Extraction technology for recycling battery-grade manganese sulfate from manganese-containing nickel-cobalt raw material at low cost

Abstract

The extraction technology for low-cost recovery of battery-grade manganese sulfate from a manganese-containing nickel-cobalt raw material comprises the following steps: (1) saponifying an extraction agent and liquid caustic soda to obtain an organic phase; a P204 extraction agent and solvent oil are mixed for use, the concentration of P204 is 5%-50%, and the balance is the solvent oil; the extraction agent and the liquid caustic soda are mixed and saponified, and the saponification rate is smaller than or equal to 23.7%; (2) mixing the saponified organic phase in the step (1) with a P204 pre-extraction solution (a manganese-containing nickel-cobalt raw material solution), and performing extraction operation by adopting a novel extractor to obtain an impurity solution and a P204 impurity extraction raffinate with the calcium content of less than or equal to 1ppm; the PH in the extraction process is controlled to be 0-4.5, and the phase ratio O / A after extraction is 0.415-5.2; and (3) sequentially carrying out extraction, washing, manganese removal, iron removal and water washing on the impurity extraction raffinate in the step (2) to finish treatment. The process is used for producing the battery-grade manganese sulfate, manganese and impurities are not enriched in a manganese enrichment liquid firstly, and then a C272 extraction agent is used for realizing manganese-calcium separation, so that the cost for producing the manganese enrichment liquid is saved, the use of the expensive C272 extraction agent is not needed, the whole process is optimized, and the production cost is greatly reduced.

Description

Technical Field

[0001] The invention relates to the technical field of manganese sulfate recovery, and in particular to an extraction technology for recovering battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials at low cost. Background Art

[0002] Manganese sulfate is an important raw material for the production of ternary lithium batteries, and has very strict requirements on the content of various impurities. In the process of recycling retired ternary lithium batteries or nickel-cobalt raw materials containing manganese, since the value of manganese is relatively low compared to nickel and cobalt, and the recycling is more difficult, many manufacturers choose to make manganese into slag, which wastes its own value and creates the possibility of secondary pollution.

[0003] However, the existing extraction process of a few manufacturers that recycle manganese is generally complicated, which leads to more equipment investment and production costs. Therefore, the applicant hopes to develop a more cost-saving process with fewer steps and guaranteed quality of manganese sulfate produced. Summary of the invention

[0004] The purpose of the present invention is to provide an extraction technology for recovering battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials at low cost to solve the above problems.

[0005] The above technical objectives of the present invention are achieved through the following technical solutions: an extraction technology for recovering battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials at low cost, comprising the following steps:

[0006] (1) saponifying the extractant and liquid alkali to obtain an organic phase; using a P204 extractant mixed with solvent oil, wherein the concentration of P204 is 5%-50%, and the rest is solvent oil; the mixed saponification of the extractant and liquid alkali has a saponification rate of ≤23.7%;

[0007] (2) the organic phase after saponification in step (1) is mixed with the P204 pre-extraction solution (nickel-cobalt raw material solution containing manganese) and then subjected to extraction using a novel extractor to obtain an anti-impurity solution and a P204 impurity extraction raffinate; during the extraction process, the pH is controlled at 0-4.5, and the post-extraction phase ratio O / A is 0.415-5.2;

[0008] (3) subjecting the extracted agent in step (2) to the steps of washing, de-doping, de-ironization and water washing in sequence to complete the treatment;

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

[0010] The de-doping process is to de-dope the extractant after washing, and the de-doping agent used is 6-12% hydrochloric acid. The de-doping liquid after de-doping is a manganese chloride solution containing calcium, and the manganese here accounts for 5-20% of the total manganese;

[0011] Among them, the anti-ferroximation process is to carry out anti-ferroximation on the extractant after anti-doping, and the anti-ferroximation agent used is 18% hydrochloric acid;

[0012] The water washing process is to wash the extractant after the anti-ironization, and the water washing agent used is washing water. The water washing liquid is incorporated into the anti-impurity for use, and the P204 extractant after washing can be refluxed to step (1) for reuse;

[0013] In addition, the P204 impurity extract raffinate produced in the above step (2) is treated, and the process flow specifically includes the following steps:

[0014] ① The extractant and liquid alkali are saponified to obtain an organic phase; P204 extractant is mixed with solvent oil, wherein the concentration of P204 is 20%-25%, and the rest is solvent oil; the mixed saponification of the extractant and liquid alkali has a saponification rate of ≤60%;

