Method for industrially producing electrolytic manganese from manganese semi-carbonate mixed ore

Abstract

The invention relates to a method for industrially producing electrolytic manganese from manganese semi-carbonate mixed ore, and belongs to the technical field of electrolytic manganese. The method for industrially producing the electrolytic manganese from the manganese semi-carbonate mixed ore comprises the following steps: mixing manganese semi-carbonate ore and high-iron manganese carbonate ore, and processing the mixture into ore powder; mineral powder is added into the anolyte for size mixing to generate pulpified liquid; concentrated sulfuric acid is added into the obtained slurrying liquid for leaching, and manganese leaching liquid and manganese leaching residues are obtained after filtering; removing residual acid and neutralizing: removing the residual acid from the obtained manganese leachate and neutralizing to 6.4-6.7; oxidizing to remove iron: oxidizing the treated manganese leachate to remove iron; sulfurizing to remove heavy metals: sulfurizing the treated manganese leachate to remove the heavy metals; re-vulcanization: re-vulcanizing the treated manganese leachate to remove zinc; purification is conducted, specifically, the manganese leachate is purified; neutralization is conducted, specifically, the manganese lixivium is neutralized; and electrolysis is conducted, specifically, the neutralized manganese leaching solution is electrolyzed to prepare electrolytic manganese. The electrolytic manganese is efficiently prepared by taking the manganese semi-carbonate ore as a main raw material, and the efficient recovery of manganese in lean ore of the manganese semi-carbonate ore is effectively realized.

Description

Technical Field

[0001] The present invention relates to a method for industrially producing electrolytic manganese from a semi-carbonate manganese mixed ore, belonging to the technical field of electrolytic manganese. Background Art

[0004] The patent application number is 201710034446.X, and the name is a production process of medium and low carbon ferromanganese in the smelting of semi-carbonate manganese ore. First, manganese slag and liquid silicomanganese alloy are mixed and charged into a rocking ladle for rocking smelting. Then, the semi-finished alloy after rocking smelting is refined for secondary desiliconization. During the refining process, semi-carbonate manganese ore, manganese ore and lime are added and melted and smelted sufficiently to prepare medium and low carbon ferromanganese. This patent application mainly prepares medium and low carbon ferromanganese by using semi-carbonate manganese ore in combination with other materials through pyrometallurgy, rather than electrolytic manganese, and semi-carbonate manganese ore is only used as a batching material in this application. At present, there is no efficient method for recycling and preparing electrolytic manganese with semi-carbonate manganese ore as the main raw material. Summary of the Invention

[0005] In view of the problems and deficiencies of the above-mentioned prior art, the present invention provides a method for industrially producing electrolytic manganese from a semi-carbonate manganese mixed ore. In the present invention, semi-carbonate manganese ore and high-iron manganese ore are mixed and then processed into ore powder. The ore powder is slurried and leached with concentrated sulfuric acid to obtain a manganese leaching solution. The leaching solution is prepared into metallic manganese through a process of eliminating residual acid, neutralization-oxidation for iron removal-sulfidation for heavy metal removal-re-sulfidation-purification-neutralization-electrolysis. The present invention is realized through the following technical solutions.

[0006] A method for industrially producing electrolytic manganese from a semi-carbonate manganese mixed ore, the steps of which include:

[0007] Step 1, mixing and processing: Mixing semi-carbonate manganese ore and high-iron carbonate manganese ore and processing them into ore powder;

[0008] Step 2, slurrying: Adding the ore powder in Step 1 to anolyte for slurrying to generate a slurried liquid;

[0009] Step 3, leaching with concentrated sulfuric acid: Adding concentrated sulfuric acid to leach the slurried liquid obtained in Step 2, and filtering to obtain a manganese leaching solution and manganese leaching residue;

[0010] Step 4, eliminating residual acid and neutralization: Eliminating residual acid and neutralizing the manganese leaching solution obtained in Step 3 to 6.4-6.7;

[0011] Step 5, oxidation for iron removal: Oxidizing and removing iron from the manganese leaching solution treated in Step 4;

[0012] Step 6, sulfidation for heavy metal removal: Sulfidizing and removing heavy metals from the manganese leaching solution treated in Step 5;

[0013] Step 7, Resulfidation: Resulfidize the manganese leaching solution treated in Step 6 to remove zinc.

