CN108486390B - Process for separating germanium and gallium from germanium and gallium material - Google Patents
Process for separating germanium and gallium from germanium and gallium material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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- C22B58/00—Obtaining gallium or indium
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Abstract
The invention belongs to the technical field of metallurgy and discloses a process for separating germanium and gallium from germanium and gallium materials. The process comprises the following steps: adding the germanium-gallium material into a sulfuric acid solution according to a liquid-solid ratio of 5-10 for leaching to obtain leaching residues and a leaching solution; adding germanium and gallium materials into the leaching solution again to adjust the pH value to 1-3, so as to obtain neutralized liquid and neutralized slag; adding zinc powder into the neutralized solution at the temperature of 40-80 ℃ for primary replacement, and obtaining germanium concentrate and a replaced solution after the reaction is finished; and adding zinc powder into the solution after the replacement at the temperature of 40-80 ℃ for secondary replacement, and obtaining gallium slag and the solution after the replacement after the reaction is finished. The process can avoid organic matters brought by germanium and gallium deposition, ensure the normal operation of a zinc recovery main process, reduce the discharge of waste water during gallium recovery, has environmental protection, can recover the added zinc powder again, saves the cost, improves the economic benefit, and is an economic and environment-friendly method for efficiently separating the scattered metal germanium and gallium.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a process for separating germanium and gallium from germanium and gallium materials.
Background
In the zinc smelting process, germanium-gallium enriched slag is obtained, the slag is generated by replacing and removing impurities from a zinc leaching solution, mainly contains zinc, germanium, gallium, cadmium and the like, and is one of main raw materials for recovering scattered metal germanium and gallium. The process flow is long, and the subsequent zinc recovery needs to add active carbon to adsorb organic matters so as to meet the process requirements. The method is simple and efficient, can directly separate germanium and gallium, can greatly simplify the process, improve the metal recovery rate, reduce the discharge of waste water, and has good economic benefit and environmental protection benefit.
In the zinc smelting process, the approximate composition of the germanium-gallium substitution slag is shown in the table 1.
TABLE 1 main chemical composition (wt%) of indium antimony lead material
| Element(s) | Zn | Ge | Ga | Cd |
| Name of article | 15～40 | 0.1～2 | 0.1～1.5 | 0.2～5 |
The table shows that the replacement slag has high value, and how to simply, efficiently and environmentally recover the replacement slag can not only obtain good economic benefit, but also ensure the smoothness of the zinc recovery process of the main process.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process for separating germanium and gallium from germanium and gallium materials, which comprises the following steps:
(1) adding the germanium-gallium material into a sulfuric acid solution according to a liquid-solid ratio of 5-10 for leaching to obtain leaching residues and a leaching solution;
(2) adding germanium and gallium materials into the leaching solution again to adjust the pH value to 1-3, so as to obtain neutralized liquid and neutralized slag;
(3) adding zinc powder into the neutralized solution at the temperature of 40-80 ℃ for primary replacement, and obtaining germanium concentrate and a replaced solution after the reaction is finished;
(4) and adding zinc powder into the solution after the replacement at the temperature of 40-80 ℃ for secondary replacement, and obtaining gallium slag and the solution after the replacement after the reaction is finished.
In the process for separating germanium and gallium from the germanium and gallium material, in the step (1), the leaching temperature is 40-80 ℃, and the stirring reaction is carried out for 0.5-4 hours; the concentration of the sulfuric acid solution is 50-150 g/L.
In the process for separating germanium and gallium from germanium and gallium materials, in the step (2), the content of metal elements contained in the neutralized liquid is as follows: 0.3-5 g/L Ge, 0.2-4 g/L Ga, 3-15 g/L Cd, 30-100 g/L Zn.
In the process for separating germanium and gallium from the germanium and gallium material, in the step (2), the neutralized slag returns to the step (1) to continue leaching.
In the process for separating germanium and gallium from the germanium and gallium material, in the step (3), the addition amount of the zinc powder is 1-1.3 times of the theoretical amount of cadmium replacement, and the reaction time is 0.5-4 hours.
In the process for separating germanium and gallium from the germanium and gallium material, in the step (3), the mass content of gallium in the germanium concentrate is less than 0.1%, and the mass content of germanium is 5-15%.
In the process for separating germanium and gallium from the germanium and gallium material, in the step (4), the addition amount of the zinc powder is 2-5 times of the theoretical amount of displacement of cadmium and gallium, and the reaction time is 0.5-4 hours.
The process for separating germanium and gallium from the germanium and gallium material further comprises the step (5) of adding hydrogen peroxide into 50-150 g/L NaOH solution to leach gallium residues, adding sodium sulfide into the leachate to remove impurities, neutralizing until the pH value is 4-6 to obtain gallium concentrate, and electrodepositing the gallium concentrate to obtain the metal gallium.
