Harmless treatment method for electrolytic manganese residues

Abstract

The invention discloses a harmless treatment method for electrolytic manganese residues. The harmless treatment method comprises the following steps: (1) crushing the electrolytic manganese residues, and uniformly mixing the crushed electrolytic manganese residues with an additive to obtain mixed residues; the additive comprises a porous aluminosilicate material and an alkaline material; and (2) roasting the mixed slag to obtain the harmless electrolytic manganese slag. According to the innocent treatment method for the electrolytic manganese residues, the electrolytic manganese residues are subjected to innocent treatment by adopting the combined roasting process of adding the additive (including the porous aluminosilicate material and the alkaline material), the solidification effect on the electrolytic manganese residues is good, and efficient treatment of manganese, ammonia nitrogen and water-soluble salt is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of solid waste treatment, and in particular relates to a method for treating electrolytic slag. Background Art

[0002] Electrolytic manganese is often used in many fields such as metallurgy, chemical industry, building materials, medicine, battery materials, etc. my country mainly uses sulfuric acid leaching to produce electrolytic manganese. According to statistics, every ton of electrolytic manganese produces about 8-10 tons of manganese slag. Due to the lack of reasonable disposal methods, manganese slag is mainly disposed of in the form of stockpiling. Electrolytic manganese slag contains heavy metals, ammonia nitrogen, sulfate and is acidic. If improperly disposed, harmful components will directly enter the soil and groundwater with the leakage liquid, which may cause serious ecological and environmental pollution. It is urgent to develop an effective method for treating electrolytic manganese slag.

[0003] CN114850194A discloses a method for treating electrolytic manganese slag, wherein the electrolytic manganese slag is mixed with an alkaline substance and then subjected to multiple stages of medium-temperature and high-temperature roasting to obtain the treated electrolytic manganese slag. The process is complicated, the high-temperature roasting cost is high, and the content of water-soluble salts in the solidified slag is not examined. CN114939595A discloses a harmless method for electrolytic manganese slag to remove ammonia, solidify manganese and magnesium. The method stirs quicklime, water and electrolytic manganese slag into a slurry mixture and roasts it at medium temperature to remove ammonia, solidify manganese and magnesium. The method requires the addition of a large amount of water, and the process energy consumption and cost are relatively high. The content of water-soluble salts in the solidified slag is also not examined.

[0004] As can be seen from the above, the treatment of electrolytic manganese slag in the prior art has the disadvantages of high cost and failure to consider the treatment of aqueous solution salts. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background technology and provide a harmless treatment method for electrolytic manganese slag with simple process flow, no secondary pollution, low cost and good solidification effect.

[0006] In order to solve the above technical problems, the technical solution proposed by the present invention is: A method for harmless treatment of electrolytic manganese slag comprises the following steps: (1) crushing the electrolytic manganese slag and mixing it with an additive to obtain a mixed slag; the additive includes a porous aluminosilicate material and an alkaline material; (2) The mixed slag is subjected to roasting treatment to obtain harmless electrolytic manganese slag.

[0007] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, the electrolytic manganese slag and the porous aluminosilicate material are first mixed evenly, and then the alkaline material is added and mixed evenly.

[0008] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, the porous aluminosilicate material includes zeolite, and the amount of the porous aluminosilicate material is 1-2% of the mass of the electrolytic manganese slag.

[0009] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, the alkaline material includes one or more of quicklime, slaked lime and carbide slag, more preferably quicklime, and the amount of the alkaline material is 4-10% of the mass of the electrolytic manganese slag.

[0010] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, the electrolytic manganese slag is a filter press residue produced in the electrolytic manganese production process; in the electrolytic manganese slag, the mass content of Mn is less than 3%, the mass content of S is less than 12%, the mass content of NH3-N is less than 1%, and the mass content of water-soluble salts is less than 15%.

[0011] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, the water content of the electrolytic manganese slag is 20-30%.

[0012] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, the electrolytic manganese slag is crushed to a particle size of less than 10 mm.

[0013] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, during the roasting treatment, the roasting temperature is 50-300° C. and the roasting time is 20-100 min.

[0014] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, in the harmless electrolytic manganese slag, the Mn ion content is less than 1 mg / L, the NH3-N content is less than 15 mg / L, and the water-soluble salt content is less than 2%.

[0015] In the above-mentioned method for harmless treatment of electrolytic manganese slag, preferably, ammonia generated during roasting treatment is absorbed by electrolytic manganese anode liquid to produce an ammonia solution, and is reused in the electrolytic manganese production process.

