CN115011800B - Method for separating indium and germanium from zinc oxide smoke dust - Google Patents
Method for separating indium and germanium from zinc oxide smoke dust Download PDFInfo
- Publication number
- CN115011800B CN115011800B CN202210030470.7A CN202210030470A CN115011800B CN 115011800 B CN115011800 B CN 115011800B CN 202210030470 A CN202210030470 A CN 202210030470A CN 115011800 B CN115011800 B CN 115011800B
- Authority
- CN
- China
- Prior art keywords
- germanium
- indium
- leaching
- low
- slag
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 112
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 106
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 53
- 239000000779 smoke Substances 0.000 title claims abstract description 51
- 239000000428 dust Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002386 leaching Methods 0.000 claims abstract description 135
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 130
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000011701 zinc Substances 0.000 claims abstract description 78
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 74
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 69
- 239000002893 slag Substances 0.000 claims abstract description 56
- SAZXSKLZZOUTCH-UHFFFAOYSA-N germanium indium Chemical compound [Ge].[In] SAZXSKLZZOUTCH-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002253 acid Substances 0.000 claims abstract description 34
- 230000007935 neutral effect Effects 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000001556 precipitation Methods 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 21
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 239000012141 concentrate Substances 0.000 claims abstract description 11
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- 239000011133 lead Substances 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- 229920001864 tannin Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GIEKGJMFQVAGJK-UHFFFAOYSA-N [O-2].[Zn+2].[Ge+2].[O-2] Chemical compound [O-2].[Zn+2].[Ge+2].[O-2] GIEKGJMFQVAGJK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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
- C22B7/02—Working-up flue dust
-
- 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
- C22B58/00—Obtaining gallium or indium
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for separating indium and germanium from zinc oxide smoke dust, and belongs to the technical field of hydrometallurgy. Mixing indium-germanium-containing zinc oxide smoke dust with a low-concentration sulfuric acid solution of zinc hydrometallurgy, and carrying out neutral germanium leaching to a final pH value of 2.5-3.5 to obtain a neutral leaching solution and a neutral leaching residue; the medium leaching solution is subjected to germanium precipitation separation to obtain germanium concentrate and germanium precipitation rear solution, medium leaching slag is mixed with a zinc hydrometallurgy high-concentration sulfuric acid solution, and low-leaching indium is carried out to a final pH value of 0.5-1.0 to obtain low leaching solution and low leaching slag; neutralizing indium germanium from low-leaching liquid by using zinc oxide smoke dust containing indium germanium to precipitate indium germanium to a final pH value of 4.0-5.0 to obtain neutralized liquid and indium germanium neutralization slag, and leaching, extracting and electrodepositing the indium germanium neutralization slag to obtain a refined indium product; mixing the low leaching slag with the zinc hydrometallurgy electrolysis waste liquid, carrying out high acid reinforcement leaching to obtain high leaching liquid and high leaching slag at a final pH value of 0.1-0.3, and washing and press-filtering the high leaching slag to obtain washing water and lead silver slag products. The method has high indium and germanium recovery rate, and can effectively realize the separation and recovery of indium and germanium in zinc oxide smoke dust.
Description
Technical Field
The invention relates to a method for separating indium and germanium from zinc oxide smoke dust, and belongs to the technical field of hydrometallurgy.
Background
The zinc leaching residue of the wet zinc smelting process is one of the important resources for extracting indium and germanium at present, and the method for recovering germanium from the zinc leaching residue containing indium and germanium mainly comprises wet high-temperature high-acid leaching and pyrogenic reduction volatilization-zinc oxide smoke leaching. At present, the zinc smelting process in China is mainly a traditional conventional process, so that indium and germanium are mainly extracted from zinc oxide smoke dust containing indium and germanium by a wet method.
Zinc oxide fume is an intermediate raw material mainly containing zinc and lead, which is produced after wet zinc smelting and fire lead smelting slag are treated by adopting a fire fuming volatilization method, and is rich in one or more rare metals such as indium, germanium and the like. The current zinc oxide smoke treatment process commonly adopts two-stage acid leaching to obtain lead-rich leaching residues and leaching liquid rich in rare metals, the leaching residues are used for recycling lead and silver, and the leaching liquid is used for separating and recycling the rare metals.
