CN116873956B - A method for recovering nickel-cobalt-manganese-oxide lithium waste by pyrolysis calcination - Google Patents
A method for recovering nickel-cobalt-manganese-oxide lithium waste by pyrolysis calcination Download PDFInfo
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Abstract
The invention discloses a recovery method of nickel cobalt lithium manganate waste, belongs to the field of waste lithium battery recovery, and solves the problems of large reagent consumption and low recovery rate in the traditional method. The method comprises the following steps: mixing and calcining the material and carbon powder; adding concentrated sulfuric acid into the calcined material, stirring uniformly, roasting, cooling and crushing; dissolving the crushed material in water, heating, adding the crushed material, heating, separating the hot solution to obtain manganese sulfate crystals, and cooling the solution to obtain cobalt sulfate and nickel sulfate mixed crystals; and (3) after the lithium is enriched by repeating the operation, adding sodium hydroxide to obtain a mixture of nickel, cobalt and manganese hydroxides and a lithium sulfate solution, and adding sodium carbonate into the solution to precipitate to obtain lithium carbonate. The invention greatly reduces the problems that the diluted sulfuric acid and the hydrogen peroxide serving as the reducing agent occupy a large amount of tanks for storing and transferring liquid in the wet process. The invention separates out various sulfates by utilizing the solubility saturated crystallization, and the process is simple and easy to operate. The recovery rate of valuable metal lithium is high.
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 fire calcination.
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 nickel cobalt lithium manganate waste mainly comprise a fire method and a wet method. When the valuable metal nickel cobalt manganese lithium in the nickel cobalt lithium manganate waste is recovered by a wet method and a fire method, the following problems exist:
(1) Because the used concentrated sulfuric acid needs to be diluted and then a large amount of reducing agent hydrogen peroxide is used, the volume of the solution is too large, and the requirements on the volume of a tank and a factory building are high. The storage of large amounts of liquid reagents also presents a great safety hazard. In addition, large volumes of liquid are produced, which in many cases can force production to stagnate to handle large volumes of accumulated liquid, which has a significant impact on the continuity of production.
(2) When lithium and valuable metals nickel cobalt manganese are recovered selectively by the traditional pyrogenic process, the recovery rate of the valuable metals and lithium is low due to the influence of a plurality of factors, such as the partial mixing with electrolyte in the process of removing the positive electrode powder and the mixing of the positive electrode powder and the negative electrode powder.
(3) When valuable metals are recovered in the conventional industry, nickel, cobalt and manganese are prepared into cobalt sulfate, nickel sulfate and manganese sulfate by using an extraction method, a large amount of organic solvents are required to be consumed, and saponification, multistage extraction and multistage back extraction procedures complicate the procedures and have high cost.
Disclosure of Invention
The invention aims to provide a method for recycling lithium nickel cobalt manganese oxide waste by fire calcination, which aims to solve the problems of large reagent consumption and low recovery rate in the traditional method.
The technical scheme of the invention is as follows: the recovery method of the nickel cobalt lithium manganate waste comprises the following steps:
A. Uniformly mixing nickel cobalt lithium manganate waste with carbon powder, and calcining in a high-temperature calciner to reduce high-valence manganese ions and cobalt ions in the nickel cobalt lithium manganate waste into 2-valence manganese and cobalt ions to obtain a calcined material;
B. Taking a certain amount of the calcined material obtained in the step A, adding concentrated sulfuric acid, fully stirring, roasting in a high-temperature furnace, taking out the material after cooling, and crushing to 80-110 meshes to obtain a crushed material; this step produces soluble salts of lithium sulfate, nickel sulfate, cobalt sulfate, and manganese sulfate;
C. Adding pure water into the crushed material obtained in the step B to obtain a solution I containing nickel, cobalt, manganese and lithium; the sulfate mixture of the crushed materials is dissolved in water to prepare the required sulfate concentration, the subsequent sulfate precipitation step can be carried out, hydrogen peroxide is not needed to be added as a reducing agent, acid is not needed to be used for leaching, and the sulfate can be dissolved only by pure water;
D. Heating the solution I containing nickel, cobalt, manganese and lithium obtained in the step C to 60-70 ℃, adding the crushed material obtained in the step B, and stirring for 20-30min to obtain a solution II containing nickel, cobalt, manganese and lithium; heating the solution II containing nickel, cobalt, manganese and lithium to 95-100 ℃, separating the hot solution, and keeping the temperature of the filtered solution at 90-95 ℃ to obtain manganese sulfate crystals and the solution III containing nickel, cobalt, manganese and lithium; continuously reducing the temperature of the solution III containing nickel cobalt, manganese and lithium to 25-35 ℃ to obtain a mixed crystal of cobalt sulfate and nickel sulfate and a solution IV containing nickel cobalt, manganese and lithium;
E. repeating the operation of the step D, continuously adding crushed materials, adjusting the temperature, continuously separating out manganese sulfate crystals and cobalt sulfate and nickel sulfate mixed crystals, stopping adding the crushed materials when the lithium content in the solution IV containing nickel cobalt manganese lithium reaches 20-25g/L, adding sodium hydroxide to adjust the pH value to 11-12, and settling to obtain a mixture of nickel cobalt manganese hydroxide and lithium sulfate solution;
F. and E, adding sulfuric acid into the lithium sulfate solution obtained in the step E to adjust the pH value to 6-7 to remove aluminum, then carrying out solid-liquid separation to obtain a purified solution, and adding sodium carbonate into the purified solution to precipitate to obtain lithium carbonate.