[0016] The present invention adopts the method of adding additives and combining low-temperature roasting process to carry out harmless treatment on electrolytic manganese slag. The porous aluminosilicate additive is added to the electrolytic manganese slag mainly to control the water content in the material and adsorb water-soluble manganese. The water molecules in the slag easily form hydrogen bonds with the silicon-aluminum skeleton to form a moisturizing effect and prevent the water from evaporating too quickly. When the humidity drops, the porous aluminosilicate additive releases water to achieve the purpose of regulating the water content of the material, promote the efficient reaction, and reduce the amount of alkaline additives. The reaction is more uniform and the curing effect is better. During the roasting process after the electrolytic manganese slag is added with the alkaline additive, the alkaline additive first reacts with the water contained in the electrolytic manganese slag to hydrolyze into hydroxide, and the hydroxide reacts with the heavy metals, ammonium ions, and sulfates in the electrolytic manganese slag to form Mn 2+ A chemical reaction occurs to generate Mn(OH)2, which is then oxidized into insoluble MnO2; NH4+ -N is converted into free NH3, and absorbs heat to convert into gaseous NH3 and escape; sulfate is converted into precipitation, and fixed with zeolite, which plays the role of solid manganese deammoniation and precipitation of water-soluble salts. Heating the reaction to evaporate ammonia can increase the rate of deammoniation and promote the efficient reaction. The processing cost is 70-150 yuan / t electrolytic manganese slag, realizing low-cost harmless treatment of electrolytic manganese slag.

[0017] The porous aluminosilicate additive is added in the present invention to mainly play a harmless treatment role. The addition of the porous aluminosilicate additive can efficiently control the water content in the electrolytic manganese slag, and there is no need to add a large amount of water. In order to ensure this effect, the electrolytic manganese slag and the porous aluminosilicate material should be mixed evenly first, and then the alkaline material should be added and mixed evenly, so that the porous aluminosilicate can react with water first. In a more preferred scheme, the alkaline material uses quicklime, which first reacts with water to release heat, and then reacts with the manganese slag to solidify the components, which can accelerate the reaction speed, reduce energy consumption and cost, and realize industrial application.

[0018] The specific steps of this treatment method are as follows: A. Crushing and breaking up The compacted electrolytic manganese slag is first crushed to -10mm.

[0019] The electrolytic manganese slag used in the present invention is an acidic waste slag produced in the process of electrolytic manganese production. The electrolytic manganese slag used in the present invention generally has the following chemical composition: Mn3% or less; S12% or less; NH3-N1% or less; Water-soluble salt less than 15%.

[0020] Where Mn 2+ NH4 + -N is determined by the horizontal oscillation leaching method in accordance with the standard "Solid Waste Leaching Toxicity Leaching Method Horizontal Oscillation Method" (HJ 557-2010). S is determined by the high-frequency infrared absorption method. Water-soluble salts are determined by the water dissolution-evaporation method in accordance with the standard "Soil Testing Part 16: Determination of Total Water-soluble Salts in Soil" (NYT / 1121.16-2017).

[0021] The electrolytic manganese slag is compacted in a block shape and has a moisture content of 20-30% (mass content).

[0022] In the present invention, the electrolytic manganese slag used is the filter press leaching slag in the leaching workshop during the electrolytic manganese production process, and its physical and chemical properties should meet the above requirements.

[0023] In the present invention, the electrolytic manganese slag has a particle size of -10 mm after being crushed and dispersed. In the present invention, if the particle size of the electrolytic manganese slag is +10 mm, the electrolytic manganese slag with additives will not react completely during the roasting process, affecting the effect of solid manganese deammoniation and precipitation of soluble salts. Therefore, the particle size of the electrolytic manganese slag after crushing is -10 mm, preferably -8 mm; more preferably -6 mm.

[0024] B. Adding additives The electrolytic manganese slag obtained in step A is mixed evenly with 1-2% by weight of additive 1 (porous aluminosilicate material), and then 4-10% by weight of additive 2 (alkaline material) is added and mixed evenly to obtain mixed slag.

[0025] In the present invention, additive 1 is a substance having the properties of absorbing and releasing water and fixing manganese; additive 2 is a substance having the properties of deammoniation and forming an exothermic reaction with substances in the slag to improve the reaction efficiency. The addition of additive 2 promotes further solidification of manganese, solidification of water-soluble salts and removal of ammonia nitrogen.

