CN114032397B - Method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement - Google Patents
Method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention relates to a method for reducing and leaching germanium-containing smoke dust in lead and zinc smelting by ultrasonic reinforcement, belonging to the technical field of hydrometallurgy. Adding lead-zinc smelting smoke dust into acid leaching solution to leach to obtain a leaching system A, and enabling germanium in germanium sulfide, alkali metal germanate and germanium monoxide to enter the leaching system A; adding a reducing agent into the leaching system A for reduction leaching to obtain a leaching system B, and reducing the hexagonal germanium and the amorphous germanium dioxide into germanium monoxide to leach into the leaching system B; and (3) carrying out ultrasonic enhanced reduction leaching on the leaching system B to obtain a leaching system C, reducing the tetragonal germanium dioxide into germanium monoxide, leaching the germanium monoxide into the leaching system C, carrying out solid-liquid separation on the leaching system C to obtain a leaching solution and leaching residues, and extracting germanium from the leaching solution. The leaching rate of the germanium is increased by 20 percent and can reach more than 90 percent, and the deep and efficient leaching of the germanium can be realized.
Description
Technical Field
The invention relates to a method for reducing and leaching germanium-containing smoke dust in lead and zinc smelting by ultrasonic reinforcement, belonging to the technical field of hydrometallurgy.
Background
Germanium is a rare metal and there is no raw ore that can meet industrial exploitation. Germanium has unique and excellent physical and chemical properties, and is widely applied to the high-tech fields of national defense industry, aerospace, modern information and the like. With the continuous development and improvement of the fields, the demand for germanium materials is increasing day by day, and the development of the germanium industry in China has obvious social benefit and economic benefit.
The smoke dust containing germanium is an important germanium extracting raw material, the mainstream process for treating the smoke dust containing germanium and zinc oxide at present is two-section countercurrent leaching, but the occurrence form of germanium in the smoke dust is complex, and germanium in the pyrometallurgical dust of lead and zinc concentrate is mainly germaniumTo use germanium sulfide (GeS), geS 2 Germanium monoxide (GeO), geO 2 And orthogermanates of metals such as Pb, zn and Ca (MeGeO) 4 ) And partial germanate (MeGeO) 3 ) Are present. GeO 2 Soluble, insoluble and glassy. Vitreous GeO 2 Is amorphous and is soluble in 0.52g of water at 30 ℃ and 100g of water 2 The crystal form of (a) is a hexagonal system, and the amount of dissolution decreases in an acidic solution as the concentration of an acid increases, while GeO reacts with both an acid and a base. In order to increase the leaching rate of germanium, several germanium-containing phases need to be leached simultaneously.
In the prior art, zinc, silicate and germanium are selectively leached out in sequence by adjusting and controlling the pH value of the slurry, so that the silicate is leached out before the germanium is leached out, and then three-stage leaching is carried out, thereby solving the technical problem of low germanium leaching caused by silicon and germanium coprecipitation, but the leaching process is too long, and no reference is made to phase treatment of the germanium. Adding organic complexing agent of germanium into sulfuric acid solution during or before leaching germanium-containing material with sulfuric acid to prevent germanium micelle from polymerizing into macromolecule group and precipitating during desiliconization or being leached by Fe (OH) when pH is high 3 The leaching loss of germanium is caused by adsorption and precipitation, the leaching rate of the germanium can be improved by 0.4-3%, the leaching rate of the germanium is improved a little, and the method has no practical technical process guiding significance; firstly, water and germanium-containing zinc hypoxide powder are subjected to wet ball milling and size mixing, then an oxidant is added for low-acid leaching, and the bottom flow of the low-acid leaching is subjected to high-acid leaching to improve the leaching rate of germanium and zinc, but the process is complex and aims at the problem of containing GeO 2 Smoke with low phase is suitable.
Therefore, none of the prior art germanium leaches involve the treatment of a specific germanium-containing phase.
Disclosure of Invention
The invention provides a method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting by ultrasonic reinforcement, aiming at the problem of germanium recovery and leaching in the prior art, wherein germanium in the lead-zinc smelting smoke dust mainly exists in the form of germanium dioxide, and the germanium dioxide can be divided into three forms of a hexagonal form, an amorphous form and a tetragonal form, wherein the hexagonal form and the amorphous germanium dioxide are slightly soluble in acid, and the tetragonal germanium dioxide is insoluble in acid.
