CN114717419A - Method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium battery - Google Patents
Method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium battery 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
- C22B7/007—Wet processes by acid leaching
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- 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
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- 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
- C22B23/0476—Separation of nickel from cobalt
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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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- 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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- 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 separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium batteries, which comprises the following steps: adding sulfuric acid and a reducing agent into the waste ternary lithium battery anode powder for leaching; removing impurity metal ions in the leaching solution to obtain solution after impurity removal; complexing and precipitating nickel in the impurity-removed liquid by using dimethylglyoxime, and separating to obtain nickel-removed liquid; extracting manganese in the nickel-removed liquid by using P204 to obtain a loaded organic phase 1 and raffinate 1, washing and back-extracting the loaded organic phase 1 by using dilute sulfuric acid to obtain a manganese sulfate solution, and adding potassium permanganate to precipitate to generate manganese dioxide; and extracting raffinate 1 by using C272 to obtain a loaded organic phase 2 and raffinate 2, washing and back-extracting the loaded organic phase 2 by using dilute sulfuric acid to obtain a cobalt sulfate solution, adding oxalic acid to precipitate to generate cobalt oxalate, and adding sodium carbonate to precipitate raffinate 2 to generate lithium carbonate. The method has the advantages of high separation efficiency, high purity of the final product and no generation of polluting substances.
Description
Technical Field
The invention relates to the technical field of waste lithium battery recovery, in particular to a method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium batteries.
Background
By virtue of long service life, low self-discharge and high specific capacity, the ternary lithium battery becomes the most attractive anode material in the new energy automobile industry, in 2018, 79.22% of passenger cars are carried ternary lithium ion batteries, and occupy most of raw materials of the passenger cars. With the issuance of policies related to energy conservation and new energy automobile industry development planning and guidance opinions on accelerating the popularization and application of new energy automobiles, the data still keeps rapid growth in the future, and with the elimination of the first new energy electric automobiles and the replacement of new and old batteries, the market proportion of the old and useless ternary lithium ion batteries is increased year by year in the future. Therefore, the recycling of the ternary lithium ion battery is particularly important.
The recycling of lithium batteries generally involves several aspects: pretreating the lithium ion battery; separating the lithium ion battery electrode material from the current collector; and (4) recovering valuable metals in the positive electrode active material.
The method mainly adopted is a pyrogenic method and a wet method, the pyrogenic method needs a large amount of energy, a large amount of harmful gas is discharged, serious environmental pollution can be caused, and the wet method has the advantages of mild reaction conditions, environmental friendliness, high recovery efficiency and the like and is widely applied. The wet recovery is generally to leach the metal in the waste lithium battery electrode material into a solution, and then separate and recover the metal by adopting a chemical precipitation method, an ion exchange method, an electrochemical deposition method, a solvent extraction method and other methods.
The precipitation method is used for separating various metals, the flow is relatively complex, and the control requirement of each step of precipitation on impurities is relatively high; the ion exchange method is a novel method for treating heavy metal wastewater, has excellent selectivity on metal ions, but is only suitable for separation and purification of a small amount of metal ions, has high cost and is difficult to be put into large-scale market; the product obtained by the electrochemical deposition method has high purity and no impurities, but the corresponding energy consumption is also high; compared with the other three methods, the solvent extraction method has the advantages of convenient operation, low energy consumption and good separation effect, and the key point is to select a proper extracting agent.
