CN111041218A - Comprehensive extraction method for metals in waste lithium ion batteries - Google Patents
Comprehensive extraction method for metals in waste lithium ion batteries Download PDFInfo
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- CN111041218A CN111041218A CN201911389279.6A CN201911389279A CN111041218A CN 111041218 A CN111041218 A CN 111041218A CN 201911389279 A CN201911389279 A CN 201911389279A CN 111041218 A CN111041218 A CN 111041218A
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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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- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
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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
- C22B23/0407—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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- 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
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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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
- 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
- C22B3/30—Oximes
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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
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
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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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- 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
- 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 comprehensive extraction method of metals in waste lithium ion batteries, which sequentially comprises the steps of acid dissolution, alkalization impurity removal, extraction 1, extraction 2, extraction 3, electrodeposition, purification and refining and purification preparation; obtaining raffinate 1 and a copper sulfate solution through the extraction step 1, and obtaining cathode copper after the copper sulfate solution is subjected to electrodeposition; extracting the raffinate 1 by the step 2 to obtain a raffinate 2 and a manganese sulfate solution, and refining the manganese sulfate solution to obtain a battery-grade manganese sulfate solution; and extracting the raffinate 2 by the step 3 to obtain raffinate 3 and a battery-grade Ni-Co mixed solution, and purifying the raffinate 3 to obtain the battery-grade lithium carbonate. According to the invention, copper, a battery-grade Ni-Co mixed solution, a battery-grade manganese sulfate solution and battery-grade lithium carbonate are sequentially recovered and obtained mainly in a three-time step-by-step extraction mode, so that comprehensive recovery of various metal elements in the waste lithium ion battery is realized, and the recovery rate of the whole metal is improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a comprehensive extraction method for metals in waste lithium ion batteries.
Background
Lithium ion batteries have the advantages of high specific capacitance, excellent cyclicity, light weight, portability and the like, so that the lithium ion batteries are widely applied to various fields such as mobile phones, notebook computers, new energy automobiles and the like, at present, most power lithium ion battery systems applied at home and abroad are mainly lithium iron phosphate systems and ternary systems, for example, battery systems composed of three metal elements of nickel, manganese, cobalt or nickel, cobalt and aluminum, along with the gradual popularization of new energy automobiles, the demand of the lithium ion batteries is increased day by day, the quantity of the generated waste lithium ion batteries is also rapidly increased, and particularly, the metal elements of nickel, cobalt, manganese and the like contained in the anode materials of the lithium ion batteries cause great pollution to the environment and can be continuously accumulated. The method has the advantages that metal elements such as nickel, cobalt, manganese and the like in the waste lithium ion batteries are recycled and reused, so that the problem of environmental pollution is solved, the preparation cost of the vehicle batteries can be obviously reduced, objective economic benefits are brought, and how to effectively recycle the elements such as nickel, cobalt, manganese and lithium in the waste lithium ion batteries becomes the current research direction.
At present, the recovery of metal elements such as nickel, cobalt, manganese and the like in waste lithium ion batteries mainly adopts a wet treatment mode, and the separation and extraction of the metal elements such as nickel, cobalt, manganese and the like are mainly carried out in an extraction mode. Patent CN201611136854 provides a method for total extraction of nickel, cobalt and manganese by using P507 extraction agent, which improves efficiency of nickel, cobalt and manganese extraction, but the method has the problems that only the P507 extraction agent is used for extraction, the obtained solution after extraction still contains a considerable part of lithium element, and the part of lithium element is difficult to remove, which not only results in low purity of the obtained nickel-containing cobalt-manganese mixed solution, but also results in great reduction of recovery amount of lithium, and the metal recovery quality is difficult to meet the requirement. Therefore, it is necessary to provide a new recovery and extraction method for solving the above technical problems.
Disclosure of Invention
The invention aims to provide a comprehensive extraction method of metals in waste lithium ion batteries, which is used for solving the problem of poor extraction effect when elements such as nickel, cobalt, manganese, lithium and the like are recovered by a wet method in the prior art.
