonated kerosene is used as the organic phase to extract the heavy rare earth, and the outlet water. Phase 2 obtained the enthalpy and lanthanum-rich enrichment, and the organic phase of the intermediate rare earth group was back-extracted with 4 mol/L hydrochloric acid. The flow ratio was V _: V _7X = 2:0.5. After multi-stage extraction, 钇 was obtained. Enriched matter, wherein the strontium content is about 75%

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 0.5mol/L, adding potassium permanganate 50g/L and mixing with the liquid, extracting agent is 1.5mol/L P507-sulfonated kerosene, and extracting light rare earth (Ce) Into the organic phase 4, with 0.2 mol / L hydrochloric acid as the pickling solution 2, the medium heavy rare earth entering the organic phase 5 is washed, the flow ratio is V: V 4: V _ffi = 2: l: 0.6, A light rare earth liquid (CeCl ₄ ) was obtained. The light rare earth was back-extracted with 1.5 mol/L hydrochloric acid, and the ratio was V _: V*=1:0.15. After multi-stage extraction, a cerium chloride solution having a purity of 99.99% was obtained.

Purification of hydrazine, using fractional fractionation extraction, the formulation liquid contains REC1 ₃ as lmol/L, extractant is 0.5mol/L P204-sulfonated kerosene, the first stage fractionation extraction: 40% saponification degree extractant and rare earth The feed liquid is simultaneously introduced into the tank and flows into the tank to form a rare earth saponification form. After the extraction, the organic phase 7 is washed with 3 mol/L hydrochloric acid, and the flow ratio V _: V | ₄ : V _ffi = 10: l: 0.8, enters the second Fractional fractionation extraction: the organic phase 8 flowing out of the first extraction section is used as the feed liquid, and the second phase is the same organic phase and washing liquid as the first stage, V: V | ₄ : V _ffi = 12:1:1, After multiple extractions, a cerium chloride solution having a purity of 99.99% was finally obtained.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1 mol/L, pH 2, and flowing it through a reduction column containing zinc particles and an extraction chromatography column containing P507 extraction resin connected thereto, and controlling The amount of the material was 5 g/100 g of resin, the flow rate was 1 ml/min · cm ² , and the effluent was a pure hydrazine solution. Then, the pure ruthenium solution is oxidized with H ₂ O _{2 to} form a trivalent ruthenium, and the acidity is adjusted to 0.7 with hydrochloric acid, and the P507 extraction color layer column is passed to control the flow rate and the feed amount of the rare earth material, and the impurity ions such as zinc and calcium are used. The effluent flows out, and the ruthenium is adsorbed on the extraction chromatography column. The concentration of 1.2 mol/L hydrochloric acid is used as the acid washing liquid 5 and flows through the P507 extraction chromatography column. The feed amount is 20 g/100 g resin, and the flow rate is 1.5 ml/ Min · cm ² , a 99.99% cerium chloride solution was obtained.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1 mol/L, pH=2, using an extractant for naphthenic acid-long-chain alcohol-kerosene, NaOH for saponification, saponification degree of 90%, concentration of organic phase after split extraction Washed with 2 mol/L hydrochloric acid, the flow ratio was V:V | ₄ : V _ffi = 7:1: 1.5. After multistage extraction and washing, the outlet aqueous phase 11 was a 99.995% cerium chloride solution. The washed organic phase 11 containing non-cerium rare earth and a small amount of cerium is subjected to secondary extraction, and the organic phase is extracted with a stripping acid I, a concentration of 1.5 mol/L hydrochloric acid, and a stripping acid II at a concentration of 0.1 mol/L hydrochloric acid. For stripping, the flow ratio is V new: V new material: V stripping acid _I: V stripping = 7:1:1.5:8.5. The second stripping solution has an outlet. The first stripping solution has a high content of cerium and a purity of about 99%. The second stripping solution mainly contains non-heavy rare earth elements, and the organic phase 13 after stripping. After washing with pure water and removing the free acid, it can be returned to sodium saponification. After multiple extractions, a solution of 99.999% ruthenium chloride is obtained.

The obtained high-purity rare earth chloride was precipitated by oxalic acid, and the precipitation reaction time was 2 hours. After washing with secondary ionized water, it was calcined at 60 CTC for 3 hours to obtain 4N~6N rare earth oxides.

Example 3

Disused fluorescent lamps and CRT monitors are disassembled and broken, and mercury vapor is collected under negative pressure. The waste fluorescent powder was washed with a 10% by weight acetone solution, and the concentration of 0.2 g/L potassium permanganate was used for oxidative demercuration for 0.5 h to remove residual mercury in the phosphor.

The cleaned rare earth luminescent material and the alkali (NaOH) are mixed and stirred uniformly, and the alkali fusion product obtained after alkali fusion for 5 hours at 120 CTC is uniformly removed by mass ratio 1:2 with water, and then washed with secondary deionized water. The remaining NaOH and part of NaA10 are added to the rare earth-containing insolubles. Acid hydrolysis was carried out at 80 ° C for 6 h with 3 mol/L hydrochloric acid. The solid-liquid ratio of insoluble matter to hydrochloric acid was 1:5, and the pH of the acid solution was adjusted to 5 with ammonia water, and 2% of 1% was added. The flocculating agent removes Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

The rare earth chloride solution was adjusted to a pH of 4, and the REC1 ₃ content was 1.5 mol/L, and the extractant was subjected to extraction and separation of rare earth by using 0.5 mol/L of P204-sulfonated kerosene. First, the light rare earth group is grouped, and the rare earth (Ce, Eu, Tb, and BY) is extracted into the organic phase, and the concentration is 0.8 mol/L hydrochloric acid as the washing liquid 1 The light rare earth Ce was washed in the organic phase, and the flow ratio was VV | ₄ : V _ffi = 3:1: 0.3 to obtain a CeCl ₃ solution. The organic phase 1 of the light rare earth group is stripped with 2 mol/L hydrochloric acid, and the flow ratio is VV i4w: V = 0.15:1:0.1. The middle rare earth is grouped, and finally the P204-sulfonated kerosene is used as the organic phase to extract the heavy rare earth. The outlet aqueous phase 2 is obtained with cerium and lanthanum-rich concentrates respectively. The organic phase 2 of the intermediate rare earth group is back-extracted with rare earth with 4.5 mol/L hydrochloric acid, and the flow ratio is V: V *=2:0.5, after multi-stage extraction. , obtaining a rich enrichment, wherein the strontium content is about 75%

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1 mol/L, adding potassium permanganate 10g/L and mixing with the liquid, extracting agent 0.5 mol/L P507-sulfonated kerosene, extracting light rare earth (Ce) Organic phase 4, with 0.4 mol/L hydrochloric acid as pickling solution 2, the intermediate heavy rare earth entering the organic phase 5 is washed, and the flow ratio is V: V _fi: V _ffi = 2.5 _: l: 0.8 to obtain a light rare earth liquid (CeCl ₄ ). The light rare earth was back-extracted with 2 mol/L hydrochloric acid, and a cerium chloride solution having a purity of 99.99% was obtained after multi-stage extraction by V _: V = 1:0.1.

