CN111593206A - Method for extracting valuable metal from rare earth secondary resource - Google Patents
Method for extracting valuable metal from rare earth secondary resource Download PDFInfo
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- CN111593206A CN111593206A CN202010649003.3A CN202010649003A CN111593206A CN 111593206 A CN111593206 A CN 111593206A CN 202010649003 A CN202010649003 A CN 202010649003A CN 111593206 A CN111593206 A CN 111593206A
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- rare earth
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- slag
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention provides a method for extracting valuable metals from rare earth secondary resources, which comprises the following steps: s1, putting the fluoride system rare earth molten salt electrolysis slag into a hydrochloric acid solution for leaching and filtering to obtain a leachate; s2, adding hydrogen peroxide and sodium hydroxide into the leachate obtained in the step S1 for pretreatment and filtration to obtain filtrate; s3, evaporating the filtrate obtained in the step S2; s4, slowly adding the supernatant evaporated in the step S3 into a hot sodium carbonate solution for reaction, filtering after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain lithium carbonate solid.
Description
Technical Field
One or more embodiments of the present disclosure relate to the technical field of industrial waste residue treatment, and in particular, to a method for extracting valuable metals from rare earth secondary resources.
Background
In the industry of the prior art, RE is often adopted2O3-REF3The molten salt electrolysis of LiF system produces rare earth metals and alloys. When rare earth oxide is electrolyzed, the melting point of the molten salt can be obviously reduced by adding LiF, the conductivity of the system can be improved, and the electrolysis efficiency is improved. Since impurities carried by raw materials, volatilization of electrolytes, deposition of rare earth oxides and fluorides and the like all deteriorate the properties of molten salts, so that the electrolysis efficiency in the electrolysis process is reduced, and the problems of excessive inspection of product quality and the like occur, the original old electrolyte needs to be replaced by a new molten salt electrolyte, thereby generating molten salt electrolysis slag. The fused salt electrolysis slag not only contains a large amount of rare earth, but also contains considerable lithium, has obvious resource property and can be used as important secondary resource of the lithium.
At present, the work of recycling rare earth molten salt electrolytic slag is centered on recycling rare earth, but the recycling of lithium in waste slag is not greatly broken through, so that the waste of lithium resources is caused.
Disclosure of Invention
In view of the above, an object of one or more embodiments of the present disclosure is to provide a method for extracting valuable metals from rare earth secondary resources, so as to solve the problems set forth in the background art.
In view of the above objects, one or more embodiments of the present specification provide a method for extracting valuable metals from rare earth secondary resources, including the steps of:
s1, putting the fluoride system rare earth molten salt electrolysis slag into a hydrochloric acid solution for leaching and filtering to obtain a leachate;
s2, adding hydrogen peroxide and sodium hydroxide into the leachate obtained in the step S1 for pretreatment and filtration to obtain filtrate;
s3, evaporating the filtrate obtained in the step S2;
and S4, slowly adding the supernatant evaporated in the step S3 into a hot sodium carbonate solution for reaction, filtering after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a lithium carbonate solid.
Preferably, the fluoride system rare earth molten salt electrolytic slag in the step S1 is obtained by electrolyzing rare earth by an electrolytic system composed of rare earth fluoride-rare earth oxide-LiF.
Preferably, in the step S1, the concentration of the hydrochloric acid solution is 2 to 6mol/L, the liquid-solid ratio of the hydrochloric acid solution to the electrolytic slag is 4:1 to 12:1, the leaching temperature is 50 to 90 ℃, and the leaching time is 2 to 4 hours.
Preferably, in the step S2, the pH value of the sodium hydroxide solution is 2-10, the concentration of the hydrogen peroxide solution is 30%, and the addition amount of the sodium hydroxide solution and the hydrogen peroxide solution is 3-3.5% of the volume amount of the original solution.
Preferably, the volume of the solution evaporated in the step S3 is 50-90% of the volume of the original filtrate.
Preferably, the concentration of the sodium carbonate solution in the step 4 is 200-400g/L, the temperature is 50-90 ℃, and the dropping speed of the supernatant is 1-5 ml/min.
From the above, it can be seen that the beneficial effects of the present invention are: according to the method for extracting lithium from the fluoride salt system rare earth molten salt electrolytic slag, a systematic, complete and feasible process is made for recovering lithium from raw materials to products in the rare earth molten salt electrolytic slag, leaching slag, pretreatment slag and the like generated in the process can be recovered, the resource utilization rate is greatly improved, lithium carbonate is finally obtained, the recovery of lithium is completed, and the cost for recovering rare earth is saved.
