阅读说明：本技术 一种电解锰渣的处理方法 (treatment method of electrolytic manganese slag ) 是由 黎贵亮 詹海青 詹海华 黄海岛 张丽云 李庆梅 李春霞 黄炳龙 于 2019-09-16 设计创作，主要内容包括：本发明一种电解锰渣的处理方法,采用电解锰阳极液高压冲刷电解锰渣化浆,电解锰阳极液的高酸低锰特性配合高压条件,使得锰渣滤饼化浆彻底,极大提升锰渣中金属锰和硫酸铵的回收率；在压滤机上对滤饼进行清水洗涤,避免了锰渣压实后再清洗遇到的洗涤效果不明显及锰渣不易化开的弊端,可高效回收酸溶锰和硫酸铵,同时减少清水消耗量；在压滤机上对滤饼进行碱液洗涤,碱液打入压滤机,垂直穿过滤饼并不断循环,实现锰渣中残锰的固化和氨氮的去除,固液比大,显著减少药剂耗量；本发明电解锰渣的处理方法,水溶锰回收率≥90%、硫酸铵回收率≥90%、锰渣含水率≤28%,达到无害化处理电解锰渣的目的。(according to the method for treating the electrolytic manganese slag, the electrolytic manganese slag slurry is flushed at high pressure by using the electrolytic manganese anolyte, and the high-acid low-manganese characteristics of the electrolytic manganese anolyte are matched with high-pressure conditions, so that the manganese slag filter cake slurry is thoroughly slurried, and the recovery rate of metal manganese and ammonium sulfate in the manganese slag is greatly improved; the filter cake is washed by clean water on the filter press, so that the defects that the washing effect is not obvious and the manganese slag is not easy to dissolve when the manganese slag is washed after being compacted are overcome, the acid-soluble manganese and the ammonium sulfate can be efficiently recycled, and the consumption of the clean water is reduced; washing the filter cake on a filter press by alkali liquor, pumping the alkali liquor into the filter press, vertically penetrating through the filter cake and continuously circulating to realize the solidification of residual manganese in the manganese slag and the removal of ammonia nitrogen, wherein the solid-liquid ratio is large, and the medicament consumption is obviously reduced; according to the method for treating the electrolytic manganese slag, the recovery rate of the water-soluble manganese is more than or equal to 90%, the recovery rate of the ammonium sulfate is more than or equal to 90%, and the water content of the manganese slag is less than or equal to 28%, so that the aim of harmlessly treating the electrolytic manganese slag is fulfilled.)

1. The method for treating the electrolytic manganese slag is characterized by comprising the following steps of:

(1) Pulping, namely brushing electrolytic manganese slag by using electrolytic manganese anolyte under the condition that the pressure is 1.2-1.5 MPa to preliminarily pulp the electrolytic manganese slag to obtain pulp, discharging the pulp into a stirring tank, and stirring the pulp for 140-160 min at the temperature of 50-55 ℃ to obtain manganese slag pulp, wherein the mass ratio of the electrolytic manganese anolyte to the electrolytic manganese slag is 0.95-1.05: 1, the content of Mn ²⁺ in the electrolytic manganese anolyte is 10-14 g/L, the content of ammonium sulfate is 90-110 g/L, and the acidity is 34-38 g/L;

(2) and (3) filter pressing: filtering the manganese slag slurry by a filter press, wherein the filtering pressure is 0.18-0.22 MPa, keeping for 8-12 min, and sending the filtrate into a filtrate pool to obtain a filter cake and a filtrate;

(3) washing with clean water: washing the filter cake in a filter press, and recovering manganese and ammonium sulfate in the filter cake through the double functions of displacement washing and clean water washing;

(4) circularly washing with alkali liquor: circularly washing the water-soluble manganese remained by solidifying the filter cake by using alkali liquor with the pH value of 12 in a filter press to remove ammonia nitrogen;

(5) High-pressure squeezing: after washing with alkali liquor, filtering the filter cake under the pressure of 0.75-0.85 MPa for 14-16 min to obtain harmless electrolytic manganese slag, and collecting the solution in the filtrate tank to recover water-soluble manganese and ammonium sulfate.