Disclosure of Invention
The invention aims to solve the technical problem of how to provide a method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium batteries, which has the advantages of wide application range, good separation efficiency, high purity of the recovered products, recyclable extracting agent and environmental friendliness.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium batteries comprises the following steps:
(1) adding sulfuric acid and a reducing agent into the anode powder of the waste ternary lithium battery, leaching valuable metals in the anode powder, and filtering to obtain a leaching solution;
(2) adding alkali into the leaching solution obtained in the step (1), adjusting the pH value of the solution, carrying out primary precipitation separation to obtain a precipitate substance 1 and a filtrate 1, then adding sulfide salt into the filtrate 1, and carrying out secondary precipitation separation to obtain a precipitate substance 2 and a filtrate 2;
(3) complexing and precipitating nickel by adopting dimethylglyoxime for the filtrate 2 in the step (2), realizing the optimal impurity removal efficiency by adjusting the pH value of the filtrate 2 in the step (2) and the molar ratio of dimethylglyoxime to nickel, and filtering to obtain a nickel-removed solution;
(4) extracting (3) manganese in the nickel-removed liquid by using P204, separating manganese and cobalt lithium to obtain a manganese-loaded organic phase 1 and raffinate 1, washing and back-extracting the manganese-loaded organic phase 1 by using dilute sulfuric acid to obtain a manganese sulfate solution, and adding potassium permanganate to precipitate to generate manganese dioxide; and extracting cobalt from the raffinate 1 by using C272, separating cobalt and lithium to obtain a loaded organic phase 2 and a raffinate 2, washing and back-extracting the loaded organic phase 2 by using dilute sulfuric acid to obtain a cobalt sulfate solution, adding oxalic acid into the cobalt sulfate solution to precipitate to generate cobalt oxalate, and adding sodium carbonate into the raffinate 2 to precipitate to generate lithium carbonate.
Preferably, in the step (1), the leaching temperature is 50-80 ℃, and the leaching time is 60-100 min.
Preferably, in the step (1), the concentration of the sulfuric acid is 1-3 mol/L, and the ratio of the sulfuric acid to the solid powder is 10-25 ml/g.
Preferably, in step (1), the reducing agent is one or more of hydrogen peroxide, sodium thiosulfate, sodium sulfite, sucrose and glucose.
Further preferably, the sulfuric acid and the reducing agent should be added simultaneously.
Preferably, in the step (2), the alkali used for precipitation is one or two of sodium hydroxide and potassium hydroxide.
Preferably, in step (2), the pH of the first precipitation is 5.0-5.5.
Preferably, in step (2), the sulfide salt is one or more of potassium sulfide and sodium sulfide.
Further preferably, the molar ratio of sulfide salt to copper ion is 1.2-2: 1.
Preferably, in the step (3), the pH of the filtrate 2 in the filtrate of the step (2) is adjusted to 3-6.
Preferably, in the step (3), the molar ratio of the dimethylglyoxime to the nickel is 1.8-2.2: 1.
Preferably, in the step (4), the saponification rate of P204 of manganese in the liquid after nickel removal in the extraction (3) is 50-70%, and the liquid is diluted by sulfonated kerosene, wherein the concentration of P204 is 8-15%.
Preferably, in the step (4), the pH value of the solution after nickel removal in the step (3) is adjusted to 3.2-4.
Preferably, in the step (4), the cobalt C272 in the extraction raffinate 1 is diluted by sulfonated kerosene, the saponification rate is 20% -60%, and the concentration of the C272 is 10% -20%.
Preferably, in step (4), the pH of the raffinate 1 is adjusted to 5.5-6.5.
Preferably, in step (4), the loaded organic phase is washed and back-extracted with dilute sulfuric acid.
Preferably, in the step (4), the extraction and the washing back extraction are both carried out at room temperature.
Preferably, in the step (4), the manganese sulfate solution is added with potassium permanganate to react, the molar ratio of potassium permanganate to manganese is 1.8-2.2:1, the temperature is 70-90 ℃, and the pH value is 1.8-2.2.
Preferably, in the step (4), the cobalt sulfate solution is added with oxalic acid for reaction, the molar ratio of the oxalic acid to the cobalt is 1.5-2:1, the temperature is 50-70 ℃, and the pH is 2-2.5.
Preferably, in the step (4), the lithium sulfate solution is added with sodium carbonate to react, the molar ratio of the sodium carbonate to the lithium is 1.2-2:1, the temperature is 90-100 ℃, and the pH is 11-14.