In order to solve the technical problems, the invention provides a comprehensive extraction method of metals in waste lithium ion batteries, which sequentially comprises the steps of acid dissolution, alkalization impurity removal, extraction 1, extraction 2, extraction 3, electrodeposition, purification and refining and purification preparation; the extraction 1 step specifically comprises: and extracting the alkalized mixed solution after alkalization and impurity removal by using a copper extractant DZ973 to obtain raffinate 1 and a copper sulfate solution.
Wherein, the acid dissolving step specifically comprises the following steps: immersing the mixed powder of the anode and the cathode of the lithium ion battery into acid liquor, and adding a reducing agent until the reducing agent is completely dissolved to obtain acid-soluble mixed liquor; wherein the acid solution is sulfuric acid or hydrochloric acid, and the reducing agent is H2O2、SO2Sodium sulfite and sodium pyrosulfiteA compound (I) is provided.
Wherein the addition amount of the acid liquor is 1-2 times of the theoretical molar amount in the reaction process; the addition amount of the reducing agent is 1-3 times of the theoretical molar amount in the reaction process.
Wherein, alkalization edulcoration step includes: adding an oxidant and an alkali liquor into the acid-soluble mixed solution, adjusting the pH value of the solution to 2.5-5.5, and filtering to remove iron and aluminum to obtain an alkalized mixed solution; the oxidant is one or a mixture of more of air, oxygen, sodium chlorate, hydrogen peroxide and sulfur dioxide/air, and the addition amount of the oxidant is more than 1.05 times of the theoretical molar amount in the reaction process; the alkali liquor is one or a mixture of more of sodium hydroxide, potassium hydroxide and ammonia water, and the concentration of the alkali liquor is 5-32%.
Wherein, the extraction 2 step specifically comprises: and extracting the raffinate 1 by using a P204 extracting agent to obtain raffinate 2 and a manganese sulfate solution.
Wherein, the copper sulfate solution obtained in the step 1 is extracted, and copper is recovered at the cathode through the electrodeposition step.
Wherein, the extraction 3 steps specifically include: and extracting the raffinate 2 by adopting P204 and Cyanex272 extracting agents to obtain raffinate 3 and a battery-grade Ni-Co mixed solution.
And (3) carrying out purification and refining on the manganese sulfate solution obtained in the extraction step 2 to obtain the battery-grade manganese sulfate solution.
And performing a purification preparation step on the raffinate 3 obtained in the extraction step 3 to obtain battery-grade lithium carbonate.
The invention has the beneficial effects that: different from the situation of the prior art, the invention provides a comprehensive extraction method for metals in waste lithium ion batteries, which can sequentially recover copper, battery-grade Ni-Co mixed liquid, battery-grade manganese sulfate solution and battery-grade lithium carbonate by means of refining or purifying after three-time step-by-step extraction, thereby realizing comprehensive recovery of various metal elements in the waste lithium ion batteries and improving the recovery rate of the whole metals.
Drawings
Fig. 1 is a process flow diagram of an embodiment of the method for comprehensively extracting metals from waste lithium ion batteries.
Detailed Description
The technical solutions in the embodiments of the present invention will be 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to fig. 1, fig. 1 is a process flow diagram of an embodiment of a method for comprehensively extracting metals from waste lithium ion batteries according to the present invention. The steps of the comprehensive extraction method for metals in the waste lithium ion batteries sequentially comprise acid dissolution S1, alkalization impurity removal S2, extraction 1S3, extraction 2S4, extraction 3S5, electrodeposition S6, purification refining S7 and purification preparation S8, and the steps are explained respectively.
