CN111334664A - Method for comprehensively recycling valuable metals from ternary lithium battery positive electrode material based on magnesium salt circulation - Google Patents
Method for comprehensively recycling valuable metals from ternary lithium battery positive electrode material based on magnesium salt circulation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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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
- C22B47/00—Obtaining manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for comprehensively recovering valuable metals from a ternary lithium battery positive electrode material based on magnesium salt circulation. The method can realize comprehensive recovery of all components of the nickel, cobalt, manganese and lithium valuable metal, and simultaneously realize recycling of magnesium sulfate in a system, thereby being beneficial to reducing the emission of magnesium-containing wastewater and reducing the production cost.
Description
Technical Field
The invention relates to a method for recovering a ternary lithium battery positive electrode material, in particular to a method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt circulation, and belongs to the technical field of valuable metal recovery.
Background
With the explosive increase of the use amount of new energy automobiles, the waste power lithium ion battery is one of main solid wastes in cities in China in the future, the content of metal of the waste power lithium ion battery is far higher than that of the metal in ores, and the waste power lithium ion battery is a typical urban mineral product and has high recycling value. The ternary lithium battery has higher and higher market proportion in the power battery due to high energy density, high tap density, large specific capacity and the like, and gradually becomes the mainstream of the power battery. The ternary power lithium ion battery contains a large amount of valuable metals, wherein the metals with the highest potential value comprise nickel, cobalt, manganese, lithium and the like, and the technical method for comprehensively recovering the relevant valuable metals gradually becomes a research hotspot of relevant technologists.
The existing ternary lithium battery material recovery process mainly comprises the steps of carrying out acid leaching on materials, and then separating and recovering valuable metals through a chemical precipitation method or an extraction method and the like, wherein lithium is generally recovered at the tail end of a process, and partial lithium elements are entrained and lost when nickel, cobalt and other elements are recovered at the front end, so that the final lithium recovery rate is low and is only about 60%.
With the rapid increase of lithium demand and the rising of lithium price, the economic benefit of lithium recovery becomes more and more prominent, and more people begin to pay attention to the research on the efficient recovery of lithium of the ternary battery. The main method is to carry out water immersion to preferentially recover lithium element by high-temperature roasting treatment, and sulfates such as ammonium sulfate, sodium sulfate, calcium sulfate and the like are generally added in the roasting process. For example, CN102163760A discloses a method for separating and recovering lithium and cobalt from a lithium battery positive electrode material, which comprises the specific steps of (1) physical disassembly and alkaline leaching; (2) roasting and washing: adding sulfate (mainly common sulfate such as magnesium sulfate, ammonium sulfate or calcium sulfate) into the black solid material containing lithium cobaltate obtained in the step (1), mixing, roasting at 600-800 ℃ for 2-6 hours, cooling, adding washing liquid, washing with water at 60-80 ℃, and filtering to obtain the material containing Li+The filtrate and the filter residue containing cobalt and a small amount of lithium; (3) reduction and acid dissolution; (4) cobalt is extracted to obtain pure Co2+And (3) solution. According to the method, the positive electrode material of the waste power battery is roasted by adding sulfate, then leaching separation is carried out to recover valuable metals, but the method mainly aims at the separation and recovery of cobalt and lithium, the recovery of nickel and manganese is not involved, and the final recovery rate of lithium is only 90%. Meanwhile, the trend of the sulfate additive added in the roasting process in the system, the final treatment mode and the like are not clear. The problems of discharge and treatment of the magnesium sulfate in workshop waste water can be caused by adding the magnesium sulfate, and a large amount of calcium sulfate slag solid waste is generated in the leaching process due to adding the calcium sulfate, so that the treatment cost is high, and the economic and effective treatment is difficult.