Further preferably, after the precipitation reaction is finished, standing, carrying out solid-liquid separation, washing and drying to obtain a precipitation product.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: 1) the method adopts low-concentration sulfuric acid and one or more of reducing agents such as hydrogen peroxide, sodium thiosulfate, sodium sulfite, cane sugar and glucose to be matched as the leaching agent, the reducing agent has no toxicity and side effects, the whole leaching process is very efficient, the leaching rates of four metals can reach more than 99 percent, the use amount of the leaching agent can be greatly saved, the temperature is controlled to be 50-80 ℃, the time is 60-100min, and the energy consumption requirement is not high.
2) The method adopts the combined method of acid leaching, precipitation and extraction to separate and recover the nickel, cobalt and manganese lithium of the waste ternary lithium battery one by one, effectively avoids the defect of a single method, realizes the efficient separation and recovery of the nickel, cobalt and manganese lithium, generates the products of the nickel dimethylglyoxime, the manganese dioxide, the cobalt oxalate and the lithium carbonate, recycles the nickel, the manganese and the lithium with the recovery rate of more than 99 percent and the cobalt with the recovery rate of more than 95 percent, changes waste into valuable and realizes the recycling of resources.
3) The method can realize the repeated use of the extracting agent, and the metal-loaded organic phase can be washed and back-extracted and can extract the metal again, thereby not producing secondary pollution and being beneficial to environmental protection.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Example 1
The method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium batteries in the embodiment is shown in fig. 1, and comprises the following steps:
(1) 10g of waste ternary lithium battery anode powder is put into a mixed system with sulfuric acid concentration of 2.5mol/L and hydrogen peroxide addition of 5% for leaching valuable metals, the liquid-solid ratio is 25ml/g, the time is 60min, the temperature is 60 ℃, and solid-liquid separation is carried out to obtain leachate and leaching residues.
(2) Adding sodium hydroxide into the leachate obtained in the step (1) to adjust the pH value to 5.0, hydrolyzing and precipitating to remove iron and aluminum ions, carrying out solid-liquid separation, adding sodium sulfide into the filtrate to remove copper, wherein the molar ratio of the sodium sulfide to the copper is 1.2:1, and carrying out solid-liquid separation to obtain an impurity-removed solution containing nickel, cobalt, manganese and lithium.
(3) Adding dimethylglyoxime into the solution after the impurity removal in the step (2) for complexing and precipitating nickel, adjusting the pH of the solution to 5, controlling the molar ratio of dimethylglyoxime to nickel to be 2:1 and the temperature to be 60 ℃, reacting for 40min, standing, filtering, cleaning and drying to obtain the dimethylglyoxime nickel and the solution after the nickel removal.
(4) Extracting manganese in the nickel-removed liquid in the step (3) by using P204, separating manganese, cobalt and lithium, diluting the P204 by using sulfonated kerosene, adjusting the concentration of the P204 to be 10%, the saponification rate to be 60% and the pH value of the solution to be 3.5, extracting and separating to obtain a loaded organic phase 1 and raffinate 1, wherein the extraction rate of manganese is 99.35%, the loaded organic phase 1 is washed and back-extracted by dilute sulfuric acid, the back-extraction rate of manganese is 99.57%, and the back-extracted manganese sulfate and potassium permanganate react for 60min under the conditions that the pH value of the solution is 2, the reaction temperature is 80 ℃ and the molar ratio of potassium permanganate to manganese is 1.8:1, so that manganese dioxide precipitate is generated.
(5) Extracting cobalt from the raffinate 1 in the step (4) by using C272, separating cobalt and lithium, diluting the C272 by using sulfonated kerosene, adjusting the concentration of the C272 to 10%, adjusting the saponification rate to 50%, adjusting the pH value of the solution to 6, extracting and separating to obtain a loaded organic phase 2 and a raffinate 2, wherein the extraction rate of the cobalt is 99.95%, washing and back-extracting the loaded organic phase 2 by using dilute sulfuric acid, the back-extraction rate of the cobalt is 99.72%, and reacting the back-extracted cobalt sulfate and oxalic acid for 60min under the conditions that the pH value of the solution is 2, the reaction temperature is 60 ℃, and the molar ratio of the oxalic acid to the cobalt is 1.5:1 to generate a cobalt oxalate precipitate; and precipitating the raffinate 2 by using sodium carbonate, and reacting for 60min under the conditions that the pH is 12, the reaction temperature is 95 ℃, and the molar ratio of the sodium carbonate to the lithium is 1.5:1 to generate lithium carbonate precipitate, wherein the recovery rate in the whole process is 99.54 percent.
