CN112501445B

CN112501445B - Method for preparing battery-grade nickel-cobalt-manganese

Info

Publication number: CN112501445B
Application number: CN202011360153.9A
Authority: CN
Inventors: 王雪
Original assignee: Beijing Bocui Recycling Technology Co ltd
Current assignee: Beijing Bocui Recycling Technology Co ltd
Priority date: 2020-11-27
Filing date: 2020-11-27
Publication date: 2023-01-24
Anticipated expiration: 2040-11-27
Also published as: CN112501445A

Abstract

The invention provides a method for preparing battery-grade nickel, cobalt and manganese. The method comprises the following steps: (1) Pre-separating and extracting the leachate containing the anode powder to obtain a water phase 1 and an organic phase 1, and washing and back-extracting the organic phase 1 to obtain a back-extraction solution 1; (2) Extracting and separating the water phase 1 obtained in the step (1) to obtain a water phase 2 and an organic phase 2; (3) The method provided by the invention can realize synchronous extraction and recovery of nickel, cobalt and manganese in the battery feed liquid containing nickel, cobalt and manganese.

Description

Method for preparing battery-grade nickel-cobalt-manganese

Technical Field

The invention relates to the field of resource recovery, in particular to a method for preparing battery-grade nickel, cobalt and manganese.

Background

The nickel-cobalt-manganese ternary cathode material has good cycle performance, stable structure and high cost performance, is a novel lithium ion battery cathode material, and the main raw materials of the precursor product of the ternary cathode material are nickel salt, cobalt salt and manganese salt. With the rapid development and popularization of electric automobiles, the demand scale of lithium ion batteries is also continuously enlarged, and the number of waste lithium ion batteries is also increased day by day. If the waste lithium battery is discarded at will, not only the environment is seriously polluted, but also a great deal of valuable metal resources are wasted, and the best way for solving the problem is to realize recycling of nickel, cobalt and manganese.

Hydrometallurgy is a scientific technology for dissolving valuable metal components in ores, concentrates, waste battery anode materials and other materials in a solution or separating out the valuable metal components in a new solid phase by using a leaching agent to separate, enrich and extract metals, has the characteristics of low energy consumption, small pollution, high resource utilization rate and the like, and is continuously concerned and developed by a plurality of researchers all the time.

CN110066925A discloses a recovery method of valuable metals in waste nickel-cobalt-manganese ternary lithium batteries, which comprises the steps of extracting and removing impurities from battery leachate by using P204, performing back extraction to obtain a back extraction solution containing manganese sulfate and raffinate containing Co, ni and Li ions, removing Cu from the back extraction solution, performing evaporation concentration and crystallization to obtain manganese sulfate; extracting Co in the raffinate by using saponified P507, and obtaining a cobalt sulfate solution after back extraction; removing Mg in the raffinate by using C272, extracting Ni in the raffinate by using P507, and performing back extraction to obtain a nickel sulfate solution; detecting the concentration of divalent Fe in the leachate, adding an oxidant to oxidize the divalent Fe into trivalent Fe, adding sodium carbonate to adjust the pH value of the leachate to =4.5-5.0, and removing Fe and Al precipitates; detecting the content of Ca and Mg, adding sodium fluoride or potassium fluoride to precipitate Ca and Mg, and filtering. The process flow is complex, the separation cost for respectively recovering nickel, cobalt and manganese elements is high, impurity metal ions such as Ca, mg and the like are removed by adopting a precipitation method, and valuable metal entrainment loss is easily caused.

CN105483382A discloses a method for synchronously recovering nickel, cobalt and manganese from waste residues containing nickel, cobalt and manganese, which comprises adding oxidants such as hypochlorite or nitric acid, adjusting pH value to be 5.0-5.5, removing Fe and Al in a leaching solution to obtain a raffinate after removing Fe and Al; adjusting pH value =2.0-2.5 by using Mextral984H or CP50 extracting agent, and removing Cu in raffinate; then P507 and kerosene are used as a diluent, the pH value is adjusted to be =2.0-2.3, zn and a small amount of Mn in the raffinate are extracted and removed, dilute sulfuric acid is used for washing, then sulfuric acid is used for back-extracting an organic phase containing Zn and a small amount of Mn to obtain a back-extraction solution containing Zn and a small amount of Mn, and Zn and Mn in the back-extraction solution are extracted and separated by P204; and finally, synchronously extracting Ni, co and Mn by adopting a mixed extracting agent of tributyl phosphate and new decanoic acid to obtain an organic phase containing Ni, co and Mn, washing the organic phase with dilute sulfuric acid to remove calcium and magnesium impurities, and performing back extraction by adopting sulfuric acid to obtain a nickel-cobalt-manganese mixed solution. The process flow is complex, and the operation is unstable due to the adoption of the mixed extractant.

