Extraction technique for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw material

Abstract

The present invention relates to an extraction technique for low-cost recovery of battery-grade manganese sulfate from a manganese-containing nickel-cobalt raw material, the extraction technique comprising the following steps: (1) subjecting an extractant and liquid caustic soda to saponification to obtain an organic phase, wherein a P204 extractant is mixed with solvent oil for use, with the concentration of the P204 being 5%-50% and the balance being the solvent oil, and the saponification rate of the saponification of the mixed extractant and liquid caustic soda is less than or equal to 23.7%; (2) mixing a saponified organic phase in step (1) with a feed liquid for P204 extraction (a manganese-containing nickel-cobalt raw material liquid), and then performing an extraction operation by using a new extractor to obtain an impurity liquid and a raffinate obtained from P204 impurity co-extraction and containing less than or equal to 1 ppm of calcium, wherein the pH is controlled at 0-4.5 during extraction, and the post-extraction O / A ratio is equal to 0.415-5.2; and (3) sequentially performing the steps of extraction, scrubbing, manganese stripping, iron scrubbing and water washing on the raffinate obtained from P204 impurity co-extraction in step (2), thereby completing the treatment. The process is used for producing battery-grade manganese sulfate, without first enriching manganese and impurities into a manganese-enriched liquid and then using a C272 extractant to achieve manganese-calcium separation; therefore, not only are the costs required for producing the manganese-enriched liquid saved on, but also the utilization of the expensive C272 extractant is not required, thereby optimizing the overall process and greatly reducing the production costs.

Description

An extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt feedstocks. Technical Field

[0001] This invention relates to the field of manganese sulfate recovery technology, specifically to an extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials. Background Technology

[0002] Manganese sulfate is a crucial raw material in the production of ternary lithium batteries, and the requirements for the content of various impurities are extremely stringent. In the recycling process of retired ternary lithium batteries or manganese-containing nickel-cobalt raw materials, many manufacturers choose to process manganese into slag because manganese has a relatively low value compared to nickel and cobalt, and is difficult to recycle. This wastes its inherent value and increases the possibility of secondary pollution.

[0003] The existing extraction processes of the few manganese recycling companies are generally too complex, leading to higher equipment investment and production costs. Therefore, the applicant hopes to develop a more cost-effective process with fewer steps that can guarantee the quality of the produced manganese sulfate. Summary of the Invention

[0004] The purpose of this invention is to provide an extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials, in order to solve the above-mentioned problems.

[0005] The above-mentioned technical objective of this invention is achieved through the following technical solution: an extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials, comprising the following steps:

[0006] (1) The extractant and liquid alkali are saponified to obtain an organic phase; P204 extractant is used in combination with solvent oil, wherein the concentration of P204 is 5%-50% and the remainder is solvent oil; the saponification rate of the mixture of extractant and liquid alkali is ≤23.7%;

[0007] (2) After mixing the saponified organic phase in step (1) with the P204 pre-extraction liquid (nickel-cobalt feed liquid containing manganese), the new type of extractor is used for extraction to obtain the reversed liquid and the P204 extraction residue; the pH is controlled at 0-4.5 during the extraction process, and the O / A ratio after extraction is 0.415-5.2;

[0008] (3) The extractant after extraction in step (2) is processed by washing, reverse impurities, reverse iron removal and water washing in sequence;

[0009] The detergent used in the washing process is 1%~5% sulfuric acid, and the washing liquid is returned to step (2) above for re-extraction.

[0010] The reverse impurity process involves impuritrifying the washed extractant using 6-12% hydrochloric acid. The resulting solution is a calcium-containing manganese chloride solution, where manganese accounts for 5-20% of the total manganese content.

[0011] The anti-iron process involves removing iron from the impurity-treated extractant, and the anti-iron agent used is 18% hydrochloric acid.

[0012] The water washing process involves washing the extractant after antiferrolysis with water. The water washing agent used is wash water. The water washing liquid is then used in anti-mixing. The P204 extractant after washing can be recycled back to step (1) for reuse.

