CN108408745B - Method for preparing battery-grade lithium carbonate from waste lithium batteries - Google Patents
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Abstract
The invention discloses a method for preparing battery-grade lithium carbonate by using waste lithium batteries. The recycled waste battery material or the waste battery is disassembled, crushed and sieved to obtain battery crushed materials; reducing and leaching the crushed battery materials, and filtering after the reaction is finished to obtain a first filtrate and a first filter residue; adding alkali into the first filtrate to adjust the pH value, and filtering to obtain a second filtrate and a second filter residue; adding zinc powder into the second filtrate for reaction, filtering to obtain a third filtrate and third filter residue, extracting the third filtrate by using a P204 extracting agent to obtain raffinate containing nickel, cobalt, magnesium and lithium, and extracting nickel, cobalt and magnesium by using a P507 extracting agent to obtain raffinate containing lithium and sodium; adding lithium-containing raffinate into sodium hydroxide for reaction to obtain fourth filtrate and fourth filter residue; and adding a complexing agent into the fourth filtrate, then adding ammonium bicarbonate and seed crystals, and then heating for reaction to obtain the battery-grade lithium carbonate. The invention can realize separation and recovery of all components and has high lithium recovery rate.
Description
Technical Field
The invention relates to a method for preparing battery-grade lithium carbonate by using waste lithium batteries, and belongs to the technical field of waste treatment of lithium battery materials.
Background
With the increasingly wide application of lithium batteries, the treatment of waste lithium batteries is also receiving attention of people, and the waste lithium batteries contain a lot of valuable metals, so that the resource utilization of the waste lithium batteries not only has great social benefits, but also has great economic benefits. Along with the rapid development of lithium ion batteries, the demand of battery-grade lithium carbonate is increasing day by day, lithium is recovered from lithium battery waste materials, and the battery-grade lithium carbonate is prepared, so that the utilization value of the battery waste materials is improved, and the pollution caused by raw ore mining is reduced.
Disclosure of Invention
In view of the above, the invention provides a method for preparing battery-grade lithium carbonate from waste lithium batteries, which has the advantages of short flow, simple process, high recovery rate, high purity of the finally obtained product and high added value of the product, and can realize separation and recovery of all components.
The invention solves the technical problems by the following technical means:
a method for preparing battery-grade lithium carbonate by using waste lithium batteries comprises the following steps:
1) preprocessing, namely disassembling, crushing and sieving the recovered waste battery materials or waste batteries to obtain battery crushed materials;
2) reducing and leaching the battery crushed aggregates, adding bottom water according to a solid-to-liquid ratio of 1:3-10, adding acid to adjust the pH value to 0.5-2.0, reacting at 50-90 ℃ for 2-6 hours, simultaneously adding a reducing agent, wherein the molar weight of the reducing agent is 0.5-4 times of that of trivalent metal, and filtering after the reaction is finished to obtain a first filtrate and a first filter residue;
3) removing iron and aluminum, adding alkali into the first filtrate to adjust the pH value to 4-5.5, precipitating iron, aluminum and chromium ions in the first filtrate to ensure that the content of iron, aluminum and chromium in the solution is lower than 10 mg/L, and then filtering to obtain a second filtrate and a second filter residue;
4) removing impurities, adding zinc powder into the second filtrate, reacting at 50-70 ℃ for 2-3 hours, filtering to obtain a third filtrate and a third filter residue, extracting the third filtrate by using a P204 extracting agent to remove iron, zinc, copper and manganese to obtain a raffinate containing nickel, cobalt, magnesium and lithium, and extracting nickel, cobalt and magnesium by using a P507 extracting agent to obtain a raffinate containing lithium and sodium;
5) deeply removing impurities, namely adding sodium hydroxide into lithium-containing raffinate at the temperature of 60-80 ℃, adjusting the pH value of the solution to 9-11, reacting for 2-3 hours under the condition, and filtering to obtain fourth filtrate and fourth filter residue;
6) and preparing battery-grade lithium carbonate, adding a complexing agent into the fourth filtrate, then adding ammonium bicarbonate, stirring and adding at 30-60 ℃, simultaneously adding battery-grade lithium carbonate with the granularity of 0.5-1 micron as a seed crystal, wherein the adding amount is 5-10g per liter of solution, then heating to the temperature of 90-95 ℃, reacting for 1-2 hours, filtering, washing, drying, sieving and packaging to obtain the battery-grade lithium carbonate.
And (2) sieving the mixture in the step (1) by using a 100-200-mesh sieve.
The reducing agent added in the step (2) is sulfur dioxide, hydrogen peroxide, sodium sulfite, iron powder or zinc powder.
And (4) after the pH value is adjusted back to 4-5.5 in the step (3), heating to 85-95 ℃, introducing air to ensure that ferrous ions are completely oxidized into ferric iron, and continuing to react for 1-2 hours.
