阅读说明：本技术 一种从电解锰硫化渣中制备高纯硫酸锰的方法 (Method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag ) 是由 陈进中 曾军 叶有明 蔡井泉 于 2020-12-02 设计创作，主要内容包括：本发明公开一种从电解锰硫化渣中制备高纯硫酸锰的方法,按如下步骤进行：(1)破碎过筛；(2)氧化浸出；(3)除钙：向浸出液中加入皂化的P204和磺化煤油混合形成的第一有机萃取剂萃取,得到负载钙有机相和富锰钴镍镁溶液；(4)锰的回收：取富锰钴镍镁溶液,加入皂化的P204和磺化煤油混合形成的第二有机萃取剂萃取,得到负载锰有机相和富钴镍镁溶液；取负载锰有机相,加入硫酸进行反萃,得到P204有机相和硫酸锰溶液；(5)高纯硫酸锰的制备。本发明具有简单可行,能实现硫化锰的浸出,并能避免硫化氢气体的产生、沉铁工艺的使用以及氟离子沉淀除钙镁离子方法的使用的优点。(The invention discloses a method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag, which comprises the following steps: (1) crushing and sieving; (2) oxidizing and leaching; (3) calcium removal: adding a first organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the leachate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution; (4) and (3) recovering manganese: adding a second organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the manganese-rich cobalt-nickel-magnesium solution for extraction to obtain a manganese-loaded organic phase and a cobalt-nickel-magnesium-rich solution; adding sulfuric acid into the manganese-loaded organic phase for back extraction to obtain a P204 organic phase and a manganese sulfate solution; (5) and (5) preparing high-purity manganese sulfate. The method has the advantages of simplicity and feasibility, can realize leaching of manganese sulfide, and can avoid the generation of hydrogen sulfide gas, the use of an iron precipitation process and the use of a method for removing calcium and magnesium ions by fluoride ion precipitation.)

1. A method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag is characterized by comprising the following steps:

(1) crushing and sieving: crushing and sieving pyrolusite and electrolytic manganese sulfide slag;

(2) oxidizing and leaching: uniformly mixing the sieved pyrolusite and electrolytic manganese sulfide slag according to a certain slag ratio, adding dilute sulfuric acid, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residue and leachate;

(3) calcium removal: adding a first organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the leachate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution;

(4) and (3) recovering manganese: adding a second organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the manganese-rich cobalt-nickel-magnesium solution for extraction to obtain a manganese-loaded organic phase and a cobalt-nickel-magnesium-rich solution; adding sulfuric acid into the manganese-loaded organic phase for back extraction to obtain a P204 organic phase and a manganese sulfate solution;

(5) preparing high-purity manganese sulfate: and (3) taking the manganese sulfate solution, evaporating, concentrating, crystallizing and centrifuging to obtain the high-purity manganese sulfate.

2. The method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: and (4) crushing and sieving, wherein the adopted sample separation sieve mesh number is 200-400 meshes.

3. The method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the pyrolusite to the electrolytic sulfide slag is 1.0: 1-2.0: 1, the mass concentration of the dilute sulfuric acid is 50-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end point pH of the leaching is 3.0-4.0.

4. The method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (3), before the first organic extractant is added for extraction, the pH of the leaching solution is adjusted to 0.5-2.0; the first organic extracting agent is prepared by adding 10-30% of sodium hydroxide into P204 and sulfonated kerosene according to the volume fraction of the P204, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is =1: 1-3: 1.

5. The method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (4), before adding a second organic extracting agent for extraction, the pH value of the manganese-cobalt-nickel-magnesium-rich solution is adjusted to 2.5-4.5; the second organic extracting agent is prepared by saponifying P204 and sulfonated kerosene by 10-40% of sodium hydroxide according to the volume fraction of P204, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is =1: 1-3: 1.