Purification of hydrazine, using fractional fractionation extraction, the formulation liquid containing REC1 ₃ is 1.5mol/L, the extracting agent is 1mol/L P204-sulfonated kerosene, the first stage fractionation extraction: 25% saponification degree extractant and rare earth The feed liquid enters the tank at the same time and flows into the trough to form a rare earth saponification form. After the extraction, the organic phase 7 is washed with 4.5 mol/L hydrochloric acid, and the flow ratio is VV | ₄ : V _ffi = 15: l: 1.2, and enters the second stage. Fractional extraction: The organic phase 8 flowing out of the first extraction section is used as the feed liquid, and the second phase is the same organic phase and washing liquid as the first stage, V: V | ₄ : V _ffi = 18:1:1.5, After multiple extractions, a cerium chloride solution having a purity of 99.99% was finally obtained.

Purification of hydrazine, the blending solution containing REC1 ₃ is 1.5 mol / L pH value 3, so that it flows through the reduction column containing zinc particles and the extraction chromatography column with P507 extraction resin connected in series, and control The amount of the material was 10 g/100 g of resin, the flow rate was 0.5 ml/min · cm ² , and the effluent was a pure hydrazine solution. Then, the pure ruthenium solution is oxidized with H ₂ O _{2 to} form a trivalent ruthenium, and the acidity is adjusted to 0.9 with hydrochloric acid, and the P507 extraction color layer column is passed to control the flow rate and the feed amount of the rare earth material, and the impurity ions such as zinc and calcium are used. The effluent flows out, and the ruthenium is adsorbed on the extraction chromatography column, and the concentration of 1.5 mol/L hydrochloric acid is used as the acid washing liquid 5 through the P507 extraction chromatography column, and the feed amount is 5 g/100 g resin, and the flow rate is 2 ml/min. · cm ² to obtain a yttrium chloride solution with a purity of 99.99%.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1.5mol/L pH=2.5, using the extractant for naphthenic acid-long-chain alcohol-kerosene, NaOH for saponification, saponification degree is 70%, concentration of organic phase after split extraction After washing with 2.5 mol/L hydrochloric acid, the flow ratio was VVV _ffi = 8:1:2. After multistage extraction and washing, the outlet aqueous phase 11 was a 99.995% cerium chloride solution. The washed organic phase 11 containing non-antimony rare earth and a small amount of cerium is subjected to secondary extraction, and the organic phase is subjected to stripping acid I, a concentration of 2 mol/L hydrochloric acid, and a stripping acid II at a concentration of 0.2 mol/L hydrochloric acid. Stripping, the flow ratio is VVV _{I :} V _π =8: 1:2:9 The second stripping solution has an outlet, the first stripping solution has a high content of cerium, the purity is about 99%, the second counter The extract contains mainly non-heavy rare earth elements. The organic phase 13 after stripping is washed with pure water and then de-acidized. After sodium saponification, it can be returned to use. After multiple extractions, a purity of 99.999% cerium chloride solution is obtained.

The obtained high-purity rare earth chloride was precipitated by oxalic acid, and the precipitation reaction time was 3 hours. After washing with secondary ionized water, it was calcined at 70 CTC for 5 hours to prepare 4N~6N rare earth oxides.

Example 4

Disused fluorescent lamps and CRT monitors are disassembled and crushed, and mercury vapor is collected under negative pressure. The waste phosphor is washed with a 20% acetone solution and oxidized for mercury removal with a concentration of 0.5 g/L potassium permanganate for 2 h. Remove residual mercury from the phosphor.

The washed rare earth luminescent material and the alkali (KOH) are mixed and stirred uniformly, and the alkali fusion product obtained after alkali fusion for 7 hours at 60 CTC is uniformly removed by mass ratio 1:4 with water, and then washed with secondary deionized water. The remaining KOH and a part of KA10 ₂ give a rare earth-containing insoluble matter. Acid hydrolysis was carried out at 5 ° C for 8 h with 5 mol/L hydrochloric acid. The solid-liquid ratio of insoluble matter to hydrochloric acid was 1:7, and the acid hydrolysis solution was adjusted to pH 3 with ammonia water to add 3^% of 1^. The flocculating agent removes Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

The rare earth chloride solution is adjusted to a pH of 4.5, and wherein the REC1 ₃ content is 0.5 mol/L, and the extractant is subjected to extraction and separation of rare earth by using 1 mol/L of P204-sulfonated kerosene. First, the light rare earth group is grouped, and the rare earth (Ce Eu Tb and Y) is extracted into the organic phase, and the light rare earth Ce entering the organic phase is washed with a concentration of 1 mol/L hydrochloric acid as the washing liquid 1, and the flow ratio is VVV _ffi = 2: l: 0.2, a solution of CeCl ₃ was obtained. The organic phase 1 of the light rare earth group is extracted with 2.5 mol/L hydrochloric acid, and the rare earth is mixed with a flow ratio of VVV=0.15:1:0.1. Finally, the P204-sulfonated kerosene is used as the organic phase to extract the heavy rare earth, and the outlet water is used. Phase 2 obtained the cerium-rich and cerium-rich aggregates respectively. The organic phase 2 after the combination of the rare earths was back-extracted with 3.5 mol/L hydrochloric acid, and the flow ratio was V _: V*=2:0.5. After multistage extraction,钇 rich, which contains about 75% bismuth

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1.5mol/L, adding potassium permanganate 20g/L and mixing with the liquid, extracting agent is 1mol/L P507-sulfonated kerosene, extracting light rare earth (Ce) The organic phase 4, with 0.6 mol/L hydrochloric acid as the pickling solution 2, is washed into the medium-heavy rare earth entering the organic phase 5, and the flow ratio is V _: V _fi: V _ffi = 2.5 _: l: 0.4 to obtain a light rare earth liquid (CeCl ₄ ). The light rare earth was back-extracted with 2.5 mol/L hydrochloric acid, and the ratio was V _: V*=1:0.15. After multistage extraction, a cerium chloride solution having a purity of 99.99% was obtained.