Disclosure of Invention
The invention aims to provide a method for comprehensively recovering valuable metals from a ternary lithium battery positive electrode material based on magnesium salt circulation, which can realize comprehensive recovery of all components of nickel, cobalt, manganese and lithium valuable metals, realize recycling of magnesium sulfate in a system and reduce discharge of magnesium salt wastewater.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for comprehensively recovering valuable metals from a ternary lithium battery positive electrode material based on magnesium salt circulation comprises the following steps:
(1) mixing magnesium sulfate and ternary lithium battery positive electrode powder in proportion, and roasting under an anaerobic condition to obtain a roasted material;
(2) mixing the roasted material obtained in the step (1) with water for water leaching, and filtering to obtain a lithium-containing filtrate and water leaching slag, wherein the water leaching slag mainly contains elements such as nickel, cobalt, manganese, magnesium and the like, and the leaching rate of lithium reaches 99.8%;
(3) removing impurities from the lithium-containing filtrate obtained in the step (2), and adding sodium carbonate to perform alkali precipitation to obtain a lithium carbonate product;
(4) mixing the water leaching residue obtained in the step (2) with an acid solution for acid leaching, and filtering to obtain an acid leaching solution, wherein the leaching rate of Ni, Co and Mg can reach more than 99%, the leaching rate of Mn can reach more than 89%, and the leaching effect is ideal;
(5) performing manganese extraction on the acid leaching filtrate obtained in the step (4) by using a P204 extracting agent with the concentration of 20-25% and the saponification rate of 50-60% to realize the separation of Mn from Ni, Co and Mg;
(6) carrying out cobalt extraction on the raffinate obtained in the step (5) by adopting a P507 extraction agent with the concentration of 20-25% and the saponification rate of 60-70% to realize the separation of Co from Ni and Mg;
(7) performing magnesium extraction on the raffinate obtained in the step (6) by using a P507 extracting agent with the concentration of 20-25% and the saponification rate of 40-50% to realize the separation of Mg and Ni; returning the obtained magnesium sulfate product or high-concentration magnesium sulfate solution to the system roasting process to realize the recycling of the magnesium salt in the system;
(8) and (3) carrying out nickel extraction on the raffinate obtained in the step (7) by adopting a P507 extracting agent with the concentration of 20-25% and the saponification rate of 60-70%.
Preferably, in the step (1), the mass ratio of the magnesium sulfate to the ternary lithium battery positive electrode powder is 3-5: 5, the roasting temperature is 300-900 ℃, and the roasting time is 1-5 h.
Preferably, in the step (2), the solid-to-liquid ratio of the water leaching solution is 3-5: 1mL/g, 50-80 ℃ and 0.5-1 h.
Preferably, in the step (4), the solid-to-solid ratio of the pickle liquor is 3-5: 1mL/g, and the mass ratio of acid ores is 1.2-1.4: 1, the temperature is 80-90 ℃, and the time is 1-2 h.
Preferably, in the step (4), the acid solution is sulfuric acid or hydrochloric acid.
Preferably, the specific steps of extracting manganese from P204 in step (5) are as follows: adjusting the pH of the acid leaching solution back to 3.5-4, and filtering a small amount of precipitate to obtain a filtrate; mixing a P204 extracting agent with sulfonated kerosene, and performing extraction for 8-10 grades to obtain a Mn-loaded organic phase and raffinate rich in Ni, Co and Mg; performing back extraction by using 1.5-2 mol/L sulfuric acid, and performing 6-8-level counter-current back extraction to obtain MnSO4And (3) precipitating manganese from the solution by using a sodium carbonate solution with the concentration of 30% to obtain a crude manganese carbonate product.
Preferably, the specific steps of P507 cobalt extraction in step (6) are as follows: mixing P507 with sulfonated kerosene, and performing extraction for 6-8 grades to obtain a Co-rich loaded organic phase and Ni-Mg-rich raffinate; carrying out back extraction on the Co-loaded organic phase by using 1.5-2 mol/L sulfuric acid, wherein the back extraction is of 8-10 grades, and obtaining CoSO4Evaporating and crystallizing the solution to produce CoSO4.7H2And (4) O products.
Preferably, the specific steps of extracting magnesium from P507 in step (7) are as follows: mixing P507 with sulfonated kerosene, extracting for 5-6 grades to obtain a Mg-rich loaded organic phase and Ni-rich raffinate, performing back extraction on the Mg-loaded organic phase by using 1.5-2 mol/L sulfuric acid, performing back extraction for 6-8 grades to obtain MgSO4Solution, p-MgSO4The solution is evaporated and crystallized to produce MgSO4.7H2The product O is concentrated by evaporation to obtain a high-concentration magnesium sulfate solution.
Preferably, the specific steps of P507 nickel extraction in step (8) are as follows: mixing P507 with sulfonated kerosene, performing extraction on the extraction section by 6-8 grades, performing back extraction on the Ni-loaded organic phase by using 1.5-2 mol/L sulfuric acid, and performing back extraction on the extraction section by 8-10 grades to obtain NiSO4Evaporating and crystallizing the solution to produce NiSO4.6H2And (4) O products.
