Method for comprehensively recycling manganese, lead, silver and selenium from manganese anode slime

Abstract

The invention provides a method for comprehensively recycling manganese, lead, silver and selenium from manganese anode slime. The method comprises the steps that firstly, the manganese anode slime, lead sulfide concentrate and ball milling liquid are mixed and subjected to wet-type ball milling; secondly, leaching of valuable metals such as manganese and selenium is conducted, leachate is reserved, and leached residues serve as lead smelting raw materials for recycling lead and silver; thirdly, a calcium-magnesium removing agent is added for impurity removing; and fourthly, a neutralizer, namely, ammonium hydroxide, and ammonium sulfate are added, a cleaning agent, namely, sodium dimethyl dithiocarbamate is dropwise added, and after stewing is conducted, activated carbon is added for adsorption, filter pressing is conducted, an electrolyzing additive is dropwise added into filtrate, and electrolytic manganese metal is prepared through electrolyzation. The method is small in investment, simple in technology, low in cost and capable of effectively increasing the comprehensive recovery rate.

Description

technical field [0001] The invention relates to a method for comprehensively recovering manganese, lead, silver and selenium from manganese anode slime, in particular to a method for recovering valuable metal manganese by using manganese electrowinning anode slime as a raw material and adopting an efficient and green all-wet process , lead, silver and selenium methods. The utility model belongs to the technical field of resource recycling and circular economy. [0002] technical background [0003] Manganese ore and its deep-processing products are widely used in various fields of the national economy. 90% of manganese is consumed in the iron and steel industry, and 10% is used in nonferrous metallurgy, chemical industry, electronics and other sectors. The demand for it continues to grow with the rapid development of my country's economy. The production of manganese metal in my country mainly adopts the electrolysis method. During the electrolysis production process, a large...

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Problems solved by technology

The disadvantage is that the roasting time of this process is long, the roasting energy consumption is large, and the production efficiency is low

[0009] 5. Inorganic reductive acid leaching method, there are many studies on this method, such as the two-mine method, under certain conditions, the leaching rate of manganese can reach 90%, the disadvantage is that 1g of manganese anode slime needs 0.75g of pyrite, the dosage Too large, high cost, large amount of slag, unable to obtain qualified lead concentrate, forming new leached slag pollution, and at the same time, the composition of pyrite is complex, and contains a certain amount of gangue and Fe with large specific surface area. 2 o 3 These substances will absorb selenium in the solution during the leaching process, so selenium cannot be recycled, and the slag contains harmful elements selenium and lead, which are very difficult to deal with; another researcher uses SO 2 As a reducing agent, the anode slag is dried and ground to a particle size of 100 mesh, made into a slurry, and added with H 2 SO 4 and SO 2 , the reducing agent sulfite reduces manganese to MnSO 4 ,, after purification, concentration, etc., it can be used as electrolytic manganese mother liquor

The disadvantage is that the sulfur dioxide method is easy to bring a large amount of disulfide and sulfide ions into the solution, which affects the purity of the product, while SO 2 It is a raw material that pollutes the environment heavily. The process of adding a large amount cannot guarantee sufficient reaction, resulting in certain residues and new pollution. At the same time, selenium is reduced to elemental selenium, which enters the leaching residue, and the leaching residue is used as lead raw material to recover lead and silver. During the process, the volatilization of selenium has not been recovered, polluting the environment and wasting resources. In addition, the raw materials need to be dried and ground, and the production cost is high.

[0010] 6. Organic reduction leaching method. Huang Qixiang et al. used cellulose-rich sawdust as a reducing agent when studying the process of manganese anode slime recovery and preparation of manganese sulfate. Under the action of relatively concentrated sulfuric acid, it expanded and hydrolyzed to form reducing sugar, and the manganese The anode slime is added to the hydrolyzate, and under acidic conditions, manganese dioxide is reduced to soluble manganese sulfate. This method has the advantages of less slag production and high recovery rate, but the leaching process requires high-temperature aging at 300°C and consumes a lot of energy. Large, and decolorization is required during the impurity removal process

[0011] To sum up, the existing reports generally only recycle the main component manganese, but do not realize the step-by-step extraction of other impurity elements, especially the selenium in manganese anode slime, which is expensive and in short supply. Inorganic selenium is A highly toxic substance that is discharged at will and easily causes pollution

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