Because of the limitation of rare metal content, technical and economic indexes and other conditions in zinc oxide smoke, only one rare metal in the zinc oxide smoke generally has the economic value of recovery, so that the prior art only carries out single recovery on one rare metal in the zinc oxide smoke, for example, the zinc oxide smoke with higher indium content mainly adopts leaching liquid to neutralize precipitation and enrich indium to obtain indium-rich slag, and then carries out sulfuric acid leaching-extraction-electrodeposition recovery on the indium-rich slag; zinc oxide dust with higher germanium content is mainly prepared by carrying out tannin precipitation and germanium enrichment on leaching liquid to obtain germanium concentrate, and then carrying out hydrochloric acid leaching-chloridizing distillation-hydrolysis on the germanium concentrate to recover germanium.
Along with the improvement of the comprehensive recovery requirement in industry, the recovery of indium and germanium in zinc oxide smoke dust, especially the separation and recovery of indium and germanium in zinc oxide smoke dust containing indium and germanium at the same time are very important, and the technology of single recovery of indium or germanium is difficult to meet the raw material change and smelting requirement of enterprises. Therefore, the development of a method for separating and recycling indium and germanium from indium-germanium-containing zinc oxide dust is of great significance.
Disclosure of Invention
The invention aims at the problem of separating and recycling indium and germanium in indium and germanium zinc oxide smoke dust, and provides a method for separating indium and germanium from zinc oxide smoke dust.
A method for separating indium and germanium from zinc oxide smoke dust comprises the following specific steps:
(1) Mixing indium-germanium-containing zinc oxide smoke dust with a zinc hydrometallurgy low-concentration sulfuric acid solution for size mixing, and performing neutral germanium leaching on the mixed ore pulp until the end point pH value is 2.5-3.5 to obtain a neutral leaching solution and a neutral leaching residue;
(2) Carrying out precipitation separation on germanium on the immersion liquid obtained in the step (1) to obtain germanium concentrate and germanium-precipitated liquid, and conveying the germanium-precipitated liquid to a zinc hydrometallurgy system for recycling;
(3) Mixing the neutral leaching slag obtained in the step (1) with a high-concentration sulfuric acid solution of zinc hydrometallurgy, and carrying out low-acid leaching of indium until the pH value reaches a terminal point of 0.5-1.0 to obtain low leaching liquid and low leaching slag;
(4) Neutralizing the low-leaching liquid obtained in the step (3) by indium-germanium-containing zinc oxide smoke dust until the pH value of the end point is 4.0-5.0, and obtaining neutralized liquid and indium-germanium neutralization slag; when the indium content in the indium-germanium neutralization slag is not less than 1wt% (namely the indium-germanium neutralization slag is indium-rich germanium slag), the indium-rich germanium slag is sent to an indium recovery system for leaching-extraction-electrodeposition, so as to obtain a refined indium product and germanium-containing raffinate; returning to the step (3) for low-acid leaching of indium when the indium content in the indium-germanium neutralization slag is less than 1 wt%; the neutralized liquid and germanium-containing raffinate are used as zinc hydrometallurgy low-concentration sulfuric acid solution to return to the step (1) to replace the zinc hydrometallurgy low-concentration sulfuric acid solution for mixing and pulping indium-germanium-containing zinc oxide smoke dust;
(5) Mixing the low leaching slag obtained in the step (3) with zinc hydrometallurgy electrolysis waste liquid, carrying out high-acid intensified leaching until the end point pH value is 0.1-0.3, obtaining high leaching liquid and high leaching slag, returning the high leaching liquid as zinc hydrometallurgy high-concentration sulfuric acid solution to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid indium leaching, washing and press-filtering the high leaching slag, producing washing water and lead silver slag products, and returning the washing water to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid indium leaching.
