Method for recycling germanium from germanium-containing solution and application of method

Abstract

The invention belongs to the technical field of energy conservation and environmental protection, and particularly relates to a method for recycling germanium from a germanium-containing solution andthe application of the method. The method comprises the following steps that germanium is selectively adsorbed in the germanium-containing solution under an alkaline condition by adopting anion exchange resin containing a meglumine functional group, and germanium desorption is carried out on anion resin loaded with germanium anions under an acidic condition to obtain a primarily enriched germanium-containing acidic solution; the pH value of the germanium-containing acidic solution is adjusted to be alkaline, the germanium in the solution is adsorbed and precipitated by using a nano alkaline-earth metal oxide, and the precipitate is dried to obtain germanium-containing concentrate; and the germanium-containing concentrate is subjected to chlorination distillation to obtain germanium tetrachloride, germanium dioxide is obtained through hydrolysis, and thus germanium recycling is achieved. The method realizes selective adsorption of germanium in the germanium-containing solution, efficient enrichment and low-cost resource recycling can be realized, the problems of high cost, large acid consumption, environmental unfriendliness and the like of traditional tannin germanium precipitation, neutralization precipitation, chlorination distillation and other processes can be effectively solved, and the method has the characteristics of simple process, low cost, environmental friendlinessand the like.

Description

technical field

[0001] The invention belongs to the technical field of energy saving and environmental protection, and in particular relates to a method for recovering germanium from a germanium-containing solution and its application. Background technique

[0002] Germanium metal is a gray-white metalloid with good semiconductor properties. Its application fields mainly include infrared optics, semiconductor electronics, optical fiber communication, aerospace, solar energy, PET catalyst, biology, etc. On the other hand, the content of germanium in the earth's crust is about 7ppm, and there is no independent deposit. It is mainly associated with lead, zinc, copper, iron, silver ore and lignite ore. high. According to the survey and statistics of the United States Geological Survey (USGS), the proven reserves of germanium in the world are only 8,600 tons, and the United States, Japan, China and other countries have listed it as a strategic reserve resource. The advancement ...

Examples

Embodiment 1

[0029] Embodiment 1 contains the preparation of the anionic resin of meglumine functional group

[0030] Chloromethylation of cross-linked polystyrene microspheres: in a 2000mL four-necked flask equipped with a stirrer and a thermometer, get 100g of cross-linked polystyrene microspheres (white balls), dissolve them in 1000mL of dichloromethane, Then add 300mL of 1,4-dichloromethoxybutane (BCMB) as a chloromethylation reagent, start stirring to fully swell the white ball, and then add 0.4mol of SnCl 4 As a catalyst, react at room temperature for 10 h, filter with suction after the reaction is over, wash the resin particles with 1mol / L dilute hydrochloric acid, wash with distilled water and ethanol, and dry in vacuo to obtain chloromethylated polystyrene crosslinked microspheres (chlorine Ball) 115g.

[0031] Meglumine functionalization of chloromethylated polystyrene crosslinked microspheres: weigh 100 g of chloromethylated polystyrene crosslinked Microspheres (chlorine balls...

Embodiment 2

[0033] Measure 500 g of germanium-containing neutral liquid, adjust the pH of the solution to 11 with 5 mol / L sodium hydroxide solution, add 50 g of meglumine-containing functional group resin, and stir for 1 h. A chromatographic column is used to separate the germanium-containing resin and the solution after adsorption. Stir the resin with 100ml of deionized water for 5 minutes, replace with new 100ml of deionized water and stir again for 5 minutes, wash until neutral, and separate the resin and deionized water. Then, 100ml of 0.5M hydrochloric acid was used for desorption treatment, stirred for 1 hour, and separated by a chromatographic column to obtain a germanium-rich solution and resin. Add 5mol / L sodium hydroxide solution in the acidic germanium-rich solution, adjust the pH of the solution=8.5, use 2g of nano-calcium oxide to absorb and precipitate to obtain a germanium-containing precipitate, add 31% industrial hydrochloric acid to the germanium-containing precipitate, ...

