CN115261643A - Method for enhancing deep leaching of germanium in germanium-containing zinc oxide smoke dust by countercurrent ultrasonic - Google Patents
Method for enhancing deep leaching of germanium in germanium-containing zinc oxide smoke dust by countercurrent ultrasonic Download PDFInfo
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 238000002386 leaching Methods 0.000 title claims abstract description 164
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 162
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000000779 smoke Substances 0.000 title claims abstract description 70
- 239000000428 dust Substances 0.000 title claims abstract description 47
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000010410 layer Substances 0.000 claims abstract description 12
- 239000002344 surface layer Substances 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 8
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 38
- 229940119177 germanium dioxide Drugs 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 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 description 6
- XKENYNILAAWPFQ-UHFFFAOYSA-N dioxido(oxo)germane;lead(2+) Chemical compound [Pb+2].[O-][Ge]([O-])=O XKENYNILAAWPFQ-UHFFFAOYSA-N 0.000 claims description 6
- -1 ferric germanate Chemical compound 0.000 claims description 2
- 239000012792 core layer Substances 0.000 claims 1
- 238000005728 strengthening Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012633 leachable Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229960004029 silicic acid Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000003331 infrared imaging Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
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- 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
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Abstract
The invention relates to a method for enhancing deep leaching of germanium in germanium-containing zinc oxide smoke dust by countercurrent ultrasonic, belonging to the technical field of deep leaching of germanium. Adding germanium-containing zinc oxide smoke dust into a sulfuric acid solution A to perform primary leaching to obtain a pre-leaching solution and pre-leaching residues; adding the pre-leached slag into a sulfuric acid solution B for secondary leaching to obtain leached ore pulp; and (3) carrying out countercurrent ultrasonic enhanced leaching on the leached ore pulp from the bottom to the top by an ultrasonic leaching device to obtain enhanced leachate and leaching residues. According to the invention, the germanium is easily leached out on the surface layer and easily leached out on the middle layer through one-stage leaching, the germanium is difficult to leach out on the surface layer and the germanium is difficult to leach out on the middle layer through two-stage leaching, and the germanium is easily leached out and difficult to leach out on the central core through countercurrent ultrasonic strengthening, so that the leaching rate of the germanium is increased by more than 20%, the leaching rate reaches more than 90%, and the deep and efficient leaching of the germanium is realized.
Description
Technical Field
The invention relates to a method for enhancing deep leaching of germanium in germanium-containing zinc oxide smoke dust by countercurrent ultrasonic, belonging to the technical field of deep leaching of germanium.
Background
Germanium has high and uniform transmittance in the infrared band of 2-14 microns with the highest transparency of infrared rays in the atmosphere, and is an irreplaceable excellent optical material for an infrared imaging system, an infrared thermal imager, an infrared tracking system, a reconnaissance monitoring system and the like. Germanium tetrachloride doping can increase the refractive index of the fiber core, reduce optical loss and enable long-distance communication. The germanium substrate three-junction solar cell has the advantages of long service life, high photoelectric conversion efficiency and high temperature resistance, and is widely applied to space satellite solar cells and ground concentrating solar power stations.
The germanium-containing smoke dust is an important germanium extraction raw material, 44.57 percent of germanium in the world is extracted from zinc fuming smoke dust, the existing process mainly adopts an acid leaching process, but the leaching is only 70 to 80 percent due to fine and hard smoke dust particles and insufficient power of the traditional mechanical leaching. In the method for ultrasonically strengthening the germanium leaching in the zinc oxide smoke, the germanium is directly leached by low acid at one time, and the easily leached germanium and the surface germanium are also strengthened by ultrasonic, so that the strengthening energy consumption is increased. The three-stage leaching can strengthen the leaching of germanium, 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, and the generated silicic acid is separated out into slag in the form of hydrated silica protein, but the germanium in the smoke dust cannot be leached out.
Disclosure of Invention
The invention provides a method for strengthening deep leaching of germanium in germanium-containing zinc oxide smoke through countercurrent ultrasonic, aiming at the problems that germanium in smoke dust particles containing germanium is fine and hard and the leaching rate of germanium in the germanium-containing smoke dust particles is low in the prior art, namely, germanium in a fine and hard smoke dust core is sequentially leached through a section to easily leach germanium from a surface layer and a middle layer to easily leach germanium, germanium in a surface layer and a middle layer to difficultly leach germanium from a second section, the core is easily leached and the germanium is difficultly leached through the central core through countercurrent ultrasonic strengthening, the core is corroded by strong cavitation force of ultrasonic during the countercurrent ultrasonic strengthening leaching process to strengthen the leaching of the germanium, so that the leaching rate of the germanium is increased by more than 20%, the leaching rate reaches more than 90%, and the deep and efficient leaching of the germanium is realized.