The granularity of the zinc powder added in the step (4) is 100-150 meshes, the mole number of the zinc powder is 1.1-1.2 times of the mole number of nickel, cobalt, manganese and copper in the second filtrate, the pH value of the zinc powder adding process is maintained to be 3.5-4, the P204 extracting agent is used for extracting iron, zinc, copper and manganese in the 8-10-level countercurrent extraction process, the volume flow ratio of the P204 extracting agent to the third filtrate is 1:3-5, the extracted organic phase is subjected to 5-6-level countercurrent washing, the washing liquid is returned to be mixed with the third filtrate for extraction, the washing liquid adopts a sulfuric acid solution with the volume flow ratio of 0.15-0.25 mol/L, the volume flow ratio of the extracted organic phase to the washing liquid is 1:0.1-0.15, when the P507 extracting agent extracts the raffinate containing nickel, cobalt, magnesium and lithium, the volume flow ratio of the P507 extracting agent to the raffinate containing nickel, the nickel, cobalt, lithium is 1:1-2, the washing liquid is returned to the washing liquid, and the raffinate containing nickel, the extraction liquid is subjected to the extraction, and the extraction liquid is subjected to the extraction by the extraction of the extraction liquid, and the extraction of the extraction.
And (5) after the reaction is finished, adding a flocculating agent, and then filtering, wherein the flocculating agent is added in an amount of 30-40g per ton of the solution, and the flocculating agent is PAM.
In the step (6), the complexing agent is ammonia water, citric acid, tartaric acid, sulfosalicylic acid or EDTA, the concentration of the complexing agent after the complexing agent is added is 0.1-0.2 mol/L, and the mole number of the added ammonium bicarbonate is 1.2-1.3 times of the mole number of lithium in the fourth filtrate.
And (4) performing magnetic separation to obtain cobalt-nickel powder and manganese-copper powder, dissolving the cobalt-nickel powder with acid, introducing ozone to obtain cobalt oxyhydroxide and a nickel solution, calcining the cobalt oxyhydroxide at the temperature of 850-.
The washed P204 extractant is subjected to 5-6-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade zinc sulfate, the industrial-grade zinc sulfate is concentrated until the Baume degree is 50-51, then the temperature is reduced to 10-15 ℃, the mother liquor is returned to be mixed with the second filtrate, the washed P507 extractant is subjected to 5-6-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade magnesium sulfate, the industrial-grade magnesium sulfate is concentrated until the Baume degree is 52-53, then the temperature is reduced to 10-15 ℃, and the mother liquor is returned to be mixed with the second filtrate.
And (3) returning the fourth filter residue to the step (2) for dissolving.
In the reduction and dissolution process, taking hydrogen peroxide as an example, the following reactions occur:
2LiMO2+6H++H2O2→2M2++4H2O+2Li++O2(M is a metal such as Ni, Co, Mn, etc.).
This patent has realized the recovery of complete set, and the flow is short, and the rate of recovery of lithium is high, has finally obtained battery level lithium carbonate, and the granularity size of battery level lithium carbonate is moderate, and the particle size distribution is narrow, and mobility is good, is fit for doing lithium battery cathode material.
The invention has the beneficial effects that: the method has the advantages of short flow, simple process, low cost, high recovery rate, high purity of the finally obtained product, high added value of the product and realization of recycling of materials, and can realize separation and recovery of all components.
Detailed Description
The present invention will be described in detail with reference to specific examples, where the method for preparing battery-grade lithium carbonate from waste lithium batteries in this example includes the following steps:
1) preprocessing, namely disassembling, crushing and sieving the recovered waste battery materials or waste batteries to obtain battery crushed materials;
2) reducing and leaching the battery crushed aggregates, adding bottom water according to a solid-to-liquid ratio of 1:3-10, adding acid to adjust the pH value to 0.5-2.0, reacting at 50-90 ℃ for 2-6 hours, simultaneously adding a reducing agent, wherein the molar weight of the reducing agent is 0.5-4 times of that of trivalent metal, and filtering after the reaction is finished to obtain a first filtrate and a first filter residue;
3) removing iron and aluminum, adding alkali into the first filtrate to adjust the pH value to 4-5.5, precipitating iron, aluminum and chromium ions in the first filtrate to ensure that the content of iron, aluminum and chromium in the solution is lower than 10 mg/L, and then filtering to obtain a second filtrate and a second filter residue;
4) removing impurities, adding zinc powder into the second filtrate, reacting at 50-70 ℃ for 2-3 hours, filtering to obtain a third filtrate and a third filter residue, extracting the third filtrate by using a P204 extracting agent to remove iron, zinc, copper and manganese to obtain a raffinate containing nickel, cobalt, magnesium and lithium, and extracting nickel, cobalt and magnesium by using a P507 extracting agent to obtain a raffinate containing lithium and sodium;
5) deeply removing impurities, namely adding sodium hydroxide into lithium-containing raffinate at the temperature of 60-80 ℃, adjusting the pH value of the solution to 9-11, reacting for 2-3 hours under the condition, and filtering to obtain fourth filtrate and fourth filter residue;
6) and preparing battery-grade lithium carbonate, adding a complexing agent into the fourth filtrate, then adding ammonium bicarbonate, stirring and adding at 30-60 ℃, simultaneously adding battery-grade lithium carbonate with the granularity of 0.5-1 micron as a seed crystal, wherein the adding amount is 5-10g per liter of solution, then heating to the temperature of 90-95 ℃, reacting for 1-2 hours, filtering, washing, drying, sieving and packaging to obtain the battery-grade lithium carbonate.
