阅读说明：本技术 一种从含钴镍锗铁的酸性溶液中选择性沉锗的方法 (Method for selectively precipitating germanium from acidic solution containing cobalt, nickel, germanium and iron ) 是由 邓维 郑泽翰 洪涛 符致远 袁正兴 蒋炎顺 于 2021-08-13 设计创作，主要内容包括：本发明涉及湿法冶金技术领域,尤其是一种从含钴镍锗铁的酸性溶液中选择性沉锗的方法,包括以下步骤：1)将含钴镍复杂酸性溶液升温至70～90℃,并将其还原至一定氧化还原电位值；2)将所述还原后溶液的pH值调节至2.4～3.8；3)向所述调pH值后溶液加入氧化剂缓慢氧化1～3h,氧化同时继续缓慢通碱至终点pH值为4.7～5.5,得到含铁锗共沉物的溶液；4)将含铁锗共沉物的溶液过滤、脱水,得到锗精矿。本发明是在含钴、镍、铁、锗等元素的复杂酸性溶液中,采用局部共沉淀方式实现锗的选择性沉淀。该方法操作条件简单,溶液中锗沉淀深度优异,产出锗精矿品位可控且二次溶解性能优异,对溶液中锗的综合回收利用起到良好的积极作用。(The invention relates to the technical field of hydrometallurgy, in particular to a method for selectively precipitating germanium from an acid solution containing cobalt, nickel, germanium and iron, which comprises the following steps: 1) heating the complex acidic solution containing cobalt and nickel to 70-90 ℃, and reducing the complex acidic solution to a certain oxidation-reduction potential value; 2) adjusting the pH value of the reduced solution to 2.4-3.8; 3) adding an oxidant into the solution after the pH value is adjusted, slowly oxidizing for 1-3 hours, and continuously and slowly introducing alkali while oxidizing until the pH value at the end point is 4.7-5.5 to obtain a solution containing the iron and germanium coprecipitation substance; 4) and filtering and dehydrating the solution containing the iron and germanium coprecipitation to obtain germanium concentrate. The invention realizes the selective precipitation of germanium by adopting a local coprecipitation mode in a complex acid solution containing elements such as cobalt, nickel, iron, germanium and the like. The method has the advantages of simple operation condition, excellent germanium precipitation depth in the solution, controllable grade of the produced germanium concentrate, excellent secondary dissolution performance and good positive effect on comprehensive recovery and utilization of germanium in the solution.)

1. A method for selectively precipitating germanium from an acidic solution containing cobalt, nickel, germanium and iron is characterized in that: the method comprises the following steps:

(1) heating the acid solution containing cobalt, nickel, germanium and iron to 70-90 ℃, and reducing the acid solution to a certain oxidation-reduction potential value;

(2) adding alkali liquor to adjust the pH value of the reduced acidic solution to 2.4-3.8;

(3) adding an oxidant into the solution after the pH value is adjusted, oxidizing for 1-3 hours, and continuously introducing alkali liquor while oxidizing until the pH value at the end point is 4.7-5.5 to obtain a solution containing the iron and germanium coprecipitation substance;

(4) and filtering and dehydrating the solution containing the iron and germanium coprecipitation to obtain germanium concentrate.

2. The method of claim 1 for selective germanium precipitation from an acidic solution containing cobalt, nickel, germanium and iron, wherein: in the step (1), the content of germanium in the acidic solution containing cobalt, nickel, germanium and iron is 0.1-0.8 g/L.

3. The method of claim 1 for selective germanium precipitation from an acidic solution containing cobalt, nickel, germanium and iron, wherein: in the step (1), the reducing agent used for reducing the acidic solution is NA₂SO₃Or SO₂(ii) a The oxidation-reduction potential value of the solution after reduction is 260 mV-340 mV.

4. The method of claim 1 for selective germanium precipitation from an acidic solution containing cobalt, nickel, germanium and iron, wherein: the alkali liquor adopted in the step (2) and the step (3) is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

5. The method of claim 1 for selective germanium precipitation from an acidic solution containing cobalt, nickel, germanium and iron, wherein: and (3) using hydrogen peroxide as an oxidant, wherein the dosage of the oxidant is based on the theoretical quantity required by oxidizing the ferrous quantity in the acidic solution, and the ferrous quantity in the acidic solution is calculated by a fixed quantity of 2-4 g/L.