The indium-germanium-containing zinc oxide smoke dust in the step (1) contains 0.03-0.20wt% of germanium and 0.02-0.15wt% of indium;
the indium-germanium-containing zinc oxide smoke dust also contains zinc, iron, lead and silver;
the concentration of sulfuric acid in the zinc hydrometallurgy low-concentration sulfuric acid solution in the step (1) is 30-50 g/L, the temperature of neutral germanium leaching is 80-90 ℃ and the time is 1.5-2 h;
the precipitation separation of the germanium in the step (2) can adopt known tannin germanium precipitation or other known germanium precipitation methods;
the concentration of sulfuric acid in the high-concentration sulfuric acid solution of the zinc hydrometallurgy in the step (3) is 60-80 g/L, the temperature of low-acid indium leaching is 80-90 ℃, and the time is 2-2.5 h;
the solid-liquid ratio g of the indium-germanium-containing zinc oxide smoke dust and the low-leaching liquid in the step (4) is 20-40:1;
the concentration of sulfuric acid in the zinc hydrometallurgy electrolysis waste liquid in the step (5) is 140-180 g/L, the temperature of high-acid intensified leaching is 80-90 ℃, and the time is 2.5-3 h.
The beneficial effects of the invention are as follows:
(1) According to the invention, by three-stage leaching, the acidity of the reaction process is regulated and controlled by utilizing the difference of leaching characteristics of indium and germanium, and the indium and the germanium are leached step by step, and the neutral germanium leaching is carried out by controlling higher pH value in the first stage leaching, so that most germanium is leached to obtain a solution capable of precipitating and recycling germanium, and indium is not leached; the second stage leaching is controlled to lower pH value for low acid leaching of indium, so that indium and a small part of germanium left in the first stage leaching are leached; three-stage high acid strengthening leaching to further improve the leaching rate of indium and germanium;
(2) The method comprises the steps of carrying out precipitation separation and enrichment on an indium-germanium-containing solution of second-stage low-acid indium leaching to obtain indium-germanium-rich slag, carrying out indium-germanium leaching to obtain the indium-germanium-containing solution, carrying out solvent extraction separation and recovery of indium and germanium by utilizing different extraction characteristics of indium and germanium, carrying out extraction separation and enrichment of indium to obtain a pure indium-containing solution, leaving germanium in the solution, and returning the solution to the first-stage neutral germanium leaching in a raffinate form to obtain a solution capable of precipitating and recovering germanium, thereby realizing separation and extraction of indium and germanium in zinc oxide smoke dust.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: a method for separating indium and germanium from zinc oxide smoke dust comprises the following specific steps:
(1) Mixing indium-germanium-containing zinc oxide smoke dust with a zinc hydrometallurgy low-concentration sulfuric acid solution, and pulping, wherein the mixed pulp is subjected to neutral germanium leaching at the temperature of 80 ℃ for 2 hours until the end point pH value is 3.06, so as to obtain a neutral leaching solution and a neutral leaching residue; the indium-germanium-containing zinc oxide fume contains 45.89wt% of zinc, 6.31wt% of iron, 11.62wt% of lead, 156g/t of silver, 0.03wt% of germanium and 0.08wt% of indium; the zinc hydrometallurgy low-concentration sulfuric acid solution is zinc hydrometallurgy electrolysis waste liquid adjusted by adding water, and the sulfuric acid concentration in the zinc hydrometallurgy low-concentration sulfuric acid solution is 42.56g/L;
(2) Carrying out precipitation separation of germanium on the immersion liquid obtained in the step (1) by a tannin germanium precipitation method to obtain germanium concentrate and germanium precipitation liquid, and conveying the germanium precipitation liquid to a zinc hydrometallurgy system for recycling;
(3) Mixing the neutral leaching residue obtained in the step (1) with a zinc hydrometallurgy high-concentration sulfuric acid solution, and carrying out low-acid indium leaching at 90 ℃ for 2 hours until the end point pH value is 0.72, thereby obtaining low leaching liquid and low leaching residue; the zinc hydrometallurgy high-concentration sulfuric acid solution is zinc hydrometallurgy electrolysis waste liquid adjusted by adding water, and the sulfuric acid concentration in the zinc hydrometallurgy high-concentration sulfuric acid solution is 71.52g/L;
(4) Neutralizing the low-leaching liquid obtained in the step (3) by indium-germanium-containing zinc oxide smoke dust at 70 ℃ for precipitating indium and germanium for 1.5 hours until the end point pH value is 4.96, and obtaining neutralized liquid and indium-germanium neutralized slag, wherein the solid-liquid ratio g of the indium-germanium-containing zinc oxide smoke dust to the low-leaching liquid is 30:1; returning to the step (3) for low-acid leaching of indium, and repeating the steps (3) and (4) until the indium content in the indium-germanium neutralization slag is 1.46wt% (namely, the indium-germanium neutralization slag is indium-rich germanium slag), and sending the indium-germanium neutralization slag to an indium recovery system for leaching-extraction-electrodeposition to obtain a refined indium product and germanium-containing raffinate; the neutralized liquid and germanium-containing raffinate are used as zinc hydrometallurgy low-concentration sulfuric acid solution to return to the step (1) to replace the zinc hydrometallurgy low-concentration sulfuric acid solution for mixing and pulping indium-germanium-containing zinc oxide smoke dust;