[0013] In addition, the P204 extraction residue generated in step (2) above needs to be treated. The specific process includes the following steps:

[0014] ① The extractant and liquid alkali are saponified to obtain an organic phase; P204 extractant is used in combination with solvent oil, wherein the concentration of P204 is 20%-25%, and the remainder is solvent oil; the saponification rate of the mixture of extractant and liquid alkali is ≤60%;

[0015] ② The organic phase obtained in step ① is mixed with the P204 extractant residue and then extracted using a new type of extractor. After extraction, manganese-containing extractant and P204 manganese extractant residue are obtained.

[0016] ③ The manganese-containing extractant from step ② is processed sequentially through washing, anti-manganese, anti-iron, and water washing steps;

[0017] The washing agent used in the washing process is sulfuric acid, and the washing liquid is returned to step ② above for re-extraction.

[0018] The manganese-removing process involves removing manganese from a manganese-containing extractant. The resulting solution is a crude manganese sulfate solution, and the manganese-removing agent used is 20% sulfuric acid.

[0019] Among them, anti-iron is to remove iron from the extractant after anti-manganese, and the anti-iron agent used is 18% hydrochloric acid;

[0020] The water washing process involves washing the extractant after antiferrolysis with water. The washing agent used is wash water. The washed liquid is then used in anti-mixing. The P204 extractant after washing can be recycled back to step ① for reuse.

[0021] 2. The extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials according to claim 1, characterized in that: it further includes a process for removing copper from the manganese sulfate produced in step ③ above, the process flow of which includes the following steps:

[0022] 1. Remove copper from the copper sulfate in step ③ above using a copper-removing agent;

[0023] 2. Solid-liquid separation treatment is carried out to obtain copper slag and battery-grade manganese sulfate.

[0024] Preferably, the concentration of liquid alkali in step (1) and step ① is controlled at 15%-35%, which facilitates the control of the saponification rate.

[0025] Preferably, calcium and manganese are completely separated with low manganese loss by controlling process parameters and procedures.

[0026] Preferably, the novel extractor includes a base, a bottom plate is fixedly connected to the base by at least two vertical rods, a mixing tank is fixed on the bottom plate, a mixing component inserted into the mixing tank is installed on the bottom plate, a first input pipe and a second input pipe are fixedly connected to the bottom of the bottom plate, a layering tank is fixed on the top of the mixing tank, a cover plate is fixed on the top of the layering tank, a layering cavity is provided inside the layering tank, and a first discharge structure and a second discharge structure are installed on the layering tank in connection with the layering cavity;

[0027] In the above structure, the liquid to be extracted is input from the first input pipe through an external water pump, and the extractant is input from the second input pipe. The liquid to be extracted and the extractant are fully mixed by the mixing component. The mixed liquid enters the layered chamber for layered extraction. The liquid with higher relative density is discharged from the first discharge structure, and the liquid with lower relative density is discharged from the second discharge structure.

[0028] However, the first drawback of the above structure is that when dealing with multiple different extraction needs like those in this application, it is difficult to control the opening and closing of the first discharge structure and the second discharge structure, making it difficult to automatically discharge liquids of different densities and control the rate.

[0029] The second drawback is that, in cases like this application where the liquid to be extracted and the extractant are continuously introduced, the newly introduced liquid is more likely to disturb the already stratified liquids of different densities, thus affecting the emissions.

[0030] Preferably, the mixing assembly includes a motor fixed to the bottom of the base plate, the motor shaft of which is inserted into the mixing chamber and fixed with at least one stirring blade.