[0015] ② The organic phase obtained in step ① is mixed with the P204 impurity extraction raffinate and then extracted using a novel extractor to obtain a manganese-containing extractant and a P204 manganese extraction raffinate;

[0016] ③ The manganese-containing extractant in step ② is subjected to washing, demanganese removal, deiron removal and water washing steps in sequence to complete the treatment;

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

[0018] The demanganese process is to demanganese the manganese-containing extractant, and the demanganese solution is a crude manganese sulfate solution, and the demanganese agent used is 20% sulfuric acid;

[0019] Among them, the anti-ferromagnetic agent is to carry out the anti-ferromagnetic agent on the extractant after the manganese removal, and the anti-ferromagnetic agent used is 18% hydrochloric acid;

[0020] Among them, the water washing process is to wash the extractant after the anti-iron, the washing agent used is washing water, the washed liquid is incorporated into the anti-impure use, and the P204 extractant after washing can be refluxed to step ① for reuse.

[0021] 2. The extraction technology for recovering battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials at low cost according to claim 1, characterized in that: there is also a process for removing copper from the manganese sulfate produced in the above step ③, and the process flow comprises the following steps:

[0022] 1. The copper sulfate in the above step ③ is subjected to copper removal treatment using a copper removal agent;

[0023] 2. Carry out solid-liquid separation treatment to obtain copper slag and battery-grade manganese sulfate.

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

[0025] Preferably, by controlling the process parameters and the flow, the complete separation of calcium and manganese is achieved under the premise of low manganese loss.

[0026] Preferably, the novel extractor comprises a base, the base is fixedly connected to a bottom plate via at least two vertical rods, a mixing box is fixed on the bottom plate, a mixing assembly inserted into the mixing box is installed on the bottom plate, a No. 1 input pipe and a No. 2 input pipe are fixedly connected at the bottom of the bottom plate, a stratification barrel is fixed on the top of the mixing box, a cover plate is fixed on the top of the stratification barrel, a stratification chamber is provided in the stratification barrel, and a No. 1 discharge structure and a No. 2 discharge structure are installed on the stratification barrel in communication with the stratification chamber;

[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 through the mixing component. The mixed liquid enters the stratification chamber for stratified extraction. The liquid with a relatively high density is discharged from the first discharge structure, and the liquid with a relatively low density is discharged from the second discharge structure.

[0028] However, the first disadvantage of the above structure is that when dealing with multiple different extraction requirements like the present application, it is difficult to control the opening and closing of the first discharge structure and the second discharge structure, and it is difficult to automatically discharge liquids with different densities, and the rate is difficult to control;

[0029] The second disadvantage is that in the case of continuous introduction of the liquid to be extracted and the extractant as in the present application, the newly introduced liquid is more likely to disturb the already stratified liquids of different densities, thereby affecting the discharge.

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

[0031] Preferably, an extraction component is installed in the stratified chamber, the extraction component includes a guide rod fixed to the bottom of the stratified chamber, an extraction block is slidably installed on the guide rod, a connecting chamber is arranged in the extraction block, at least one extraction groove is provided at the top and the bottom of the extraction block, at least one extraction tube connecting the connecting chamber and the stratified chamber is fixedly installed in the extraction groove, a blocking switching component is also installed on the extraction block, a No. 1 extraction head is fixedly connected to one side of the connecting chamber, one end of a connecting hose is fixedly connected to the No. 1 extraction head, and the other end of the connecting hose is fixedly connected to the No. 2 extraction head, and the No. 2 extraction head is fixedly installed on the stratified barrel; the blocking switching component The switching assembly is used to switch whether the extraction tube on the upper side is blocked or the extraction tube on the lower side is blocked. The density of the extraction block should be between the two layered liquids mentioned above. 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 layered liquids mentioned above. At this time, the liquid extracted from the No. 2 extraction head can be extracted from the upper layer of liquid from the upper extraction tube or from the lower layer of liquid from the lower extraction tube (depending on whether the blocking assembly blocks the upper extraction tube or the lower extraction tube), so that regardless of the amount of liquid in the layered cavity, the required layered liquid can be continuously extracted, which is convenient for subsequent operations and very efficient.

