CN116694933A - Method for recycling nickel cobalt lithium manganate waste by wet method - Google Patents
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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
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
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- 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
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- C22B7/007—Wet processes by acid leaching
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Abstract
The invention discloses a method for recycling nickel cobalt lithium manganate waste by a wet method, belongs to the field of waste lithium battery recycling, and solves the problem of lithium loss in the existing wet process. The method comprises the following steps: adding concentrated sulfuric acid, hydrogen peroxide and pure water after calcining the lithium nickel cobalt manganese oxide waste, and filtering to obtain a leaching solution I; heating the leaching solution I, adding calcined materials, hydrogen peroxide and concentrated sulfuric acid, and filtering to obtain a leaching solution II; heating the leaching solution II, filtering to obtain manganese sulfate crystals and leaching solution III, and cooling the leaching solution III to obtain cobalt sulfate and nickel sulfate mixed crystals and leaching solution IV; repeating the operation of the leaching solution IV, adding sodium hydroxide after the lithium content in the leaching solution is enriched, and filtering to obtain a ternary precursor and a lithium sulfate solution; and (3) carbonizing the lithium sulfate solution, adding sulfuric acid, freezing, and filtering to obtain sodium sulfate decahydrate and a lithium sulfate solution without sodium sulfate. The invention uses a method of combining hot melting and freezing to recycle valuable metal lithium in the sodium sulfate decahydrate crystal water, thereby reducing lithium loss.
Description
Technical Field
The invention belongs to the field of waste lithium battery recovery, and particularly relates to a method for recovering nickel cobalt lithium manganate waste by a wet method.
Background
With the rapid development of the lithium battery industry, more and more waste lithium batteries are generated, so that the waste of resources and the environmental pollution are caused. Therefore, the method has great significance in recovering valuable metals in the waste lithium batteries. At present, the treatment modes of the positive electrode material of the nickel cobalt lithium manganate mainly comprise a fire method and a wet method. During wet recovery, valuable metals are prepared into cobalt sulfate, manganese sulfate and cobalt sulfate by using a solvent extraction method, and the solvent extraction method is used for preparing cobalt sulfate, manganese sulfate and cobalt sulfate by firstly saponifying a solvent and finally back-extracting the solvent when nickel, cobalt and manganese are recovered. The method needs a large amount of organic solvent, has complex production process, is easy to cause environmental pollution and can produce a large amount of sodium sulfate decahydrate to carry away valuable metal lithium.
Disclosure of Invention
The invention aims to provide a method for recycling lithium nickel cobalt manganese oxide waste by a wet method, which aims to solve the problem that lithium is lost due to the fact that a large amount of organic solvents are used and a large amount of sodium sulfate decahydrate is produced in the existing wet method process.
The technical scheme of the invention is as follows: a method for recycling lithium nickel cobalt manganese oxide waste by a wet method, comprising the following steps:
A. calcining the nickel cobalt lithium manganate waste under the condition of air flow to obtain a calcined material;
B. adding concentrated sulfuric acid, hydrogen peroxide and pure water into the calcined material obtained in the step A, raising the temperature to 80-90 ℃, reacting for 1-3h, carrying out solid-liquid separation to obtain leaching slag I and leaching liquid I, wherein the concentration of manganese in the leaching liquid I is 85-90g/L, the total concentration of nickel and cobalt is 200-210g/L, and the temperature of the leaching liquid I after filtration is kept at 60-70 ℃;