[0031] Preferably, an extraction assembly is installed within the layered cavity. The extraction assembly includes a guide rod fixed to the bottom of the layered cavity, an extraction block slidably mounted on the guide rod, a communicating cavity within the extraction block, and at least one extraction slot at both the top and bottom of the extraction block. At least one extraction tube communicating with the communicating cavity and the layered cavity is fixedly installed within each extraction slot. A sealing and switching assembly is also installed on the extraction block. A first extraction head is fixedly connected to one side of the communicating cavity, and one end of a connecting hose is fixedly connected to the first extraction head. The other end of the connecting hose is fixedly connected to a second extraction head, which is fixedly mounted on the layered container. The sealing and switching assembly... The switching component is used to switch between blocking the upper extraction tube and blocking the lower extraction tube. The density of the extraction block should be between the two liquids in the above-mentioned layers. In this way, under the action of buoyancy, the middle position of the extraction block can always be maintained at the separation position between the two liquids in the above-mentioned layers. At this time, the liquid can be extracted from the second extraction head from the upper extraction tube or from the lower extraction tube (depending on whether the blocking component blocks the upper or lower extraction tube). Thus, regardless of the amount of liquid in the layered chamber, the required layered liquid can be continuously extracted, which is convenient for subsequent operations and has high efficiency.

[0032] Preferably, the blocking and switching assembly includes a connecting plate slidably disposed within the communicating cavity. Both the upper and lower surfaces of the connecting plate are fixed with blocking heads. The upper blocking head is used to block the upper extraction tube, and the lower blocking head is used to block the lower extraction tube. A storage groove is formed on the extraction block, and a handle is provided within the storage groove. A threaded rod is fixed to the bottom of the connecting hose, and the threaded rod is threadedly connected to a threaded hole formed on the extraction block. The bottom of the threaded rod is rotatably mounted on the connecting plate. By rotating the handle, the threaded rod is lowered, causing the connecting plate to lower, so that the upper blocking head no longer blocks the upper extraction tube, and the lower blocking head blocks the extraction tube.

[0033] Preferably, since the liquids to be extracted have different densities, a weight can be placed on the guide rod to press down the extraction block, so that the combined density of the extraction block and the weight is between that of the upper and lower liquid layers.

[0034] Preferably, to address the second drawback, at least one fixing plate is fixedly installed on the extraction block, and a first connecting pipe is fixed on the fixing plate. A second connecting pipe, connecting the layering chamber and the mixing tank, is fixedly installed on the bottom wall of the layering chamber. A connecting hose is fixed between the second connecting pipe and the first connecting pipe. When the extraction block rises, the hose is straightened; when the extraction block descends, the hose bends between the extraction block and the layering tank. The first connecting pipe is also located at the separation point between the two liquids in the layering process. In this way, newly introduced liquids can be quickly layered with minimal impact on the original layered liquids.

[0035] In summary, the present invention has the following beneficial effects:

[0036] 1. This process is used to produce battery-grade manganese sulfate. It eliminates the need to first enrich manganese and impurities in a manganese enrichment solution, thus saving the cost of producing the manganese enrichment solution, optimizing the overall process, and greatly improving production efficiency.

[0037] 2. By optimizing the process and the proportion of related material formulations, this invention enables the extraction operation to be completed using only P204 extractant, greatly saving costs.

[0038] 3. In the entire process, the manganese phase is extracted one less time compared to the traditional process, which can save on auxiliary material costs and reduce wastewater generation.

[0039] 4. The novel extractor of the present invention includes an extraction component installed within the layering chamber. The extraction component includes a guide rod fixed to the bottom of the layering chamber, an extraction block slidably mounted on the guide rod, a communicating cavity within the extraction block, and at least one extraction groove formed at both the top and bottom of the extraction block. At least one extraction tube communicating with the communicating cavity and the layering chamber is fixedly installed within the extraction groove. A blocking and switching component is also installed on the extraction block. A first extraction head is fixedly connected to one side of the communicating cavity, and one end of a connecting hose is fixedly connected to the first extraction head. The other end of the connecting hose is fixedly connected to a second extraction head, which is fixedly mounted on the layering tank. The blocking and switching component... This is used to switch between blocking the upper or lower extraction tube. The density of the extraction block must be between the two liquids in the above-mentioned layers. Under the action of buoyancy, the middle position of the extraction block can always be maintained at the separation point between the two liquids in the above-mentioned layers. At this time, liquid can be extracted from the second extraction head from either the upper liquid or the lower liquid (depending on whether the blocking component blocks the upper or lower extraction tube). Thus, regardless of the amount of liquid in the layered chamber, the required layered liquid can be continuously extracted, which is convenient for subsequent operations and has high efficiency.