Compared with the prior art, the invention has the following beneficial effects:
1. the magnesium sulfate is mixed with the battery anode powder to be subjected to oxygen-free roasting, lithium is converted into lithium sulfate which is easy to dissolve in water, and then the lithium is dissolved by water immersion, while other elements such as nickel, cobalt, manganese, magnesium and the like are basically insoluble, so that the lithium can be preferentially extracted. The lithium is subjected to anaerobic roasting by magnesium sulfate and then is subjected to water leaching, the leaching rate can reach more than 99.8 percent, the lithium leaching solution is subjected to alkali precipitation to prepare a lithium carbonate product, the final recovery rate of the lithium reaches more than 99 percent, and the purity is 98.5-99 percent. Compared with the traditional recovery process, the recovery rate of lithium is greatly improved, the improvement rate is nearly 10%, meanwhile, the preferential extraction of lithium is also beneficial to improving the purity of subsequent products such as nickel, cobalt, manganese and the like, and the effect of preferential extraction of lithium by sulfating roasting water is very obvious.
2. And after the water leaching process, acid leaching the water leaching residue, and extracting and recovering nickel, cobalt, manganese, magnesium and the like from the leaching solution, wherein the recovery rate of nickel can reach more than 99%, the recovery rate of cobalt can reach more than 99%, and the recovery rate of manganese can reach more than 89%. The magnesium is recovered by P507 extraction, and the magnesium sulfate solution after back extraction and washing is evaporated and crystallized to prepare a magnesium sulfate product, so that the magnesium sulfate product can return to a magnesium sulfate roasting process, the system recycling of magnesium element is realized, the magnesium sulfate is not discharged, and the pollution to the environment is reduced.
3. The process is based on the recycling of magnesium salts, the recovery rate of lithium is remarkably improved by nearly 10%, valuable elements such as nickel, cobalt, manganese, magnesium and the like are comprehensively recovered, and meanwhile, the magnesium salts are recycled in the system, so that the discharge of waste water is greatly reduced, the production cost is greatly reduced, the environmental benefit and the economic benefit are remarkable, and the process has great popularization and application values.
Drawings
FIG. 1 is a flow diagram of the recovery process of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The invention relates to a lithium secondary battery anode material (nickel cobalt lithium manganate, LiNi)xCoyMn1-x-yO2) Recovering valuable metals, adopting the processes of sulfating oxygen-free roasting, water leaching, acid leaching and extraction, and having the flow shown in figure 1: firstly, the lithium salt can be converted into water-soluble lithium sulfate by mixing the ternary lithium battery anode powder with magnesium sulfate and then carrying out anaerobic roasting, so that the preferential extraction of lithium element is realized. Acid leaching the water leaching residue to obtain a mixed solution containing nickel, cobalt, manganese and magnesium, and passing through P204 can realize the separation of manganese from nickel, cobalt and magnesium, and adopts a chemical precipitation method to recover manganese. The separation of cobalt, nickel and magnesium can be realized by P507 extraction, and the cobalt is recovered by back extraction washing. The separation of nickel and magnesium can be realized through P507 extraction, magnesium sulfate solution can be obtained through back extraction and washing, the magnesium sulfate solution is evaporated and crystallized to prepare a magnesium sulfate product, the magnesium sulfate product is returned to the roasting process, and the system recycling of the magnesium salt is realized. And finally, recovering nickel from the raffinate.
Example 1
(1) Sulfating roasting: weighing 30g MgSO4.7H2And mixing O and 50g of ternary lithium battery positive electrode powder, and roasting at 900 ℃ for 1 hour under an anaerobic condition to obtain 53.6g of roasting slag.
(2) Water leaching: mixing the roasted material with water, and performing water leaching, wherein the solid ratio of the water leaching solution is 3: 1mL/g, 50 ℃ and 0.5 h. After water immersion and filtration, a lithium-containing solution with a lithium concentration of 9.8g/L was obtained. 41.84g of filter residue is obtained, wherein the filter residue contains 0.019% of lithium, 15.4% of nickel, 9.3% of cobalt and 44.3% of manganese.
(3) And concentrating the lithium-containing filtrate, removing impurities, and adding sodium carbonate for alkali precipitation to obtain a lithium carbonate product.
(4) Acid leaching: taking the water immersion slag in the step (2), and mixing the water immersion slag according to a liquid-solid ratio of 5: adding water into the mixture in a volume ratio of 1mL/g to 1.2: 1, adding concentrated sulfuric acid, reacting for 1h at 90 ℃, and filtering to obtain filtrate containing nickel, Ni30.8g/L, cobalt, manganese and magnesium, wherein the filtrate contains 18.7g/L, 78.9g/L and 14.5 g/L.
