CN110117723B - Germanium-rich zinc oxide smoke leaching method - Google Patents
Germanium-rich zinc oxide smoke leaching method Download PDFInfo
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- CN110117723B CN110117723B CN201910387083.7A CN201910387083A CN110117723B CN 110117723 B CN110117723 B CN 110117723B CN 201910387083 A CN201910387083 A CN 201910387083A CN 110117723 B CN110117723 B CN 110117723B
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B7/007—Wet processes by acid leaching
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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Abstract
The invention relates to a germanium-rich zinc oxide smoke leaching method, and belongs to the technical field of hydrometallurgy. According to the invention, by adopting a two-stage leaching and three-step control method, zinc oxide smoke dust is divided into two types of leaching raw materials and neutralizing raw materials during one-stage leaching, two types of slag (underflow) of the one-stage leaching is subjected to synergistic leaching during the second-stage leaching, the acidic (the end-point acidity is 20-40 g/L) leaching (namely low-acid oxygen-controlled leaching) of the zinc oxide smoke dust is firstly carried out in the first stage, then the acid leaching solution and the acid leaching underflow are respectively subjected to process configuration of neutralization reduction and synergistic leaching, and the high-efficiency leaching of zinc and germanium, the reduction of iron ions and the control of the pH of the leaching solution are realized step by. On the basis of the process flow of firstly carrying out weak acid (end-point pH is 1.5-3.5) leaching and then carrying out high acid leaching, the leaching process of zinc oxide smoke dust is optimized, so that the acid concentration of a leaching system is between that of the traditional weak acid (end-point pH is 1.5-3.5) leaching and that of high acid (end-point acidity is 80-120 g/L), and thus, the reaction condition is favorable for oxidizing sulfide by oxygen, so that the leaching rate of zinc and germanium is improved.
Description
Technical Field
The invention relates to a germanium-rich zinc oxide smoke leaching method, and belongs to the technical field of hydrometallurgy.
Background
Germanium, as a rare metal, is widely used in high-tech fields due to its unique physical and chemical properties. At present, the recovery of germanium mainly comes from zinc smelting industry, and in the hydrometallurgical process of zinc blende, germanium can be enriched in zinc leaching residue, and the zinc leaching residue becomes an important resource for recovering gallium and germanium. The method for recovering germanium from the germanium-containing zinc leaching residue mainly comprises a pyrogenic reduction volatilization method and wet high-temperature high-acid leaching, and also comprises direct oxygen pressure leaching of germanium-containing zinc concentrate. For example, Yunnan Chihong zinc germanium GmbH adopts a conventional zinc smelting process and a fuming furnace zinc oxide process for volatilizing germanium; the method is characterized in that gallium and germanium in the slag are leached by a liquid sulfur dioxide reduction acid leaching method in Japan Millettia smelting plants, research work of sulfur dioxide high-pressure reduction leaching is carried out by Beijing mining and metallurgy research institute (research on high-pressure leaching of gallium and germanium from zinc leaching slag, nonferrous metals (smelting part), 2012 and 8 th), and a smelting process of sulfur dioxide high-pressure reduction leaching zinc leaching slag is established for effectively recovering valuable metals in zinc leaching slag by Yunnan Hualian zinc-indium limited company; the Guangdong Shaoguan Danxia smeltery adopts a direct two-end high-temperature acid leaching process of zinc sulfide concentrate (comprehensively recovering gallium, germanium and nonferrous metals from zinc leaching slag of the Danxia smeltery, 4 th stage in 2009).
However, because the prior zinc smelting process in China is mainly the conventional process, the raw material for extracting germanium is mainly from germanium-containing zinc oxide smoke dust. The method for treating zinc oxide smoke dust containing germanium is an intermediate raw material mainly containing valuable metals such as zinc, lead, germanium, silver and the like, which is produced after zinc hydrometallurgy and lead pyrometallurgy slag are treated by a pyrogenic fuming volatilization method. However, long-term production practice shows that the recovery flow of germanium is long in the conventional zinc smelting process, the recovery rate of zinc and germanium in the zinc oxide containing germanium is low, and the zinc content is only about 85%; less than 60% of germanium. The low recovery rate of zinc and germanium mainly comprises the main existing forms of zinc in the germanium-containing zinc oxide smoke dust, such as zinc oxide, zinc sulfate, zinc sulfide and the like, more insoluble sulfides are present, the zinc oxide smoke dust has larger particles and uneven particle size, and the leaching rate of zinc and germanium is low by adopting a conventional treatment process. Therefore, how to improve the leaching rate of zinc and germanium and reduce the content of zinc and germanium in the final leaching residue (lead-silver residue) is a key link for restricting the recovery rate of zinc and germanium.