C. heating the leaching solution I obtained in the step B to 65-70 ℃, then adding calcined materials, hydrogen peroxide and concentrated sulfuric acid, reacting for 1-3 hours, and keeping the temperature of the filtered solution at 60-65 ℃ to obtain a leaching solution II and a leaching residue II, wherein the concentration of manganese in the leaching solution II is 170-180g/L, and the total concentration of cobalt and nickel is 400-420g/L; heating the leaching solution II to not lower than 95 ℃, separating the hot solution, keeping the temperature of the filtered solution at 90-95 ℃ to obtain manganese sulfate crystals and leaching solution III, and continuously reducing the temperature of the leaching solution III to 25-30 ℃ to obtain cobalt sulfate and nickel sulfate mixed crystals and leaching solution IV;
D. heating the leaching solution IV to 65-70 ℃, adding calcined materials, hydrogen peroxide and concentrated sulfuric acid, repeating the operation of the step C, and continuously repeating the operation to continuously separate out manganese sulfate crystals and mixed crystals of cobalt sulfate and nickel sulfate; in the repeated process, stopping feeding when the lithium content in the leaching solution is enriched to 20-25g/L, raising the temperature of the leaching solution to not lower than 90 ℃, adding sodium hydroxide to adjust the pH to 11-12, and carrying out solid-liquid separation to obtain a ternary precursor and a lithium sulfate solution;
E. adding sodium carbonate into the lithium sulfate solution obtained in the step D for reaction, and carrying out solid-liquid separation to obtain lithium carbonate and carbonized liquid;
F. adding sulfuric acid into the carbonized liquid to regulate the pH value to 5-6, then freezing the liquid at the freezing temperature of-10-0 ℃ for 30-60min, and carrying out solid-liquid separation to obtain sodium sulfate decahydrate and lithium sulfate solution without sodium sulfate.
As a further development of the invention, in step A, the calcination temperature is 600-700℃and the calcination time is 1-3h.
As a further development of the invention, in step E, the reaction time is 40-60min and the reaction temperature is 90-100 ℃.
As a further improvement of the invention, in step E, sodium carbonate is used in an amount of 9 to 9.5 times the total lithium mass in the lithium sulphate solution.
As a further improvement of the invention, in step F, the obtained lithium sulfate solution without sodium sulfate is returned to step B for further leaching.
As a further improvement of the invention, in the step F, the obtained sodium sulfate decahydrate is subjected to hot melting treatment, the evaporation concentration volume is 1/3-1/2 of the original volume, and the solution containing lithium and anhydrous sodium sulfate are obtained by separating the hot liquid.
As a further improvement of the invention, in the step F, phosphoric acid is added into the obtained lithium-containing solution, and sodium hydroxide is added to adjust the pH to 10-11, so as to prepare the lithium phosphate.
As a further improvement of the invention, in the step F, when preparing lithium phosphate, the reaction temperature is not lower than 90 ℃ and the reaction time is 40-60min.
As a further improvement of the invention, in step F, the amount of phosphoric acid used in the preparation of lithium phosphate is 1.04 to 1.05 times the theoretical amount.
The beneficial effects of the invention are as follows:
the invention skillfully utilizes the characteristic that the solubility of nickel sulfate, cobalt sulfate and manganese sulfate is different along with the temperature rise, the solubility of cobalt sulfate and nickel sulfate is increased along with the temperature rise, the solubility of manganese sulfate is firstly increased along with the temperature rise and then is reduced, and the saturation of manganese sulfate and nickel sulfate is different at the same temperature, so that the manganese sulfate and nickel sulfate reach respective supersaturation points, and the mixed crystal of manganese sulfate and cobalt sulfate and nickel sulfate is respectively crystallized by utilizing the supersaturation after the temperature change. And the manganese sulfate and the cobalt sulfate nickel sulfate mixed crystals can be continuously separated out after repeated cyclic feeding. The invention uses a method of combining hot melting and freezing to recycle valuable metal lithium in byproduct sodium sulfate decahydrate crystal water, thereby greatly reducing lithium loss.
When the valuable metal nickel cobalt manganese lithium is recovered, sodium hydroxide is only used after the lithium is enriched to 20-25g/L. The generated sodium sulfate decahydrate is very little, so that the amount of valuable metal lithium which can be taken away by the sodium sulfate decahydrate is very little, and the recovery rate of lithium is high. The invention does not use a large amount of organic solvent, and compared with the traditional process, the method has the advantages of less used sodium hydroxide, low recovery cost and great reduction.