(5) Extracting manganese: and (4) adjusting the pH value of the leaching solution in the step (4) back to 3.5, and filtering a small amount of precipitate to obtain a filtrate. The concentration of the used P204 is 20 percent, the saponification rate is 50 percent, the extraction section is 10 grades, and a Mn-loaded organic phase and raffinate containing Ni, Co and Mg are obtained after extraction. With 1.5mol/L H2SO4Carrying out back extraction and 8-grade countercurrent back extraction to obtain Mn2+MnSO with a concentration of 82.5g/L4The solution was then treated with 30% Na2CO3And precipitating manganese from the solution to obtain a manganese carbonate product.
(6) And (3) extracting cobalt: and (4) further extracting the raffinate in the step (5) by adopting P507, and effectively separating Co from Ni and Mg. The concentration of P507 was 20%, the saponification rate was 60%, and the extraction was carried outAnd stage 8, obtaining a Co-rich loaded organic phase and Ni-Mg-rich raffinate. 1.5mol/L H for Co-loaded organic phase2SO4Carrying out back extraction washing, carrying out back extraction at 8 levels to obtain Co2+CoSO with concentration of 88.5g/L4Evaporating and crystallizing the solution to produce CoSO4.7H2And (4) O products.
(7) And (3) extracting magnesium: and (4) further extracting the raffinate in the step (6) by using P507, and separating Ni from Mg. The concentration of P507 is 25 percent, the saponification rate is 40 percent, and the extraction section is 5-grade, so that a Mg-rich loaded organic phase and Ni-rich raffinate are obtained. 1.5mol/L of H for Mg-loaded organic phase2SO4Performing back extraction to obtain Mg with grade 62+MgSO with a concentration of 36g/L4Solution, p-MgSO4The solution is evaporated and crystallized to produce MgSO4.7H2And (4) O products.
(8) Extracting nickel: and (3) adopting P507 to carry out nickel extraction on the raffinate obtained in the step (7), wherein the specific conditions are as follows: the concentration of P507 is 20 percent, the saponification rate is 70 percent, the extraction section is 8 grades, 1.5mol/L H is used for the Ni-loaded organic phase2SO4Performing back extraction, and obtaining Ni at 8 levels in the back extraction section2+NiSO with concentration of 85g/L4The solution is then evaporated and crystallized to produce NiSO4.6H2And (4) O products.
In the embodiment, the lithium is preferentially extracted by sulfate oxygen-free roasting, the leaching rate of the lithium can reach 99.5 percent, and the recovery rate of the lithium reaches 99.1 percent. The recovery rate of nickel can reach 99.2%, the recovery rate of cobalt can reach 98.1%, the recovery rate of manganese can reach 89.2%, and the recovery rate of magnesium can reach 95.7%. Manganese carbonate and lithium carbonate reach the industrial grade standard, and cobalt sulfate and nickel sulfate reach the battery grade requirement.
Example 2
(1) Sulfating roasting: weighing 35g MgSO4.7H2And O, 50g of ternary lithium battery positive electrode powder, mixing, and roasting at 300 ℃ for 3h under an anaerobic condition to obtain 56.9g of roasting slag.
(2) Water leaching: mixing the roasted material with water, and performing water leaching, wherein the solid-to-solid ratio of the water leaching solution is 4: 1mL/g, 60 ℃ and 1 h. After water immersion and filtration, a lithium-containing solution with a lithium concentration of 6.97g/L was obtained. 42.4g of filter residue is obtained, wherein the filter residue contains 0.015% of lithium, 14.4% of nickel, 8.8% of cobalt and 41.7% of manganese.
(3) Concentrating the lithium-containing filtrate, removing impurities, adding sodium carbonate, and performing alkali precipitation to obtain lithium carbonate product
(4) Acid leaching: taking the water immersion slag in the step (2), and mixing the water immersion slag according to a liquid-solid ratio of 4: adding water into the mixture in a volume ratio of 1mL/g to 1.3: 1, adding concentrated sulfuric acid, reacting for 1.5h at 85 ℃, and filtering to obtain filtrate containing nickel Ni29.1g/L, cobalt 17.7g/L, manganese 74.3g/L and magnesium 15.9 g/L.
(5) Extracting manganese: and (4) adjusting the pH value of the leaching solution in the step (4) back to 4.0, and filtering a small amount of precipitate to obtain a filtrate. The concentration of P204 is 25%, the saponification rate is 55%, and the extraction section is 9 grades, and a Mn-loaded organic phase and raffinate containing Ni, Co and Mg are obtained after extraction. With 1.5mol/L H2SO4Carrying out back extraction and 6-grade countercurrent back extraction to obtain Mn2+MnSO with a concentration of 82.5g/L4Solution, followed by 30% Na2CO3And precipitating manganese from the solution to obtain a manganese carbonate product.