[0040] 5. At least one fixing plate is fixedly installed on the extraction block, and a first connecting pipe is fixed on the fixing plate. A second connecting pipe connecting the layering chamber and the mixing tank is fixedly installed on the bottom wall of the layering chamber. A connecting hose (not shown) is fixed between the second connecting pipe and the first connecting pipe. When the extraction block rises, the hose will be straightened. When the extraction block descends, the hose will bend between the extraction block and the layering tank. The first connecting pipe is also located at the separation point between the two liquids in the above-mentioned layering. In this way, the newly introduced liquid can be quickly layered with little impact on the original layered liquid, further improving the extraction efficiency. Attached Figure Description

[0041] To more clearly illustrate the technical solutions in the embodiments of the invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0042] Figure 1 is a process flow diagram of an embodiment of the present invention;

[0043] Figure 2 is a first external schematic diagram of the novel extractor according to an embodiment of the present invention;

[0044] Figure 3 is a first cross-sectional view of the novel extractor according to an embodiment of the present invention;

[0045] Figure 4 is an enlarged view of point A in Figure 3;

[0046] Figure 5 is a second cross-sectional view of the novel extractor according to an embodiment of the present invention;

[0047] Figure 6 is a schematic diagram of the appearance of the novel extractor of this invention after the cover plate is removed.

[0048] In the diagram: 10. Base; 11. Vertical rod; 12. Motor; 13. Base plate; 14. Mixing tank; 15. First discharge structure; 16. Layered bucket; 17. Second discharge structure; 18. Cover plate; 20. First input pipe; 21. Second input pipe; 22. Stirring blade; 23. Layered chamber; 24. Guide rod; 25. Connecting hose; 26. Second extraction head; 27. Extraction block; 28. Extraction groove; 29. ​​Extraction pipe; 31. Connecting chamber; 32. Connecting plate; 33. Sealing head; 34. Storage groove; 35. Handle; 36. Threaded rod; 37. First extraction head; 38. Second connecting pipe; 39. First connecting pipe; 40. Fixing plate; 50. Mixing component; 60. Extraction component. Detailed Implementation

[0049] An extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials, as described in Figures 1-6, includes the following steps:

[0050] (1) The extractant and liquid alkali are saponified to obtain an organic phase; in order to reduce the cost of the extractant, P204 extractant [di(2-ethylhexyl) phosphate] is used in combination with solvent oil, wherein the concentration of P204 is 5%-50% and the remainder is solvent oil; the saponification rate of the mixture of extractant and liquid alkali is ≤23.7%; wherein the concentration of liquid alkali is controlled at 15%-35%.

[0051] (2) After the saponified organic phase in step (1) is mixed with the P204 pre-extraction liquid (nickel-cobalt raw material liquid containing manganese), the extraction operation is carried out using a new type of extractor to obtain the impurity liquid and the P204 extraction residue. In order to optimize the extraction effect, the new type of extractor is a special product of our company. During the extraction process, the pH is controlled at 0-4.5, and the O / A ratio after extraction is 0.415-5.2. This extraction step is used to separate metals such as iron, zinc, calcium and aluminum (in the impurity liquid) and leave manganese (in the P204 extraction residue).

[0052] (3) The extractant after extraction in step (2) is processed by washing, reverse impurities, reverse iron removal and water washing in sequence;

[0053] The detergent used in the washing process is 1%~5% sulfuric acid, and the washing liquid is returned to step (2) above for re-extraction.

[0054] The reverse impurity process involves impuritrifying the washed extractant using 6-12% hydrochloric acid. The impurity solution is collected separately and is a calcium-containing manganese chloride solution, where manganese accounts for 5-20% of the total manganese content.