A method for enhancing deep leaching of germanium in germanium-containing zinc oxide smoke by countercurrent ultrasonic comprises the following specific steps:
(1) Adding the germanium-containing zinc oxide smoke dust into a sulfuric acid solution A for primary leaching to obtain a pre-leaching solution and pre-leaching residues;
(2) Adding the pre-leached slag into a sulfuric acid solution B for secondary leaching to obtain leached ore pulp;
(3) Carrying out countercurrent ultrasonic enhanced leaching on the leached ore pulp from bottom to top by an ultrasonic leaching device to obtain enhanced leachate and leaching residues;
the germanium content in the smoke dust containing germanium and zinc oxide in the step (1) is 50-5000 g/t, and the germanium objects comprise hexagonal germanium dioxide, amorphous germanium dioxide, ferric germanate, zinc germanate, calcium germanate, lead germanate, silicate containing germanium and tetragonal germanium dioxide; the hexagonal germanium dioxide, amorphous germanium dioxide, ferric germanate and zinc germanate are easily leached germanium, and the content of the germanium in the easily leached germanium accounts for 50-90% of the weight of the germanium in the germanium-containing zinc oxide smoke dust; calcium germanate, lead germanate, silicate containing germanium and tetragonal germanium dioxide are difficult to leach germanium, and the content of germanium in the difficult-to-leach germanium accounts for 10-50% of the weight of germanium in the germanium-containing zinc oxide smoke;
the grain diameter of the germanium-containing zinc oxide smoke dust in the step (1) is 2-10 mu m, the volume of the surface layer accounts for 30-40% of the volume of the grains, the volume of the middle layer accounts for 40-50% of the volume of the grains, and the volume of the core body accounts for 10-30% of the volume of the grains;
the liquid-solid ratio mL of the sulfuric acid solution A to the germanium-containing zinc oxide smoke dust in the step (1) is (g) 4-15, the concentration of the sulfuric acid solution A is 60-150 g/L, the first-stage leaching temperature is 50-95 ℃, and the first-stage leaching time is 30-120 min;
g is 2-5:1, and the liquid-solid ratio of the sulfuric acid solution B to the pre-leaching residue in the step (2) is less than that of the sulfuric acid solution A to the germanium-containing zinc oxide smoke dust;
the concentration of the sulfuric acid solution B is 90-200 g/L, and the concentration of the sulfuric acid solution B is not lower than that of the sulfuric acid solution A;
the second-stage leaching temperature in the step (2) is 70-95 ℃, the second-stage leaching temperature is higher than the first-stage leaching temperature, and the second-stage leaching time is 60-240 min;
the ultrasonic leaching device in the step (3) gradually increases the ultrasonic intensity from the top to the bottom;
preferably, the ultrasonic intensity at the top of the ultrasonic leaching device is 5w/cm 2 The ultrasonic intensity of the bottom part was 10w/cm 2 The ultrasonic countercurrent enhanced leaching time of the ore pulp is 10-30 min;
the leaching rate of germanium in the first-stage leaching is 35-81%, the leaching rate of germanium in the second-stage leaching is 7-45%, the leaching rate of germanium in the countercurrent ultrasonic enhanced leaching is 9-27%, and the total leaching rate of germanium reaches 90-95%.
The beneficial effects of the invention are:
(1) According to the invention, the surface layer easy-to-leach germanium and the middle layer easy-to-leach germanium are sequentially leached in one stage, the surface layer hard-to-leach germanium and the middle layer hard-to-leach germanium are leached in the second stage, the central core easy-to-leach germanium and the middle layer hard-to-leach germanium are leached in a countercurrent ultrasonic strengthening manner, so that the leaching rate of germanium is increased by more than 20%, the leaching rate reaches more than 90%, and the deep and efficient leaching of germanium is realized;
(2) The energy consumption of the first-stage leaching and the second-stage leaching is low, and the treatment capacity is large; the advantages of ultrasonic countercurrent leaching of micromanipulation and strong cavitation force are utilized to realize leaching of internal hard nuclei, and deep leaching of germanium is realized under the optimal energy consumption;
(3) According to the invention, the germanium in the hard core of the core is treated by ultrasonic countercurrent leaching, namely the smaller the core is, the stronger the ultrasonic intensity is, and the deep leaching of the germanium can be realized;
(4) In metallurgy, a two-stage leaching process is generally adopted, wherein the first stage leaches easily-leachable phase, the time control is needed, the acid is low, the dissolution of impurities can be reduced, the second stage leaches difficultly-leachable phase, the high-temperature and high-acid time is needed for prolonging and reducing the liquid-solid ratio, although the impurities can be dissolved, the liquid-solid ratio is low, the dissolution balance is achieved after a period of time, the impurity leaching is relatively low, and the acid consumption is relatively high compared with the first stage leaching. The invention adopts a two-stage leaching process to strengthen the leaching of germanium, the initial concentration of germanium in the secondary leaching solution is 0, the forward proceeding of the germanium leaching is facilitated, and the process reaction is improved.
