CN-121992204-A - Method and equipment for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation

CN121992204ACN 121992204 ACN121992204 ACN 121992204ACN-121992204-A

Abstract

The invention provides a method and equipment for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation, and relates to the field of metal material recycling. The method for separating manganese, nickel, cobalt and lithium from the waste batteries by complexing oxidation comprises the following steps of S1, flushing the waste battery positive plate, removing surface electrolyte and impurities to obtain a pretreated positive plate, S2, crushing the pretreated positive plate into small pieces, placing the small pieces in an ultrasonic cleaner, washing and drying the small pieces to obtain a positive electrode material and a current collector, S3, dissolving the positive electrode material in 2-4 mol/L hydrochloric acid, stirring at the temperature of 60-90 ℃, and filtering after the reaction is completed to obtain a metal chloride solution. The method for complexing, oxidizing and separating manganese, nickel, cobalt and lithium from the waste batteries is coupled with the nickel and cobalt separation step by the recovery process of the invention, and a manganese removal process is not required to be independently arranged, so that the flow is shortened, complex operations of acid leaching and alkali precipitation for a plurality of times in the traditional method are avoided, ammonia and ammonium chloride can be recycled in the reaction, and the consumption of raw materials is reduced.

Inventors

YAO LI
WEI DONGDONG
YU JINXIANG
PAN RUI
LIAO XIN
PAN LONGHUI
LIAO QIANG
XIAO ZHEN

Assignees

宜丰九岭锂业有限公司

Dates

Publication Date: 20260508
Application Date: 20260316

Claims (10)

1. The method for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation is characterized by comprising the following steps: s1, washing a waste battery positive plate, and removing surface electrolyte and impurities to obtain a pretreated positive plate; S2, crushing the pretreated positive plate into small blocks, placing the small blocks in an ultrasonic cleaner, and cleaning, washing and drying to obtain a positive electrode material and a current collector; s3, dissolving the anode material in 2-4 mol/L hydrochloric acid, stirring at 60-90 ℃, and filtering after the reaction is completed to obtain a metal chloride solution; S4, adding ammonium persulfate into the metal chloride solution, stirring at 50-70 ℃, and centrifuging to obtain manganese dioxide and filtrate after the reaction is completed; S5, evaporating the filtrate, adding the filtrate into a mixed solution of ammonium chloride and ammonia water, and stirring in a closed manner to obtain a divalent nickel cobalt ammonia complex solution; S6, adding an oxidant into the divalent nickel-cobalt ammine complex solution, stirring and filtering to obtain divalent nickel-cobalt ammine complex and trivalent cobalt ammine complex filtrate; S7, adding hydrochloric acid into the divalent nickel ammonia complex and the trivalent cobalt ammonia complex filtrate for acidification, evaporating and crystallizing after the reaction is completed, and filtering to obtain cobalt salt crystals and divalent nickel ammonia complex solution; s8, adding 6-8 mol/L potassium hydroxide into the divalent nickel ammonia complex solution, adjusting the pH to 7-9, filtering, washing and drying after the reaction is finished to obtain precipitate nickel hydroxide and filtrate; s9, adding saturated sodium carbonate or carbon dioxide into the filtrate, and filtering, washing and drying after the reaction is finished to obtain lithium carbonate.
2. The method for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation according to claim 1, wherein cobalt salt crystals in the step S7 are calcined and ground to obtain cobaltosic oxide.
3. The method for separating manganese nickel cobalt lithium from waste batteries by complexation and oxidation according to claim 2, wherein chlorine and ammonia released during calcination of cobalt salt crystals are converted into ammonium chloride for step S5.
4. The method for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation according to claim 1, wherein the waste batteries comprise one or more of nickel-hydrogen batteries, ternary lithium batteries, lithium cobalt oxide lithium ion batteries and lithium manganate batteries.
5. The method for separating manganese nickel cobalt lithium from waste batteries by complexation and oxidation according to claim 1, wherein the oxidant in S6 is 30wt% hydrogen peroxide solution.
6. An apparatus for the complex oxidative separation of manganese nickel cobalt lithium from waste batteries, characterized by a method for the complex oxidative separation of manganese nickel cobalt lithium from waste batteries according to any one of claims 1-5; Comprises a reaction cylinder, wherein the reaction cylinder comprises a cylinder body and a cylinder cover, and the cylinder cover is detachably arranged at the top end of the cylinder body; The stirring device comprises a motor, a driving rod and stirring blades, wherein the motor is arranged on the cylinder cover, the driving rod is connected with the output end of the motor and the stirring blades, and a square groove is formed in the bottom end of the driving rod; The filter frame structure comprises a filter plate and a square shaft, the filter plate is detachably arranged in the cylinder, and the square shaft is arranged in the center of the filter plate and is positioned below the square groove; The connecting frame comprises a connecting plate and a connecting shaft, the bottom end of the connecting shaft penetrates through the cylinder cover and then is rotatably connected with the filter frame structure, a supporting block is arranged on the connecting shaft, the supporting block is positioned below the cylinder cover, a movable distance is reserved between the supporting block and the cylinder cover, and the connecting plate is arranged at the top end of the connecting shaft; And the lifting device is used for lifting the connecting plate.
7. The apparatus for separating manganese, nickel, cobalt and lithium from waste batteries according to claim 6, wherein the filter frame structure further comprises a side wall and bolts, the side wall is mounted on the top of the filter plate through bolts, and the bottom end of the connecting shaft is rotatably connected with the side wall.
8. The apparatus for the complex oxidative separation of manganese, nickel, cobalt and lithium from waste batteries according to claim 7, wherein the lifting device comprises a mounting frame, a lifting cylinder and a positioning rod, the lifting cylinder is mounted on the mounting frame and is arranged adjacent to the reaction cylinder, the connecting plate is mounted at the output end of the lifting cylinder, one end of the positioning rod is mounted on the mounting frame, and the other end of the positioning rod penetrates through the connecting plate.
9. The apparatus for complex oxidative separation of manganese, nickel, cobalt and lithium from waste batteries according to claim 8, further comprising a receiving cylinder and a driving member, wherein the receiving cylinder and the reaction cylinder are arranged at a preset angle relative to the center of the lifting cylinder; The connecting plate is rotatably arranged at the output end of the lifting cylinder, and when the filter frame structure moves out of the cylinder body, the connecting plate is separated from the positioning rod, and the driving piece is used for driving the connecting plate to rotate.
10. The apparatus for complex oxidation separation of manganese, nickel, cobalt and lithium from waste batteries according to claim 9, wherein the cylinder cover comprises a cover main body, an annular part and a driving sleeve, the annular part is rotatably arranged at the bottom of the cover main body, the driving sleeve is horizontally arranged in the annular part, one end of the driving sleeve extends to the inside of the cylinder body through a notch, and a through hole is formed in the driving sleeve; the filter frame structure further comprises a driving rod, the bottom end of the driving rod is arranged on the side wall, and the top end of the driving rod is positioned below the through hole; the driving piece is a tooth surface, the tooth surface is arranged outside the annular part, an arc toothed plate is fixedly arranged above the tooth surface, and when the filter frame structure moves out of the cylinder body, the tooth surface is meshed with the arc toothed plate.

