Harmless treatment method for electrolytic manganese residues

Abstract

The invention provides a harmless treatment method for electrolytic manganese residues, and belongs to the technical field of harmless treatment of the electrolytic manganese residues. The method comprises the following steps: mixing electrolytic manganese residues and carbide slag, and carrying out ball-milling treatment to obtain a ball-milled product; and mixing the ball-milled product, the excitation material and water, and sequentially reacting and drying to obtain the harmless electrolytic manganese residue. According to the method, the electrolytic manganese residues and the carbide slag are subjected to ball milling treatment, the obtained ball milling product is mixed with the excitation material and the water for reaction, and the harmless electrolytic manganese residues can be obtained under the low-temperature condition. The harmless treatment method for the electrolytic manganese residues has a good removal effect on manganese ions and ammonia nitrogen, the concentration of the manganese ions can be reduced to 0.43 mg / L, and the concentration of the ammonia nitrogen can be reduced to 6.55 mg / L.

Description

Technical Field

[0001] The invention relates to the technical field of harmless treatment of electrolytic manganese slag, and in particular to a harmless treatment method of electrolytic manganese slag. Background Art

[0002] Due to the huge demand and industrial volume of electrolytic manganese, the amount of electrolytic manganese slag produced is also increasing day by day. Electrolytic manganese slag contains ammonia nitrogen and heavy metal ions. If it is piled in the open air for a long time and washed by rainwater, these free ammonia nitrogen and heavy metal ions will continue to penetrate into the surrounding environment, which will have a long-term negative impact on the surrounding environment, not only polluting the water body, but also endangering human health. At present, the main method to solve the pollution of electrolytic manganese slag is to reduce the amount of electrolytic manganese slag, make it harmless and recycle it.

[0003] There are two main ways to harmlessly treat electrolytic manganese slag. One is to remove harmful ions, such as high-temperature desulfurization, washing and leaching, biological leaching and electric repair; the second is to solidify harmful substances in electrolytic manganese slag, such as soluble manganese ions and ammonia nitrogen, such as cement solidification, alkaline reagent solidification and other reagent solidification. However, the harmless treatment of electrolytic manganese slag in the prior art has problems such as high energy consumption, easy to cause secondary pollution, and long treatment time. Therefore, it is of great significance to study a harmless treatment method for electrolytic manganese slag, which can reduce the treatment cost, the process is environmentally friendly and can effectively remove manganese ions and ammonia nitrogen. Summary of the invention

[0004] The object of the present invention is to provide a harmless treatment method for electrolytic manganese slag to solve the problem of poor removal effect of manganese ions and ammonia nitrogen in the harmless treatment process of electrolytic manganese slag in the prior art.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a harmless treatment method for electrolytic manganese slag, comprising the following steps:

[0007] (1) mixing electrolytic manganese slag and carbide slag and then subjecting them to ball milling to obtain a ball milling product;

[0008] (2) The ball mill product, the exciting material and water are mixed and reacted and dried in sequence to obtain harmless electrolytic manganese slag.

[0009] Preferably, in step (1), the mass ratio of electrolytic manganese slag to carbide slag is 100:20-40.

[0010] Preferably, the mass ratio of the electrolytic manganese slag to the carbide slag is 100:25-35.

[0011] Preferably, in step (1), the rotation speed of the ball milling treatment is 2000-3000 rpm, and the time of the ball milling treatment is 4-6 hours.

[0012] Preferably, in step (2), the exciting material is a mixture of phosphate, sulfate and quicklime.

[0013] Preferably, the mass ratio of the phosphate, sulfate and quicklime is 10-20:0.5-5:3-10.

[0014] Preferably, the mass ratio of the phosphate, sulfate and quicklime is 12-14:1-3:6-8.

[0015] Preferably, in step (2), the mass ratio of the ball milling product to the excited material is 100:15-25.

[0016] Preferably, in step (2), the reaction temperature is 30-50° C., and the reaction time is 1-3 h.

[0017] Beneficial effects of the present invention:

[0018] (1) The harmless treatment method of electrolytic manganese slag of the present invention has a good effect on the removal of manganese ions and ammonia nitrogen. The concentration of manganese ions can be reduced to 0.43 mg / L, and the concentration of ammonia nitrogen can be reduced to 6.55 mg / L.

