A harmless treatment method for electrolytic manganese slag

Abstract

The present invention provides a harmless treatment method for electrolytic manganese slag, which belongs to the technical field of harmless treatment of electrolytic manganese slag. The present invention mixes electrolytic manganese slag and carbide slag and then performs ball milling to obtain a ball milling product; then the ball milling product, an excitation material and water are mixed and reacted in sequence, and dried to obtain harmless electrolytic manganese slag. The present invention ball mills electrolytic manganese slag and carbide slag, and the obtained ball milling product is then mixed with an excitation material and water and reacted to obtain harmless electrolytic manganese slag under low temperature conditions. The harmless treatment method of electrolytic manganese slag of the present invention has a good effect on removing manganese ions and ammonia nitrogen, and 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.

Description

Technical Field

[0001] The present 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 enormous demand and industrial scale for electrolytic manganese metal (EMM), the amount of EMM slag generated is also increasing. EMM slag contains ammonia nitrogen and heavy metal ions. When stored outdoors for long periods of time, these free ammonia nitrogen and heavy metal ions will continuously seep into the surrounding environment through rainwater, causing long-term negative impacts, not only polluting water bodies but also endangering human health. Currently, the primary approach to addressing EMM slag pollution is to reduce its volume, render it harmless, and recycle it as a resource.

[0003] There are two main methods for harmlessly treating electrolytic manganese slag. One involves removing harmful ions, such as through high-temperature desulfurization, washing and leaching, bioleaching, and electroremediation. The other involves solidifying harmful substances in the slag, such as soluble manganese ions and ammonia nitrogen, using methods such as cement, alkaline reagents, or other reagents. However, existing technologies for harmlessly treating electrolytic manganese slag suffer from high energy consumption, high risk of secondary pollution, and long treatment times. Therefore, developing a harmless treatment method for electrolytic manganese slag that can reduce treatment costs, be environmentally friendly, and effectively remove manganese ions and ammonia nitrogen is of great significance. 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 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 ball milling them to obtain a ball milled 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-milled 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 removing 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 ball milling them to obtain a ball milled 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., more preferably 140-160° C., and the drying time is 8-14 hours, preferably 9-13 hours, more preferably 10-12 hours.

[0024] In the present invention, in 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, more preferably 100:30.

[0026] In the present invention, in 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, 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 step (2), the mass ratio of the ball-milled product to the excited material is 100:15-25, preferably 100:20.

[0032] In the present invention, in the step (2), the ball milled product, the excitation material and water are mixed. Preferably, the ball milled product and the excitation 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 step (2), the reaction temperature is 30-50°C, preferably 35-45°C, more preferably 40°C, and the reaction time is 1-3h, preferably 1.5-2.5h, more preferably 2h.

[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 with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0037] Example 1

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

[0039] Example 2

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

[0041] Example 3

[0042] 100 g of electrolytic manganese slag was dried at 180° C. for 14 h, 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 were mixed in a mass ratio of 100:10:1:4, water was added by spraying (the amount of water added was 30% by mass of the ball-milled product), reacted at 50° C. for 1 h under stirring, 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 slags 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 and ammonium ferrous sulfate titration”.

[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 removing 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 principles of the present invention. These improvements and modifications should also be regarded as within 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 ball milling them to obtain a ball milled product; (2) mixing the ball mill product, the exciting material and water, reacting and drying them in sequence to obtain harmless electrolytic manganese slag; In the step (1), the mass ratio of electrolytic manganese slag to carbide slag is 100:20-40; In the step (1), the ball milling speed is 2000-3000 rpm, and the ball milling time is 4-6 hours; In the step (2), the exciting material is a mixture of phosphate, sulfate and quicklime; The mass ratio of the phosphate, sulfate and quicklime is 10-20:0.5-5:3-10; In the step (2), the mass ratio of the ball milling product to the exciting material is 100:15~25.

2. The harmless treatment method for electrolytic manganese slag according to claim 1, characterized in that: The mass ratio of the electrolytic manganese slag to the carbide slag is 100:25-35.

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

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

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