CN111533174B - Method for removing zinc, calcium and magnesium ions in manganese sulfate solution by synergistic extraction method - Google Patents
Method for removing zinc, calcium and magnesium ions in manganese sulfate solution by synergistic extraction method Download PDFInfo
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Abstract
The invention discloses a method for removing zinc, calcium and magnesium ions in a manganese sulfate solution by a synergistic extraction method, which belongs to the technical field of hydrometallurgy and has the advantages of low raw material cost, large reduction of alkali consumption, simple process, short flow, high production efficiency, clean production process, no wastewater discharge and the like.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for removing zinc ions, calcium ions and magnesium ions in a manganese sulfate solution by adopting a synergistic extraction method, so as to prepare high-purity battery-grade manganese sulfate.
Background
The intermediate smelted product of the wet process is used as a raw material for producing nickel salt and cobalt salt, because the raw material contains a large amount of manganese, most enterprises treat the manganese in the raw material as crude manganese sulfate or manganese slag due to technical limitation at present, and some enterprises adopt a precipitation method, an extraction method and a precipitation and extraction mixing method to prepare high-purity manganese sulfate in production, but the method has the following problems that the precipitation method mostly adopts fluoride to remove calcium and magnesium and then carries out subsequent treatment, and has the defects of long process line, residual fluorine ions and large equipment loss; the extraction method adopts organic phosphoric acid extractant full extraction or carboxylic acid extractant to separate manganese, but the cost is higher in actual production, calcium and manganese cannot be completely separated, the water solubility of the extractant is high, and the extractant cannot be recycled for a long time.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for removing zinc, calcium and magnesium ions in the manganese sulfate solution by adopting the synergistic extraction method is provided, so that the high-purity battery-grade manganese sulfate is prepared, and the method has the advantages of simple process, no damage to equipment, no pollution in the production process, high production efficiency and low cost.
The invention adopts the following scheme: the method for removing zinc, calcium and magnesium ions in a manganese sulfate solution by a synergistic extraction method is characterized by comprising the following steps of:
step one, according to the weight ratio of di (2-ethylhexyl) phosphate, tributyl phosphate and dinonyl naphthalene sulfonic acid being 5: (1-2): (3-4) preparing an extracting agent, mixing the prepared extracting agent and sulfonated kerosene in proportion, and preparing an organic phase with the concentration of the extracting agent being 20% -30%; taking a crude manganese sulfate solution as a water phase;
step two, adding the organic phase prepared in the step one into a sodium hydroxide solution with the concentration of 30%, stirring, and carrying out saponification reaction, wherein the saponification rate is controlled to be 30-40%;
step three, adding 93 percent sulfuric acid into pure water, uniformly stirring and preparing the mixture to be used as a water phase for a regeneration section of an extraction system, wherein the acidity of the water phase is 140-160 g/L;
step four, mixing the saponified organic phase and the manganese sulfate liquid in the step two for reaction to prepare manganese soap, and performing manganese-sodium displacement reaction, wherein the zinc content in the manganese sulfate liquid is less than 0.005g/L, the calcium content is less than 0.003g/L, the magnesium content is less than 0.003g/L, the manganese content is 30 g/L-50 g/L, the reaction temperature is 30-40 ℃, and the phase ratio of the organic phase to the aqueous phase is 1:1, stirring at the speed of 200-300 rpm for 2.5 minutes, discharging an aqueous phase of a sodium sulfate solution, and feeding an organic phase into the fifth step;
step five: and (3) feeding the organic phase and the crude manganese sulfate solution, namely the water phase in the first step, into an extraction section extraction box for extraction and impurity removal, wherein the reaction temperature is 35-40 ℃, and the phase ratio is organic phase/water phase (O/A) = (1-2): 1, stirring at the speed of 200-300 r/min, mixing and reacting for 3 min, wherein the discharged aqueous phase is a purified and impurity-removed manganese sulfate solution, and the organic phase enters the sixth step;
wherein the manganese content in the manganese sulfate solution after purification and impurity removal is 90 g/L-110 g/L, the iron content is less than 0.001g/L, the zinc content is less than 0.002g/L, the calcium content is less than 0.01g/L, the magnesium content is less than 0.005g/L, the nickel content is less than 0.005g/L, and the sodium content is less than 0.01g/L;
step six: and (4) feeding the organic phase in the step five and the water phase in the step three into a regeneration section extraction box for regeneration and acid washing, wherein the reaction temperature is 30-40 ℃, and the ratio of the organic phase to the water phase (O/A) =5:1, stirring at 200-300 rpm, mixing and reacting for 4 minutes, discharging an aqueous phase of zinc sulfate solution, and recycling an organic phase.