6. The method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: and (3) carrying out back extraction on the calcium-loaded organic phase by adopting sulfuric acid with the concentration of 100-200 g/L, and returning the organic phase to the step (3) for recycling, wherein the ratio of the organic phase to the water phase is O/A =1: 5-1: 10 to obtain a P204 organic phase.

7. The method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (4), the manganese-loaded organic phase is subjected to back extraction by using sulfuric acid with the concentration of 100 g/L-200 g/L, and the O/A ratio of the organic phase to the aqueous phase is =1: 5-1: 10.

8. The method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (4), the P204 organic phase is returned to the manganese-cobalt-nickel-magnesium-rich solution for recycling.

Technical Field

The invention belongs to the field of wet metallurgy and clean metallurgy, and particularly relates to a method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag.

Background

Cobalt is an important industrial raw material, and the electrolytic method is a common method for producing manganese, and comprises the following basic steps: leaching manganese ore to obtain manganese-containing leachate, then neutralizing and deironing, removing heavy metals by using a vulcanizing agent, finally electrolyzing to obtain electrolytic manganese, and precipitating a large amount of cobalt in the form of cobalt sulfide in the heavy metals removal by using the vulcanizing agent to cause cobalt loss, so that the recovery of the cobalt in the electrolytic manganese is of great significance. At present, sulfuric acid is adopted to directly leach electrolytic manganese sulfide slag, toxic hydrogen sulfide gas is easily generated, a leached liquid is subjected to iron removal by a neutralization iron precipitation method, the process operation flow is increased, calcium and magnesium ions are removed by a fluoride ion precipitation method after iron removal, a site is needed for depositing and accumulating fluoride, and secondary pollution is easily caused to the fluoride. We have now found patents relating to the preparation of cobalt sulphate from waste residues, including the following:

1. application No.: 201710213431.X, invention name: the method for enriching and recovering nickel and cobalt from manganese-containing waste comprises the following steps: pulping manganese-containing waste sulfide slag, adding acid liquor into the sulfide slag for stirring and filtering, repulping the obtained acid-washed waste slag, adding an oxidant and the acid liquor, controlling the reaction temperature and the reaction pH value, carrying out a first stirring reaction, adding alkali liquor to increase the pH value after the reaction is completed, carrying out a second stirring reaction, filtering, adjusting the pH value to acidity in the obtained nickel-cobalt mixed solution, adding sulfide for precipitation again, and filtering to obtain nickel-cobalt-containing enriched slag and a supernatant which can be returned to a manganese sulfate production line. The method has the advantages of effective utilization of waste resources, low cost, good impurity removal effect, small environmental risk and the like. The invention has the following disadvantages: after a complex process flow is adopted, only cobalt-nickel-containing enriched slag is obtained, and a leaching-extraction process is further adopted for utilizing the cobalt-nickel-containing enriched slag, so that the process is complicated.

2. Application No.: 201610737450.8, title of the invention: the method comprises the steps of removing iron and aluminum in a leaching solution by an oxidation precipitation method, extracting copper, extracting zinc, and finally synchronously extracting nickel, cobalt and manganese by tributyl phosphate and saponified neodecanoic acid. The invention has the following disadvantages: after the manganese-cobalt-nickel-containing waste residue is leached, an oxidation precipitation method is further adopted to remove impurities from iron and aluminum.

3. Application No.: 201810855039.X, title of the invention: a method for treating copper and manganese impurities in a nickel-containing cobalt sulfate solution comprises the following steps: 1) adjusting the pH value of the nickel-containing cobalt sulfate raw material liquid; 2) preparation of P204 cobalt soap: mixing an extracting agent P204 and a diluent sulfonated kerosene, sequentially adding a NaOH solution and a cobalt soap precursor solution, and taking an organic phase as P204 cobalt soap; 3) extracting copper and manganese by using P204 cobalt soap: adding P204 cobalt soap into a cobalt sulfate raw material solution, extracting, transferring copper and manganese in the cobalt sulfate raw material solution into an organic phase, retaining cobalt and nickel into a water phase, and using the water phase as P204 raffinate containing cobalt and nickel; 4) cobalt washing: the cobalt in the incompletely reacted P204 cobalt soap is transferred into the water phase; 5) back extraction: and producing a chloride salt stripping solution with cobalt content less than 1.0 g/L. The method can effectively remove copper and manganese impurities from the cobalt sulfate solution containing nickel, does not introduce other impurities, and the quality of the produced product meets the requirements of producing refined cobalt sulfate or refined cobalt chloride. The invention has the following disadvantages: cobalt soap is used to extract copper and manganese, sodium soap is formed first and then cobalt soap is formed, and the extraction capacity of sodium soap is stronger than that of cobalt soap, so that waste of front liquid of cobalt soap is unnecessary.