[0026] More specifically, additive 1 is selected from zeolite. Additive 2 is selected from one or more of quicklime, slaked lime, and carbide slag. The particle size of additive 1 and additive 2 is -200 mesh.

[0027] The additives 1 and 2 used in the present invention are both products currently sold on the market.

[0028] When the amount of additive 1 added is less than 1%, the reaction will be incomplete, and the effects of water absorption and release and manganese fixation will be unsatisfactory; if the proportion of additive 1 is greater than 2%, it will cause excessive additive 1, and additive 1 will react with alkaline substances in the mixture, affecting the harmless treatment effect of manganese slag. Therefore, it is reasonable to add additive 1 at a ratio of 1-2%, preferably 1.2-1.8%.

[0029] When the amount of additive 2 is less than 4%, the reaction will be incomplete, the ammonia nitrogen removal effect is not ideal, and the stabilization degree of harmful components is insufficient; if the additive ratio is greater than 10%, the mixed slag will be alkaline, and at the same time, it will cause a waste of raw materials and increase the processing cost. Therefore, it is reasonable to add 4-10% of the additive, preferably 5-8%.

[0030] C. Low temperature roasting The mixed slag obtained in step B is placed in a roasting furnace and roasted at 50-300° C. to obtain harmless electrolytic manganese slag, and the ammonia generated by the roasting is recovered and utilized as a resource.

[0031] If the mixed slag roasting temperature is lower than 50°C, the reaction will be incomplete and the ammonia nitrogen removal effect will be unsatisfactory; if the roasting temperature is higher than 300°C, it will cause unnecessary energy consumption and affect the solidification effect of water-soluble salts. Therefore, it is reasonable to roast at a temperature of 50-300°C, preferably 60-250°C, and more preferably 80-200°C.

[0032] Similarly, if the calcination time is less than 20 minutes, the reaction will be incomplete and the ammonia nitrogen removal effect will be unsatisfactory; if the calcination time is longer than 100 minutes, excessive and unnecessary energy consumption will be generated; therefore, a calcination time of 20-100 minutes is appropriate, preferably 30-90 minutes, and more preferably 40-80 minutes.

[0033] The harmless electrolytic manganese slag prepared in this step has greatly reduced contents of ammonia nitrogen, water-soluble manganese and water-soluble salts. The manganese ion content in the electrolytic manganese slag treatment product is less than 1 mg / L, the ammonia nitrogen content is less than 15 mg / L, and the water-soluble salt content is less than 2%.

[0034] The ammonia is absorbed by the anolyte produced during the preparation of electrolytic manganese, and the ammonia-containing solution produced is recycled into the electrolytic manganese production process, thereby safely treating the ammonia produced by the process and making resource use of the anolyte, thereby reducing the production cost of electrolytic manganese.

[0035] Compared with the prior art, the advantages of the present invention are: 1. The harmless treatment method of electrolytic manganese slag of the present invention adopts a roasting process combined with additives (including porous aluminosilicate materials and alkaline materials) to carry out harmless treatment of electrolytic manganese slag, has a good solidification effect on the electrolytic manganese slag, and realizes efficient treatment of manganese, ammonia nitrogen, and water-soluble salts. The electrolytic manganese slag treated sample obtained by the method of the present invention has a manganese ion content of less than 1 mg / L, an ammonia nitrogen content of less than 15 mg / L, and a water-soluble salt content of less than 2%, which meets the relevant standard requirements for general industrial solid waste entering Class I storage yards, realizes the "one-step" harmless treatment of electrolytic manganese slag, and provides strong technical support for further resource utilization of manganese slag.

[0036] 2. The harmless treatment method of electrolytic manganese slag of the present invention adopts a roasting process combined with an additive to carry out harmless treatment of the electrolytic manganese slag. The process flow is simple, the curing effect is good, and the properties of the roasting product are stable. The operating cost of the present invention is 70-150 yuan / t electrolytic manganese slag, which is low in cost. At the same time, no three wastes are generated in the process, and no secondary pollution occurs, which meets the requirements of safe, green and economical treatment of electrolytic manganese slag. DETAILED DESCRIPTION

[0037] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully in combination with preferred embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments.

[0038] Unless otherwise defined, all the professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0039] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0040] Embodiment 1: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 1.87% Mn, 9.11% S, 0.51% NH3-N, 12.98% water-soluble salt by weight, and the water content of the electrolytic manganese slag is 21.64%.