And (2) sieving the mixture in the step (1) by using a 100-200-mesh sieve.
The reducing agent added in the step (2) is sulfur dioxide, hydrogen peroxide, sodium sulfite, iron powder or zinc powder.
And (4) after the pH value is adjusted back to 4-5.5 in the step (3), heating to 85-95 ℃, introducing air to ensure that ferrous ions are completely oxidized into ferric iron, and continuing to react for 1-2 hours.
The granularity of the zinc powder added in the step (4) is 100-150 meshes, the mole number of the zinc powder is 1.1-1.2 times of the mole number of nickel, cobalt, manganese and copper in the second filtrate, the pH value of the zinc powder adding process is maintained to be 3.5-4, the P204 extracting agent is used for extracting iron, zinc, copper and manganese in the 8-10-level countercurrent extraction process, the volume flow ratio of the P204 extracting agent to the third filtrate is 1:3-5, the extracted organic phase is subjected to 5-6-level countercurrent washing, the washing liquid is returned to be mixed with the third filtrate for extraction, the washing liquid adopts a sulfuric acid solution with the volume flow ratio of 0.15-0.25 mol/L, the volume flow ratio of the extracted organic phase to the washing liquid is 1:0.1-0.15, when the P507 extracting agent extracts the raffinate containing nickel, cobalt, magnesium and lithium, the volume flow ratio of the P507 extracting agent to the raffinate containing nickel, the nickel, cobalt, lithium is 1:1-2, the washing liquid is returned to the washing liquid, and the raffinate containing nickel, the extraction liquid is subjected to the extraction, and the extraction liquid is subjected to the extraction by the extraction of the extraction liquid, and the extraction of the extraction.
And (5) after the reaction is finished, adding a flocculating agent, and then filtering, wherein the flocculating agent is added in an amount of 30-40g per ton of the solution, and the flocculating agent is PAM.
In the step (6), the complexing agent is ammonia water, citric acid, tartaric acid, sulfosalicylic acid or EDTA, the concentration of the complexing agent after the complexing agent is added is 0.1-0.2 mol/L, and the mole number of the added ammonium bicarbonate is 1.2-1.3 times of the mole number of lithium in the fourth filtrate.
And (4) performing magnetic separation to obtain cobalt-nickel powder and manganese-copper powder, dissolving the cobalt-nickel powder with acid, introducing ozone to obtain cobalt oxyhydroxide and a nickel solution, calcining the cobalt oxyhydroxide at the temperature of 850-.
The washed P204 extractant is subjected to 5-6-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade zinc sulfate, the industrial-grade zinc sulfate is concentrated until the Baume degree is 50-51, then the temperature is reduced to 10-15 ℃, the mother liquor is returned to be mixed with the second filtrate, the washed P507 extractant is subjected to 5-6-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade magnesium sulfate, the industrial-grade magnesium sulfate is concentrated until the Baume degree is 52-53, then the temperature is reduced to 10-15 ℃, and the mother liquor is returned to be mixed with the second filtrate.
And (3) returning the fourth filter residue to the step (2) for dissolving.
Example 1
A method for preparing battery-grade lithium carbonate by using waste lithium batteries comprises the following steps:
1) preprocessing, namely disassembling, crushing and sieving the recovered waste battery materials or waste batteries to obtain battery crushed materials;
2) reducing and leaching the battery crushed materials, adding bottom water according to a solid-to-liquid ratio of 1:7, adding acid to adjust the pH to 1.85, reacting at 80 ℃ for 4 hours, simultaneously adding a reducing agent, wherein the molar quantity of the added reducing agent is 0.9 times of the molar quantity of trivalent metal, and filtering after the reaction is finished to obtain a first filtrate and first filter residue;
3) removing iron and aluminum, adding alkali into the first filtrate to adjust the pH value back to 4.8, precipitating iron, aluminum and chromium ions in the first filtrate to ensure that the content of iron, aluminum and chromium in the solution is lower than 10 mg/L, and then filtering to obtain a second filtrate and a second filter residue;
4) removing impurities, adding zinc powder into the second filtrate, reacting for 2.7 hours at the temperature of 65 ℃, filtering to obtain a third filtrate and third filter residue, extracting the third filtrate by using a P204 extracting agent to remove iron, zinc, copper and manganese to obtain raffinate containing nickel, cobalt, magnesium and lithium, and extracting nickel, cobalt and magnesium by using a P507 extracting agent to obtain raffinate containing lithium and sodium;
5) deeply removing impurities, namely adding sodium hydroxide into lithium-containing raffinate at 72 ℃, adjusting the pH value of the solution to 10.5, reacting for 2.5 hours under the condition, and filtering to obtain fourth filtrate and fourth filter residue;
6) and preparing battery-grade lithium carbonate, adding a complexing agent into the fourth filtrate, then adding ammonium bicarbonate, stirring and adding at 55 ℃, simultaneously adding battery-grade lithium carbonate with the granularity of 0.8 micron as a seed crystal, wherein the addition amount is 8g per liter of solution, then heating to 93 ℃, reacting for 1.5 hours, filtering, washing, drying, sieving and packaging to obtain the battery-grade lithium carbonate.