[0055] The anti-iron process involves removing iron from the extractant after impurities are removed. The anti-iron agent used is 18% hydrochloric acid, and the liquid after anti-iron removal is collected separately.

[0056] The water washing process involves washing the extractant after antiferrolysis with water. The water used is washing water. After washing, the extractant is incorporated into the impurity treatment. Finally, the blank P204 extractant can be recycled back to step (1) for reuse.

[0057] In addition, the P204 extraction residue generated in step (2) above needs to be treated. The specific process includes the following steps:

[0058] ① The extractant and liquid alkali are saponified to obtain an organic phase. To reduce the cost of the extractant, P204 extractant [di(2-ethylhexyl) phosphate] is mixed with solvent oil. The concentration of P204 is 20%-25%, and the remainder is solvent oil. The saponification rate of the mixture of extractant and liquid alkali is ≤60%. The concentration of liquid alkali is controlled at 15%-35%.

[0059] ② The organic phase obtained in step ① is mixed with the P204 extractant residue and then extracted using a new type of extractor. After extraction, manganese-loaded extractant and P204 manganese extractant residue are obtained.

[0060] ③ The loaded manganese extractant from step ② is processed sequentially through washing, demanganese removal, deiron removal, and water washing.

[0061] The washing agent used in the washing process is sulfuric acid. After washing, the liquid is separated and refluxed back to step ② above for re-extraction.

[0062] The manganese-removing process involves removing manganese from the washed extractant. The manganese-removing agent used is 20% sulfuric acid, and the liquid after manganese removal is crude manganese sulfate.

[0063] Among them, anti-iron is to remove iron from the extractant after anti-manganese, and the anti-iron agent used is 18% hydrochloric acid. The liquid after anti-iron is collected separately.

[0064] The water washing process involves washing the antiferric extractant with water, and the water used is wash water. The water after washing is incorporated into the antiferric extractant, and the blank P204 extractant can be recycled back to step ①.

[0065] By controlling process parameters and procedures, complete separation of calcium and manganese can be achieved with low manganese loss.

[0066] There is also a process for removing copper from the manganese sulfate produced in step ③ above, the process flow of which includes the following steps:

[0067] First, remove the copper sulfate from step ③ above using a copper-removing agent.

[0068] 2. Solid-liquid separation treatment is carried out to obtain copper slag and battery-grade manganese sulfate.

[0069] In addition, the novel extractor includes a base 10, a base plate 13 fixedly connected to the base 10 by at least two vertical rods 11, a mixing box 14 fixed on the base plate 13, a mixing component 50 installed on the base plate 13 and inserted into the mixing box 14, a first input pipe 20 and a second input pipe 21 fixedly connected to the bottom of the base plate 13, a layering barrel 16 fixed on the top of the mixing box 14, a cover plate 18 fixed on the top of the layering barrel 16, a layering cavity 23 provided inside the layering barrel 16, and a first discharge structure 15 and a second discharge structure 17 installed on the layering barrel 16 in connection with the layering cavity 23.

[0070] The mixing assembly 50 includes a motor 12 fixed to the bottom of the base plate 13, the motor shaft of the motor 12 being inserted into the mixing box 14 and having at least one stirring blade 22 fixed thereon.

[0071] In the above structure, the liquid to be extracted is input from the first input pipe 20 through an external water pump, and the extractant is input from the second input pipe 21. The liquid to be extracted and the extractant are fully mixed by the mixing component 50. The mixed liquid enters the layered chamber 23 for layered extraction. The liquid with higher relative density is discharged from the first discharge structure 15, and the liquid with lower relative density is discharged from the second discharge structure 17.

[0072] However, the first drawback of the above structure is that when dealing with multiple different extraction needs like those in this application, it is difficult to control the opening and closing of the first discharge structure 15 and the second discharge structure 17, making it difficult to automatically discharge liquids with different densities and control the rate.

[0073] The second drawback is that, in cases like this application where the liquid to be extracted and the extractant are continuously introduced, the newly introduced liquid is more likely to disturb the already stratified liquids of different densities, thus affecting the discharge.