Further, the crude manganese sulfate solution is a by-product produced in the production of nickel sulfate or cobalt sulfate.
As a preferred technical scheme of the invention, the volume ratio of the extracting agent to the sulfonated kerosene in the first step is 3:7, the extracting agent is prepared from di (2-ethylhexyl) phosphate, tributyl phosphate and dinonylnaphthalene sulfonic acid according to the weight ratio of 5:1.5:3.5 in proportion.
Wherein, the crude manganese sulfate solution in the step one, namely the zinc content in the water phase is 8-10 g/L, the calcium content is 0.2-0.3 g/L, and the magnesium content is less than or equal to 0.005g/L.
As a preferred technical scheme of the invention, four-stage countercurrent extraction is adopted in the four-stage manganese soap section.
As a preferred technical scheme of the invention, eight-stage countercurrent extraction is adopted in the extraction section in the fifth step.
As a preferred technical scheme of the invention, five-stage countercurrent extraction is adopted in the regeneration section in the sixth step.
Through the design scheme, the invention can bring the following beneficial effects: the whole process adopts a chemical precipitation method, no waste water and waste residue are generated, and the zinc in the raw materials is recovered; the separation effect of manganese and calcium is good, the organic phase can be recycled, and the water solubility is low, so that the environmental pollution can not be caused; co-extraction and repeated extraction are not generated, the consumption of sodium hydroxide is low, energy and auxiliary materials are saved, and the quality of products is improved. Compared with the prior art, the technical scheme of the invention has wider application prospect.
Drawings
The invention is further described in the following detailed description in conjunction with the drawings in which:
FIG. 1 is a flow chart of a method for producing high-purity battery-grade manganese sulfate by synergistically extracting and purifying zinc, calcium and magnesium ions in manganese sulfate according to an embodiment of the invention.
Detailed Description
To more clearly illustrate the present invention, the present invention is further illustrated below in conjunction with a specific embodiment and fig. 1, as will be understood by those skilled in the art. The following detailed description is illustrative and not restrictive, and should not be taken as limiting the scope of the invention, and nothing in this specification applies to the prior art, with the solid arrows in fig. 1 being in the direction of organic phase flow and the dashed arrows in the direction of aqueous phase flow.