[0041] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0042] B. Adding additives According to the weight ratio of additive 1 zeolite to electrolytic manganese slag being 1%, the electrolytic manganese slag and zeolite are evenly mixed, and then according to the weight ratio of additive 2 calcium oxide to electrolytic manganese slag being 10%, calcium oxide is added and mixed evenly to obtain mixed slag.

[0043] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 100°C for 60 min using a SX2-8-13 roasting furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 5.46µg / L, an ammonia nitrogen content of 10.02mg / L, and a water-soluble salt content of 1.55%, thereby achieving harmless treatment of the electrolytic manganese slag.

[0044] Embodiment 2: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 1.93% Mn, 9.33% S, 0.55% NH3-N, 12.31% water-soluble salt by weight, and the water content of the electrolytic manganese slag is 20.85%.

[0045] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0046] B. Adding additives According to the weight ratio of additive 1 zeolite to electrolytic manganese slag being 1.6%, the electrolytic manganese slag and zeolite are evenly mixed, and then according to the weight ratio of additive 2 calcium oxide to electrolytic manganese slag being 10%, calcium oxide is added and mixed evenly to obtain mixed slag.

[0047] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 200°C for 60 min using a SX2-8-13 roasting furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 10.40 µg / L, an ammonia nitrogen content of 13.88 mg / L, and a water-soluble salt content of 1.98%, thereby achieving harmless treatment of the electrolytic manganese slag.

[0048] Embodiment 3: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 2.13% Mn, 8.96% S, 0.48% NH3-N, 12.07% water-soluble salt by weight, and the water content of the electrolytic manganese slag is 22.65%.

[0049] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0050] B. Adding additives According to the weight ratio of additive 1 zeolite to electrolytic manganese slag being 1.2%, the electrolytic manganese slag and zeolite are evenly mixed, and then according to the weight ratio of additive 2 calcium oxide to electrolytic manganese slag being 10%, calcium oxide is added and mixed evenly to obtain mixed slag.

[0051] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 100°C for 80 min using a SX2-8-13 roasting furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 0.20µg / L, an ammonia nitrogen content of 14.05mg / L, and a water-soluble salt content of 1.90%, thereby achieving harmless treatment of the electrolytic manganese slag.

[0052] Embodiment 4: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 2.06% by weight of Mn, 9.35% by weight of S, 0.45% by weight of NH3-N, and 12.86% by weight of water-soluble salts. The water content of the electrolytic manganese slag is 22.33%.

[0053] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0054] B. Adding additives According to the weight ratio of additive 1 zeolite to electrolytic manganese slag being 1.2%, the electrolytic manganese slag and zeolite are evenly mixed, and then according to the weight ratio of additive 2 calcium oxide to electrolytic manganese slag being 7.5%, calcium oxide is added and mixed evenly to obtain mixed slag.

[0055] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 100°C for 60 min using a SX2-8-13 roasting furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 1.50µg / L, an ammonia nitrogen content of 3.36mg / L, and a water-soluble salt content of 1.21%, thereby achieving harmless treatment of the electrolytic manganese slag.

[0056] Embodiment 5: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 2.25% Mn, 9.36% S, 0.46% NH3-N, 13.03% water-soluble salt by weight, and the water content of the electrolytic manganese slag is 22.27%.

[0057] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0058] B. Adding additives According to the weight ratio of additive 1 zeolite to electrolytic manganese slag being 1%, the electrolytic manganese slag and zeolite are evenly mixed, and then according to the weight ratio of additive 2 calcium oxide to electrolytic manganese slag being 5%, calcium oxide is added and mixed evenly to obtain mixed slag.

[0059] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 100°C for 80 min using a SX2-8-13 roasting furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 2.28µg / L, an ammonia nitrogen content of 10.68mg / L, and a water-soluble salt content of 0.88%, thereby achieving harmless treatment of the electrolytic manganese slag.

[0060] Embodiment 6: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 1.93% Mn, 9.33% S, 0.55% NH3-N, 12.31% water-soluble salt by weight, and the water content of the electrolytic manganese slag is 20.85%.

[0061] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0062] B. Adding additives According to the weight ratio of additive 1 zeolite to electrolytic manganese slag being 1.6%, the electrolytic manganese slag and zeolite are evenly mixed, and then according to the weight ratio of additive 2 slaked lime to electrolytic manganese slag being 10%, slaked lime is added and mixed evenly to obtain mixed slag.