A method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting by ultrasonic reinforcement comprises the following specific steps:
(1) Adding lead-zinc smelting smoke dust into acid leaching solution to leach to obtain a leaching system A, and enabling germanium in germanium sulfide, alkali metal germanate and germanium monoxide to enter the leaching system A;
(2) Adding a reducing agent into the leaching system A for reduction leaching to obtain a leaching system B, and reducing the hexagonal germanium dioxide and the amorphous germanium dioxide into germanium monoxide to leach into the leaching system B;
(3) Carrying out ultrasonic enhanced reduction leaching on the leaching system B to obtain a leaching system C, carrying out solid-liquid separation on the leaching system C to obtain a leaching solution and leaching residues, and extracting germanium from the leaching solution; the tetragonal germanium dioxide is reduced into germanium monoxide under the double actions of ultrasound and a reducing agent, and the germanium monoxide is leached into a leaching system C;
the content of germanium in the lead-zinc smelting smoke dust in the step (1) is 100-2000 g/t, and by taking the total molar weight of germanium in the lead-zinc smelting smoke dust as 100%, hexagonal germanium dioxide accounts for 5-80%, amorphous germanium dioxide accounts for 5-80%, tetragonal germanium dioxide accounts for 0.5-30%, and the total germanium content of germanium sulfide, alkali metal germanate and germanium monoxide accounts for 0.1-30%;
the acid leaching solution in the step (1) is a sulfuric acid solution, the concentration of the sulfuric acid solution is 50-300 g/L, the solid-to-solid ratio mL/g of the sulfuric acid solution to the germanium-containing smoke dust solution is 1-1, the leaching temperature is 50-95 ℃, and the leaching time is 5-30 min;
the reducing agent in the step (2) is lead powder, iron powder or aluminum powder, and the addition amount of the reducing agent is 0.1-20% of the mass of the smoke dust;
the reduction leaching time of the step (2) is 2-15 min;
the ultrasonic intensity in the step (3) is more than 0.05W/cm 2 The time of ultrasonic reinforced reduction leaching is 2-15 min.
The phase transformation process of germanium-containing phase in the whole leaching process is as follows: germanium sulfide, alkali metal germanate and germanium monoxide are preferentially leached before reduction leaching, hexagonal germanium and amorphous germanium dioxide are reduced into germanium monoxide for leaching in the reduction leaching stage, and tetragonal germanium dioxide is reduced into germanium monoxide for leaching in the ultrasonic strengthening stage; the reduction leaching mechanism of the germanium-containing smoke dust in the lead-zinc smelting process is strengthened by ultrasonic under different reducing agents,
GeO 2 +Zn+H 2 SO 4 ＝GeO+ZnSO 4 +H 2 O (a)
GeO 2 +Pb+H 2 SO 4 ＝GeO+PbSO 4 +H 2 O (b)
GeO 2 +Fe+H 2 SO 4 ＝GeO+FeSO 4 +H 2 O (c)
2GeO 2 +2Al+0.5O 2 (g)+3H 2 SO 4 ＝2GeO+Al 2 (SO 4 ) 3 +3H 2 O (d)
gibbs free energy (shown in figure 1) and stability constant (shown in figure 2) of reduction leaching reaction of germanium-containing smoke dust in lead and zinc smelting are strengthened by ultrasonic under different reducing agents;
it can be seen from the figure that the gibbs free energy of the reaction is less than 0 and the stability constant of the reaction (logK) is greater than 5, indicating that steps can occur and that the driving force for the reaction to occur is large, i.e. the ultrasonic energy converts all of the germanium dioxide to germanium monoxide.
The invention has the beneficial effects that:
(1) According to the invention, the pickle liquor is directly leached, so that germanium in germanium sulfide, alkali metal germanate and germanium monoxide is preferentially leached, hexagonal germanium dioxide and amorphous germanium dioxide are reduced into germanium monoxide by a reducing agent for leaching, and tetragonal germanium dioxide is reduced into germanium monoxide for leaching under the double actions of ultrasound and the reducing agent;
(2) The invention reduces the slightly soluble or slightly soluble germanium dioxide into the easily treated germanium monoxide, thereby realizing the improvement of the germanium leaching rate, and the germanium leaching rate can reach more than 90 percent and is improved by about 20 percent compared with the prior art;
(3) The invention is suitable for treating the germanium-containing smoke dust in the smelting of lead and zinc with low germanium and high germanium.