Example 1
The method for removing zinc, calcium and magnesium ions in a manganese sulfate solution by using the synergistic extraction method is characterized by comprising the following steps of:
step one, according to the weight ratio of di (2-ethylhexyl) phosphate, tributyl phosphate and dinonyl naphthalene sulfonic acid being 5:2:3, adding sulfonated kerosene into the extractant according to the volume ratio of the extractant to the sulfonated kerosene being 3; taking a crude manganese sulfate solution as a water phase; the pH value of the rough manganese sulfate solution is 2.0, the content of each element in the rough manganese sulfate solution is 115g/L manganese, 0.0008g/L iron, 8.55g/L zinc, 0.3g/L calcium, 0.005g/L magnesium, 0.003g/L nickel and 0.005g/L sodium;
step two, adding the organic phase prepared in the step one into a sodium hydroxide solution with the concentration of 30%, stirring, and carrying out saponification reaction, wherein the saponification rate is controlled at 40%;
step three, adding 93 percent sulfuric acid into pure water, uniformly stirring, and preparing the mixture to be used as a water phase for a regeneration section of an extraction system, wherein the acidity of the water phase is 140g/L;
step four, mixing the saponified organic phase and the manganese sulfate liquid in the step two for reaction to prepare manganese soap, and performing manganese sodium replacement reaction, wherein the zinc content in the manganese sulfate liquid is less than 0.005g/L, the calcium content is less than 0.003g/L, the magnesium content is less than 0.003g/L, the manganese content is 30 g/L-50 g/L, the reaction temperature is 30 ℃, and the phase ratio of the organic phase to the aqueous phase is 1:1, stirring at 200 revolutions per minute, mixing for 2.5 minutes, discharging an aqueous phase of a sodium sulfate solution, preparing an anhydrous sodium sulfate product from the sodium sulfate solution, and feeding an organic phase to the fifth step;
step five: and (3) feeding the organic phase and the crude manganese sulfate solution, namely the water phase in the first step, into an extraction section extraction box for extraction and impurity removal, wherein the reaction temperature is 35 ℃, and the phase ratio is organic phase/water phase (O/A) =1:1, stirring at 200 revolutions per minute, carrying out mixed reaction for 3 minutes, discharging a water phase which is a purified and impurity-removed manganese sulfate solution, and allowing an organic phase to enter the sixth step;
the pH value of the purified and impurity-removed manganese sulfate solution is 3.98, the manganese content in the purified and impurity-removed manganese sulfate solution is 108.5g/L, the iron content is 0.0001g/L, the zinc content is 0.001g/L, the calcium content is 0.008g/L, the magnesium content is 0.004g/L, the nickel content is 0.0045g/L, and the sodium content is 0.008g/L, and the purified and impurity-removed manganese sulfate solution is used for preparing high-purity battery-grade manganese sulfate;
step six: and (4) feeding the organic phase in the step five and the water phase in the step three into a regeneration section extraction box for regeneration and acid washing, wherein the reaction temperature is 30 ℃, and the ratio of the organic phase to the water phase (O/A) =5:1, stirring speed is 200 r/min, mixing reaction is carried out for 4 min, the discharged aqueous phase is zinc sulfate solution, and the organic phase enters an organic regeneration storage tank and can be recycled.
Example 2
The method for removing zinc, calcium and magnesium ions in a manganese sulfate solution by a synergistic extraction method is characterized by comprising the following steps of:
step one, according to the weight ratio of di (2-ethylhexyl) phosphate, tributyl phosphate and dinonyl naphthalene sulfonic acid being 5:1.5:3.5, adding sulfonated kerosene into the extractant according to the volume ratio of the extractant to the sulfonated kerosene being 3; taking a crude manganese sulfate solution as a water phase; the pH value of the crude manganese sulfate solution is 1.7, the content of each element in the crude manganese sulfate solution is 122g/L of manganese, 0.0009g/L of iron, 8.13g/L of zinc, 0.26g/L of calcium, 0.003g/L of magnesium, 0.004g/L of nickel and 0.001g/L of sodium;
step two, adding the organic phase prepared in the step one into a sodium hydroxide solution with the concentration of 30%, stirring, and carrying out saponification reaction, wherein the saponification rate is controlled to be 30%;
step three, adding 93 percent sulfuric acid into pure water, uniformly stirring, and preparing the mixture to be used as a water phase for a regeneration section of an extraction system, wherein the acidity of the water phase is 160g/L;
step four, mixing the saponified organic phase and the manganese sulfate solution obtained in the step two to react to prepare manganese soap, and performing manganese sodium displacement reaction, wherein the zinc content in the manganese sulfate solution is less than 0.005g/L, the calcium content is less than 0.003g/L, the magnesium content is less than 0.003g/L, the manganese content is 30 g/L-50 g/L, the reaction temperature is 40 ℃, and the ratio of the organic phase to the aqueous phase is 1:1, stirring at 300 revolutions per minute, mixing for 2.5 minutes, discharging an aqueous phase of a sodium sulfate solution for preparing an anhydrous sodium sulfate product, and feeding an organic phase to a fifth step;