(6) Neglecting the impurities in the product, the recovery rate of nickel in the whole process is 99.63%, the recovery rate of manganese is 99.24%, the recovery rate of cobalt is 95.37%, and the recovery rate of lithium is 99.47%.
Example 2
The method for separating and recovering nickel, cobalt, manganese and lithium from the waste ternary lithium battery comprises the following steps:
(1) 50g of waste ternary lithium battery positive electrode powder is put into a mixed system with sulfuric acid concentration of 2.5mol/L and hydrogen peroxide addition of 5% for leaching valuable metals, the liquid-solid ratio is 25ml/g, the time is 60min, the temperature is 60 ℃, and solid-liquid separation is carried out to obtain leachate and leaching residues.
(2) Adding sodium hydroxide into the leachate obtained in the step (1) to adjust the pH value to 5.0, hydrolyzing and precipitating to remove iron and aluminum ions, carrying out solid-liquid separation, adding sodium sulfide into the filtrate to remove copper, wherein the molar ratio of the sodium sulfide to the copper is 1.2:1, and carrying out solid-liquid separation to obtain an impurity-removed solution containing nickel, cobalt, manganese and lithium.
(3) Adding dimethylglyoxime into the solution obtained after the impurity removal in the step (2) for complexing and precipitating nickel, adjusting the pH of the solution to be 5, controlling the molar ratio of dimethylglyoxime to nickel to be 2:1, controlling the temperature to be 60 ℃, reacting for 40min, standing, filtering, cleaning and drying to obtain dimethylglyoxime nickel and the solution obtained after the nickel removal.
(4) Extracting manganese in the nickel-removed liquid in the step (3) by using P204, separating manganese, cobalt and lithium, diluting the P204 by using sulfonated kerosene, adjusting the concentration of the P204 to be 15%, the saponification rate to be 50% and the pH value of the solution to be 3.5, extracting and separating to obtain a loaded organic phase 1 and raffinate 1, wherein the extraction rate of manganese is 99.15%, the loaded organic phase 1 is washed and back-extracted by dilute sulfuric acid, the back-extraction rate of manganese is 99.27%, and the back-extracted manganese sulfate and potassium permanganate react for 60min under the conditions that the pH value of the solution is 2, the reaction temperature is 80 ℃ and the molar ratio of potassium permanganate to manganese is 1.8:1, so that manganese dioxide precipitate is generated.
(5) Extracting cobalt from the raffinate 1 in the step (4) by using C272, separating cobalt and lithium, diluting the C272 by using sulfonated kerosene, adjusting the concentration of the C272 to be 20%, the saponification rate to be 30% and the pH value of the solution to be 6, extracting and separating to obtain a loaded organic phase 2 and a raffinate 2, wherein the extraction rate of the cobalt is 99.45%, the loaded organic phase 2 is washed and back-extracted by using dilute sulfuric acid, the back-extraction rate of the cobalt is 99.62%, and the back-extracted cobalt sulfate and oxalic acid react for 60min under the conditions that the pH value of the solution is 2, the reaction temperature is 60 ℃ and the molar ratio of the oxalic acid to the cobalt is 1.5:1 to generate a cobalt oxalate precipitate; and precipitating the raffinate 2 by using sodium carbonate, and reacting for 60min under the conditions that the pH is 12, the reaction temperature is 95 ℃, and the molar ratio of the sodium carbonate to the lithium is 1.5:1 to generate lithium carbonate precipitate.
(6) Neglecting the impurities in the product, the recovery rate of nickel in the whole process is 99.43%, the recovery rate of manganese is 99.03%, the recovery rate of cobalt is 98.46%, and the recovery rate of lithium is 99.74%.