Disclosure of Invention

The invention aims to solve the technical problems and provide a simple and feasible method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag, which can realize leaching of manganese sulfide, and can avoid generation of hydrogen sulfide gas, use of an iron precipitation process and use of a method for removing calcium and magnesium ions by fluoride ion precipitation.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag comprises the following steps:

(1) crushing and sieving: crushing and sieving pyrolusite and electrolytic manganese sulfide slag;

(2) oxidizing and leaching: uniformly mixing the sieved pyrolusite and electrolytic manganese sulfide slag according to a certain slag ratio, adding dilute sulfuric acid, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residue and leachate;

(3) calcium removal: adding a first organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the leachate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution;

(4) and (3) recovering manganese: adding a second organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the manganese-rich cobalt-nickel-magnesium solution for extraction to obtain a manganese-loaded organic phase and a cobalt-nickel-magnesium-rich solution; adding sulfuric acid into the manganese-loaded organic phase for back extraction to obtain a P204 organic phase and a manganese sulfate solution;

(5) preparing high-purity manganese sulfate: and (3) taking the manganese sulfate solution, evaporating, concentrating, crystallizing and centrifuging to obtain the high-purity manganese sulfate.

As a further technical scheme, the crushing and sieving are carried out, and the number of sample separation meshes is 200-400 meshes.

As a further technical scheme, in the step (2), the mass ratio of the pyrolusite to the electrolytic sulfide slag is 1.0: 1-2.0: 1, the mass concentration of the dilute sulfuric acid is 50 g/L-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end point pH of the leaching is 3.0-4.0.

As a further technical scheme, in the step (3), before the first organic extracting agent is added for extraction, the pH of the leaching solution is adjusted to 0.5-2.0; the first organic extracting agent is prepared by adding 10-30% of P204 and sulfonated kerosene according to the volume fraction of P204 into sodium hydroxide for saponification, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1.

As a further technical scheme, in the step (4), before the second organic extracting agent is added for extraction, the pH value of the manganese-cobalt-nickel-magnesium-rich solution is adjusted to 2.5-4.5; the second organic extracting agent is prepared by saponifying P204 and sulfonated kerosene by 10-40% of P204 by volume with sodium hydroxide, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1.

As a further technical scheme, the calcium-loaded organic phase is subjected to back extraction by using sulfuric acid with the concentration of 100 g/L-200 g/L, the O/A ratio of the organic phase to the water phase is 1: 5-1: 10, a P204 organic phase is obtained, and the organic phase is returned to the step (3) for recycling.

In the step (4), the manganese-loaded organic phase is back-extracted by using sulfuric acid with the concentration of 100 g/L-200 g/L, and the O/A ratio of the organic phase to the aqueous phase is 1: 5-1: 10.

As a further technical scheme, in the step (4), the P204 organic phase is returned to the manganese-cobalt-nickel-magnesium-rich solution for recycling.

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

1. the method has simple and feasible process, realizes leaching of manganese sulfide, and has the basic principle of oxidative leaching as follows:

4MnO₂+2MnS+2O₂+4H₂SO₄＝6MnSO₄+4H₂O；

4MnO₂+2NiS+4O₂+4H₂SO₄＝4MnSO₄+2NiSO₄+4H₂O；

4MnO₂+2CoS+4O₂+4H₂SO₄＝4MnSO₄+2CoSO₄+4H₂O；

in the step, the negative divalent sulfur is oxidized into sulfate radicals, so that the generation of hydrogen sulfide is avoided, and the safety is improved.