In the prior art, a method for recovering germanium from zinc oxide smoke dust provides a two-stage countercurrent leaching process of normal-pressure low-temperature low-acid leaching at a first stage and high-temperature oxygen pressure leaching at a second stage, and sodium sulfite is adopted to reduce a leaching solution; the method for efficiently extracting zinc and germanium from zinc oxide smoke dust provides a two-stage countercurrent leaching process of the first-stage normal-pressure low-temperature low-acid leaching and the second-stage oxygen-pressure low-temperature high-acid leaching, and reduces the temperature of the second-stage oxygen-pressure leaching in comparison. The leaching rate of zinc and germanium can be greatly improved by oxygen pressure leaching, but compared with the normal pressure leaching process, the required equipment requirement is high, the concentration of ferric iron in the leaching solution is difficult to control, the influence of high-concentration ferric iron on the subsequent recovery of germanium from the leaching solution is large, and a special reduction process needs to be added to ensure that iron in the leaching solution is ferrous iron.
Therefore, how to realize the high-efficiency leaching of zinc and germanium from the germanium-containing zinc oxide smoke under a normal pressure system and synchronously control the iron valence state in the solution, the production process is simplified, and no report is provided.
Disclosure of Invention
Aiming at the problem of low leaching rate of the traditional two-stage countercurrent leaching process flow, the method realizes the high-efficiency leaching of zinc and germanium, the reduction of iron ions and the control of the pH value of the leaching solution step by optimizing and adjusting the process flow configuration, solves the problems of the high-efficiency leaching of zinc and germanium, the control of ferric iron in the leaching solution and the like in the smelting process, has the advantages of simple process flow, low energy consumption, cleanness, environmental protection and contribution to the comprehensive recycling of resources.
A germanium-rich zinc oxide smoke leaching method comprises the following specific steps:
(1) uniformly mixing germanium-rich zinc oxide smoke dust with a sulfur dispersant to obtain a mixture A, adding water for size mixing, and performing wet grinding and activation to obtain fine grinding ore pulp with the smoke dust particle size not more than 0.074 mm;
(2) adding the zinc hydrometallurgy electrolytic waste liquid into the finely ground ore pulp obtained in the step (1), uniformly mixing, introducing oxygen, and carrying out low-acid oxygen-controlled leaching reaction for 1.5-2.5 h under the conditions of stirring and 80-90 ℃ to obtain low-acid leachate A and low-acid bottom flow;
(3) adding the finely ground ore pulp obtained in the step (1) into the low-acid leaching solution A obtained in the step (2), and carrying out neutralization reduction reaction for 1.0-2.0 h at the temperature of 70-80 ℃ under the stirring condition to obtain a leaching solution B and a neutralization underflow; carrying out germanium precipitation treatment on the leaching solution B;
(4) uniformly mixing the neutralization bottom flow in the step (3), the low-acid bottom flow in the step (2) and the zinc hydrometallurgy electrolytic waste liquid, and performing a peracid synergistic leaching reaction for 2-3 hours at the temperature of 80-90 ℃ under a stirring condition to obtain a peracid leaching solution C and a peracid bottom flow; returning the high-acid leaching solution C to the step (2) to replace the zinc hydrometallurgy electrolysis waste liquid for carrying out low-acid oxygen control leaching reaction; and (3) performing filter pressing on the high acid bottom flow to obtain filter pressing residues, mixing the filter pressing residues with water, performing low-temperature slurrying and washing, performing centrifugal filtration to obtain zinc and germanium containing washing water and leached final slag, returning the zinc and germanium washing water to the step (1) to replace water for size mixing, and obtaining the leached final slag, namely the zinc-lead-silver slag smelted by the wet method.
The mass ratio of the germanium-rich zinc oxide smoke dust to the sulfur dispersant in the step (1) is 1 (0.001-0.003).
The solid-to-liquid ratio kg of the germanium-rich zinc oxide smoke dust and water in the step (1) is 1 (1-2).
And (3) the solid-to-liquid ratio kg of the dry basis of the finely ground ore pulp in the step (2) to the zinc hydrometallurgy electrolytic waste liquid is 1 (5.5-7.5).
The solid-to-liquid ratio kg of the dry basis of the fine grinding ore pulp to the low-acid leaching liquid A in the step (3) is (0.40-0.50) to (5.5-7.5).