Example 3
The method for separating and recovering nickel, cobalt, manganese and lithium from the waste ternary lithium battery comprises the following steps:
(1) 100g of waste ternary lithium battery anode powder is put into a mixed system with sulfuric acid concentration of 2.5mol/L and hydrogen peroxide addition of 5% for leaching valuable metals, the liquid-solid ratio is 25ml/g, the time is 70min, the temperature is 70 ℃, and solid-liquid separation is carried out to obtain leachate and leaching residues.
(2) Adding sodium hydroxide into the leachate obtained in the step (1) to adjust the pH value to 5.0, hydrolyzing and precipitating to remove iron and aluminum ions, carrying out solid-liquid separation, adding sodium sulfide into the filtrate to remove copper, wherein the molar ratio of the sodium sulfide to the copper is 1.2:1, and carrying out solid-liquid separation to obtain an impurity-removed solution containing nickel, cobalt, manganese and lithium.
(3) Adding dimethylglyoxime into the solution after the impurity removal in the step (2) for complexing and precipitating nickel, adjusting the pH of the solution to 5, controlling the molar ratio of dimethylglyoxime to nickel to be 2:1 and the temperature to be 60 ℃, reacting for 40min, standing, filtering, cleaning and drying to obtain the dimethylglyoxime nickel and the solution after the nickel removal.
(4) Extracting manganese in the nickel-removed liquid in the step (3) by using P204, separating manganese, cobalt and lithium, diluting the P204 by using sulfonated kerosene, adjusting the concentration of the P204 to be 12%, the saponification rate to be 60% and the pH value of the solution to be 3.5, extracting and separating to obtain a loaded organic phase 1 and raffinate 1, wherein the extraction rate of manganese is 99.15%, the loaded organic phase 1 is washed and back-extracted by dilute sulfuric acid, the back-extraction rate of manganese is 99.67%, and the back-extracted manganese sulfate and potassium permanganate react for 60min under the conditions that the pH value of the solution is 2, the reaction temperature is 80 ℃ and the molar ratio of potassium permanganate to manganese is 1.8:1, so that manganese dioxide precipitate is generated.
(5) Extracting cobalt from the raffinate 1 in the step (4) by using C272, separating cobalt and lithium, diluting the C272 by using sulfonated kerosene, adjusting the concentration of the C272 to be 20%, the saponification rate to be 50% and the pH value of the solution to be 6, extracting and separating to obtain a loaded organic phase 2 and a raffinate 2, wherein the extraction rate of the cobalt is 99.65%, the loaded organic phase 2 is washed and back-extracted by using dilute sulfuric acid, the back-extraction rate of the cobalt is 99.82%, and the back-extracted cobalt sulfate and oxalic acid react for 60min under the conditions that the pH value of the solution is 2, the reaction temperature is 60 ℃ and the molar ratio of the oxalic acid to the cobalt is 1.5:1 to generate a cobalt oxalate precipitate; the raffinate 2 was precipitated with ammonium carbonate at a pH of 12, a reaction temperature of 95 ℃, a molar ratio of sodium carbonate to lithium of: and reacting for 60min under the condition of 1.5:1 to generate lithium carbonate precipitate.
(6) Neglecting the impurities in the product, the recovery rate of nickel in the whole process is 99.57%, the recovery rate of manganese is 99.11%, the recovery rate of cobalt is 96.58% and the recovery rate of lithium is 99.62%.
In summary, the present application has the following advantages:
1) the method adopts low-concentration sulfuric acid and one or more of reducing agents such as hydrogen peroxide, sodium thiosulfate, sodium sulfite, cane sugar and glucose to be matched as the leaching agent, the reducing agent has no toxicity and side effects, the whole leaching process is very efficient, the leaching rates of four metals can reach more than 99 percent, the use amount of the leaching agent can be greatly saved, the temperature is controlled to be 50-80 ℃, the time is 60-100min, and the energy consumption requirement is not high.