As a further improvement of the invention, in step A, the calcination temperature is 600-700 ℃ and the calcination time is 2-3h.
As a further improvement of the invention, in the step A, the carbon powder is used according to the mass ratio of 12% -15% of carbon in the mixed material.
As a further improvement of the invention, in step B, the calcination temperature is 600-700 ℃ and the calcination time is 2-3h.
As a further development of the invention, in step B, concentrated sulfuric acid is used in an amount of 1g of calcined material corresponding to 1.1 to 1.5ml of concentrated sulfuric acid.
As a further improvement of the invention, in step C, the concentration of manganese in the solution I containing nickel cobalt manganese lithium is 80-90g/L and the total concentration of nickel and cobalt is 200-210g/L.
As a further improvement of the invention, in step D, the concentration of manganese in the solution II containing nickel cobalt manganese lithium is 160-180g/L and the total concentration of cobalt and nickel is 400-420g/L.
As a further improvement of the invention, in step F, sodium carbonate is added in an amount of 9 to 9.5 times the total lithium mass.
As a further improvement of the invention, in the step F, after adding sodium carbonate, the reaction time is 1-2h, and the reaction temperature is not lower than 90 ℃.
As a further improvement of the invention, in the step F, the lithium carbonate is washed by pure water at the temperature of not lower than 90 ℃ for 30-50min, and the battery grade lithium carbonate is obtained by solid-liquid separation.
Compared with the traditional wet leaching, the method has the advantages that the co-calcination process of the materials and the concentrated sulfuric acid is adopted, the leaching time is greatly reduced, the volume of the used liquid is small, and the requirements on equipment and plants are not high. The co-calcination process may also improve the recovery of lithium, nickel, cobalt and manganese.
The solubility of cobalt sulfate and nickel sulfate increases gradually with the rise of temperature, and the solubility of manganese sulfate increases and then decreases with the rise of temperature. The invention utilizes the characteristic that the saturation degree of manganese sulfate, cobalt sulfate and nickel sulfate is different at the same temperature to ensure that the manganese sulfate, the cobalt sulfate and the nickel sulfate reach respective supersaturation points, and the manganese sulfate, the cobalt sulfate and the nickel sulfate are crystallized and separated out after the temperature change. And manganese sulfate crystals and mixed crystals of cobalt sulfate and nickel sulfate are continuously separated out through repeated cyclic feeding, so that the aim of recovering valuable metals in nickel cobalt lithium manganate waste is fulfilled.
Compared with the prior art, the invention has the following advantages:
1. The invention greatly reduces the problems of diluting sulfuric acid and using reducing agent hydrogen peroxide to occupy a large amount of tank for storing and transferring liquid in the wet process, solves the problem of large requirement of the traditional production process on the volume of a production system, and is beneficial to the serialization of production.
2. The invention uses pure water to dissolve after calcining and crushing the materials, and utilizes the solubility saturation crystallization to separate out various sulfates, and the process is simple and easy to operate.
3. The method does not need a large amount of organic solvent for extraction when preparing the sulfate, has simple process, low cost and easy mass production.
4. The recovery rate of valuable metal lithium is high. When valuable metal lithium in the lithium manganate waste is recovered by the traditional ternary precipitation, a large amount of sodium hydroxide is used for precipitating nickel cobalt manganese from the pickle liquor to obtain nickel cobalt manganese hydroxide, and the produced nickel cobalt manganese hydroxide is large in amount and high in water content of colloid substances and can take away more lithium. In addition, when nickel cobalt manganese hydroxide is produced, a large amount of sodium sulfate decahydrate is produced in the solution, and a large amount of lithium is carried away by the sodium sulfate decahydrate after crystallization. The large precipitation of both products results in low recovery of lithium in the conventional process. The method of the present invention avoids this problem.
