1. The method for recovering germanium from the copper-lead-zinc-arsenic-germanium material is characterized by comprising the following steps: the method specifically comprises the following steps:

firstly, crushing a copper-lead-zinc-arsenic-germanium material, then adding an oxidant, and uniformly mixing to obtain a mixture;

secondly, oxidizing the mixture obtained in the first step;

thirdly, crushing the metal oxide obtained in the third step;

fourthly, mixing the crushed metal oxide with hydrochloric acid, performing chlorination distillation, and condensing and collecting to obtain germanium tetrachloride;

and fifthly, hydrolyzing, washing, filtering and drying the germanium tetrachloride to obtain the crude germanium dioxide.

2. The method for recovering germanium from a copper-lead-zinc-arsenic-germanium material as claimed in claim 1, wherein: in the first step, the particle size of the crushed material is less than or equal to 120 meshes.

3. A method of recovering germanium from a copper lead zinc arsenic germanium feed as claimed in claim 1 or claim 2, wherein: in the first step, the weight of the oxidizing agent is 5-10% of the weight of the material.

4. The method for recovering germanium from a copper-lead-zinc-arsenic-germanium material as claimed in claim 1, wherein: in the second step, the oxidation treatment is specifically low-temperature oxidation at 300 ℃ for 2 hours, then the temperature is raised to 400 ℃ for oxidation for 2 hours, then the temperature is raised to 600 ℃ for oxidation for 2 hours, then the temperature is raised to 750 ℃ for oxidation for 2 hours, and the metal oxide is obtained after cooling and discharging.

5. The method for recovering germanium from a copper-lead-zinc-arsenic-germanium material as claimed in claim 1, wherein: in the third step, the particle size of the crushed material is less than or equal to 120 meshes.

6. The method for recovering germanium from a copper-lead-zinc-arsenic-germanium material as claimed in claim 1, wherein: in the fourth step, the solid-liquid mass ratio of the metal oxide to the hydrochloric acid was 1: 12.

7. The method for recovering germanium from a copper-lead-zinc-arsenic-germanium material as claimed in claim 1 or 6, wherein: in the fourth step, chlorine is introduced for about 2 hours during chlorination distillation, the distillation temperature is 85-95 ℃, and the distillation time is 3 hours.

Background

Germanium is an important rare metal, is the most important semiconductor material except silicon, and has wide and important application in various fields such as infrared optics, optical fiber communication, aerospace, chemical catalysts, solar cells, biomedicine and the like. On the other hand, the world germanium resource is relatively poor, the proven germanium reserves all over the world are about 8600 tons of metal reserves, and the global reserves only can be used for 40 years. At present, most developed countries are in vigorous development of aerospace technology and new energy technology, and the continuous development of the technologies can not leave germanium. With the continuous and high-speed development of economy in China, the technology level is continuously improved, the industrial structure is continuously upgraded, and the germanium consumption level in China will keep increasing at a high speed in future.

The germanium raw material of the germanium slag is accompanied by valuable metals such as copper, lead, zinc, aluminum, silver, indium and the like, the existing recovery process mostly adopts neutral leaching firstly, and zinc enters a zinc sulfate production system to produce zinc sulfate after the neutral leaching; recycling lead in residues; recovering sponge copper formed by copper; the silver respectively enters the lead slag and the sponge copper lead-copper recovery process to be recovered; indium is neutralized and precipitated in the residual liquid to form indium-rich slag for recycling; precipitating germanium in solution to obtain tannin germanium, oven drying, crushing, and distilling. The advantage of this method is that the germanium can be further enriched. The disadvantages are that: in the presence of acid, arsenic-containing substances in the solution can be separated out in the form of AsH3 gas by a strong reducing agent (such as active metal as a displacer) (namely, three elements generated by arsenic hydride are acid, arsenic and a reducing metal simple substance), namely, arsenic-containing materials contact with the metal reducing agent in an acidic solution to generate arsenic hydride gas. The arsenic hydride gas has great harm and is easy to cause poisoning accidents.

Disclosure of Invention

The invention aims to provide a method for recovering germanium from a copper-lead-zinc-arsenic-germanium material aiming at the defects in the prior art.

