Method for recycling electrolytic manganese anode slime

Abstract

The present application relates to a kind of electrolytic manganese anode slime recycling method, belong to electrolytic manganese technology field.The present application is by water washing (including the water washing of front section and the ultrasonic water washing of rear section) to electrolytic manganese anode slime-H2O2 acid leaching obtains manganese leaching solution-manganese leaching solution manganese sulfide impurity removal-adjust pH-calcification organic phase extraction manganese-stripping manganese-concentrated crystallization obtains high-purity manganese sulfate product.The present application is by series of sequential processing steps to recover manganese and lead in electrolytic manganese anode slime, obtains high-purity manganese sulfate product and lead concentrate, with the advantages of shorter processing flow, efficient separation of impurities.

Description

Technical Field

[0001] This invention relates to a method for recycling electrolytic manganese anode mud, belonging to the field of electrolytic manganese technology. Background Technology

[0002] In the electrolytic production of metallic manganese, the Mn in the anode region 2+ Inevitably, it will be oxidized and form Mn. 4+ The hydrated oxides in the anode plate are oxidized, and the lead-tin alloy in the anode plate is also oxidized and precipitated together with manganese oxide hydrate to form electrolytic manganese anode mud. The manganese and lead content in electrolytic manganese anode mud is 42-55% and 3%-10%, respectively. Because electrolytic manganese anode mud contains valuable metals, it is generally sold directly. However, selling it directly results in low economic value for manganese anode mud, and it cannot realize the high-value utilization of manganese and lead in manganese anode mud.

[0003] Manganese sulfate, manganese dioxide, or lithium manganese oxide products can be prepared from electrolytic manganese anode mud by recycling the manganese in it and based on the basic properties of the anode mud.

[0004] For example, patent application number 2021105370325 discloses a method for high-value utilization of electrolytic manganese anode mud. This invention relates to the field of manganese slag recycling technology and solves the technical problem that the high-value utilization of electrolytic manganese anode mud is limited by the lack of deep purification of impurities such as Ca, Mg, and sulfates in the recycling process of existing technologies. The method of this invention uses water washing, alkali washing, and acid leaching to efficiently remove impurities such as Ca, Mg, and sulfates from the electrolytic manganese anode mud. Then, hydrogen peroxide and sulfuric acid are used to leach the impurity-removed anode mud, obtaining a high-purity manganese sulfate solution as the leaching liquid and lead concentrate as the leaching residue. However, this invention removes impurities such as Ca, Mg, and sulfates from the electrolytic manganese anode mud through pretreatment, but does not involve the removal of other impurities, and therefore cannot obtain the corresponding high-purity manganese sulfate product. More importantly, when sulfuric acid and hydrogen peroxide are used as leaching agents, the reaction temperature is 30-60℃, which will inevitably cause the decomposition of hydrogen peroxide, and the amount of sulfuric acid used is relatively large.

[0005] In the preparation of high-purity manganese sulfate, a reducing agent is often used in a sulfuric acid system to remove Mn from the electrolytic manganese anode mud. 4+ Transform into Mn 2+ The manganese enters the solution, while lead and other impurities exist in the solid phase, thus achieving comprehensive utilization of manganese. This is typical of conventional Mn... 2+ The solution will use precipitation to remove impurities such as lead, selenium, calcium, and magnesium. However, precipitation requires the addition of a precipitant, which introduces new impurity ions, such as those used to remove Mn. 2+When dealing with iron impurities in the solution, Wang Dequan, Song Shuangqing, and others disclosed a method for treating low-grade manganese ore by directly leaching it with iron pickling solution while simultaneously precipitating iron alum. This method involves leaching the low-grade manganese ore with ferrous sulfate while simultaneously treating the leachate with iron alum precipitation. In other words, iron removal requires the introduction of a new precipitant.

[0006] To remove Mn 2+ When heavy metal ion impurities are present in the solution, a sulfiding agent needs to be added as a precipitant.