(5) Mixing the low leaching residue obtained in the step (3) with zinc hydrometallurgy electrolysis waste liquid, and carrying out high-acid enhanced leaching at 90 ℃ for 2.5 hours until the end point pH value is 0.23 to obtain high leaching liquid and high leaching residue, wherein the sulfuric acid concentration in the zinc hydrometallurgy electrolysis waste liquid is 168g/L; the high leaching solution is used as a zinc hydrometallurgy high-concentration sulfuric acid solution to be returned to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid leaching of indium, the high leaching slag is washed and filter-pressed to produce washing water and lead silver slag products, and the washing water is returned to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid leaching of indium;
the recovery rate of germanium in the zinc oxide smoke dust is 85.76%, and the grade of germanium concentrate is 4.73%; the recovery rate of indium is 86.25%, and the purity of the refined indium product is 99.995%.
Example 2: a method for separating indium and germanium from zinc oxide smoke dust comprises the following specific steps:
(1) Mixing indium-germanium-containing zinc oxide smoke dust with a zinc hydrometallurgy low-concentration sulfuric acid solution (the neutralized liquid produced in the step (4) of the embodiment 1 and germanium-containing raffinate), and pulping, wherein the mixed pulp is subjected to neutral germanium leaching at the temperature of 85 ℃ for 2h until the end point pH value is 3.48, so as to obtain a neutral leaching liquid and a neutral leaching slag; the indium-germanium-containing zinc oxide fume contains 37.51wt% of zinc, 13.15wt% of iron, 13.62wt% of lead, 218g/t of silver, 0.20wt% of germanium and 0.15wt% of indium; the concentration of sulfuric acid in the zinc hydrometallurgy low-concentration sulfuric acid solution is 31.05g/L;
(2) Carrying out precipitation separation on germanium on the immersion liquid obtained in the step (1) by a neutralization germanium precipitation method to obtain germanium concentrate and germanium precipitation liquid, and conveying the germanium precipitation liquid to a zinc hydrometallurgy system for recycling;
(3) Mixing the neutral leaching residue obtained in the step (1) with a zinc hydrometallurgy high-concentration sulfuric acid solution (high leaching solution and washing water produced in the step (5) of the example 1), and carrying out low-acid leaching of indium at the temperature of 85 ℃ for 2.5 hours until the end point pH value is 0.51, thereby obtaining low leaching solution and low leaching residue; the concentration of sulfuric acid in the zinc hydrometallurgy high-concentration sulfuric acid solution is 79.58g/L;
(4) Neutralizing the low-leaching liquid obtained in the step (3) by indium-germanium-containing zinc oxide smoke dust at the temperature of 80 ℃ for precipitating indium and germanium for 2.0 hours until the end point pH value is 4.91, and obtaining neutralized liquid and indium-germanium neutralized slag, wherein the solid-liquid ratio g of the indium-germanium-containing zinc oxide smoke dust to the low-leaching liquid is 40:1; when the indium content in the indium-germanium neutralization slag is 1.13wt% (namely the indium-germanium neutralization slag is indium-rich germanium slag), the indium-rich germanium slag is sent to an indium recovery system for leaching-extraction-electrodeposition, so as to obtain a refined indium product and germanium-containing raffinate; the neutralized liquid and germanium-containing raffinate are used as zinc hydrometallurgy low-concentration sulfuric acid solution to return to the step (1) to replace the zinc hydrometallurgy low-concentration sulfuric acid solution for mixing and pulping indium-germanium-containing zinc oxide smoke dust;
(5) Mixing the low leaching residue obtained in the step (3) with zinc hydrometallurgy electrolysis waste liquid, and carrying out high-acid intensified leaching at the temperature of 80 ℃ for 3.0h until the end point pH value is 0.12 to obtain high leaching liquid and high leaching residue, wherein the sulfuric acid concentration in the zinc hydrometallurgy electrolysis waste liquid is 179g/L; the high leaching solution is used as a zinc hydrometallurgy high-concentration sulfuric acid solution to be returned to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid leaching of indium, the high leaching slag is washed and filter-pressed to produce washing water and lead silver slag products, and the washing water is returned to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid leaching of indium;
the recovery rate of germanium in the zinc oxide smoke dust is 84.96%, and the grade of germanium concentrate is 2.96%; the recovery rate of indium is 85.37%, and the purity of the refined indium product is 99.995%.