And (2) sieving the mixture in the step (1) by using a 150-mesh sieve.
The reducing agent added in the step (2) is sulfur dioxide.
And (4) after the pH value is adjusted back to 4.8 in the step (3), heating to 89 ℃, introducing air to oxidize ferrous ions into ferric iron completely, and continuing to react for 1.8 hours.
The granularity of the zinc powder added in the step (4) is 125 meshes, the mole number of the added zinc powder is 1.18 times of that of nickel, cobalt, manganese and copper in the second filtrate, the pH value in the zinc powder adding process is maintained to be 3.8, the P204 extracting agent is used for extracting iron, zinc, copper and manganese, the process is 9-level countercurrent extraction, the volume flow ratio of the P204 extracting agent to the third filtrate is 1:4.2, the extracted organic phase is subjected to 6-level countercurrent washing, the washing liquid is mixed with the third filtrate for extraction after being returned, the washing liquid adopts 0.21 mol/L sulfuric acid solution, the volume flow ratio of the extracted organic phase to the washing liquid is 1:0.13, when the P507 extracting agent is used for extracting raffinate containing nickel, cobalt, magnesium and lithium, the volume flow ratio of the P507 extracting agent to raffinate containing nickel, cobalt, magnesium and lithium is 1:1.8, the extracted organic phase is subjected to 3-level countercurrent washing, the washing liquid is returned to be mixed with raffinate containing nickel, the extraction liquid is extracted, the washing liquid adopts 0.13 mol/L, and the volume ratio of the washing liquid to the organic phase to the washing liquid is 0.22.
And (5) after the reaction is finished, adding a flocculating agent, and then filtering, wherein the flocculating agent is added in an amount of 35g per ton of the solution, and the flocculating agent is PAM.
In the step (6), the complexing agent is ammonia water, the concentration of the complexing agent after the complexing agent is added is 0.15 mol/L, and the mole number of the added ammonium bicarbonate is 1.25 times of the mole number of lithium in the fourth filtrate.
And (4) performing magnetic separation to obtain cobalt-nickel powder and manganese-copper powder, dissolving the cobalt-nickel powder with acid, and introducing ozone to obtain cobalt oxyhydroxide and a nickel solution, calcining the cobalt oxyhydroxide at 880 ℃ for 3 hours to obtain battery-grade cobaltosic oxide, concentrating and crystallizing the nickel solution to obtain nickel sulfate crystals, adding 0.15 mol/L of sulfuric acid solution to the manganese-copper powder to obtain a manganese solution and copper powder, and concentrating and crystallizing the manganese solution to obtain manganese sulfate crystals.
The washed P204 extractant is subjected to 5-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade zinc sulfate, the industrial-grade zinc sulfate is concentrated until the Baume degree is 50.5, then the temperature is reduced to 13 ℃, the mother solution is returned to be mixed with the second filtrate, the washed P507 extractant is subjected to 5.8-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade magnesium sulfate, the industrial-grade magnesium sulfate is concentrated until the Baume degree is 52.5, then the temperature is reduced to 13 ℃, and the mother solution is returned to be mixed with the second filtrate.
And (3) returning the fourth filter residue to the step (2) for dissolving.
The finally obtained lithium carbonate meets the requirements of the industry standard YS/T582 and 2013, wherein:
| index (I) | D10 | D50 | D90 | D100 | Fluidity of the resin |
| Numerical value | 3.5 micron | 5.8 micron | 9.1 micron | 9.8 micron | 15s/50g |
The purity of the obtained nickel sulfate crystal is 99.2 percent, the purity of the manganese sulfate crystal is 99.1 percent, the purity of the copper powder is 99.2 percent, the purity of the industrial-grade zinc sulfate is 98.8 percent, and the purity of the magnesium sulfate is 99.1 percent.
The obtained detection data of the battery grade cobaltosic oxide are as follows:
| Co | Na | Cd | Ni | Mn | Ca |
| 72.1％ | 25ppm | 2ppm | 12ppm | 6ppm | 7ppm |
| D10 | D50 | D90 | BET | sulfate radical | Tap density |
| 2.7 micron | 5.6 microns | 8.7 microns | 8.4m2/g | 51ppm | 2.6g/mL |
The comprehensive recovery rate of the final lithium is 99.5 percent, and the comprehensive recovery rates of the nickel, the cobalt, the manganese and the magnesium are respectively 99.1 percent, 98.7 percent and 98.3 percent.