[0007] To remove impurities such as calcium and magnesium from manganese sulfate solutions, Wang Yongbin et al. disclosed a process for deep removal of calcium and magnesium impurities from industrial manganese sulfate. This process involves adding manganese fluoride precipitant to deeply remove calcium and magnesium impurities, introducing new fluoride ions. Therefore, the question arises: how can these impurity ions be combined with Mn... 2+ Achieving effective separation without introducing other ions and efficiently recovering and utilizing manganese from electrolytic manganese anode mud to obtain high-purity manganese sulfate products is a technical challenge. Summary of the Invention

[0008] To address the problems and shortcomings of the existing technology, this invention provides a method for recycling electrolytic manganese anode mud. This invention involves washing the electrolytic manganese anode mud with water (including initial water washing and subsequent ultrasonic water washing), acid leaching with H2O2 to obtain a manganese leaching solution, removing impurities with manganese sulfide from the leaching solution, adjusting the pH, extracting manganese with a calcified organic phase, back-extracting manganese, and concentrating and crystallizing to obtain a high-purity manganese sulfate product. This method introduces minimal precipitant for impurity removal, and the resulting high-purity manganese sulfate product meets the first-grade standard of "Manganese Sulfate for Batteries" (HG / T4823-2015). This invention is achieved through the following technical solution.

[0009] A method for recycling electrolytic manganese anode mud, the specific steps of which include:

[0010] Step 1, Wash with water:

[0011] Pre-wash: Add the electrolytic manganese anode mud to water at a solid-liquid ratio of 1:5-1:10 g / mL and perform a pre-wash for 5-10 minutes at room temperature;

[0012] Post-ultrasonic water washing: After the initial water washing, ultrasonic power of 1-5W / cm is applied. 2 The ultrasonic waves are then used to continue the subsequent ultrasonic water washing for 10-20 minutes. After the water washing is completed, the washed manganese anode sludge is obtained by filtration.

[0013] Step 2, Acid Immersion:

[0014] Add the washed manganese anode sludge obtained in step 1 to H2SO4 solution, H2O2 and tartaric acid, heat to 42-48℃ and acid leaching for 30-90 minutes. After completion, filter to obtain manganese leaching solution and lead concentrate.

[0015] Step 3, Impurity Removal:

[0016] Adjust the pH of the manganese leaching solution obtained in step 2 to 4.2-5.8, add MnS, and sulfide the solution at a temperature of 50-78℃ for 50-120 minutes to remove impurities. After filtration, the purified manganese leaching solution is obtained.

[0017] Step 4: Adjust pH:

[0018] Adjust the pH of the manganese leaching solution obtained in step 3 to 3-4;

[0019] Step 5, Extraction:

[0020] Step 5.1: Dilute the acidic phosphorus extractant with sulfonated kerosene to an extractant concentration of 15-40% to obtain the extractable organic phase;

[0021] Step 5.2: The extracted organic phase obtained in step 5.1 is passed through saturated clear lime water at a ratio of 1 to 5:1, and subjected to 3 to 5 stages of countercurrent calcium soap to remove the aqueous phase, thus obtaining the calcium soap organic phase.

[0022] Step 5.3: The calcium soap organic phase obtained in step 5.2 and the manganese leaching solution with pH 3-4 from step 4 are subjected to 3-5 stages of countercurrent extraction at a flow ratio of organic phase to aqueous phase of 1-6:1 to obtain the manganese-loaded organic phase.

[0023] Step 6, Back-extraction:

[0024] After washing the manganese-loaded organic phase obtained in step 5 with 0.1–0.5 mmol / L dilute sulfuric acid, the organic phase to aqueous phase was subjected to 3–5 stages of countercurrent back-extraction with 3–5 mol / L sulfuric acid solution at a flow ratio of 8–18:1 to prepare a high-purity manganese sulfate solution.

[0025] Step 7, Concentration and Crystallization:

[0026] The high-purity manganese sulfate solution obtained in step 6 is concentrated and crystallized to obtain the high-purity manganese sulfate product.

[0027] The electrolytic manganese anode mud in step 1 mainly comprises the following components by mass percentage: manganese content is 40%-55%, lead content is 4%-6%; the main phase of manganese is MnO2, and the main phase of lead is lead-manganese miscible oxide and lead sulfate.

[0028] In step 2, during the acid leaching process, the liquid-to-solid ratio of the manganese anode sludge to water is 1:3-8 g / mL.

[0029] In step 2, the mass ratio of H2O2 to water-washed manganese anode sludge during acid leaching is 0.4-0.8:1.

[0030] In step 2, the sulfuric acid concentration during acid leaching is 1.0–2.5 mol / L, and the liquid-to-solid ratio is 3–6:1 g / mL.