(6) And (3) extracting cobalt: and (4) further extracting the raffinate in the step (5) by adopting P507, and effectively separating Co from Ni and Mg. The concentration of P507 is 25 percent, the saponification rate is 65 percent, and the Co-rich loaded organic phase and the Ni-Mg-rich raffinate are obtained in the extraction stage 7. 1.5mol/L H for Co-loaded organic phase2SO4Carrying out back extraction washing, and carrying out back extraction for 9 grades to obtain Co2+CoSO with concentration of 88.5g/L4Evaporating and crystallizing the solution to produce CoSO4.7H2And (4) O products.
(7) And (3) extracting magnesium: and (4) further extracting the raffinate in the step (6) by using P507, and separating Ni from Mg. The concentration of P507 is 25 percent, the saponification rate is 45 percent, and the extraction section is 5 grades, so that a Mg-rich loaded organic phase and Ni-rich raffinate are obtained. 1.5mol/L H for Mg-loaded organic phase2SO4Performing back extraction to obtain Mg with grade 72+MgSO with a concentration of 36g/L4Solution, p-MgSO4The solution is evaporated and crystallized to produce MgSO4.7H2And (4) O products.
(8) Extracting nickel: and (3) adopting P507 to carry out nickel extraction on the raffinate obtained in the step (7), wherein the specific conditions are as follows: p507 concentration of 25%, saponification rate of 60%, extraction stageGrade 7, 1.5mol/L H for Ni-loaded organic phase2SO4Performing back extraction, and obtaining Ni at 8 levels in the back extraction section2+NiSO with concentration of 85g/L4The solution is then evaporated and crystallized to produce NiSO4.6H2O products
In the embodiment, the lithium is preferentially extracted by sulfate oxygen-free roasting, the leaching rate of the lithium can reach 99.6%, and the recovery rate of the lithium reaches 99.2%. The recovery rate of nickel can reach 99.3%, the recovery rate of cobalt can reach 98.3%, the recovery rate of manganese can reach 89.4%, and the recovery rate of magnesium can reach 95.8%. The manganese carbonate and nickel carbonate products reach the industrial grade standard. Manganese carbonate and lithium carbonate reach the industrial grade standard, and cobalt sulfate and nickel sulfate reach the battery grade requirement.
Example 3
(1) Sulfating roasting: weighing 50g MgSO4.7H2O, 50g of ternary lithium battery positive electrode powder, mixing, and roasting at 700 ℃ for 5h under an anaerobic condition to obtain 63.39g of roasting slag.
(2) Water leaching: mixing the roasted material with water, and performing water leaching, wherein the solid ratio of the water leaching solution is 5: 1mL/g, temperature 80 ℃, time 1 h. After water immersion filtration, a lithium-containing solution having a lithium concentration of 6.59g/L was obtained. 41.61g of filter residue is obtained, wherein the filter residue contains 0.01 percent of lithium, 13.7 percent of nickel, 8.3 percent of cobalt and 39.4 percent of manganese.
(3) And concentrating the lithium-containing filtrate, removing impurities, and adding sodium carbonate for alkali precipitation to obtain a lithium carbonate product.
(4) Acid leaching: taking the water immersion slag in the step (2), and mixing the water immersion slag according to a liquid-solid ratio of 3: adding water into the mixture in a volume ratio of 1mL/g to 1.4: 1, adding concentrated sulfuric acid, reacting for 2 hours at the temperature of 80 ℃, and filtering to obtain filtrate containing nickel, Ni27.4g/L, cobalt, manganese and magnesium, 16.7g/L, 70.2g/L and 17.2 g/L.
(5) Extracting manganese: and (4) adjusting the pH value of the leaching solution in the step (4) back to 3.8, and filtering a small amount of precipitate to obtain a filtrate. The concentration of the used P204 is 20 percent, the saponification rate is 60 percent, the extraction section is 8-grade, and a Mn-loaded organic phase and raffinate containing Ni, Co and Mg are obtained after extraction. With 2mol/L of H2SO4Carrying out back extraction and 6-grade countercurrent back extraction to obtain Mn2+MnSO with a concentration of 103.6g/L4Solution, followed by 30% Na2CO3And precipitating manganese from the solution to obtain a manganese carbonate product.
(6) And (3) extracting cobalt: and (4) further extracting the raffinate in the step (5) by adopting P507, and effectively separating Co from Ni and Mg. The concentration of the used P507 is 20 percent, the saponification rate is 60 percent, and the Co-rich loaded organic phase and the Ni-Mg-rich raffinate are obtained in 6 stages of the extraction section. 2mol/L H for Co-loaded organic phase2SO4Carrying out back extraction washing, carrying out back extraction for 10 grades to obtain Co2+CoSO with concentration of 106.8g/L4Evaporating and crystallizing the solution to produce CoSO4.7H2And (4) O products.