Example 2
A method for preparing battery-grade lithium carbonate by using waste lithium batteries comprises the following steps:
1) preprocessing, namely disassembling, crushing and sieving the recovered waste battery materials or waste batteries to obtain battery crushed materials;
2) reducing and leaching the battery crushed aggregates, adding bottom water according to a solid-to-liquid ratio of 1:6, adding acid to adjust the pH to 1.32, reacting at 65 ℃ for 4.2 hours, simultaneously adding a reducing agent, wherein the molar weight of the added reducing agent is 1.8 times of that of trivalent metals, and filtering after the reaction is finished to obtain a first filtrate and a first filter residue;
3) removing iron and aluminum, adding alkali into the first filtrate to adjust the pH value to 5.2, precipitating iron, aluminum and chromium ions in the first filtrate to ensure that the content of the iron, the aluminum and the chromium in the solution is lower than 10 mg/L, and then filtering to obtain a second filtrate and second filter residue;
4) removing impurities, adding zinc powder into the second filtrate, reacting for 2.5 hours at the temperature of 62 ℃, filtering to obtain a third filtrate and third filter residue, extracting the third filtrate by using a P204 extracting agent to remove iron, zinc, copper and manganese to obtain raffinate containing nickel, cobalt, magnesium and lithium, and extracting nickel, cobalt and magnesium by using a P507 extracting agent to obtain raffinate containing lithium and sodium;
5) deeply removing impurities, namely adding sodium hydroxide into lithium-containing raffinate at 75 ℃, adjusting the pH value of the solution to 10.2, reacting for 2.3 hours under the condition, and filtering to obtain fourth filtrate and fourth filter residue;
6) and preparing battery-grade lithium carbonate, adding a complexing agent into the fourth filtrate, then adding ammonium bicarbonate, stirring and adding at 45 ℃, simultaneously adding battery-grade lithium carbonate with the granularity of 0.8 micron as a seed crystal, wherein the addition amount is 8g per liter of solution, then heating to 93 ℃, reacting for 1.8 hours, filtering, washing, drying, sieving and packaging to obtain the battery-grade lithium carbonate.
And (2) sieving the mixture in the step (1) by using a 150-mesh sieve.
The reducing agent added in the step (2) is sodium sulfite.
And (4) after the pH value is adjusted back to 5.2 in the step (3), heating to 92 ℃, introducing air to oxidize ferrous ions into ferric iron completely, and continuing to react for 1.3 hours.
The granularity of the zinc powder added in the step (4) is 125 meshes, the mole number of the added zinc powder is 1.16 times of that of nickel, cobalt, manganese and copper in the second filtrate, the pH value in the zinc powder adding process is maintained to be 3.8, the P204 extracting agent is used for extracting iron, zinc, copper and manganese, the 10-level countercurrent extraction process is adopted, the volume flow ratio of the P204 extracting agent to the third filtrate is 1:5, the extracted organic phase is subjected to 6-level countercurrent washing, the washing liquid is returned to be mixed with the third filtrate for extraction, the washing liquid adopts 0.19 mol/L sulfuric acid solution, the volume flow ratio of the extracted organic phase to the washing liquid is 1:0.13, when the P507 extracting agent is used for extracting raffinate containing nickel, cobalt, magnesium and lithium, 9-level countercurrent extraction is adopted, the volume flow ratio of the P507 extracting agent to raffinate containing nickel, cobalt, magnesium and lithium is 1:1.8, the extracted organic phase is subjected to 3-level countercurrent washing, the washing liquid is returned to be mixed with raffinate containing nickel, the extraction liquid is extracted, and 0.13 mol/L, and the volume flow ratio of the washing liquid is 0.22.
And (5) after the reaction is finished, adding a flocculating agent, and then filtering, wherein the flocculating agent is added in an amount of 38g per ton of the solution, and the flocculating agent is PAM.
In the step (6), the complexing agent is EDTA, the concentration of the complexing agent after the complexing agent is added is 0.12 mol/L, and the mole number of the added ammonium bicarbonate is 1.23 times of the mole number of lithium in the fourth filtrate.
And (4) performing magnetic separation to obtain cobalt-nickel powder and manganese-copper powder, dissolving the cobalt-nickel powder with acid, and introducing ozone to obtain a cobalt oxyhydroxide solution and a nickel solution, calcining the cobalt oxyhydroxide at the temperature of 885 ℃ for 3.5 hours to obtain battery-grade cobaltosic oxide, concentrating and crystallizing the nickel solution to obtain a nickel sulfate crystal, adding 0.15 mol/L of sulfuric acid solution to the manganese-copper powder to obtain a manganese solution and copper powder, and concentrating and crystallizing the manganese solution to obtain a manganese sulfate crystal.
The washed P204 extractant is subjected to 6-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade zinc sulfate, the industrial-grade zinc sulfate is concentrated until the Baume degree is 50.6, then the temperature is reduced to 12 ℃, the mother liquor is returned to be mixed with the second filtrate, the washed P507 extractant is subjected to 6-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade magnesium sulfate, the industrial-grade magnesium sulfate is concentrated until the Baume degree is 52.3, then the temperature is reduced to 13 ℃, and the mother liquor is returned to be mixed with the second filtrate.