step five: and (3) feeding the organic phase in the fourth step and the crude manganese sulfate solution aqueous phase in the first step into an extraction section extraction box for extraction and impurity removal, wherein the reaction temperature is 40 ℃, and the phase ratio is organic phase/aqueous phase (O/A) =2:1, stirring at 300 revolutions per minute, mixing and reacting for 3 minutes, discharging a water phase which is a purified and impurity-removed manganese sulfate solution, and feeding an organic phase to the sixth step;
the pH value of the manganese sulfate solution after purification and impurity removal is 3.65, the manganese content in the manganese sulfate solution after purification and impurity removal is 110g/L, the iron content is 0.0001g/L, the zinc content is 0.0008g/L, the calcium content is 0.009g/L, the magnesium content is 0.003g/L, the nickel content is 0.004g/L, and the sodium content is 0.006g/L; the purified manganese sulfate solution is used for preparing high-purity battery-grade manganese sulfate;
step six: and (3) feeding the organic phase in the step five and the water phase in the step three into a regeneration section extraction box for regeneration and acid washing, wherein the reaction temperature is 40 ℃, and the phase ratio is that organic phase/water phase (O/A) =5:1, stirring speed is 300 r/min, mixing reaction is carried out for 4 min, the discharged aqueous phase is zinc sulfate solution, and the organic phase enters an organic regeneration storage tank and can be recycled.
Example 3
The method for removing zinc, calcium and magnesium ions in a manganese sulfate solution by a synergistic extraction method is characterized by comprising the following steps of:
step one, according to the weight ratio of di (2-ethylhexyl) phosphate, tributyl phosphate and dinonyl naphthalene sulfonic acid being 5:1.5:3.5, adding sulfonated kerosene into the extracting agent according to the volume ratio of the extracting agent to the sulfonated kerosene being 2; taking a crude manganese sulfate solution as a water phase; the pH value of the rough manganese sulfate solution is 2.5, the content of each element in the rough manganese sulfate solution is 95g/L of manganese, 0.0003g/L of iron, 9.71g/L of zinc, 0.20g/L of calcium, 0.005g/L of magnesium, 0.002g/L of nickel and 0.001g/L of sodium;
step two, adding the organic phase prepared in the step one into a sodium hydroxide solution with the concentration of 30%, stirring, and carrying out saponification reaction, wherein the saponification rate is controlled to be 35%;
step three, adding 93% sulfuric acid into pure water, stirring uniformly and preparing the mixture to be used as a water phase for a regeneration section of an extraction system, wherein the acidity of the water phase is 150g/L;
step four, mixing the saponified organic phase and the manganese sulfate solution obtained in the step two to react to prepare manganese soap, and performing manganese sodium displacement reaction, wherein the zinc content in the manganese sulfate solution is less than 0.005g/L, the calcium content is less than 0.003g/L, the magnesium content is less than 0.003g/L, the manganese content is 30 g/L-50 g/L, the reaction temperature is 35 ℃, and the ratio of the organic phase to the aqueous phase is 1:1, stirring at 280 revolutions per minute, mixing for 2.5 minutes, discharging an aqueous phase of a sodium sulfate solution, preparing an anhydrous sodium sulfate product from the sodium sulfate solution, and feeding an organic phase to the fifth step;
step five: and (3) feeding the organic phase in the fourth step and the crude manganese sulfate solution aqueous phase in the first step into an extraction section extraction box for extraction and impurity removal, wherein the reaction temperature is 37 ℃, and the phase ratio is organic phase/aqueous phase (O/A) =1.5:1, stirring at 260 revolutions per minute, carrying out mixed reaction for 3 minutes, discharging a water phase which is a purified and impurity-removed manganese sulfate solution, and allowing an organic phase to enter the sixth step;
the pH value of the purified and impurity-removed manganese sulfate solution is 3.35, the manganese content of the manganese sulfate solution is 93g/L, the iron content is 0.0001g/L, the zinc content is 0.0012g/L, the calcium content is 0.0095g/L, the magnesium content is 0.004g/L, the nickel content is 0.002g/L, the sodium content is 0.007g/L, and the purified and impurity-removed manganese sulfate solution is used for preparing high-purity battery-grade manganese sulfate;
step six: and (4) feeding the organic phase in the step five and the water phase in the step three into a regeneration section extraction box for regeneration and acid washing, wherein the reaction temperature is 35 ℃, and the ratio of the organic phase to the water phase (O/A) =5:1, stirring at 250 r/min, mixing and reacting for 4 min, discharging zinc sulfate solution as an aqueous phase, and feeding an organic phase into an organic regeneration storage tank for recycling.