Drawings
FIG. 1 is a diagram of a leaching model according to the present invention;
FIG. 2 is a raw material morphology;
FIG. 3 shows the morphology of conventional three-stage leaching slag;
figure 4 is the leach residue profile of example 1.
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 and the nuclear distribution of germanium in the lead-zinc smelting germanium-containing smoke dust in the embodiment are shown in tables 1 and 2,
TABLE 1 Smoke germanium phase distribution
TABLE 2 Smoke germanium phase distribution
As can be seen from the table, the content of germanium in the smoke dust is 50g/t, and the easily leached germanium in the smoke dust mainly comprises hexagonal germanium dioxide, amorphous germanium dioxide, ferric germanate and zinc germanate, and the proportion is 90 percent; the difficult-to-leach germanium mainly comprises calcium germanate, lead germanate, germanium-containing silicate and tetragonal germanium dioxide, the proportion is 10%, the particle size of smoke dust is 2 mu m, the volume of a surface layer accounts for 30% of the volume of particles, the volume of a middle layer accounts for 40% of the volume of the particles, and the volume of a core body accounts for 30% of the volume of the particles;
a method for enhancing the deep leaching of germanium in germanium-containing zinc oxide smoke by countercurrent ultrasonic (see figure 1) comprises the following specific steps:
(1) Adding the germanium-containing zinc oxide smoke dust into a sulfuric acid solution A with the concentration of 60g/L, carrying out primary leaching for 30min at the temperature of 50 ℃, and carrying out solid-liquid separation to obtain a pre-leaching solution and pre-leaching residues; wherein the liquid-solid ratio mL of the sulfuric acid solution A to the germanium-containing zinc oxide smoke is 4:1;
(2) Adding the pre-leached slag into a sulfuric acid solution B with the concentration of 90g/L, and performing secondary leaching at the temperature of 70 ℃ for 60min to obtain leached ore pulp; wherein the liquid-solid ratio mL of the sulfuric acid solution B to the germanium-containing zinc oxide smoke is 2:1;
(3) Reversing the leach pulp from bottom to topCarrying out countercurrent ultrasonic enhanced leaching on the flow for 10min by an ultrasonic leaching tank to obtain an enhanced leaching solution and leaching residues; wherein the ultrasonic intensity of the ultrasonic leaching device is gradually increased from the top to the bottom, and the ultrasonic intensity of the top of the ultrasonic leaching device is 5w/cm 2 The ultrasonic intensity of the bottom is 10w/cm 2 ；
The morphology of the germanium-containing zinc oxide smoke dust as the raw material is shown in figure 2, the morphology of the conventional three-stage leaching residue is shown in figure 3, and the morphology of the leaching residue in the embodiment is shown in figure 4, as can be seen from figures 2-4, the germanium-containing zinc oxide smoke dust is hard and compact hexagonal solid particles, when the conventional three-stage leaching is carried out, the leaching power is insufficient, only the surface layer of the smoke dust particles is washed, and the leaching residue is in a local crack shape; under the condition of two-stage leaching and countercurrent ultrasonic reinforcement, the stirring power is more sufficient, a large number of micropores are flushed on the surface of smoke dust, and the leaching rate of germanium can be greatly improved;
in this example, the leaching rate of germanium in the first-stage leaching is 60%, the leaching rate of germanium in the second-stage leaching is 7%, the leaching rate of germanium in the countercurrent ultrasonic enhanced leaching is 23%, and the total leaching rate of germanium reaches 90%.