[0032] Preferably, the blocking switching assembly includes a connecting plate slidably arranged in the connecting cavity, and blocking heads are fixed on the upper and lower surfaces of the connecting plate, the blocking head on the upper side is used to block the extraction tube on the upper side, and the blocking head on the lower side is used to block the extraction tube on the lower side, a receiving groove is provided on the extraction block, and a handle is provided in the storage groove, a threaded rod is fixed at the bottom of the connecting hose, and the threaded rod is threadedly connected to the threaded hole provided on the extraction block, and the bottom of the threaded rod is rotatably mounted on the connecting plate, and the threaded rod is driven to descend by rotating the handle, and the threaded rod drives the connecting plate to descend, so that the blocking head on the upper side no longer blocks the extraction tube on the upper side, and the blocking head on the lower side realizes the blocking of the extraction tube.

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

[0034] Preferably, in order to solve the second drawback, at least one fixed plate is fixedly installed on the extraction block, a No. 1 connecting pipe is fixed on the fixed plate, a No. 2 connecting pipe connecting the stratification chamber and the mixing box is fixedly installed on the bottom wall of the stratification chamber, and a connecting hose is fixed between the No. 2 connecting pipe and the No. 1 connecting pipe. When the extraction block rises, the hose will be straightened, and when the extraction block descends, the hose will bend between the extraction block and the stratification barrel. The position of the No. 1 connecting pipe is also at the separation position between the two stratified liquids mentioned above. In this way, the newly introduced liquid can be quickly stratified, and the impact on the original stratified liquid is very small.

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

[0036] 1. This process is used to produce battery-grade manganese sulfate. Manganese and impurities are not first enriched in a manganese-enriched solution, which not only saves the cost of producing manganese-enriched solution, but also optimizes the overall process and greatly improves production efficiency.

[0037] 2. The present invention optimizes the process and the ratio of related material formulas, so that only P204 extraction agent is needed to complete the related extraction operations, which greatly saves costs.

[0038] 3. During the entire process, manganese is extracted once less than in the traditional process, which can save auxiliary material costs and reduce the generation of wastewater.

[0039] 4. The novel extractor of the present invention is equipped with an extraction component in the stratified chamber, the extraction component includes a guide rod fixed at the bottom of the stratified chamber, an extraction block is slidably installed on the guide rod, a connecting chamber is arranged in the extraction block, at least one extraction groove is provided at the top and bottom of the extraction block, at least one extraction tube connecting the connecting chamber and the stratified chamber is fixedly installed in the extraction groove, a blocking switching component is also installed on the extraction block, a No. 1 extraction head is fixedly connected to one side of the connecting chamber, one end of a connecting hose is fixedly connected to the No. 1 extraction head, the other end of the connecting hose is fixedly connected to the No. 2 extraction head, and the No. 2 extraction head is fixedly installed on the stratified barrel; the blocking switching component It is used to switch whether the upper extraction tube is blocked or the lower extraction tube is blocked. The density of the extraction block should be between the two layered liquids mentioned above. 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 layered liquids mentioned above. At this time, the liquid extracted from the No. 2 extraction head can be extracted from the upper extraction tube or the lower extraction tube (depending on whether the blocking component blocks the upper extraction tube or the lower extraction tube). Therefore, regardless of the amount of liquid in the layered cavity, the required layered liquid can be continuously extracted, which is convenient for subsequent operations and very efficient.

[0040] 5. At least one fixed plate is fixedly installed on the extraction block, a No. 1 connecting pipe is fixed on the fixed plate, a No. 2 connecting pipe connecting the stratification chamber and the mixing box is fixedly installed on the bottom wall of the stratification chamber, and a connecting hose (not shown) is fixed between the No. 2 connecting pipe and the No. 1 connecting pipe. When the extraction block rises, the hose will be straightened, and when the extraction block descends, the hose will bend between the extraction block and the stratification barrel. The position of the No. 1 connecting pipe is also at the separation position between the two stratified liquids mentioned above. In this way, the newly introduced liquid can be quickly stratified, with little impact on the original stratified liquid, further improving the extraction efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

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

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

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

[0045] Figure 4 yes Figure 3 The enlarged schematic diagram at A in the middle;

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

[0047] Figure 6 It is a schematic diagram of the appearance of the novel extractor after removing the cover plate according to an embodiment of the present invention.