And (3) returning the fourth filter residue to the step (2) for dissolving.
The finally obtained lithium carbonate meets the requirements of the industry standard YS/T582 and 2013, wherein:
| index (I) | D10 | D50 | D90 | D100 | Fluidity of the resin |
| Numerical value | 3.8 micron | 5.8 micron | 9.2 micron | 9.7 microns | 16s/50g |
The purity of the obtained nickel sulfate crystal is 99.1 percent, the purity of the manganese sulfate crystal is 99.1 percent, the purity of the copper powder is 99.2 percent, the purity of the industrial-grade zinc sulfate is 98.7 percent, and the purity of the magnesium sulfate is 99.1 percent.
The obtained detection data of the battery grade cobaltosic oxide are as follows:
| Co | Na | Cd | Ni | Mn | Ca |
| 72.1％ | 22ppm | 1ppm | 13ppm | 8ppm | 9ppm |
| D10 | D50 | D90 | BET | sulfate radical | Tap density |
| 2.7 micron | 5.7 microns | 8.8 micron | 8.2m2/g | 59ppm | 2.58g/mL |
The comprehensive recovery rate of the final lithium is 99.6 percent, and the comprehensive recovery rates of the nickel, the cobalt, the manganese and the magnesium are respectively 99.2 percent, 99.1 percent, 98.3 percent and 98.8 percent.
Example 3
A method for preparing battery-grade lithium carbonate by using waste lithium batteries comprises the following steps:
1) preprocessing, namely disassembling, crushing and sieving the recovered waste battery materials or waste batteries to obtain battery crushed materials;
2) reducing and leaching the battery crushed aggregates, adding bottom water according to a solid-to-liquid ratio of 1:5.5, adding acid to adjust the pH to 1.85, reacting at 83 ℃ for 4.5 hours, simultaneously adding a reducing agent, wherein the molar weight of the reducing agent added is 1.8 times of that of trivalent metal, and filtering after the reaction is finished to obtain a first filtrate and a first filter residue;
3) removing iron and aluminum, adding alkali into the first filtrate to adjust the pH value to 5.3, precipitating iron, aluminum and chromium ions in the first filtrate to ensure that the content of the iron, the aluminum and the chromium in the solution is lower than 10 mg/L, and then filtering to obtain a second filtrate and second filter residue;
4) removing impurities, adding zinc powder into the second filtrate, reacting for 2.8 hours at the temperature of 65 ℃, filtering to obtain a third filtrate and third filter residue, extracting the third filtrate by using a P204 extracting agent to remove iron, zinc, copper and manganese to obtain raffinate containing nickel, cobalt, magnesium and lithium, and extracting nickel, cobalt and magnesium by using a P507 extracting agent to obtain raffinate containing lithium and sodium;
5) deeply removing impurities, namely adding sodium hydroxide into lithium-containing raffinate at 72 ℃, adjusting the pH value of the solution to 10.7, reacting for 2.8 hours under the condition, and filtering to obtain fourth filtrate and fourth filter residue;
6) and preparing battery-grade lithium carbonate, adding a complexing agent into the fourth filtrate, then adding ammonium bicarbonate, stirring and adding at 55 ℃, simultaneously adding battery-grade lithium carbonate with the granularity of 0.8 micron as a seed crystal, wherein the adding amount is 8.5g per liter of solution, then heating to 93 ℃, reacting for 1.8 hours, filtering, washing, drying, sieving and packaging to obtain the battery-grade lithium carbonate.
And (2) sieving by a 175-mesh sieve during sieving in the step (1).
The reducing agent added in the step (2) is zinc powder.
And (4) after the pH value is adjusted back to 5.3 in the step (3), heating to 94 ℃, introducing air to oxidize ferrous ions into ferric iron completely, and continuing to react for 1.8 hours.
The granularity of the zinc powder added in the step (4) is 125 meshes, the mole number of the added zinc powder is 1.15 times of that of nickel, cobalt, manganese and copper in the second filtrate, the pH value in the zinc powder adding process is maintained to be 3.8, the P204 extracting agent is used for extracting iron, zinc, copper and manganese, the process is 8-level countercurrent extraction, the volume flow ratio of the P204 extracting agent to the third filtrate is 1:4.3, the extracted organic phase is subjected to 6-level countercurrent washing, the washing liquid is mixed with the third filtrate for extraction, the washing liquid adopts 0.18 mol/L sulfuric acid solution, the volume flow ratio of the extracted organic phase to the washing liquid is 1:0.13, when the P507 extracting agent is used for extracting raffinate containing nickel, cobalt and lithium, 10-level countercurrent extraction is adopted, the volume flow ratio of the P507 extracting agent to raffinate containing nickel, cobalt, magnesium and lithium is 1:1.2, the extracted organic phase is subjected to 3-level countercurrent washing, the washing liquid is mixed with raffinate containing nickel, the extraction liquid is extracted by adopting 0.12 mol/L, and the volume ratio of the washing liquid is 0.22.