(7) And (3) extracting magnesium: and (4) further extracting the raffinate in the step (6) by using P507, and separating Ni from Mg. The concentration of P507 is 20 percent, the saponification rate is 50 percent, and the extraction section is 6 grades, so that a Mg-rich loaded organic phase and Ni-rich raffinate are obtained. 2mol/L of H for Mg-loaded organic phase2SO4Performing back extraction to obtain Mg with grade 72+MgSO with a concentration of 47.5g/L4Solution, p-MgSO4The solution is evaporated and crystallized to produce MgSO4.7H2And (4) O products.
(8) Extracting nickel: and (3) adopting P507 to carry out nickel extraction on the raffinate obtained in the step (7), wherein the specific conditions are as follows: the concentration of P507 is 20 percent, the saponification rate is 70 percent, the extraction section is 6 grades, 2mol/L H is used for the Ni-loaded organic phase2SO4Performing back extraction, wherein the back extraction section is 10 grades to obtain Ni2+NiSO with concentration of 103.9g/L4The solution is then evaporated and crystallized to produce NiSO4.6H2And (4) O products.
In the embodiment, the lithium is preferentially extracted by sulfate oxygen-free roasting, the leaching rate of the lithium can reach 99.8 percent, and the recovery rate of the lithium reaches 99.4 percent. The recovery rate of nickel can reach 99.5%, the recovery rate of cobalt can reach 98.6%, the recovery rate of manganese can reach 89.7%, and the recovery rate of magnesium can reach 95.9%. The manganese carbonate and nickel carbonate products reach the industrial grade standard. Manganese carbonate and lithium carbonate reach the industrial grade standard, and cobalt sulfate and nickel sulfate reach the battery grade requirement.
Aiming at the sulfating roasting procedure in the first step of the recovery process, the inventor explores that under the conditions that the roasting temperature is set to 700 ℃, the roasting time is 5h and 50g of ternary lithium battery positive electrode powder, the dosage of magnesium sulfate and aerobic/anaerobic conditions are changed to obtain the relation data of the lithium leaching rate and the dosage of magnesium sulfate, which is shown in the following table:
| test number | Magnesium sulfate dosage/g | Lithium leaching rate% (aerobic) | Lithium leaching rate% (without oxygen) |
| 1 | 50.00 | 82.09 | 99.80 |
| 2 | 37.51 | 82.45 | 99.52 |
| 3 | 27.78 | 75.88 | 94.33 |
| 4 | 22.73 | 70.93 | 79.56 |
| 5 | 19.23 | 64.77 | 65.52 |
As can be seen from the above table, (1) with the increase of the amount of magnesium sulfate, no matter the anode material is immersed in water after aerobic roasting or the anode material is immersed in water after anaerobic roasting, the leaching rate of lithium shows a rising trend, which indicates that with the increase of the mass of magnesium sulfate, the anode material reacts with magnesium sulfate more sufficiently, more metal oxide is converted into sulfate, and further the leaching rate is correspondingly increased; (2) no matter how the quality ratio of magnesium sulfate and the ternary lithium battery anode powder is changed, the leaching rate of lithium is higher than that of lithium leached under an aerobic condition after roasting under the anaerobic condition, and the anaerobic roasting is more beneficial to leaching of lithium.
Claims (9)
1. A method for comprehensively recovering valuable metals from a ternary lithium battery positive electrode material based on magnesium salt circulation is characterized by comprising the following steps:
(1) mixing magnesium sulfate and ternary lithium battery positive electrode powder in proportion, and roasting under an anaerobic condition to obtain a roasted material;
(2) mixing the roasted material obtained in the step (1) with water for water leaching, and filtering to obtain a lithium-containing filtrate and water leaching slag;
(3) removing impurities from the lithium-containing filtrate obtained in the step (2), and adding sodium carbonate to perform alkali precipitation to obtain a lithium carbonate product;
(4) mixing the water leaching residue obtained in the step (2) with an acid solution for acid leaching, and filtering to obtain an acid leaching solution;
(5) performing manganese extraction on the acid leaching filtrate obtained in the step (4) by using a P204 extracting agent with the concentration of 20-25% and the saponification rate of 50-60% to realize the separation of Mn from Ni, Co and Mg;
(6) carrying out cobalt extraction on the raffinate obtained in the step (5) by adopting a P507 extraction agent with the concentration of 20-25% and the saponification rate of 60-70% to realize the separation of Co from Ni and Mg;
(7) performing magnesium extraction on the raffinate obtained in the step (6) by using a P507 extraction agent with the concentration of 20-25% and the saponification rate of 40-50% to realize the separation of Mg and Ni; returning the obtained magnesium sulfate product or high-concentration magnesium sulfate solution to the roasting process in the step (1) to realize the recycling of the magnesium salt in the system;
(8) and (3) carrying out nickel extraction on the raffinate obtained in the step (7) by adopting a P507 extracting agent with the concentration of 20-25% and the saponification rate of 60-70%.