Example 4
The method for removing zinc, calcium and magnesium ions in a manganese sulfate solution by a synergistic extraction method is characterized by comprising the following steps of:
step one, according to the weight ratio of di (2-ethylhexyl) phosphate, tributyl phosphate and dinonyl naphthalene sulfonic acid being 5:1:4, adding sulfonated kerosene into the extractant according to the volume ratio of the extractant to the sulfonated kerosene being 2.5; taking a crude manganese sulfate solution as a water phase; the pH value of the crude manganese sulfate solution is 1.99, the content of each element in the crude manganese sulfate solution is 107g/L of manganese, 0.0007g/L of iron, 9.23g/L of zinc, 0.22g/L of calcium, 0.0021g/L of magnesium, 0.003g/L of nickel and 0.006g/L of sodium;
step two, adding the organic phase prepared in the step one into a sodium hydroxide solution with the concentration of 30%, stirring, and carrying out saponification reaction, wherein the saponification rate is controlled to be 30%;
step three, adding 93 percent sulfuric acid into pure water, uniformly stirring, and preparing a water phase used for a re-rising section of an extraction system, wherein the acidity of the water phase is 155g/L;
step four, mixing the saponified organic phase in the step two with manganese sulfate solution to react to prepare manganese soap, carrying out manganese sodium displacement reaction, wherein the zinc content in the manganese sulfate solution is less than 0.005g/L, the calcium content is less than 0.003g/L, the magnesium content is less than 0.003g/L, the manganese content is 30-50 g/L, the reaction temperature is 33 ℃, and the phase ratio of the organic phase to the aqueous phase is 1:1, stirring at 210 revolutions per minute, mixing for 2.5 minutes, discharging an aqueous phase of a sodium sulfate solution for preparing an anhydrous sodium sulfate product, and feeding an organic phase to a fifth step;
step five: and (3) feeding the organic phase in the fourth step and the crude manganese sulfate solution aqueous phase in the first step into an extraction section extraction box for extraction and impurity removal, wherein the reaction temperature is 39 ℃, and the ratio of the organic phase to the aqueous phase (O/A) =1.3:1, stirring at 220 r/min, mixing and reacting for 3 min, discharging a water phase which is a purified and impurity-removed manganese sulfate solution, and allowing an organic phase to enter the sixth step;
the pH value of the manganese sulfate solution after purification and impurity removal is 3.81, the manganese content in the manganese sulfate solution is 103g/L, the iron content is 0.0003g/L, the zinc content is 0.001g/L, the calcium content is 0.005g/L, the magnesium content is 0.0013g/L, the nickel content is 0.003g/L, and the sodium content is 0.007g/L; the purified manganese sulfate solution is used for preparing high-purity battery-grade manganese sulfate;
step six: and (3) feeding the organic phase in the step five and the water phase in the step three into a regeneration section extraction box for regeneration and acid washing, wherein the reaction temperature is 30 ℃, and the phase ratio is organic phase/water phase (O/A) =5:1, stirring speed is 300 r/min, mixing reaction is carried out for 4 min, discharged aqueous phase is zinc sulfate solution, and organic phase enters an organic regeneration storage tank for recycling.