Embodiment 3

[0035] Weigh 100 g of strongly alkaline germanium-containing solution, add 50 g of meglumine-containing functional group resin, and stir for 2 h. Solid-liquid separation to obtain germanium-containing resin and strong alkaline solution after adsorption. Wash the resin with 100ml of deionized water, soak it again with a new 100ml of deionized water, wash the resin until it is neutral. Then, 100 ml of 2M hydrochloric acid was used for desorption treatment, stirred for 2 hours, and separated by a chromatographic column to obtain a germanium-rich solution and resin. Add 5mol / L sodium hydroxide solution in the germanium-rich solution, adjust the pH of the solution=9, absorb and precipitate the germanium-rich solution with nano-magnesium oxide to obtain a germanium-containing precipitate, add 31% industrial hydrochloric acid to the germanium-containing precipitate, Distill to get germanium tetrachloride, and hydrolyze germanium tetrachloride to get germanium dioxide. After calcula...

technical field

[0001] The invention belongs to the technical field of energy saving and environmental protection, and in particular relates to a method for recovering germanium from a germanium-containing solution and its application. Background technique

[0002] Germanium metal is a gray-white metalloid with good semiconductor properties. Its application fields mainly include infrared optics, semiconductor electronics, optical fiber communication, aerospace, solar energy, PET catalyst, biology, etc. On the other hand, the content of germanium in the earth's crust is about 7ppm, and there is no independent deposit. It is mainly associated with lead, zinc, copper, iron, silver ore and lignite ore. high. According to the survey and statistics of the United States Geological Survey (USGS), the proven reserves of germanium in the world are only 8,600 tons, and the United States, Japan, China and other countries have listed it as a strategic reserve resource. The advancement ...

Examples

Embodiment 1

[0029] Embodiment 1 contains the preparation of the anionic resin of meglumine functional group

[0030] Chloromethylation of cross-linked polystyrene microspheres: in a 2000mL four-necked flask equipped with a stirrer and a thermometer, get 100g of cross-linked polystyrene microspheres (white balls), dissolve them in 1000mL of dichloromethane, Then add 300mL of 1,4-dichloromethoxybutane (BCMB) as a chloromethylation reagent, start stirring to fully swell the white ball, and then add 0.4mol of SnCl 4 As a catalyst, react at room temperature for 10 h, filter with suction after the reaction is over, wash the resin particles with 1mol / L dilute hydrochloric acid, wash with distilled water and ethanol, and dry in vacuo to obtain chloromethylated polystyrene crosslinked microspheres (chlorine Ball) 115g.

[0031] Meglumine functionalization of chloromethylated polystyrene crosslinked microspheres: weigh 100 g of chloromethylated polystyrene crosslinked Microspheres (chlorine balls...

Embodiment 2

[0033] Measure 500 g of germanium-containing neutral liquid, adjust the pH of the solution to 11 with 5 mol / L sodium hydroxide solution, add 50 g of meglumine-containing functional group resin, and stir for 1 h. A chromatographic column is used to separate the germanium-containing resin and the solution after adsorption. Stir the resin with 100ml of deionized water for 5 minutes, replace with new 100ml of deionized water and stir again for 5 minutes, wash until neutral, and separate the resin and deionized water. Then, 100ml of 0.5M hydrochloric acid was used for desorption treatment, stirred for 1 hour, and separated by a chromatographic column to obtain a germanium-rich solution and resin. Add 5mol / L sodium hydroxide solution in the acidic germanium-rich solution, adjust the pH of the solution=8.5, use 2g of nano-calcium oxide to absorb and precipitate to obtain a germanium-containing precipitate, add 31% industrial hydrochloric acid to the germanium-containing precipitate, ...

Embodiment 3

[0035] Weigh 100 g of strongly alkaline germanium-containing solution, add 50 g of meglumine-containing functional group resin, and stir for 2 h. Solid-liquid separation to obtain germanium-containing resin and strong alkaline solution after adsorption. Wash the resin with 100ml of deionized water, soak it again with a new 100ml of deionized water, wash the resin until it is neutral. Then, 100 ml of 2M hydrochloric acid was used for desorption treatment, stirred for 2 hours, and separated by a chromatographic column to obtain a germanium-rich solution and resin. Add 5mol / L sodium hydroxide solution in the germanium-rich solution, adjust the pH of the solution=9, absorb and precipitate the germanium-rich solution with nano-magnesium oxide to obtain a germanium-containing precipitate, add 31% industrial hydrochloric acid to the germanium-containing precipitate, Distill to get germanium tetrachloride, and hydrolyze germanium tetrachloride to get germanium dioxide. After calcula...

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