[0014] Step 8, Purification: Purify the manganese leaching solution treated in Step 7.

[0015] Step 9, Neutralization: Neutralize the manganese leaching solution treated in Step 8.

[0016] Step 10, Electrolysis: Electrolyze the manganese leaching solution neutralized in Step 9 to prepare electrolytic manganese.

[0017] In the above Step 1, the total manganese content in the semi-carbonate manganese ore is 16 - 38 wt%, and the divalent manganese content is 8 - 20 wt%; the manganese content in the high-iron carbonate manganese ore is 14 - 21 wt%, and the iron content is 3 - 10 wt%; the addition amount of the high-iron carbonate manganese ore is 1 - 2 times the theoretical amount for the complete reaction of reducing the high-valent manganese in the semi-carbonate manganese ore to divalent manganese by the iron in the high-iron carbonate manganese ore.

[0018] In the above Step 2, the pulp concentration of the ore powder and the anode solution is 20 - 30 wt%.

[0019] The specific process of the concentrated sulfuric acid leaching in Step 3 is as follows:

[0020] 3.1. Add concentrated sulfuric acid to the pulp solution obtained in Step 2 according to a volume ratio of ore to acid of 1:0.4 - 0.8. The concentrated sulfuric acid reacts and generates heat to a temperature of 65 - 90 °C for leaching for 3 - 5 h.

[0021] 3.2. Process the second batch of carbonate manganese ore into ore powder, use the anode solution to make pulp to generate a 20 - 30 wt% pulp solution, add the pulp solution to the leaching process in Step 3.2, continue to add the anode solution until the volume of the chemical reaction barrel is full (the empty height of the chemical reaction barrel is 0.3 - 0.5 m), continue to leach at a temperature of ≥50 °C for 8 - 11 h, and then obtain the leaching solution and the leaching residue.

[0022] The specific process of eliminating the residual acid and neutralization in Step 4 is as follows: Add ammonia water, low-grade carbonate manganese powder or double-flying powder to the manganese leaching solution obtained in Step 3 until the pH is 4 - 5, and then continue to adjust the pH to 6.4 - 6.7 with ammonia water.

[0023] The specific process of oxidizing and removing iron in Step 5 is as follows: Add hydrogen peroxide or introduce air, and the addition amount is 1 - 2 times the theoretical amount for the complete reaction of oxidizing divalent iron in the manganese leaching solution to trivalent iron, and then adjust the pH to 6.4 - 6.7.

[0024] The specific process of sulfidizing and removing heavy metals in Step 6 is as follows: Add catechol-3,5-disulfonic acid sodium, and the addition amount is 1.2 - 1.5 times the theoretical amount for the complete reaction of generating sulfides of heavy metals in the manganese leaching solution.

[0025] The specific process of step 7 of polysulfidization is as follows: with or without filtration of the manganese leaching solution treated in step 6, add ammonium sulfide or barium sulfide, and the addition amount is 1.0 - 1.8 times of the theoretical amount required for the complete reaction of zinc in the manganese leaching solution to form sulfide.

[0026] The specific process of step 8 of purification is as follows: filter-press the manganese leaching solution treated in step 7, add hydrogen peroxide to the filtered leaching solution according to the volume ratio of 1 - 2:5000 and stir, then add activated carbon and react for 1 - 2 h, and add aluminum sulfate or polyferric precipitant to react as the case may be.

[0027] The specific process of step 9 of neutralization is as follows: after filtering the manganese leaching solution treated in step 8, add selenium, sulfur dioxide or ammonium sulfite.

[0028] The above-mentioned semi-carbonate manganese ore can also be mixed with reduced iron powder and processed into ore powder, and then prepared into metallic manganese through the specific process of anolyte pulping - concentrated sulfuric acid leaching - eliminating residual acid, neutralization - iron removal by oxidation - heavy metal removal by sulfidation - polysulfidization - purification - neutralization - electrolysis.

[0029] The above-mentioned concentrated sulfuric acid is analytical pure concentrated sulfuric acid, and other reagents are analytical pure reagents if the concentration is not specifically specified.