Example 3: a method for separating indium and germanium from zinc oxide smoke dust comprises the following specific steps:
(1) Mixing indium-germanium-containing zinc oxide smoke dust with zinc hydrometallurgy low-concentration sulfuric acid solution (neutralized liquid produced in the step (4) of the embodiment 2 and germanium-containing raffinate), and pulping, wherein the mixed pulp is subjected to neutral germanium leaching at the temperature of 90 ℃ for 1.5 hours until the end point pH value is 2.52, so as to obtain a neutral leaching liquid and a neutral leaching slag; the indium-germanium-containing zinc oxide smoke dust contains 56.74wt% of zinc, 2.31wt% of iron, 8.57wt% of lead, 70g/t of silver, 0.09wt% of germanium and 0.02wt% of indium; the concentration of sulfuric acid in the zinc hydrometallurgy low-concentration sulfuric acid solution is 49.27g/L;
(2) Carrying out precipitation separation on germanium on the immersion liquid obtained in the step (1) by a zinc powder germanium precipitation method to obtain germanium concentrate and germanium precipitation liquid, and conveying the germanium precipitation liquid to a zinc hydrometallurgy system for recycling;
(3) Mixing the neutral leaching residue obtained in the step (1) with a zinc hydrometallurgy high-concentration sulfuric acid solution (high leaching solution and washing water produced in the step (5) of the example 2), and carrying out low-acid leaching of indium at the temperature of 80 ℃ for 2.5 hours until the end point pH value is 1.0, thereby obtaining low leaching solution and low leaching residue; the concentration of sulfuric acid in the zinc hydrometallurgy high-concentration sulfuric acid solution is 60.63g/L;
(4) Neutralizing the low-leaching liquid obtained in the step (3) by indium-germanium-containing zinc oxide smoke dust at the temperature of 60 ℃ for precipitating indium and germanium for 1.0h until the end point pH value is 4.08, and obtaining neutralized liquid and indium-germanium neutralized slag, wherein the solid-liquid ratio g of the indium-germanium-containing zinc oxide smoke dust to the low-leaching liquid is 20:1; returning to the step (3) for low-acid leaching of indium, and repeating the steps (3) and (4) until the indium content in the indium-germanium neutralization slag is 1.05wt% (namely, the indium-germanium neutralization slag is indium-rich germanium slag), and sending the indium-germanium neutralization slag to an indium recovery system for leaching-extraction-electrodeposition to obtain a refined indium product and germanium-containing raffinate; the neutralized liquid and germanium-containing raffinate are used as zinc hydrometallurgy low-concentration sulfuric acid solution to return to the step (1) to replace the zinc hydrometallurgy low-concentration sulfuric acid solution for mixing and pulping indium-germanium-containing zinc oxide smoke dust;
(5) Mixing the low leaching residue obtained in the step (3) with zinc hydrometallurgy electrolysis waste liquid, and carrying out high-acid enhanced leaching at the temperature of 85 ℃ for 3.0h until the end point pH value is 0.29 to obtain high leaching liquid and high leaching residue, wherein the sulfuric acid concentration in the zinc hydrometallurgy electrolysis waste liquid is 143g/L; the high leaching solution is used as a zinc hydrometallurgy high-concentration sulfuric acid solution to be returned to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid leaching of indium, the high leaching slag is washed and filter-pressed to produce washing water and lead silver slag products, and the washing water is returned to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid leaching of indium;