2) The method adopts the combined method of acid leaching, precipitation and extraction to separate and recover the nickel, cobalt and manganese lithium of the waste ternary lithium battery one by one, effectively avoids the defect of a single method, realizes the efficient separation and recovery of the nickel, cobalt and manganese lithium, generates the products of the nickel dimethylglyoxime, the manganese dioxide, the cobalt oxalate and the lithium carbonate, recycles the nickel, the manganese and the lithium with the recovery rate of more than 99 percent and the cobalt with the recovery rate of more than 95 percent, changes waste into valuable and realizes the recycling of resources.
3) The method can realize the repeated use of the extracting agent, and the metal-loaded organic phase can be washed and back-extracted and can extract the metal again, thereby not producing secondary pollution and being beneficial to environmental protection.
Claims (10)
1. A method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium batteries is characterized by comprising the following steps: the method comprises the following steps:
(1) adding sulfuric acid and a reducing agent into the anode powder of the waste ternary lithium battery, leaching valuable metals in the anode powder, and filtering to obtain a leaching solution;
(2) adding alkali into the leaching solution obtained in the step (1), adjusting the pH value of the solution, carrying out primary precipitation separation to obtain a precipitate substance 1 and a filtrate 1, then adding sulfide salt into the filtrate 1, and carrying out secondary precipitation separation to obtain a precipitate substance 2 and a filtrate 2;
(3) complexing and precipitating nickel by adopting dimethylglyoxime for the filtrate 2 in the step (2), realizing the optimal impurity removal efficiency by adjusting the pH value of the filtrate 2 in the step (2) and the molar ratio of dimethylglyoxime to nickel, and filtering to obtain a nickel-removed solution;
(4) extracting (3) manganese in the nickel-removed liquid by using P204, separating manganese and cobalt lithium to obtain a manganese-loaded organic phase 1 and raffinate 1, washing and back-extracting the manganese-loaded organic phase 1 by using dilute sulfuric acid to obtain a manganese sulfate solution, and adding potassium permanganate to precipitate to generate manganese dioxide; and extracting cobalt from the raffinate 1 by using C272, separating cobalt and lithium to obtain a loaded organic phase 2 and a raffinate 2, washing and back-extracting the loaded organic phase 2 by using dilute sulfuric acid to obtain a cobalt sulfate solution, adding oxalic acid into the cobalt sulfate solution to precipitate to generate cobalt oxalate, and adding sodium carbonate into the raffinate 2 to precipitate to generate lithium carbonate.
2. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (1), the leaching temperature of the sulfuric acid and the reducing agent is 60-80 ℃, the concentration of the sulfuric acid is 0.8-3 mol/L, the liquid-solid ratio is 10-25 ml/g, and the leaching time is 60-100 min.
3. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (1), the reducing agent is one or more of hydrogen peroxide, sodium thiosulfate, sodium sulfite, sucrose and glucose.
4. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (2), the alkali used for precipitation is one or two of sodium hydroxide or potassium hydroxide.
5. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (2), the sulfide salt is one or more of potassium sulfide and sodium sulfide instead of potassium sulfate or sodium sulfate.
6. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (2), the pH value of the solution is adjusted to 5.0-5.5 by the first precipitation.
7. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (3), the pH value of the filtrate 2 in the filtrate obtained in the step (2) is adjusted to 3-6, and the molar ratio of the dimethylglyoxime to the nickel is 1.8:1-2.2: 1.
8. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (4), the saponification rate of P204 of manganese in the liquid obtained after nickel removal in the step (3) is 50-70%, the liquid is diluted by sulfonated kerosene, the concentration of P204 is 8-15%, and extraction is carried out at room temperature.
9. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (4), C272 of cobalt in the extraction raffinate 1 is diluted by sulfonated kerosene, the saponification rate is 20% -60%, the concentration of C272 is 10% -20%, and extraction is carried out at room temperature.
10. The method for separating and recovering nickel, cobalt, manganese and lithium from waste lithium ternary batteries according to claim 1, characterized in that: in the step (4), dilute sulfuric acid is adopted for washing and back-extracting the loaded organic phases 1 and 2.
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