6. The method of claim 1 for selective germanium precipitation from an acidic solution containing cobalt, nickel, germanium and iron, wherein: and (4) aging the solution containing the iron and germanium coprecipitation material obtained in the step (3) for 10-30 min, and then filtering and dehydrating.

Technical Field

The invention relates to the technical field of hydrometallurgy, in particular to a method for selectively precipitating germanium from an acid solution containing cobalt, nickel, germanium and iron.

Background

Germanium is a light grey metal, also second only to silicon, an important semiconductor material, and was discovered by the german chemist wenckelle in 1885 by spectroscopic analysis. Germanium is present in the earth's crust in seven parts per million, naturally in a lesser amount than the usual elements such as oxygen, silicon, etc., but in a greater amount than arsenic, uranium, mercury, iodine, silver, gold, etc. However, germanium is very dispersed and there is little more concentrated germanite, and is therefore known as "rare metals". Germanium is widely applied to the fields of electronics, optics, chemical engineering, biomedicine, energy and other high and new technologies, but independent germanium ore deposits rarely exist in the nature, germanium is mainly semi-grown in other non-ferrous metal ores, and the current approach for obtaining germanium is mainly two ways of enriching and recovering germanium-containing waste materials by smelting metal ores. The enrichment and recovery of germanium can be further divided into chlorination distillation method, extraction method, ion exchange method, tannin precipitation method, etc.

The germanium-containing liquid produced in the non-ferrous metal smelting industry generally has low germanium concentration, complex components and large treatment capacity, and the prior conventional method is to recover germanium by regulating the pH value of the solution and then utilizing a tannin precipitation method. However, the method is easy to generate free tannin in the sedimentation process, not only reduces the utilization efficiency of the tannin, but also is easy to cause the coprecipitation of other impurity metals, and causes the secondary pollution of sediments. For the solution with low germanium concentration, the production cost of the method is higher than the use value of germanium, and resource waste is easily caused, so that the method has great significance for exploring other precipitation methods to recover germanium.

Disclosure of Invention

The invention provides a method for selectively precipitating germanium from an acid solution containing cobalt, nickel, germanium and iron to solve the technical defects, and the selective precipitation of the germanium is realized by adopting a partial coprecipitation mode.

The invention discloses a method for selectively precipitating germanium from an acid solution containing cobalt, nickel, germanium and iron, which comprises the following steps:

(1) heating the acid solution containing cobalt, nickel, germanium and iron to 70-90 ℃, and reducing the acid solution to a certain oxidation-reduction potential value;

(2) adding alkali liquor to adjust the pH value of the reduced acidic solution to 2.4-3.8;

(3) adding an oxidant into the solution after the pH value is adjusted, oxidizing for 1-3 hours, and continuously introducing alkali liquor while oxidizing until the pH value at the end point is 4.7-5.5 to obtain a solution containing the iron and germanium coprecipitation substance;

(4) and filtering and dehydrating the solution containing the iron and germanium coprecipitation to obtain germanium concentrate.

In the step (1), the content of germanium in the acidic solution containing cobalt, nickel, germanium and iron is 0.1-0.8 g/L.

In the step (1), the reducing agent used for reducing the acidic solution is NA₂SO₃Or SO₂Of course, the reducing agent is not limited to the above two reducing agents, and the oxidation-reduction potential value after the solution is reduced is 260mV to 340 mV.

The alkali liquor adopted in the step (2) and the step (3) is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

The oxidant used in the step (3) is hydrogen peroxide, certainly the oxidant is not limited to the hydrogen peroxide, the dosage of the oxidant is based on the theoretical quantity required for oxidizing the ferrous iron quantity in the acidic solution, and the ferrous iron quantity in the acidic solution is calculated by a fixed quantity of 2-4 g/L.

And (4) aging the solution containing the iron and germanium coprecipitation material obtained in the step (3) for 10-30 min, and then filtering and dehydrating.