[0074] To address the first drawback mentioned above, an extraction component 60 is installed inside the layered cavity 23. The extraction component 60 includes a guide rod 24 fixed to the bottom of the layered cavity 23, an extraction block 27 slidably mounted on the guide rod 24, a connecting cavity 31 provided inside the extraction block 27, at least one extraction slot 28 opened at the top and bottom of the extraction block 27, at least one extraction tube 29 connecting the connecting cavity 31 and the layered cavity 23 is fixedly installed in the extraction slot 28, and a blocking switching component is also installed on the extraction block 27. A first extraction head 37 is fixedly connected to one side of the connecting cavity 31, one end of a connecting hose 25 is fixedly connected to the first extraction head 37, and the other end of the connecting hose 25 is fixedly connected to a second extraction head 26, which is fixedly installed on the layered bucket 16.

[0075] The blocking and switching assembly is used to switch whether the upper extraction tube 29 or the lower extraction tube 29 is blocked. The density of the extraction block 27 should be between the two liquids in the above-mentioned layering. In this way, under the action of buoyancy, the middle position of the extraction block 27 can always be maintained at the separation position between the two liquids in the above-mentioned layering. At this time, the liquid can be extracted from the second extraction head 26 from the upper extraction tube 29 or from the lower extraction tube 29 (depending on whether the blocking assembly blocks the upper extraction tube 29 or the lower extraction tube 29). Thus, regardless of the amount of liquid in the layering chamber 23, the required layered liquid can be continuously extracted, which is convenient for subsequent operations and has high efficiency.

[0076] The blocking and switching assembly includes a connecting plate 32 slidably disposed within the communicating cavity 31. Blocking heads 33 are fixed to both the upper and lower surfaces of the connecting plate 32. The upper blocking head 33 is used to block the upper extraction tube 29, and the lower blocking head 33 is used to block the lower extraction tube 29. A receiving groove 34 is formed on the extraction block 27, and a handle 35 is provided within the receiving groove 34. A threaded rod 36 is fixed to the bottom of the connecting hose 25. The threaded rod 36 is threadedly connected to a threaded hole formed on the extraction block 27. The bottom of the threaded rod 36 is rotatably mounted on the connecting plate 32. By rotating the handle 35, the threaded rod 36 is driven to descend, causing the connecting plate 32 to descend, so that the upper blocking head 33 no longer blocks the upper extraction tube 29, and the lower blocking head 33 blocks the extraction tube 29.

[0077] Furthermore, since the liquids to be extracted have different densities, a weight can be placed on the guide rod 24 to press down the extraction block 27, so that the combined density of the extraction block 27 and the weight can be between the upper and lower liquid layers.

[0078] To address the second drawback, the applicant fixedly installed at least one fixing plate 40 on the extraction block 27, and fixed a first connecting pipe 39 on the fixing plate 40. A second connecting pipe 38 connecting the layering chamber 23 and the mixing tank 14 was fixedly installed on the bottom wall of the layering chamber 23. A connecting hose (not shown) was fixed between the second connecting pipe 38 and the first connecting pipe 39. When the extraction block 27 rises, the hose is straightened; when the extraction block 27 descends, the hose bends between the extraction block 27 and the layering tank 16. The first connecting pipe 39 is also located at the separation point between the two liquids in the layering process. In this way, newly introduced liquids can be quickly layered with minimal impact on the original layered liquids.