Example 5
The method for removing zinc, calcium and magnesium ions in a manganese sulfate solution by using the synergistic extraction method is characterized by comprising the following steps of:
step one, according to the weight ratio of di (2-ethylhexyl) phosphate, tributyl phosphate and dinonyl naphthalene sulfonic acid being 5:1:4, adding sulfonated kerosene into the extractant according to the volume ratio of the extractant to the sulfonated kerosene being 3; taking a crude manganese sulfate solution as a water phase; the pH value of the crude manganese sulfate solution is 2.12, the content of each element in the crude manganese sulfate solution is 112.6g/L of manganese, 0.0005g/L of iron, 8.04g/L of zinc, 0.25g/L of calcium, 0.0011g/L of magnesium, 0.0012g/L of nickel and 0.005g/L of sodium;
step two, adding the organic phase prepared in the step one into a sodium hydroxide solution with the concentration of 30%, stirring, and carrying out saponification reaction, wherein the saponification rate is controlled to be 30%;
step three, adding 93 percent sulfuric acid into pure water, stirring uniformly and preparing the mixture to be used as a water phase for a regeneration section of an extraction system, wherein the acidity of the water phase is 145g/L;
step four, mixing the saponified organic phase and the manganese sulfate liquid in the step two for reaction to prepare manganese soap, and performing manganese sodium replacement reaction, wherein the zinc content in the manganese sulfate liquid is less than 0.005g/L, the calcium content is less than 0.003g/L, the magnesium content is less than 0.003g/L, the manganese content is 30 g/L-50 g/L, the reaction temperature is 36 ℃, and the phase ratio of the organic phase to the aqueous phase is 1:1, stirring at 270 rpm for 2.5 minutes, discharging an aqueous phase of a sodium sulfate solution for preparing an anhydrous sodium sulfate product, and feeding an organic phase to the fifth step;
step five: and (3) feeding the organic phase in the fourth step and the crude manganese sulfate solution aqueous phase in the first step into an extraction section extraction box for extraction and impurity removal, wherein the reaction temperature is 36 ℃, and the ratio of the organic phase to the aqueous phase (O/A) =1.2:1, stirring at 250 revolutions per minute, mixing and reacting for 3 minutes, discharging a water phase which is a purified and impurity-removed manganese sulfate solution, and feeding an organic phase to the sixth step;
the pH value of the manganese sulfate solution after purification and impurity removal is 3.83, the manganese content in the manganese sulfate solution is 108.5g/L, the iron content is 0.0001g/L, the zinc content is 0.0007g/L, the calcium content is 0.0022g/L, the magnesium content is 0.001g/L, the nickel content is 0.0012g/L, and the sodium content is 0.006g/L; the purified manganese sulfate solution is used for preparing high-purity battery-grade manganese sulfate;
step six: and (3) feeding the organic phase in the step five and the water phase in the step three into a regeneration section extraction box for regeneration and acid washing, wherein the reaction temperature is 30 ℃, and the phase ratio is organic phase/water phase (O/A) =5:1, stirring speed is 300 r/min, mixing reaction is carried out for 4 min, discharged aqueous phase is zinc sulfate solution, and organic phase enters an organic regeneration storage tank for recycling.