Description

Method and equipment for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation Technical Field The invention relates to the field of metal material recycling, in particular to a method and equipment for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation. Background With the rapid development of the electric automobile market, the large-scale application of the power battery causes rapid consumption of metal mineral resources such as nickel, cobalt, lithium and the like. Meanwhile, if the waste batteries are improperly disposed, toxic metal or chemical substances can be released, so that pollution is caused to soil, water and air, and the health of a human body is threatened. The method for recycling the metal from the waste batteries in the prior art has the problems of low recycling efficiency, high cost, complex process, environmental pollution and the like. For example, mechanical methods are environment-friendly but low in efficiency, pyrometallurgy is high in energy consumption and not environment-friendly, solvent extraction methods in hydrometallurgy are common, but solvent loss and regeneration energy consumption are high, the process of removing impurities is complicated, the traditional metallurgy has more subsequent separation steps, energy consumption and cost are increased, and the step of recovering metals from waste batteries is still improved. Therefore, it is necessary to provide a method for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation to solve the technical problems. Disclosure of Invention The invention provides a method for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation, which solves the problem of how to further simplify the step of recovering metals from the waste batteries and still has an improved space. In order to solve the technical problems, the method for separating manganese, nickel, cobalt and lithium from waste batteries by complexation and oxidation provided by the invention comprises the following steps: s1, washing a waste battery positive plate, and removing surface electrolyte and impurities to obtain a pretreated positive plate; S2, crushing the pretreated positive plate into small blocks, placing the small blocks in an ultrasonic cleaner, and cleaning, washing and drying to obtain a positive electrode material and a current collector; s3, dissolving the anode material in 2-4 mol/L hydrochloric acid, stirring at 60-90 ℃, and filtering after the reaction is completed to obtain a metal chloride solution; S4, adding ammonium persulfate into the metal chloride solution, stirring at 50-70 ℃, and centrifuging to obtain manganese dioxide and filtrate after the reaction is completed; S5, evaporating the filtrate, adding the filtrate into a mixed solution of ammonium chloride and ammonia water, and stirring in a closed manner to obtain a divalent nickel cobalt ammonia complex solution; S6, adding an oxidant into the divalent nickel-cobalt ammine complex solution, stirring and filtering to obtain divalent nickel-cobalt ammine complex and trivalent cobalt ammine complex filtrate; S7, adding hydrochloric acid into the divalent nickel ammonia complex and the trivalent cobalt ammonia complex filtrate for acidification, evaporating and crystallizing after the reaction is completed, and filtering to obtain cobalt salt crystals and divalent nickel ammonia complex solution; s8, adding 6-8 mol/L potassium hydroxide into the divalent nickel ammonia complex solution, adjusting the pH to 7-9, filtering, washing and drying after the reaction is finished to obtain precipitate nickel hydroxide and filtrate; s9, adding saturated sodium carbonate or carbon dioxide into the filtrate, and filtering, washing and drying after the reaction is finished to obtain lithium carbonate. Preferably, the cobalt salt crystal in S7 is calcined and ground to obtain tricobalt tetraoxide. Chlorine and ammonia released during calcination of the cobalt salt crystals are converted to ammonium chloride for use in step S5. Preferably, the waste battery comprises one or more of a nickel-hydrogen battery, a ternary lithium battery, a lithium cobalt oxide lithium ion battery and a lithium manganate battery. Preferably, the oxidizing agent in S6 is a 30wt% hydrogen peroxide solution. The invention also provides equipment for carrying out complexation, oxidation and separation on the manganese, nickel, cobalt and lithium from the waste batteries, and the equipment is used for the method for carrying out complexation, oxidation and separation on the manganese, nickel, cobalt and lithium from the waste batteries; Comprises a reaction cylinder, wherein the reaction cylinder comprises a cylinder body and a cylinder cover, and the cylinder cover is detachably arranged at the top end of the cylinder body; The stirring device compr