the recovery rate of germanium in the zinc oxide smoke dust is 87.13%, and the grade of germanium concentrate is 3.26%; the recovery rate of indium is 85.86%, and the purity of the refined indium product is 99.996%.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. The method for separating indium and germanium from zinc oxide smoke dust is characterized by comprising the following specific steps:
(1) Mixing indium-germanium-containing zinc oxide smoke dust with a zinc hydrometallurgy low-concentration sulfuric acid solution for size mixing, and performing neutral germanium leaching on the mixed ore pulp until the end point pH value is 2.5-3.5 to obtain a neutral leaching solution and a neutral leaching residue; the concentration of sulfuric acid in the zinc hydrometallurgy low-concentration sulfuric acid solution is 30-50 g/L, the temperature of neutral germanium leaching is 80-90 ℃ and the time is 1.5-2 h;
(2) Carrying out precipitation separation on germanium on the immersion liquid obtained in the step (1) to obtain germanium concentrate and germanium-precipitated liquid, and conveying the germanium-precipitated liquid to a zinc hydrometallurgy system for recycling;
(3) Mixing the neutral leaching slag obtained in the step (1) with a high-concentration sulfuric acid solution of zinc hydrometallurgy, and carrying out low-acid leaching of indium until the pH value reaches a terminal point of 0.5-1.0 to obtain low leaching liquid and low leaching slag;
(4) Neutralizing the low-leaching liquid obtained in the step (3) by indium-germanium-containing zinc oxide smoke dust until the pH value of the end point is 4.0-5.0, and obtaining neutralized liquid and indium-germanium neutralization slag; when the indium content in the indium-germanium neutralization slag is not less than 1wt%, the indium is sent to an indium recovery system for leaching-extraction-electrodeposition, so as to obtain a refined indium product and germanium-containing raffinate; returning to the step (3) for low-acid leaching of indium when the indium content in the indium-germanium neutralization slag is less than 1 wt%; the neutralized liquid and germanium-containing raffinate are used as zinc hydrometallurgy low-concentration sulfuric acid solution to return to the step (1) to replace the zinc hydrometallurgy low-concentration sulfuric acid solution for mixing and pulping indium-germanium-containing zinc oxide smoke dust;
(5) Mixing the low leaching slag obtained in the step (3) with zinc hydrometallurgy electrolysis waste liquid, carrying out high-acid intensified leaching until the end point pH value is 0.1-0.3, obtaining high leaching liquid and high leaching slag, returning the high leaching liquid as zinc hydrometallurgy high-concentration sulfuric acid solution to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid indium leaching, washing and press-filtering the high leaching slag, producing washing water and lead silver slag products, and returning the washing water to the step (3) to replace the zinc hydrometallurgy high-concentration sulfuric acid solution for low-acid indium leaching; the concentration of sulfuric acid in the zinc hydrometallurgy electrolysis waste liquid is 140-180 g/L, the high-acid intensified leaching temperature is 80-90 ℃, and the time is 2.5-3 h.
2. The method for separating indium and germanium from zinc oxide fume according to claim 1, wherein: the smoke dust of the zinc oxide containing indium and germanium in the step (1) contains 0.03 to 0.20 weight percent of germanium and 0.02 to 0.15 weight percent of indium.
3. The method for separating indium and germanium from zinc oxide fume according to claim 2, wherein: the indium-germanium-containing zinc oxide dust also contains zinc, iron, lead and silver.
4. The method for separating indium and germanium from zinc oxide fume according to claim 1, wherein: the concentration of sulfuric acid in the high-concentration sulfuric acid solution of the zinc hydrometallurgy in the step (3) is 60-80 g/L, the temperature of low-acid leaching indium is 80-90 ℃, and the time is 2-2.5 h.