S1: and (4) acid dissolution. The method specifically comprises the following steps: immersing the mixed powder of the positive electrode and the negative electrode of the lithium ion battery into the combined acid solution, and adding a reducing agent until the mixed powder is completely dissolved to obtain an acid-soluble mixed solution; wherein the acid solution is sulfuric acid or hydrochloric acid, the addition amount of the acid solution is 1-2 times of the theoretical molar amount in the reaction process, and the reducing agent is H2O2、SO2The addition amount of the reducing agent is 1-3 times of the theoretical molar amount in the reaction process, and the actually added acid solution and the actually added reducing agent are both excessive compared with the theoretical value, so that the metal elements such as nickel, cobalt, manganese, lithium and the like in the positive and negative electrode mixed powder of the lithium ion battery can be fully dissolved. In this embodiment, the mixed powder of positive and negative electrodes of the lithium ion battery is a lithium ion battery system mixture containing nickel-cobalt-manganese element, such as a system mixture composed of one or more of a Ni-Co-Mo-Li system, a lithium cobaltate system, and a Ni-Co-Al system containing nickel-cobalt-manganese element, and these system mixtures can be used as the mixed powder of positive and negative electrodes of the lithium ion battery and applied to the preparation process of the present invention.
S2: alkalizing and removing impurities. The method specifically comprises the following steps: adding an oxidant and an alkali liquor into the acid-soluble mixed solution, adjusting the pH value of the solution to 2.5-5.5, and filtering to remove iron and aluminum to obtain an alkalized mixed solution; the oxidant is one or a mixture of more of air, oxygen, sodium chlorate, hydrogen peroxide and sulfur dioxide/air, and the addition amount of the oxidant is more than 1.05 times of the theoretical molar amount in the reaction process; the alkali liquor is one or a mixture of more of sodium hydroxide, potassium hydroxide and ammonia water, and the concentration of the alkali liquor is 5-32%; the purpose of this step is to adjust the acid-soluble mixed solution to an appropriate alkaline range, and to remove mainly iron and aluminum elements in the solution as hydroxides.
S3: and (5) extracting 1. The method specifically comprises the following steps: extracting the alkalized mixed solution after alkalization and impurity removal by using a copper extractant DZ973 to obtain raffinate 1 and a copper sulfate solution; the purpose of this step is to separate copper ions from the alkalized mixed solution for subsequent electrolytic recovery of copper, but the present embodiment is preferably DZ973 as the copper extractant, and in other embodiments, similar copper extractants may be selected according to actual circumstances, and this is not limited herein. In the embodiment, the organic solvent is DZ973 and sulfonated kerosene are preferably configured according to the volume ratio of 1: 1-1: 10, saponification recycling is not needed, the extraction ratio is (1-4): 1, 3-5 grade countercurrent extraction, 5-8 grade back extraction, and the concentration of counter acid is 1-5 mol/L.
S4: and (3) extracting 2. The method specifically comprises the following steps: extracting raffinate 1 by using a P204 extracting agent to obtain raffinate 2 and a manganese sulfate solution; the purpose of this step is to separate the manganese ions from the extract 1. In the embodiment, the organic solvent is P204 and sulfonated kerosene are configured according to a volume ratio of 1 (3-4), the saponification rate is 20% -60%, the extraction ratio is (1-6): 1, 5-15 grade countercurrent extraction, 5-15 grade countercurrent washing, the washing ratio is (1-6): 1, the washing acid is 0.1-2 mol/L sulfuric acid, 5-15 grade countercurrent back extraction, the back extraction ratio is (1-15): 1, and the back acid concentration is 2-6 mol/L.
S5: and (3) extracting. The method specifically comprises the following steps: extracting raffinate 2 by adopting P204 and Cyanex272 extracting agents to obtain raffinate 3 and battery-grade Ni-Co mixed liquor; the purpose of this step is to separate the lithium from the nickel cobalt in the extraction solution 1. In the embodiment, the organic solvent P204 and Cyanex272 and sulfonated kerosene are configured according to the volume ratio of 1 (3-4), the saponification rate is 40% -100%, the extraction ratio is (1-6): 1, 5-15 grade countercurrent extraction, 5-15 grade countercurrent washing, the washing ratio is (1-6): 1, the washing acid is 0.1-2 mol/L sulfuric acid, 5-15 grade countercurrent back extraction, the back extraction ratio is (1-15): 1, and the back acid concentration is 2-6 mol/L.