[0048] In the figure: 10, base; 11, vertical rod; 12, motor; 13, bottom plate; 14, mixing box; 15, discharge structure No. 1; 16, stratification barrel; 17, discharge structure No. 2; 18, cover plate; 20, input pipe No. 1; 21, input pipe No. 2; 22, stirring blade; 23, stratification chamber; 24, guide rod; 25, connecting hose; 26, extraction head No. 2; 27, extraction block; 28, extraction slot; 29, extraction pipe; 31, connecting chamber; 32, connecting plate; 33, plugging head; 34, storage slot; 35, handle; 36, threaded rod; 37, extraction head No. 1; 38, connecting pipe No. 2; 39, connecting pipe No. 1; 40, fixing plate; 50, mixing assembly; 60, extraction assembly. DETAILED DESCRIPTION

[0049] Combined with Figure 1-Figure 6 The extraction technology for recovering battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials at low cost comprises the following steps:

[0050] (1) The extractant and the 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 mixed with solvent oil, wherein the concentration of P204 is 5%-50% and the rest is solvent oil; the extractant and the liquid alkali are mixed and saponified, and the saponification rate is ≤23.7%; wherein the concentration of the liquid alkali is controlled at 15%-35.

[0051] (2) The organic phase after saponification in step (1) is mixed with P204 pre-extraction liquid (nickel-cobalt raw material liquid containing manganese) and then extracted using a new extractor to obtain an impurity liquid and a P204 impure extraction raffinate; in order to optimize the extraction effect, the new extractor is a special product of our company; during the extraction process, the pH is controlled at 0-4.5, and the post-extraction ratio O / A 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 impure extraction raffinate).

[0052] (3) subjecting the extracted agent in step (2) to the steps of washing, de-doping, de-ironization and water washing in sequence to complete the treatment;

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

[0054] The de-doping process is to de-dope the extractant after washing, and the de-doping agent used is 6-12% hydrochloric acid. The de-doping liquid is collected separately. The de-doping liquid is a manganese chloride solution containing calcium, and the manganese here accounts for 5-20% of the total manganese.

[0055] Among them, the anti-ferroximation process is to carry out anti-ferroximation on the extractant after anti-doping, and the anti-ferroximation agent used is 18% hydrochloric acid, and the liquid after anti-ferroximation is collected separately;

[0056] Among them, the water washing process is to wash the extractant after the anti-ironization, and the water washing agent used is washing water. After washing, it is merged into the impurity section for treatment, and finally the blank P204 extractant can be refluxed to step (1) for reuse.

[0057] In addition, the P204 impurity extract raffinate produced in the above step (2) is treated, and the process flow specifically includes the following steps:

[0058] 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 mixed with solvent oil, wherein the concentration of P204 is 20%-25%, and the rest is solvent oil; the mixed saponification of the extractant and liquid alkali has a saponification rate of ≤60%; wherein the concentration of the liquid alkali is controlled at 15%-35.

[0059] ② The organic phase obtained in step ① is mixed with the P204 impurity extraction raffinate and then extracted using a new extractor to obtain a manganese-loaded extractant and a P204 manganese-extracted raffinate.

[0060] ③ The loaded manganese extractant in step ② is sequentially subjected to washing, demanganese, deiron and water washing steps to complete the treatment;

[0061] The detergent used in the washing process is sulfuric acid, and the separated liquid after washing is refluxed to the above step ② for re-extraction;

[0062] The demanganeseization process is to demanganize the extracted agent after washing, and the demanganeseization agent used is 20% sulfuric acid, and the demanganeseization liquid is crude manganese sulfate;

[0063] Among them, the anti-ferromagnetic process is to carry out anti-ferromagnetic treatment on the extractant after the manganese removal, and the anti-ferromagnetic agent used is 18% hydrochloric acid, and the liquid after the anti-ferromagnetic process is collected separately;

[0064] Among them, the water washing process is to wash the anti-iron extractant with water, and the water washing agent used is washing water. After washing, the water is incorporated into the anti-impurity, and the blank P204 extractant can be refluxed to step ① for reuse;

[0065] By controlling the process parameters and processes, the 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 the above step ③, and its process flow includes the following steps:

[0067] 1. The copper sulfate in the above step ③ is treated with a copper removal agent to remove copper.

[0068] 2. Carry out solid-liquid separation treatment to obtain copper slag and battery-grade manganese sulfate.