2. The method adopts dilute sulfuric acid as a leaching agent, oxygen is introduced to reduce the acid dosage and improve the leaching rate, the end point pH value is 3.0-4.0 by controlling the acid dosage, a small amount of leached iron is directly precipitated in the form of ferric hydroxide after being oxidized, and the subsequent complex iron precipitation process is avoided.

3. The invention adopts the first organic extractant formed by mixing the saponified P204 and the sulfonated kerosene to extract and remove calcium, thereby avoiding secondary pollution of fluoride caused by a fluoride ion precipitation method, and the extractant can be recycled, thereby reducing the production cost.

Drawings

FIG. 1 is a process flow chart of the method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited to the scope of the examples.

The materials involved in the examples are all available from the factory or on the market.

A method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag comprises the following steps:

(1) crushing and sieving: crushing and sieving pyrolusite and electrolytic manganese sulfide slag; crushing and sieving, wherein the adopted sample separation sieve mesh number is 200-400 meshes.

(2) Oxidizing and leaching: uniformly mixing the sieved pyrolusite and electrolytic manganese sulfide slag according to a certain slag ratio, adding dilute sulfuric acid, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residue and leachate; the mass ratio of the pyrolusite to the electrolytic sulfide slag is 1.0: 1-2.0: 1, the mass concentration of the dilute sulfuric acid is 50-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end point pH of the leaching is 3.0-4.0.

(3) Calcium removal: adjusting the pH value of the leachate to 0.5-2.0, and then adding a first organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the leachate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution; the first organic extractant is prepared by adding sodium hydroxide into P204 and sulfonated kerosene in the amount of 10-30 vol% of P204 for saponification, with the saponification rate being 10-50% and the organic phase and water phase being 1: 1-3: 1 in terms of O/A ratio.

And (3) carrying out back extraction on the calcium-loaded organic phase by adopting sulfuric acid with the concentration of 100 g/L-200 g/L, comparing the organic phase with the water phase by the ratio of O/A (1: 5-1: 10) to obtain a P204 organic phase, and returning to the step (3) for recycling.

(4) And (3) recovering manganese: taking the manganese-cobalt-nickel-magnesium-rich solution, and adjusting the pH value to 2.5-4.5; adding a second organic extracting agent formed by mixing saponified P204 and sulfonated kerosene for extraction to obtain a manganese-loaded organic phase and a cobalt-nickel-magnesium-rich solution; the second organic extractant is prepared by saponifying P204 and sulfonated kerosene by 10-40% of P204 by volume with sodium hydroxide, wherein the saponification rate is 10-50%, and the O/A ratio of the organic phase to the aqueous phase is 1: 1-3: 1; carrying out back extraction on the manganese-loaded organic phase by adopting sulfuric acid with the concentration of 100-200 g/L, wherein the ratio of O/A of the organic phase to the aqueous phase is 1: 5-1: 10, so as to obtain a P204 organic phase and a manganese sulfate solution; and returning the P204 organic phase to the manganese-cobalt-nickel-magnesium-rich solution for recycling.

(5) Preparing high-purity manganese sulfate: and (3) taking the manganese sulfate solution, evaporating, concentrating, crystallizing and centrifuging to obtain the high-purity manganese sulfate.

The component detection of the electrolytic manganese sulfide slag adopted by the invention is shown in the table 1:

TABLE 1

The following example was carried out in accordance with the above method for producing high purity manganese sulfate.