[0079] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand and implement the present invention. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. An extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials, characterized in that: Includes the following steps: (1) The extractant and liquid alkali are saponified to obtain an organic phase; The extractant, P204, is used in combination with solvent oil, with the concentration of P204 ranging from 5% to 50%, and the remainder being solvent oil. The saponification rate of the mixture of extractant and liquid alkali is ≤23.7%. (2) After mixing the saponified organic phase in step (1) with the P204 pre-extraction liquid (nickel-cobalt feed liquid containing manganese), the new type of extractor is used for extraction to obtain the reversed liquid and the P204 extraction residue; the pH is controlled at 0-4.5 during the extraction process, and the O / A ratio after extraction is 0.415-5.2; (3) The extractant after extraction in step (2) is processed by washing, reverse impurities, reverse iron removal and water washing in sequence; The detergent used in the washing process is 1%~5% sulfuric acid, and the washing liquid is returned to step (2) above for re-extraction. The reverse impurity process involves impuritrifying the washed extractant using 6-12% hydrochloric acid. The resulting solution is a calcium-containing manganese chloride solution, where manganese accounts for 5-20% of the total manganese content. The anti-iron process involves removing iron from the impurity-treated extractant, and the anti-iron agent used is 18% hydrochloric acid. The water washing process involves washing the extractant after antiferrolysis with water. The water washing agent used is wash water. The water washing liquid is then used in anti-mixing. The P204 extractant after washing can be recycled back to step (1) for reuse. In addition, the P204 extraction residue generated in step (2) above needs to be treated. The specific process includes the following steps: ① The extractant and liquid alkali are saponified to obtain an organic phase; P204 extractant is used in combination with solvent oil, wherein the concentration of P204 is 20%-25%, and the remainder is solvent oil; the saponification rate of the mixture of extractant and liquid alkali is ≤60%; ② The organic phase obtained in step ① is mixed with the P204 extractant residue and then extracted using a new type of extractor. After extraction, manganese-containing extractant and P204 manganese extractant residue are obtained. ③ The manganese-containing extractant from step ② is processed sequentially through washing, anti-manganese, anti-iron, and water washing steps; The washing agent used in the washing process is sulfuric acid, and the washing liquid is returned to step ② above for re-extraction. The manganese-removing process involves removing manganese from a manganese-containing extractant. The resulting solution is a crude manganese sulfate solution, and the manganese-removing agent used is 20% sulfuric acid. Among them, anti-iron is to remove iron from the extractant after anti-manganese, and the anti-iron agent used is 18% hydrochloric acid; The water washing process involves washing the extractant after antiferrolysis with water. The washing agent used is wash water. The washed liquid is then incorporated into the anti-hybridization process. The P204 extractant after washing can be recycled back to step ① for reuse.

2. The extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials according to claim 1, characterized in that: There is also a process for removing copper from the manganese sulfate produced in step ③ above, the process flow of which includes the following steps:

1. Remove copper from the copper sulfate in step ③ above using a copper-removing agent; 2. Solid-liquid separation treatment is carried out to obtain copper slag and battery-grade manganese sulfate.

3. The extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials according to claim 1, characterized in that: The concentration of liquid alkali in step (1) and step ① is controlled at 15-35% to facilitate control of the saponification rate.

4. The extraction technology for low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials according to claim 1, characterized in that: By controlling process parameters and procedures, complete separation of calcium and manganese can be achieved with low manganese loss.

