阅读说明：本技术 一种电解锰渣源头减量的方法 (Method for reducing electrolytic manganese slag source ) 是由 舒建成 曾祥菲 陈梦君 王瑞 黄金凤 罗正刚 赵航 于 2020-06-04 设计创作，主要内容包括：本发明公开一种电解锰渣源头减量的方法。其特征在于将菱锰矿粉按一定固液比制成矿浆液,将矿浆液送入反应器内,控制合适的反应温度与矿酸比,搅拌混合后加入一定浓度范围的表面活性剂,反应结束后采用碱性药剂调节矿浆pH,随后固液分离。本发明相比传统不加表面活性剂工艺其锰浸出率提高了7~14个百分点,锰渣含水率降低2-5个百分点。此方法通过添加表面活性剂能够调控锰矿浸出过程锰渣颗粒尺寸,强化锰渣颗粒分散,提高锰矿资源利用率,降低锰渣中夹带的有价资源和污染物。本发明与现有技术相比,具有工艺简单、成本低、可操作性强等优势。(The invention discloses a method for reducing electrolytic manganese slag sources. The method is characterized in that rhodochrosite powder is prepared into ore pulp according to a certain solid-liquid ratio, the ore pulp is fed into a reactor, the proper reaction temperature and the ore-acid ratio are controlled, a surfactant with a certain concentration range is added after stirring and mixing, the pH value of the ore pulp is adjusted by adopting an alkaline agent after the reaction is finished, and then solid-liquid separation is carried out. Compared with the traditional process without adding the surfactant, the manganese leaching rate of the method is improved by 7-14%, and the water content of the manganese slag is reduced by 2-5%. According to the method, the size of manganese slag particles in the leaching process of manganese ore can be regulated and controlled by adding the surfactant, the dispersion of the manganese slag particles is enhanced, the utilization rate of manganese ore resources is improved, and valuable resources and pollutants carried in the manganese slag are reduced. Compared with the prior art, the method has the advantages of simple process, low cost, strong operability and the like.)

1.A method for reducing the electrolytic manganese slag source comprises the following specific steps:

(1) dissolving one or more surfactants of sodium oleate, trisodium citrate, sodium dodecyl sulfate and tetradecyl trimethyl ammonium bromide in water to obtain a solution A, and preparing the rhodochrosite powder pretreated in the electrolytic manganese industry into ore slurry B according to a certain solid-to-liquid ratio; the dosage of the surfactant is 3-100 mg/L, and the solid-to-liquid ratio of the rhodochrosite to the solution is 1: 3-7.

(2) Adding the ore pulp B into a reactor, adding the solution A into the ore pulp B under a certain temperature reaction condition, adding concentrated sulfuric acid into the ore pulp B according to an ore acid ratio after uniformly stirring, and fully reacting for a period of time to obtain leached ore pulp C; wherein the ratio of the mineral acids is 1: 0.3-0.8, the reaction time is 2-6 h, and the reaction temperature is 40-80 ℃.

(3) Adding an alkaline agent into the leached ore pulp C to adjust the pH value of the leached ore pulp C to 6.5-7.0, reacting for a period of time, performing solid-liquid separation by using filter pressing equipment, directly feeding filter residues into a residue field, and purifying filtrate to prepare qualified electrolytic manganese metal liquid; the alkaline agent is one or more of calcium oxide, calcium carbonate, ammonia water and the like, and the reaction time is 1-3 h.

Technical Field

The invention relates to the field of clean production of wet metallurgy, in particular to a method for reducing sources of electrolytic manganese residues.

Background

The electrolytic manganese slag is an industrial solid waste with high water content generated after leaching manganese ore in the production process of wet electrolytic manganese metal, and the main components of the electrolytic manganese slag are calcium sulfate dihydrate, silicon dioxide and a large amount of soluble manganese and ammonia nitrogen. In 2019, the output of electrolytic manganese in China accounts for more than 98% of the world, and with the development of electrolytic manganese industry in China, the grade of mainstream manganese ore in the market is reduced to 13%. Due to the fact that the grade of manganese ore is low and leaching efficiency is not high, 8-10 tons of electrolytic manganese slag can be generated when 1 ton of metal manganese is produced. 1.5-1.6 million tons exist in China, 1000 million tons are newly increased every year, a large amount of electrolytic manganese slag is stockpiled, a large amount of cultivated land is occupied, and meanwhile, as the electrolytic manganese slag has high water content (25% -30%), fine particles (40-120 microns), poor dispersibility, good mobility and good fluidity, leachate containing manganese and ammonium is easily formed in a stock dump, enters a water body and pollutes the environment; the large amount of ammonium sulfate double salt in the manganese slag is difficult to remove (the particles are fine), and the manganese slag has poor activity, so that the resource utilization difficulty is high. Therefore, the development of electrolytic manganese industry in China is severely limited due to the problem that a large amount of soluble pollutants are carried in the electrolytic manganese slag with high water content.