Compared with a tannin precipitation method, the method for selectively precipitating germanium from the acidic solution containing cobalt, nickel, germanium and iron, which is obtained by the invention, has the advantages that:

1) the method adopts an iron-germanium coprecipitation mode to realize the selective precipitation of germanium, reduces the secondary pollution of impurity metal precipitates such as cobalt, nickel and the like to precipitates and reduces the waste of valuable metals such as cobalt and nickel.

2) The invention realizes the recovery and reclamation of germanium in the low-concentration germanium solution, has no toxic and harmful substances in the whole process, and does not cause secondary pollution to the environment.

3) The germanium precipitation depth in the solution is excellent, the germanium precipitation rate can reach more than 90%, the grade of the produced germanium concentrate is controllable, and the secondary dissolution performance is excellent.

4) The process has simple operation condition and easily controlled reaction condition.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments.

Example 1:

as shown in figure 1, the invention discloses a method for selectively precipitating germanium from an acidic solution containing cobalt, nickel, germanium and iron, which comprises the following steps:

1) take 8L of acidic solution (ingredients of acidic solution: Ge0.632g/L; Fe5.64g/L; Co3.194g/L; cu 0.125 g/L; Ni2.34g/L; pH2.15) is put in a reaction kettle, saturated Na is added by a peristaltic pump₂SO₃Reduction of the solution (Na)₂SO₃The addition rate was 10mL/min and the reduction temperature was 80 ℃). Stopping adding when the potential of the reaction solution is reduced to 300mV, and finishing the reduction;

2) adjusting the pH of the reduced solution to 3.0 by using an aqueous solution of sodium hydroxide, and continuously adding the sodium hydroxideAdding 30% H by mass concentration into the sodium water solution by using a peristaltic pump₂O₂Is subjected to oxidation of H₂O₂In an amount to oxidize Fe in an acidic solution of 3g/L²⁺Calculating theoretical amount, and controlling the oxidation time to be 1.5 h;

3) and after the oxidation is finished, continuously adding a sodium hydroxide aqueous solution to the final pH value of 4.7, and filtering and separating to obtain a germanium-containing precipitate and a germanium-precipitated liquid. Measuring the main components of the solution after germanium precipitation: Ge0.049g/L; Fe1.932g/L; Co2.82g/L; cu 0.001 g/L; Ni2.08g/L. The components of the precipitate are as follows: ge: 6.738 percent; fe: 40.41 percent; co: 0.859%; cu: 1.534 percent; ni: 0.798%. The calculated germanium precipitation rate is 92.24 percent.

Example 2:

the invention discloses a method for selectively precipitating germanium from an acid solution containing cobalt, nickel, germanium and iron, which comprises the following steps:

1) take 8L of acidic solution (ingredients of acidic solution: Ge0.764g/L; Fe5.28g/L; Co3.34g/L; cu 0.231 g/L; Ni2.18g/L; pH2.31) is put in a reaction kettle, saturated Na is added by a peristaltic pump₂SO₃Reduction of the solution (Na)₂SO₃The addition rate was 10mL/min and the reduction temperature was 80 ℃). The addition was stopped when the potential of the reaction solution was reduced to 280mV, at which point the reduction was complete.

2) Adjusting the pH of the reduced solution to 3.0 by using an aqueous sodium hydroxide solution, continuously adding the aqueous sodium hydroxide solution, and simultaneously adding 30% H by mass concentration by using a peristaltic pump₂O₂Is subjected to oxidation of H₂O₂In an amount to oxidize Fe in 4g/L of the acidic solution²⁺Calculating theoretical amount, and controlling the oxidation time for 1.5 h;

3) and after the oxidation is finished, continuously adding a sodium hydroxide aqueous solution to the final pH value of 5.0, and filtering and separating to obtain a germanium-containing precipitate and a germanium-precipitating solution. Measuring the main components of the solution after germanium precipitation: Ge0.061g/L; Fe2.051g/L; Co3.12g/L; cu 0.001 g/L; Ni1.91g/L. The components of the precipitate are as follows: ge: 7.281 percent; fe: 35.50 percent; co: 0.870%; cu: 1.732 percent; ni: 0.957 percent. The calculated germanium precipitation rate is 92.02%.

Although the present invention has been described with reference to the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but may be embodied or carried out in various forms without departing from the spirit and scope of the invention.