S6: and (4) electrodeposition. The method specifically comprises the following steps: and (3) extracting the copper sulfate solution obtained in the step (1), and recovering at the cathode through an electrodeposition step to obtain a cathode copper plate.
S7: and (5) purification and refining. And (3) after the manganese sulfate solution obtained in the step (2) of extraction is subjected to a purification and refining step, obtaining a battery-grade manganese sulfate solution, wherein the step can be carried out by adopting a P204 extraction mode, and the aim of removing impurities such as calcium and the like in the manganese sulfate solution obtained in the step (2) of extraction is to obtain the high-purity battery-grade manganese sulfate solution.
S8: and (5) purifying and preparing. And (3) after the raffinate 3 obtained in the step of extraction 3 is subjected to a purification preparation step, obtaining battery-grade lithium carbonate, wherein the purpose is to remove impurities of the raffinate obtained in the step of extraction 3 so as to obtain a high-purity battery-grade manganese sulfate solution.
The copper, the battery-grade Ni-Co mixed solution, the battery-grade manganese sulfate solution and the battery-grade lithium carbonate sequentially recovered through the steps can be applied to the production of new lithium ion batteries in the form of raw materials, so that the recycling of various metal elements in waste lithium batteries is realized, and the overall metal recovery rate is high.
The method for comprehensively extracting metals from the waste lithium ion batteries according to the present invention is further described in detail with reference to specific examples.
Example 1
Weighing 10kg of lithium ion battery anode and cathode mixed powder, adding 50L of pure water according to a liquid-solid ratio of 5:1 for slurrying, adding 12.3L of sulfuric acid and 13.5kg of 30% hydrogen peroxide for acid leaching, and filtering to remove insoluble residues to obtain a leaching solution, wherein the leaching rates of cobalt, nickel and manganese are respectively as follows: 99.64%, 99.65% and 98.67%. And (3) adjusting the pH of the leachate to 5.0 by using 10% caustic soda solution while introducing air, reacting for 2 hours, and filtering to remove iron and aluminum to obtain an alkalized mixed solution. Carrying out 4-stage countercurrent extraction separation on the alkalized mixed solution by using a copper extractant DZ973 with the concentration of 25% to obtain raffinate 1 and a copper sulfate solution; wherein, when the step 1 of extraction is carried out, the organic solvent is DZ973 and sulfonated kerosene are prepared according to the volume ratio of 1:5, saponification recycling is not needed, the extraction ratio is 3:1, 3-grade countercurrent extraction and 5-grade back extraction, and the concentration of back acid is 1 mol/L.
Carrying out electrodeposition on the obtained copper sulfate solution to recover copper at a cathode, and carrying out 12-stage countercurrent extraction on the obtained raffinate 1 by using P204 with the saponification rate of 30% to obtain raffinate 2 and a manganese sulfate solution; wherein, when the extraction 2 is carried out, the organic solvent is P204 and sulfonated kerosene are prepared according to the volume ratio of 1:3, the saponification rate is 20%, the extraction ratio is 2:1, 12-grade countercurrent extraction, 12-grade countercurrent washing, the washing ratio is 3:1, the washing acid is 0.1mol/L sulfuric acid, 8-grade countercurrent back extraction, the back extraction ratio is 6:1, and the back acid concentration is 1 mol/L.
Purifying and refining the obtained manganese sulfate solution to obtain a battery-grade manganese sulfate solution, and re-extracting the obtained raffinate 2 by using P204 with the saponification rate of 68% to obtain raffinate 3 and a battery-grade Ni-Co mixed solution; wherein, when the 3 steps of extraction are carried out, the organic solvent P204 and Cyanex272 are prepared with sulfonated kerosene according to the volume ratio of 1:3, the extraction ratio is 2:1, 12-grade countercurrent extraction, 12-grade countercurrent washing, the washing ratio is 3:1, the acid washing is 0.1mol/L sulfuric acid, 8-grade countercurrent back extraction, the back extraction ratio is 3:1, and the back acid concentration is 1 mol/L. Thus obtaining the battery-grade nickel cobalt sulfate mixed solution, and then purifying the obtained raffinate 3 to obtain the battery-grade lithium carbonate product.