And (5) after the reaction is finished, adding a flocculating agent, and then filtering, wherein the flocculating agent is added in an amount of 33g per ton of the solution, and the flocculating agent is PAM.
In the step (6), the complexing agent is sulfosalicylic acid, the concentration of the complexing agent after the complexing agent is added is 0.11 mol/L, and the mole number of the added ammonium bicarbonate is 1.27 times of the mole number of lithium in the fourth filtrate.
And (4) performing magnetic separation to obtain cobalt-nickel powder and manganese-copper powder, dissolving the cobalt-nickel powder with acid, and introducing ozone to obtain a cobalt oxyhydroxide solution and a nickel solution, calcining the cobalt oxyhydroxide at the temperature of 885 ℃ for 3.2 hours to obtain battery-grade cobaltosic oxide, concentrating and crystallizing the nickel solution to obtain a nickel sulfate crystal, adding a 0.14 mol/L sulfuric acid solution to the manganese-copper powder to obtain a manganese solution and a copper powder, and concentrating and crystallizing the manganese solution to obtain a manganese sulfate crystal.
The washed P204 extractant is subjected to 6-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade zinc sulfate, the industrial-grade zinc sulfate is concentrated until the Baume degree is 50.3, then the temperature is reduced to 13 ℃, the mother liquor is returned to be mixed with the second filtrate, the washed P507 extractant is subjected to 6-stage countercurrent back extraction, the obtained back extraction solution is subjected to concentration and crystallization to obtain industrial-grade magnesium sulfate, the industrial-grade magnesium sulfate is concentrated until the Baume degree is 52.5, then the temperature is reduced to 14 ℃, and the mother liquor is returned to be mixed with the second filtrate.
And (3) returning the fourth filter residue to the step (2) for dissolving.
The finally obtained lithium carbonate meets the requirements of the industry standard YS/T582 and 2013, wherein:
| index (I) | D10 | D50 | D90 | D100 | Fluidity of the resin |
| Numerical value | 3.8 micron | 6.1 micron | 9.3 micron | 9.9 micron | 15s/50g |
The purity of the obtained nickel sulfate crystal is 99.1 percent, the purity of the manganese sulfate crystal is 99.1 percent, the purity of the copper powder is 99.1 percent, the purity of the industrial-grade zinc sulfate is 98.9 percent, and the purity of the magnesium sulfate is 99.1 percent.
The obtained detection data of the battery grade cobaltosic oxide are as follows:
| Co | Na | Cd | Ni | Mn | Ca |
| 72.2％ | 22ppm | 1ppm | 11ppm | 7ppm | 8ppm |
| D10 | D50 | D90 | BET | sulfate radical | Tap density |
| 2.8 micron | 5.7 microns | 8.6 micron | 8.2m2/g | 43ppm | 2.55g/mL |
The comprehensive recovery rate of the final lithium is 99.6 percent, and the comprehensive recovery rates of the nickel, the cobalt, the manganese and the magnesium are respectively 99.2 percent, 99.1 percent, 98.8 percent and 98.3 percent.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (7)
1. A method for preparing battery-grade lithium carbonate by using waste lithium batteries is characterized by comprising the following steps:
1) preprocessing, namely disassembling, crushing and sieving the recovered waste battery materials or waste batteries to obtain battery crushed materials;
2) reducing and leaching the battery crushed aggregates, adding bottom water according to a solid-to-liquid ratio of 1:3-10, adding acid to adjust the pH value to 0.5-2.0, reacting at 50-90 ℃ for 2-6 hours, simultaneously adding a reducing agent, wherein the molar weight of the reducing agent is 0.5-4 times of that of trivalent metal, and filtering after the reaction is finished to obtain a first filtrate and a first filter residue;
3) removing iron and aluminum, adding alkali into the first filtrate to adjust the pH value to 4-5.5, precipitating iron, aluminum and chromium ions in the first filtrate to ensure that the content of iron, aluminum and chromium in the solution is lower than 10 mg/L, and then filtering to obtain a second filtrate and a second filter residue;
4) removing impurities, adding zinc powder into the second filtrate, reacting for 2-3 hours at the temperature of 50-70 ℃, filtering to obtain a third filtrate and a third filter residue, extracting iron, zinc, copper and manganese from the third filtrate by using a P204 extracting agent to obtain raffinate containing nickel, cobalt, magnesium and lithium, extracting nickel, cobalt and magnesium by using a P507 extracting agent to obtain raffinate containing lithium and sodium, magnetically separating the third filter residue to obtain cobalt-nickel powder and manganin powder, dissolving the cobalt-nickel powder by using acid, introducing ozone to obtain cobalt oxyhydroxide and a nickel solution, calcining the cobalt oxyhydroxide at the temperature of 850-;
5) deeply removing impurities, namely adding sodium hydroxide into lithium-containing raffinate at the temperature of 60-80 ℃, adjusting the pH value of the solution to 9-11, reacting for 2-3 hours under the condition, and filtering to obtain fourth filtrate and fourth filter residue;
6) preparing battery-grade lithium carbonate, adding a complexing agent into the fourth filtrate, then adding ammonium bicarbonate, stirring and adding at 30-60 ℃, simultaneously adding battery-grade lithium carbonate with the granularity of 0.5-1 micron as a seed crystal, wherein the adding amount is 5-10g per liter of solution, then heating to 90-95 ℃ for reaction for 1-2 hours, filtering, washing, drying, sieving and packaging to obtain the battery-grade lithium carbonate, wherein the complexing agent is ammonia water, citric acid, tartaric acid, sulfosalicylic acid or EDTA, the concentration of the complexing agent after the complexing agent is added is 0.1-0.2 mol/L, and the mole number of the added ammonium bicarbonate is 1.2-1.3 times of the mole number of lithium in the fourth filtrate.