2. The method for treating the electrolytic manganese slag according to claim 1, wherein in the step (1), the electrolytic manganese slag is flushed by using an electrolytic manganese anolyte under the condition that the pressure is 1.3MPa to carry out primary slurrying to obtain slurry, the slurry is discharged into a stirring tank and stirred for 150min at the temperature of 52 ℃ to obtain manganese slag slurry, the mass ratio of the electrolytic manganese anolyte to the electrolytic manganese slag is 1.02: 1, the content of Mn ²⁺ in the electrolytic manganese anolyte is 12g/L, the content of ammonium sulfate is 100g/L, and the acidity is 36 g/L.

3. the method for treating electrolytic manganese slag according to claim 1, wherein: and (3) filtering the manganese slag slurry by using a filter press in the step (2), wherein the filtering pressure is 0.20MPa, keeping for 10min, and sending the filtrate into a filtrate pool to obtain a filter cake and a filtrate.

4. The method for treating electrolytic manganese slag according to claim 1, wherein: and (3) the consumption of the clean water of each ton of the electrolytic manganese slag in the step (3) is 0.40-0.43 ton.

5. The method for treating electrolytic manganese residues according to claim 4, wherein the solution with the Mn ²⁺ content of less than 30g/L is returned to the slurrying pond in the step (1) during the filter cake washing in the step (3), and the solution with the Mn ²⁺ content of more than 30g/L is discharged into the filtrate pond.

6. The method for treating electrolytic manganese slag according to claim 1, wherein: the alkali liquor in the step (4) is sodium hydroxide solution.

7. The method for treating electrolytic manganese slag according to claim 6, wherein: and in the step (4), the consumption of sodium hydroxide in each ton of electrolytic manganese residues is 4.5 kg to 5.0 kg.

8. the method for treating electrolytic manganese slag according to claim 1, wherein: and (5) after the washing of the alkaline solution is finished, filter pressing the filter cake under the condition that the pressure is 0.8MPa, keeping for 15min to obtain harmless electrolytic manganese slag, and collecting the solution in the filter solution pool to finish the recovery of the water-soluble manganese and the ammonium sulfate.

Technical Field

The invention relates to the technical field of metallurgy, in particular to a method for treating electrolytic manganese slag.

background

The method comprises the steps of adding a sulfuric acid solution into a reactor to react with manganese carbonate ore to generate manganese sulfate, adding a small amount of reducing agent when the pH value is close to 4, oxidizing Fe ²⁺ in the solution, hydrolyzing the precipitate, neutralizing excessive acid by using liquid ammonia, adding a vulcanizing agent when the pH value is close to 7 to enable heavy metal ions in the solution to generate corresponding sulfide precipitate, filtering by using a filter press, feeding filtrate into an electrolytic cell for electrolysis, and discharging a filter cake, namely the electrolytic manganese residue, wherein the filter cake is a so-called electrolytic manganese residue, about 30-35% of electrolyte solution is remained in the manganese residue due to the fact that the conventional filter pressing process for producing electrolytic manganese is roughly placed, equipment is lagged and the mechanical automation degree is low, wherein the manganese sulfate concentration (calculated by Mn) is 30-36 g/L, so that high manganese loss is caused, in addition, the chemical leaching is not thorough, about 1.5-2.0% of manganese carbonate in the manganese residue is not converted into manganese sulfate in one-time acid leaching, only the filter pressing process, about 3-4 g/L of manganese sulfate in the manganese ore accounts for a large amount, about 18-18% of manganese carbonate in the manganese ore, and the waste of leachate caused by the seepage prevention of the conventional leaching process of the conventional electrolytic manganese residue, the landfill water, the landfill waste of enterprises, the landfill water and the conventional landfill waste of the land is caused, and the conventional seepage prevention of the conventional landfill waste of the land is caused, and the conventional landfill waste of the conventional landfill water.

disclosure of Invention

aiming at the defects of the prior art, the invention aims to provide a method for treating electrolytic manganese slag, which has the advantages of simple process, energy conservation and environmental protection.

in order to achieve the purpose, the technical scheme adopted by the invention is as follows: the method for treating the electrolytic manganese slag comprises the following steps:

(1) Pulping, namely brushing electrolytic manganese slag by using electrolytic manganese anolyte under the condition that the pressure is 1.2-1.5 MPa to preliminarily pulp the electrolytic manganese slag to obtain pulp, discharging the pulp into a stirring tank, and stirring the pulp for 140-160 min at the temperature of 50-55 ℃ to obtain manganese slag pulp, wherein the mass ratio of the electrolytic manganese anolyte to the electrolytic manganese slag is 0.95-1.05: 1, the content of Mn ²⁺ in the electrolytic manganese anolyte is 10-14 g/L, the content of ammonium sulfate is 90-110 g/L, and the acidity is 34-38 g/L;

(2) and (3) filter pressing: filtering the manganese slag slurry by a filter press, wherein the filtering pressure is 0.18-0.22 MPa, keeping for 8-12 min, and sending the filtrate into a filtrate pool to obtain a filter cake and a filtrate;

(3) washing with clean water: washing the filter cake in a filter press, and recovering manganese and ammonium sulfate in the filter cake through the double functions of displacement washing and clean water washing;

(4) Circularly washing with alkali liquor: circularly washing the water-soluble manganese remained by solidifying the filter cake by using alkali liquor with the pH value of 12 in a filter press to remove ammonia nitrogen;

(5) High-pressure squeezing: after washing with alkali liquor, filtering the filter cake under the pressure of 0.75-0.85 MPa for 14-16 min to obtain harmless electrolytic manganese slag, and collecting the solution in the filtrate tank to recover water-soluble manganese and ammonium sulfate.

Further, in the step (1), the electrolytic manganese slag is flushed by using an electrolytic manganese anolyte under the condition that the pressure is 1.3MPa, so that the electrolytic manganese slag is preliminarily slurried to obtain slurry, the slurry is discharged into a stirring tank, and the stirring is carried out for 150min at the temperature of 52 ℃ to obtain manganese slag slurry, wherein the mass ratio of the electrolytic manganese anolyte to the electrolytic manganese slag is 1.02: 1, the content of Mn ²⁺ in the electrolytic manganese anolyte is 12g/L, the content of ammonium sulfate is 100g/L, and the acidity is 36 g/L.

Further, in the step (2), the manganese slag slurry is filtered by a filter press, the filtering pressure is 0.20MPa, the manganese slag slurry is kept for 10min, and the filtrate is sent to a filtrate pool to obtain a filter cake and a filtrate.

Furthermore, the consumption of the clean water per ton of the electrolytic manganese slag in the step (3) is 0.40-0.43 ton.

further, during the process of washing the filter cake in the step (3), the solution with the content of Mn ²⁺ being less than 30g/L is returned to the slurrying pool in the step (1), and the solution with the content of Mn ²⁺ being more than 30g/L is discharged into the filtrate pool.

Further, the alkali liquor in the step (4) is sodium hydroxide solution.

Further, in the step (4), the consumption of sodium hydroxide per ton of electrolytic manganese residue is 4.5 kg to 5.0 kg.

And (3) further, after the washing of the alkaline solution in the step (5) is finished, filter pressing is carried out on the filter cake under the pressure of 0.8MPa, the filter cake is kept for 15min, electrolytic manganese slag which is subjected to innocent treatment is obtained, and the solution in the filter solution pool is collected, so that the recovery of water-soluble manganese and ammonium sulfate can be completed.

according to the method for treating the electrolytic manganese slag, the manganese slag filter cake is compact and high in viscosity, so that the pulping in the traditional process is incomplete, the energy consumption is high, and the cost is high; the filter cake is washed by clean water on the filter press, so that the defects that the washing effect is not obvious and the manganese slag is not easy to dissolve when the manganese slag is washed after being compacted are overcome, the acid-soluble manganese and the ammonium sulfate can be efficiently recycled, and the consumption of the clean water is reduced; washing the filter cake on a filter press by alkali liquor, pumping the alkali liquor into the filter press, vertically penetrating through the filter cake and continuously circulating to realize the solidification of residual manganese in the manganese slag and the removal of ammonia nitrogen, wherein the solid-liquid ratio is large, and the medicament consumption is obviously reduced; the traditional electrolytic manganese slag is treated by acid leaching and water washing, the concentration of manganese and ammonia nitrogen in a leaching solution is greatly reduced, but still exceeds the requirements of the integrated wastewater discharge standard, and the aim of harmless treatment cannot be achieved.

Detailed Description

The following examples may help one skilled in the art to more fully understand the present invention, but are not intended to limit the invention in any way.