Example 1:

crushing and sieving 10g of electrolytic manganese sulfide slag and 17g of pyrolusite to 200 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 10:1, introducing oxygen of 0.1Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, measuring the end point pH of 3.0, filtering, adjusting the pH of the leachate to 0.5 by using dilute sulfuric acid, removing calcium by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 20%, extracting for 10min, separating in a separating funnel to obtain a calcium-removed rich manganese cobalt nickel magnesium solution, adjusting the pH of the manganese cobalt nickel magnesium solution to 3.5 by using sodium hydroxide, recovering the manganese cobalt nickel magnesium solution by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 2:1, wherein the saponification rate of the extracting agent is 40%, extracting for 10min to obtain a manganese-loaded organic phase, and back extracting the manganese-loaded organic phase by using 200g/L of sulfuric acid according to a ratio of O/A to 10:1, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. The recovery rate of manganese was found to be 91.2%, and the purity of high-purity manganese sulfate was found to be 99.95%.

Example 2:

crushing and sieving 10g of electrolytic manganese sulfide slag and 17g of pyrolusite to 200 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 10:1, introducing oxygen of 0.2Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, measuring the end point pH to be 3.0, filtering, adjusting the pH of the leachate to be 1 by using dilute sulfuric acid, removing calcium by using 20% P204+ 80% sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 30%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed cobalt-nickel-magnesium-rich solution, adjusting the pH of a water phase to be 4.0 by using dilute sulfuric acid, recovering manganese by using 30% P204+ 70% sulfonated kerosene according to a ratio of O/A to 2.5:1, wherein the saponification rate of the extracting agent is 30%, extracting for 10min to obtain a manganese-loaded organic phase, then back extracting the manganese-loaded organic phase by using 150g/L sulfuric acid according to a ratio of O/A to be 1:8, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. The recovery rate of manganese was found to be 92.2%, and the purity of high purity manganese sulfate was found to be 99.93%.

Example 3:

crushing 10g of electrolytic manganese sulfide slag and 15g of pyrolusite, sieving to 400 meshes, mixing uniformly, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 9:1, introducing oxygen of 0.3Mpa, heating to 85 ℃, mechanically stirring, leaching for 180min, measuring the end point pH value of 3.0, filtering, adjusting the pH value of the leachate to 1.0 by using dilute sulfuric acid, removing calcium by using 20% of P204+ 80% of sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 40%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed manganese-rich cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to 3.0 by using dilute sulfuric acid, recovering manganese by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 2.0:1, wherein the saponification rate of the extracting agent is 30%, extracting for 10min to obtain a manganese-loaded organic phase, then back extracting the manganese-loaded organic phase by using 150g/L sulfuric acid according to a ratio of O/A to 1:8, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. The recovery rate of manganese was found to be 89.2%, and the purity of high-purity manganese sulfate was found to be 99.09%.

Example 4:

crushing 10g of electrolytic manganese sulfide slag and 15g of pyrolusite, sieving to 400 meshes, mixing uniformly, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 9:1, introducing oxygen of 0.1Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, measuring the end point pH value of 3.0, filtering, adjusting the pH value of the leachate to 1.0 by using dilute sulfuric acid, removing calcium by using 20% of P204+ 80% of sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 40%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed, manganese-enriched, cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to 3.0 by using dilute sulfuric acid, recovering manganese by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 2.5:1, wherein the saponification rate of the extracting agent is 30%, extracting for 10min to obtain a manganese-loaded organic phase, then back extracting the manganese-loaded organic phase by using 150g/L sulfuric acid according to a ratio of O/A to 1:8, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. The recovery rate of manganese was found to be 90.2%, and the purity of high purity manganese sulfate was found to be 99.89%.

Example 5:

crushing 10g of electrolytic manganese sulfide slag and 15g of pyrolusite, sieving to 400 meshes, mixing uniformly, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 8:1, introducing oxygen of 0.3Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, measuring the end point pH value of 3.0, filtering, adjusting the pH value of the leachate to 1.5 by using dilute sulfuric acid, removing calcium by using 20% of P204+ 80% of sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 40%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed, manganese-enriched, cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to 3.0 by using dilute sulfuric acid, recovering manganese by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 2.5:1, wherein the saponification rate of the extracting agent is 25%, extracting for 10min to obtain a manganese-loaded organic phase, then back extracting the manganese-loaded organic phase by using 150g/L sulfuric acid according to a ratio of O/A to 1:8, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. The recovery rate of manganese was found to be 89.6%, and the purity of high-purity manganese sulfate was found to be 99.89%.