Compared with the traditional sulfate recovery process by a solvent extraction method, the method has the advantages of simplicity and easiness in operation, and safety and environmental protection accidents caused by using a large amount of organic solvents and sodium hydroxide are avoided.
Detailed Description
The present invention will be described in detail with reference to the following specific embodiments.
Example 1,
A method for recycling lithium nickel cobalt manganese oxide waste by a wet method, comprising the following steps:
A. taking 3000g of nickel cobalt lithium manganate waste material, calcining at 600 ℃ under the condition of air flow, wherein the calcining time is 2 hours, and obtaining a calcined material;
B. taking 1000g of the calcined material obtained in the step A, adding 250ml of concentrated sulfuric acid, 350ml of hydrogen peroxide and 2700ml of pure water, heating to 95 ℃, reacting for 80min, and carrying out solid-liquid separation to obtain leaching residue I and leaching liquid I, wherein the temperature of the leaching liquid I is 64 ℃, the concentration of manganese in the leaching liquid I is 90g/L, and the total concentration of nickel and cobalt is 210g/L; b, returning the leaching residue I to the step B to continuously leaching and dissolving;
C. heating the leaching solution I obtained in the step B to 68 ℃, then adding calcined materials, hydrogen peroxide and concentrated sulfuric acid, wherein the reaction temperature is 90 ℃, the reaction time is 2 hours, and the temperature of the filtered solution is kept at 64 ℃ to obtain a leaching solution II and a leaching residue II, wherein the concentration of manganese in the leaching solution II is 180g/L, and the total concentration of cobalt and nickel is 420g/L; heating the leaching solution II to 98 ℃, separating the hot liquid, filtering, keeping the temperature of the filtered liquid at 95 ℃ to obtain manganese sulfate crystals and leaching solution III, and continuously cooling the temperature of the leaching solution III to 27 ℃ to obtain cobalt sulfate and nickel sulfate mixed crystals and leaching solution IV; b, returning the leaching residue II to the step B to continuously leach and dissolve;
D. heating the leaching solution IV to 68 ℃, adding calcined materials, hydrogen peroxide and concentrated sulfuric acid, and continuously repeating the operation of the step C to continuously separate out manganese sulfate crystals and mixed crystals of cobalt sulfate and nickel sulfate; in the repeated process, stopping feeding when the lithium content in the leaching solution is enriched to 20g/L, raising the temperature of the leaching solution to not lower than 90 ℃, adding sodium hydroxide to adjust the pH to 12, and carrying out sedimentation and filtration to obtain a mixture of cobalt hydroxide, nickel hydroxide and manganese hydroxide and a lithium sulfate solution;
E. adding sodium carbonate into the lithium sulfate solution obtained in the step D for reaction, wherein the dosage of the sodium carbonate is 9 times of the total lithium mass in the lithium sulfate solution, the reaction time is 60min, the reaction temperature is 90 ℃, and the solid-liquid separation is carried out to obtain lithium carbonate and carbonized liquid;
F. adding sulfuric acid into the carbonized liquid to adjust the pH value to 5, then freezing the liquid at the freezing temperature of-10 ℃ for 60min, and carrying out solid-liquid separation to obtain sodium sulfate decahydrate and lithium sulfate solution without sodium sulfate;
returning the obtained lithium sulfate solution without sodium sulfate to the step B for continuous leaching;
carrying out hot melting treatment on the obtained sodium sulfate decahydrate, evaporating and concentrating the sodium sulfate decahydrate to 1/2 of the original volume, and separating the hot liquid to obtain a lithium-containing solution and anhydrous sodium sulfate;
adding 1.05 times of theoretical amount of phosphoric acid into the obtained lithium-containing solution, adding sodium hydroxide to adjust the pH to 10, reacting at 90 ℃ for 50min, and carrying out solid-liquid separation to obtain lithium phosphate.
Examples 2 to 4,
Examples 2-4 differ from example 1 in that: in step a, the calcination temperature is different. The effect of calcination temperature on the overall recovery of nickel cobalt manganese lithium is shown in table 1.