2. The method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt recycling as claimed in claim 1, wherein in the step (1), the mass ratio of magnesium sulfate to the ternary lithium battery positive electrode powder is 3-5: 5, the roasting temperature is 300-900 ℃, and the roasting time is 1-5 h.
3. The method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt recycling as claimed in claim 1, wherein in the step (2), the water leaching solution solid-to-solid ratio is 3-5: 1mL/g, 50-80 ℃ and 0.5-1 h.
4. The method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt recycling as claimed in claim 1, wherein in the step (4), the acid leaching solution solid-to-solid ratio is 3-5: 1mL/g, and the mass ratio of acid ores is 1.2-1.4: 1, the temperature is 80-90 ℃, and the time is 1-2 h.
5. The method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt recycling as claimed in claim 1, wherein in the step (4), the acid solution is sulfuric acid or hydrochloric acid.
6. The method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt recycling as claimed in claim 1, wherein the specific steps of P204 manganese extraction in step (5) are as follows: adjusting the pH of the acid leaching solution back to 3.5-4, and filtering a small amount of precipitate to obtain a filtrate; mixing a P204 extracting agent with sulfonated kerosene, and performing extraction for 8-10 grades to obtain a Mn-loaded organic phase and raffinate rich in Ni, Co and Mg; performing back extraction by using 1.5-2 mol/L sulfuric acid, and performing 6-8-level counter-current back extraction to obtain MnSO4Solution, followed byAnd (3) precipitating manganese by using a sodium carbonate solution with the concentration of 30% to obtain a crude manganese carbonate product.
7. The method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt recycling as claimed in claim 1, wherein the specific steps of P507 cobalt extraction in step (6) are as follows: mixing P507 with sulfonated kerosene, and performing extraction for 6-8 grades to obtain a Co-rich loaded organic phase and Ni-Mg-rich raffinate; carrying out back extraction on the Co-loaded organic phase by using 1.5-2 mol/L sulfuric acid, wherein the back extraction is of 8-10 grades, and obtaining CoSO4Evaporating and crystallizing the solution to produce CoSO4.7H2And (4) O products.
8. The method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt recycling as claimed in claim 1, wherein the specific steps of extracting magnesium from P507 in step (7) are as follows: mixing P507 with sulfonated kerosene, extracting for 5-6 grades to obtain a Mg-rich loaded organic phase and Ni-rich raffinate, performing back extraction on the Mg-loaded organic phase by using 1.5-2 mol/L sulfuric acid, performing back extraction for 6-8 grades to obtain MgSO4Solution, p-MgSO4The solution is evaporated and crystallized to produce MgSO4.7H2The product O is concentrated by evaporation to obtain a high-concentration magnesium sulfate solution.
9. The method for comprehensively recovering valuable metals from the ternary lithium battery positive electrode material based on magnesium salt recycling as claimed in claim 1, wherein the specific steps of P507 nickel extraction in step (8) are as follows: mixing P507 with sulfonated kerosene, performing extraction on the extraction section by 6-8 grades, performing back extraction on the Ni-loaded organic phase by using 1.5-2 mol/L sulfuric acid, and performing back extraction on the extraction section by 8-10 grades to obtain NiSO4Evaporating and crystallizing the solution to produce NiSO4.6H2And (4) O products.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111996378A (en) * | 2020-08-26 | 2020-11-27 | 界首市南都华宇电源有限公司 | Method for extracting nickel and cobalt from high-nickel battery waste |
| CN112375913A (en) * | 2020-11-18 | 2021-02-19 | 中南大学 | Waste lithium ion battery recovery method |
| CN112652807A (en) * | 2020-12-18 | 2021-04-13 | 中北大学 | Method for selectively recovering lithium in anode material of waste lithium ion battery by using Lewis acid |
| CN114150155A (en) * | 2021-12-20 | 2022-03-08 | 中国科学院过程工程研究所 | Optimization method for extraction process for simultaneously recovering battery-grade cobalt salt and nickel salt |