Example 2
Weighing 10kg of lithium ion battery anode and cathode mixed powder, adding 50L of pure water according to a liquid-solid ratio of 5:1 for slurrying, adding 12.3L of sulfuric acid and 13.5kg of 30% hydrogen peroxide for acid leaching, and filtering to remove insoluble residues to obtain a leaching solution, wherein the leaching rates of cobalt, nickel and manganese are respectively as follows: 99.64%, 99.65% and 98.67%. And (3) adjusting the pH of the leachate to 4.5 by using 10% caustic soda solution while introducing air, and filtering to remove iron and aluminum after reacting for 2 hours to obtain an alkalized mixed solution. Carrying out 4-stage countercurrent extraction separation on the alkalized mixed solution by using a copper extractant DZ973 with the concentration of 25% to obtain raffinate 1 and a copper sulfate solution; wherein, when the step 1 of extraction is carried out, the organic solvent is DZ973 and sulfonated kerosene are prepared according to the volume ratio of 1:6, saponification recycling is not needed, the extraction ratio is 3:1, 4-grade countercurrent extraction and 6-grade back extraction, and the concentration of back acid is 3 mol/L.
Carrying out electrodeposition on the obtained copper sulfate solution to recover copper at a cathode, and carrying out 12-stage countercurrent extraction on the obtained raffinate 1 by using P204 with the saponification rate of 30% to obtain raffinate 2 and a manganese sulfate solution; wherein, when the extraction 2 is carried out, the organic solvent is P204 and sulfonated kerosene are prepared according to the volume ratio of 1:3, the saponification rate is 30%, the extraction ratio is 5:1, 8-stage countercurrent extraction, 8-stage countercurrent washing, the washing ratio is 5:1, the washing acid is 0.5mol/L sulfuric acid, 12-stage countercurrent back extraction, the back extraction ratio is 6:1, and the back acid concentration is 3 mol/L.
Purifying and refining the obtained manganese sulfate solution to obtain a battery-grade manganese sulfate solution, and re-extracting the obtained raffinate 2 by using P204 with the saponification rate of 68% to obtain raffinate 3 and a battery-grade Ni-Co mixed solution; wherein, when the 3 steps of extraction are carried out, the organic solvent P204 and Cyanex272 are prepared with sulfonated kerosene according to the volume ratio of 1:3, the extraction ratio is 4:1, 12-grade countercurrent extraction, 12-grade countercurrent washing, the washing ratio is 4:1, the acid washing is 0.5mol/L sulfuric acid, 8-grade countercurrent back extraction, the back extraction ratio is 5:1, and the back acid concentration is 4 mol/L. Thus obtaining the battery-grade nickel cobalt sulfate mixed solution, and then purifying the obtained raffinate 3 to obtain the battery-grade lithium carbonate product.
Example 3
Weighing 10kg of lithium ion battery anode and cathode mixed powder, adding 50L of pure water according to a liquid-solid ratio of 5:1 for slurrying, adding 12.3L of sulfuric acid and 13.5kg of 30% hydrogen peroxide for acid leaching, and filtering to remove insoluble residues to obtain a leaching solution, wherein the leaching rates of cobalt, nickel and manganese are respectively as follows: 99.64%, 99.65% and 98.67%. And (3) adjusting the pH of the leachate to 5.5 by using 10% caustic soda solution while introducing air, and filtering to remove iron and aluminum after reacting for 2 hours to obtain an alkalized mixed solution. Carrying out 4-stage countercurrent extraction separation on the alkalized mixed solution by using a copper extractant DZ973 with the concentration of 25% to obtain raffinate 1 and a copper sulfate solution; wherein, when the step 1 of extraction is carried out, the organic solvent is DZ973 and sulfonated kerosene are prepared according to the volume ratio of 1:8, saponification recycling is not needed, the extraction ratio is 4:1, 5-grade countercurrent extraction and 8-grade back extraction, and the concentration of back acid is 4 mol/L.
