Method for treating electrolytic manganese residue

Abstract

The application relates to the chemical field and the solid waste treatment field, and discloses a treatment method of electrolytic manganese residue.(1) First mixing is carried out on anode waste liquid of an electrolytic manganese process and electrolytic manganese residue, then first solid-liquid separation is carried out, and first solid phase and first liquid phase are obtained;(2) The first liquid phase is adjusted, second mixing is carried out on the first liquid phase and a sulfuration agent, then second solid-liquid separation is carried out, and second solid phase and second liquid phase are obtained;(3) Carbon dioxide is introduced into the second liquid phase until precipitation is generated, third solid-liquid separation is carried out on the material, and third solid phase and third liquid phase are obtained;(4) Third mixing is carried out on the first solid phase and water, ammonia gas and carbon dioxide are introduced, then fourth solid-liquid separation is carried out, and fourth solid phase and fourth liquid phase are obtained. By adopting the method, manganese elements can be extracted at a high recovery rate, sulfur can also be extracted at a high recovery rate, ammonium sulfate can be produced, the operation cost is low, and the method is more beneficial for enterprise implementation.

Description

TECHNICAL FIELD

[0001] The present application relates to the fields of chemical industry and solid waste treatment, and in particular to a treatment method of electrolytic manganese residue. BACKGROUND

[0002] Electrolytic manganese residue is an acidic waste residue produced after the acid leaching, neutralization and filter pressing processes of manganese ore (such as manganese oxide, manganese carbonate ore, etc.) in the production process of electrolytic manganese. Due to the technical limitations of each process link, part of the soluble manganese remains in the electrolytic manganese residue in the form of manganese sulfate. At the same time, the ammonia water adjusting liquid added in the production process cannot be completely utilized and is also present in the electrolytic manganese residue. Therefore, the electrolytic manganese residue often contains manganese sulfate, manganese, ammonia nitrogen, quartz and part of other metals (such as iron, aluminum, calcium and magnesium, etc.). The large amount of sulfate in the electrolytic manganese residue limits the large-scale utilization of the electrolytic manganese residue. At present, electrolytic manganese production enterprises in China mainly dispose of electrolytic manganese residue by means of residue field stacking. The high concentration of heavy metal ions and ammonia nitrogen contained in the leachate produced in the residue field seriously pollutes the surrounding environment.

[0003] Currently, there are also some treatment technologies for electrolytic manganese residue. Among them, there is a scheme of high-temperature calcination, but it fails to effectively utilize other effective components in the manganese residue and fully extract manganese elements. In addition, high-temperature calcination consumes a large amount of energy, has super-high energy consumption, and correspondingly increases the cost. It has large investment and high operating cost. In addition, CN202210368715.7 discloses another treatment route, which mainly includes: first, placing a mixture of electrolytic manganese residue and alkaline residue in a first container, adding water and stirring to obtain ammonia gas and slurry; second, introducing the ammonia gas into a second container containing water, and then introducing industrial tail gas containing CO2 to obtain an ammonium carbonate solution; solid-liquid separation to obtain modified manganese residue; third, mixing the ammonium carbonate solution with the electrolytic manganese residue to prepare calcium carbonate and ammonium sulfate; pressure filtration of the modified manganese residue to obtain modified manganese residue cake and alkaline wastewater; finally, introducing the alkaline wastewater into the first container; drying and pulverizing the modified manganese residue cake to obtain an alkaline sulfate composite activator. However, in this way, the conversion rate of sulfur in the electrolytic manganese residue to ammonium sulfate is low, and the manganese elements are not fully extracted.