As can be seen from Table 1, the overall recovery of nickel cobalt manganese lithium was higher when the calcination temperature was 600-700℃, and the continued increase in temperature had little effect on the recovery of lithium. Therefore, the calcination temperature is preferably 600 ℃.
Examples 6 to 11,
Examples 6-11 differ from example 1 in that: in the step B, the concentration of nickel, cobalt and manganese in the leaching solution I is different. The effect of the concentration of nickel, cobalt and manganese in the leaching solution I on the precipitation of manganese sulfate and the mixed crystal of cobalt sulfate and nickel sulfate is shown in Table 2.
As is clear from Table 2, when the concentration of manganese is 50 to 95g/L and the concentration of nickel and cobalt is 100 to 200g/L, manganese sulfate, nickel sulfate and cobalt sulfate crystals are not precipitated. Therefore, the concentration of the preferential leaching manganese is controlled to be 85-90g/L, and the concentration of nickel and cobalt is controlled to be 200-210g/L.
Examples 12 to 22,
Examples 12-22 differ from example 1 in that: in the step C, the concentration of nickel, cobalt and manganese in the leaching solution II is different. The effect of whether the concentration of nickel, cobalt and manganese in the leaching solution II is different or not can separate out manganese sulfate crystals and mixed crystals of cobalt sulfate and nickel sulfate is shown in Table 3.
As is clear from Table 3, the manganese sulfate crystals and the mixed crystals of nickel sulfate and cobalt sulfate were not precipitated at the manganese concentration of 120 to 180g/L and the nickel and cobalt concentrations of 240 to 420g/L. Therefore, the concentration of manganese in the leaching solution is preferably controlled to be 180-190g/L, and the concentration of nickel and cobalt is preferably controlled to be 400-420g/L.
Examples 23 to 29,
Examples 23-29 differ from example 1 in that: in the step C, after solid-liquid separation, the temperature of the filtered liquid is different. The effect of the temperature of the filtered solution on whether crystals of manganese sulfate could be obtained is shown in Table 4.
As is clear from Table 4, the temperature of the solution after filtration was 80 to 95℃and manganese sulfate crystals were precipitated. Therefore, the temperature of the filtered liquid is preferably 90-95 ℃. The higher the temperature of the solution after filtration, the more crystals of manganese sulfate are precipitated. The solubility of manganese sulfate is inversely related to temperature.
Examples 30 to 37,
Examples 30-37 differ from example 1 in that: in step C, the leaching solution III is reduced to different temperatures. The effect of reducing the leach solution III to different temperatures on whether a mixed crystal of nickel sulfate and cobalt sulfate can be obtained is shown in Table 5.
As is clear from Table 5, the temperature of the solution after filtration was 25 to 50℃and crystals of nickel sulfate and cobalt sulfate were precipitated. Therefore, the temperature of the cooling is preferably 25-30 ℃. The lower the temperature is, the more crystals of nickel sulfate and cobalt sulfate are precipitated. The solubility of nickel sulfate and cobalt sulfate is positively correlated to temperature.
Examples 38 to 47,
Examples 38-47 differ from example 1 in that: in step D, the enriched concentration of lithium is different. The effect of the concentration of lithium enrichment on the precipitation of lithium sulfate at various room temperatures is shown in Table 6.
As is clear from Table 6, lithium sulfate crystals were not precipitated at the concentration of 10 to 25g/L of the enriched lithium. Therefore, the concentration of the preferentially enriched lithium is 20-25g/L.
Examples 48 to 52,
Examples 48-52 differ from example 1 in that: in step E, the reaction times are different. The effect of reaction time on the conversion of lithium carbonate is shown in Table 7.
As is clear from Table 7, the conversion of lithium carbonate was high at a reaction time of 40 to 60 minutes. Therefore, the preferred rich reaction time is 40min.
Examples 53 to 57,
Examples 53-57 differ from example 1 in that: in step E, the amount of sodium carbonate used varies. The effect of reaction time on the conversion of lithium carbonate is shown in Table 8.
