CN109055783A - The recovery method of the middle rare earth of waste material containing rare earth oxide - Google Patents

The recovery method of the middle rare earth of waste material containing rare earth oxide Download PDF

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CN109055783A
CN109055783A CN201810927475.3A CN201810927475A CN109055783A CN 109055783 A CN109055783 A CN 109055783A CN 201810927475 A CN201810927475 A CN 201810927475A CN 109055783 A CN109055783 A CN 109055783A
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rare earth
waste material
earth oxide
material containing
containing rare
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CN109055783B (en
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吴希桃
王志坚
包新军
陈建波
翁国庆
夏楚平
兰石琨
胡婷
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HUNAN RESEARCH INSTITUTE OF RARE EARTH METAL MATERIALS
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HUNAN RESEARCH INSTITUTE OF RARE EARTH METAL MATERIALS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

This application involves a kind of recovery methods of middle rare earth of waste material containing rare earth oxide, comprising the following steps: will contain rare earth oxide waste material, highly basic and auxiliary agent mixing and roast, and obtain product of roasting；Product of roasting is washed using hot water multi-stage countercurrent, until the pH value of eluate is 7~9, obtains the washing slag containing rare earth oxide；Washing slag is used into strong acid multilevel counter-flow extraction, filtering obtains the leachate containing rare earth ion；Leachate is isolated and purified, with oxalic acid precipitation, calcination, obtains the rare earth oxide of high-purity.

Description

The recovery method of the middle rare earth of waste material containing rare earth oxide
Technical field
The present invention relates to technical field of rare earth resource recovery, more particularly to dilute in a kind of waste material containing rare earth oxide The recovery method of native oxide.
Background technique
The main composition of polishing powder from rare earth is cerium oxide, and epigranular, hardness are moderate, polishing efficiency is high, quality of finish Good, long service life and clean and environmental protection, are widely used for optical glass, liquid crystal glass base and touched panel glass cover board Polishing.In recent years as the industries such as handset touch panel, Vehicular display device, large-screen liquid crystal display television are risen, high-performance cerium base is dilute Native polishing powder is rapidly developed, and domestic dosage is more than 30,000 tons, derivative aqueous 150,000 tons/year of the useless mud of polishing powder from rare earth. In The Next 3-5 Years, the application market of polishing powder from rare earth will be thrown with 20~30% speed rapid growth, the rare earth of formation Light powder waste material is also by sustainable growth.
Rare earth resources are non-renewable, and are unevenly distributed in the earth's crust, cause its processing cost high, in European Union, the U.S. and day Originally narrow resources are had been cited as.Although China rare earth resource-niche is at the forefront in the world, as important strategic resource and can not It is alternative, it is valued by people it increasingly.
Realize the regeneration of polishing powder from rare earth waste material, it is possible to provide be used for nickel-metal hydride battery, rare earth energy storing material and rare earth The raw material of polishing powder are significant for sustainable development and environmental protection.
Have prior art discloses a kind of method of recovering rare earth oxide from polishing powder from rare earth waste material, it is pre- using calcination Processing, then using sulfuric acid, glacial acetic acid, cosolvent mixed liquor dissolve polishing powder from rare earth waste material, filtrate enter multitple extraction slot into The separation of row rare earth extraction, and use zinc powder reduction Eu3+Method obtain high-purity europium oxide.However this method is not in polishing powder waste material Impurity separated, and introduce new impurity Zn, be actually difficult to be made high-purity rare earth oxide.
Separately have and roasted polishing powder from rare earth waste material by alkali, after washed with impurities prior art discloses a kind of, using hydrochloric acid Acidification, NaOH tune pH, acidified filtrate obtain rare earth oxide finished product through oxalic acid precipitation, and acidification slag is dried through pure water to be aoxidized Rare earth finished product.However rare earth oxide purity made from this method is relatively low.
Summary of the invention
Based on this, it is necessary to provide rare earth oxygen in a kind of waste material containing rare earth oxide that high-purity rare earth oxide can be obtained The recovery method of compound.
A kind of recovery method of the middle rare earth of waste material containing rare earth oxide, comprising the following steps:
Rare earth oxide waste material, highly basic and auxiliary agent mixing will be contained to roast, obtain product of roasting；
The product of roasting is washed using hot water multi-stage countercurrent, until the pH value of eluate is 7~9, obtains oxygen containing rare earth The washing slag of compound；
The washing slag containing rare earth oxide is used into strong acid multilevel counter-flow extraction, filtering is obtained containing rare earth ion Leachate；
The leachate containing rare earth ion is isolated and purified, with oxalic acid precipitation, calcination, obtains rare earth oxide.