[0004] Therefore, it is necessary to develop a treatment process for electrolytic manganese residue which has low energy consumption and cost, can fully extract effective components in the manganese residue, and can safely dispose of the manganese residue to reduce environmental pollution and realize the resource utilization of waste. It is necessary to base on the basic principles of resource recycling and safe utilization. SUMMARY

[0005] The present application aims to overcome the above problems existing in the prior art, and provides a treatment method of electrolytic manganese residue, which can extract manganese elements with a high recovery rate, and can also extract sulfur with a high recovery rate and produce ammonium sulfate, the electrolytic manganese residue treated by the method has a significantly reduced content of manganese and sulfate, and can be used for the production of building materials and the like.

[0006] To achieve the above-mentioned purpose, the present application provides a treatment method of electrolytic manganese residue, which comprises:

[0007] (1) mixing electrolytic manganese process anode waste liquid and electrolytic manganese residue for the first time, and then performing first solid-liquid separation to obtain first solid phase and first liquid phase;

[0008] The mass ratio of the electrolytic manganese process anode waste liquid to the electrolytic manganese residue is (4-7):1, and the particle size of the electrolytic manganese residue is not higher than 3 mm;

[0009] (2) adjusting the first liquid phase to pH 7-9, and mixing with a sulfidizing agent for the second time, and then performing second solid-liquid separation to obtain second solid phase and second liquid phase;

[0010] The mass amount of the sulfidizing agent is 0.01-0.03wt% of the mass of the first liquid phase;

[0011] (3) introducing carbon dioxide into the second liquid phase to generate a precipitate, and performing third solid-liquid separation to obtain third solid phase and third liquid phase;

[0012] (4) mixing the first solid phase with water for the third time, introducing ammonia gas and carbon dioxide, and then performing fourth solid-liquid separation to obtain fourth solid phase and fourth liquid phase, and returning the fourth liquid phase to be mixed with the first liquid phase for step (2).

[0013] The above technical solution can extract manganese elements with a high recovery rate, and can also extract sulfur with a high recovery rate and produce ammonium sulfate, the electrolytic manganese residue treated by the method has a significantly reduced content of manganese and sulfate, and can be used for the production of building materials and the like. The treatment method provided by the present application has a low operation cost, and can obtain recyclable products with a high yield under the condition that harmful components are fully removed, thereby improving economic benefits and being more beneficial for enterprises to implement. DETAILED DESCRIPTION

[0014] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the practice of the application. The endpoints of the ranges and any numerical values are to be understood as approximations, and are to be rounded to the nearest significant figure, unless otherwise indicated. The numerical values are approximations that can vary by 10% or more units in either direction.

[0015] The application provides a treatment method of electrolytic manganese residue, the method comprises:

[0016] (1) mixing the electrolytic manganese process anode waste liquid and the electrolytic manganese residue, and then performing first solid-liquid separation to obtain a first solid phase and a first liquid phase;

[0017] The mass ratio of the electrolytic manganese process anode waste liquid to the electrolytic manganese residue is (4-7):1, and the particle size of the electrolytic manganese residue is not higher than 3 mm.

[0018] (2) adjusting the first liquid phase to pH 7-9 (for example, it can be 7, 7.1, 7.3, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, and a range formed by any two of the above values and values in the range), and mixing with a sulfidizing agent, and then performing second solid-liquid separation to obtain a second solid phase and a second liquid phase;

[0019] The mass amount of the sulfidizing agent is 0.01-0.03wt% of the mass of the first liquid phase.

[0020] (3) introducing carbon dioxide into the second liquid phase to generate a precipitate, and performing third solid-liquid separation to obtain a third solid phase and a third liquid phase;

[0021] (4) mixing the first solid phase with water, introducing ammonia gas and carbon dioxide, and then performing fourth solid-liquid separation to obtain a fourth solid phase and a fourth liquid phase, and returning the fourth liquid phase to be mixed with the first liquid phase to perform step (2) together.