2. The method for preparing battery-grade lithium carbonate from waste lithium batteries according to claim 1, wherein the method comprises the following steps: and (2) sieving the mixture in the step (1) by using a 100-200-mesh sieve.
3. The method for preparing battery-grade lithium carbonate from waste lithium batteries according to claim 1, wherein the method comprises the following steps: the reducing agent added in the step (2) is sulfur dioxide, hydrogen peroxide, sodium sulfite, iron powder or zinc powder.
4. The method for preparing battery-grade lithium carbonate from waste lithium batteries according to claim 1, wherein the method comprises the following steps: and (4) after the pH value is adjusted back to 4-5.5 in the step (3), heating to 85-95 ℃, introducing air to ensure that ferrous ions are completely oxidized into ferric iron, and continuing to react for 1-2 hours.
5. The method for preparing battery-grade lithium carbonate from waste lithium batteries as claimed in claim 1, wherein the particle size of the zinc powder added in the step (4) is 100-150 meshes, the mole number of the added zinc powder is 1.1-1.2 times of the mole number of nickel, cobalt, manganese and copper in the second filtrate, the pH value of the zinc powder adding process is maintained at 3.5-4, the P204 extraction agent is used for extraction iron, zinc, copper and manganese removal process at 8-10-grade countercurrent extraction, the volume flow ratio of the P204 extraction agent to the third filtrate is 1:3-5, the extracted organic phase is subjected to 5-6-grade countercurrent washing, the washing liquid is returned to be mixed with the third filtrate for extraction, the washing liquid is a sulfuric acid solution with 0.15-0.25 mol/L, the volume flow ratio of the extracted organic phase to the washing liquid is 1:0.1-0.15, when the P507 extraction agent is used for extraction of magnesium and lithium, the extraction raffinate containing magnesium and nickel, the extraction raffinate is extracted by 8-10-grade countercurrent extraction, the volume flow ratio of the P507 extraction agent to lithium containing nickel, the washing liquid is 1:0.2, the raffinate containing magnesium and the extraction raffinate is returned to the extraction liquid after extraction, and the extraction of the extraction liquid is subjected to extraction liquid, and the extraction liquid is extracted by 0.2-0.2, the extraction liquid.
6. The method for preparing battery-grade lithium carbonate from waste lithium batteries according to claim 1, wherein the method comprises the following steps: and (5) after the reaction is finished, adding a flocculating agent, and then filtering, wherein the flocculating agent is added in an amount of 30-40g per ton of the solution, and the flocculating agent is PAM.
7. The method for preparing battery-grade lithium carbonate from waste lithium batteries according to claim 1, wherein the method comprises the following steps: and (3) returning the fourth filter residue to the step (2) for dissolving.
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| CN109536728A (en) * | 2019-01-25 | 2019-03-29 | 广东省稀有金属研究所 | A method of recycling nickel cobalt from battery electrode material leachate |
| CN110205491B (en) * | 2019-06-25 | 2020-05-15 | 中南大学 | Metallic lithium elementary substance and preparation method and application thereof |
| CN110724818B (en) * | 2019-09-29 | 2021-05-18 | 湖南雅城新材料有限公司 | Full-wet recovery process of waste lithium battery |
| CN111519031B (en) * | 2020-04-29 | 2022-06-28 | 江苏北矿金属循环利用科技有限公司 | Method for recycling nickel, cobalt, manganese and lithium from waste power lithium ion battery black powder |
| CN112366304A (en) * | 2020-11-16 | 2021-02-12 | 湖南上临新材料科技有限公司 | Nanocrystalline iron-silicon alloy-based cathode material for lithium ion battery and preparation method thereof |
| CN112499694A (en) * | 2020-12-02 | 2021-03-16 | 贵州鹏程新材料有限公司 | Method for extracting battery-grade cobalt chloride from waste battery materials |
| CN113003589B (en) * | 2021-04-25 | 2023-04-25 | 湖南金源新材料股份有限公司 | Method and extraction device for extracting and preparing battery grade lithium carbonate from P507 raffinate |
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| CN101628869B (en) * | 2009-08-18 | 2013-06-26 | 沈阳张明化工有限公司 | Method for preparing cobalt octoate by using LiCoO, anode material of waste lithium battery |
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