The scheme has the problems of resource waste, complex process or high operation difficulty and the like, so that the development of the method for recovering the nickel, the cobalt and the manganese with high recovery efficiency and simple flow is necessary.

Disclosure of Invention

The invention aims to provide a method for preparing battery-grade nickel, cobalt and manganese, which comprises the following steps: (1) Pre-separating and extracting the leachate containing the anode powder to obtain a water phase 1 and an organic phase 1, and washing and back-extracting the organic phase 1 to obtain a back-extraction solution 1; (2) Extracting and separating the water phase 1 obtained in the step (1) to obtain a water phase 2 and an organic phase 2; (3) The method provided by the invention can realize synchronous extraction and recovery of nickel, cobalt and manganese in the battery feed liquid containing nickel, cobalt and manganese.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a method for preparing battery-grade nickel-cobalt-manganese, which comprises the following steps:

(1) Pre-separating and extracting the leachate containing the anode powder to obtain a water phase 1 and an organic phase 1, and washing and back-extracting the obtained organic phase 1 to obtain a back-extraction solution 1;

(2) Extracting and separating the water phase 1 obtained in the step (1) to obtain a water phase 2 and an organic phase 2;

(3) And (3) carrying out extraction separation on the stripping solution 1 obtained in the step (1) and the organic phase 2 obtained in the step (2) to obtain a water phase 3 and an organic phase 3, and washing and stripping the obtained organic phase 3 to obtain a solution containing iron, aluminum, zinc and copper.

The extracting agents in the steps (1) and (2) are carboxylic acid extracting agents, and the structural general formula of the carboxylic acid extracting agent is as follows:

wherein 10. Ltoreq. M + n. Ltoreq.22, for example: 10. 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, etc.

Preferably, said C _n H _2n+1 Is a linear or branched alkyl group having 1 to 21 carbon atoms (e.g., 1, 3, 5, 7, 9, 14, 16, 18, 21, etc.).

Preferably, said C _m H _2m+1 Is a linear or branched alkyl group having 1 to 21 carbon atoms (for example, 1, 3, 5, 7, 9, 14, 16, 18 or 21).

The adopted carboxylic acid extractant can synchronously extract nickel, cobalt and manganese, has high extraction efficiency and good separation effect with impurity ions; the water solubility is low, and the environment is friendly; the organic phase can be recycled, the operation cost is low, and the economic benefit is good.

Preferably, the carboxylic acid extractant comprises 5 to 30% by volume of the total extractant, for example: 5%, 8%, 10%, 15%, 20%, 25%, 30%, etc.

Preferably, the diluent of the extractant comprises any one of mineral spirit, kerosene, escaid110, hexane, heptane or dodecane or a combination of at least two thereof.

Preferably, the extractant of step (1) and step (2) is saponified before use.

Preferably, the saponifying agent used for saponification is an alkaline solution.

Preferably, the alkaline solution comprises any one of sodium hydroxide solution, potassium hydroxide solution or ammonia water or a combination of at least two thereof.

Preferably, the concentration of the alkaline solution is 6 to 14mol/L, for example: 6mol/L, 8mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, etc.

Preferably, the extraction method of step (1) comprises single-stage extraction and/or multi-stage countercurrent extraction, preferably multi-stage countercurrent extraction.

Preferably, the multistage countercurrent extraction in step (1) has 2 to 40 stages, for example: stage 2, stage 5, stage 10, stage 15, stage 20, stage 25, stage 30, stage 40, or the like.

Preferably, the volume ratio of the extracting agent used in the extraction in the step (1) to the leaching solution is (0.1-10): 2.