In the process for separating germanium and gallium from the germanium and gallium material, cadmium slag obtained after gallium is leached in the step (5) enters a cadmium recovery system; and (4) returning the replaced liquid to the main flow to recover the zinc.
Compared with the prior art, the invention has the beneficial effects that: compared with the traditional process, the process is simplified, organic matters brought by deposited germanium and gallium can be avoided, the normal operation of a zinc recovery main process is ensured, the discharge of waste water during gallium recovery is reduced, the process is more environment-friendly, the added zinc powder can be recovered again, the cost is saved, the economic benefit is improved, and the method is an economic and environment-friendly method for efficiently separating scattered metal germanium and gallium.
Drawings
Fig. 1 is a block diagram of a process flow for separating ge and ga from a ge and ga material according to embodiment 1 of the present invention.
Detailed Description
The invention provides a process for separating germanium and gallium from germanium and gallium materials, which comprises the following steps:
(1) adding germanium gallium materials into 50-150 g/L sulfuric acid solution according to the liquid-solid ratio of 5-10 for leaching, wherein the leaching temperature is 40-80 ℃, and stirring for reaction for 0.5-4 h to obtain leaching residues and leaching liquid;
(2) adding germanium and gallium materials into the leaching solution again to adjust the pH value to 1-3, so as to obtain neutralized liquid and neutralized slag; the content of metal elements in the neutralized liquid is as follows: 0.3-5 g/L Ge, 0.2-4 g/L GaI, 3-15 g/L Cd and 30-100 g/L Zn;
(3) adding zinc powder into the neutralized solution at the temperature of 40-80 ℃ for primary replacement, wherein the addition amount of the zinc powder is 1-1.3 times of the theoretical amount of cadmium replacement, the reaction time is 0.5-4 h, and germanium concentrate and the replaced solution are obtained after the reaction is finished;
(4) and (3) adding zinc powder into the solution after the replacement at the temperature of 40-80 ℃ for secondary replacement, wherein the addition amount of the zinc powder is 2-5 times of the theoretical amount of cadmium and gallium replacement, the reaction time is 0.5-4 h, and gallium slag and the solution after the replacement are obtained after the reaction is finished.
In the process for separating germanium and gallium from the germanium and gallium material, in the step (2), the neutralized slag returns to the step (1) to continue leaching.
In the process for separating germanium and gallium from the germanium and gallium material, in the step (3), the mass content of gallium in the germanium concentrate is less than 0.1%, and the mass content of germanium is 5-15%.
The process for separating germanium and gallium from the germanium and gallium material further comprises the step (5) of adding hydrogen peroxide into 50-150 g/L NaOH solution to leach gallium residues, adding sodium sulfide into the leachate to remove impurities, neutralizing until the pH value is 4-6 to obtain gallium concentrate, and electrodepositing the gallium concentrate to obtain the metal gallium.
In the process for separating germanium and gallium from the germanium and gallium material, cadmium slag obtained after gallium is leached in the step (5) enters a cadmium recovery system; and (4) returning the replaced liquid to the main flow to recover the zinc.
The process principle of the invention is as follows: the main component of the material is zinc cadmium germanium gallium, after the material is leached by sulfuric acid solution, because the potential of cadmium is between germanium and gallium, germanium can be well replaced by adopting cadmium powder replacement method, and the material is added into the solution, and zinc powder is added for secondary replacement, so that two kinds of rare metals can be separated. In the process, the amount of added zinc powder is controlled, namely the zinc powder with cadmium replacing theoretical amount is added, and the produced fresh cadmium powder can replace germanium and directly obtain germanium concentrate. Cadmium is less active than gallium and remains in solution without being displaced, selectively separating germanium from gallium. The germanium gallium cadmium standard electrode potential is shown in table 2.
TABLE 2 GeGa-Cd standard electrode potential table
As can be seen from the standard electrode potential, the metal activity of cadmium is between that of germanium and gallium, germanium can be easily replaced by adding fresh cadmium, and the activity of gallium is greater than that of cadmium and remains in the solution, so that germanium and gallium can be efficiently and simply separated.
2H2GeO3+2Cd＝2Ge+2Cd+6H2O；
Cd2++Zn＝Cd+Zn2+；
2Ga3++3Zn＝2Ga+3Zn2+。
The invention is further illustrated and described with reference to specific examples, which do not limit the scope of the invention.
The germanium-gallium materials used in the following examples have the following metal element compositions (wt%): ge 0.93, Ga 0.86, Cd 3.65, Zn 35.38.