Claims (7)
1. The method for removing zinc, calcium and magnesium ions in a manganese sulfate solution by a synergistic extraction method is characterized by comprising the following steps of:
step one, according to the weight ratio of di (2-ethylhexyl) phosphate, tributyl phosphate and dinonyl naphthalene sulfonic acid being 5: (1-2): (3-4) preparing an extracting agent, mixing the prepared extracting agent and sulfonated kerosene in proportion, and preparing an organic phase with the concentration of the extracting agent being 20% -30%; taking a crude manganese sulfate solution as a water phase;
step two, adding the organic phase prepared in the step one into a sodium hydroxide solution with the concentration of 30%, stirring, and carrying out saponification reaction, wherein the saponification rate is controlled to be 30-40%;
step three, adding 93 percent sulfuric acid into pure water, uniformly stirring and preparing the mixture to be used as a water phase for a regeneration section of an extraction system, wherein the acidity of the water phase is 140-160 g/L;
step four, mixing the saponified organic phase and the manganese sulfate liquid in the step two for reaction to prepare manganese soap, and performing manganese-sodium displacement reaction, wherein the zinc content in the manganese sulfate liquid is less than 0.005g/L, the calcium content is less than 0.003g/L, the magnesium content is less than 0.003g/L, the manganese content is 30 g/L-50 g/L, the reaction temperature is 30-40 ℃, and the phase ratio of the organic phase to the aqueous phase is 1:1, stirring at the speed of 200-300 rpm for 2.5 minutes, discharging an aqueous phase of a sodium sulfate solution, and feeding an organic phase to the fifth step;
step five: and (3) feeding the organic phase and the crude manganese sulfate solution, namely the water phase in the first step, into an extraction section extraction box for extraction and impurity removal, wherein the reaction temperature is 35-40 ℃, and the phase ratio is organic phase/water phase (O/A) = (1-2): 1, stirring at the speed of 200-300 r/min, mixing and reacting for 3 minutes, wherein the discharged water phase is a purified and impurity-removed manganese sulfate solution, and the organic phase enters the sixth step;
wherein the manganese content in the manganese sulfate solution after purification and impurity removal is 90 g/L-110 g/L, the iron content is less than 0.001g/L, the zinc content is less than 0.002g/L, the calcium content is less than 0.01g/L, the magnesium content is less than 0.005g/L, the nickel content is less than 0.005g/L, and the sodium content is less than 0.01g/L;
step six: and (4) feeding the organic phase in the step five and the water phase in the step three into a regeneration section extraction box for regeneration and acid washing, wherein the reaction temperature is 30-40 ℃, and the ratio of the organic phase to the water phase (O/A) =5:1, stirring at 200-300 rpm, mixing and reacting for 4 minutes, discharging an aqueous phase of zinc sulfate solution, and recycling an organic phase.
2. The method for removing zinc ions, calcium ions and magnesium ions in manganese sulfate solution by the synergistic extraction method according to claim 1, is characterized in that: the crude manganese sulfate solution is a byproduct produced in the production of nickel sulfate or cobalt sulfate.
3. The method for removing zinc, calcium and magnesium ions in manganese sulfate solution by the synergistic extraction method according to claim 1, is characterized in that: step one, the volume ratio of an extracting agent to sulfonated kerosene is 3:7, the extracting agent is prepared from di (2-ethylhexyl) phosphate, tributyl phosphate and dinonylnaphthalene sulfonic acid according to the weight ratio of 5:1.5:3.5 in proportion.
4. The method for removing zinc, calcium and magnesium ions in manganese sulfate solution by the synergistic extraction method according to claim 1, is characterized in that: in the first step, the crude manganese sulfate solution, namely the water phase, has the zinc content of 8-10 g/L, the calcium content of 0.2-0.3 g/L and the magnesium content of less than or equal to 0.005g/L.
5. The method for removing zinc, calcium and magnesium ions in manganese sulfate solution by the synergistic extraction method according to claim 1, is characterized in that: four-stage countercurrent extraction is adopted in the manganese soap section.
6. The method for removing zinc ions, calcium ions and magnesium ions in manganese sulfate solution by the synergistic extraction method according to claim 1, is characterized in that: and in the fifth step, eight-stage countercurrent extraction is adopted in the extraction section.
7. The method for removing zinc, calcium and magnesium ions in manganese sulfate solution by the synergistic extraction method according to claim 1, is characterized in that: in the sixth step, five-stage countercurrent extraction is adopted in the regeneration section.
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