As is clear from Table 8, the conversion rate of lithium carbonate was high when the amount of sodium carbonate was 9 to 10 times the total mass. Therefore, the amount of sodium carbonate to be used is preferably 9 times the total mass.
Examples 58 to 67,
Examples 58-67 differ from example 1 in that: in step F, the freezing is different. The effect of freezing temperature on sodium ion content in the solution is shown in table 9.
As is clear from Table 9, the sodium ion content was low at the freezing temperature of-8 to-10 ℃. Therefore, the preferred freezing temperature is-10 ℃.
Examples 68 to 74,
Examples 68-74 differ from example 1 in that in step F, the pH value of the pH adjustment was adjusted by adding sodium hydroxide, and the effect of the different pH values on the recovery rate of lithium phosphate to obtain lithium phosphate is shown in Table 10.
As is clear from Table 10, the recovery of lithium phosphate was high at pH 10-12. Therefore, a pH of 10-11 is preferred.
Examples 75 to 79,
Examples 75-79 differ from example 1 in that in step F the reaction time is different. The effect of reaction time on recovery of lithium phosphate is shown in Table 11.
As is clear from Table 11, the recovery of lithium phosphate was high when the reaction time was 40 to 60 minutes. Therefore, the preferred reaction time is 40min.
Examples 80 to 84,
Examples 80-84 differ from example 1 in that in step F the amount of phosphoric acid used is different. The effect of phosphoric acid usage on recovery of lithium phosphate is shown in Table 12.
As is clear from Table 11, the recovery of lithium phosphate was high when the amount of phosphoric acid was 1.04 to 1.05 times. Therefore, the amount of phosphoric acid to be used is preferably 1.05 times the theoretical amount.
Comparative example 1,
The comparative example uses a conventional ternary recovery process, which is approximately to use sulfuric acid and hydrogen peroxide as leaching solvents, dissolve valuable metals nickel cobalt manganese lithium in nickel cobalt lithium manganate to generate leaching solutions of nickel sulfate, cobalt sulfate, manganese sulfate and lithium sulfate, then add a large amount of sodium hydroxide to adjust the pH to 12, obtain hydroxide of nickel cobalt manganese and lithium sulfate solution, and in the process of adding sodium hydroxide, a large amount of nickel cobalt sulfate and manganese sulfate is converted into mixed precipitate of nickel hydroxide cobalt hydroxide and dream manganese hydroxide, and is generated along with a large amount of sodium sulfate decahydrate. The obtained lithium sulfate solution is continuously added with sodium carbonate to precipitate out to obtain lithium carbonate, thereby achieving the purpose of lithium recovery and also being accompanied with the generation of sodium sulfate decahydrate. The recovery of the 2 times of valuable metals is accompanied by the generation of a large amount of sodium sulfate decahydrate, and the crystallization water in the sodium sulfate decahydrate can take away more valuable metal lithium after solid-liquid separation, so that lithium is lost.
Five parallel experiments were performed for this comparative example, and the recovery rates of lithium obtained were 90%, 89%, 88%, and 90%, respectively.
In addition, five parallel experiments were performed in example 1, and the recovery rates of lithium were 97.2%, 97.1%, 97.3%, and 97.1%, respectively.
Therefore, the recovery rate of valuable metal lithium in the waste nickel cobalt lithium manganate waste material in the traditional process is about 90%. The recovery rate of lithium is about 97%, and compared with the traditional method, the method has the advantages of high recovery rate of lithium, great improvement, simple process and easy mass production.