Detailed Description
The present invention will be described in detail with reference to the following specific embodiments.
Example 1,
The recovery method of the nickel cobalt lithium manganate waste comprises the following steps:
A. Adding 120g of carbon powder into 880g of waste of nickel cobalt lithium manganate, uniformly mixing, and calcining in a high-temperature calciner at 650 ℃ for 2 hours to obtain a calcined material;
B. Taking 500g of the calcined material obtained in the step A, adding 550ml of concentrated sulfuric acid, fully stirring, roasting in a high-temperature furnace at 650 ℃ for 2 hours, taking out the material after cooling, and crushing to 100 meshes to obtain a crushed material;
C. adding pure water into the crushed material obtained in the step B to obtain a solution I containing nickel, cobalt, manganese and lithium, wherein the temperature of the solution I is kept at 65 ℃, the concentration of manganese in the solution I containing nickel, cobalt, manganese and lithium is 90g/L, and the total concentration of nickel and cobalt is 210g/L;
D. Heating the solution I containing nickel, cobalt, manganese and lithium obtained in the step C to 68 ℃, adding the crushed material obtained in the step B, and stirring for 30min to obtain a solution II containing nickel, cobalt, manganese and lithium, wherein the concentration of manganese in the solution II containing nickel, cobalt, manganese and lithium is 180g/L, and the total concentration of cobalt and nickel is 420g/L; heating a solution II containing nickel, cobalt, manganese and lithium to above 95 ℃, separating the solution while the solution is hot, and keeping the temperature of the filtered solution at 92 ℃ to obtain manganese sulfate crystals and a solution III containing nickel, cobalt, manganese and lithium; continuously reducing the temperature of the solution III containing nickel cobalt, manganese and lithium to 27 ℃ to obtain a mixed crystal of cobalt sulfate and nickel sulfate and a solution IV containing nickel cobalt, manganese and lithium;
E. Repeating the operation of the step D on the solution IV, continuously adding crushed materials, adjusting the temperature, continuously precipitating to obtain manganese sulfate crystals and cobalt sulfate and nickel sulfate mixed crystals, stopping adding the crushed materials when the lithium content in the solution IV containing nickel cobalt manganese lithium reaches 18g/L, adding sodium hydroxide to adjust the pH value to 12, and settling to obtain a nickel cobalt manganese hydroxide mixture and a lithium sulfate solution;
F. Adding sulfuric acid into the lithium sulfate solution obtained in the step E to adjust the pH value to 7 to remove aluminum, then carrying out solid-liquid separation to obtain a purified solution, adding sodium carbonate with the mass 9 times of the total lithium into the purified solution, reacting for 1h at the temperature of more than 90 ℃, and separating out to obtain lithium carbonate; and washing the lithium carbonate by using pure water at 90 ℃ for 30min, and carrying out solid-liquid separation to obtain the battery grade lithium carbonate.
Examples 2 to 15,
Examples 2-15 differ from example 1 in that: in the step A, the carbon powder dosage is different. The effect of the amount of carbon powder on the leaching rate of nickel, cobalt and manganese during water dissolution is shown in table 1.
As shown in Table 1, when the carbon powder is used in an amount of 12% -15%, the total leaching rate of nickel, cobalt and manganese is high, and the effect of continuously increasing the carbon powder is not great. Therefore, the carbon powder is preferably used in an amount of 12%.
Examples 16 to 20,
Examples 16-20 differ from example 1 in that: in step a, the calcination temperature is different. The effect of calcination temperature on leaching rate of nickel cobalt manganese when water-soluble is shown in table 2.
As can be seen from Table 2, the total leaching rate of nickel cobalt manganese is higher when the calcination temperature is 650-750 ℃. Therefore, the calcination temperature is preferably 650 ℃.
Examples 21 to 25,
Examples 21-25 differ from example 1 in that: in step B, the amount of concentrated sulfuric acid used varies. The effect of the amount of concentrated sulfuric acid on the leaching rate of nickel cobalt manganese in water dissolution is shown in Table 3. The dosage of the concentrated sulfuric acid is 1g of calcined material corresponding to 1.1-1.5ml of concentrated sulfuric acid.