Drawings
FIG. 1 shows Gibbs free energy of reduction leaching reaction of germanium-containing smoke in lead-zinc smelting by ultrasonic enhancement under different reducing agents;
FIG. 2 is a stable constant of the reduction leaching reaction of the germanium-containing smoke dust in lead-zinc smelting by ultrasonic strengthening under different reducing agents.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: the phase distribution of germanium in the lead-zinc smelting germanium-containing smoke dust in the embodiment is shown in the table 1,
TABLE 1 Smoke germanium phase distribution
As can be seen from the table, the germanium content in the smoke dust is 1820g/t, which belongs to high germanium smoke dust, and the germanium in the smoke dust is mainly hexagonal GeO 2 Amorphous GeO 2 And other germanium-containing phases (germanium sulfide, alkali metal germanate and germanium monoxide), wherein the insoluble germanium accounts for only 0.83%;
a method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting by ultrasonic reinforcement comprises the following specific steps:
(1) Adding lead-zinc smelting smoke dust into the acid leaching solution, leaching for 30min at the temperature of 95 ℃ to obtain a leaching system A, and enabling germanium in germanium sulfide, alkali metal germanate and germanium monoxide to enter the leaching system A; wherein the acid leaching solution is a sulfuric acid solution with the mass concentration of 300g/L, and the ratio of the acid leaching solution to lead-zinc smelting smoke dust is mL, g is 10;
the leaching rate of germanium is 21.35 percent;
(2) Adding a reducing agent (iron powder) into the leaching system A, reducing and leaching for 15min at the temperature of 95 ℃ to obtain a leaching system B, and reducing the hexagonal germanium dioxide and the amorphous germanium dioxide into germanium monoxide to leach into the leaching system B; wherein the addition amount of the reducing agent (iron powder) is 20 percent of the mass of the smoke dust;
the leaching rate of germanium is 93.76%;
(3) Leaching at a temperature of 95 DEG CCarrying out ultrasonic enhanced reduction leaching on the system B for 15min to obtain a leaching system C, carrying out solid-liquid separation on the leaching system C to obtain a leaching solution and leaching residues, and extracting germanium from the leaching solution; the tetragonal germanium dioxide is reduced into germanium monoxide under the double actions of ultrasound and a reducing agent, and the germanium monoxide is leached into a leaching system C; wherein the ultrasonic intensity is 5W/cm 2 ；
The leaching rate of the germanium reaches 96.12 percent.
Example 2: the phase distribution of germanium in the lead-zinc smelting germanium-containing smoke dust in the embodiment is shown in Table 2,
TABLE 2 Smoke germanium phase distribution
As can be seen from the table, the content of germanium in the smoke dust is 750g/t, the smoke dust belongs to high-germanium smoke dust, the occurrence form of germanium in the smoke dust is relatively average, and the content of insoluble germanium reaches 15.01 percent;
a method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting by ultrasonic reinforcement comprises the following specific steps:
(1) Adding lead-zinc smelting smoke dust into acid leaching solution, leaching for 15min at 75 ℃ to obtain a leaching system A, and enabling germanium in germanium sulfide, alkali metal germanate and germanium monoxide to enter the leaching system A; wherein the acid leaching solution is a sulfuric acid solution with the mass concentration of 200g/L, and the ratio of the acid leaching solution to lead-zinc smelting smoke dust is mL, g is 5;
the leaching rate of germanium is 17.02%;
(2) Adding a reducing agent (lead powder) into the leaching system A, reducing and leaching for 10min at the temperature of 75 ℃ to obtain a leaching system B, and reducing hexagonal germanium dioxide and amorphous germanium dioxide into germanium monoxide to leach into the leaching system B; wherein the addition amount of the reducing agent (lead powder) is 5 percent of the mass of the smoke dust;
the leaching rate of germanium is 83.46 percent;
(3) Leaching the leaching system B at the temperature of 75 ℃ for 10min by ultrasonic enhanced reduction leaching to obtain a leaching system C, performing solid-liquid separation on the leaching system C to obtain a leaching solution and leaching residues, and extracting germanium from the leaching solution; tetragonal germanium dioxide is coated under the dual action of ultrasound and reducing agentReducing the germanium monoxide to leach the germanium monoxide into a leaching system C; wherein the ultrasonic intensity is 2W/cm 2 ；
The leaching rate of the germanium reaches 92.88 percent.
