Method for extracting germanium from high-silicon high-iron low-grade germanium-containing material

A low-grade, high-speed iron technology, applied in the direction of improving process efficiency, can solve problems such as low leaching rate, equipment corrosion, and low recovery rate, and achieve the effects of accelerating diffusion speed, increasing contact probability, and improving reaction rate

Inactive Publication Date: 2017-06-13
GUIZHOU HONGDA ENVIRONMENTAL PROTECTION TECHNOLOGY CO LTD
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  • Abstract
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  • Application Information

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Problems solved by technology

[0002] Germanium is a rare metal element, and it is difficult to form independent deposits in nature. It is mainly distributed in polymetallic or non-metallic ores and waste residues generated during the smelting process. These germanium-containing materials, whether they are germanium-containing polymetallic ores or The grades of germanium-containing non-metallic ores and germanium-containing smelting residues are relatively low (10%). More importantly, these germanium-containing Germanium materials usually contain a large amount of base metals and impurity elements, such as Zn, Pb, Fe, Si, etc., and the content of impurities Fe and Si is relatively high. In addition, germanium has the properties of iron and silicon, so it is usually mixed with The occurrence state of the package exists in the material, which belongs to a complex germanium-containing material. This feature makes the leaching of germanium difficult, the leaching rate is low, the separation and enrichment is difficult, and the recovery rate is low.
[0003] The key to extracting germanium from high-silicon, high-iron and low-grade germanium-containing materials lies in the efficient leaching, separation and enrichment of germanium; at present, the recovery methods for germanium in germanium-containing materials include fire method and wet process, and the recovery of germanium by using the rotary kiln volatilization process, Only about 85% of germanium is enriched in the dust, and some germanium will enter the kiln slag and cannot be fully recovered. At the same time, the rotary kiln volatilization process still has disadvantages such as high energy consumption and serious pollution; due to the high silicon and high iron slag The phase of germanium is complex, in addition to oxides, there are elemental metals and sulfides, etc., and it is wrapped by silicon; the leaching effect is poor when using conventional acid leaching technology, and the leaching rate of germanium is usually only about 60%; The leaching rate of germanium can reach about 80% in stage acid leaching treatment of germanium-containing materials, but the process is long and requires strict acidity control; the process of atmospheric pressure acid leaching and adding leaching aids can increase the leaching rate of germanium, It can reach more than 90%, but the filtration performance of the leaching slurry is poor; the leaching rate of ge

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  • Method for extracting germanium from high-silicon high-iron low-grade germanium-containing material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] (1) After mixing the high-silicon, high-iron and low-grade germanium-containing materials with 50g / L sulfuric acid and immersion aid, add them to the high-pressure reaction kettle, control the temperature at 120°C, feed oxygen-containing gas, adjust the oxygen partial pressure to 0.5MPa, and carry out Oxygen pressure acid leaching, the material is discharged after 1 hour of reaction, and the obtained material is separated from solid and liquid to obtain a germanic acid immersion solution;

[0030] (2) adding reductant iron powder earlier in the germanium-containing acid immersion solution that step (1) obtains iron ion is reduced to ferrous ion, then adds gelatin desiliconization in the solution after reduction, obtains after removing iron and desilicon purification solution;

[0031] (3) add stabilizer in the purification solution that step (2) obtains, adopt germanium extractant to extract germanium or adopt tannic acid to precipitate germanium, obtain extracting germ...

Embodiment 2

[0033] (1) After mixing the high-silicon, high-iron and low-grade germanium-containing materials with 150g / L sulfuric acid and immersion aid, add them to the high-pressure reactor, control the temperature at 220°C, feed oxygen-containing gas, adjust the oxygen partial pressure to 1.2MPa, and carry out Oxygen pressure acid leaching, the material is discharged after 4 hours of reaction, and the obtained material is separated from solid and liquid to obtain a germanic acid immersion solution;

[0034] (2) adding reductant iron powder earlier in the germanium-containing acid immersion solution that step (1) obtains iron ion is reduced to ferrous ion, then adds gelatin desiliconization in the solution after reduction, obtains after removing iron and desilicon purification solution;

[0035] (3) add stabilizer in the purification solution that step (2) obtains, adopt germanium extractant to extract germanium or adopt tannic acid to precipitate germanium, obtain extracting germanium ...

Embodiment 3

[0037] (1) After mixing the high-silicon, high-iron and low-grade germanium-containing materials with 100g / L sulfuric acid and leaching aid, add them to the high-pressure reactor, control the temperature at 180°C, feed oxygen-containing gas, adjust the oxygen partial pressure to 0.8MPa, and carry out Oxygen pressure acid leaching, the material is discharged after 3 hours of reaction, and the obtained material is separated from solid and liquid to obtain a germanic acid immersion solution;

[0038] (2) adding reductant iron powder earlier in the germanium-containing acid immersion solution that step (1) obtains iron ion is reduced to ferrous ion, then adds gelatin desiliconization in the solution after reduction, obtains after removing iron and desilicon purification solution;

[0039] (3) add stabilizer in the purification solution that step (2) obtains, adopt germanium extractant to extract germanium or adopt tannic acid to precipitate germanium, obtain extracting germanium r...

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Abstract

The invention belongs to the technical field of wet metallurgy, and in particular, relates to a method for extracting germanium from a high-silicon high-iron low-grade germanium-containing material. The method comprises the steps: mixing the high-silicon high-iron low-grade germanium-containing material with sulfuric acid and a leaching aid agent, adding the mixture into a high pressure reaction kettle, introducing oxygen-containing gas, adjusting the oxygen partial pressure, carrying out oxygen pressure acid leaching, and carrying out solid-liquid separation of the obtained material, to obtain a germanium-containing acid leaching solution; adding an iron powder and gelatin, to obtain a purified solution; and extracting and carrying out back extraction, and finally, calcining to obtain a refined germanium ore with the germanium content of more than 30%. The method has the advantages of short flow, low energy consumption, high metal germanium leaching rate and recovery rate, low production cost, easy operation, and convenience in industrialized production.

Description

technical field [0001] The invention belongs to the technical field of hydrometallurgy, in particular to a method for extracting germanium from high-silicon, high-iron and low-grade germanium-containing materials. Background technique [0002] Germanium is a rare metal element, and it is difficult to form independent deposits in nature. It is mainly distributed in polymetallic or non-metallic ores and waste residues generated during the smelting process. These germanium-containing materials, whether they are germanium-containing polymetallic ores or The grades of germanium-containing non-metallic ores and germanium-containing smelting residues are relatively low (<0.5%), which are far below the index of germanium concentrates (>10%). More importantly, these germanium-containing Germanium materials usually contain a large amount of base metals and impurity elements, such as Zn, Pb, Fe, Si, etc., and the content of impurities Fe and Si is relatively high. In addition, ge...

Claims

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Application Information

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IPC IPC(8): C22B41/00C22B3/08C22B3/44C22B3/26
CPCC22B3/08C22B3/44C22B41/00C22B3/26Y02P10/20
Inventor 曾光祥韦国龙王志斌杨跃文卢宇王明兴
Owner GUIZHOU HONGDA ENVIRONMENTAL PROTECTION TECHNOLOGY CO LTD
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