The technical scheme for solving the problems comprises the following steps: the method for recovering germanium from the copper-lead-zinc-arsenic-germanium material specifically comprises the following steps:

firstly, crushing a copper-lead-zinc-arsenic-germanium material, then adding an oxidant, and uniformly mixing to obtain a mixture;

secondly, oxidizing the mixture obtained in the first step;

thirdly, crushing the metal oxide obtained in the third step;

fourthly, mixing the crushed metal oxide with hydrochloric acid, performing chlorination distillation, and condensing and collecting to obtain germanium tetrachloride;

and fifthly, hydrolyzing, washing, filtering and drying the germanium tetrachloride to obtain the crude germanium dioxide.

Further, in the first step, the granularity of the crushed material is less than or equal to 120 meshes.

Further, in the first step, the weight of the oxidizing agent is 5-10% of the weight of the material.

Further, in the second step, the oxidation treatment is specifically low-temperature oxidation at 300 ℃ for 2 hours, then the temperature is raised to 400 ℃ for oxidation for 2 hours, then the temperature is raised to 600 ℃ for oxidation for 2 hours, then the temperature is raised to 750 ℃ for oxidation for 2 hours, and the metal oxide is obtained after cooling and discharging.

Further, in the third step, the granularity of the crushed material is less than or equal to 120 meshes.

Further, in the fourth step, the solid-liquid mass ratio of the metal oxide to the hydrochloric acid is 1: 12.

Furthermore, in the fourth step, chlorine gas is introduced for about 2 hours during chlorination distillation, the distillation temperature is 85-95 ℃, and the distillation time is 3 hours.

The invention has the following beneficial effects:

the invention provides a method for recovering germanium from copper-lead-zinc-arsenic-germanium materials, which has the advantages of small production pollution, no hydrogen and arsenic hydride gas and reduced harm, and the condition for generating arsenic hydride is destroyed; when heating and oxidizing, the heating is divided into four sections to heat, so that the elements in the material are fully oxidized.

Drawings

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

Detailed Description

In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.

Example 1

As shown in figure 1, the method for recovering germanium from copper-lead-zinc-arsenic-germanium materials comprises the following steps:

firstly, crushing a copper-lead-zinc-arsenic-germanium material to 120 meshes, adding an oxidant, wherein the weight of the oxidant is 8% of the weight of the material, and uniformly mixing to obtain a mixture;

secondly, oxidizing the mixture obtained in the first step at a low temperature of 300 ℃ for 2 hours, then raising the temperature to 400 ℃ for oxidation for 2 hours, then raising the temperature to 600 ℃ for oxidation for 2 hours, then raising the temperature to 750 ℃ for oxidation for 2 hours, cooling and discharging to obtain metal oxide;

thirdly, crushing the metal oxide obtained in the third step to 120 meshes;

fourthly, mixing the crushed metal oxide with hydrochloric acid, chlorination distillation, wherein the solid-liquid mass ratio of the metal oxide to the hydrochloric acid is 1:12, chlorine is introduced for about 2 hours during chlorination distillation, the distillation temperature is 85-95 ℃, the distillation time is 3 hours, germanium tetrachloride is obtained by condensation collection, the distillation residual liquid is sent to a zinc production workshop for recovering zinc, indium and copper, and the distillation residue is sent to a lead workshop for recovering lead and silver;

fifthly, hydrolyzing germanium tetrachloride, wherein the volume ratio of the germanium tetrachloride to water is as follows: 1:7, feeding speed: 6000ml/h, standing for 2 hours after the blanking, washing, filtering, drying the filtered germanium dioxide in a micro-negative pressure oven at the drying temperature of 140 ℃ and the drying time of 16 hours to obtain the coarse germanium dioxide, wherein the effective recovery rate of the germanium is 97.02 percent.

Example 2

This example differs from example 1 in that in the first step the weight of oxidant is 5% of the weight of the feed and the effective recovery of germanium is 96.88%.

Example 3

This example differs from example 1 in that in the first step the weight of oxidant was 10% of the weight of the feed and the effective recovery of germanium was 97.13%.

Example 4

This example differs from example 1 in that the effective recovery of germanium was 95.13% when the oxidation was carried out by heating, from 300 ℃ for 2 hours at low temperature, then increasing the temperature until 600 ℃ for 2 hours, and then oxidizing at 750 ℃ for 2 hours.

The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.