| WO2024042115A1 (en) | 2022-08-24 | 2024-02-29 | Umicore | Process for preparing a high-purity nickel sulphate solution |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271392A (en) * | 1997-08-15 | 2000-10-25 | 康明柯工程服务有限公司 | Chloride assisted hydrometallurgical extraction of nickel and cobalt fro m sulphide or laterite ores |
| CN1861817A (en) * | 2005-05-13 | 2006-11-15 | 河南科技大学 | Tech. of extracting metallic cobait from magnetic-iron ore tailing slag |
| CN101532094A (en) * | 2008-03-11 | 2009-09-16 | 江西稀有稀土金属钨业集团有限公司 | Technology for full-process extracting and separating nickel and cobalt from acid material system with high content of calcium and magnesium impurities |
| WO2011082444A1 (en) * | 2010-01-07 | 2011-07-14 | Galaxy Resources Limited | Process for the production of lithium carbonate |
| CN102163760A (en) * | 2011-03-17 | 2011-08-24 | 江西格林美资源循环有限公司 | Method for separating and recovering lithium and cobalt from positive electrode material of lithium battery |
| CN104073635A (en) * | 2014-06-12 | 2014-10-01 | 金川集团股份有限公司 | Method of removing impurities out of nickel chloride leachate |
| CN106684486A (en) * | 2016-12-28 | 2017-05-17 | 天津先众新能源科技股份有限公司 | Method for extracting lithium from waste lithium iron phosphate |
| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| CN107666022A (en) * | 2017-09-25 | 2018-02-06 | 湖南工业大学 | Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material |
| CN108832215A (en) * | 2018-06-14 | 2018-11-16 | 中国科学院过程工程研究所 | A kind of method of selective recovery anode material for lithium-ion batteries |
| CN109935922A (en) * | 2019-03-14 | 2019-06-25 | 北京矿冶科技集团有限公司 | A method of recycling valuable metal from waste and old lithium ion battery material |
-
2020
- 2020-03-07 CN CN202010153834.1A patent/CN111334664B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271392A (en) * | 1997-08-15 | 2000-10-25 | 康明柯工程服务有限公司 | Chloride assisted hydrometallurgical extraction of nickel and cobalt fro m sulphide or laterite ores |
| CN1861817A (en) * | 2005-05-13 | 2006-11-15 | 河南科技大学 | Tech. of extracting metallic cobait from magnetic-iron ore tailing slag |
| CN101532094A (en) * | 2008-03-11 | 2009-09-16 | 江西稀有稀土金属钨业集团有限公司 | Technology for full-process extracting and separating nickel and cobalt from acid material system with high content of calcium and magnesium impurities |
| WO2011082444A1 (en) * | 2010-01-07 | 2011-07-14 | Galaxy Resources Limited | Process for the production of lithium carbonate |
| CN102163760A (en) * | 2011-03-17 | 2011-08-24 | 江西格林美资源循环有限公司 | Method for separating and recovering lithium and cobalt from positive electrode material of lithium battery |
| CN104073635A (en) * | 2014-06-12 | 2014-10-01 | 金川集团股份有限公司 | Method of removing impurities out of nickel chloride leachate |
| CN106684486A (en) * | 2016-12-28 | 2017-05-17 | 天津先众新能源科技股份有限公司 | Method for extracting lithium from waste lithium iron phosphate |
| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| CN107666022A (en) * | 2017-09-25 | 2018-02-06 | 湖南工业大学 | Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material |
| CN108832215A (en) * | 2018-06-14 | 2018-11-16 | 中国科学院过程工程研究所 | A kind of method of selective recovery anode material for lithium-ion batteries |
| CN109935922A (en) * | 2019-03-14 | 2019-06-25 | 北京矿冶科技集团有限公司 | A method of recycling valuable metal from waste and old lithium ion battery material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111996378A (en) * | 2020-08-26 | 2020-11-27 | 界首市南都华宇电源有限公司 | Method for extracting nickel and cobalt from high-nickel battery waste |
| CN112375913A (en) * | 2020-11-18 | 2021-02-19 | 中南大学 | Waste lithium ion battery recovery method |
| CN112652807A (en) * | 2020-12-18 | 2021-04-13 | 中北大学 | Method for selectively recovering lithium in anode material of waste lithium ion battery by using Lewis acid |
| CN114150155A (en) * | 2021-12-20 | 2022-03-08 | 中国科学院过程工程研究所 | Optimization method for extraction process for simultaneously recovering battery-grade cobalt salt and nickel salt |
| WO2024042115A1 (en) | 2022-08-24 | 2024-02-29 | Umicore | Process for preparing a high-purity nickel sulphate solution |
| WO2024045529A1 (en) * | 2022-08-29 | 2024-03-07 | 广东邦普循环科技有限公司 | Method for comprehensive recycling of ternary positive electrode waste slurry |
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