Example 3: the phase distribution of germanium in the lead-zinc smelting germanium-containing smoke dust in the embodiment is shown in Table 3,
TABLE 3 Smoke germanium phase distribution
As can be seen from the table, the germanium content in the smoke dust is 150g/t, which belongs to low germanium smoke dust, and the germanium in the smoke dust is mainly amorphous GeO 2 And tetragonal GeO 2 The content of insoluble germanium reaches 20.01 percent;
a method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting by ultrasonic reinforcement comprises the following specific steps:
(1) Adding lead-zinc smelting smoke dust into the acid leaching solution, leaching for 5min at the temperature of 50 ℃ to obtain a leaching system A, and enabling germanium in germanium sulfide, alkali metal germanate and germanium monoxide to enter the leaching system A; wherein the acid leaching solution is a sulfuric acid solution with the mass concentration of 50g/L, and the ratio of the acid leaching solution to lead-zinc smelting smoke dust is mL, g is 1;
the leaching rate of germanium is 5.26%;
(2) Adding a reducing agent (aluminum powder) into the leaching system A, carrying out reduction leaching for 5min at the temperature of 50 ℃ to obtain a leaching system B, and reducing the hexagonal germanium dioxide and the amorphous germanium dioxide into germanium monoxide to leach into the leaching system B; wherein the addition amount of the reducing agent (aluminum powder) is 0.1 percent of the mass of the smoke dust;
the leaching rate of germanium is 73.76 percent;
(3) Leaching the leaching system B at 50 ℃ for 2min by ultrasonic enhanced reduction to obtain a leaching system C, performing solid-liquid separation on the leaching system C to obtain a leaching solution and leaching residues, and extracting germanium from the leaching solution; the tetragonal germanium dioxide is reduced into germanium monoxide under the double actions of ultrasound and a reducing agent, and the germanium monoxide is leached into a leaching system C; wherein the ultrasonic intensity is 1W/cm 2 ；
The leaching rate of the germanium reaches 90.05 percent.
While the present invention has been described in detail with reference to the embodiments, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (3)
1. A method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement is characterized by comprising the following specific steps:
(1) Adding lead-zinc smelting smoke dust into acid leaching solution to leach to obtain a leaching system A; wherein the content of germanium in the lead-zinc smelting smoke is 100 to 2000g/t, the total molar weight of germanium in the lead-zinc smelting smoke is 100 percent, the hexagonal germanium dioxide accounts for 5 to 80 percent, the amorphous germanium dioxide accounts for 5 to 80 percent, the tetragonal germanium dioxide accounts for 0.5 to 30 percent, and the total germanium content of germanium sulfide, alkali metal germanate and germanium monoxide accounts for 0.1 to 30 percent;
(2) Adding a reducing agent into the leaching system A for reduction leaching to obtain a leaching system B; wherein the reducing agent is lead powder, iron powder or aluminum powder, and the addition amount of the reducing agent is 0.1-20% of the mass of the smoke dust;
(3) Carrying out ultrasonic enhanced reduction leaching on the leaching system B to obtain a leaching system C, carrying out solid-liquid separation on the leaching system C to obtain a leaching solution and leaching residues, and extracting germanium from the leaching solution; wherein the ultrasonic intensity is more than 0.05W/cm 2 And the time of ultrasonic reinforced reduction leaching is 2-15min.
2. The method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement according to claim 1 is characterized by comprising the following steps: the acid leaching solution in the step (1) is a sulfuric acid solution, the concentration of the sulfuric acid solution is 50 to 300g/L, the solid ratio mL of the sulfuric acid solution to the germanium-containing smoke solution is 1 to 1, the leaching temperature is 50 to 95 ℃, and the leaching time is 5 to 30min.
3. The method for ultrasonically enhancing the reduction leaching of the germanium-containing smoke dust in the lead-zinc smelting process according to claim 1, wherein the method comprises the following steps: and (3) reducing and leaching time in the step (2) is 2 to 15min.
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| CN114574706B (en) * | 2022-03-09 | 2023-11-24 | 昆明理工大学 | Method for leaching germanium in ultrasonic reinforced zinc oxide smoke dust |
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| CN115354158B (en) * | 2022-08-22 | 2023-11-10 | 昆明理工大学 | Method for cooperatively degrading germanium-silicon polymer colloid in germanium-containing zinc oxide smoke dust leaching by double-frequency ultrasound |
| CN115386732A (en) * | 2022-09-06 | 2022-11-25 | 昆明冶金研究院有限公司 | Method for efficiently recycling zinc, germanium and indium in zinc oxide smoke dust |
| CN115216651A (en) * | 2022-09-06 | 2022-10-21 | 昆明冶金研究院有限公司 | Method for efficiently recycling zinc and germanium in zinc oxide smoke dust |
| CN115537584B (en) * | 2022-11-29 | 2023-03-10 | 昆明理工大学 | Method for reinforcing tannin germanium precipitation through ultrasonic and tannic acid modification |
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