Example 1
The process for separating germanium and gallium from germanium and gallium materials comprises the following steps:
(1) adding germanium gallium material into 50g/L sulfuric acid solution for leaching according to the liquid-solid ratio of 5mL/g, wherein the leaching temperature is 50 ℃, and stirring for reacting for 2h to obtain leaching residue and leaching liquid;
(2) adding germanium and gallium materials into the leaching solution again to adjust the pH value to 3, so as to obtain neutralized solution and neutralized slag; the content of metal elements in the neutralized liquid is as follows: 0.3-5 g/L Ge, 0.2-4 g/L Ga, 3-15 g/L Cd and 30-100 g/L Zn; returning the neutralized slag to the step (1) for continuous leaching;
(3) adding zinc powder into the neutralized solution at 50 ℃ for primary replacement, wherein the addition of the zinc powder is 1.3 times of the theoretical amount of cadmium replacement, the reaction time is 4 hours, and germanium concentrate and the replaced solution are obtained after the reaction is finished; the mass content of gallium in the germanium concentrate is less than 0.1%, and the mass content of germanium is 5-15%; returning the displaced liquid to the main process to recover zinc;
(4) adding zinc powder into the solution after the replacement at the temperature of 50 ℃ for secondary replacement, wherein the addition amount of the zinc powder is 2 times of the theoretical amount of cadmium and gallium replacement, the reaction time is 2 hours, and gallium slag and the solution after the replacement are obtained after the reaction is finished; and returning the replaced liquid to the main process to recover the zinc.
Example 2
The process for separating germanium and gallium from germanium and gallium materials comprises the following steps:
(1) adding the germanium-gallium material into 80g/L sulfuric acid solution for leaching according to the liquid-solid ratio of 7mL/g, wherein the leaching temperature is 60 ℃, and stirring for reacting for 4 hours to obtain leaching residues and leaching liquid;
(2) adding germanium and gallium materials into the leaching solution again to adjust the pH value to 2, so as to obtain neutralized solution and neutralized slag; the content of metal elements in the neutralized liquid is as follows: 0.3-5 g/L Ge, 0.2-4 g/L Ga, 3-15 g/L Cd and 30-100 g/L Zn; returning the neutralized slag to the step (1) for continuous leaching;
(3) adding zinc powder into the neutralized solution at the temperature of 60 ℃ for primary replacement, wherein the addition of the zinc powder is 1.2 times of the theoretical amount of cadmium replacement, the reaction time is 2.5 hours, and germanium concentrate and the replaced solution are obtained after the reaction is finished; the mass content of gallium in the germanium concentrate is less than 0.1%, and the mass content of germanium is 5-15%; returning the displaced liquid to the main process to recover zinc;
(4) at the temperature of 60 ℃, adding zinc powder into the solution after the replacement for secondary replacement, wherein the adding amount of the zinc powder is 3 times of the theoretical amount of cadmium and gallium replacement, the reaction time is 3 hours, and gallium slag and the solution after the replacement are obtained after the reaction is finished; returning the displaced liquid to the main process to recover zinc;
(5) adding hydrogen peroxide into 90g/L NaOH solution to leach gallium slag, adding sodium sulfide into leachate to remove impurities, neutralizing until the pH value is 5 to obtain gallium concentrate, and electrodepositing the gallium concentrate to obtain metal gallium; and feeding cadmium slag after leaching gallium into a cadmium recovery system.
Example 3
The process for separating germanium and gallium from germanium and gallium materials comprises the following steps:
(1) adding germanium gallium material into 120g/L sulfuric acid solution according to the liquid-solid ratio of 10mL/g for leaching, wherein the leaching temperature is 70 ℃, and stirring for reaction for 3.5h to obtain leaching residue and leaching liquid;
(2) adding germanium and gallium materials into the leaching solution again to adjust the pH value to 1, so as to obtain neutralized solution and neutralized slag; the content of metal elements in the neutralized liquid is as follows: 0.3-5 g/L Ge, 0.2-4 g/L Ga, 3-15 g/L Cd and 30-100 g/L Zn; returning the neutralized slag to the step (1) for continuous leaching;
(3) adding zinc powder into the neutralized solution at the temperature of 70 ℃ for primary replacement, wherein the addition of the zinc powder is 1.1 times of the theoretical amount of cadmium replacement, the reaction time is 4 hours, and germanium concentrate and the replaced solution are obtained after the reaction is finished; the mass content of gallium in the germanium concentrate is less than 0.1%, and the mass content of germanium is 5-15%; returning the displaced liquid to the main process to recover zinc;
(4) at the temperature of 70 ℃, adding zinc powder into the solution after the replacement for secondary replacement, wherein the adding amount of the zinc powder is 4 times of the theoretical amount of cadmium and gallium replacement, the reaction time is 2.5 hours, and gallium slag and the solution after the replacement are obtained after the reaction is finished; returning the displaced liquid to the main process to recover zinc;
(5) adding hydrogen peroxide into 100g/L NaOH solution to leach gallium slag, adding sodium sulfide into leachate to remove impurities, neutralizing until the pH value is 6 to obtain gallium concentrate, and electrodepositing the gallium concentrate to obtain metal gallium; and feeding cadmium slag after leaching gallium into a cadmium recovery system.