The rare earth oxide in the waste material containing rare earth oxide is cerium oxide and oxygen flower in one of the embodiments, Lanthanum；The waste material containing rare earth oxide also contains impurity, the impurity be in aluminium oxide, silica and fluorochemical at least It is a kind of.
The highly basic is sodium hydroxide or potassium hydroxide, mole of the impurity and highly basic in one of the embodiments, Than for 1:(1.2~4).
The auxiliary agent is carbon dust, ammonium chloride or ammonium hydrogen carbonate in one of the embodiments, described useless containing rare earth oxide The mass ratio of material and the auxiliary agent is (10~5): 1.
The temperature of the roasting is 550 DEG C~800 DEG C in one of the embodiments, and the time of the roasting is 1~4 Hour.
The series of the multi-stage countercurrent washing is 2~5 grades in one of the embodiments,.
The strong acid is hydrochloric acid, sulfuric acid or nitric acid in one of the embodiments,.
The series of the multilevel counter-flow extraction is 2~4 grades in one of the embodiments,.
The method isolated and purified in one of the embodiments, are as follows: use extractant multi-stage counter current extraction, washing and Back extraction.
The extractant is di-(2-ethylhexyl)phosphoric acid ester or 2- ethylhexyl phosphoric acid list in one of the embodiments, The combination of 2- ethylhexyl and kerosene, di-(2-ethylhexyl)phosphoric acid ester or 2- ethylhexyl phosphoric acid list 2- in the extractant The concentration of ethylhexyl is 1mol/L~2mol/L, and the saponification rate of the extractant is 30%~50%.
The recovery method of the above-mentioned middle rare earth of waste material containing rare earth oxide is made in waste material by highly basic and auxiliary agent roasting Impurity be converted to soluble-salt, then washed away using hot water multi-stage countercurrent, substantially increase impurity-eliminating effect, then is more by strong acid Stage countercurrent leaching makes the rare earth oxide in waste material be converted to rare earth ion as far as possible to be dissolved in leachate, by isolating and purifying Rare-earth ion solution after purification is obtained, finally by rare-earth ion solution oxalic acid precipitation after purification, calcination, height can be obtained The rare earth oxide of purity.
Detailed description of the invention
Fig. 1 is the process flow chart of the recovery method of the middle rare earth of waste material containing rare earth oxide of an embodiment.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases Any and all combinations of the listed item of pass.
Referring to Fig. 1, the recovery method of the middle rare earth of waste material containing rare earth oxide of an embodiment, including it is following Step S110~S160:
S110, waste material containing rare earth oxide is provided.
In the present embodiment, the rare earth oxide in above-mentioned waste material containing rare earth oxide is cerium oxide (CeO2) and oxidation Lanthanum (La2O3)。
Further, above-mentioned waste material containing rare earth oxide also contains impurity, which is aluminium oxide (Al2O3), silica (SiO2At least one of) and fluorochemical (F).
S120, the mixing of above-mentioned waste material containing rare earth oxide, highly basic and auxiliary agent is roasted, obtains product of roasting.
In the present embodiment, highly basic is sodium hydroxide or potassium hydroxide.
Further, the molar ratio of impurity and highly basic is 1:(1.2~4 in above-mentioned waste material containing rare earth oxide), being used for will Impurity in waste material is completely converted into soluble-salt.
In the present embodiment, auxiliary agent is carbon dust, ammonium chloride or ammonium hydrogen carbonate.
Further, the mass ratio of above-mentioned waste material containing rare earth oxide and auxiliary agent be (10~5): 1, for promote impurity with Highly basic reaction, makes the impurity in waste material fast and effeciently be transformed into soluble-salt.
Further, the temperature of roasting is 550 DEG C~800 DEG C, and the time of roasting is 1~4 hour.
Waste material, highly basic and auxiliary agent are mixed and roasted, by the molar ratio of impurity and highly basic in control waste material and useless The mass ratio of material and auxiliary agent, can make the impurity in waste material fast and effeciently be converted to soluble-salt.
In the present embodiment, oxidation-containing cerium, lanthana, meta-aluminate, silicate and fluoride salt in above-mentioned product of roasting.
S130, above-mentioned product of roasting is washed using hot water multi-stage countercurrent, until the pH value of eluate is 7~9, is obtained containing dilute The washing slag of native oxide.
In the present embodiment, the series of multi-stage countercurrent washing is 2~5 grades.