[0019] (2) The present invention ball-mills electrolytic manganese slag and carbide slag, and then mixes the obtained ball-milled product with an exciting material and water to react, thereby obtaining harmless electrolytic manganese slag under low temperature conditions. DETAILED DESCRIPTION

[0020] The present invention provides a harmless treatment method for electrolytic manganese slag, comprising the following steps:

[0021] (1) mixing electrolytic manganese slag and carbide slag and then subjecting them to ball milling to obtain a ball milling product;

[0022] (2) The ball mill product, the exciting material and water are mixed and reacted and dried in sequence to obtain harmless electrolytic manganese slag.

[0023] In the present invention, it is preferred to dry the electrolytic manganese slag and then mix it with the carbide slag. The drying temperature of the electrolytic manganese slag is 100-200°C, preferably 120-180°C, and more preferably 140-160°C. The drying time is 8-14h, preferably 9-13h, and more preferably 10-12h.

[0024] In the present invention, in the step (1), the mass ratio of electrolytic manganese slag to carbide slag is 100:20-40.

[0025] In the present invention, the mass ratio of the electrolytic manganese slag to the carbide slag is 100:25-35, and more preferably 100:30.

[0026] In the present invention, in the step (1), the rotation speed of the ball milling treatment is 2000-3000 rpm, preferably 2200-2800 rpm, and more preferably 2400-2600 rpm; the time of the ball milling treatment is 4-6 hours, and preferably 5 hours.

[0027] In the present invention, in step (2), the exciting material is a mixture of phosphate, sulfate and quicklime.

[0028] In the present invention, the mass ratio of the phosphate, sulfate and quicklime is 10-20:0.5-5:3-10.

[0029] In the present invention, the mass ratio of the phosphate, sulfate and quicklime is 12-14:1-3:6-8.

[0030] In the embodiment of the present invention, sodium phosphate is preferably used; in the embodiment of the present invention, sodium sulfate is preferably used.

[0031] In the present invention, in the step (2), the mass ratio of the ball milling product to the excited material is 100:15-25, preferably 100:20.

[0032] In the present invention, in the step (2), the ball milling product, the exciting material and water are mixed. Preferably, the ball milling product and the exciting material are mixed, and then water is added in a spraying manner.

[0033] In the present invention, the amount of water added is 30-60% of the mass of the ball-milled product.

[0034] In the present invention, in the step (2), the reaction temperature is 30 to 50°C, preferably 35 to 45°C, more preferably 40°C, and the reaction time is 1 to 3 hours, preferably 1.5 to 2.5 hours, more preferably 2 hours.

[0035] In the present invention, the reaction is carried out under stirring conditions.

[0036] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0037] Example 1

[0038] 100 g of electrolytic manganese slag is dried at 140° C. for 12 h, then mixed with 30 g of carbide slag, transferred to a ball mill, and ball milled at 2500 rpm for 4 h to obtain a ball milled product; the ball milled product, sodium phosphate, sodium sulfate and quicklime are mixed, wherein the mass ratio of the ball milled product, sodium phosphate, sodium sulfate and quicklime is 100:12:2:6, then water is added in a spraying manner (the amount of water added accounts for 40% of the mass percentage of the ball milled product), reacted at 40° C. for 2 h under stirring, and finally dried at 100° C. to obtain a harmless electrolytic manganese slag.

[0039] Example 2

[0040] 100 g of electrolytic manganese slag is dried at 160° C. for 10 h, then mixed with 20 g of carbide slag, transferred to a ball mill, and ball milled at 3000 rpm for 6 h to obtain a ball milled product; the ball milled product, sodium phosphate, sodium sulfate and quicklime are mixed, wherein the mass ratio of the ball milled product, sodium phosphate, sodium sulfate and quicklime is 100:14:3:8, then water is added in a spraying manner (the amount of water added accounts for 50% of the mass percentage of the ball milled product), reacted at 30° C. for 3 h under stirring conditions, and finally dried at 100° C. to obtain a harmless electrolytic manganese slag.