Purification of hydrazine, using fractional fractionation extraction, the formulation liquid containing REC1 ₃ is 0.5mol/L, the extracting agent is 1.5mol/L P204-sulfonated kerosene, the first stage fractionation extraction: 30% saponification degree extractant and The rare earth liquid enters the tank at the same time and flows into the trough after 10 stages. After the extraction, the organic phase 7 is washed with 3 mol/L hydrochloric acid. The flow ratio V _: V _f4 : V _ffi = 20: l: 1.8, enters the second Fractional fractionation extraction: the organic phase 8 flowing out of the first extraction section is used as the feed liquid, and the second phase is the same organic phase and washing liquid as the first stage, V _: V _f4 : Y = 6.5:1:1.2, After the second extraction, a cerium chloride solution having a purity of 99.99% was finally obtained.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 0.5 mol/L and having a pH of 4, passing it through a reduction column containing zinc particles and an extraction chromatography column containing P507 extraction resin connected thereto, and controlling The feed amount is 15 g/100 g of resin, the flow rate is 1 ml/min · cm ² , and the effluent is a pure hydrazine solution. Then, the pure ruthenium solution is oxidized with 3⁄40 _{2 to} form a trivalent ruthenium, and the acidity is adjusted to 0.2 with hydrochloric acid, and the P507 extraction chromatography column is passed to control the flow rate and the feed amount of the rare earth material, and the impurity ions such as zinc and calcium accompany the effluent. When flowing out, the ruthenium is adsorbed on the extraction chromatography column, and the concentration of 0.4 mol/L hydrochloric acid is used as the pickling solution 5 to flow through the P507 extraction chromatography column, and the feed amount is 10 g/100 g of resin, and the flow rate is 2.5 ml/min. Cm ² , a 99.99% cerium chloride solution was obtained.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 0.5 mol/L pH=3, using an extractant for naphthenic acid-long-chain alcohol-kerosene, NaOH for saponification, saponification degree of 80%, concentration of organic phase after split extraction Washed with 2 mol/L hydrochloric acid, the flow ratio is V _: V _f4 : V _ffi = 7:1:1. After multistage extraction and washing, the outlet aqueous phase 11 is a 99.995% cerium chloride solution. The washed organic phase 11 containing non-cerium rare earth and a small amount of cerium is subjected to secondary extraction, and the organic phase is extracted with a stripping acid I at a concentration of 1 mol/L hydrochloric acid and a stripping acid II at a concentration of 0.3 mol/L. Hydrochloric acid, stripping, flow ratio VVV _{I :} V _π =7:1:1:8. The second stripping solution has an outlet. The first stripping solution has a high content of cerium and a purity of about 99%. The second stripping solution mainly contains non-heavy rare earth elements, and the organic phase 13 after stripping. After washing with pure water and removing the free acid, it can be returned to sodium saponification. After multiple extractions, a solution of 99.999% ruthenium chloride is obtained.

The obtained high-purity rare earth chloride was precipitated by oxalic acid, and the precipitation reaction time was 4 hours. After washing with secondary ionized water, it was calcined at 80 CTC for 7 hours to prepare 4N~6N rare earth oxides.

Example 5

Disused fluorescent lamps and CRT monitors are disassembled and broken, and mercury vapor is collected under negative pressure. The used phosphors were washed with a 10% acetone solution and oxidized and dehydrated for 3 h at a concentration of 0.8 g/L potassium permanganate to remove residual mercury from the phosphor.

The cleaned rare earth luminescent material and the alkali (NaOH) are mixed and stirred uniformly, and the alkali fusion product obtained after alkali fusion for 9 hours at 80 CTC is uniformly removed by mass ratio 1:6 with water and then washed with secondary deionized water. The remaining NaOH and part of NaA10 are added to the rare earth-containing insolubles. The acid-solution ratio of insoluble matter to hydrochloric acid was 1:10 using 6 mol/L hydrochloric acid, and the pH of the insoluble matter to hydrochloric acid was 1:10. The pH of the acid solution was adjusted to 4 with ammonia water, and 4% of the compound was added. The flocculating agent removes Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

The rare earth chloride solution was adjusted to a pH of 3.5, and the REC1 ₃ content was 1 mol/L, and the extractant was subjected to extraction and separation of rare earth by using 1.5 mol/L of P204-sulfonated kerosene. First, the light rare earth group is grouped, and the rare earth (Ce, Eu, Tb, and BY) is extracted into the organic phase, and the light rare earth Ce entering the organic phase is washed with a concentration of 0.6 mol/L hydrochloric acid as the washing liquid 1, and the flow ratio is V _: V _l4 : V _ffi = 2.5: l: 0.2, a solution of CeCl ₃ was obtained. The organic phase 1 of the light rare earth group is stripped with 1.5 mol/L hydrochloric acid, and the flow ratio is VVV _7K = 0.1 _: 1:0.1. The middle rare earth is grouped. Finally, the P204-sulfonated kerosene is used as the organic phase to extract the heavy rare earth. The aqueous phase 2 is obtained with cerium-rich and cerium-rich aggregates respectively. The organic phase 2 of the intermediate rare earth group is back-extracted with 4mol/L hydrochloric acid, and the flow ratio is V _: V _7X = 2: 0.5. After multi-stage extraction, the obtained钇 rich, which contains about 75% bismuth

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 0.5mol/L, adding potassium permanganate 30g/L and mixing with the liquid, extracting agent is 1.5mol/L P507-sulfonated kerosene, and extracting light rare earth (Ce) Into the organic phase 4, with 0.8 mol / L hydrochloric acid as the pickling solution 2, the intermediate heavy rare earth entering the organic phase 5 is washed, the flow ratio is V: V 4: V _ffi = 2: l: 0.4, to obtain a light rare earth liquid ( CeCl ₄ ). The light rare earth was further stripped with 1.5 mol/L hydrochloric acid, and compared with V _: V*=l:0.2, a cerium chloride solution having a purity of 99.99% was obtained after multistage extraction.