[0022] It can be understood that the electrolytic manganese residue is an acidic waste residue produced after the manganese ore (such as manganese oxide, manganese carbonate ore, etc.) is subjected to acid leaching, neutralization and pressure filtration in the production process of the electrolytic manganese process, wherein the content of Mn (calculated as metallic manganese) is generally 2-4wt%, the content of SiO2 is generally 15-30wt%, the content of Fe2O3 (calculated as the content of iron in diiron trioxide) is generally 5-15wt%, the content of Al2O3 (calculated as the content of aluminum in di-aluminum trioxide) is generally 5-15wt%, the content of SO3 (calculated as the content of sulfur in trioxide) is generally 20-40wt%, the content of CaO (calculated as the content of calcium in oxide) is generally 10-20wt%, the content of MgO (calculated as the content of magnesium in oxide) is generally 1-3wt%, the content of ammonium sulfate is generally 2-5wt%, and the water content is generally 10-30wt%.

[0023] The inventors of the present application found in research that, by using the first mixing as described above, the manganese element in the electrolytic manganese residue can be extracted into the liquid phase at a relatively high recovery rate. Moreover, as a waste material produced in the internal production process of an electrolytic manganese production enterprise, the use of the electrolytic manganese process anode waste liquid fully utilizes the waste resources, and the process operation is more economical. It is more easily accepted by enterprises. Under the action of the sulfurizing agent, heavy metal elements such as cobalt and nickel can be fully precipitated. Moreover, in step (3), the introduction of carbon dioxide can fully precipitate the manganese element in the form of manganese carbonate, and the third liquid phase contains a large amount of ammonium sulfate, which can be obtained in the form of an ammonium sulfate product through evaporation crystallization in the subsequent process, and the sulfate radical in the electrolytic manganese residue is fully extracted. The fourth solid phase obtained in step (4) mainly includes calcium carbonate, a small amount of metal elements and other insoluble silicates, and can be used for the production of building materials and the like, fully realizing the resource utilization of the electrolytic manganese residue.

[0024] According to the present application, preferably, in step (1), the mass ratio of the electrolytic manganese process anode waste liquid to the electrolytic manganese residue is (5-6):1.

[0025] According to the present application, preferably, the particle size of the electrolytic manganese residue is 0.05-3mm.

[0026] Under the above conditions, the manganese element can be extracted from the electrolytic manganese residue at a higher extraction rate.

[0027] The electrolytic manganese process anode waste liquid is a common waste material produced in the internal production process of an electrolytic manganese production enterprise, and the present application does not have special requirements for the composition of the electrolytic manganese process anode waste liquid itself. According to the present application, preferably, in step (1), the mass content of H2SO4 in the electrolytic manganese process anode waste liquid is 32-48g / l. The electrolytic manganese process anode waste liquid also contains other substances, such as Mn 2+ (content can be 14.5-16.6g / L), (NH4)2SO4 (content can be 75-85g / L), Mg2+ (The content can be 18-23g / L), which may also contain some silicates (mainly potassium, aluminum, calcium and sodium), the content of which can be 100-200g / L.

[0028] According to the present invention, preferably, in step (1), the temperature of the first mixing is 20-45 °C (for example, it can be 20, 23, 25, 28, 30, 32, 35, 38, 39, 40, 42, 45, or any two of the above values) °C, and the time is 20-60 min (for example, it can be 20, 23, 25, 28, 30, 32, 35, 38, 40, 45, 50, 55, 60, or any two of the above values). The first mixing can be carried out under stirring conditions, and the rotation speed can be 40-60 rpm. Using the method provided by the present invention, the mixing can be carried out at the relatively low temperature mentioned above, thus avoiding the high energy consumption problem in high-temperature calcination processes.

[0029] According to the present invention, preferably, in step (1), the first mixing further includes introducing Fe into the mixture. 2+ In electrolytic manganese slag, insoluble high-valence manganese is reduced to easily soluble Mn. 2+ This can further significantly improve the recovery rate of manganese.

[0030] Preferably, Fe 2+ Introduced in the form of FeO.

[0031] Preferably, Fe 2+ The amount of [material] introduced is [amount], and the mass ratio of electrolytic manganese slag to FeO is (0.5-3):500.

[0032] The inventors of this invention have specifically discovered in their research that when the method described above is followed, the recovery rate of manganese can be significantly improved.

[0033] According to the present invention, preferably, in step (2), the pH of the first liquid phase is adjusted by introducing ammonia gas into the first liquid phase.

[0034] According to the present invention, preferably, in step (2), the pH of the first liquid phase is adjusted to 7.5-8.5.

[0035] According to the present invention, preferably, the vulcanizing agent is selected from ammonium sulfide and / or sodium N,N-dimethylaminodithiocarbamate.

[0036] Under the above conditions, it is possible to further ensure that heavy metals such as cobalt and nickel extracted from the liquid phase are fully precipitated.

[0037] According to the present application, preferably, in step (3), the mass amount of carbon dioxide is 3-8wt% of the mass of the second liquid phase. In this way, manganese can be sufficiently precipitated in the form of manganese carbonate.

[0038] According to the present application, preferably, in step (3), the third liquid phase is subjected to evaporation crystallization. In this way, ammonium sulfate product can be obtained. The evaporation crystallization can be performed such that the water content in the solid is less than 0.5wt%.

[0039] According to the present application, preferably, in step (4), the mass amount ratio of water to the first solid phase is (5-6):1.

[0040] According to the present application, preferably, in step (4), after the third mixing, ammonia gas is first introduced until the pH of the material is 8.2-10 (for example, it can be 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10, and any two of the above values or a range formed by the above values and values within the range), preferably 8.5-9.5, and then carbon dioxide is introduced, the mass amount of carbon dioxide is 5-15wt% of the mass of water, preferably 8-11wt%. The introduction of carbon dioxide can be completed within 30-120min, and stirring is performed during the introduction. In this way, calcium sulfate contained in the first solid phase can be converted into calcium carbonate through reaction, and ammonium sulfate exists in the liquid phase. The fourth liquid phase is returned to be mixed with the first liquid phase, and step (2) is performed together, and the ammonium sulfate in this part can also be extracted, and higher ammonium sulfate yield can be obtained.

[0041] In the present application, the specific method of solid-liquid separation is not particularly limited, and can be filtration (suction filtration), centrifugation, etc.

[0042] The carbon dioxide generated in the electrolytic manganese process can be introduced into the present application for use. In this way, the carbon dioxide can also be solidified, carbon emission can be reduced, and the production process is more environmentally friendly.

[0043] As described above, the present application provides a treatment method for electrolytic manganese residue, which recovers carbon dioxide produced in the production process of the electrolytic manganese production enterprise by using the material of the electrolytic manganese production enterprise itself, develops an economically feasible resource utilization process route for extracting sulfate to prepare ammonium sulfate, sufficiently reduces the content of sulfate in the waste residue, obtains ammonium sulfate product with high yield, and fully extracts manganese from the manganese residue. The treated electrolytic manganese residue can be used as a building material raw material, and the above operations can be completed at a low operating cost. In this way, the electrolytic manganese production process and the electrolytic manganese residue treatment process can be fully combined, the material can be recycled, and waste can be reduced.

[0044] The application will be described in detail below by way of examples.

[0045] In the following examples, the carbon dioxide used comes from an electrolytic manganese production process.

[0046] The electrolytic manganese slag used in the following examples has a Mn (calculated as metallic manganese) content of 2.87wt%, a SiO2content of 17.45wt%, a Fe2O3(content calculated as iron content of diiron trioxide) content of 10.12wt%, an Al2O3(content calculated as aluminum content of di-aluminum trioxide) content of 10.57wt%, a SO3(content calculated as sulfur content of sulfur trioxide) content of 30.23wt%, a CaO(content calculated as calcium content of calcium oxide) content of 16.16wt%, a MgO(content calculated as magnesium content of magnesium oxide) content of 2.28wt%, ammonium sulfate of 2.43wt%, and a water content of 23.61wt%.