[0069] In addition, the novel extractor comprises a base 10, a bottom plate 13 fixedly connected to the base 10 by at least two vertical rods 11, a mixing box 14 fixed on the bottom plate 13, a mixing assembly 50 inserted into the mixing box 14 is installed on the bottom plate 13, a first input pipe 20 and a second input pipe 21 are fixedly connected at the bottom of the bottom plate 13, a stratification barrel 16 is fixed on the top of the mixing box 14, a cover plate 18 is fixed on the top of the stratification barrel 16, a stratification chamber 23 is provided in the stratification barrel 16, and a first discharge structure 15 and a second discharge structure 17 are installed on the stratification barrel 16 to communicate with the stratification chamber 23;

[0070] The mixing assembly 50 includes a motor 12 fixed to the bottom of the bottom plate 13, the motor shaft of the motor 12 is inserted into the mixing box 14 and fixed with at least one stirring blade 22;

[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 through the mixing assembly 50. The mixed liquid enters the stratification chamber 23 for stratified extraction. The liquid with a relatively high density is discharged from the first discharge structure 15, and the liquid with a relatively low 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 requirements like the present application, it is difficult to control the opening and closing of the first discharge structure 15 and the second discharge structure 17, and it is difficult to automatically discharge liquids with different densities, and the rate is difficult to control;

[0073] The second disadvantage is that in the case of continuous introduction of the liquid to be extracted and the extractant as in the present application, the newly introduced liquid is more likely to disturb the already stratified liquids of different densities, thereby affecting the discharge;

[0074] In order to deal with the first drawback mentioned above, an extraction component 60 is installed in the stratified chamber 23, and the extraction component 60 includes a guide rod 24 fixed at the bottom of the stratified chamber 23, an extraction block 27 is slidably installed on the guide rod 24, a connecting chamber 31 is arranged in the extraction block 27, at least one extraction groove 28 is provided at the top and bottom of the extraction block 27, at least one extraction pipe 29 connecting the connecting chamber 31 and the stratified chamber 23 is fixedly installed in the extraction groove 28, and a blocking switching component is also installed on the extraction block 27, and a No. 1 extraction head 37 is fixedly connected to one side of the connecting chamber 31, and one end of the connecting hose 25 is fixedly connected to the No. 1 extraction head 37, and the other end of the connecting hose 25 is fixedly connected to the No. 2 extraction head 26, and the No. 2 extraction head 26 is fixedly installed on the stratified barrel 16;

[0075] The blocking switching assembly is used to switch whether the upper extraction tube 29 is blocked or the lower extraction tube 29 is blocked. The density of the extraction block 27 should be between the two stratified liquids. In this way, under the action of buoyancy, the middle position of the extraction block 27 can be kept at the separation position between the two stratified liquids. At this time, the liquid extracted from the second extraction head 26 can be extracted 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). Therefore, regardless of the amount of liquid in the stratified chamber 23, the required stratified liquid can be continuously extracted, which is convenient for subsequent operations and very efficient.

[0076] The blocking switching assembly includes a connecting plate 32 slidably arranged in the connecting cavity 31, and blocking heads 33 are fixed on the upper and lower surfaces of the connecting plate 32. The blocking head 33 on the upper side is used to block the extraction tube 29 on the upper side, and the blocking head 33 on the lower side is used to block the extraction tube 29 on the lower side. A receiving groove 34 is provided on the extraction block 27, and a handle 35 is provided in the receiving groove 34. A threaded rod 36 is fixed at the bottom of the connecting hose 25, and the threaded rod 36 is threadedly connected to the threaded hole provided on the extraction block 27. The bottom of the threaded rod 36 is rotatably installed on the connecting plate 32. The threaded rod 36 is driven to descend by rotating the handle 35, and the threaded rod 36 drives the connecting plate 32 to descend, so that the blocking head 33 on the upper side no longer blocks the extraction tube 29 on the upper side, and the blocking head 33 on the lower side realizes the blocking of the extraction tube 29.