Drawings
In order to more clearly illustrate one or more embodiments or prior art solutions of the present specification, the drawings that are needed in the description of the embodiments or prior art will be briefly described below, and it is obvious that the drawings in the following description are only one or more embodiments of the present specification, and that other drawings may be obtained by those skilled in the art without inventive effort from these drawings.
FIG. 1 is a flow chart of a method for extracting lithium from fluoride salt system rare earth molten salt electrolysis slag provided by the invention;
fig. 2 is an XRD pattern of the lithium carbonate product prepared by the method.
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to specific embodiments.
Referring to fig. 1-2, a method for extracting valuable metals from rare earth secondary resources includes the following steps:
s1, putting the fluoride system rare earth molten salt electrolysis slag into a hydrochloric acid solution for leaching and filtering to obtain a leachate;
s2, adding hydrogen peroxide and sodium hydroxide into the leachate obtained in the step S1 for pretreatment and filtration to obtain filtrate;
s3, evaporating the filtrate obtained in the step S2;
and S4, slowly adding the supernatant evaporated in the step S3 into a hot sodium carbonate solution for reaction, filtering after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a lithium carbonate solid.
As a modification of the above scheme, the fluoride system rare earth molten salt electrolytic slag in step S1 is obtained after rare earth is electrolyzed by an electrolytic system composed of rare earth fluoride, rare earth oxide and LiF.
As a modified scheme of the scheme, in the step S1, the concentration of the hydrochloric acid solution is 2-6mol/L, the liquid-solid ratio of the hydrochloric acid solution to the electrolytic slag is 4:1-12:1, the leaching temperature is 50-90 ℃, and the leaching time is 2-4 h.
As an improvement of the above scheme, in the step S2, the pH value of the sodium hydroxide solution is 2-10, the concentration of the hydrogen peroxide solution is 30%, and the addition amount of the sodium hydroxide solution and the hydrogen peroxide solution is 3-3.5% of the volume amount of the original solution.
As a modification of the above, the volume of the solution evaporated in step S3 is 50-90% of the original volume of the filtrate.
As a modification of the above scheme, the concentration of the sodium carbonate solution in the step 4 is 200-400g/L, the temperature is 50-90 ℃, and the dropping speed of the supernatant is 1-5 ml/min.
Example one
Taking 0.5kg of rare earth fluoride system rare earth molten salt electrolysis slag to react with hydrochloric acid solution, wherein the content of Li is 2.92%, the concentration of hydrochloric acid is 3mol/L, the solid-to-solid ratio of hydrochloric acid to electrolysis slag solution is 10:1, the leaching temperature is 80 ℃, the leaching time is 2h, and filtering after the leaching process is finished to obtain leachate.
Adding hydrogen peroxide solution and sodium hydroxide solution into the leachate for pretreatment, wherein the volume of the added hydrogen peroxide solution is 3% of the volume of the treated solution, and the pH value of the solution is 6.
And filtering after the pretreatment is finished to obtain a filtrate, evaporating the filtrate to obtain 50% of the original volume, slowly adding the supernatant into the heated sodium carbonate solution after evaporation (wherein the concentration of the sodium carbonate is adjusted to 250g/L, the dropwise adding speed of the supernatant is 2ml/min, and the temperature is 90 ℃), and filtering after the reaction is finished to obtain a solid product lithium carbonate, wherein the total recovery rate of lithium is 40.15%.
Example two
Reacting 1kg of rare earth fused salt electrolytic slag of a rare earth fluoride system with a hydrochloric acid solution, wherein the content of Li is 3.02%, the concentration of hydrochloric acid is 6mol/L, the solid-to-solid ratio of hydrochloric acid to electrolytic slag solution is 12:1, the leaching temperature is 80 ℃, the leaching time is 4h, and filtering after the leaching process is finished to obtain a leaching solution.
Adding hydrogen peroxide solution and sodium hydroxide solution into the leachate for pretreatment, wherein the volume of the added hydrogen peroxide solution is 3.5 percent of the volume of the treated solution, and the pH value of the solution is 12.
And filtering after the pretreatment is finished to obtain a filtrate, evaporating the filtrate to obtain a filtrate with the evaporation ratio of 80% of the original volume, slowly adding a supernatant into the heated sodium carbonate solution after evaporation (wherein the concentration of the sodium carbonate is adjusted to 300g/L, the dropwise adding speed of the supernatant is 5ml/min, and the temperature is 80 ℃), and filtering after the reaction is finished to obtain a solid product lithium carbonate, wherein the total recovery rate of lithium is 40.11%.