[0063] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 200°C for 60 min using a SX2-8-13 roasting furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 0.58 mg / L, an ammonia nitrogen content of 14.63 mg / L, and a water-soluble salt content of 1.95%, thereby achieving harmless treatment of the electrolytic manganese slag.

[0064] Embodiment 7: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 1.87% Mn, 9.11% S, 0.51% NH3-N, 12.98% water-soluble salt by weight, and the water content of the electrolytic manganese slag is 21.64%.

[0065] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0066] B. Adding additives A mixed additive is prepared according to the weight ratio of additive 1 zeolite, additive 2 calcium oxide and electrolytic manganese slag of 1% and 10% respectively, and then the electrolytic manganese slag is added at the same time and mixed evenly to obtain a mixed slag.

[0067] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 100°C for 60 min using a SX2-8-13 calcining furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 21.36 µg / L, an ammonia nitrogen content of 11.08 mg / L, and a water-soluble salt content of 1.63%, thereby achieving harmless treatment of the electrolytic manganese slag. However, simultaneous addition of zeolite and calcium oxide would affect the curing effect of the electrolytic manganese slag, and the reaction uniformity during the curing process would be lower than that in Example 1, where zeolite was first added and mixed evenly, and then calcium oxide was added.

[0068] Embodiment 8: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 2.18% Mn, 9.32% S, 0.42% NH3-N, 12.58% water-soluble salt by weight, and the water content of the electrolytic manganese slag is 22.88%.

[0069] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0070] B. Adding additives According to the weight ratio of additive 1 zeolite to electrolytic manganese slag being 1%, the electrolytic manganese slag and zeolite are evenly mixed, and then according to the weight ratio of additive 2 calcium oxide to electrolytic manganese slag being 5%, calcium oxide is added and mixed evenly to obtain mixed slag.

[0071] C. Low temperature roasting Using an externally heated rotary kiln, the electrolytic manganese slag mixed slag obtained in step B was subjected to a continuous roasting test at a temperature of 100°C and a time of 60 min. The obtained product was analyzed. The average water-soluble manganese content of the product obtained by this method was 13.00µg / L, the average ammonia nitrogen content was 1.53mg / L, and the average water-soluble salt content was 0.32%, thereby achieving harmless treatment of the electrolytic manganese slag.

[0072] Comparative Example 1: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this comparative example is derived from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is based on weight: Mn is 1.87%, S is 9.11%, NH3-N is 0.51%, and water-soluble salt is 12.98%. The moisture content of the electrolytic manganese slag is 21.64%.

[0073] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0074] B. Low temperature roasting Without adding additives, the electrolytic manganese slag obtained in step A was roasted at 100° C. for 60 min in a SX2-8-13 roasting furnace. The obtained product was analyzed. The water-soluble manganese content, ammonia nitrogen content and water-soluble salt content of the product obtained by this method were 8.70 mg / L, 410.12 mg / L and 7.60%, respectively. The harmless treatment effect was not ideal.

[0075] Comparative Example 2: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this comparative example comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is based on weight: Mn is 1.93%, S is 9.33%, NH3-N is 0.55%, water-soluble salt is 12.31%, and the water content of the electrolytic manganese slag is 20.85%.

[0076] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0077] B. Low temperature roasting Without adding any additives, the electrolytic manganese slag obtained in step A was roasted at 200° C. for 60 min in a SX2-8-13 roasting furnace. The obtained product was analyzed. The water-soluble manganese content, ammonia nitrogen content and water-soluble salt content of the product obtained by this method were 12.51 mg / L, 398.27 mg / L and 7.15%, respectively. The harmless treatment effect was not ideal.

[0078] Comparative Example 3: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this comparative example is derived from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 2.13% by weight of Mn, 8.96% by weight of S, 0.48% by weight of NH3-N, and 12.07% by weight of water-soluble salts, and the moisture content of the electrolytic manganese slag is 22.65%.

[0079] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0080] B. Adding additives According to the weight ratio of additive 1 zeolite to electrolytic manganese slag of 1.2%, the electrolytic manganese slag and zeolite are evenly mixed, and then calcium oxide is added according to the weight ratio of additive 2 calcium oxide to electrolytic manganese slag of 10% to obtain mixed slag. No roasting treatment is performed, and the obtained product is directly stored for 80 minutes. The product obtained by this method has a water-soluble manganese content of 2.62 mg / L, an ammonia nitrogen content of 229.35 mg / L, and a water-soluble salt content of 3.26%. The harmless treatment effect is not ideal.