[0031] In step 2, the concentration of tartaric acid after its addition is 0.2–0.5 mol / L.

[0032] In step 3, the amount of MnS added during the impurity removal process is stoichiometric in a ratio of 1-1.5:1 between MnS and the theoretical lead content in the manganese leaching solution.

[0033] In steps 3 and 4, ammonia is used to adjust the pH value.

[0034] The acidic phosphorus extractant in step 5.1 includes one or more of P204, P507, and Cyanex 272 in any proportion.

[0035] In step 5.2, the saponification rate of the organic phase of the calcium soap is controlled to be 30-50%.

[0036] The manganese leaching solution obtained in step 2 above contains Mg 2+ Content 0.7g / L-1.5g / L; compared to conventional manganese-containing solutions such as qualified electrolytic manganese solutions, it has Mg content. 2+ The property of relatively low content.

[0037] The beneficial effects of this invention are:

[0038] (1) This invention obtains high-purity manganese sulfate product through a comprehensive treatment process of washing electrolytic manganese anode mud with water (including water washing in the first stage and ultrasonic water washing in the second stage) - obtaining manganese leaching solution with H2O2 acid leaching - removing impurities with manganese sulfide from manganese leaching solution - adjusting pH - extracting manganese with calcified organic phase - back-extracting manganese - concentration and crystallization. It introduces the minimum amount of precipitant for impurity removal, and efficiently achieves deep separation of manganese from impurities such as lead, selenium, calcium, and magnesium. The high-purity manganese sulfate product obtained meets the first-grade standard of "Manganese Sulfate for Batteries" (HG / T4823-2015).

[0039] (2) The washing process of this invention includes a pre-washing stage and a post-washing stage with ultrasonic washing. The pre-washing stage removes soluble salts and small amounts of calcium and magnesium salts from the electrolytic manganese anode mud. The post-washing stage incorporates ultrasonic treatment, which, on the one hand, more efficiently removes soluble salts and small amounts of calcium and magnesium salts, and on the other hand, fully exposes the Mn encapsulated in the anode mud through ultrasonic action, facilitating efficient leaching of Mn by subsequent H2O2 acid leaching. 2+ By performing a proper pretreatment process and introducing ultrasonic waves, the water washing temperature will directly reach 40-55℃ under the action of ultrasonic power, eliminating the need for separate water heating and making the water washing effect more obvious.

[0040] (3) The addition of tartaric acid to assist leaching in this invention can effectively slow down the decomposition of H2O2, ensuring maximum utilization of hydrogen peroxide in the redox reaction process, while reducing the amount of sulfuric acid used. The use of sulfuric acid and hydrogen peroxide as leaching agents and tartaric acid as an auxiliary leaching agent in this invention results in good leaching effect and economic benefits, enabling enterprises to reduce production costs and obtain higher economic benefits in later applications.

[0041] (4) In the extraction process of this invention, while ensuring the effective separation of manganese and calcium and magnesium ions, the cost of saponification can also be reduced. The residual tartaric acid organic matter added in the leaching section is also purified in the extraction section, ensuring that the manganese back-extraction solution extracts manganese in the manganese leaching solution with a pH of 3-4. Basically, the magnesium ions in the manganese leaching solution will not be extracted. Then, by calcium soaping the extractant, the calcium soap organic phase after calcium soaping will also not extract the calcium ions in the manganese leaching solution. This achieves efficient separation of manganese and calcium and magnesium ions in the manganese leaching solution without introducing new impurity ions.

[0042] (5) The present invention recovers manganese and lead from electrolytic manganese anode mud through a series of sequential processing steps to obtain high-purity manganese sulfate product and lead concentrate, which has the advantages of shorter processing flow and efficient separation of impurities. Attached Figure Description

[0043] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0044] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0045] Example 1

[0046] like Figure 1 As shown, the specific steps of this method for recycling electrolytic manganese anode mud include:

[0047] Step 1, Wash with water:

[0048] Pre-washing: Electrolytic manganese anode mud (the main components of electrolytic manganese anode mud are: manganese 40%, lead 5%, Ca 1.32wt%, Mg 0.44wt%, Se 0.15% by mass percentage; the main phase of manganese is MnO2, and the main phase of lead is lead-manganese schistose oxide and lead sulfate) is added to water at a solid-liquid ratio of 1:5 g / mL, and pre-washing is carried out at room temperature for 5 min;

[0049] Post-ultrasonic water washing: After the initial water washing, an ultrasonic power of 1W / cm is applied. 2 The ultrasonic waves (the reaction temperature can reach about 42℃ under the action of ultrasonic waves) are then used to continue the subsequent ultrasonic water washing for 10 minutes. After the water washing is completed, the manganese anode sludge is obtained by filtration.

