Method for enriching and recycling germanium from germanium-containing solution

Abstract

The invention discloses a method for enriching germanium from a solution which contains trace germanium, and is particularly suitable for neutral and weakly acidic low-contention germanium-containing solution with a plurality of complicated components. The method comprises the following steps: regulating the pH value of the germanium-containing solution and adding a certain amount of iron adsorbent-lepidocrocite (gamma-FeOOH) into the solution, so that more than 95 percent of the germanium in the solution is enriched by the lepidocrocite; filtering a reaction solution after full reaction to obtain germanium concentrate which contains more than 1 percent of the germanium; leaching by using 25 to 35 percent concentrated hydrochloric acid; distilling to recycle GeCl4; regulating the pH value of distillation mother solution again; adding the iron adsorbent-lepidocrocite (gamma-FeOOH) to perform secondary adsorption. The method is simple in process and low in cost; the separating effect of the germanium from other metal ions is good; the germanium enrichment ratio is high; the method is suitable for industrial application.

Description

technical field [0001] The invention belongs to the technical field of chemical separation, and specifically relates to a method for enriching germanium from a germanium-containing solution. Background technique [0002] Germanium is one of the important scattered metals with unique properties. It is mainly used in the manufacture of semiconductor devices, infrared, optical fibers and chemical catalysts in the electronics industry. It is one of the supporting materials for contemporary high-tech. The abundance of germanium on the earth is extremely low (6.7×10 ??4 %), and the distribution is too scattered, rarely ore-forming alone, mainly associated with other non-ferrous metal minerals and coal mines, and its extraction is difficult, so scientific and technological workers have always attached great importance to the extraction of germanium. [0003] For the recovery of germanium in the germanium-containing solution, the methods of tannic acid precipitation and solvent ext...

AI Technical Summary

Problems solved by technology

The tannic acid precipitation method is easy to operate and has good precipitation effect, but the loss of germanium in the process of preparing germanium concentrate by roasting the tannic germanium slag obtained from the precipitation is relatively large, and the price of tannic acid is high, which leads to low direct yield of the whole process and high production cost

There are many researches on solvent extraction methods, such as LIX63, Kelex100, N235, H106 (tridecyl tertiary carbon isooxytransferric acid), YW100 (isooxyanthoic acid with a carbon chain of 7-9), 7815, HGS98 and G8315, etc. , these extractants are generally only suitable for relatively strong acidic solutions with a Ge content greater than 30mg / L, but because these extractants are either expensive, or due to their high water solubility, the loss during the extraction process is large, resulting in high production costs. If it is extracted from zinc sulfate solution, the residual organic matter will also seriously affect the electrodeposition of zinc

[0004] In addition, some researchers have also adopted the method of precipitation and adsorption to recover germanium from the solution. For example, the patent CN 103540755B discloses a method for enriching germanium from a low-concentration germanium-containing solution. Add silicon reagents to generate silica gel, and utilize the "silicon-friendly" nature of germanium, so that more than 91% of germanium in the solution is absorbed and enriched by silica gel, and then filter the reaction solution to obtain germanium concentrate containing more than 2% germanium, but It is also limited to use in dilute solutions with very low concentrations of various valuable metals. If silicon is added to the zinc sulfate solution of hydrometallurgy, the solution cannot be filtered, and germanium-rich silica gel cannot be separated. And it will seriously affect the normal production operation

[0005] Therefore, the existing methods for recovering germanium from solutions have many shortcomings, such as narrow application range, long process, poor enrichment effect, etc. The industry urgently needs to develop a new simple and low-cost enrichment and recovery of germanium. The process makes it suitable for various complex germanium-containing solution systems, especially for the enrichment and recovery of germanium in hydrometallurgy