[0030] The beneficial effects of the present invention are as follows:

[0031] (1) The present invention efficiently prepares electrolytic manganese using semi-carbonate manganese ore as the main raw material, effectively solving the problem of efficient recovery of manganese in lean semi-carbonate manganese ore; at the same time, by mixing high-iron manganese ore with semi-carbonate manganese ore, on the one hand, the high-valent manganese in the semi-carbonate manganese ore can be reduced, and on the other hand, the problem of high iron removal and high reuse cost in high-iron manganese ore can be solved. At the same time, the manganese in the high-iron manganese ore can also be efficiently comprehensively recycled, saving energy and reducing consumption, and having high economic value.

[0032] (2) In view of the material characteristics of the mixed ore of semi-carbonate manganese ore and high-iron manganese ore, the present invention adopts the specific process of processing into ore powder - anolyte pulping - concentrated sulfuric acid leaching - eliminating residual acid, neutralization - iron removal by oxidation - heavy metal removal by sulfidation - polysulfidization - purification - neutralization - electrolysis to prepare metallic manganese; during the concentrated sulfuric acid leaching process, the manganese leaching rate is relatively high, reaching more than 95%, and the total manganese recovery rate in the semi-carbonate manganese ore and high-iron manganese ore reaches more than 80 - 82%, efficiently recovering the manganese in the semi-carbonate manganese ore and high-iron manganese ore.

[0033] (3) The present invention processes the mixed ore of semi-carbonate manganese ore and high-iron manganese ore into ore powder, uses anolyte for pulping, recovers 10 - 15 g / L of manganese and high-concentration acid in the anolyte, and at the same time conducts pre-leaching treatment on the ore powder, laying a foundation for subsequent efficient concentrated sulfuric acid leaching.

[0034] (4) In the present invention, the pulp liquid of the first batch of pulp preparation is leached with concentrated sulfuric acid for 3 - 5 h, then the pulp liquid of the second batch of pulp preparation is added and anolyte is supplemented, and leaching is continued to eliminate the problem of reduced manganese leaching rate caused by the change in manganese content in each batch of semi-carbonate manganese ore and high-iron manganese ore.

[0035] (5) Using the treatment method of the present invention, calculated based on an annual output of 100,000 tons of electrolytic metallic manganese, 50,000 - 60,000 tons of semi-carbonate manganese ore can be processed, and the electrolytic metallic manganese products obtained based on semi-carbonate manganese reach 18,000 - 22,000 tons, and an actual economic benefit of 17 - 22 million yuan is generated. Description of the Drawings

[0036] Figure 1 is a schematic process flow diagram of the present invention;

[0037] Figure 2 is a physical diagram of the electrolytic manganese product prepared in Example 1 of the present invention. Detailed Embodiments

[0038] The present invention will be further described below in conjunction with the drawings and detailed embodiments.

[0039] Example 1

[0040] As Figure 1 shown, the method for industrially producing electrolytic manganese from the semi-carbonate manganese mixed ore includes the following steps:

[0041] Step 1, Mixing and Processing: Mix the semi-carbonate manganese ore (the total manganese content in the semi-carbonate manganese ore is 35.8 wt%, among which the divalent manganese content is 11.2 wt%, the iron content is 4.57 wt%, the heavy metal nickel content is 0.0009 wt%, the zinc content is 0.00082 wt%, and the magnesium content is 1.68 wt%) and the high-iron carbonate manganese ore (the manganese content in the high-iron carbonate manganese ore is 20 wt%, and the iron content is 6.10 wt%) and process them into ore powder; the addition amount of the high-iron carbonate manganese ore is 1 time of the theoretical amount for the complete reaction of reducing the high-valent manganese in the semi-carbonate manganese ore to divalent manganese by the iron in the high-iron carbonate manganese ore;

[0042] Step 2, Pulp Preparation: Add the ore powder in Step 1 to the anolyte (the anolyte contains 13 g / L of manganese and 38 g / L of sulfuric acid) for pulp preparation to generate a pulp liquid; the pulp preparation concentration of the ore powder and the anolyte is 20 wt%;