[0050] Step 2, Acid Immersion:

[0051] The water-washed manganese anode sludge prepared in step 1 was added to H2SO4 solution, H2O2, and tartaric acid, heated to 42℃, and acid-leached for 30 minutes. After leaching, the solution was filtered to obtain manganese leaching solution and lead concentrate. The mass ratio of H2O2 (analytical grade) to water-washed manganese anode sludge was 0.4:1; the concentration of sulfuric acid solution was 1.5 mol / L, and the liquid-to-solid ratio of sulfuric acid solution to water-washed manganese anode sludge was 1:3 g / mL; the concentration of tartaric acid after adding tartaric acid was 0.2 mol / L.

[0052] Step 3, Impurity Removal:

[0053] The pH of the manganese leaching solution obtained in step 2 was adjusted to 4.2, MnS was added, and the solution was sulfided at 50°C for 50 min to remove impurities. After filtration, the purified manganese leaching solution was obtained. The amount of MnS added during the purification process was 1:1, which was the stoichiometric ratio of MnS to the theoretical lead content in the manganese leaching solution.

[0054] Step 4: Adjust pH:

[0055] Adjust the pH of the manganese leaching solution obtained in step 3 to 3-4;

[0056] Step 5, Extraction:

[0057] Step 5.1: Dilute P204 with sulfonated kerosene to a P204 extractant concentration of 15% to obtain the extractable organic phase;

[0058] Step 5.2: The extracted organic phase obtained in step 5.1 is passed through saturated clear limewater at a ratio of 1:1, and calcium soap is used in a three-stage countercurrent process to control the saponification rate of the calcium soap organic phase to 30%. After removing the aqueous phase, the calcium soap organic phase is obtained.

[0059] Step 5.3: The calcium soap organic phase obtained in step 5.2 and the manganese leaching solution with pH 3-4 from step 4 are subjected to three-stage countercurrent extraction at a flow ratio of 1:1 between the organic phase and the aqueous phase to obtain the manganese-loaded organic phase.

[0060] Step 6, Back-extraction:

[0061] After washing the manganese-loaded organic phase obtained in step 5 with 0.1 mmol / L dilute sulfuric acid, a 3 mol / L sulfuric acid solution was used for three-stage countercurrent back-extraction at a flow ratio of 8:1 between the organic phase and the aqueous phase to obtain a high-purity manganese sulfate solution.

[0062] Step 7, Concentration and Crystallization:

[0063] The high-purity manganese sulfate solution obtained in step 6 was de-oiled by adsorption with activated carbon, and then high-purity manganese carbonate was added to neutralize the pH to 4.0-4.2. Finally, the solution was concentrated and crystallized to obtain the high-purity manganese sulfate product.

[0064] In step 2 of this invention, the leaching rate of manganese in acid leaching reaches 98.2%. The H2O2 decomposition rate decreases by 10-30% after adding tartaric acid to assist leaching. The amount of sulfuric acid added is reduced by 50% compared to the conventional method of using sulfuric acid and hydrogen peroxide as leaching agents. This indicates that the leaching effect of the present invention, which uses sulfuric acid and hydrogen peroxide as leaching agents and tartaric acid as an auxiliary leaching agent, is economically efficient, enabling enterprises to reduce production costs and obtain higher economic benefits in later applications.

[0065] The high-purity manganese sulfate product prepared in step 7 of this invention has a manganese sulfate (MnSO4·H2O) mass percentage of 99.0%, and the mass percentages of Ca and Mg are both less than 0.01%. The high-purity manganese sulfate product prepared meets the first-grade standard of "Manganese Sulfate for Batteries" (HG / T4823-2015).