At present, the manganese ore enhanced leaching technology is researched in China, but the research on reducing the manganese slag source is few when the manganese ore enhanced leaching is carried out and the water content of the manganese slag is reduced. For example, patent No. cn102443711.a provides a method for enhancing manganese ore leaching, which utilizes a novel device to enhance manganese ore leaching, improves a venturi nozzle of a traditional manganese ore leaching tank, forms a larger nozzle spray amplitude to improve reaction efficiency and enhance manganese ore leaching, and although the method can improve manganese ore leaching rate, the enhanced leaching effect is not obvious, and the reduction of manganese slag water content while the improvement of manganese ore leaching rate cannot be realized. And the leaching rate of manganese ore is improved by adopting a flow field mixing process and an energy transfer process in a novel rigid-flexible combined stirring paddle strengthened leaching tank as in the patent CN109589815.A. Similarly, the problem of high moisture content of manganese slag due to fine manganese slag particles cannot be considered while enhancing leaching of manganese ore.

The invention utilizes the surfactant to regulate and control the growth mechanism of calcium sulfate crystals in the leaching process of manganese ore, reduces the interfacial tension between manganese slag particles and leaching solution, improves the sedimentation performance of the particles, strengthens the dispersion and wetting capacity of the particles in solution leaching, forms a more stable leaching system, strengthens the leaching of manganese ore, reduces the water content of manganese slag and reduces the amount of pollutants carried in the manganese slag.

In conclusion, the method is characterized in that the manganese ore enhanced leaching and the water content control of the electrolytic manganese slag are organically combined. By adding the surfactant in the leaching reaction, the particle size of the manganese ore is regulated and controlled, the leaching of the manganese ore is enhanced, and the water content of the manganese slag is reduced. The method not only improves the utilization rate of manganese ore resources, but also directly reduces valuable resources and pollutants carried by the electrolytic manganese slag, reduces the pollutant yield of the electrolytic manganese industry from the source, and is beneficial to energy conservation and emission reduction of the electrolytic manganese industry. The method not only can provide theoretical support for reduction treatment and resource utilization of the electrolytic manganese slag, but also can provide a new research idea for controlling the moisture content of the traditional hydrometallurgy slag.

Disclosure of Invention

Aiming at the problems, the invention mainly aims to provide a method for reducing the source amount of electrolytic manganese slag on the basis of the traditional wet electrolytic manganese production method, and solves the problems of low leaching rate of manganese ore and high water content of manganese slag. According to the method, the water content of the manganese slag is reduced while the manganese ore is efficiently leached, so that the amount of manganese sulfate and ammonium sulfate taken away by electrolytic manganese slag can be directly reduced, the pollution production amount of electrolytic manganese metal production is reduced from the source, and the method is one of effective ways for realizing energy conservation and emission reduction in the electrolytic manganese industry.

In order to achieve the purpose, the invention adopts the technical scheme that the method for reducing the electrolytic manganese slag source comprises the following specific steps:

(1) dissolving one or more surfactants of sodium oleate, trisodium citrate, sodium dodecyl sulfate and tetradecyl trimethyl ammonium bromide in water to obtain a solution A, and preparing the rhodochrosite powder pretreated in the electrolytic manganese industry into ore slurry B according to a certain solid-to-liquid ratio; the dosage of the surfactant is 3-100 mg/L, and the solid-to-liquid ratio of the rhodochrosite to the solution is 1: 3-7.

(2) Adding the ore slurry B in the claim (1) into a reactor, adding the solution A into the ore slurry B under a certain temperature reaction condition, adding concentrated sulfuric acid into the ore slurry according to an ore acid ratio after uniformly stirring, and fully reacting for a period of time to obtain leached ore pulp C; wherein the ratio of the mineral acids is 1: 0.3-0.8, the reaction time is 2-6 h, and the reaction temperature is 40-80 ℃.

(3) Adding an alkaline agent into the leached ore pulp C obtained in the step (2) to adjust the pH value to 6.5-7.0, after reacting for a period of time, performing solid-liquid separation by using filter pressing equipment, directly feeding filter residues into a residue field, and purifying filtrate to prepare qualified electrolytic manganese metal liquid; the alkaline agent is one or more of calcium oxide, calcium carbonate, ammonia water and the like, and the reaction time is 1-3 h.

Compared with the existing invention for strengthening leaching of manganese ore, the invention has the following remarkable advantages:

(1) the addition of the surfactant can essentially regulate and control the particle size of the manganese ore powder in the leaching solution, strengthen the dispersion of electrolytic manganese slag particles in the leaching solution, control the crystal form of calcium sulfate in the manganese slag and improve the hydrophilicity and hydrophobicity of the electrolytic manganese slag.

(2) According to the invention, only a small amount of surfactant is added in the traditional wet electrolytic manganese production process, the manganese ore is efficiently leached, the moisture content of manganese slag is reduced, additional equipment and pretreatment process are not required, and the surfactant is cheap and easy to obtain, is environment-friendly and safe, and does not influence the subsequent production process.

(3) The method not only can provide theoretical support for the safe stockpiling, resource utilization and new water content control process of the electrolytic manganese slag, but also can provide a new research idea for the water content control of the traditional hydrometallurgy slag.

Detailed Description

The invention will now be described in more detail by way of the following examples, which are given for the purpose of better illustrating the invention, the scope of protection of the invention being not limited to the examples given.