[0043] Step 3, Leaching with Concentrated Sulfuric Acid: Add concentrated sulfuric acid to the pulp liquid obtained in Step 2 for leaching, and after filtration, a manganese leaching solution and manganese leaching residue are obtained; the specific leaching with concentrated sulfuric acid is as follows:

[0044] 3.1, Add concentrated sulfuric acid (98.3 wt% concentrated sulfuric acid) to the pulp liquid obtained in Step 2 according to an ore-acid ratio of 1:0.6, and the concentrated sulfuric acid reacts and generates heat to a temperature of 75 °C for leaching for 3 h;

[0045] 3.2. Process the second batch of low-grade manganese carbonate ore into ore powder (with a total manganese content of 6.5 wt% and a divalent manganese content of 6.0 wt%). Use anolyte to prepare a 20 wt% slurry, add the slurry to the leaching process in Step 3.2, then fill the reaction barrel with anolyte (the empty height of the reaction barrel is 0.3 - 0.5 m), and continue leaching at 50 °C for 11 h. Filter to obtain a leachate (where manganese is 38 - 40 g / L, divalent iron is 0.5 - 0.8 g / L, heavy metal nickel content is 10 mg / L, and zinc content is 19 mg / L) and leaching residues.

[0046] Step 4. Eliminate residual acid and neutralize: Eliminate the residual acid and neutralize the manganese leachate obtained in Step 3 to 6.4 - 6.7; specifically: First, add ammonia water to the manganese leachate obtained in Step 3 until the pH is 4 - 5, and then continue to adjust the pH to 6.4 - 6.7 with ammonia water;

[0047] Step 5. Oxidize and remove iron: Oxidize and remove iron from the manganese leachate treated in Step 4; specifically, add hydrogen peroxide, and the addition amount is 1.5 times the theoretical amount required for the complete reaction of oxidizing divalent iron in the manganese leachate to trivalent iron, and then adjust the pH to 6.4 - 6.7; after iron removal by oxidation, the manganese content in the manganese leachate is 37 - 39 g / L, the divalent iron content is only 0.1 mg / L, the heavy metal nickel content is 10 mg / L, and the zinc content is 19 mg / L;

[0048] Step 6. Sulfurize to remove heavy metals: Sulfurize to remove heavy metals from the manganese leachate treated in Step 5; add sodium 3,5-disulfonate catechol to the manganese leachate after iron removal by oxidation, and the addition amount is 1.2 times the theoretical amount required for the complete reaction of heavy metals in the manganese leachate to form sulfides. After heavy metal removal, the manganese content in the manganese leachate is 37 - 39 g / L, the iron content is only ≤0.1 mg / L, the heavy metal nickel content is ≤0.1 g / L, and the zinc content is 18 mg / L;

[0049] Step 7. Re-sulfurize: Re-sulfurize to remove zinc from the manganese leachate treated in Step 6; specifically, filter or not filter the manganese leachate treated in Step 6, add ammonium sulfide, and the addition amount is 1.8 times the theoretical amount required for the complete reaction of zinc in the manganese leachate to form sulfide until the zinc content in the manganese leachate ≤5 mg / L;

[0050] Step 8. Purify: Purify the manganese leachate treated in Step 7; filter-press the manganese leachate treated in Step 7, add hydrogen peroxide to the filtered leachate and stir according to a volume ratio of 1:5000, and then add activated carbon (the addition amount of activated carbon is 0.05 g - 0.1 g / L of manganese leachate) and react for 1 h;

[0051] Step 9, Neutralization: Neutralize the manganese leaching solution treated in Step 8; filter the manganese leaching solution treated in Step 8 and add selenium to adjust the pH to 6.4 - 6.5;

[0052] Step 10, Electrolysis: Electrolyze the manganese leaching solution neutralized in Step 9 to prepare electrolytic manganese.

[0053] During the concentrated sulfuric acid leaching process of the present invention, the manganese leaching rate is as high as over 96%, while the leaching rate of conventional lean manganese ore is only about 80 - 95%. The leaching rate of the present invention is significantly improved. The manganese recovery rate in the semi-carbonate manganese ore of the present invention is as high as 82%, and the recovery rate is also significantly improved.

[0054] The physical diagram of the electrolytic manganese product prepared in this example is as Figure 2 shown. It can be seen from Figure 2 that the electrolytic manganese product obtained by the present invention has high gloss, good electrolytic uniformity, and no scaling, proving that the performance of the electrolytic manganese product of the present invention is excellent.

[0055] Example 2

[0056] As Figure 1 shown, the method for industrially producing electrolytic manganese from the semi-carbonate manganese mixed ore includes the following steps:

[0057] Step 1, Mixing and processing: Mix the semi-carbonate manganese ore (the total manganese content in the semi-carbonate manganese ore is 32.4 wt%, of which the divalent manganese content is 12.8 wt%, the iron content is 5.6 wt%, the heavy metal nickel content is 0.00075 wt%, the zinc content is 0.00094 wt%, and the magnesium content is 1.74 wt%) and the high-iron carbonate manganese ore (the manganese content in the high-iron carbonate manganese ore is 21 wt% and the iron content is 5.8 wt%) and process them into ore powder; the addition amount of the high-iron carbonate manganese ore is 2 times the theoretical amount of the iron in the high-iron carbonate manganese ore to completely react to reduce the high-valent manganese in the semi-carbonate manganese ore to divalent;

[0058] Step 2, Pulp adjustment: Add the ore powder in Step 1 to the anolyte (the manganese content in the anolyte is 13 g / L and the sulfuric acid is 30 g / L) to adjust the pulp to generate a pulp solution; the pulp adjustment concentration of the ore powder and the anolyte is 30 wt%;

[0059] Step 3, Concentrated sulfuric acid leaching: Add the pulp solution obtained in Step 2 to concentrated sulfuric acid for leaching, and filter to obtain a manganese leaching solution and a manganese leaching residue; the concentrated sulfuric acid leaching is specifically as follows:

[0060] 3.1. Add concentrated sulfuric acid (98.3 wt% concentrated sulfuric acid) to the pulp solution obtained in Step 2 according to the ore-acid ratio of 1:0.4, and the concentrated sulfuric acid reacts and heats up to a temperature of 65 °C for leaching for 5 h;

[0061] 3.2. Mix the second batch of manganous carbonate ore and high-iron manganous carbonate ore and process them into ore powder (with a total manganese content of 8.2 wt% and a divalent manganese content of 7.1 wt%). Use anolyte to prepare a 30 wt% slurry, add the slurry to the leaching process in Step 3.2, then fill the reaction barrel with anolyte (the empty height of the reaction barrel is 0.3 - 0.5 m), continue leaching at 60 °C for 8 h, and filter to obtain a leachate (where manganese is 37 - 39.2 g / L, divalent iron is 0.82 - 0.9 g / L, the heavy metal nickel content is 9.2 mg / L, and the zinc content is 21 mg / L) and leaching residues.

[0062] Step 4. Eliminate residual acid and neutralize: Eliminate the residual acid and neutralize the manganese leachate obtained in Step 3 to 6.4 - 6.7; specifically: Add low-grade manganous carbonate powder to the manganese leachate obtained in Step 3 until the pH is 4 - 5, and then continue to adjust the pH to 6.4 - 6.7 with ammonia water;

[0063] Step 5. Oxidize and remove iron: Oxidize and remove iron from the manganese leachate treated in Step 4; specifically, add hydrogen peroxide, and the addition amount is 1 times the theoretical amount for completely reacting divalent iron in the manganese leachate to trivalent iron, and then adjust the pH to 6.4 - 6.7; After oxidizing and removing iron, the manganese in the manganese leachate is 36.8 - 39 g / L, the iron is only ≤0.1 mg / L, the heavy metal nickel content is 9.4 mg / L, and the zinc content is 20 mg / L;

[0064] Step 6. Sulfide to remove heavy metals: Sulfide to remove heavy metals from the manganese leachate treated in Step 5; Add sodium 3,5-disulfocatechol to the manganese leachate after oxidizing and removing iron, and the addition amount is 1.5 times the theoretical amount for completely reacting heavy metals in the manganese leachate to form sulfides. After removing heavy metals, the manganese in the manganese leachate is 36 - 38 g / L, the iron is only ≤0.1 mg / L, the heavy metal nickel content is ≤0.1 g / L, and the zinc content is 19 mg / L;

[0065] Step 7. Re-sulfide: Re-sulfide to remove zinc from the manganese leachate treated in Step 6; Specifically, filter or not filter the manganese leachate treated in Step 6, add barium sulfide, and the addition amount is 1.0 times the theoretical amount for completely reacting zinc in the manganese leachate to form sulfides until the zinc in the manganese leachate ≤8 mg / L;

[0066] Step 8. Purify: Purify the manganese leachate treated in Step 7; Press-filter the manganese leachate treated in Step 7, add hydrogen peroxide to the filtered leachate and stir according to a volume ratio of 2:5000, then add activated carbon (the addition amount of activated carbon is 0.05 g per milliliter of manganese leachate) and react for 1.5 h, and add aluminum sulfate (the addition amount is 0.01 g per milliliter of leachate) and react for 2 h;

[0067] Step 9, Neutralization: Neutralize the manganese leaching solution treated in Step 8; Filter the manganese leaching solution treated in Step 8 and then add sulfur dioxide to adjust the pH to 6.4 - 6.5;

[0068] Step 10, Electrolysis: Electrolyze the manganese leaching solution neutralized in Step 9 to prepare electrolytic manganese.

[0069] During the concentrated sulfuric acid leaching process of the present invention, the manganese leaching rate is as high as over 90%. In contrast, the leaching rate of conventional lean manganese ore is only about 80%. The leaching rate of the present invention is significantly improved. The manganese recovery rate in the semi-carbonate manganese ore of the present invention is as high as 80%, and the recovery rate is also significantly improved.

[0070] Example 3

[0071] As Figure 1 shown, the method for industrial production of electrolytic manganese from the semi-carbonate manganese mixed ore includes the following steps:

[0072] Step 1, Mixing and processing: Mix semi-carbonate manganese ore (the total manganese content in the semi-carbonate manganese ore is 24.6 wt%, of which the divalent manganese content is 11.8 wt%, the iron content is 7.2 wt%, the heavy metal nickel content is 0.0012 wt%, the zinc content is 0.00096 wt%, and the magnesium content is 2.1 wt%) and high-iron carbonate manganese ore (the manganese content in the high-iron carbonate manganese ore is 18 wt% and the iron content is 8.2 wt%) and process them into ore powder; The addition amount of high-iron carbonate manganese ore is 1.5 times the theoretical amount for the complete reaction of reducing the high-valent manganese in the semi-carbonate manganese ore to divalent manganese by the iron in the high-iron carbonate manganese ore.

[0073] Step 2, Pulp preparation: Add the ore powder in Step 1 to the anolyte (the anolyte contains 13 g / L of manganese and 30 g / L of sulfuric acid) to prepare a pulp solution; The pulp concentration of the ore powder and the anolyte is 25 wt%.

[0074] Step 3, Concentrated sulfuric acid leaching: Add concentrated sulfuric acid to leach the pulp solution obtained in Step 2, and filter to obtain a manganese leaching solution and manganese leaching residue; The concentrated sulfuric acid leaching is specifically as follows:

[0075] 3.1. Add concentrated sulfuric acid (98.3 wt% concentrated sulfuric acid) to the pulp solution obtained in Step 2 according to a ore-acid ratio of 1:0.8. The concentrated sulfuric acid reacts and generates heat to a temperature of 90 °C and leaches for 4 h;

[0076] 3.2. Mix the second batch of manganese carbonate ore and high-iron manganese carbonate ore and process them into ore powder (with a total manganese content of 8.4 wt% and a divalent manganese content of 7.2 wt%). Use anolyte to adjust the pulp to form a 25 wt% pulp liquid, add the pulp liquid to the leaching process in step 3.2, then fill the reaction barrel with anolyte (the empty height of the reaction barrel is 0.3 - 0.5 m), and continue leaching at 68 °C for 10 h. Filter to obtain the leaching solution (where manganese is 28 - 30 g / L, divalent iron is 0.9 - 1.2 g / L, the heavy metal nickel content is 14 mg / L, and the zinc content is 23 mg / L) and the leaching residue.

[0077] Step 4. Eliminate residual acid and neutralize: Eliminate the residual acid and neutralize the manganese leaching solution obtained in step 3 to 6.4 - 6.7; the specific process is as follows: Add calcite powder to the manganese leaching solution obtained in step 3 until the pH is 4 - 5, and then continue to adjust the pH to 6.4 - 6.7 with ammonia water;

[0078] Step 5. Oxidize and remove iron: Oxidize and remove iron from the manganese leaching solution treated in step 4; specifically, for oxidizing and removing iron: Add hydrogen peroxide, and the addition amount is 2 times the theoretical amount for completely reacting divalent iron in the manganese leaching solution to trivalent iron, and then adjust the pH to 6.4 - 6.7; after oxidizing and removing iron, the manganese in the manganese leaching solution is 28 - 29 g / L, the divalent iron is only 0.1 mg / L, the heavy metal nickel content is 13.8 mg / L, and the zinc content is 22.8 mg / L;

[0079] Step 6. Sulfurize to remove heavy metals: Sulfurize to remove heavy metals from the manganese leaching solution treated in step 5; add sodium 3,5-disulfonate catechol to the manganese leaching solution after oxidizing and removing iron, and the addition amount is 1.3 times the theoretical amount for completely reacting heavy metals in the manganese leaching solution to form sulfides. After removing heavy metals, the manganese in the manganese leaching solution is 27.8 - 28.8 g / L, the divalent iron is only 0.1 mg / L, the heavy metal nickel content is ≤0.1 g / L, and the zinc content is 22.6 mg / L;

[0080] Step 7. Re-sulfurize: Re-sulfurize to remove zinc from the manganese leaching solution treated in step 6; specifically, for the manganese leaching solution treated in step 6, filter or not filter, add barium sulfide, and the addition amount is 1.5 times the theoretical amount for completely reacting zinc in the manganese leaching solution to form sulfides until the zinc in the manganese leaching solution ≤5 mg / L;

[0081] Step 8. Purify: Purify the manganese leaching solution treated in step 7; filter-press the manganese leaching solution treated in step 7, add hydrogen peroxide to the filtered leaching solution and stir according to a volume ratio of 1.5:5000, then add activated carbon (the addition amount of activated carbon is 0.05 g - 0.1 g / L of the manganese leaching solution) and react for 2 h, and add polyferric sulfate (the addition amount is 0.1 g / L of the manganese leaching solution) and react for 1.5 h;

[0082] Step 9, Neutralization: Neutralize the manganese leaching solution treated in Step 8; Filter the manganese leaching solution treated in Step 8 and add ammonia to adjust the pH to 6.4 - 6.5;

[0083] Step 10, Electrolysis: Electrolyze the manganese leaching solution neutralized in Step 9 to prepare electrolytic manganese.

[0084] In the concentrated sulfuric acid leaching process of the present invention, the manganese leaching rate is as high as over 94%. Compared with the conventional lean manganese ore with a leaching rate of only about 82%, the leaching rate of the present invention is significantly improved. The manganese recovery rate in the semi-carbonate manganese ore of the present invention is as high as 81%, and the recovery rate is also significantly improved.

[0085] The specific embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various changes can be made without departing from the gist of the present invention.

Claims

1. A method for industrially producing electrolytic manganese from a semi-carbonate manganese ore mixture, characterized by the steps Including: Step 1, Mixed processing: Mix semi-carbonate manganese ore and high-iron carbonate manganese ore and process them into ore powder; Step 2, Slurry preparation: Add the ore powder in Step 1 to the anolyte to prepare a slurry to generate a slurried liquid; Step 3, Sulfuric acid leaching: Add concentrated sulfuric acid to leach the slurried liquid obtained in Step 2, and after filtration, obtain a manganese leaching solution and manganese leaching residue; Step 4, Residual acid elimination and neutralization: Eliminate the residual acid and neutralize the manganese leaching solution obtained in Step 3 to 6.4 - 6.7; Step 5, Iron removal by oxidation: Oxidize and remove iron from the manganese leaching solution treated in Step 4; Step 6, Heavy metal removal by sulfidation: Remove heavy metals from the manganese leaching solution treated in Step 5 by sulfidation; Step 7, Re-sulfidation: Re-sulfidate the manganese leaching solution treated in Step 6 to remove zinc; Step 8, Purification: Purify the manganese leaching solution treated in Step 7; Step 9, Neutralization: Neutralize the manganese leaching solution treated in Step 8; Step 10, Electrolysis: Electrolyze the manganese leaching solution neutralized in Step 9 to prepare electrolytic manganese.

2. The method for industrial production of electrolytic manganese from semi-carbonate manganese ore mixture according to claim 1, characterized in that: In Step 1, the total manganese content in the semi-carbonate manganese ore is 16 - 38 wt%, and the divalent manganese content is 8 - 20 wt%; the manganese content in the high-iron carbonate manganese ore is 14 - 21 wt%, and the iron content is 3 - 10 wt%; the addition amount of the high-iron carbonate manganese ore is 1 - 2 times the theoretical amount of the complete reaction of reducing the high-valent manganese in the semi-carbonate manganese ore to divalent manganese by the iron in the high-iron carbonate manganese ore.

3. The method for industrial production of electrolytic manganese from semi-carbonate manganese ore mixture according to claim 1, characterized in that: In Step 2, the slurry concentration of the ore powder and the anolyte is 20 - 30 wt%.

4. The method for industrial production of electrolytic manganese from semi-carbonated manganese ore mixture according to claim 1, characterized in that: The specific process of the concentrated sulfuric acid leaching in Step 3 is as follows: 3.

1. Add concentrated sulfuric acid to the slurried liquid obtained in Step 2 according to an ore-acid ratio of 1:0.4 - 0.8, and leach for 3 - 5 h; 3.

2. Process the second batch of carbonate manganese ore into ore powder, use the anolyte to prepare a 20 - 30 wt% slurried liquid, add the slurried liquid to the leaching process in Step 3.2, continue to add the anolyte until the volume of the reaction barrel is full, and continue to leach at a temperature of ≥50°C for 8 - 11 h, and filter to obtain a leaching solution and a leaching residue.

5. The method for industrial production of electrolytic manganese from semi-carbonate manganese ore mixture according to claim 1, characterized in that: The specific process of eliminating the residual acid and neutralization in Step 4 is as follows: Add ammonia water, low-grade manganese carbonate powder or double-fly powder to the manganese leaching solution obtained in Step 3 until the pH is 4 - 5, and then use ammonia water to continue adjusting the pH to 6.4 - 6.

7.

6. The method for industrial production of electrolytic manganese from semi-carbonated manganese ore mixture according to claim 1, characterized in that: The specific process of iron removal by oxidation in Step 5 is as follows: Add hydrogen peroxide or introduce air, and the addition amount is 1 - 2 times the theoretical amount of the complete reaction of oxidizing divalent iron in the manganese leaching solution to trivalent iron, and then adjust the pH to 6.4 - 6.

7.

7. The method for industrial production of electrolytic manganese from semi-carbonated manganese ore mixture according to claim 1, characterized in that: The specific process of heavy metal removal by sulfidation in Step 6 is as follows: Add catechol-3,5-disulfonic acid sodium, and the addition amount is 1.2 - 1.5 times the theoretical amount of the complete reaction of forming sulfides of heavy metals in the manganese leaching solution.

8. The method for industrially producing electrolytic manganese from semi-carbonated manganese ore mixture according to claim 1, characterized in that: The specific process of re-sulfidation in Step 7 is as follows: Filter or not filter the manganese leaching solution treated in Step 6, add ammonium sulfide or barium sulfide, and the addition amount is 1.0 - 1.8 times the theoretical amount of the complete reaction of forming sulfides of zinc in the manganese leaching solution.

9. The method for industrially producing electrolytic manganese from semi-carbonate manganese ore mixture according to claim 1, characterized in that: The specific process of purification in Step 8 is as follows: Press-filter the manganese leaching solution treated in Step 7, add hydrogen peroxide to the filtered leaching solution according to a volume ratio of 1 - 2:5000 and stir, then add activated carbon and react for 1 - 2 h, and add aluminum sulfate or poly-ferric precipitant to react as the case may be.

10. The method for industrially producing electrolytic manganese from semi-carbonate manganese ore mixture according to claim 1, characterized in that: In step 9 specifically: after filtering the manganese leaching solution processed in step 8, add selenium, sulfur dioxide or ammonium sulfite.

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