It is appreciated that the series of above-mentioned multi-stage countercurrent washing is unlimited, as long as can be by the soluble-salt in product of roasting, residue Highly basic and auxiliary agent removal.
Product of roasting is washed using hot water multi-stage countercurrent, the impurity for being converted to soluble-salt by step S120 is i.e. solvable It is removed in hot water, rare earth oxide then stays in washing slag.
Product of roasting is washed using hot water multi-stage countercurrent, the amount of washes on the one hand can be reduced, it is dirty to reduce environment On the other hand dye can greatly improve impurity-eliminating effect, reduce the difficulty of later separation purifying.
In the present embodiment, oxidation-containing cerium and lanthana in above-mentioned washing slag.
S140, by the above-mentioned washing slag containing rare earth oxide use strong acid multilevel counter-flow extraction, filtering, obtain containing rare earth from The leachate of son.
In the present embodiment, strong acid is hydrochloric acid, sulfuric acid or nitric acid.
Further, the series of multilevel counter-flow extraction is 2~4 grades.
It is appreciated that the series of above-mentioned multilevel counter-flow extraction is unlimited, as long as can be whole by the rare earth oxide in washing slag It is converted to rare earth ion.
Washing slag containing rare earth oxide is used into strong acid multilevel counter-flow extraction, acid consumption can be greatly reduced.
In the present embodiment, cerium ion and lanthanum ion are contained in above-mentioned leachate, and the pH value of leachate is 1~3.
S150, the above-mentioned leachate containing rare earth ion is isolated and purified, obtains rare-earth ion solution after purification.
In the present embodiment, the method isolated and purified are as follows: use extractant multi-stage counter current extraction, washing and back extraction.
Further, extractant be di-(2-ethylhexyl)phosphoric acid ester (P204) or 2- ethylhexyl phosphoric acid single 2-ethyl oneself The combination of base ester (P507) and kerosene, di-(2-ethylhexyl)phosphoric acid ester or 2- ethylhexyl phosphoric acid single 2-ethyl in the extractant The concentration of hexyl ester is 1mol/L~2mol/L, and the saponification rate of the extractant is 30%~50%.
Above-mentioned extractant combines P204 or P507 with kerosene, by control extractant in P204 or P507 concentration with And the saponification rate of extractant, effectively the cerium ion in leachate can be extracted.
In the present embodiment, the acidity of the leachate as made from step S140 containing rare earth ion is just suitable for extracting System is taken, extraction process can directly be carried out by needing not move through acidity adjustment, reduce operation link.
It is appreciated that after the leachate containing cerium ion and lanthanum ion is used extractant multi-stage counter current extraction, cerium ion quilt It is extracted in extractant step by step, then (the hydrochloric acid three-level of 1.3mol/L is washed), (the hydrochloric acid two-stage of 3mol/L is anti-for back extraction by washing Extraction), the strip liquor containing cerium ion is obtained, lanthanum ion then rests in leachate.
It should be noted that the above-mentioned method isolated and purified is unlimited, as long as can make difference in leachate by isolating and purifying Rare earth ion separate, obtain several rare-earth ion solutions after purification.
S160, by above-mentioned rare-earth ion solution oxalic acid precipitation after purification, calcination, obtain rare earth oxide.
Wherein, the temperature of calcination is 800 DEG C.
Several rare-earth ion solutions after purification are used oxalic acid precipitation, calcination by step S160 respectively, and corresponding height can be obtained The rare earth oxide of purity.
In the present embodiment, the leachate oxalic acid precipitation containing lanthanum ion, calcination, obtain 99.5% or more purity alumina Lanthanum.Strip liquor oxalic acid precipitation containing cerium ion, calcination obtain the cerium oxide of 99.5% or more purity.
The recovery method of the above-mentioned middle rare earth of waste material containing rare earth oxide is made in waste material by highly basic and auxiliary agent roasting Impurity be converted to soluble-salt, then using hot water multi-stage countercurrent wash, 90% or more Impurity elution in waste material can be made, greatly Improve impurity-eliminating effect greatly, then by strong acid multilevel counter-flow extraction make the rare earth oxide in waste material be converted to as far as possible rare earth from Son is dissolved in leachate, separates rare earth ion different in leachate by isolating and purifying, obtain it is several after purification Rare-earth ion solution, finally several rare-earth ion solutions after purification are used into oxalic acid precipitation, calcination respectively, can be obtained corresponding The rate of recovery of the rare earth oxide of high-purity, rare earth oxide reaches 85% or more.