5. The method for separating indium and germanium from zinc oxide fume according to claim 1, wherein: and (4) the solid-liquid ratio g of the indium-germanium-containing zinc oxide smoke dust and the low-leaching liquid is 20-40:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210030470.7A CN115011800B (en) | 2022-01-12 | 2022-01-12 | Method for separating indium and germanium from zinc oxide smoke dust |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210030470.7A CN115011800B (en) | 2022-01-12 | 2022-01-12 | Method for separating indium and germanium from zinc oxide smoke dust |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115011800A CN115011800A (en) | 2022-09-06 |
| CN115011800B true CN115011800B (en) | 2024-03-19 |
Family
ID=83064426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210030470.7A Active CN115011800B (en) | 2022-01-12 | 2022-01-12 | Method for separating indium and germanium from zinc oxide smoke dust |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115011800B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882228A (en) * | 2013-12-20 | 2014-06-25 | 河南豫光锌业有限公司 | Method for enrichment and recovery of gallium and germanium from raffinate of indium smelting system |
| CN109897966A (en) * | 2019-03-29 | 2019-06-18 | 何耀 | A kind of secondary zinc oxide raw material high-efficiency resource recycling method |
| CN110117723A (en) * | 2019-05-10 | 2019-08-13 | 昆明理工大学 | A kind of richness germanium zinc oxide fumes leaching method |
-
2022
- 2022-01-12 CN CN202210030470.7A patent/CN115011800B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882228A (en) * | 2013-12-20 | 2014-06-25 | 河南豫光锌业有限公司 | Method for enrichment and recovery of gallium and germanium from raffinate of indium smelting system |
| CN109897966A (en) * | 2019-03-29 | 2019-06-18 | 何耀 | A kind of secondary zinc oxide raw material high-efficiency resource recycling method |
| CN110117723A (en) * | 2019-05-10 | 2019-08-13 | 昆明理工大学 | A kind of richness germanium zinc oxide fumes leaching method |
Non-Patent Citations (1)
| Title |
|---|
| 湿法炼锌过程中铟锗的综合回收;张博亚等;云南冶金;第36卷(第05期);25-28 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115011800A (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110093506B (en) | Method for efficiently extracting valuable metals from germanium-containing zinc leaching residues and reducing valuable metals | |
| CN102766765B (en) | Zinc oxide powder recycling method | |
| CN109897966B (en) | Efficient resource utilization method for secondary zinc oxide raw material | |
| CN110079676B (en) | Germanium-rich zinc oxide smoke dust gradient leaching process | |
| CN109161688B (en) | Method for recycling copper and cadmium from copper-cadmium slag | |
| CN101538650A (en) | Method for wet-separation of manganese from lead and silver in electrolytic-zinc anode slime | |
| CN109628746B (en) | Method for extracting tin from silver separating slag | |
| CN102502532B (en) | Method for extracting high-purity tellurium oxides from copper anode mud | |
| CN100443604C (en) | Extraction and separation technology for reclaiming main impurity in indium in hydrochloric acid system | |
| CN110541070B (en) | Method for comprehensively extracting valuable metals from white alloy | |
| CN110540252B (en) | Method for preparing battery-grade cobalt sulfate and high-purity germanium dioxide from white alloy | |
| CN115011800B (en) | Method for separating indium and germanium from zinc oxide smoke dust | |
| CN105567999B (en) | A method of recycling valuable metal from zinc hydrometallurgy purified cobalt nickel slag | |
| CN113265544A (en) | Process for recovering indium from high-lead and high-indium soot by using full wet method | |
| CN116574908B (en) | Process for jointly recycling zinc and indium by means of open-circuit impurity removal of electrolyte in zinc smelting process | |
| CN109797295B (en) | Method for extracting cobalt from cobalt-containing iron concentrate | |
| CN112458306A (en) | Method for reducing zinc content of flotation silver concentrate in zinc hydrometallurgy process | |
| CN110541074B (en) | Method for extracting germanium and cobalt from white alloy | |
| CN115029562A (en) | Method for separating copper and germanium in zinc hydrometallurgy process | |
| CN114774695A (en) | Method for extracting precious metals from silver anode mud pickle liquor | |
| CN115011810A (en) | Leaching process for improving copper recovery rate in zinc roasted ore | |
| CN110484747B (en) | Process for selectively extracting palladium from crude silver | |
| CN113969354A (en) | Method for recovering indium and zinc from zinc smelting soot | |
| CN111961869A (en) | Non-ferrous smelting waste recovery system and use method thereof | |
| CN114933285B (en) | Method for selectively recovering tellurium from copper anode slime |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |