Technological method for recovering germanium from low-concentration germanium-containing waste liquid

Abstract

The invention relates to the field of hydrometallurgy, in particular to a technological method for recovering germanium from low-concentration germanium-containing waste liquid. The method comprises the following steps that reacted acid generated through chloridizing distillation of the low-concentration germanium-containing waste liquid and germanium concentrate is combined into a distillation still, the germanium-containing waste liquid is subjected to heating distillation, the temperature of heating distillation is 110-120 DEG C, distilled germanium tetrachloride and hydrogen chloride are cooled firstly and then subjected to reverse absorption through hydrochloric acid, recovered germanium-containing acid liquid is transferred to a germanium concentrate chloridizing distillation working section, and the recovered germanium-containing acid liquid and the newly added hydrochloric acid are used for extracting germanium in the germanium concentrate through chloridizing distillation. By adopting the technological method, 90% of germanium in the germanium-containing waste liquid can be effectively recovered in an energy-saving mode, the using amount of new hydrochloric acid can be reduced by 80% or more by the germanium concentrate chloridizing distillation working section, germanium metal recovered each year can reach 500-1200 kg, and wastewater processing and discharging can be reduced by 90% or more. The efficient recovery of germanium is achieved, and circulation recycling of the hydrochloric acid is also achieved.

Description

Technical field [0001] The invention relates to the technical field of hydrometallurgy, in particular to a process method for recovering germanium from a low-concentration germanium-containing waste liquid. Background technique [0002] In the process of wet germanium metallurgy and production and processing, it is often accompanied by the production of waste liquid, waste slag and waste gas. The germanium-containing waste gas is generally absorbed by the absorption liquid and converted into germanium-containing waste liquid. Due to the scarcity and preciousness of germanium resources, there are proprietary germanium recovery methods for the three germanium-containing wastes. But the most difficult germanium recovery is the germanium waste liquid. The normal smelting and processing of germanium will produce a large amount of germanium-containing waste liquid, and the absorption of waste gas will also produce germanium-containing waste liquid. The wet extraction of germanium from...

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Problems solved by technology

However, the recovery rate of the above-mentioned methods for recovering germanium from high-concentration germanium waste liquid is difficult to break through 95%, and the germanium content in the discharged waste liquid still exceeds 50 mg / L, so it is also necessary to recycle this type of waste liquid

However, germanium-containing waste liquids with a germanium-containing concentration of less than 30 mg / L have a large amount of treatment and high processing costs. Generally, such germanium-containing waste liquids are rarely treated for germanium recovery, basically to make the wastewater discharge up to the standard. The waste slag generated in the process of neutralization or impurity removal is recycled. If the germanium-containing waste slag obtained is low in germanium content, it will be piled up, and if it contains high germanium content, it will be recycled by pyromethod secondary smelting.

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