Example 2: in the embodiment, the phase distribution and the nuclear distribution of germanium in the lead-zinc smelting germanium-containing smoke dust are shown in tables 3 and 4,
TABLE 3 Smoke germanium phase distribution
TABLE 4 Smoke germanium phase distribution
As can be seen from the table, the content of germanium in the smoke dust is 1000g/t, and the easily leached germanium in the smoke dust mainly comprises hexagonal germanium dioxide, amorphous germanium dioxide, ferric germanate and zinc germanate, and accounts for 60 percent; the difficult-to-leach germanium mainly comprises calcium germanate, lead germanate, germanium-containing silicate and tetragonal germanium dioxide, the proportion is 40%, the particle size of smoke dust is 4 mu m, the volume of a surface layer accounts for 35% of the volume of particles, the volume of a middle layer accounts for 45% of the volume of the particles, and the volume of a core body accounts for 20% of the volume of the particles;
a method for enhancing the deep leaching of germanium in germanium-containing zinc oxide smoke by countercurrent ultrasonic (see figure 1) comprises the following specific steps:
(1) Adding the germanium-containing zinc oxide smoke dust into a sulfuric acid solution A with the concentration of 100g/L, carrying out primary leaching for 100min at the temperature of 75 ℃, and carrying out solid-liquid separation to obtain a pre-leaching solution and pre-leaching residues; wherein the liquid-solid ratio mL/g of the sulfuric acid solution A to the germanium-containing zinc oxide smoke dust is 10;
(2) Adding the pre-leached slag into a sulfuric acid solution B with the concentration of 130g/L, and performing secondary leaching at the temperature of 85 ℃ for 200min to obtain leached ore pulp; wherein the liquid-solid ratio mL of the sulfuric acid solution B to the germanium-containing zinc oxide smoke is 4:1;
(3) Carrying out countercurrent ultrasonic enhanced leaching on the leached ore pulp from the bottom to the top for 20min by an ultrasonic leaching tank to obtain an enhanced leaching solution and leaching residues; wherein the ultrasonic intensity of the ultrasonic leaching device is gradually increased from the top to the bottom, and the ultrasonic intensity of the top of the ultrasonic leaching device is 5w/cm 2 The ultrasonic intensity of the bottom is 10w/cm 2 ；
In this example, the leaching rate of germanium in the first-stage leaching is 45%, the leaching rate of germanium in the second-stage leaching is 28%, the leaching rate of germanium in the countercurrent ultrasonic enhanced leaching is 19%, and the total leaching rate of germanium reaches 92%.
Example 3: the phase distribution and the nuclear distribution of germanium in the lead-zinc smelting germanium-containing smoke dust in the embodiment are shown in tables 5 and 6,
TABLE 5 Smoke germanium phase distribution
TABLE 6 Smoke germanium phase distribution
As can be seen from the table, the content of germanium in the smoke dust is 5000g/t, and the easily leached germanium in the smoke dust mainly comprises hexagonal germanium dioxide, amorphous germanium dioxide, ferric germanate and zinc germanate, and accounts for 50 percent; the difficult-to-leach germanium mainly comprises calcium germanate, lead germanate, germanium-containing silicate and tetragonal germanium dioxide, the proportion is 50%, the particle size of smoke dust is 10 mu m, the volume of a surface layer accounts for 40% of the volume of particles, the volume of a middle layer accounts for 50% of the volume of the particles, and the volume of a core body accounts for 10% of the volume of the particles;
a method for enhancing the deep leaching of germanium in germanium-containing zinc oxide smoke by countercurrent ultrasonic (see figure 1) comprises the following specific steps:
(1) Adding the germanium-containing zinc oxide smoke dust into a sulfuric acid solution A with the concentration of 150g/L, performing primary leaching for 120min at the temperature of 90 ℃, and performing solid-liquid separation to obtain a pre-leaching solution and pre-leaching residues; wherein the liquid-solid ratio mL/g of the sulfuric acid solution A to the germanium-containing zinc oxide smoke dust is 15;
(2) Adding the pre-leached slag into a sulfuric acid solution B with the concentration of 200g/L, and performing secondary leaching at the temperature of 95 ℃ for 240min to obtain leached ore pulp; wherein the liquid-solid ratio mL of the sulfuric acid solution B to the germanium-containing zinc oxide smoke is 5:1;
(3) Carrying out countercurrent ultrasonic enhanced leaching on the leached ore pulp from the bottom to the top for 20min by an ultrasonic leaching tank to obtain an enhanced leaching solution and leaching residues; wherein the ultrasonic intensity of the ultrasonic leaching device is gradually increased from the top to the bottom, and the ultrasonic intensity of the top of the ultrasonic leaching device is 5w/cm 2 The ultrasonic intensity of the bottom part was 10w/cm 2 ；
In this example, the leaching rate of germanium in the first-stage leaching is 42%, the leaching rate of germanium in the second-stage leaching is 38%, the leaching rate of germanium in the countercurrent ultrasonic enhanced leaching is 15%, and the total leaching rate of germanium reaches 95%.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
Claims (9)
1. A method for enhancing the deep leaching of germanium in germanium-containing zinc oxide smoke dust by countercurrent ultrasonic is characterized by comprising the following steps: the method comprises the following specific steps:
(1) Adding the germanium-containing zinc oxide smoke dust into a sulfuric acid solution A for primary leaching to obtain a pre-leaching solution and pre-leaching residues;
(2) Adding the pre-leached slag into a sulfuric acid solution B for secondary leaching to obtain leached ore pulp;
(3) And carrying out countercurrent ultrasonic enhanced leaching on the leached ore pulp from bottom to top by an ultrasonic leaching device to obtain an enhanced leaching solution and leaching residues.