[0077] Furthermore, since the density of the liquid to be extracted is different, a weight can be put on the guide rod 24 to press the extraction block 27, so that the combined density of the extraction block 27 and the weight can be between the upper liquid and the lower liquid;

[0078] In order to solve the second drawback, the applicant fixedly installed at least one fixed plate 40 on the extraction block 27, and a No. 1 connecting pipe 39 was fixed on the fixed plate 40. A No. 2 connecting pipe 38 connecting the stratification chamber 23 and the mixing box 14 was fixedly installed on the bottom wall of the stratification chamber 23. A connecting hose (not shown) was fixed between the No. 2 connecting pipe 38 and the No. 1 connecting pipe 39. When the extraction block 27 rises, the hose will be straightened. When the extraction block 27 descends, the hose will bend between the extraction block 27 and the stratification barrel 16. The position of the No. 1 connecting pipe 39 is also at the separation position between the two stratified liquids mentioned above. In this way, the newly introduced liquid can be quickly stratified with little impact on the original stratified liquid.

[0079] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology in this field to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A low-cost extraction technology for recovering battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials, characterized in that: The following steps are involved: (1) saponifying the extractant and liquid alkali to obtain an organic phase; P204 extractant is mixed with solvent oil, wherein the concentration of P204 is 5%-50% and the rest is solvent oil; the mixed saponification of the extractant and liquid alkali has a saponification rate of ≤23.7%; (2) the organic phase after saponification in step (1) is mixed with the P204 pre-extraction solution (nickel-cobalt raw material solution containing manganese) and then subjected to extraction using a novel extractor to obtain an anti-impurity solution and a P204 impurity extraction raffinate; during the extraction process, the pH is controlled at 0-4.5, and the post-extraction phase ratio O / A is 0.415-5.2; (3) subjecting the extracted agent in step (2) to the steps of washing, de-doping, de-ironization and water washing in sequence to complete the treatment; The washing agent used in the washing process is 1% to 5% sulfuric acid, and the washed liquid is returned to the above step (2) for re-extraction; The de-doping process is to de-dope the extractant after washing, and the de-doping agent used is 6-12% hydrochloric acid. The de-doping liquid after de-doping is a manganese chloride solution containing calcium, and the manganese here accounts for 5-20% of the total manganese; Among them, the anti-ferroximation process is to carry out anti-ferroximation on the extractant after anti-doping, and the anti-ferroximation agent used is 18% hydrochloric acid; The water washing process is to wash the extractant after the anti-ironization, and the water washing agent used is washing water. The water washing liquid is incorporated into the anti-impurity for use, and the P204 extractant after washing can be refluxed to step (1) for reuse; In addition, the P204 impurity extract raffinate produced in the above step (2) is treated, and the process flow specifically includes the following steps: ① The extractant and liquid alkali are saponified to obtain an organic phase; P204 extractant is mixed with solvent oil, wherein the concentration of P204 is 20%-25%, and the rest is solvent oil; the mixed saponification of the extractant and liquid alkali has a saponification rate of ≤60%; ② The organic phase obtained in step ① is mixed with the P204 impurity extraction raffinate and then extracted using a novel extractor to obtain a manganese-containing extractant and a P204 manganese extraction raffinate; ③ The manganese-containing extractant in step ② is subjected to washing, demanganese removal, deiron removal and water washing steps in sequence to complete the treatment; The detergent used in the washing process is sulfuric acid, and the washed liquid is returned to the above step ② for re-extraction; The demanganese process is to demanganese the manganese-containing extractant, and the demanganese solution is a crude manganese sulfate solution, and the demanganese agent used is 20% sulfuric acid; Among them, the anti-ferromagnetic agent is to carry out the anti-ferromagnetic agent on the extractant after the manganese removal, and the anti-ferromagnetic agent used is 18% hydrochloric acid; Among them, the water washing process is to wash the extractant after the anti-ironization, and the water washing agent used is washing water. The liquid after washing is incorporated into the anti-impurity use, and the P204 extractant after washing can be returned to step ① for repeated use.

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

1. The copper sulfate in the above step ③ is subjected to copper removal treatment using a copper removal agent; 2. Carry out solid-liquid separation treatment to obtain copper slag and battery-grade manganese sulfate.