[0066] Example 2

[0067] like Figure 1 As shown, the specific steps of this method for recycling electrolytic manganese anode mud include:

[0068] Step 1, Wash with water:

[0069] Pre-washing: Electrolytic manganese anode mud (the main components of electrolytic manganese anode mud are: manganese 54.8%, lead 6%, Ca 1.53wt%, Mg 0.46wt%, Se 0.13% by mass percentage; the main phase of manganese is MnO2, and the main phase of lead is lead-manganese schistose oxide and lead sulfate) is added to water at a solid-liquid ratio of 1:10 g / mL, and pre-washing is carried out at room temperature for 10 min;

[0070] Post-ultrasonic water washing: After the initial water washing, an ultrasonic power of 5W / cm is applied. 2 The ultrasonic waves (the reaction temperature can reach about 55℃ under the action of ultrasonic waves) are then used to continue the subsequent ultrasonic water washing for 20 minutes. After the water washing is completed, the manganese anode sludge is obtained by filtration.

[0071] Step 2, Acid Immersion:

[0072] The water-washed manganese anode sludge prepared in step 1 was added to H2SO4 solution, H2O2, and tartaric acid, and heated to 48℃ for acid leaching for 90 min. After leaching, the solution was filtered to obtain manganese leaching solution and lead concentrate. The mass ratio of H2O2 (analytical grade) to water-washed manganese anode sludge was 0.8:1; the concentration of sulfuric acid solution was 2.5 mol / L, and the liquid-to-solid ratio was 1:6 g / mL; the concentration of tartaric acid after adding tartaric acid was 0.5 mol / L.

[0073] Step 3, Impurity Removal:

[0074] The pH of the manganese leaching solution obtained in step 2 was adjusted to 5.8, MnS was added, and the solution was sulfided at 78℃ for 120 min to remove impurities. After filtration, the purified manganese leaching solution was obtained. The amount of MnS added during the purification process was 1.5:1, which is the stoichiometric ratio of MnS to the theoretical lead content in the manganese leaching solution.

[0075] Step 4: Adjust pH:

[0076] Adjust the pH of the manganese leaching solution obtained in step 3 to 3-4;

[0077] Step 5, Extraction:

[0078] Step 5.1: Dilute P204 with sulfonated kerosene to a P204 extractant concentration of 40% to obtain the extractable organic phase;

[0079] Step 5.2: The extracted organic phase obtained in step 5.1 is passed through saturated clear limewater at a ratio of 5:1, and a 5-stage countercurrent calcium soap is used to control the saponification rate of the calcium soap organic phase to 50%. After removing the aqueous phase, the calcium soap organic phase is obtained.

[0080] Step 5.3: The calcium soap organic phase obtained in step 5.2 and the manganese leaching solution with pH 3-4 from step 4 are subjected to 5-stage countercurrent extraction at a flow ratio of organic phase to aqueous phase of 5:1 to obtain the manganese-loaded organic phase.

[0081] Step 6, Back-extraction:

[0082] After washing the manganese-loaded organic phase obtained in step 5 with 0.5 mmol / L dilute sulfuric acid, a 5-stage countercurrent back-extraction was performed with 5 mol / L sulfuric acid solution at a flow ratio of 6:1 between the organic phase and the aqueous phase to obtain a high-purity manganese sulfate solution.

[0083] Step 7, Concentration and Crystallization:

[0084] The high-purity manganese sulfate solution obtained in step 6 was de-oiled by adsorption with activated carbon, and then high-purity manganese carbonate was added to neutralize the pH to 4.0-4.2. Finally, the solution was concentrated and crystallized to obtain the high-purity manganese sulfate product.

[0085] In step 2 of this invention, the leaching rate of manganese in acid leaching reaches 98.6%. The H2O2 decomposition rate decreases by 10-60% after adding tartaric acid as an auxiliary leaching agent. The amount of sulfuric acid added is reduced by 30-40% compared to the conventional method using sulfuric acid and hydrogen peroxide as leaching agents. This demonstrates that the leaching effect and economic benefits of this invention, using sulfuric acid and hydrogen peroxide as leaching agents and tartaric acid as an auxiliary leaching agent, are good, enabling enterprises to reduce production costs and obtain higher economic benefits in later applications.

[0086] The high-purity manganese sulfate product prepared in step 7 of this invention has a manganese sulfate (MnSO4·H2O) mass percentage of 99.4%, and the mass percentages of Ca and Mg are both less than 0.01%. The high-purity manganese sulfate product prepared meets the first-grade standard of "Manganese Sulfate for Batteries" (HG / T4823-2015).