Example 4
The process for separating germanium and gallium from germanium and gallium materials comprises the following steps:
(1) adding germanium gallium material into 150g/L sulfuric acid solution according to the liquid-solid ratio of 8mL/g for leaching, wherein the leaching temperature is 80 ℃, and stirring for reacting for 1.5h to obtain leaching residue and leaching solution;
(2) adding germanium and gallium materials into the leaching solution again to adjust the pH value to 3, so as to obtain neutralized solution and neutralized slag; the content of metal elements in the neutralized liquid is as follows: 0.3-5 g/L Ge, 0.2-4 g/L Ga, 3-15 g/L Cd and 30-100 g/L Zn; returning the neutralized slag to the step (1) for continuous leaching;
(3) adding zinc powder into the neutralized solution at the temperature of 80 ℃ for primary replacement, wherein the addition of the zinc powder is 1.3 times of the theoretical amount of cadmium replacement, the reaction time is 1.0h, and germanium concentrate and the replaced solution are obtained after the reaction is finished; the mass content of gallium in the germanium concentrate is less than 0.1%, and the mass content of germanium is 5-15%; returning the displaced liquid to the main process to recover zinc;
(4) adding zinc powder into the solution after the replacement at the temperature of 80 ℃ for secondary replacement, wherein the addition amount of the zinc powder is 5 times of the theoretical amount of cadmium and gallium replacement, the reaction time is 1.5h, and gallium slag and the solution after the replacement are obtained after the reaction is finished; returning the displaced liquid to the main process to recover zinc;
(5) adding hydrogen peroxide into 150g/L NaOH solution to leach gallium slag, adding sodium sulfide into leachate to remove impurities, neutralizing until the pH value is 4 to obtain gallium concentrate, and electrodepositing the gallium concentrate to obtain metal gallium; and feeding cadmium slag after leaching gallium into a cadmium recovery system.
Claims (3)
1. A process for separating germanium and gallium from a germanium and gallium material is characterized by comprising the following steps:
(1) adding the germanium-gallium material into a sulfuric acid solution according to a liquid-solid ratio of 5-10 for leaching, wherein the leaching temperature is 40-80 ℃, and stirring for reaction for 0.5-4 h; the concentration of the sulfuric acid solution is 50-150 g/L, and leaching residues and a leaching solution are obtained;
(2) adding germanium and gallium materials into the leaching solution again to adjust the pH value to 1-3, so as to obtain neutralized liquid and neutralized slag, and returning the neutralized slag to the step (1) for continuous leaching; the content of metal elements in the neutralized liquid is as follows: 0.3-5 g/L Ge, 0.2-4 g/L Ga, 3-15 g/L Cd and 30-100 g/L Zn;
(3) adding zinc powder into the neutralized liquid at the temperature of 40-80 ℃ for primary replacement, wherein the addition amount of the zinc powder is 1-1.3 times of the theoretical amount of cadmium replacement, the reaction time is 0.5-4 h, and after the reaction is finished, germanium concentrate and the replaced liquid are obtained, wherein the mass content of gallium in the germanium concentrate is less than 0.1%, and the mass content of germanium is 5-15%;
(4) adding zinc powder into the solution after the replacement at the temperature of 40-80 ℃ for secondary replacement, wherein the addition amount of the zinc powder is 2-5 times of the theoretical amount of cadmium and gallium replacement, the reaction time is 0.5-4 h, and gallium slag and the solution after the replacement are obtained after the reaction is finished;
(5) adding hydrogen peroxide into 50-150 g/L NaOH solution to leach the gallium slag, adding sodium sulfide into the leachate to remove impurities, neutralizing until the pH is = 4-6 to obtain gallium concentrate, and carrying out liquid making and electrodeposition on the gallium concentrate to obtain metal gallium.
2. The process for separating germanium and gallium from a germanium and gallium material according to claim 1, wherein the cadmium slag after the gallium is leached in the step (5) enters a cadmium recovery system.
3. The process for separating germanium and gallium from a germanium and gallium material according to claim 1, wherein the liquid obtained after the replacement in the steps (3) and (4) is returned to a main process for recovering zinc.
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