CN-116555569-B - Electrolytic manganese anode slime recycling method

Abstract

The invention relates to a recycling method of electrolytic manganese anode slime, and belongs to the technical field of electrolytic manganese metal. The invention obtains a manganese leaching solution by washing electrolytic manganese anode slime (comprising washing in the front section and ultrasonic washing in the rear section) -H 2 O 2 acid leaching, removes impurities of manganese sulfide in the manganese leaching solution, adjusts pH value, calcifies organic phase to extract manganese, strip manganese, and concentrates and crystallizes to obtain a high-purity manganese sulfate product. According to the invention, the manganese and lead in the electrolytic manganese anode slime are recovered through a series of sequential treatment steps, so that a high-purity manganese sulfate product and lead concentrate are obtained, and the method has the advantages of shorter treatment flow and high-efficiency impurity separation.

Inventors

• CHANG JUN
• QIN LIN
• ZHANG CHAO
• REN FUZHONG
• XIE ZINAN
• YUAN YA
• WANG ZIYANG
• LI XUEPENG

Assignees

• 贵州武陵锰业有限公司
• 铜仁学院

Dates

Publication Date

20260512

Application Date

20230531

Claims (9)

1. 1. The method for recycling the electrolytic manganese anode slime is characterized by comprising the following specific steps of: Step 1, washing: Front-stage water washing, namely adding water into electrolytic manganese anode slime according to the solid-to-liquid ratio of 1:5-1:10g/mL, and carrying out front-stage water washing for 5-10min at normal temperature; the back-stage ultrasonic washing, namely after the front-stage washing, controlling the ultrasonic power to be 1-5W/cm 2 , continuing the back-stage ultrasonic washing for 10-20min, and filtering after the washing is finished to obtain washing manganese anode sludge; Step 2, acid leaching: Adding H 2 SO 4 solution, H 2 O 2 and tartaric acid into the water-washed manganese anode sludge prepared in the step 1, heating to 42-48 ℃ for pickling for 30-90 min, and filtering to obtain manganese leaching liquid and lead concentrate; Step 3, removing impurities: Regulating the pH value of the manganese immersion liquid obtained in the step 2 to 4.2-5.8, adding MnS, vulcanizing at 50-78 ℃ for removing impurities for 50-120min, and filtering to obtain an impurity-removed manganese immersion liquid; step 4, adjusting pH: adjusting the pH value of the impurity-removed manganese immersion liquid obtained in the step3 to 3-4; step 5, extraction: step 5.1, diluting an acidic phosphorus extractant with sulfonated kerosene to a concentration of 15-40% to obtain an extracted organic phase; step 5.2, carrying out 3-5-grade countercurrent calcium soap on the extracted organic phase obtained in the step 5.1 and saturated clarified lime water according to the ratio of 1-5:1, and removing the water phase to obtain a calcium soap organic phase; Step 5.3, carrying out countercurrent extraction on the calcium soap organic phase obtained in the step 5.2 and the impurity-removed manganese leaching liquid with the pH value of 3-4 obtained in the step 4 according to the flow ratio of the organic phase to the water phase of 1-5:1, and obtaining a manganese-loaded organic phase; Step 6, back extraction: washing the manganese-loaded organic phase obtained in the step 5 with 0.1-0.5 mmol/L dilute sulfuric acid, and carrying out 3-5-level countercurrent back extraction with 3-5 mol/L sulfuric acid solution according to the flow ratio of the organic phase to the water phase of 2-8:1 to obtain a high-purity manganese sulfate solution; Step 7, concentrating and crystallizing: And (3) concentrating and crystallizing the high-purity manganese sulfate solution obtained in the step (6) to obtain a high-purity manganese sulfate product.
2. 2. The method for recycling the electrolytic manganese anode slime according to claim 1, wherein the electrolytic manganese anode slime in the step 1 comprises 40-55% of manganese content and 4-6% of lead content by mass percent, wherein the phase of manganese is MnO 2 , and the phase of lead is lead-manganese complex crystal oxide and lead sulfate.
3. 3. The method for recycling electrolytic manganese anode slime according to claim 1, wherein the concentration of sulfuric acid solution in the acid leaching process of the step 2 is 1.5-3.0mol/L, and the liquid-solid ratio is 1:3-6 g/mL.
4. 4. The method for recycling electrolytic manganese anode slime according to claim 3, wherein the mass ratio of H 2 O 2 to water-washed manganese anode slime in the acid leaching process of the step 2 is 0.4-0.8:1.
5. 5. The method for recycling electrolytic manganese anode slime according to claim 4, wherein the concentration of tartaric acid added in the step 2 is 0.2-0.5 mol/L.
6. 6. The method for recycling electrolytic manganese anode slime according to claim 1, wherein the addition amount of MnS in the impurity removing process in the step 3 satisfies the stoichiometric ratio of MnS to the theoretical lead content in the manganese immersion liquid of 1-1.5:1.
7. 7. The method for recycling the anode slime of the electrolytic manganese according to claim 1, wherein the step 3 and the step 4 are characterized in that ammonia water is adopted to adjust the pH value.
8. 8. The method for recycling electrolytic manganese anode slime according to claim 1, wherein the acidic phosphorus extractant in the step 5.1 comprises one or a combination of more of P204, P507 and Cyanex272 according to any proportion.
9. 9. The method for recycling electrolytic manganese anode slime according to claim 1, wherein the saponification rate of the calcium soap organic phase is controlled to be 30-50% in the step 5.2.