[0087] Example 3

[0088] like Figure 1 As shown, the specific steps of this method for recycling electrolytic manganese anode mud include:

[0089] Step 1, Wash with water:

[0090] Pre-washing: Electrolytic manganese anode mud (the main components of electrolytic manganese anode mud are: manganese 49.6%, lead 5%, Ca 1.45wt%, Mg 0.52wt%, Se 0.18% by mass percentage; the main phase of manganese is MnO2, and the main phase of lead is lead-manganese schistose oxide and lead sulfate) is added to water at a solid-liquid ratio of 1:8 g / mL, and pre-washing is carried out at room temperature for 8 min;

[0091] Post-ultrasonic water washing: After the initial water washing, an ultrasonic power of 3W / cm is applied. 2 The ultrasonic waves (the reaction temperature can reach about 50℃ under the action of ultrasonic waves) are then used to continue the subsequent ultrasonic water washing for 15 minutes. After the water washing is completed, the manganese anode sludge is obtained by filtration.

[0092] Step 2, Acid Immersion:

[0093] The water-washed manganese anode sludge prepared in step 1 was added to H2SO4 solution, H2O2, and tartaric acid, heated to 46℃ for acid leaching for 60 min, and then filtered to obtain manganese leaching solution and lead concentrate; the mass ratio of H2O2 (analytical grade) to water-washed manganese anode sludge was 0.6:1; the concentration of sulfuric acid solution was 2.0 mol / L, and the liquid-to-solid ratio of sulfuric acid solution to water-washed manganese anode sludge was 1:4 g / mL; after adding tartaric acid, the concentration of tartaric acid was 0.6 mol / L.

[0094] Step 3, Impurity Removal:

[0095] The pH of the manganese leaching solution obtained in step 2 was adjusted to 5.0, MnS was added, and the solution was sulfided at 60℃ for 100 min to remove impurities. After filtration, the purified manganese leaching solution was obtained. The amount of MnS added during the purification process was 1.2:1, which is the stoichiometric ratio of MnS to the theoretical lead content in the manganese leaching solution.

[0096] Step 4: Adjust pH:

[0097] Adjust the pH of the manganese leaching solution obtained in step 3 to 3-4;

[0098] Step 5, Extraction:

[0099] Step 5.1: Dilute P204 with sulfonated kerosene to a P204 extractant concentration of 25% to obtain the extractable organic phase;

[0100] Step 5.2: The extracted organic phase obtained in step 5.1 is passed through saturated clear limewater at a ratio of 3:1, and a 4-stage countercurrent calcium soap is used to control the saponification rate of the calcium soap organic phase to 40%. After removing the aqueous phase, the calcium soap organic phase is obtained.

[0101] Step 5.3: The calcium soap organic phase obtained in step 5.2 is mixed with the manganese-removing leaching solution with a pH of 3-4 from step 4.

[0102] The manganese-loaded organic phase was obtained by four-stage countercurrent extraction with an organic phase to aqueous phase flow ratio of 4:1.

[0103] Step 6, Back-extraction:

[0104] After washing the manganese-loaded organic phase obtained in step 5 with 0.4 mmol / L dilute sulfuric acid, a 4-stage countercurrent back-extraction was performed using a 4 mol / L sulfuric acid solution at a flow ratio of 4:1 between the organic phase and the aqueous phase to obtain a high-purity manganese sulfate solution.

[0105] Step 7, Concentration and Crystallization:

[0106] The high-purity manganese sulfate solution obtained in step 6 was de-oiled by adsorption with activated carbon, and then high-purity manganese carbonate was added to neutralize the pH to 4.0-4.2. Finally, the solution was concentrated and crystallized to obtain the high-purity manganese sulfate product.

[0107] In step 2 of this invention, the leaching rate of manganese in acid leaching reaches 99%. The H2O2 decomposition rate decreases by 10-60% after adding tartaric acid as an auxiliary leaching agent. The amount of sulfuric acid added is reduced by 40-60% compared to the conventional method using sulfuric acid and hydrogen peroxide as leaching agents. This demonstrates that the leaching effect of this invention, using sulfuric acid and hydrogen peroxide as leaching agents and tartaric acid as an auxiliary leaching agent, is economically efficient, enabling enterprises to reduce production costs and achieve higher economic benefits in later applications.

[0108] The high-purity manganese sulfate product prepared in step 7 of this invention has a manganese sulfate (MnSO4·H2O) mass percentage of 99.2%, and the mass percentages of Ca and Mg are both less than 0.01%. The high-purity manganese sulfate product prepared meets the first-grade standard of "Manganese Sulfate for Batteries" (HG / T4823-2015).