[0081] Comparative Example 4: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 2.06% by weight of Mn, 9.35% by weight of S, 0.45% by weight of NH3-N, and 12.86% by weight of water-soluble salts. The water content of the electrolytic manganese slag is 22.33%.

[0082] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0083] B. Adding additives The additive 1 zeolite is mixed evenly with the electrolytic manganese slag in a weight ratio of 1.2% to obtain a mixed slag.

[0084] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 100°C for 60 min using a SX2-8-13 roasting furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 22.08 mg / L, an ammonia nitrogen content of 433.28 mg / L, and a water-soluble salt content of 8.02%. The harmless treatment effect was not ideal.

[0085] Comparative Example 5: A method for harmless treatment of electrolytic manganese slag comprises the following steps: A. Crushing and breaking up The electrolytic manganese slag in this embodiment comes from the electrolytic manganese slag obtained from Guizhou Jinrui New Materials Co., Ltd., and its chemical composition is 2.25% Mn, 9.36% S, 0.46% NH3-N, 13.03% water-soluble salt by weight, and the water content of the electrolytic manganese slag is 22.27%.

[0086] The compacted electrolytic manganese slag is first crushed to a particle size of -10 mm.

[0087] B. Adding additives The additive 2 calcium oxide is mixed evenly with the electrolytic manganese slag in a weight ratio of 5% to the electrolytic manganese slag to obtain a mixed slag.

[0088] C. Low temperature roasting The electrolytic manganese slag mixed slag obtained in step B was roasted at 100°C for 80 min using a SX2-8-13 roasting furnace. The obtained product was analyzed. The product obtained by this method had a water-soluble manganese content of 1.23 mg / L, an ammonia nitrogen content of 22.31 mg / L, and a water-soluble salt content of 2.89%. The harmless treatment effect was not ideal.

Claims

1. A method for harmless treatment of electrolytic manganese slag, characterized in that: The following steps are involved: (1) crushing electrolytic manganese slag and mixing it with additives to obtain mixed slag; the additives include porous aluminosilicate materials and alkaline materials; (2) The mixed slag is subjected to roasting treatment to obtain harmless electrolytic manganese slag.

2. The method for harmless treatment of electrolytic manganese slag according to claim 1, characterized in that: Firstly, the electrolytic manganese slag and the porous aluminosilicate material are mixed evenly, and then the alkaline material is added and mixed evenly.

3. The method for harmless treatment of electrolytic manganese slag according to claim 1, characterized in that: The porous aluminosilicate material includes zeolite, and the amount of the porous aluminosilicate material is 1-2% of the mass of the electrolytic manganese slag.

4. The method for harmless treatment of electrolytic manganese slag according to claim 1, characterized in that: The alkaline material includes one or more of quicklime, slaked lime and carbide slag, and the amount of the alkaline material is 4-10% of the mass of the electrolytic manganese slag.

5. The method for harmless treatment of electrolytic manganese slag according to claim 1, characterized in that: The electrolytic manganese slag is a filter press residue produced in the electrolytic manganese production process; in the electrolytic manganese slag, the mass content of Mn is less than 3%, the mass content of S is less than 12%, the mass content of NH3-N is less than 1%, and the mass content of water-soluble salts is less than 15%.

6. The method for harmless treatment of electrolytic manganese slag according to claim 1, characterized in that: The water content of the electrolytic manganese slag is 20-30%.

7. The harmless treatment method for electrolytic manganese slag according to claim 1, characterized in that: The electrolytic manganese slag is crushed to a particle size less than 10 mm.

8. The method for harmless treatment of electrolytic manganese slag according to claim 1, characterized in that: During the calcination treatment, the calcination temperature is 50-300°C and the calcination time is 20-100min.

9. The method for harmless treatment of electrolytic manganese slag according to claim 1, characterized in that: In the harmless electrolytic manganese slag, the Mn ion content is lower than 1 mg / L, the NH3-N content is lower than 15 mg / L, and the water-soluble salt content is lower than 2%.

10. The harmless treatment method for electrolytic manganese slag according to claim 1, characterized in that: The ammonia generated during the roasting process is absorbed by the electrolytic manganese anode liquid to produce an ammonia solution, which is then recycled into the electrolytic manganese production process.