EXAMPLE III
Taking 1.5kg of rare earth fused salt electrolytic slag of a rare earth fluoride system, wherein the content of Li is 2.95%, the concentration of hydrochloric acid is 5mol/L, the solid-to-solid ratio of the hydrochloric acid to the electrolytic slag is 5:1, the leaching temperature is 90 ℃, the leaching time is 3h, and filtering after the leaching process is finished to obtain a leaching solution.
Adding hydrogen peroxide solution and sodium hydroxide solution into the leachate for pretreatment, wherein the volume of the added hydrogen peroxide solution is 3.2 percent of the volume of the treated solution, and the pH value of the solution is 10.
And filtering after the pretreatment is finished to obtain a filtrate, evaporating the filtrate to obtain a filtrate with the evaporation proportion of 90% of the original volume, slowly adding a supernatant into a hot sodium carbonate solution after evaporation (wherein the concentration of sodium carbonate is adjusted to 350g/L, the dropwise adding speed of the supernatant is 1ml/min, and the temperature is set to 75 ℃), and filtering after the reaction is finished to obtain a solid product lithium carbonate with the total lithium recovery rate of 40.24%.
It is intended that the one or more embodiments of the present specification embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (6)
1. A method for extracting valuable metals from rare earth secondary resources is characterized by comprising the following steps:
s1, putting the fluoride system rare earth molten salt electrolysis slag into a hydrochloric acid solution for leaching and filtering to obtain a leachate;
s2, adding hydrogen peroxide and sodium hydroxide into the leachate obtained in the step S1 for pretreatment and filtration to obtain filtrate;
s3, evaporating the filtrate obtained in the step S2;
and S4, slowly adding the supernatant evaporated in the step S3 into a hot sodium carbonate solution for reaction, filtering after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a lithium carbonate solid.
2. The method for extracting valuable metals from rare earth secondary resources according to claim 1, wherein the fluoride system rare earth molten salt electrolytic slag in the step S1 is slag obtained after rare earth is electrolyzed by an electrolytic system consisting of rare earth fluoride-rare earth oxide-LiF.
3. The method for extracting valuable metals from rare earth secondary resources according to claim 1, wherein in the step S1, the concentration of the hydrochloric acid solution is 2-6mol/L, the liquid-solid ratio of the hydrochloric acid solution to the electrolytic slag is 4:1-12:1, the leaching temperature is 50-90 ℃, and the leaching time is 2-4 h.
4. The method for extracting valuable metals from rare earth secondary resources according to claim 1, wherein the pH of the sodium hydroxide solution in the step S2 is 2-10, the concentration of the hydrogen peroxide solution is 30%, and the addition amount of the sodium hydroxide solution and the hydrogen peroxide solution is 3-3.5% of the volume amount of the original solution.
5. The method of claim 1, wherein the volume of the solution evaporated in step S3 is 50-90% of the volume of the original filtrate.
6. The method as claimed in claim 5, wherein the concentration of the sodium carbonate solution in step 4 is 200-400g/L, the temperature is 50-90 ℃, and the dropping speed of the supernatant is 1-5 ml/min.
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| CN202010649003.3A CN111593206A (en) | 2020-07-08 | 2020-07-08 | Method for extracting valuable metal from rare earth secondary resource |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115959688A (en) * | 2022-12-20 | 2023-04-14 | 江西赣锋循环科技有限公司 | Method for preparing high-quality lithium salt by recycling rare earth molten salt slag |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567985A (en) * | 2015-12-28 | 2016-05-11 | 江苏金石稀土有限公司 | Recovery method of rare earth metal electrolysis fused salt slag |
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- 2020-07-08 CN CN202010649003.3A patent/CN111593206A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567985A (en) * | 2015-12-28 | 2016-05-11 | 江苏金石稀土有限公司 | Recovery method of rare earth metal electrolysis fused salt slag |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115959688A (en) * | 2022-12-20 | 2023-04-14 | 江西赣锋循环科技有限公司 | Method for preparing high-quality lithium salt by recycling rare earth molten salt slag |
| CN115959688B (en) * | 2022-12-20 | 2024-04-09 | 江西赣锋循环科技有限公司 | Method for preparing high-quality lithium salt by recycling rare earth molten salt slag |
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