Harmless treatment method of black copper mud

Abstract

The invention relates to a treatment method for resourceful and harmless black copper slime, including oxidative leaching, which adopts normal pressure hot acid oxidative leaching or pressure oxidative leaching, and if normal pressure hot acid oxidative leaching, the ratio of liquid to solid is 4 to 20 , mix black copper mud with sulfuric acid with a concentration of 20-200g / L, control the reaction temperature and fill it with air, according to 0.5‑2t / t 黑铜泥 Add hydrogen peroxide to react to obtain leaching solution and leaching residue; extraction-electrodeposition, add a specific organic phase to the diluted leaching solution, control the phase and time, load the organic phase after washing for extraction-electrodeposition; precipitate arsenic and fix arsenic, add arsenic to the raffinate Add alkali to neutralize and reduce acid, thicken, acidify and remove arsenic, wash to obtain solution and gypsum slag, add iron-containing reagents and hydrogen peroxide to the solution to make Fe 3+ and As 5+ , adding scorodite seed crystals, controlling the pH value and reacting will carry out arsenic fixation, thickening, alkali neutralization and liquid-solid separation, and the arsenic residue will be deposited into the landfill. It has the advantages of efficient recovery of valuable metals such as copper, open circuit of arsenic and harmless treatment, simple process, low cost, good treatment effect, and low risk of environmental pollution. It is suitable for non-ferrous metal smelting and environmental protection applications.

Description

technical field [0001] The invention relates to a treatment method for resourceful and harmless black copper slime, which is suitable for nonferrous metal smelting and environmental protection fields. Background technique [0002] Black copper slime is the black slime produced at the cathode during the process of copper electrolytic refining, electrolyte purification, decopper removal and impurity removal process. Black copper mud contains 30-60% copper, 20-40% arsenic, and a small amount of antimony, bismuth, and lead. [0003] The traditional processing method of black copper slime is to return the smelting system as an ingredient, which will cause arsenic to circulate and accumulate in the smelting system, which not only deteriorates the furnace condition, reduces the processing capacity of the smelting system, but also increases the smoke production and impurities such as arsenic, bismuth, and lead. It cannot be removed, and it also accumulates in the smelting process. ...

AI Technical Summary

Problems solved by technology

For example, Chinese patent CN 103290221A discloses a "method for oxidative leaching of black copper mud by sulfuric acid", in which air is introduced into the leaching process for oxidation, and the leaching solution is evaporated and crystallized to obtain copper sulfate, and the crystallization mother liquor is prepared by controlling the ratio of copper to arsenic and the pH value. To obtain copper arsenate, there is a small market demand for copper arsenate obtained in this method, unstable chemical properties, difficult follow-up treatment, and untreated liquid after precipitation of copper arsenate; as Chinese patent CN106148702A discloses a "from black copper mud Method for Separating Copper and Arsenic in China", which adopts normal pressure sulfuric acid oxidation to leaching black copper mud, adding hydrogen peroxide during the leaching process, the leaching solution is a copper and arsenic rich solution, and the copper and arsenic rich solution is evaporated and crystallized to obtain copper sulfate pentahydrate, and ferrous iron is added to the solution after crystallization Precipitation of arsenic, this method does not effectively recover the copper in the liquid after crystallization, the impact of copper on the subsequent iron salt precipitation of arsenic is not mentioned, how to deal with the liquid after iron salt precipitation of arsenic, whether the toxicity of the generated iron and arsenic slag meets the standard, etc. None of these problems are explained; Jiangxi Copper Co., Ltd. adopts a "staged pressurized oxidation acid leaching black copper mud and copper arsenic slag", and uses concentrated crystallization-arsenic reduction to obtain As 2 o 3 After the reduction, the liquid returns to the first-stage pressure leaching, the first-stage leaching residue is subjected to the second-stage pressure leaching, the leaching liquid returns to the first-stage pressure leaching, the leaching residue is removed by alkaline leaching, and then enters the antimony-bismuth recovery system, the leachate enters the arsenic reduction system, and the first-stage leaching Press leaching process control discloses copper arsenic slag: sulfuric acid = 1:0.1~0.3:1.4~1.8(w / w), temperature 100~130℃, total pressure 0.8~1.5Mpa, time ≥8h, sulfuric acid concentration ≤130g / L process conditions;

[0013] For example, Chinese patent CN102851497B discloses a "processing method for arsenic-containing materials", which is to first carry out atmospheric pressure acid leaching of arsenic-containing materials to obtain a leaching solution rich in copper, arsenic, and zinc, and then leaching the resulting atmospheric pressure The slag is further subjected to acidic oxygen-enriched leaching. The reaction temperature is controlled at 0-200°C and the oxygen partial pressure is 0-500kPa. The leaching solution is produced by electrowinning to produce cathode copper, or evaporating and crystallizing to produce copper sulfate, and the raffinate is reduced by sulfur dioxide to produce arsenic trioxide. This process can solve the accumulation of arsenic in the system and produce arsenic trioxide with a purity of 99.9%. However, this method uses two-stage acid leaching , there is a long process flow and As 2 o 3 Product sales difficulties and other issues

[0014] In short, the fire treatment process of black copper mud has problems such as poor working environment, low recovery rate, and easy to produce secondary pollution, etc., and is gradually being eliminated

At present, most enterprises tend to use wet process to process black copper mud, but among them As 2 o 3为 The wet treatment process of the product has problems such as high production cost, low recovery rate, small product market space, and difficult sales

The open circuit treatment of black copper mud is a difficult problem in nonferrous metallurgy. Many enterprises have made long-term efforts, but there has been a lack of an economical and environmentally friendly treatment method.

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