Carrying out electrodeposition on the obtained copper sulfate solution to recover copper at a cathode, and carrying out 12-stage countercurrent extraction on the obtained raffinate 1 by using P204 with the saponification rate of 30% to obtain raffinate 2 and a manganese sulfate solution; wherein, when the extraction 2 is carried out, the organic solvent is P204 and sulfonated kerosene are prepared according to the volume ratio of 1:4, the saponification rate is 40%, the extraction ratio is 6:1, 12-grade countercurrent extraction, 12-grade countercurrent washing, the washing ratio is 6:1, the washing acid is 1mol/L sulfuric acid, 8-grade countercurrent back extraction, the back extraction ratio is 6:1, and the back acid concentration is 4 mol/L.
Purifying and refining the obtained manganese sulfate solution to obtain a battery-grade manganese sulfate solution, and re-extracting the obtained raffinate 2 by using P204 with the saponification rate of 72% to obtain raffinate 3 and a battery-grade Ni-Co mixed solution; wherein, when the 3 steps of extraction are carried out, the organic solvent P204 and Cyanex272 are prepared with sulfonated kerosene according to the volume ratio of 1:4, the extraction ratio is 6:1, 12-grade countercurrent extraction, 12-grade countercurrent washing, the washing ratio is 6:1, the washing acid is 1mol/L sulfuric acid, 8-grade countercurrent back extraction, the back extraction ratio is 8:1, and the back acid concentration is 4 mol/L. Thus obtaining the battery-grade nickel cobalt sulfate mixed solution, and then purifying the obtained raffinate 3 to obtain the battery-grade lithium carbonate product.
Different from the situation of the prior art, the invention provides a comprehensive extraction method for metals in waste lithium ion batteries, which can sequentially recover copper, battery-grade Ni-Co mixed liquid, battery-grade manganese sulfate solution and battery-grade lithium carbonate by means of refining or purifying after three-time step-by-step extraction, thereby realizing comprehensive recovery of various metal elements in the waste lithium ion batteries and improving the recovery rate of the whole metals.
It should be noted that the above embodiments belong to the same inventive concept, and the description of each embodiment has a different emphasis, and reference may be made to the description in other embodiments where the description in individual embodiments is not detailed.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A comprehensive extraction method of metals in waste lithium ion batteries is characterized by comprising the steps of acid dissolution, alkalization impurity removal, extraction 1, extraction 2, extraction 3, electrodeposition, purification and refining and purification preparation in sequence;
the step 1 of extraction specifically comprises: and extracting the alkalized mixed solution subjected to alkalization and impurity removal by using a copper extractant DZ973 to obtain raffinate 1 and a copper sulfate solution.
2. The method for comprehensively extracting metals from waste lithium ion batteries according to claim 1, wherein the step of acid dissolution specifically comprises:
immersing the mixed powder of the anode and the cathode of the lithium ion battery into acid liquor, and adding a reducing agent until the reducing agent is completely dissolved to obtain acid-soluble mixed liquor;
wherein the acid solution is sulfuric acid or hydrochloric acid, and the reducing agent is H2O2、SO2One or more of sodium sulfite and sodium pyrosulfite.
3. The comprehensive extraction method of metals in waste lithium ion batteries according to claim 2, characterized in that the addition amount of the acid solution is 1-2 times of the theoretical molar amount in the reaction process; the addition amount of the reducing agent is 1-3 times of the theoretical molar amount in the reaction process.
4. The method for comprehensively extracting metals from waste lithium ion batteries according to claim 2, wherein the alkalization impurity removal step comprises the following steps:
adding an oxidant and an alkali liquor into the acid-soluble mixed solution, adjusting the pH value of the solution to 2.5-5.5, and filtering to remove iron and aluminum to obtain the alkalized mixed solution;
the oxidant is one or a mixture of more of air, oxygen, sodium chlorate, hydrogen peroxide and sulfur dioxide/air, and the addition amount of the oxidant is more than 1.05 times of the theoretical molar amount in the reaction process;
the alkali liquor is one or a mixture of more of sodium hydroxide, potassium hydroxide and ammonia water, and the concentration of the alkali liquor is 5-32%.