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

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

5. A novel extractor for the extraction technology of low-cost recovery of battery-grade manganese sulfate from manganese-containing nickel-cobalt raw materials as claimed in claim 1, characterized in that: The invention comprises a base (10), wherein the base (10) is fixedly connected to a bottom plate (13) via at least two vertical rods (11), a mixing box (14) is fixed on the bottom plate (13), a mixing assembly (50) inserted into the mixing box (14) is installed on the bottom plate (13), a first input pipe (20) and a second input pipe (21) are fixedly connected at the bottom of the bottom plate (13), a stratification barrel (16) is fixed on the top of the mixing box (14), a cover plate (18) is fixed on the top of the stratification barrel (16), a stratification chamber (23) is provided in the stratification barrel (16), and a first discharge structure (15) and a second discharge structure (17) are installed on the stratification barrel (16) in communication with the stratification chamber (23); 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 through the mixing component (50). The mixed liquid enters the stratification chamber (23) for stratified extraction. The liquid with a relatively high density is discharged from the first discharge structure (15), and the liquid with a relatively low density is discharged from the second discharge structure (17). However, the first drawback of the above structure is that, when dealing with such multiple extraction requirements, it is difficult to control the opening and closing of the first discharge structure (15) and the second discharge structure (17), and it is difficult to automatically discharge liquids of different densities, and the rate is difficult to control; The second disadvantage is that when 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; An extraction assembly (60) is installed in the stratified chamber (23), the extraction assembly (60) comprising a guide rod (24) fixed at the bottom of the stratified chamber (23), an extraction block (27) slidably installed on the guide rod (24), a connecting chamber (31) is arranged in the extraction block (27), at least one extraction groove (28) is provided at the top and the bottom of the extraction block (27), at least one extraction pipe (29) connecting the connecting chamber (31) and the stratified chamber (23) is fixedly installed in the extraction groove (28), a blocking switching assembly is also installed on the extraction block (27), one side of the connecting chamber (31) is fixedly connected to a No. 1 extraction head (37), one end of the No. 1 extraction head (37) is fixedly connected to a connecting hose (25), and the other end of the connecting hose (25) is fixedly connected to a connecting hose (25). The second extraction head (26) is connected to the second extraction head (26), and the second extraction head (26) is fixedly mounted on the stratification barrel (16); the blocking switching assembly is used to switch the upper extraction pipe (29) to be blocked or the lower extraction pipe (29) to be blocked. The density of the extraction block (27) should be between the two stratified liquids. In this way, under the action of buoyancy, the middle position of the extraction block (27) can be kept at the separation position between the two stratified liquids. At this time, the liquid extracted from the second extraction head (26) can be extracted from the upper extraction pipe (29) or the lower extraction pipe (29). Therefore, regardless of the amount of liquid in the stratification chamber (23), the required stratified liquid can be continuously extracted, which is convenient for subsequent operations and very efficient.

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

7. The novel extractor according to claim 5 is characterized in that: The blocking switching assembly comprises a connecting plate (32) slidably arranged in the connecting cavity (31), and blocking heads (33) are fixed on the upper and lower surfaces of the connecting plate (32), the blocking head (33) on the upper side is used to block the extraction tube (29) on the upper side, and the blocking head (33) on the lower side is used to block the extraction tube (29) on the lower side, and a receiving groove (34) is provided on the extraction block (27), and a handle (35) is provided in the receiving groove (34), and the bottom of the connecting hose (25) is fixed A threaded rod (36), wherein the threaded rod (36) is threadedly connected to a threaded hole provided on the extraction block (27), and the bottom of the threaded rod (36) is rotatably mounted on the connecting plate (32). The threaded rod (36) is driven downward by rotating the handle (35), and the threaded rod (36) drives the connecting plate (32) downward, 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 is characterized in that: Since the density of the liquid to be extracted is different, a weight can be put on the guide rod (24) to press the extraction block (27), so that the combined density of the extraction block (27) and the weight can be between the upper liquid and the lower liquid.

9. The novel extractor according to claim 5 is characterized in that: In order to solve the second drawback, at least one fixing plate (40) is fixedly mounted on the extraction block (27), a No. 1 connecting pipe (39) is fixedly mounted on the fixing plate (40), a No. 2 connecting pipe (38) connecting the stratification chamber (23) and the mixing box (14) is fixedly mounted on the bottom wall of the stratification chamber (23), a connecting hose is fixedly mounted between the No. 2 connecting pipe (38) and the No. 1 connecting pipe (39), when the extraction block (27) rises, the hose will be straightened, when the extraction block (27) falls, the hose will be bent between the extraction block (27) and the stratification barrel (16), the No. 1 connecting pipe (39) is also located at the separation position between the two stratified liquids, so that the newly introduced liquid can be quickly stratified, and the original stratified liquid is little affected.

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