阅读说明：本技术 一种提高低品位锰矿中的锰浸出率的方法 (Method for improving manganese leaching rate in low-grade manganese ore ) 是由 郭爱民 明宪权 黄冠汉 谢彦 黄炳龙 刘登祥 卢国贤 何溯结 于 2019-10-12 设计创作，主要内容包括：本发明一种提高低品位锰矿中的锰浸出率的方法,在低品位锰矿浸出过程中,加入适量表面活性剂,改善矿物颗粒的表面活性,提高矿石颗粒对氢离子吸附作用,不仅有效去除油性有机质,同时提高锰的浸出率；锰矿浸出液在压滤过程中,表面活性剂不断被过滤出去,使得锰矿浸出液的表面张力持续下降,使得锰矿浸出液的电流效率存在先上升后下降的趋势,在低品位锰矿电解过程中,加入适量表面活性剂,使得锰矿浸出液的表面张力数值最优,显著提高电解锰的电流效率；合理控制电解液的氧化还原电位,使溶液电流效率最高；电解时向电解液中添加一定浓度的二氧化硒,可以抑制析氢反应的发生,可以显著提高电解锰过程的电流效率,使得电解锰能耗低,锰的浸出率高。(According to the method for improving the leaching rate of manganese in the low-grade manganese ore, a proper amount of surfactant is added in the leaching process of the low-grade manganese ore, so that the surface activity of mineral particles is improved, the adsorption effect of the mineral particles on hydrogen ions is improved, oily organic matters are effectively removed, and the leaching rate of manganese is improved; in the filter pressing process of the manganese ore leachate, the surfactant is continuously filtered out, so that the surface tension of the manganese ore leachate is continuously reduced, the current efficiency of the manganese ore leachate tends to rise first and then fall, and in the low-grade manganese ore electrolysis process, a proper amount of surfactant is added, so that the surface tension value of the manganese ore leachate is optimal, and the current efficiency of electrolytic manganese is obviously improved; reasonably controlling the oxidation-reduction potential of the electrolyte to ensure that the current efficiency of the solution is highest; selenium dioxide with a certain concentration is added into the electrolyte during electrolysis, so that the occurrence of hydrogen evolution reaction can be inhibited, the current efficiency in the manganese electrolysis process can be obviously improved, the energy consumption of the manganese electrolysis is low, and the leaching rate of manganese is high.)

1. A method for improving the leaching rate of manganese in low-grade manganese ore is characterized by comprising the following steps:

(1) in the ore leaching process, the weight ratio of the low-grade manganese ore to the liquid in the feeding process is 0.95-1.05: 5, the weight ratio of the sulfuric acid to the low-grade manganese ore is 2.9-3.1: 1, adding 19-21 ppm of a surfactant, reacting for 4.8-5.2 h at the temperature of 55-65 ℃, standing for 15min to obtain a manganese ore leachate, wherein the mass percent of + 2-valent manganese metal in the low-grade manganese ore is 19.00-19.10%, the mass percent of + 4-valent manganese metal is 0.45-0.55%, and the surfactant is OP-10;

(2) removing iron from the manganese ore leachate, adjusting the pH value of the manganese ore leachate to 6.5-7.0, and performing primary filter pressing to obtain primary filter pressing filtrate;

(3) carrying out vulcanization impurity removal on the first filter pressing filtrate, and carrying out second filter pressing to obtain a second filter pressing filtrate;

(4) adding active carbon into the secondary filter-pressing filtrate, blowing air, standing for 22-26 h, and carrying out third filter pressing to obtain third filter-pressing filtrate;

(5) the third filter-pressed filtrate is prepared into initial electrolyte with the oxidation-reduction potential of 210 mV-230 mV and the current density of 340A/m²～360 A/m²Electrolyzing the initial electrolyte under the conditions that the temperature in the cathode region is 35-45 ℃ and the pH value of catholyte is 6.9-7.1 to obtain an electrolytic manganese metal product; the content of the + 2-valent metal manganese in the initial electrolyte is 28-32 g/L, the content of ammonium sulfate is 110-130 g/L, and the content of selenium dioxide is 28-32 mg/L, OP-10, and is 25-30 ppm.

2. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 1, characterized by comprising the following steps: the sulfuric acid in the step (1) is concentrated sulfuric acid with the mass percent of 96.5% -98.5%.

3. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 1, characterized by comprising the following steps: and (3) oxidizing and removing iron by using manganese powder in the step (2).

4. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 1, characterized by comprising the following steps: and (3) adjusting the pH value of the manganese ore leaching solution by using double flying powder in the step (2).

5. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 1, characterized by comprising the following steps: and (3) carrying out first pressure filtration in the step (2) under the condition that the pressure is 0.05 MPa-0.15 MPa.

6. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 1, characterized by comprising the following steps: and (3) vulcanizing agent used for vulcanizing and removing impurities from the first filter-pressed filtrate is one of sodium sulfide, barium sulfide, ferrous sulfide or ammonium sulfide.

7. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 6, characterized by comprising the following steps: and (3) carrying out secondary filter pressing under the condition that the pressure is 0.25-0.35 MPa.

8. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 1, characterized by comprising the following steps: the pressure of the third filter pressing in the step (4) is 0.15 MPa-0.25 MPa.

9. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 1, characterized by comprising the following steps: in the step (5), the third filter-pressed filtrate is prepared into initial electrolyte with the oxidation-reduction potential of 220 mV and the current density of 350A/m²Electrolyzing the initial electrolyte under the conditions that the temperature in the cathode region is 40 ℃ and the pH value of catholyte is 7 to obtain an electrolytic manganese metal product; the content of the + 2-valent metal manganese in the initial electrolyte is 30g/L, the content of ammonium sulfate is 120 g/L, and the content of selenium dioxide is 30mg/L, OP-10 and 28 ppm.

10. The method for improving the leaching rate of manganese in low-grade manganese ore according to claim 1, characterized by comprising the following steps: the electrolysis period in the step (5) is 22-26 h per electrolysis, and the cell is taken out and the plate is replaced.

Technical Field

The invention relates to the technical field of metallurgy, in particular to a method for improving the leaching rate of manganese in low-grade manganese ore.

Background

At present, China has become the first major manganese resource utilization country in the world, the resource potential of domestic high-quality manganese ore reaches 2 hundred million tons, the manganese ore resource is mainly complex low-grade manganese carbonate ore, domestic electrolytic manganese enterprises generally adopt manganese carbonate ore as a manganese metal production raw material, and the manganese ore leaching method has the advantages that the ore leaching process is simple, and the leaching of manganese ore can be directly carried out by using sulfuric acid. But the manganese slag has huge yield and higher energy consumption for electrolysis due to lower grade and more harmful impurities. Manganese ore in China is mainly deposited manganese carbonate, and manganese oxide ore is inferior. In terms of ore grade, manganese ore resources in China mainly comprise lean ores (accounting for 93.6 percent of reserves), and the average grade is less than 20 percent. In terms of ore phase components, manganese ores in China are complex in material composition, high in phosphorus, sulfur and chlorine, and contain associated (co) metal elements (copper, cobalt, nickel and the like) and other impurities (oxides of aluminum, fluorine, magnesium, calcium and the like), and some special manganese ores are associated with high-value-added precious metal elements (such as silver, lead, zinc, cobalt and the like). The complex low-grade manganese resources in China are rich in reserves, and new energy-saving and efficient low-grade manganese ore extraction technologies are urgently needed.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a method for improving the leaching rate of manganese in low-grade manganese ore, which has simple process and low raw material consumption.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for improving the leaching rate of manganese in low-grade manganese ore comprises the following steps:

(1) in the ore leaching process, the weight ratio of the low-grade manganese ore to the liquid in the feeding process is 0.95-1.05: 5, the weight ratio of the sulfuric acid to the low-grade manganese ore is 2.9-3.1: 1, adding 19-21 ppm of a surfactant, reacting for 4.8-5.2 h at the temperature of 55-65 ℃, standing for 15min to obtain a manganese ore leachate, wherein the mass percent of + 2-valent manganese metal in the low-grade manganese ore is 19.00-19.10%, the mass percent of + 4-valent manganese metal is 0.45-0.55%, and the surfactant is OP-10;

(2) removing iron from the manganese ore leachate, adjusting the pH value of the manganese ore leachate to 6.5-7.0, and performing primary filter pressing to obtain primary filter pressing filtrate;