Preferably, the stirring speed in the extraction in the step (1) is 150-200 r/min, for example: 150r/min, 160r/min, 170r/min, 180r/min, 190r/min or 200r/min, etc.

Preferably, the stirring time in the extraction in step (1) is 2 to 10min, for example: 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min and the like.

Preferably, the organic phase 1 containing iron, aluminum, zinc, copper, nickel, cobalt and manganese obtained in the step (1) is washed after extraction;

preferably, the detergent used in the washing treatment comprises sulfuric acid or hydrochloric acid.

Preferably, the method of washing treatment comprises a multi-stage counter current wash.

Preferably, the number of stages of the multistage countercurrent washing is 1 to 15 stages, for example: stage 1, stage 3, stage 5, stage 9, stage 10, or stage 15.

Preferably, after washing, back extraction treatment is required to obtain the iron-containing aluminum zinc copper nickel cobalt manganese solution and a blank organic phase.

Preferably, the extractant used in the stripping treatment comprises sulfuric acid or hydrochloric acid.

Preferably, the number of stages of the stripping treatment is 1 to 10, for example: stage 1, stage 2, stage 3, stage 4, stage 5, stage 6, stage 7, stage 8, stage 9, or stage 10.

Preferably, the blank organic phase may be used as an extractant.

Preferably, the extraction method of step (2) comprises single-stage extraction and/or multi-stage countercurrent extraction, preferably multi-stage countercurrent extraction.

Preferably, the multistage countercurrent extraction in the step (2) has 2 to 40 stages, such as: stage 2, stage 5, stage 10, stage 15, stage 20, stage 25, stage 30, stage 40, or the like.

Preferably, the volume ratio of the extracting agent used in the extraction in the step (2) to the leaching solution is (0.1-10): 1.5.

Preferably, the stirring speed in the extraction in the step (2) is 150-200 r/min, for example: 150r/min, 160r/min, 170r/min, 180r/min, 190r/min or 200r/min, etc.

Preferably, the stirring time in the extraction in step (2) is 2 to 10min, for example: 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min and the like.

Preferably, the pH of the aqueous phase 2 in step (2) is 5 to 7.5, for example: 5. 5.2, 5.5, 5.7, 5.9, 6, 6.2, 6.5, 6.8, 7, 7.5, etc.

Preferably, the manganese-containing organic phase 2 obtained in step (2) is subjected to a washing treatment.

Preferably, the method of ground washing treatment comprises a multistage counter current wash.

Preferably, the number of stages of the multistage countercurrent washing is 1 to 15 stages, for example: stage 1, stage 2, stage 3, stage 4, stage 5, stage 8, stage 10, stage 12, stage 14, or stage 15.

Preferably, the washed manganese-containing organic phase 2 can be used as a saponifier in step (3).

Preferably, the extraction method of step (3) comprises single-stage extraction and/or multi-stage countercurrent extraction, preferably multi-stage countercurrent extraction.

Preferably, the number of stages of the multistage countercurrent extraction in the step (3) is 2 to 40, such as: stage 2, stage 5, stage 10, stage 15, stage 20, stage 25, stage 30, stage 40, or the like.

Preferably, the volume ratio of the extracting agent used in the extraction in the step (3) to the leachate is (0.1-10): 2.

Preferably, the stirring speed in the extraction in the step (3) is 150-200 r/min, for example: 150r/min, 160r/min, 170r/min, 180r/min, 190r/min or 200r/min, etc.

Preferably, the stirring time in the extraction in step (3) is 2 to 10min, for example: 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min and the like.

Preferably, the manganese-containing organic phase 2 obtained in step (3) is subjected to washing treatment after extraction.

Preferably, after washing, a back extraction treatment is required to obtain a nickel-cobalt-manganese-containing solution, an iron-aluminum-zinc-copper back extraction solution and a blank organic phase.

Preferably, the number of stages of the stripping treatment is 1 to 10 stages.

Preferably, the blank organic phase may be used as an extractant.