[0047] In the following, the recovery rate of manganese in the electrolytic manganese slag is calculated as follows: the mass of manganese in the original electrolytic manganese slag minus the mass of manganese in the fourth solid phase, and the ratio of the difference to the mass of manganese in the original electrolytic manganese slag. The recovery rate of sulfur in the electrolytic manganese slag is calculated as follows: the mass of sulfur in the original electrolytic manganese slag minus the mass of sulfur in the fourth solid phase, and the ratio of the difference to the mass of sulfur in the original electrolytic manganese slag.

[0048] In the following, the content of manganese and sulfur in the material is determined by JY / T0569-2020 General Method for Wavelength Dispersive X-ray Fluorescence Spectrometry.

[0049] Example 1

[0050] (1) 2500g of electrolytic manganese process anode waste liquid (Mn 2+ : 15.5g / l, (NH4)2SO4: 80g / l, H2SO4: 40g / l, Mg 2+ : 21g / l, silicate 150g / l) is mixed with 500g of ground electrolytic manganese slag powder (particle size 0.05-2mm), 1g of FeO powder, stirred (speed 60rpm) at a constant temperature of 30℃ for 50min, and then first solid-liquid separation (suction filtration) is performed to obtain a first solid phase and a first liquid phase;

[0051] (2) Ammonia gas is introduced into the first liquid phase to adjust the pH to 7.5, and then ammonium sulfide with a mass of 0.01wt% of the mass of the first liquid phase is added to obtain a precipitate. Second solid-liquid separation (filtration) is performed to obtain a second solid phase and a second liquid phase;

[0052] (3) Carbon dioxide is introduced into the second liquid phase, with a mass of 6wt% of the mass of the second liquid phase. A precipitate is obtained, and third solid-liquid separation (filtration) is performed to obtain a third solid phase (manganese carbonate) and a third liquid phase;

[0053] The third liquid phase is subjected to evaporation crystallization to obtain an ammonium sulfate product;

[0054] (4) The first solid phase is taken, 5 times the mass of the solid is added to the water, and ammonia gas is introduced to make the pH 9, and then carbon dioxide is introduced (the mass usage is 8wt% of the mass of the water), the introduction of carbon dioxide is completed within 50 min, and stirring is performed during the period. Then the fourth solid-liquid separation (filtration) is performed to obtain a fourth solid phase and a fourth liquid phase.

[0055] The fourth liquid phase is returned to be mixed with the first liquid phase to jointly perform step (2).

[0056] The recovery rate of manganese in the electrolytic manganese residue is 73wt%, and the recovery rate of sulfur in the electrolytic manganese residue is 61wt%.

[0057] Example 2

[0058] (1) The electrolytic manganese process anode waste liquid (Mn 2+ : 15.2g / l, (NH4)2SO4: 78g / l, H2SO4: 42g / l, Mg 2+ : 21g / l, silicate is 162g / l) 2750g, is mixed with 500g of ground electrolytic manganese residue powder (particle size is 0.05-2.5mm), 0.9g of FeO powder, constant temperature 35℃ stirring (rotation speed 55rpm) 40min, then the first solid-liquid separation (suction filtration) is performed to obtain a first solid phase and a first liquid phase;

[0059] (2) Ammonia gas is introduced into the first liquid phase to adjust the pH to 8, and then 0.03wt% of ammonium sulfide with respect to the mass of the first liquid phase is added to obtain a precipitate. The second solid-liquid separation (filtration) is performed to obtain a second solid phase and a second liquid phase;

[0060] (3) Carbon dioxide is introduced into the second liquid phase, and the mass usage is 6.5wt% of the mass of the second liquid phase; a precipitate is obtained, and the third solid-liquid separation (filtration) is performed to obtain a third solid phase and a third liquid phase;

[0061] The third liquid phase is subjected to evaporation crystallization to obtain an ammonium sulfate product;

[0062] (4) The first solid phase is taken, 5 times the mass of the solid is added to the water, and ammonia gas is introduced to make the pH 9, and then carbon dioxide is introduced (the mass usage is 8wt% of the mass of the water), the introduction of carbon dioxide is completed within 50 min, and stirring is performed during the period. Then the fourth solid-liquid separation (filtration) is performed to obtain a fourth solid phase and a fourth liquid phase.

[0063] The fourth liquid phase is returned to be mixed with the first liquid phase to jointly perform step (2).

[0064] The recovery rate of manganese in the electrolytic manganese residue is 74wt%, and the recovery rate of sulfur in the electrolytic manganese residue is 64wt%.

[0065] Example 3

[0066] (1) Take the electrolytic manganese process anode waste liquid (Mn 2+ : 15.7g / l, (NH4)2SO4: 81g / l, H2SO4: 38g / l, Mg 2+ : 21g / l, silicate is 148g / l) 3000g, mix with 500g of ground electrolytic manganese residue powder (particle size is 0.05-1.5mm), 1g of FeO powder, constant temperature 40℃ stirring (speed 50rpm) for 30min, then first solid-liquid separation (suction filtration) is carried out to obtain the first solid phase and the first liquid phase;

[0067] (2) Ammonia gas is introduced into the first liquid phase to adjust the pH to 8.5, then 0.02wt% of ammonium sulfide with the mass of the first liquid phase is added to obtain the precipitate. The second solid-liquid separation (filtration) is carried out to obtain the second solid phase and the second liquid phase;

[0068] (3) Carbon dioxide is introduced into the second liquid phase, and the mass usage is 5.5wt% of the mass of the second liquid phase; the precipitate is obtained, and the third solid-liquid separation (filtration) is carried out to obtain the third solid phase and the third liquid phase;

[0069] The third liquid phase is subjected to evaporation crystallization to obtain the ammonium sulfate product;

[0070] (4) Take the first solid phase solid, add 5.5 times the mass of the solid to the water, and introduce ammonia gas to make the pH 9.3, then introduce carbon dioxide (the mass usage is 11wt% of the mass of the water), and the introduction of carbon dioxide is completed within 80min, and stirring is carried out during the period. Then the fourth solid-liquid separation (filtration) is carried out to obtain the fourth solid phase and the fourth liquid phase.

[0071] The fourth liquid phase is returned to be mixed with the first liquid phase to carry out step (2) together.

[0072] The recovery rate of manganese in the electrolytic manganese residue is 74wt%, and the recovery rate of sulfur in the electrolytic manganese residue is 66wt%.

[0073] Example 4

[0074] According to the method of example 1, except that in step (4) ammonia gas is introduced to make the pH 8.2. The recovery rate of manganese is 72wt%, and the recovery rate of sulfur is 57wt%.

[0075] Example 5

[0076] The method of example 1 was followed, except that in step (4), the pH was adjusted to 7.5 by bubbling ammonia gas. The recovery rate of manganese was 72.5wt%, and the recovery rate of sulfur was 34wt%.

[0077] Example 6

[0078] The method of example 1 was followed, except that in step (2), the pH was adjusted to 7.2 by bubbling ammonia gas. The recovery rate of manganese was 69wt%, and the recovery rate of sulfur was 61wt%.

[0079] Example 7

[0080] The method of example 1 was followed, except that in step (4), the amount of carbon dioxide added was 7wt% of the mass of water. The recovery rate of manganese was 69wt%, and the recovery rate of sulfur was 57wt%.

[0081] Example 8

[0082] The method of example 1 was followed, except that in step (1), FeO was not introduced.

[0083] The recovery rate of manganese in the electrolytic manganese residue was 68wt%, and the recovery rate of sulfur in the electrolytic manganese residue was 61wt%.

[0084] Comparative Example 1

[0085] The method of example 1 was followed, except that in step (1), the particle size of the electrolytic manganese residue was 3-5mm. The recovery rate of manganese was 72wt%, and the recovery rate of sulfur was 53wt%.

[0086] In the case of using the method provided by the present application, taking an enterprise with an annual production of 25,000 tons of manganese and an annual processing of about 200,000 tons of electrolytic manganese residue as an example, about 4,000 tons of soluble manganese (calculated based on a manganese recovery rate of 70%) and 55,905 tons of ammonium sulfate (calculated based on a sulfur recovery rate of 60%) can be recovered annually, which can provide raw materials for 400,000 tons / year of cement. About 40,000 tons of carbon dioxide can be solidified annually, which makes a positive contribution to reducing carbon emissions.

[0087] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A method for treating electrolytic manganese residue, characterized in that, The method comprises: (1) mixing electrolytic manganese process anode waste liquid and electrolytic manganese residue first, then performing first solid-liquid separation to obtain first solid phase and first liquid phase; Wherein, the mass ratio of electrolytic manganese process anode waste liquid to electrolytic manganese residue is (4-7):1, and the particle size of electrolytic manganese residue is not higher than 3mm; (2) adjusting the pH of the first liquid phase to 7-9, and mixing with a sulfiding agent second, then performing second solid-liquid separation to obtain second solid phase and second liquid phase; Wherein, the mass amount of sulfiding agent is 0.01-0.03wt% of the mass of the first liquid phase; (3) introducing carbon dioxide into the second liquid phase to generate a precipitate, and performing third solid-liquid separation to obtain third solid phase and third liquid phase; (4) mixing the first solid phase with water third, introducing ammonia gas and carbon dioxide, then performing fourth solid-liquid separation to obtain fourth solid phase and fourth liquid phase, and returning the fourth liquid phase to mix with the first liquid phase to perform step (2) together.

2. The method of claim 1, wherein, In step (1), the mass ratio of electrolytic manganese process anode waste liquid to electrolytic manganese residue is (5-6):1; And / or, the particle size of electrolytic manganese residue is 0.05-3mm.

3. The method of claim 1, wherein, In step (1), the mass content of H2SO4 in the electrolytic manganese process anode waste liquid is 32-48g / l.

4. The method of claim 1 or 3, wherein, In step (1), the temperature of the first mixing is 20-45℃, and the time is 20-60min.

5. The method of claim 1 or 2, wherein, In step (1), the first mixing also includes introducing Fe 2+ to the mixture.

6. The method of claim 5, wherein, Fe 2+ Introduced via the form of FeO.

7. The method of claim 5, wherein, Fe 2+ The amount of Fe introduced is such that the mass ratio of FeO to electrolytic manganese residue is between 0.5 and 3:

500.

8. The method of claim 1 or 3, wherein, In step (2), the way to adjust the pH of the first liquid phase is to introduce ammonia gas into the first liquid phase; And / or, in step (2), the pH of the first liquid phase is adjusted to 7.5-8.

5.

9. The method of claim 1 or 3, wherein, In step (2), the sulfiding agent is selected from ammonium sulfide and / or sodium N,N-dimethylaminodithiocarbamate.

10. The method of claim 1 or 2, wherein, In step (3), the mass amount of carbon dioxide is 3-8wt% of the mass of the second liquid phase; And / or, in step (3), further comprising: evaporating and crystallizing the third liquid phase.

11. The method of claim 1 or 2, wherein, In step (4), the mass ratio of water to the first solid phase is (5-6):

1.

12. The method of claim 1 or 2, wherein, In step (4), further comprising: after the third mixing, first introducing ammonia gas to make the pH of the material 8.2-10, then introducing carbon dioxide, and the mass amount of carbon dioxide is 5-15wt% of the mass of the water.

13. The method of claim 1 or 2, wherein, In step (4), further comprising: after the third mixing, first introducing ammonia gas to make the pH of the material 8.5-9.5, then introducing carbon dioxide, and the mass amount of carbon dioxide is 8-11wt% of the mass of the water.