2. The method for enhancing the deep leaching of germanium in the germanium-containing zinc oxide smoke through the countercurrent ultrasonic waves as claimed in claim 1, wherein the method comprises the following steps: the germanium content in the smoke dust containing germanium and zinc oxide in the step (1) is 50-5000 g/t, and the germanium objects comprise hexagonal germanium dioxide, amorphous germanium dioxide, ferric germanate, zinc germanate, calcium germanate, lead germanate, silicate containing germanium and tetragonal germanium dioxide.
3. The method for enhancing the deep leaching of germanium in the germanium-containing zinc oxide smoke through the countercurrent ultrasonic waves as claimed in claim 1, wherein the method comprises the following steps: the grain diameter of the germanium-containing zinc oxide smoke dust in the step (1) is 2-10 mu m, the volume of the surface layer accounts for 30-40% of the volume of the grains, the volume of the middle layer accounts for 40-50% of the volume of the grains, and the volume of the core layer accounts for 10-30% of the volume of the grains.
4. The method for enhancing the deep leaching of germanium in the germanium-containing zinc oxide smoke through the countercurrent ultrasonic waves as claimed in claim 1, wherein the method comprises the following steps: the liquid-solid ratio mL/g of the sulfuric acid solution A to the germanium-containing zinc oxide smoke dust in the step (1) is 4-15, the concentration of the sulfuric acid solution A is 60-150 g/L, the first-stage leaching temperature is 50-95 ℃, and the first-stage leaching time is 30-120 min.
5. The method for enhancing the deep leaching of germanium in the germanium-containing zinc oxide smoke through the countercurrent ultrasonic waves as claimed in claim 1, wherein the method comprises the following steps: and (3) the liquid-solid ratio mL of the sulfuric acid solution B to the pre-leaching residue in the step (2) is 2-5:1, and the liquid-solid ratio of the sulfuric acid solution B to the pre-leaching residue is smaller than that of the sulfuric acid solution A to the germanium-containing zinc oxide smoke dust.
6. The method for enhancing the deep leaching of germanium in the germanium-containing zinc oxide smoke dust by the countercurrent ultrasonic waves as claimed in claim 5, wherein the method comprises the following steps: the concentration of the sulfuric acid solution B is 90-200 g/L, and the concentration of the sulfuric acid solution B is not lower than that of the sulfuric acid solution A.
7. The method for enhancing the deep leaching of germanium in the germanium-containing zinc oxide smoke dust by the countercurrent ultrasonic waves as claimed in claim 6, wherein the method comprises the following steps: the second-stage leaching temperature is 70-95 ℃, the second-stage leaching temperature is higher than the first-stage leaching temperature, and the second-stage leaching time is 60-240 min.
8. The method for enhancing the deep leaching of germanium in the germanium-containing zinc oxide smoke through the countercurrent ultrasonic waves as claimed in claim 1, wherein the method comprises the following steps: and (3) gradually increasing the ultrasonic intensity of the ultrasonic leaching device from the top to the bottom.
9. The method for enhancing the deep leaching of germanium in the germanium-containing zinc oxide smoke through the countercurrent ultrasonic waves as claimed in claim 8, wherein the method comprises the following steps: the ultrasonic intensity at the top of the ultrasonic leaching device is 5w/cm 2 The ultrasonic intensity of the bottom is 10w/cm 2 The ultrasonic countercurrent reinforced leaching time of the ore pulp is 10-30 min.
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