Purification of hydrazine, using fractional fractionation extraction, the formulation liquid contains REC1 ₃ as lmol/L, extractant is 0.5mol/L P204-sulfonated kerosene, the first stage fractionation extraction: saponification degree 35% extractant and rare earth The feed liquid is simultaneously introduced into the tank and flows into the tank to form a rare earth saponification form into the tank. After the extraction, the organic phase 7 is washed with 3.5 mol/L hydrochloric acid, and the flow ratio V: V | ₄ : V _ffi = 20: 1:0.3, enters the first Two-stage fractional extraction: the organic phase 8 flowing out of the first extraction section is used as the feed liquid, and the second phase is the same organic phase and washing liquid as the first stage, V : V | ₄ : V _ffi = 12: l: 0.35 After multiple extractions, a cerium chloride solution having a purity of 99.99% is finally obtained.

Purification of hydrazine, adjusting the compound solution containing REC1 ₃ to 1 mol/L, pH value 1, and flowing it through the reduction column containing zinc particles and the extraction chromatography column containing P507 extraction resin connected thereto, and controlling The feed amount was 20 g/100 g of resin, the flow rate was 1.5 ml/min · cm ² , and the effluent was a pure hydrazine solution. Then use the pure bismuth solution with 3⁄40 ₂ oxygen The divalent bismuth is converted into trivalent ruthenium, and the acidity is adjusted to 0.4 with hydrochloric acid. The P507 extraction color layer column is passed to control the flow rate and the feed amount of the rare earth material. The impurity ions such as zinc and calcium flow out with the effluent, and the ruthenium is adsorbed in the extraction color. On the layer column, a concentration of 0.6 mol/L hydrochloric acid was used as the pickling solution 5 to flow through the P507 extraction chromatography column, the feed amount was 15 g/100 g of resin, the flow rate was 1.5 ml/min · cm ² , and the purity was 99.99%. Barium chloride solution.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1 mol/L, pH=2, using an extractant for naphthenic acid-long-chain alcohol-kerosene, NaOH for saponification, saponification degree of 90%, concentration of organic phase after split extraction After washing with 2.5 mol/L hydrochloric acid, the flow ratio was V:V | ₄ : V _ffi = 7:1: 1.5. After multistage extraction and washing, the outlet aqueous phase 11 was a 99.995% cerium chloride solution. The washed organic phase 11 containing non-cerium rare earth and a small amount of cerium is subjected to secondary extraction. The organic phase is extracted with a stripping acid I, a concentration of 1.5 mol/L hydrochloric acid, and a stripping acid II at a concentration of 0.4 mol/L hydrochloric acid. For stripping, the flow ratio is VVV _{I :} V _π =7:1:2:8·5 times, the stripping solution has an outlet, and the first stripping solution has a high content of cerium, and the purity is about 99%. The secondary stripping solution mainly contains non-heavy rare earth elements. The organic phase 13 after stripping is washed with pure water and then removed to free acid. After sodium saponification, it can be returned to use. After multiple extractions, the purity is 99.999%. Solution.

The obtained high-purity rare earth chloride was precipitated by oxalic acid, and the precipitation reaction time was 5 hours. After washing with secondary ionized water, it was calcined at 90 CTC for 9 hours to prepare 4N~6N rare earth oxides.

Example 6

Disused fluorescent lamps and CRT monitors are disassembled and broken, and mercury vapor is collected under negative pressure. The used phosphors were washed with a 20% acetone solution and oxidized and dehydrated for 0.5 h at a concentration of lg/L potassium permanganate to remove residual mercury from the phosphor.

The cleaned rare earth luminescent material and the alkali (KOH) are mixed and stirred uniformly, and the alkali fusion product obtained after alkali fusion at 100 CTC for 2 hours is uniformly removed by mass ratio 1:8 with water and then washed with secondary deionized water. The remaining KOH and a part of KA10 ₂ give a rare earth-containing insoluble matter. The acid-liquid ratio of insoluble matter to hydrochloric acid was 1:4 using 8 mol/L hydrochloric acid at 80 ° C, and the pH of the acid solution was adjusted to 3 with ammonia water, and 5^% of 1^ was added. The flocculating agent removes Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

The rare earth chloride solution was adjusted to a pH of 4, and the REC1 ₃ content was 1.5 mol/L, and the extractant was subjected to extraction and separation of rare earth by using 0.5 mol/L of P204-sulfonated kerosene. First, the light rare earth group is grouped, and the rare earth (Ce, Eu, Tb, and BY) is extracted into the organic phase, and the light rare earth Ce entering the organic phase is washed with a concentration of 0.8 mol/L hydrochloric acid as the washing liquid 1, and the flow ratio is V _: V _l4 : V _ffi = 3: 1 : 0.2, to obtain a CeCl ₃ solution. The organic phase 1 of the light rare earth group is stripped with 2 mol/L hydrochloric acid, and the flow ratio is VV _f 4w : V *=0.15:1:0.15. The middle rare earth is grouped, and finally the Ρ204-sulfonated kerosene is used as the organic phase extraction weight. The rare earth, the outlet aqueous phase 2 respectively obtained the cerium-rich and cerium-rich aggregates, and the organic phase 2 after the middle rare earth grouping was back-extracted with the rare earth with 4.5 mol/L hydrochloric acid, and the flow ratio was V _: V _7X = 2: 0.5. Stage extraction, obtained cerium enrichment, wherein the cerium content is about 75%

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ as lmol/L, adding potassium permanganate 40g/L and mixing with the liquid, extracting agent is 0.5mol/L P507-sulfonated kerosene, extracting light rare earth (Ce) The organic phase 4, with 1 mol/L hydrochloric acid as the pickling solution 2, is washed into the medium-heavy rare earth entering the organic phase 5, and the flow ratio is V: V _fi: V _ffi = 1.5 _: l: 0.8, to obtain a light rare earth liquid (CeCl ₄ ). The light rare earth was back-extracted with 2 mol/L hydrochloric acid, and compared with V _: V*=l:0.1, a cerium chloride solution having a purity of 99.99% was obtained after multistage extraction. Purification of hydrazine, using fractional fractionation extraction, the formulation liquid containing REC1 ₃ is 1.5mol/L, the extracting agent is 1mol/L P204-sulfonated kerosene, the first stage fractionation extraction: 40% saponification degree extractant and rare earth The feed liquid is simultaneously introduced into the tank and flows into the trough to form a rare earth saponification form. After the extraction, the organic phase 7 is washed with 4 mol/L hydrochloric acid, and the flow ratio is VV | ₄ : V _ffi = 10:1: 1.2, and the second stage is fractionated. Extraction: The organic phase 8 flowing out of the first extraction section is used as the feed liquid, and the second phase is the same organic phase and washing liquid as the first stage, V : V | ₄ : V _ffi = 18:1:2, After the second extraction, a cerium chloride solution having a purity of 99.99% was finally obtained.

Purification of hydrazine, the blending solution containing REC1 ₃ is 1.5mol/L pH 2, and it flows through the reduction column containing zinc particles and the extraction chromatography column with P507 extraction resin connected in series, and the control is carried out. The amount of the material was 25 g/100 g of resin, the flow rate was 0.5 ml/min · cm ² , and the effluent was a pure hydrazine solution. Then, the pure ruthenium solution is oxidized with H ₂ O _{2 to} form a trivalent ruthenium, and the acidity is adjusted to 0.6 with hydrochloric acid, and the P507 extraction color layer column is passed, and the flow rate and the feed amount of the rare earth material are controlled, and impurity ions such as zinc and calcium are used. The effluent flows out, and the ruthenium is adsorbed on the extraction chromatography column. The concentration of 0.8 mol/L hydrochloric acid is used as the acid washing liquid 5 and flows through the P507 extraction chromatography column. The feed amount is 20 g/100 g resin, and the flow rate is 2 ml/min. · cm ² to obtain a yttrium chloride solution with a purity of 99.99%.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1.5 mol/L pH=2.5, using the extractant for naphthenic acid-long-chain alcohol-kerosene, NaOH for saponification, saponification degree of 70%, concentration of organic phase after split extraction After washing with 3 mol/L hydrochloric acid, the flow ratio was V:V | ₄ : V _ffi = 6:1:2. After multistage extraction and washing, the outlet aqueous phase 11 was a 99.995% cerium chloride solution. The washed organic phase 11 containing non-cerium rare earth and a small amount of cerium is subjected to secondary extraction, and the organic phase is subjected to stripping acid I, a concentration of 2 mol/L hydrochloric acid, and a stripping acid II at a concentration of 0.5 mol/L hydrochloric acid. Stripping, the flow ratio is VVV _{I :} V _π =8:1:2:2.5. The second stripping solution has an outlet. The first stripping solution has a high content of cerium and a purity of about 99%. The second stripping solution mainly contains non-heavy rare earth elements, and the organic phase 13 after stripping. After washing with pure water and removing the free acid, it can be returned to sodium saponification. After multiple extractions, a solution of 99.999% ruthenium chloride is obtained.

The obtained high-purity rare earth chloride was precipitated by oxalic acid, and the precipitation reaction time was lh. After washing with secondary ionized water, it was calcined at 100CTC for 8 hours to prepare 4N~6N rare earth oxides.

Example 7

Disused fluorescent lamps and CRT monitors are disassembled and broken, and mercury vapor is collected under negative pressure. The waste phosphor was washed with a 30% by weight acetone solution, and the residual mercury in the phosphor was removed by oxidative demercuration for 1.5 h at a concentration of 0.2 g/L potassium permanganate.

The cleaned rare earth luminescent material and the alkali (NaOH) are mixed and stirred uniformly, and the alkali fusion product obtained after alkali fusion for 6 hours at 120 CTC is uniformly removed by mass ratio 1:1 with water, and washed with secondary deionized water. The remaining NaOH and part of NaA10 are added to the rare earth-containing insolubles. Acid hydrolysis was carried out at 30 ° C for 5 h with 3 mol/L hydrochloric acid. The solid-liquid ratio of insoluble matter to hydrochloric acid was 1:6, and the acid hydrolysis solution was adjusted to pH 4 with ammonia water, and 2% of 1% was added. The flocculating agent removes Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

The rare earth chloride solution is adjusted to a pH of 4.5, and wherein the REC1 ₃ content is 0.5 mol/L, and the extractant is subjected to extraction and separation of rare earth by using 1 mol/L of P204-sulfonated kerosene. First, the light rare earth group is grouped, and the rare earth (Ce Eu Tb and Y) is extracted into the organic phase, and the light rare earth Ce entering the organic phase is washed with a concentration of 1 mol/L hydrochloric acid as the washing liquid 1, and the flow ratio is VVV _ffi = 2: 1:0.25, a solution of CeCl ₃ was obtained. The light rare earth group is exported to the organic phase 1 by stripping the rare earth with 2.5 mol/L hydrochloric acid, and the flow ratio is VV. V water = 0.15:1:0.1 for medium rare earth grouping. Finally, P204-sulfonated kerosene is used as organic phase to extract heavy rare earth, and outlet water phase 2 is respectively obtained to obtain cerium and lanthanum-rich concentrates. The heavy rare earth was back-extracted with 3.5 mol/L hydrochloric acid, and the flow ratio was V _: V * = 2: 0.5. After multi-stage extraction, a cerium-rich concentrate was obtained, wherein the cerium content was about 75%.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1.5mol/L, adding potassium permanganate 50g/L and mixing with the liquid, extracting agent is 1mol/L P507-sulfonated kerosene, extracting light rare earth (Ce) Organic phase 4, with 0.3 mol/L hydrochloric acid as pickling solution 2, the medium heavy rare earth entering the organic phase 5 is washed, and the flow ratio is V: V _fi: V _ffi = 2.5 _: l: 0.4, and a light rare earth liquid (CeCl) is obtained. ₄ ). The light rare earth was back-extracted with 2.5 mol/L hydrochloric acid, and the ratio was V _: V*=1:0.15. After multistage extraction, a cerium chloride solution having a purity of 99.99% was obtained.

Purification of hydrazine, using fractional fractionation extraction, the formulation liquid containing REC1 ₃ is 0.5mol/L, the extracting agent is 1.5mol/L P204-sulfonated kerosene, the first stage fractionation extraction: saponification degree 25% extractant and The rare earth liquid enters the tank at the same time and flows into the trough after 10 stages. After the extraction, the organic phase 7 is washed with 4.5 mol/L hydrochloric acid, and the flow ratio V: V | ₄ : V _ffi = 15: l: 0.8, enters The second stage fractionation extraction: the organic phase 8 flowing out of the first extraction section is used as the feed liquid, and the second stage is the same organic phase and washing liquid as the first stage, V: V | ₄ : V _ffi = 12: l: 1.5, After multiple extractions, a cerium chloride solution having a purity of 99.99% is finally obtained.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 0.5 mol/L, pH 3, and flowing it through a reduction column containing zinc particles and an extraction chromatography column containing P507 extraction resin in series, controlled The feed amount was 30 g/100 g of resin, the flow rate was 1 ml/min · cm ² , and the effluent was a pure hydrazine solution. Then, the pure ruthenium solution is oxidized with 3⁄40 _{2 to} form a trivalent ruthenium, and the acidity is adjusted to 0.8 with hydrochloric acid, and the P507 extraction chromatography column is passed to control the flow rate and the feed amount of the rare earth material, and the impurity ions such as zinc and calcium accompany the effluent. When flowing out, the ruthenium is adsorbed on the extraction chromatography column, and the concentration of 1 mol/L hydrochloric acid is used as the acid washing liquid 5 through the P507 extraction chromatography column, and the feed amount is 5 g/100 g resin, and the flow rate is 2.5 ml/min · cm. ² , a purity of 99.99% cerium chloride solution is obtained.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 0.5 mol/L, pH=3, using the extractant for naphthenic acid-long-chain alcohol-kerosene, NaOH for saponification, saponification degree of 80%, and organic phase after split extraction The concentration was 2 mol/L hydrochloric acid washing, and the flow ratio was V:V | ₄ : V _ffi = 8:1:1. After multistage extraction and washing, the outlet aqueous phase 11 was a 99.995% cerium chloride solution. After washing, the organic phase 11 containing non-cerium rare earth and a small amount of cerium is subjected to secondary extraction, and the organic phase is subjected to stripping acid I, the concentration is 1 mol/L hydrochloric acid, and the stripping acid II is at a concentration of 0.1 mol/L hydrochloric acid. For stripping, the flow ratio is V. New: V new material: V stripping acid _I: V stripping acid _π = 8:1:1:8. The second stripping solution has an outlet. The first stripping solution has a high content of cerium and a purity of about 99%. The second stripping solution mainly contains non-heavy rare earth elements, and the organic phase 13 after stripping. After washing with pure water and removing the free acid, it can be returned to sodium saponification. After multiple extractions, a solution of 99.999% ruthenium chloride is obtained.

The obtained high-purity rare earth chloride was precipitated by oxalic acid, and the precipitation reaction time was 2 hours. After washing with secondary ionized water, it was baked at 110 CTC for 6 hours to obtain 4N~6N rare earth oxides.

Example 8

Disused fluorescent lamps and CRT monitors are disassembled and broken, and mercury vapor is collected under negative pressure. The used phosphors were washed with a 10% acetone solution and oxidized for mercury removal for 0.5 h at a concentration of 0.5 g/L potassium permanganate to remove residual mercury from the phosphor.

Mix the cleaned rare earth luminescent material with alkali (KOH) and mix well, according to the mass ratio of 1:3 After the water was uniformly stirred, the alkali fusion product obtained after alkali fusion for 10 hours at 60 CTC was washed with secondary deionized water to remove residual KOH and a part of KA10 _{2 to} obtain a rare earth-containing insoluble matter. Acid hydrolysis was carried out at 5 °C for 7 h with 5 mol/L hydrochloric acid. The solid-liquid ratio of insoluble matter to hydrochloric acid was 1:8, and the acid hydrolysis solution was adjusted to pH 5 with aqueous ammonia, and 3% was added. The flocculating agent removes Al ³⁺ from the acid hydrolysis solution to obtain a rare earth chloride solution.

The rare earth chloride solution was adjusted to a pH of 3.5, and the REC1 ₃ content was 1 mol/L, and the extractant was subjected to extraction and separation of rare earth by using 1.5 mol/L of P204-sulfonated kerosene. First, the light rare earth group is grouped, the rare earth (Ce, Eu, Tb and BY) is extracted into the organic phase, and the light rare earth Ce entering the organic phase is washed with a concentration of 0.7 mol/L hydrochloric acid as the washing liquid 1, and the flow ratio is V: V | ₄ : V _ffi = 2.5: 1:0.3, a solution of CeCl ₃ was obtained. Light rare earth group outlet organic phase 1 with 2mol/L hydrochloric acid stripped rare earth, flow ratio is V new: V i4w: V water = 0.15:1:0.1 for medium rare earth grouping, and finally P204-sulfonated kerosene for organic The phase extraction heavy rare earth, the outlet water phase 2 respectively obtain the cerium-rich and cerium-rich concentrates, and the intermediate organic phase 2 is combined with the organic phase 2 to back-extract the heavy rare earth with 4 mol/L hydrochloric acid, and the flow ratio is V _: V*=2:0.5. After multistage extraction, a ruthenium enrichment is obtained, wherein the ruthenium content is about 75%.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ as 1mol/L, adding potassium permanganate 10g/L and mixing with the liquid, extracting agent is 1.5mol/L P507-sulfonated kerosene, extracting light rare earth (Ce) Organic phase 4, with 0.5 mol/L hydrochloric acid as pickling solution 2, the intermediate heavy rare earth entering the organic phase 5 is washed, and the flow ratio is V: V _fi: V _ffi = 1.5 _: l: 0.6, and a light rare earth liquid (CeCl) is obtained. ₄ ). The light rare earth was further stripped with 1.5 mol/L hydrochloric acid, and compared with V _: V*=l:0.2, a cerium chloride solution having a purity of 99.99% was obtained after multistage extraction.

Purification of hydrazine, using fractional fractionation extraction, the formulation liquid contains REC1 ₃ as lmol/L, extractant is 0.5mol/L P204-sulfonated kerosene, the first stage fractionation extraction: 30% saponification degree extractant and rare earth The feed liquid enters the tank at the same time and flows into the trough to form a rare earth saponification form. After the extraction, the organic phase 7 is washed with 5 mol/L hydrochloric acid, and the flow ratio V _: V | ₄ : V _ffi = 6: l: 1.8, enters the second Fractional fractionation extraction: the organic phase 8 flowing out of the first extraction section is used as the feed liquid, and the second phase is the same organic phase and washing liquid as the first stage, V: VV _ffi = 18:1:0.35, multiple extraction Finally, a cerium chloride solution having a purity of 99.99% was obtained.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1 mol/L, pH 4, and flowing it through the reduction column containing zinc particles and the extraction chromatography column containing P507 extraction resin connected thereto, and controlling The feed amount was 20 g/100 g of resin, the flow rate was 1.5 ml/min · cm ² , and the effluent was a pure hydrazine solution. Then, the pure ruthenium solution is oxidized with 3⁄40 _{2 to} form a trivalent ruthenium, and the acidity is adjusted to 1 with hydrochloric acid, and the P507 extraction chromatography column is passed to control the flow rate and the feed amount of the rare earth material, and the impurity ions such as zinc and calcium accompany the effluent. When flowing out, the ruthenium is adsorbed on the extraction chromatography column, and the concentration of 0.3 mol/L hydrochloric acid is used as the pickling solution 5 to flow through the P507 extraction chromatography column, and the feed amount is 10 g/100 g of resin, and the flow rate is 1.5 ml/min. Cm ² , a 99.99% cerium chloride solution was obtained.

Purification of hydrazine, adjusting the dosage solution containing REC1 ₃ to 1 mol/L, pH=2, using an extractant for naphthenic acid-long-chain alcohol-kerosene, NaOH for saponification, saponification degree of 90%, concentration of organic phase after split extraction After washing with 2.5 mol/L hydrochloric acid, the flow ratio was V:V | ₄ : V _ffi = 7:1:2. After multistage extraction and washing, the outlet aqueous phase 11 was a 99.995% cerium chloride solution. The washed organic phase 11 containing non-cerium rare earth and a small amount of cerium is subjected to secondary extraction, and the organic phase is extracted with a stripping acid I, a concentration of 1.5 mol/L hydrochloric acid, and a stripping acid II at a concentration of 0.2 mol/L hydrochloric acid. For stripping, the flow ratio is V new: V new material: V stripping acid _I: V stripping = 9:1:1.5:8.5. The second stripping solution has an outlet, and the first stripping solution has a high content of cerium, and the purity is about 99%. The liquid mainly contains non-heavy rare earth elements. The organic phase 13 after stripping is washed with pure water and then removed to free acid. After sodium saponification, it can be returned to use. After multiple extractions, a purity of 99.999% cerium chloride solution is obtained.

The obtained high-purity rare earth chloride was precipitated by oxalic acid, and the precipitation reaction time was 3 hours. After washing with secondary ionized water, it was calcined at 120 CTC for 4 hours to prepare 4N~6N rare earth oxides.

Claims

claims

1. A method for recovering rare earths from waste rare earth luminescent materials, characterized in that: the recovery method includes the collection of waste phosphors, pretreatment, extraction and separation, extraction and purification, precipitation, and roasting, and mainly includes the following steps:

1) Collection of waste rare earth luminescent materials, including the rapid identification and dismantling of rare earth fluorescent lamps, the crushing of CRT monitors, and the separation and collection of waste rare earth luminescent materials and glass substrates;

2) Pretreatment of waste rare earth luminescent materials, including mercury removal oxidation precipitation, alkali fusion and acid hydrolysis;

4) Extraction and purification of rare earth elements to obtain 99.9%-99.9999% rare earth chloride;

5) Precipitation and separation of rare earth elements to obtain 99.9%-99.9999% rare earth oxalate or rare earth carbonate precipitates;

6) Calcination of rare earth oxalate or rare earth carbonate precipitates to obtain 99.9%-99.9999% rare earth oxides; the rare earth elements are mainly cerium, terbium, europium, and yttrium.

2. The method of recovering rare earths from waste rare earth luminescent materials according to claim 1, characterized in that: the pretreatment of waste rare earth luminescent materials in step 2):

(a) Mercury removal: Waste fluorescent lamps and CRT monitors are dismantled and broken, and mercury vapor is collected under negative pressure. Waste phosphors are cleaned with an acetone solution with a concentration of 10~30%, potassium permanganate with a concentration of 0.2~lg/L is used for oxidation reaction, zinc sulfide is added at 0.3~0.8g/L, and Hg ²⁺ is precipitated through a sulfidation reaction to remove The mercury treatment time is 0.5~5h, and finally the residual mercury in the phosphor is removed through activated carbon;

(b) Alkali fusion: Mix the cleaned waste rare earth luminescent materials with alkali and stir evenly. (Based on mass ratio) Waste rare earth luminescent materials: NaOH or KOH is 1:1~10, and the alkali is heated at 600~1200°C. After melting for 1 to 10 hours, the alkali fusion product undergoes secondary deionization and multiple washings before entering the next step of the acidolysis process;

(c) Acidolysis: The washed alkali fusion product is prepared with 3~8mol/L hydrochloric acid to prepare an acidolysis solution with a solid-liquid ratio of 1:3~10, and ammonia is used to adjust the pH value to a range of 3~5. Add 2~5^% of 1^. The flocculant is acidolyzed at 20~80°C for 1~8 hours to remove Al ³⁺ in the acidolysis solution to obtain a rare earth chloride solution.

3. The method for recovering rare earths from waste rare earth luminescent materials according to claim 1, characterized in that: in step 3), the rare earth chloride solution obtained by acidolysis in step 2 (c) is adjusted within a range of 3.5 ~4.5, and the REC1 ₃ content is 0.5~1.5mol/L. The extraction agent uses 0.5~1.5mol/L P204-sulfonated kerosene to extract and separate rare earths. First, group the light rare earths. Extract the rare earth Ce, Eu, Tb and Y into the organic phase. Use hydrochloric acid with a concentration of 0.6~1 mol/L as pickling solution 1 to wash the light rare earth Ce that enters the organic phase. Use V to represent the organic phase. The volume of the extraction agent, " represents the volume of the feed liquid, V _ffi represents the volume of the washing liquid, and the flow ratio is V: V 4: V _ffi =2~3: 1:0.2-0.3, to obtain the CeCl ₃ solution; the organic phase at the outlet of the light rare earth group 1 Use 1.5~2.5mol/L hydrochloric acid to strip the rare earths. Use Vxinyou to represent the volume of the new organic phase, Vmaterialyou to represent the volume of the organic phase in the feed liquid, Vwater to represent the volume of the water phase, and the flow ratio is Vxin There are: V materials include: V *=0.1~0.15:l:0.1~0.15. Group the medium rare earths. Finally, use P204-sulfonated kerosene as the organic phase to extract the heavy rare earths, and export the aqueous phase 2 to obtain europium- and terbium-containing concentrates respectively. , the outlet organic phase 2 after the medium rare earths are grouped is back-extracted with 3.5~4.5mol/L hydrochloric acid to extract the heavy rare earths. V represents the volume of the organic phase, V ₇ K represents the volume of the aqueous phase, V :V ₇ K=1:0.1~0.2, After multi-stage extraction, the yttrium enrichment is obtained; the heavy rare earth stripping solution uses concentration dialysis or evaporation to recover hydrochloric acid. 4. A method for recovering rare earths from waste rare earth luminescent materials according to claim 1, characterized in that: the purification of cerium in step 4) is to precipitate and roast the cerium enriched product with oxalic acid, and then use Dissolve sulfuric acid, prepare the liquid containing REC1 ₃ to 0.5~1.5mol/L, add 10~50g/L potassium permanganate and mix with the material, use the extraction agent as 0.5~1.5mol/L P507-sulfonated kerosene, and mix the light Rare earth Ce is extracted into the organic phase 4, using 0.2~1mol/L hydrochloric acid as the pickling liquid 2, and washing the medium and heavy rare earths entering the organic phase 5, using V to represent the organic extractant, V 4 to represent the volume of the feed liquid, V i* Indicates the volume of washing liquid, and the flow ratio is V _: V _4: V _ffi =1.5-2.5:1:0.

4-0.8, to obtain light rare earth liquid CeCl ₄ , and then back-extract the light rare earth with 1.5~2.5mol/L hydrochloric acid. Use V to represent the organic phase volume, V _7K to represent the aqueous phase volume, V: V *=l:0.1~0.2, After multi-stage extraction, a cerium chloride solution with a purity of 99.99% was obtained.

5. A method for recovering rare earths from waste rare earth luminescent materials according to claim 1, characterized in that: the purification of terbium in step 4) uses terbium enrichment as raw material and adopts staged fractional distillation extraction. The preparation liquid contains REC1 ₃ at 0.5~1.5mol/L, and the extraction agent is P204-sulfonated kerosene at 0.5~1.5mol/L mol/L. The first stage of fractional distillation extraction: an extraction agent with a saponification degree of 25%~40% and The rare earth material liquid enters the tank at the same time and flows for 10 stages and then enters the rare earth saponified form into the tank. After extraction, the organic phase 7 is washed with 3~5.5 mol/L hydrochloric acid. V represents the organic extractant, V 4 represents the volume of the material liquid, V i * represents the volume of washing liquid, flow ratio V _: V, ₄ : V _ffi =6~20:l: 0.3-1.8, enter the second stage of fractional distillation extraction: use the organic phase 8 flowing out of the first extraction stage as the feed liquid, use the The second stage uses the same organic phase and washing liquid as the first stage, using V to represent the organic extractant, V _fi to represent the feed liquid volume, V to represent the washing liquid volume, V : V : V _ffi =6.5~18:l:0.35 ~2.0, after multiple extractions, a terbium chloride solution with a purity of 99.99% was obtained.

6. A method for recovering rare earths from waste rare earth luminescent materials according to claim 1, characterized in that: the purification of europium in step 4) uses europium enrichment as raw material, and the prepared liquid contains REC1 ₃ The pH value is 0.5-1.5mol/L, and the pH value is 1~4. Let it flow through the reduction column equipped with zinc particles and the extraction chromatography column equipped with P507 extraction resin connected in series. Control the feed amount to 5~ 30g/hundred grams of resin, the flow rate is 0.5~1.5 ml/min - cm ² , the effluent is pure europium solution, and then the pure europium solution is oxidized with H ₂ 0 ₂ to convert divalent europium into trivalent europium, and use hydrochloric acid to adjust the acidity to 0.5 , flows through the P507 extraction chromatography column, and controls the flow rate and feed amount of rare earth materials. Impurity ions such as zinc and calcium flow out with the effluent, and europium is adsorbed on the extraction chromatography column. Hydrochloric acid with a concentration of 0.3~1.5 mol/L is used as the Acid wash solution 5 flows through the P507 extraction chromatography column, the feed amount is 5~20g/hundred grams of resin, the flow rate is 1.5~2.2ml/min·cm ² , and a europium chloride solution with a purity of 99.99% is obtained.

7. A method for recovering rare earths from waste rare earth luminescent materials according to claim 1, characterized in that: in the purification of yttrium in step 4), yttrium enrichment is used as raw material, and the preparation liquid contains REC1 ₃ is 0.5~1.5 mol/L, pH=2~3, the extraction agent is naphthenic acid-long chain alcohol-kerosene, NaOH is used for saponification, the saponification degree is 70~90%, and the concentration of the organic phase after split extraction is 2 ~3mol/L hydrochloric acid washing, V represents the organic extractant, V 4 represents the volume of the feed liquid, V ffi represents the volume of the washing liquid, the flow ratio is V _: V |4: V _ffi

=6-8:1:1-2, after multi-stage extraction and washing, the outlet water phase 11 is a yttrium chloride solution with a purity of 99.995%, and the washed organic phase 11 containing non-yttrium rare earths and a small amount of yttrium is subjected to secondary Second extraction, the organic phase is stripped with stripping acid I, with a concentration of 1~2mol/L hydrochloric acid, and stripping acid II, with a concentration of 0.1~0.5mol/L hydrochloric acid, V represents the newly added material liquid volume, V _β¾£βΙ represents the volume of stripping acid I, Vβ¾ _£βΙI represents the volume of stripping acid II, the flow ratio is VVVΙ _: _Vπ =6~8:1:1~2:8~9, the secondary stripping liquid There are separate exits, The organic phase 13 after stripping is washed with pure water to remove free acid, and then returned to use through sodium saponification. After multiple extractions, a yttrium chloride solution with a purity of 99.999% is obtained.

8. A method for recovering rare earths from waste rare earth luminescent materials according to claim 1, characterized in that: the step 5) uses oxalic acid with a purity of 99.5% to perform a precipitation reaction for 1 to 5 hours, and the precipitate is After washing with deionized water twice, it is sent to roasting.

9. A method for recovering rare earths from waste rare earth luminescent materials according to claim 1, characterized in that: the step 6) 4N is obtained by roasting the rare earth oxalate precipitate at high temperature, dehydrating, carbonizing, oxidizing, etc. ~6N rare earth oxide, the roasting temperature is 600~1200°C, and the roasting time is 1~10h.