Description

Electrolytic manganese anode slime recycling method Technical Field The invention relates to a recycling method of electrolytic manganese anode slime, and belongs to the technical field of electrolytic manganese metal. Background In the electrolytic manganese metal production process, the anode region Mn 2+ is inevitably oxidized and forms a hydrated oxide of Mn 4+, and meanwhile, lead-tin alloy in the anode plate is oxidized and is precipitated together with manganese oxide hydrate to form electrolytic manganese anode mud. The content of manganese and lead in the electrolytic manganese anode slime is 42-55% and 3-10% respectively. Because the electrolytic manganese anode slime contains valuable metals, the electrolytic manganese anode slime is generally directly sold. However, the economic value of the manganese anode slime is low when the manganese anode slime is sold, and the high-value utilization of manganese and lead in the manganese anode slime cannot be realized. And (3) preparing manganese sulfate, manganese dioxide or lithium manganate products according to the basic properties of the anode slime after recycling manganese in the electrolytic manganese anode slime. For example, patent application number 2021105370325, a high-value utilization method of electrolytic manganese anode slime. The invention discloses a high-value utilization method of electrolytic manganese anode slime, relates to the technical field of manganese slag recycling, and solves the technical problem that in the recycling process of electrolytic manganese anode slime in the prior art, impurities such as Ca, mg, sulfate and the like are not deeply purified to limit the high-value utilization of electrolytic manganese anode slime. According to the high-value utilization method of the electrolytic manganese anode slime, ca, mg, sulfate and other impurities in the electrolytic manganese anode slime are removed efficiently by adopting water washing, alkali washing and acid leaching methods in sequence, the anode slime after impurity removal is leached by adopting hydrogen peroxide and sulfuric acid, and the obtained leaching liquid is a high-purity manganese sulfate solution, and leaching residues are lead concentrate. However, the method removes Ca, mg, sulfate and other impurities in the electrolytic manganese anode slime through pretreatment, and does not relate to the removal of other impurities, so that a corresponding high-purity manganese sulfate product cannot be obtained. More importantly, when sulfuric acid and hydrogen peroxide are used as leaching agents, the reaction temperature is 30-60 ℃, the decomposition of the hydrogen peroxide is unavoidable, and the sulfuric acid consumption is large. In the process of preparing the high-purity manganese sulfate product, a reducing agent is usually adopted in a sulfuric acid system to convert Mn 4+ in electrolytic manganese anode slime into Mn 2+ to enter a solution, and other impurities such as lead exist in a solid phase, so that comprehensive utilization of manganese is realized. The common conventional Mn 2+ solution can adopt a precipitation method to remove impurities such as lead, selenium, calcium, magnesium and the like. However, in the process of removing by precipitation, a precipitant is required to be added, and new impurity ions are introduced by adding the precipitant, for example, wang Dequan, song Shuangqing and the like when iron impurities in Mn 2+ solution are removed, so that the pyrolusite is directly leached by steel pickling solution, the low-grade manganese ore is treated by a ferric alum precipitation method, the low-grade manganese ore is leached by ferrous sulfate, and the leaching solution is treated by the ferric alum precipitation method. I.e. iron removal, requires the introduction of a new precipitant. In order to remove heavy metal ion impurities in the Mn 2+ solution, a vulcanizing agent is required to be added as a precipitant. In order to remove impurities such as calcium and magnesium in manganese sulfate solution, wang Yong and the like, a process study of deep impurity removal of calcium and magnesium in industrial manganese sulfate is disclosed, and new fluoride ions are introduced by adding a manganese fluoride precipitant to deeply remove the impurities of calcium and magnesium. Therefore, how to effectively separate impurity ions from Mn 2+, does not need to introduce other ions, and realizes the efficient recycling of manganese in electrolytic manganese anode slime, thus obtaining a high-purity manganese sulfate product is a technical problem. Disclosure of Invention Aiming at the problems and the defects existing in the prior art, the invention provides a recycling method of electrolytic manganese anode slime. The invention carries out water washing (comprising water washing in the front section and ultrasonic water washing in the rear section) -H 2O2 acid leaching to obtain manganese immersion liquid-manganese sulfide impurity remov