5. The method for comprehensively extracting metals from waste lithium ion batteries according to claim 1, wherein the step 2 of extracting specifically comprises the following steps: and extracting the raffinate 1 by using a P204 extracting agent to obtain raffinate 2 and a manganese sulfate solution.
6. The method for comprehensively extracting metals from waste lithium ion batteries according to claim 1, wherein the copper sulfate solution obtained in the step of extracting 1 is subjected to the electrodeposition step to obtain a cathode copper plate.
7. The method for comprehensively extracting metals from waste lithium ion batteries according to claim 5, wherein the step 3 of extracting specifically comprises the following steps: and extracting the raffinate 2 by adopting P204 and Cyanex272 extracting agents to obtain raffinate 3 and battery-grade Ni-Co mixed liquor.
8. The method for comprehensively extracting metals from waste lithium ion batteries according to claim 5, wherein the manganese sulfate solution obtained in the extraction 2 step is subjected to the purification and refining step to obtain a battery-grade manganese sulfate solution.
9. The method for comprehensively extracting metals from waste lithium ion batteries according to claim 7, wherein the raffinate 3 obtained in the step of extracting 3 is subjected to the step of purifying and preparing to obtain battery-grade lithium carbonate.
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| PCT/CN2019/130635 WO2021134517A1 (en) | 2019-12-30 | 2019-12-31 | Method for comprehensive extraction of metals from spent lithium-ion batteries |
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| CN111559912A (en) * | 2020-05-14 | 2020-08-21 | 湖北中环新材料科技有限公司 | Method for preparing high-purity graphite by recycling waste lithium batteries |
| CN112267024A (en) * | 2020-09-29 | 2021-01-26 | 荆门市格林美新材料有限公司 | Comprehensive recycling method for waste lithium ion batteries |
| CN113981230A (en) * | 2021-11-01 | 2022-01-28 | 中国科学院过程工程研究所 | Method for leaching nickel cobalt slag |
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| CN106684489A (en) * | 2017-03-24 | 2017-05-17 | 赣南师范大学 | Method for recycling valuable metal from waste polybasic lithium ion batteries |
| 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 |
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| CN107117661B (en) * | 2017-05-26 | 2019-01-25 | 金川集团股份有限公司 | The method for preparing ternary hydroxide using nickel cobalt manganese in the waste and old lithium ion battery of liquid phase method recycling |
| CN109207727A (en) * | 2017-07-03 | 2019-01-15 | 荆门市格林美新材料有限公司 | A method of metal material is prepared from waste and old nickel cobalt copper ternary lithium ion battery recycling |
| CN109449523B (en) * | 2018-10-31 | 2021-09-10 | 天齐锂业资源循环技术研发(江苏)有限公司 | Comprehensive recovery method for waste lithium ion battery |
| CN109735709B (en) * | 2018-12-13 | 2021-01-08 | 江西赣锋循环科技有限公司 | Method for recycling lithium from calcium and magnesium removing slag and preparing ternary precursor material |
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| CN106684489A (en) * | 2017-03-24 | 2017-05-17 | 赣南师范大学 | Method for recycling valuable metal from waste polybasic lithium ion batteries |
| 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 |
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| CN111559912A (en) * | 2020-05-14 | 2020-08-21 | 湖北中环新材料科技有限公司 | Method for preparing high-purity graphite by recycling waste lithium batteries |
| CN112267024A (en) * | 2020-09-29 | 2021-01-26 | 荆门市格林美新材料有限公司 | Comprehensive recycling method for waste lithium ion batteries |
| CN113981230A (en) * | 2021-11-01 | 2022-01-28 | 中国科学院过程工程研究所 | Method for leaching nickel cobalt slag |
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Application publication date: 20200421 |