As is clear from Table 3, the total leaching rate of nickel cobalt manganese is higher when the amount of acid is 1g of calcine to 1.1-1.5ml of sulfuric acid. Thus, the preferred acid is used in an amount of 1g calcine to 1.1ml.
Examples 26 to 30,
Examples 26-30 differ from example 1 in that: in step B, the effect of different mesh sizes of the crushed materials on the leaching rate of nickel, cobalt and manganese in water dissolution is shown in Table 4.
As can be seen from Table 4, the total leaching rate of nickel cobalt manganese was higher when the mesh number of the crushed material was 80-110 mesh. Therefore, the mesh number of the crushed material is preferably 80 mesh.
Examples 31 to 38,
Examples 31-38 differ from example 1 in that: in step C, the concentration of manganese, nickel and cobalt in the nickel, cobalt, manganese and lithium containing solution I is different. The effect of the concentration of manganese nickel cobalt on the precipitation of manganese sulfate crystals and nickel cobalt sulfate mixed crystals is shown in Table 5.
As is clear from Table 5, when the concentration of manganese is less than 110g/L and the total concentration of nickel and cobalt is less than 200g/L, no crystal is precipitated. Therefore, the preferred concentration of manganese is 80-90g/L and the total concentration of nickel and cobalt is 200-210g/L.
Examples 39 to 48,
Examples 39-48 differ from example 1 in that: in the step D, the concentration of manganese in the solution II containing nickel cobalt manganese lithium is different. The effect of varying manganese concentration in solution II on the precipitation of manganese sulfate crystals at 60-70℃is shown in Table 6.
As is clear from Table 6, when the concentration of manganese is 120-180g/L, the leaching solution II does not precipitate manganese sulfate crystals. Therefore, the concentration of manganese is preferably 160-180g/L.
Examples 49 to 58,
Examples 49-58 differ from example 1 in that: in the step D, the concentration of nickel and cobalt in the nickel-cobalt-manganese-lithium-containing solution II is different. The effect of the different concentrations of nickel and cobalt in solution II on whether mixed crystals of nickel sulfate and cobalt sulfate will precipitate at 60-70℃is shown in Table 7.
As is clear from Table 7, when the total concentration of nickel and cobalt is 240-420g/L, the leaching solution II does not precipitate mixed crystals of nickel sulfate and cobalt sulfate. Therefore, the total concentration of nickel and cobalt is preferably 400-420g/L.
Examples 59 to 66,
Examples 59-66 differ from example 1 in that: in the step D, the filtered solution of the solution II containing nickel cobalt manganese lithium has different temperatures. The effect of whether the manganese sulfate crystals are precipitated or not depending on the temperature of the solution II after filtration is shown in Table 8.
As is clear from Table 8, manganese sulfate crystals were precipitated at a temperature of 80 to 95℃in the leachate II after filtration. Therefore, the temperature of the filtered liquid is preferably controlled to be 90-95 ℃.
Examples 59 to 66,
Examples 59-66 differ from example 1 in that: in step D, the lowering temperature of the solution III is different. The effect of whether the reduced temperature of solution III would precipitate a mixed crystal of nickel sulfate and cobalt sulfate is shown in Table 9.
As is clear from Table 9, when the temperature of the leaching solution III was lowered to 25-50 ℃, mixed crystals of nickel sulfate and cobalt sulfate were precipitated. Thus, the preferred temperature is reduced to 25-30 ℃.
Examples 76 to 82,
Examples 76-82 differ from example 1 in that: in step F, the amount of sodium carbonate added is different. The effect of the amount of sodium carbonate added on the conversion of lithium carbonate is shown in Table 10.
As is clear from Table 10, when the amount of sodium carbonate used was 9 to 9.5 times the total lithium mass in the solution, the conversion rate of lithium carbonate was 99%, and the conversion rate was high. Therefore, the preferred addition of sodium carbonate is 9 times the total lithium mass in the solution.
Examples 83 to 85,
Examples 83-85 differ from example 1 in that: in step F, the reaction time of the added amount of sodium carbonate is different. The effect of reaction time on the conversion of lithium carbonate is shown in Table 11.
As is clear from Table 11, the conversion of lithium carbonate was 99% and the conversion was high at a reaction time of 1 to 2 hours. Therefore, the reaction time of 1h is preferentially selected.
Examples 86 to 89,
Examples 86-89 differ from example 1 in that: in step F, the washing times are different. The effect of wash time on purity of lithium carbonate is shown in table 12.