As a preferable scheme of the invention, the preparation method comprises the following steps:

(1) Diluting the carboxylic acid extractant by using a diluent until the volume fraction is 5-30%, and then performing saponification treatment by using an alkaline solution with the concentration of 6-14 mol/L;

(2) Stirring the leachate containing the anode powder for 2-10 min at the speed of 150-200 r/min by using the saponified extractant obtained in the step (1), and separating to obtain a calcium-magnesium-manganese-containing aqueous phase 1 and an iron-aluminum-zinc-copper-nickel-cobalt-manganese-containing organic phase 1;

(3) Washing and back extracting the organic phase 1 containing iron, aluminum, zinc, copper, nickel, cobalt and manganese obtained in the step (2) to obtain a back extraction solution containing iron, aluminum, zinc, copper, nickel, cobalt and manganese and a blank organic phase;

(4) Stirring the water phase 1 obtained in the step (2) for 2-10 min at the speed of 150-200 r/min by using the saponified extractant obtained in the step (1), and separating to obtain a water phase 2 with the pH value of 5-7.5 and a manganese-containing organic phase 2;

(5) Stirring the strip liquor obtained in the step (3) and the manganese-containing organic phase 2 obtained in the step (4) at a speed of 150-200 r/min for 2-10 min, and separating to obtain a nickel-cobalt-manganese-containing aqueous phase 3 and an iron-aluminum-zinc-copper-containing organic phase 3;

(6) And (4) washing and back-extracting the organic phase 3 containing iron, aluminum, zinc, copper, nickel, cobalt and manganese obtained in the step (5) to obtain a back-extraction solution containing iron, aluminum, zinc, copper, nickel, cobalt and manganese and a blank organic phase.

Compared with the prior art, the invention has the following beneficial effects:

(1) The method provided by the invention has good separation effect on metal ions, realizes synchronous extraction and recovery of nickel, cobalt and manganese in the nickel-cobalt-manganese battery leaching solution by utilizing the coupling effect between the extracting agent and the extraction pH value, is not influenced by impurity metal ions such as calcium, magnesium, iron, aluminum and the like, is simple to operate, reduces the separation cost of respectively recovering nickel, cobalt and manganese and the extraction and purification cost of impurity metal ions, and in addition, the adopted carboxylic acid extracting agent has small water solubility and can be recycled.

(2) The recovery method provided by the invention has the impurity removal rate of more than or equal to 99 percent, the extraction rate of nickel, cobalt and manganese of more than or equal to 99.5 percent and the back extraction rate of more than or equal to 99.5 percent.

Drawings

FIG. 1 is a schematic diagram of the recovery process in example 1 of the present invention.

Detailed Description

The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

In the embodiment 1 and the comparative embodiment 1, the volume fraction of the extracting agent is 25 percent, the diluent is Escaid110, and 6mol/L NaOH solution is used for saponification.

The BC196 extracting agent used in the embodiment of the invention is prepared by the following method:

28.6g of isooctanol, 200mL of Tetrahydrofuran (THF) and 8.8g of 60% sodium hydride (dispersed in mineral oil) are added into a three-neck flask, and the mixture reacts for 6 hours at 60 ℃, so that a large amount of white solid is generated, and a small amount of sodium particles are left; dripping 20mL of 10mol/L THF solution of 2-bromohexanoic acid at 60 ℃ and continuously reacting for 4 hours at 60 ℃; after cooling, THF is removed through rotary evaporation, 200mL of water and 200mL of Ethyl Acetate (EA) are added into the concentrated solution, shaking is carried out to separate layers, and a water layer is taken; the aqueous layer was acidified with hydrochloric acid to pH 1, extracted with ethyl acetate, and the organic phase was washed with water 2 times and spin-dried to obtain 38g of a pale yellow product, compound BC196.

Characterization data: ¹³ C NMR(101MHz，CDCl ₃ )δ3.97(1H)，3.41(1H)，3.26(1H)，1.70(2H)，1.45(3H)，1.05-1.24(10H)，0.91(9H)； ¹³ C NMR(101MHz，CDCl ₃ )δ175(s)，82(s)，76(s)，40(s)，32(s)，30(s)，29(s)，27(s)，22–23(m)，14(s)，11(s)；MS[M-H] ^- :243。

example 1

This example provides a method for preparing battery grade nickel-cobalt-manganese by pre-separation extraction, and the schematic diagram of the method is shown in fig. 1.

In this example, BC196 was used as the extractant, 25% by volume, and Escaid110 as the diluent, and saponified with 6mol/L NaOH solution.