Claims (9)
1. The method for recycling the lithium nickel cobalt manganese oxide waste by the wet method is characterized by comprising the following steps of:
A. calcining the nickel cobalt lithium manganate waste under the condition of air flow to obtain a calcined material;
B. adding concentrated sulfuric acid, hydrogen peroxide and pure water into the calcined material obtained in the step A, raising the temperature to 80-90 ℃, reacting for 1-3h, carrying out solid-liquid separation to obtain leaching slag I and leaching liquid I, wherein the concentration of manganese in the leaching liquid I is 85-90g/L, the total concentration of nickel and cobalt is 200-210g/L, and the temperature of the leaching liquid I after filtration is kept at 60-70 ℃;
C. heating the leaching solution I obtained in the step B to 65-70 ℃, then adding calcined materials, hydrogen peroxide and concentrated sulfuric acid, reacting for 1-3 hours, and keeping the temperature of the filtered solution at 60-65 ℃ to obtain a leaching solution II and a leaching residue II, wherein the concentration of manganese in the leaching solution II is 170-180g/L, and the total concentration of cobalt and nickel is 400-420g/L; heating the leaching solution II to not lower than 95 ℃, separating the hot solution, keeping the temperature of the filtered solution at 90-95 ℃ to obtain manganese sulfate crystals and leaching solution III, and continuously reducing the temperature of the leaching solution III to 25-30 ℃ to obtain cobalt sulfate and nickel sulfate mixed crystals and leaching solution IV;
D. heating the leaching solution IV to 65-70 ℃, adding calcined materials, hydrogen peroxide and concentrated sulfuric acid, repeating the operation of the step C, and continuously repeating the operation to continuously separate out manganese sulfate crystals and mixed crystals of cobalt sulfate and nickel sulfate; in the repeated process, stopping feeding when the lithium content in the leaching solution is enriched to 20-25g/L, raising the temperature of the leaching solution to not lower than 90 ℃, adding sodium hydroxide to adjust the pH to 11-12, and carrying out solid-liquid separation to obtain a ternary precursor and a lithium sulfate solution;
E. adding sodium carbonate into the lithium sulfate solution obtained in the step D for reaction, and carrying out solid-liquid separation to obtain lithium carbonate and carbonized liquid;
F. adding sulfuric acid into the carbonized liquid to regulate the pH value to 5-6, then freezing the liquid at the freezing temperature of-10-0 ℃ for 30-60min, and carrying out solid-liquid separation to obtain sodium sulfate decahydrate and lithium sulfate solution without sodium sulfate.
2. The method for recycling lithium nickel cobalt manganese oxide waste material by wet method according to claim 1, wherein the method comprises the following steps: in the step A, the calcination temperature is 600-700 ℃ and the calcination time is 1-3h.
3. A method for wet recycling lithium nickel cobalt manganese oxide waste according to claim 1 or 2, characterized in that: in the step E, the reaction time is 40-60min, and the reaction temperature is 90-100 ℃.
4. A method for wet recycling lithium nickel cobalt manganese oxide waste according to claim 3, wherein: in step E, sodium carbonate is used in an amount of 9 to 9.5 times the total lithium mass in the lithium sulfate solution.
5. The method for recycling lithium nickel cobalt manganese oxide waste material by wet method according to claim 4, wherein the method comprises the following steps: in the step F, the obtained lithium sulfate solution without sodium sulfate is returned to the step B to be leached continuously.
6. The method for recycling lithium nickel cobalt manganese oxide waste material by wet method according to claim 4, wherein the method comprises the following steps: in the step F, the obtained sodium sulfate decahydrate is subjected to hot melting treatment, the evaporation concentration volume is 1/3-1/2 of the original volume, and the solution containing lithium and anhydrous sodium sulphate are obtained by separating the hot liquid.
7. The method for recycling lithium nickel cobalt manganese oxide waste material by wet method according to claim 6, wherein the method comprises the following steps: in the step F, adding phosphoric acid into the obtained lithium-containing solution, and adding sodium hydroxide to adjust the pH to 10-11 to prepare the lithium phosphate.
8. The method for recycling lithium nickel cobalt manganese oxide waste material by wet method according to claim 7, wherein the method comprises the following steps: in the step F, when preparing lithium phosphate, the reaction temperature is not lower than 90 ℃ and the reaction time is 40-60min.
9. The method for recycling lithium nickel cobalt manganese oxide waste material by wet method according to claim 8, wherein the method comprises the following steps: in step F, the amount of phosphoric acid used in the preparation of lithium phosphate is 1.04 to 1.05 times the theoretical amount.
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