CN114032397A - 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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- CN114032397A CN114032397A CN202111366151.5A CN202111366151A CN114032397A CN 114032397 A CN114032397 A CN 114032397A CN 202111366151 A CN202111366151 A CN 202111366151A CN 114032397 A CN114032397 A CN 114032397A
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- 238000002386 leaching Methods 0.000 title claims abstract description 160
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 107
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000000779 smoke Substances 0.000 title claims abstract description 61
- 239000000428 dust Substances 0.000 title claims abstract description 51
- 238000003723 Smelting Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 75
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229940119177 germanium dioxide Drugs 0.000 claims abstract description 30
- 230000009467 reduction Effects 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims 5
- 239000011701 zinc Substances 0.000 abstract description 9
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002787 reinforcement Effects 0.000 abstract description 7
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 229910005842 GeS2 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UQMCSSLUTFUDSN-UHFFFAOYSA-N sulfanylidenegermane Chemical compound [GeH2]=S UQMCSSLUTFUDSN-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/02—Working-up flue dust
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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 hexagonal germanium and amorphous germanium dioxide into germanium monoxide to be leached 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 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 mainly comprises germanium sulfide (GeS) and GeS2Germanium monoxide (GeO), GeO2And salts of metal germanates (MeGeO) of Pb, Zn, Ca and the like4) And partial germanate (MeGeO)3) Are present. GeO2Soluble, insoluble and glassy. Vitreous GeO2The crystalline form of (A) is amorphous and is soluble in 0.52g of soluble GeO in 100g of water at 30 DEG2The 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 germanium organic complexing agent into sulfuric acid solution during or before leaching germanium-containing material to prevent germanium micelle from polymerizing into macromolecule group and precipitating along with desiliconization process, or being Fe (OH) when leaching pH is higher3Adsorption precipitation causes leaching loss of germanium, 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; wet ball milling and size mixing of water and germanium-containing zinc hypoxide powder, adding oxidant for low acid leaching, and high acid leaching in the bottom flow of low acid leaching to raise the leaching rate of germanium and zincHigh yield, but complicated process, and is aimed at containing GeO2Smoke 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 which can be divided into a hexagonal form, an amorphous form and a tetragonal form, wherein the hexagonal form and the amorphous form of germanium dioxide are slightly soluble in acid, and the tetragonal form of 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 based on 100 percent of the total molar amount of germanium in the lead-zinc smelting smoke dust, 5-80 percent of hexagonal germanium dioxide, 5-80 percent of amorphous germanium dioxide, 0.5-30 percent of tetragonal germanium dioxide, and 0.1-30 percent of total germanium amount of germanium sulfide, alkali metal germanate and germanium monoxide;
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 of the sulfuric acid solution to the germanium-containing smoke dust solution is 1: 1-10: 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 adding amount of the reducing agent is 0.1-20% of the mass of the smoke dust;
the reduction leaching time in the step (2) is 2-15 min;
the ultrasonic intensity in the step (3) is more than 0.05W/cm2And the time of ultrasonic enhanced 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,
GeO2+Zn+H2SO4＝GeO+ZnSO4+H2O (a)
GeO2+Pb+H2SO4＝GeO+PbSO4+H2O (b)
GeO2+Fe+H2SO4＝GeO+FeSO4+H2O (c)
2GeO2+2Al+0.5O2(g)+3H2SO4＝2GeO+Al2(SO4)3+3H2O (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 (logK) of the reaction is greater than 5, indicating that steps can occur and that the driving force for the reaction to occur is large, i.e. that the ultrasonic energy converts all 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 reduction leaching reaction of germanium-containing smoke dust in lead-zinc smelting by ultrasonic enhancement 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 is 1820g/t, which belongs to high germanium smoke, and the germanium in the smoke is mainly hexagonal GeO2Amorphous GeO2And 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 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 liquid-solid ratio mL of the acid leaching solution to the lead-zinc smelting smoke dust is 10: 1;
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 the leaching system B at the temperature of 95 ℃ for 15min 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 5W/cm2；
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 the temperature of 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 liquid-solid ratio mL of the acid leaching solution to the lead-zinc smelting smoke dust is 5: 1;
the leaching rate of germanium is 17.02%;
(2) adding a reducing agent (lead powder) into the leaching system A, carrying out reduction leaching for 10min at the temperature of 75 ℃ to obtain a leaching system B, and reducing the hexagonal germanium dioxide and the amorphous germanium dioxide into germanium monoxide to be leached 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; 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 2W/cm2；
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 is 150g/t, which belongs to low germanium smoke, and the germanium in the smoke is mainly amorphous GeO2And tetragonal GeO2The 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 acid leaching solution, leaching for 5min at 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 liquid-solid ratio mL of the acid leaching solution to the lead-zinc smelting smoke dust is 1: 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%;
(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/cm2；
The leaching rate of the germanium reaches 90.05 percent.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (6)
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;
(2) adding a reducing agent into the leaching system A for reduction leaching to obtain a leaching system B;
(3) and (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 leachate and leaching residues, and extracting germanium from the leachate.
2. 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: the content of germanium in the lead-zinc smelting smoke dust is 100-2000 g/t, the total molar amount of germanium in the lead-zinc smelting smoke dust is 100%, the content of hexagonal germanium dioxide is 5-80%, the content of amorphous germanium dioxide is 5-80%, the content of tetragonal germanium dioxide is 0.5-30%, and the total germanium content of germanium sulfide, alkali metal germanate and germanium monoxide is 0.1-30%.
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: 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 liquid is 1: 1-10: 1, the leaching temperature is 50-95 ℃, and the leaching time is 5-30 min.
4. 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) the reducing agent in the step (2) is lead powder, iron powder or aluminum powder, and the adding amount of the reducing agent is 0.1-20% of the mass of the smoke dust.
5. The method for ultrasonically enhancing the reduction leaching of the germanium-containing smoke dust in the lead-zinc smelting process according to claim 4, wherein the method comprises the following steps: and (3) reducing and leaching time of the step (2) is 2-15 min.
6. 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: the ultrasonic intensity in the step (3) is more than 0.05W/cm2And the time of ultrasonic enhanced reduction leaching is 2-15 min.
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| CN115537584A (en) * | 2022-11-29 | 2022-12-30 | 昆明理工大学 | Method for strengthening tannin germanium precipitation through ultrasonic and tannic acid modification |
| CN117607080A (en) * | 2024-01-22 | 2024-02-27 | 昆明理工大学 | Analysis method of germanium chemical phase in germanium-containing complex minerals |
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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 |
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| CN115537584A (en) * | 2022-11-29 | 2022-12-30 | 昆明理工大学 | Method for strengthening tannin germanium precipitation through ultrasonic and tannic acid modification |
| 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 |
| CN117607080A (en) * | 2024-01-22 | 2024-02-27 | 昆明理工大学 | Analysis method of germanium chemical phase in germanium-containing complex minerals |
| CN117607080B (en) * | 2024-01-22 | 2024-03-29 | 昆明理工大学 | Analysis method of germanium chemical phase in germanium-containing complex minerals |
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