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A method for separating germanium by inorganic precipitation in zinc hydrometallurgy solution

A technology of hydrometallurgy and inorganic precipitation, which is applied to the improvement of process efficiency, can solve the problems of large consumption of tannin, large consumption of germanium in tannin deposition, and loss of germanium, so as to avoid the generation of hydrogen arsine, The effect of clean and efficient process and easy subsequent processing

Active Publication Date: 2021-12-07
KUNMING UNIV OF SCI & TECH
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  • Description
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AI Technical Summary

Problems solved by technology

The zinc powder neutralization method is easy to make the solution arsine, which requires precise protection; the lime neutralization method produces a large amount of gypsum, and the second leaching of the gypsum is easy to cause the loss of germanium; 25 times or even higher than germanium
[0004] At present, the recovery of germanium in zinc concentrate mainly adopts fuming volatilization of zinc oxide dust-acid leaching-tannin precipitation process. This method has a high recovery efficiency of germanium and is easy to chlorinate and volatilize germanium in the future. Large, high cost, and the addition of a large amount of tannin increases the content of organic matter in the zinc hydrometallurgy system, which has an adverse effect on subsequent electrolysis

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Example 1: Precipitation and separation of germanium was carried out using a germanium-rich zinc oxide fume leach solution (Zn 142 g / L, Fe 8.52 g / L, Ge 0.167 g / L, pH 1.56) as a raw material;

[0022] The method for separating germanium by inorganic precipitation in zinc hydrometallurgy solution, the specific steps are as follows:

[0023] (1) By controlling the acidity at the end point of the hydro-smelting zinc leaching process, the pH value of the hydro-smelting zinc leaching solution is adjusted to 1.0-2.0; the pH of the germanium-rich zinc oxide fume leaching solution in this embodiment is 1.56, and no further adjustment is required;

[0024] (2) The temperature of the zinc hydro-smelting solution is 50°C, and air is introduced into the zinc hydro-smelting solution to react with ferrous ions until the ferric ion concentration is 4.11g / L to obtain solution A;

[0025] (3) Heat the mixed liquid A to a temperature of 70~75°C for 3 hours to react for 3 hours, so that ir...

Embodiment 2

[0027] Example 2: Precipitation and separation of germanium was carried out using a germanium-rich zinc oxide fume leaching solution (Zn 139 g / L, Fe 10.33 g / L, Ge 0.289 g / L, pH 3.11) as a raw material;

[0028] The method for separating germanium by inorganic precipitation in zinc hydrometallurgy solution, the specific steps are as follows:

[0029] (1) Regulate the pH value of the hydro-smelting zinc leaching solution to 1.12 through the hydro-smelting zinc waste electrolyte;

[0030] (2) The temperature of the zinc hydrometallurgy solution is 55°C, and air is introduced into the zinc hydrometallurgy solution to react with ferrous ions until the ferric ion concentration is 5.93g / L to obtain solution A;

[0031] (3) Raise the temperature of the mixture A to a temperature of 80~85°C and react for 4 hours, so that iron ions and germanate ions are precipitated synchronously to form germanium slag, and the germanium content in the germanium slag is mainly Fe 3 GeO 2 (OH) 5 (SO ...

Embodiment 3

[0033] Example 3: Precipitation and separation of germanium was carried out using a germanium-rich zinc oxide fume leach solution (Zn 145 g / L, Fe 6.85 g / L, Ge 0.096 g / L, pH 2.72) as a raw material;

[0034] The method for separating germanium by inorganic precipitation in zinc hydrometallurgy solution, the specific steps are as follows:

[0035] (1) Regulate the pH value of the hydro-smelting zinc leaching solution to 1.98 through the hydro-smelting zinc waste electrolyte;

[0036] (2) The temperature of the zinc hydrometallurgy solution is 60°C, and air is introduced into the zinc hydrometallurgy solution to react with ferrous ions until the ferric ion concentration is 5.21g / L to obtain solution A;

[0037] (3) Raise the temperature of the mixture A to a temperature of 95~100°C for 3 hours to react for 3 hours, so that iron ions and germanate ions are precipitated simultaneously to form a germanium deposit slag, and the germanium object in the germanium deposit slag is mainly...

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Abstract

The invention relates to a method for separating germanium by inorganic precipitation in a zinc hydrometallurgy solution, and belongs to the technical field of hydrometallurgy. The present invention adjusts the pH value of the hydro-smelting zinc leaching solution to 1.0-2.0, passes air or oxygen-enriched gas into the hydro-smelting zinc solution to react until the ferric ion concentration is 4-6 g / L, and raises the temperature at a uniform speed until the temperature is React at 70-100°C for 2-4 hours, and iron ions and germanate ions are precipitated simultaneously to form germanium precipitation slag. The invention adopts the non-organic system to enrich germanium, which can completely replace the germanium precipitation technology with tannic acid, and recovers germanium from the leaching solution without the need for organic reagents such as tannic acid, extraction agent, ion exchange resin, etc. The introduction of organic matter does not require zinc powder replacement, which avoids the generation of arsine.

Description

technical field [0001] The invention relates to a method for separating germanium by inorganic precipitation in a zinc hydrometallurgy solution, and belongs to the technical field of hydrometallurgy. Background technique [0002] As a scattered metal, germanium is widely used in high-tech fields because of its unique physical and chemical properties. There are very few germanium deposits that can be independently mined in nature. At present, the recovery of germanium mainly comes from the zinc smelting industry. In the hydrometallurgy process of sphalerite, germanium will be enriched in the zinc leaching slag, which has become a recycling An important source of gallium germanium. [0003] The methods for recovering germanium from germanium-containing zinc leaching slag are mainly fire reduction volatilization method and wet high-temperature high-acid leaching, in addition to direct oxygen pressure leaching of germanium-containing zinc concentrate. For example, using the co...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C22B7/02C22B19/20C22B41/00
CPCC22B7/007C22B7/02C22B19/26C22B41/00Y02P10/20
Inventor 邓志敢魏昶朱应旭杨源孙朴李兴彬李旻廷樊刚
Owner KUNMING UNIV OF SCI & TECH
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