In addition, the alkaline wash water generated through multi-stage countercurrent washing can be neutralized with the acid waste water after oxalic acid precipitation, entire mistake Journey does not have extra waste water to generate, environmentally friendly, pollution-free.
The recovery method of the above-mentioned middle rare earth of waste material containing rare earth oxide, being suitable for any impurity can by alkali roasting To be converted into the waste material containing rare earth oxide of soluble-salt.
The following are specific embodiments.
It should be noted that the waste material containing rare earth oxide and impurity is polishing powder from rare earth waste material in embodiment 1-4, Chemical composition is as shown in table 1:
Table 1
Embodiment 1
(1) polishing powder from rare earth waste material 500g, sodium hydroxide 168g and carbon dust 50g are weighed, is uniformly mixed, obtains in batch mixer To mixture；Wherein, in molar ratio, (Al in polishing powder from rare earth waste material2O3+SiO2+ F): highly basic=(1:1.2)；In mass ratio, Polishing powder from rare earth waste material: carbon dust=(10:1)；
(2) mixture is placed in crucible, crucible is placed in Muffle furnace, roasted, calcination temperature is 550 DEG C, the calcination time is 4h, obtains product of roasting；
(3) product of roasting is cooling, four-stage counter-current is carried out using hot water and is washed to pH value nearly 7, washing slag is obtained.
(4) leachate and filter residue that pH is 1 is obtained by filtration with the leaching of hydrochloric acid two-stage countercurrent in washing slag；
(5) leachate is extracted through ten stage countercurrent of 1.5mol/LP507+ kerosene extraction system, then using 1.3mol/L's The washing of hydrochloric acid three-level, the hydrochloric acid two-stage back extraction of 3mol/L, raffinate and strip liquor use oxalic acid precipitation respectively, and obtained filter cake exists Calcination is carried out at 800 DEG C, respectively obtains high-purity lanthana and cerium oxide product.The results are shown in Table 2 for its analysis
Table 2
Ingredient La2O3 CeO2 Al2O3 CaO MgO SiO2 F Other
Product La2O3, mass content/% 99.65 0.08 0.015 0.05 0.03 0.016 0.013 0.146
Products C eO2, mass content/% 0.05 99.51 0.017 0.03 0.07 0.016 0.013 0.294
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, unlike, comparative example 1 is substituted by the way of directly washing using heat The washing of water multi-stage countercurrent, obtained product purity and embodiment 1 are close, but compared with embodiment 1 compared to leaching requirement consumed by it Big 3 times or more, also big 3 times or more of the wastewater flow rate of generation.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, unlike, comparative example 2 is substituted by the way of being directly added into strong acid adopts With strong acid multilevel counter-flow extraction, obtained product purity and embodiment 1 are close, but its leaching rate is with respect to the decline of embodiment 1 5% Left and right.
Embodiment 2
(1) polishing powder from rare earth waste material 500g, potassium hydroxide 391g and ammonium chloride 50g are weighed, is uniformly mixed in batch mixer, Obtain mixture；Wherein, in molar ratio, (Al in polishing powder from rare earth waste material2O3+SiO2+ F): potassium hydroxide=(1:2)；By quality Than polishing powder from rare earth waste material: ammonium chloride=(10:1)；
(2) mixture is placed in crucible, crucible is placed in Muffle furnace, roasted, calcination temperature is 800 DEG C, the calcination time is 1h, obtains product of roasting；
(3) product of roasting is cooling, two-stage countercurrent is carried out using hot water and is washed to nearly pH9, washing slag is obtained.
(4) leachate and filter residue that pH is 3 is obtained by filtration with the leaching of sulfuric acid four-stage counter-current in washing slag；
(5) leachate is respectively obtained into high-purity lanthana and cerium oxide finished product by extraction and separation.It analyzes result such as Shown in table 3.Other conditions in the present embodiment are in the same manner as in Example 1.
Table 3
Embodiment 3
(1) polishing powder from rare earth waste material 500g, potassium hydroxide 588g and ammonium hydrogen carbonate 62.5g are weighed, is mixed in batch mixer Uniformly, mixture is obtained；Wherein, in molar ratio, (Al in polishing powder from rare earth waste material2O3+SiO2+ F): potassium hydroxide=(1:3)； In mass ratio, polishing powder from rare earth waste material: ammonium hydrogen carbonate=(8:1)；
(2) mixture is placed in crucible, crucible is placed in Muffle furnace, roasted, calcination temperature is 600 DEG C, the calcination time is 3h, obtains product of roasting；
(3) product of roasting is cooling, three-level countercurrent washing is carried out to nearly pH9 using hot water, obtains washing slag.