As can be seen from Table 12, the purity of lithium carbonate can reach 99.5% and the standard of battery grade lithium carbonate at 30-50 min. Therefore, the preferred washing time is 30min.
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 recovery method of the nickel cobalt lithium manganate waste is characterized by comprising the following steps of:
A. uniformly mixing nickel cobalt lithium manganate waste with carbon powder, and calcining in a high-temperature calciner to obtain a calcined material;
B. Taking a certain amount of the calcined material obtained in the step A, adding concentrated sulfuric acid, fully stirring, roasting in a high-temperature furnace, taking out the material after cooling, and crushing to 80-110 meshes to obtain a crushed material;
C. Adding pure water into the crushed material obtained in the step B to obtain a solution I containing nickel, cobalt, manganese and lithium;
D. Heating the solution I containing nickel, cobalt, manganese and lithium obtained in the step C to 60-70 ℃, adding the crushed material obtained in the step B, and stirring for 20-30min to obtain a solution II containing nickel, cobalt, manganese and lithium; the concentration of manganese in the solution II containing nickel cobalt manganese lithium is 160-180g/L, and the total concentration of cobalt and nickel is 400-420g/L; heating the solution II containing nickel, cobalt, manganese and lithium to 95-100 ℃, separating the hot solution, and keeping the temperature of the filtered solution at 90-95 ℃ to obtain manganese sulfate crystals and the solution III containing nickel, cobalt, manganese and lithium; continuously reducing the temperature of the solution III containing nickel cobalt, manganese and lithium to 25-35 ℃ to obtain a mixed crystal of cobalt sulfate and nickel sulfate and a solution IV containing nickel cobalt, manganese and lithium;
E. Repeating the operation of the step D on the solution IV, continuously separating out manganese sulfate crystals and cobalt sulfate and nickel sulfate mixed crystals, stopping adding crushed materials when the lithium content in the solution IV containing nickel cobalt manganese lithium reaches 20-25g/L, adding sodium hydroxide to adjust the pH value to 11-12, and settling to obtain a mixture of nickel cobalt manganese hydroxide and lithium sulfate solution;
F. and E, adding sulfuric acid into the lithium sulfate solution obtained in the step E to adjust the pH value to 6-7 to remove aluminum, then carrying out solid-liquid separation to obtain a purified solution, and adding sodium carbonate into the purified solution to precipitate to obtain lithium carbonate.
2. The method for recycling lithium nickel cobalt manganese oxide waste 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 2-3h.
3. The method for recycling lithium nickel cobalt manganese oxide waste according to claim 1 or 2, characterized in that: in the step A, the use amount of the carbon powder is calculated according to the mass ratio of 12% -15% of carbon in the mixed material.
4. A method for recycling lithium nickel cobalt manganese oxide waste according to claim 3, characterized in that: in the step B, the calcination temperature is 600-700 ℃ and the calcination time is 2-3h.
5. The method for recycling lithium nickel cobalt manganese oxide waste according to claim 4, wherein: in step B, the amount of concentrated sulfuric acid is 1.1-1.5ml of concentrated sulfuric acid corresponding to 1g of calcined material.
6. The method for recycling lithium nickel cobalt manganese oxide waste according to claim 5, wherein the method comprises the following steps: in the step C, the concentration of manganese in the solution I containing nickel cobalt manganese lithium is 80-90g/L, and the total concentration of nickel and cobalt is 200-210g/L.
7. The method for recycling lithium nickel cobalt manganese oxide waste according to claim 6, wherein: in step F, sodium carbonate is added in an amount of 9 to 9.5 times the total lithium mass.
8. The method for recycling lithium nickel cobalt manganese oxide waste according to claim 7, wherein: in the step F, after adding sodium carbonate, the reaction time is 1-2h, and the reaction temperature is not lower than 90 ℃.
9. The method for recycling lithium nickel cobalt manganese oxide waste according to claim 8, wherein: in the step F, the lithium carbonate is washed by pure water at the temperature of not lower than 90 ℃ for 30-50min, and the battery grade lithium carbonate is obtained through solid-liquid separation.
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| WO2023077788A1 (en) * | 2021-11-02 | 2023-05-11 | 赣州有色冶金研究所有限公司 | Method for recovering lithium in positive electrode material for lithium-ion battery |
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| WO2023077788A1 (en) * | 2021-11-02 | 2023-05-11 | 赣州有色冶金研究所有限公司 | Method for recovering lithium in positive electrode material for lithium-ion battery |
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