(3) carrying out vulcanization impurity removal on the first filter pressing filtrate, and carrying out second filter pressing to obtain a second filter pressing filtrate;

(4) adding active carbon into the secondary filter-pressing filtrate, blowing air, standing for 22-26 h, and carrying out third filter pressing to obtain third filter-pressing filtrate;

(5) the third filter-pressed filtrate is prepared into initial electrolyte with the oxidation-reduction potential of 210 mV-230 mV and the current density of 340A/m²～360 A/m²Electrolyzing the initial electrolyte under the conditions that the temperature in the cathode region is 35-45 ℃ and the pH value of catholyte is 6.9-7.1 to obtain an electrolytic manganese metal product; the content of the + 2-valent metal manganese in the initial electrolyte is 28-32 g/L, the content of ammonium sulfate is 110-130 g/L, and the content of selenium dioxide is 28-32 mg/L, OP-10, and is 25-30 ppm.

Further, the sulfuric acid in the step (1) is concentrated sulfuric acid with the mass percent of 96.5% -98.5%.

Further, manganese powder is used for oxidizing and removing iron in the step (2).

Further, in the step (2), the pH value of the manganese ore leaching solution is adjusted by using double flying powder.

Further, in the step (2), the first pressure filtration is carried out under the condition that the pressure is 0.05 MPa-0.15 MPa.

Further, in the step (3), a vulcanizing agent used for vulcanizing and removing impurities from the first filter-pressing filtrate is one of sodium sulfide, barium sulfide, ferrous sulfide and ammonium sulfide.

Further, in the step (3), secondary pressure filtration is carried out under the condition that the pressure is 0.25 MPa-0.35 MPa.

Further, the pressure of the third filter pressing in the step (4) is 0.15 MPa-0.25 MPa.

Further, in the step (5), the third filter-pressing filtrate is prepared into an initial electrolyte with the oxidation-reduction potential of 220 mV and the current density of 350A/m²Electrolyzing the initial electrolyte under the conditions that the temperature in the cathode region is 40 ℃ and the pH value of catholyte is 7 to obtain an electrolytic manganese metal product; the content of the + 2-valent metal manganese in the initial electrolyte is 30g/L, the content of ammonium sulfate is 120 g/L, and the content of selenium dioxide is 30mg/L, OP-10 and 28 ppm.

Furthermore, the electrolysis period in the step (5) is 22-26 h per electrolysis, and the cell is taken out and the plate is replaced.

According to the method for improving the leaching rate of manganese in the low-grade manganese ore, a proper amount of surfactant is added in the leaching process of the low-grade manganese ore, so that the surface activity of mineral particles is improved, the adsorption effect of the mineral particles on hydrogen ions is improved, oily organic matters are effectively removed, and the leaching rate of manganese is improved; in the filter pressing process of the manganese ore leachate, the surfactant is continuously filtered out, so that the surface tension of the manganese ore leachate is continuously reduced, the current efficiency of the manganese ore leachate tends to rise first and then fall, and in the low-grade manganese ore electrolysis process, a proper amount of surfactant is added, so that the surface tension value of the manganese ore leachate is optimal, and the current efficiency of electrolytic manganese is obviously improved; reasonably controlling the oxidation-reduction potential of the electrolyte to ensure that the current efficiency of the solution is highest; during electrolysis, selenium dioxide with a certain concentration is added into the electrolyte to inhibit the occurrence of hydrogen evolution reaction, so that the current efficiency in the manganese electrolysis process can be obviously improved, the energy consumption of the manganese electrolysis is low, and the leaching rate of manganese is high.

According to the method for improving the leaching rate of manganese in low-grade manganese ore, the manganese ore leaching solution is subjected to first filter pressing under specific pressure after iron removal, is subjected to second filter pressing under specific pressure after vulcanization and impurity removal, and is subjected to third filter pressing under specific pressure after activated carbon adsorption, so that the effects of iron removal, vulcanization and impurity removal and activated carbon adsorption are greatly enhanced, the leaching of manganese is improved, the recovery rate of manganese is over 95%, the manganese content in manganese slag is reduced, the comprehensive utilization rate of manganese is improved, resources are saved, and the pollution to the environment is reduced.

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.