(4) leachate and filter residue that pH is 2 is obtained by filtration with nitric acid three-level counterflow leaching in washing slag；
(5) leachate is respectively obtained into high-purity lanthana and cerium oxide finished product by extraction and separation.It analyzes result such as Shown in table 4.Other conditions in the present embodiment are in the same manner as in Example 1.
Table 4
Embodiment 4
(1) polishing powder from rare earth waste material 500g, sodium hydroxide 558g and carbon dust 100g are weighed, is uniformly mixed in batch mixer, Obtain mixture；Wherein, in molar ratio, (Al in polishing powder from rare earth waste material2O3+SiO2+ F): sodium hydroxide=(1:4)；By quality Than polishing powder from rare earth waste material: carbon dust=(5:1)；
(2) mixture is placed in crucible, crucible is placed in Muffle furnace, roasted, calcination temperature is 800 DEG C, the calcination time is 4h, obtains product of roasting；
(3) product of roasting is cooling, Pyatyi countercurrent washing is carried out to nearly pH8 using hot water, obtains washing slag.
(4) leachate and filter residue that pH is 2 is obtained by filtration with sulfuric acid three-level counterflow leaching in washing slag；
(5) leachate is respectively obtained into high-purity lanthana and cerium oxide finished product by extraction and separation.It analyzes result such as Shown in table 5.Other conditions in the present embodiment are in the same manner as in Example 1.
Table 5
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of recovery method of the middle rare earth of waste material containing rare earth oxide, which comprises the following steps:
Rare earth oxide waste material, highly basic and auxiliary agent mixing will be contained to roast, obtain product of roasting；
The product of roasting is washed using hot water multi-stage countercurrent, until the pH value of eluate is 7~9, is obtained containing rare earth oxide Washing slag；
The washing slag containing rare earth oxide is used into strong acid multilevel counter-flow extraction, filtering obtains the leaching containing rare earth ion Liquid；
The leachate containing rare earth ion is isolated and purified, with oxalic acid precipitation, calcination, obtains rare earth oxide.
2. the recovery method of the middle rare earth of waste material containing rare earth oxide according to claim 1, which is characterized in that institute Stating the rare earth oxide in waste material containing rare earth oxide is cerium oxide and lanthana；Also contain in the waste material containing rare earth oxide Impurity, the impurity are at least one of aluminium oxide, silica and fluorochemical.
3. the recovery method of the middle rare earth of waste material containing rare earth oxide according to claim 2, which is characterized in that institute Highly basic is stated as sodium hydroxide or potassium hydroxide, the molar ratio of the impurity and highly basic is 1:(1.2~4).
4. the recovery method of the middle rare earth of waste material containing rare earth oxide according to claim 2, which is characterized in that institute Stating auxiliary agent is carbon dust, ammonium chloride or ammonium hydrogen carbonate, the mass ratio of the waste material containing rare earth oxide and the auxiliary agent be (10~ 5):1。
5. the recovery method of the middle rare earth of waste material containing rare earth oxide according to claim 1, which is characterized in that institute The temperature for stating roasting is 550 DEG C~800 DEG C, and the time of the roasting is 1~4 hour.
6. the recovery method of the middle rare earth of waste material containing rare earth oxide according to claim 1, which is characterized in that institute The series for stating multi-stage countercurrent washing is 2~5 grades.
7. the recovery method of the middle rare earth of waste material containing rare earth oxide according to claim 1, which is characterized in that institute Stating strong acid is hydrochloric acid, sulfuric acid or nitric acid.
8. the recovery method of the middle rare earth of waste material containing rare earth oxide according to claim 1, which is characterized in that institute The series for stating multilevel counter-flow extraction is 2~4 grades.
9. special according to the recovery method of the described in any item middle rare earths of waste material containing rare earth oxide of claim 2~8 Sign is, the method isolated and purified are as follows: uses extractant multi-stage counter current extraction, washing and back extraction.
10. the recovery method of the middle rare earth of waste material containing rare earth oxide according to claim 9, which is characterized in that The extractant is the combination of di-(2-ethylhexyl)phosphoric acid ester or 2- ethylhexyl phosphoric acid single 2-ethyl hexyl ester and kerosene, institute State in extractant the concentration of di-(2-ethylhexyl)phosphoric acid ester or 2- ethylhexyl phosphoric acid single 2-ethyl hexyl ester be 1mol/L~ 2mol/L, the saponification rate of the extractant are 30%~50%.
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