The leachate in this example is a battery leachate containing nickel, cobalt and manganese, the pH of the leachate is 1.59, and the components are shown in table 1:

TABLE 1

Element(s)	Fe	Al	Zn	Cu	Ni	Co	Mn	Ca	Mg	Li
											Content (g/L)	0.5	0.01	0.3	0.6	48	22	18	0.5	0.5	10

(1) Using saponified BC196

Performing 15-stage countercurrent extraction on leachate containing nickel, cobalt and manganese, wherein the volume ratio of an extracting agent to battery leachate is 0.2.

(2) Performing multistage countercurrent extraction on the water phase 1 by using saponified BC196, wherein the volume ratio of the organic phase to the water phase 1 is 4:1, the mixing time is 8min, the stirring speed is 150r/min, standing is 15min, the experimental temperature is 25 ℃, mixed liquor of organic phase 2 and calcium sulfate and magnesium sulfate with the pH value of 6.4 is obtained respectively, 10-stage countercurrent washing is performed on the organic phase 2 by using dilute sulfuric acid with the pH value of 1.5, the organic phase 2 enters a third extraction section to perform countercurrent extraction with a strip liquor 1, mixed liquor of cobalt sulfate, nickel sulfate and manganese sulfate with the pH value of 6.4 is obtained respectively, 12-stage countercurrent washing is performed on the organic phase 3 by using dilute sulfuric acid with the pH value of 1.5, then back extraction is performed for 3 times by using 2.5mol/L sulfuric acid, and the volumes of the organic phase 3 and a washing liquor or a back extraction liquor are 10, so that a mixed solution of ferric sulfate, copper sulfate, zinc sulfate and aluminum sulfate is obtained.

Example 2

This example differs from example 1 only in that the stirring speed in step (1) is 100r/min, and the other conditions and parameters are exactly the same as in example 1.

Example 3

This example is different from example 1 only in that the stirring speed in step (1) is 200r/min, and other conditions and parameters are exactly the same as example 1.

Example 4

This example differs from example 1 only in that the stirring speed in step (1) is 250r/min, and the other conditions and parameters are exactly the same as in example 1.

Comparative example 1

The comparative example provides a traditional method for recovering nickel, cobalt and manganese in feed liquid containing nickel, cobalt and manganese, the leachate in the comparative example is battery leachate containing nickel, cobalt and manganese, the pH value of the leachate is 1.59, and the components are shown in Table 2:

TABLE 2

(1) Carrying out 15-stage countercurrent extraction on the leachate containing nickel, cobalt and manganese by using saponified P204, wherein the volume ratio of an extractant to the battery leachate is 0.2.

(2) Performing multistage countercurrent extraction on the water phase 1 by using saponified P507, wherein the extraction stage number is 15, the volume ratio of the organic phase to the water phase 1 is 4:1, the mixing time is 8min, the stirring speed is 150r/min, the standing is 15min, the experimental temperature is 25 ℃, mixed liquid of organic phase 2 and magnesium sulfate and nickel sulfate with the pH value of 5 is respectively obtained, 10-stage countercurrent washing is performed on the organic phase 2 by using 1mol/L dilute sulfuric acid, then back extraction is performed for 3 times by using 2.5mol/L sulfuric acid, and the volume of the organic phase 3 and a washing solution or a back extraction solution is 10, so that the cobalt sulfate solution is obtained.

(3) Performing multistage countercurrent extraction on the water phase 2 by using saponified C272, wherein the extraction stage number is 15, the volume ratio of the organic phase to the water phase 1 is 4:1, the mixing time is 8min, the stirring speed is 150r/min, standing is 15min, the experimental temperature is 25 ℃, respectively obtaining an organic phase 3 and a nickel sulfate solution with the pH value of 5, performing 10-stage countercurrent washing on the organic phase 2 by using 1mol/L dilute sulfuric acid, and performing back extraction for 3 times by using 2.5mol/L sulfuric acid, wherein the volume of the organic phase 3 and a washing solution or a back extraction solution is 10.

(4) Carrying out 15-stage countercurrent extraction on a mixed solution containing copper sulfate and manganese sulfate by using saponified P204, wherein the volume ratio of an extractant to a battery leachate is 0.2.

The test results of examples 1-4 and comparative example 1 are shown in table 3:

TABLE 3

Comparing example 1 with comparative example 1, it can be seen that the pre-separation extraction method has a shorter flow than the traditional separation method, less types of extracting agents, avoids cross contamination of the extracting agents, has a high metal extraction rate, and can greatly save investment and operation cost.

As can be seen from Table 3, in the method of the present invention, the stirring speed in step (1) needs to be controlled to be 150-200 r/min, the stirring speed is too high, the solvent is dissociated among the particles due to the centrifugal effect, so that the saponifier and the leachate in the stirring process flow dynamically and cannot be turned over, and the internal friction force among the particles is greatly reduced, so that the stirring is not uniform; the stirring speed is too low and the interparticle friction is low, also resulting in non-uniformity.

According to the method provided by the invention, through a pre-separation extraction method, the nickel, cobalt and manganese in the leachate of the anode material of the waste lithium ion battery are synchronously extracted and recovered, the method is not influenced by impurity metal ions such as calcium, magnesium, iron, aluminum, zinc, copper and the like, the operation is simple, and the separation cost for respectively recovering nickel, cobalt and manganese and the extraction and purification cost for the impurity metal ions are reduced. Meanwhile, the impurity removal rate of the carboxylic acid extractant reaches 99.4 percent, and the sulfuric acid back extraction rate reaches more than 99.5 percent.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. A method for preparing battery-grade nickel-cobalt-manganese is characterized by comprising the following steps:

(1) Pre-separating and extracting the leachate containing the anode powder, wherein the stirring speed in the extraction is 150-200 r/min to obtain a water phase 1 containing calcium, magnesium and manganese and an organic phase 1 containing iron, aluminum, zinc, copper, nickel, cobalt and manganese, washing and back-extracting the obtained organic phase 1 containing iron, aluminum, zinc, copper, nickel, cobalt and manganese to obtain a back-extraction solution 1 containing iron, aluminum, zinc, copper, nickel, cobalt and manganese and a blank organic phase, and recycling the blank organic phase as an extracting agent;

the extraction method in the step (1) is multi-stage countercurrent extraction;

(2) Extracting and separating the calcium-magnesium-manganese-containing water phase 1 obtained in the step (1) to obtain a water phase 2 and a manganese-containing organic phase 2;

the extraction method in the step (2) is multi-stage countercurrent extraction;

(3) Extracting and separating the back extraction solution 1 containing iron, aluminum, zinc, copper, nickel, cobalt and manganese obtained in the step (1) and the manganese-containing organic phase 2 obtained in the step (2) to obtain a nickel, cobalt and manganese-containing aqueous phase 3 and an iron, aluminum, zinc and copper-containing organic phase 3, washing and back extracting the obtained iron, aluminum, zinc and copper-containing organic phase 3 to obtain an iron, aluminum, zinc and copper-containing solution and a blank organic phase, wherein the blank organic phase can be used as an extracting agent for recycling;

the extraction method in the step (3) is multi-stage countercurrent extraction.

2. The method of claim 1, wherein the extractant used in step (1) and the extractant used in step (2) are both carboxylic acid type extractants.

3. The method of claim 2, wherein the carboxylic acid extractant has the general structural formula:

wherein m + n is more than or equal to 10 and less than or equal to 22.

4. The method of claim 3, wherein C is _n H _2n+1 Is a linear or branched alkyl group having 1 to 21 carbon atoms.

5. The method of claim 3, wherein C is _m H _2m+1 Is a linear or branched alkyl group having 1 to 21 carbon atoms.

6. The process of claim 2, wherein the carboxylic acid extractant comprises 5 to 30 volume percent of the total extractant.

7. The method of claim 2, wherein the extractant further comprises a diluent.

8. The method of claim 7, wherein the diluent comprises any one of, or a combination of at least two of, mineral spirits, kerosene, escaid110, hexane, heptane, or dodecane.

9. The method of claim 2, wherein the extractant of steps (1) and (2) is saponified prior to use.

10. The method of claim 9, wherein the saponifying agent used in the saponifying is an alkaline solution.

11. The method of claim 10, wherein the alkaline solution comprises any one of a sodium hydroxide solution, a potassium hydroxide solution, or ammonia water, or a combination of at least two thereof.

12. The method of claim 10, wherein the concentration of the alkaline solution is 6 to 14mol/L.

13. The method of claim 1, wherein the multistage countercurrent extraction of step (1) has 2 to 40 stages.

14. The method according to claim 1, wherein the volume ratio of the extractant used in the extraction in step (1) to the leachate is (0.1-10): 2.

15. The method of claim 1, wherein the stirring time in the extraction of step (1) is 2 to 10min.

16. The method according to claim 1, wherein the organic phase 1 containing iron, aluminum, zinc, copper, nickel, cobalt and manganese obtained in step (1) is subjected to a washing treatment after extraction, and the washing agent used in the washing treatment comprises sulfuric acid or hydrochloric acid.

17. The method of claim 16, wherein the method of washing treatment comprises a multi-stage counter-current wash.

18. The method of claim 17, wherein the number of stages of the multistage countercurrent washing is 1 to 15 stages.

19. The method of claim 16, wherein the washing is followed by a stripping process using an extractant comprising sulfuric acid or hydrochloric acid.

20. The method of claim 19, wherein the number of stages of the stripping process is 1 to 10 stages.

21. The method of claim 1, wherein the multistage countercurrent extraction of step (2) has 2 to 40 stages.

22. The method according to claim 1, wherein the volume ratio of the extracting agent used in the extraction in the step (2) to the leachate is (0.1-10): 1.5.

23. The method of claim 1, wherein the stirring speed in the extraction in step (2) is 150 to 200r/min.

24. The method of claim 1, wherein the stirring time in the extraction of step (2) is 2 to 10min.

25. The process of claim 1, wherein the pH of the aqueous phase 2 in step (2) is from 5 to 7.5.

26. The process according to claim 1, wherein the manganese-containing organic phase 2 obtained in step (2) is subjected to a washing treatment.

27. The method of claim 26, wherein the washing process uses a detergent comprising sulfuric acid or hydrochloric acid.

28. The method of claim 27, wherein the method of washing treatment comprises a multi-stage counter-current wash.

29. The method of claim 28, wherein the multiple counter-current washing stages are from 1 to 15 stages.

30. The method of claim 26, wherein the washed manganese-containing organic phase 2 is used as a saponifier in step (3).

31. The method of claim 1, wherein the multistage countercurrent extraction of step (3) has 2 to 40 stages.

32. The method according to claim 1, wherein the volume ratio of the extracting agent used in the extraction in the step (3) to the leachate is (0.1-10): 2.

33. The method of claim 1, wherein the stirring speed in the extraction in step (3) is 150 to 200r/min.

34. The method of claim 1, wherein the stirring time in the extraction of step (3) is 2 to 10min.

35. The process according to claim 1, wherein the manganese-containing organic phase 2 obtained in step (2) is subjected to washing after extraction.

36. The method of claim 35, wherein the washing process uses a detergent comprising sulfuric acid or hydrochloric acid.

37. The method of claim 36, wherein the method of washing treatment comprises a multi-stage counter-current wash.

38. The method of claim 37, wherein the number of stages of the multistage countercurrent washing is 1 to 15 stages.

39. The method of claim 35, wherein said washing is followed by stripping to produce a nickel cobalt manganese containing solution, an iron aluminum zinc copper strip solution, and a blank organic phase.

40. The process of claim 39, wherein the extractant used in the stripping process comprises sulfuric acid or hydrochloric acid.

41. The method of claim 39, wherein the stripping treatment is performed in stages of 1 to 10.

42. The method of claim 1, wherein the method comprises the steps of:

(4) Stirring the water phase 1 obtained in the step (2) by using the saponified extractant obtained in the step (1) at a speed of 150-200 r/min for 2-10 min, and separating to obtain a water phase 2 with a pH value of 5-7.5 and a manganese-containing organic phase 2;

(5) Stirring the back extraction solution obtained in the step (3) and the manganese-containing organic phase 2 obtained in the step (4) at the speed of 150-200 r/min for 2-10 min, and separating to obtain a nickel-cobalt-manganese-containing aqueous phase 3 and an iron-aluminum-zinc-copper-containing organic phase 3;