[0109] The specific embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A method for recycling electrolytic manganese anode mud, characterized in that... The specific steps include: Step 1, Wash with water: Pre-wash: Add the electrolytic manganese anode mud to water at a solid-liquid ratio of 1:5-1:10 g / mL and perform a pre-wash for 5-10 minutes at room temperature; Post-ultrasonic water washing: After the initial water washing, the ultrasonic power is controlled at 1-5W / cm. 2 Continue with subsequent ultrasonic water washing for 10-20 minutes. After water washing is completed, filter to obtain water-washed manganese anode sludge. Step 2, Acid Immersion: Add the washed manganese anode sludge obtained in step 1 to H2SO4 solution, H2O2 and tartaric acid, heat to 42-48℃ and acid leaching for 30-90 minutes. After completion, filter to obtain manganese leaching solution and lead concentrate. Step 3, Impurity Removal: Adjust the pH of the manganese leaching solution obtained in step 2 to 4.2-5.8, add MnS, and sulfide the solution at a temperature of 50-78℃ for 50-120 minutes to remove impurities. After filtration, the purified manganese leaching solution is obtained. Step 4: Adjust pH: Adjust the pH of the manganese leaching solution obtained in step 3 to 3-4; Step 5, Extraction: Step 5.1: Dilute the acidic phosphorus extractant with sulfonated kerosene to a concentration of 15-40% to obtain the extractable organic phase; Step 5.2: Mix the extracted organic phase obtained in step 5.1 with saturated clear limewater at a ratio of 1 to 5:1 and perform 3 to 5 stages of countercurrent calcium soaping to remove the aqueous phase and obtain the calcium soap organic phase. Step 5.3: The calcium soap organic phase obtained in step 5.2 and the manganese leaching solution with pH 3-4 from step 4 are subjected to 3-5 stages of countercurrent extraction at a flow ratio of organic phase to aqueous phase of 1-5:1 to obtain the manganese-loaded organic phase. Step 6, Back-extraction: The manganese-loaded organic phase obtained in step 5 is washed with 0.1~0.5 mmol / L dilute sulfuric acid, and then subjected to 3~5 stages of countercurrent back-extraction with 3~5 mol / L sulfuric acid solution at an organic phase to water phase flow ratio of 2~8:1 to prepare a high-purity manganese sulfate solution. Step 7, Concentration and Crystallization: The high-purity manganese sulfate solution obtained in step 6 is concentrated and crystallized to obtain the high-purity manganese sulfate product.

2. The method for recycling electrolytic manganese anode mud according to claim 1, characterized in that: The electrolytic manganese anode mud in step 1 comprises the following components by mass percentage: manganese content is 40%-55%, lead content is 4%-6%; the phase of manganese is MnO2, and the phase of lead is lead-manganese miscible oxide and lead sulfate.

3. The method for recycling electrolytic manganese anode mud according to claim 1, characterized in that: In step 2, the concentration of sulfuric acid solution during acid leaching is 1.5-3.0 mol / L, and the liquid-to-solid ratio is 1:3-6 g / mL.

4. The method for recycling electrolytic manganese anode mud according to claim 3, characterized in that: In step 2, the mass ratio of H2O2 to water-washed manganese anode sludge during acid leaching is 0.4-0.8:

1.

5. The method for recycling electrolytic manganese anode mud according to claim 4, characterized in that: The concentration of tartaric acid added in step 2 is 0.2~0.5 mol / L.

6. The method for recycling electrolytic manganese anode mud according to claim 1, characterized in that: In step 3, the amount of MnS added during the impurity removal process satisfies the stoichiometric ratio of MnS to the theoretical lead content in the manganese leaching solution as 1-1.5:

1.

7. The method for recycling electrolytic manganese anode mud according to claim 1, characterized in that: In steps 3 and 4, ammonia is used to adjust the pH value.

8. The method for recycling electrolytic manganese anode mud according to claim 1, characterized in that: The acidic phosphorus extractant in step 5.1 includes one or more of P204, P507, and Cyanex272 in any proportion.

9. The method for recycling electrolytic manganese anode mud according to claim 1, characterized in that: In step 5.2, the saponification rate of the organic phase of the calcium soap is controlled to be 30-50%.

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