5. A novel extractor for the low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials as described in claim 1, characterized in that: Includes a base (10), on which a base plate (13) is fixedly connected by at least two vertical rods (11), a mixing box (14) is fixed on the base plate (13), a mixing component (50) inserted into the mixing box (14) is installed on the base plate (13), a first input pipe (20) and a second input pipe (21) are fixedly connected to the bottom of the base plate (13), a layering bucket (16) is fixed on the top of the mixing box (14), a cover plate (18) is fixed on the top of the layering bucket (16), a layering cavity (23) is provided inside the layering bucket (16), and a first discharge structure (15) and a second discharge structure (17) are installed on the layering bucket (16) in connection with the layering cavity (23). In the above structure, the liquid to be extracted is input from the first input pipe (20) by an external water pump, and the extractant is input from the second input pipe (21). The liquid to be extracted and the extractant are fully mixed by the mixing component (50). The mixed liquid enters the layered chamber (23) for layered extraction. The liquid with higher relative density is discharged from the first discharge structure (15), and the liquid with lower relative density is discharged from the second discharge structure (17). However, the first drawback of the above structure is that when dealing with multiple different extraction needs, it is difficult to control the opening and closing of the first discharge structure (15) and the second discharge structure (17), making it difficult to automatically discharge liquids with different densities and the rate is difficult to control. The second drawback is that with the continuous introduction of the liquid to be extracted and the extractant, the newly introduced liquid is more likely to disturb the already stratified liquids of different densities, thus affecting the discharge. An extraction assembly (60) is installed inside the layered cavity (23). The extraction assembly (60) includes a guide rod (24) fixed to the bottom of the layered cavity (23). An extraction block (27) is slidably installed on the guide rod (24). A connecting cavity (31) is provided inside the extraction block (27). At least one extraction groove (28) is opened at the top and bottom of the extraction block (27). At least one extraction tube (29) connecting the connecting cavity (31) and the layered cavity (23) is fixedly installed in the extraction groove (28). A blocking switching assembly is also installed on the extraction block (27). A first extraction head (37) is fixedly connected to one side of the connecting cavity (31). One end of a connecting hose (25) is fixedly connected to the first extraction head (37). The other end of the connecting hose (25) is fixedly connected to... The second extraction head (26) is fixedly installed on the layered tank (16). The blocking switching component is used to switch the upper extraction tube (29) or the lower extraction tube (29) to be blocked. The density of the extraction block (27) should be between the two liquids in the above layer. In this way, under the action of buoyancy, the middle position of the extraction block (27) can always be maintained at the separation position between the two liquids in the above layer. At this time, the liquid can be extracted from the second extraction head (26) by continuously extracting the upper liquid from the upper extraction tube (29) or continuously extracting the lower liquid from the lower extraction tube (29). Thus, regardless of the amount of liquid in the layered chamber (23), the required layered liquid can be continuously extracted, which is convenient for subsequent operations and has high efficiency.

6. The novel extractor according to claim 5, characterized in that: The mixing assembly (50) includes a motor (12) fixed to the bottom of the base plate (13), the motor shaft of the motor (12) being inserted into the mixing box (14) and fixed with at least one stirring blade (22).

7. The novel extractor according to claim 5, characterized in that: The blocking and switching assembly includes a connecting plate (32) slidably disposed within the communicating cavity (31). Both the upper and lower surfaces of the connecting plate (32) are fixed with blocking heads (33). The upper blocking head (33) is used to block the upper extraction tube (29), and the lower blocking head (33) is used to block the lower extraction tube (29). A storage groove (34) is provided on the extraction block (27), and a handle (35) is provided within the storage groove (34). The bottom of the connecting hose (25) is fixed. A threaded rod (36) is threadedly connected to a threaded hole on the extraction block (27). The bottom of the threaded rod (36) is rotatably mounted on the connecting plate (32). By rotating the handle (35), the threaded rod (36) is driven to descend. The threaded rod (36) drives the connecting plate (32) to descend, so that the upper sealing head (33) no longer blocks the upper extraction tube (29), and the lower sealing head (33) blocks the extraction tube (29).

8. The novel extractor according to claim 7, characterized in that: Since the liquids to be extracted have different densities, a weight can be placed on the guide rod (24) to press down the extraction block (27), so that the combined density of the extraction block (27) and the weight can be between the upper and lower liquid layers.

9. The novel extractor according to claim 5, characterized in that: To address the second drawback, at least one fixing plate (40) is fixedly installed on the extraction block (27), and a first connecting pipe (39) is fixed on the fixing plate (40). A second connecting pipe (38) connecting the layering chamber (23) and the mixing tank (14) is fixedly installed on the bottom wall of the layering chamber (23). A connecting hose is fixed between the second connecting pipe (38) and the first connecting pipe (39). When the extraction block (27) rises, the hose will be straightened. When the extraction block (27) falls, the hose will bend between the extraction block (27) and the layering tank (16). The first connecting pipe (39) is also located at the separation point between the two liquids in the above layering. In this way, the newly introduced liquid can be quickly layered with little impact on the original layered liquid.

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