[0041] Example 3

[0042] 100 g of electrolytic manganese slag is dried at 180° C. for 14 h, then mixed with 40 g of carbide slag, transferred to a ball mill, and ball milled at 2000 rpm for 4 h to obtain a ball milled product; the ball milled product, sodium phosphate, sodium sulfate and quicklime are mixed, wherein the mass ratio of the ball milled product, sodium phosphate, sodium sulfate and quicklime is 100:10:1:4, then water is added in a spraying manner (the amount of water added accounts for 30% of the mass percentage of the ball milled product), reacted at 50° C. for 1 h under stirring conditions, and finally dried at 100° C. to obtain a harmless electrolytic manganese slag.

[0043] Comparative Example 1

[0044] The difference from Example 1 is that no carbide slag is added, and other conditions are the same.

[0045] Comparative Example 2

[0046] The difference from Example 1 is that no sodium phosphate is added to the exciting material, and other conditions are the same.

[0047] Comparative Example 3

[0048] The difference from Example 1 is that no sodium sulfate is added to the exciting material, and other conditions are the same.

[0049] Comparative Example 4

[0050] The difference from Example 1 is that the rotation speed of the ball mill is 1000 rpm, and other conditions are the same.

[0051] Detection method:

[0052] (1) The concentration of manganese ions in the harmless electrolytic manganese slag of Examples 1 to 3 and Comparative Examples 1 to 4 was determined according to GB / T 1506-2002 "Determination of manganese content in manganese ore - Potentiometric titration method and ammonium ferrous sulfate titration method".

[0053] (2) The concentration of ammonia nitrogen in the harmless electrolytic manganese slag of Examples 1 to 3 and Comparative Examples 1 to 4 was determined according to HT 535-2009 "Determination of ammonia nitrogen in water - Nessler's reagent spectrophotometry".

[0054] The results of the determination of the concentration of manganese ions and the concentration of ammonia nitrogen in the harmless electrolytic manganese slag of Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 1:

[0055] Table 1 Determination results of manganese ion and ammonia nitrogen concentrations

[0056]

[0057]

[0058] As can be seen from Table 1, the harmless treatment method of electrolytic manganese slag of the present invention has a good effect on the removal of manganese ions and ammonia nitrogen, wherein the concentration of manganese ions can be reduced to 0.43 mg / L, and the concentration of ammonia nitrogen can be reduced to 6.55 mg / L.

[0059] The present invention firstly ball-mills carbide slag and electrolytic manganese slag, and the electrolytic manganese slag and the carbide slag undergo physical and chemical reactions during the high-energy ball-milling process. Then, exciting materials and water are added in a spray state, and the electrolytic manganese slag can be harmlessly treated under low-temperature conditions.

[0060] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for harmless treatment of electrolytic manganese slag, characterized in that: The steps include: (1) mixing electrolytic manganese slag and carbide slag and then subjecting them to ball milling to obtain a ball milling product; (2) The ball mill product, the exciting material and water are mixed and reacted and dried in sequence to obtain harmless electrolytic manganese slag.

2. The harmless treatment method for electrolytic manganese slag according to claim 1, characterized in that: In the step (1), the mass ratio of electrolytic manganese slag to carbide slag is 100:20-40.

3. The harmless treatment method for electrolytic manganese slag according to claim 2, characterized in that: The mass ratio of the electrolytic manganese slag to the carbide slag is 100:25-35.

4. The harmless treatment method for electrolytic manganese slag according to any one of claims 1 to 3, characterized in that: In the step (1), the rotation speed of the ball milling treatment is 2000-3000 rpm, and the time of the ball milling treatment is 4-6 hours.

5. The harmless treatment method for electrolytic manganese slag according to claim 4, characterized in that: In the step (2), the exciting material is a mixture of phosphate, sulfate and quicklime.

6. The harmless treatment method for electrolytic manganese slag according to claim 5, characterized in that: The mass ratio of the phosphate, sulfate and quicklime is 10-20:0.5-5:3-10.

7. The harmless treatment method for electrolytic manganese slag according to claim 6, characterized in that: The mass ratio of the phosphate, sulfate and quicklime is 12-14:1-3:6-8.

8. The harmless treatment method for electrolytic manganese slag according to claim 5 or 7, characterized in that: In the step (2), the mass ratio of the ball milling product to the excited material is 100:15-25.

9. The harmless treatment method for electrolytic manganese slag according to claim 8, characterized in that: In the step (2), the reaction temperature is 30 to 50° C. and the reaction time is 1 to 3 hours.

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