Example 6:

crushing and sieving 10g of electrolytic manganese sulfide slag and 10g of pyrolusite to 400 meshes, uniformly mixing, adding 200g/L sulfuric acid solution according to a liquid-solid ratio of 5:1, introducing oxygen gas under 1Mpa, heating to 50 ℃, mechanically stirring, leaching for 160min, measuring the end point pH value to be 4.0, filtering, adjusting the pH value of the leachate to be 2.0 by using dilute sulfuric acid, removing calcium by using 20% P204+ 80% sulfonated kerosene according to a ratio of O/A to 3:1, wherein the saponification rate of an extracting agent is 10%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed rich cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to be 2.5 by using dilute sulfuric acid, recovering manganese by using 10% P204+ 90% sulfonated kerosene according to a ratio of O/A to 3:1, wherein the saponification rate of the extracting agent is 10%, extracting for 10min to obtain a manganese-loaded organic phase, then back extracting the manganese-loaded organic phase by using 100g/L sulfuric acid according to a ratio of O/A to be 1:5, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. The recovery rate of manganese was found to be 85.1%, and the purity of high purity manganese sulfate was found to be 97.82%.

Example 7:

crushing and sieving 10g of electrolytic manganese sulfide slag and 20g of pyrolusite to 400 meshes, uniformly mixing, adding 50g/L sulfuric acid solution according to a liquid-solid ratio of 10:1, introducing oxygen of 0.1Mpa, heating to 50 ℃, mechanically stirring, leaching for 60min, measuring the end point pH value to be 4.0, filtering, adjusting the pH value of the leaching solution to be 2.0 by using dilute sulfuric acid, removing calcium by using 10% P204+ 90% sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 50%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed manganese-rich cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to be 4.5 by using dilute sulfuric acid, recovering manganese by using 40% P204+ 60% sulfonated according to a ratio of O/A to 1:1, wherein the saponification rate of the extracting agent is 50%, extracting for 10min to obtain a manganese-loaded organic phase, back extracting the manganese-loaded organic phase by using 100g/L sulfuric acid according to a ratio of O/A to be 1:5, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. The recovery rate of manganese was found to be 84.2%, and the purity of high purity manganese sulfate was found to be 98.16%.

The invention uses example 1 as an oxygen introduction comparative test:

example 1: crushing and sieving 10g of electrolytic manganese sulfide slag and 17g of pyrolusite to 200 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to the liquid-solid ratio of 10:1, introducing oxygen of 0.2Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, and measuring the end point pH to be 3.0.

Comparative example 1: crushing and sieving 10g of electrolytic manganese sulfide slag and 17g of pyrolusite to 200 meshes, uniformly mixing, adding 120g/L sulfuric acid solution according to the liquid-solid ratio of 10:1, heating to 90 ℃, mechanically stirring, and leaching for 180 min.

The results are shown in table 2:

TABLE 2

Example 1	Acidity (g/L)	Manganese leaching rate/%	Cobalt leaching rate/%)	Nickel leaching rate/%)
						90	95.2	90.3	89.5
Comparative example 1	Acidity (g/L)	Manganese leaching rate/%	Cobalt leaching rate/%)	Nickel leaching rate/%)
						120	83.1	79.1	78.4

As shown in Table 2, the acid dosage of example 1 is reduced by 30g/L, and the leaching rate of manganese is improved by 12.1%, which shows that the acid dosage can be effectively reduced by introducing oxygen, and the leaching rate of manganese can be improved.

The above-described embodiments are only specific examples for further explaining the object, technical solution and advantageous effects of the present invention in detail, and the present invention is not limited thereto. Any modification, equivalent replacement, improvement and the like made within the scope of the present disclosure are included in the protection scope of the present invention.