And (3) the solid-to-liquid ratio kg of the dry basis of the neutralization underflow and the dry basis of the low-acid underflow in the step (4) to the zinc hydrometallurgy electrolytic waste liquid is that L is (0.20-0.30): (0.35-0.45): 5.5-7.5).
And (4) in the step (4), the solid-to-liquid ratio kg of the dry basis of the filter residue to water is (0.55-0.65) to (1.5-2.5).
The germanium-rich zinc oxide smoke dust is zinc-containing smoke dust obtained when the conventional wet-process zinc smelting slag and the fire-process lead smelting slag are treated by a fire-process fuming volatilization method, wherein the smoke dust contains 0.05-0.20 wt% of germanium and 2-8 wt% of sulfur except zinc and iron; the zinc hydrometallurgy electrolytic waste liquid is zinc sulfate aqueous solution containing 155-185 g/L of sulfuric acid and produced by a known conventional zinc hydrometallurgy electrolytic process.
The low-acid leaching solution A contains 0.3-1 g/L of ferric iron and 20-40 g/L of sulfuric acid; the low acid bottom flow contains 10-20 wt.% of zinc;
the leaching solution B contains less than 30mg/L of ferric iron, and the pH value of the leaching solution B is 2.5-3.5; the neutralization underflow contains 15-25 wt.% of zinc and 5-10 wt.% of iron;
the high-acid leaching solution C contains 0.5-1.5 g/L of ferric iron, 80-120 g/L of sulfuric acid, 5-10 wt% of zinc, 0.02-0.03 wt% of germanium and 0.5-1.5 wt% of iron;
according to the invention, by adopting a two-stage leaching and three-step control method, zinc oxide smoke dust is divided into two types of leaching raw materials and neutralizing raw materials during one-stage leaching, two types of residues (underflow) of the one-stage leaching are subjected to synergistic leaching during the second-stage leaching, the acidic (the end-point acidity is 20-40 g/L) leaching (namely low-acid oxygen-controlled leaching) of the zinc oxide smoke dust is firstly carried out in the first stage, then the acid leaching solution and the acid leaching underflow are respectively subjected to the process configuration of neutralization reduction and synergistic leaching, and the high-efficiency leaching of zinc and germanium, the reduction of iron ions and the control of the pH of the leaching solution are realized step. On the basis of the traditional process flow of firstly carrying out weak acid (end-point pH is 1.5-3.5) leaching and then carrying out high-acid leaching, the first-stage leaching condition of zinc oxide smoke dust is optimized, so that the acid concentration of a leaching system is between that of the traditional weak acid (end-point pH is 1.5-3.5) leaching and that of high-acid (end-point acidity is 80-120 g/L), and thus the reaction condition is favorable for oxidizing sulfide by oxygen, and the leaching rate of zinc and germanium is improved.
The invention has the beneficial effects that:
(1) the method has high leaching rate of zinc and germanium, and can utilize ferric iron in the neutralization underflow to oxidize, convert and leach sulfides in the acid leaching underflow through the synergistic leaching of the acid leaching underflow and the neutralization underflow so as to reduce the content of zinc and germanium in the final leaching residue and realize the high-efficiency leaching of zinc and germanium, and compared with the traditional process that the first stage is firstly leached by weak acid (the end point is pH1.5-3.5) and then leached by high acid, the leaching rate can be improved by about 10 percent;
(2) the invention is easy to separate the zinc, the germanium and the iron in the subsequent step: zinc oxide smoke dust is self-contained in the process, the acid leaching solution produced by acid leaching is neutralized and reduced, the control of the valence state and the pH value of iron ions in the leaching solution is realized, the ferric iron in the obtained leaching solution is less than 30mg/L, the pH value is 2.5-3.5, and the subsequent precipitation and recovery of germanium from the leaching solution are easy;
(3) the process and the equipment of the invention are simple: the invention adopts the normal pressure leaching process, does not need a pressurized reaction kettle, simplifies the process compared with the normal pressure-pressurized combined process, and has simple operation and easy process control.
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FIG. 1 is a process flow diagram of the present invention.
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 main components of the germanium-rich zinc oxide smoke dust provided by a certain factory are as follows: 47.26 wt% of Zn, 5.03 wt% of Fe, 7.98 wt% of S, 12.57 wt% of Pb12, 506g/t of Ge, and the main components of the wet-process zinc-smelting electrolytic waste liquid are as follows: h2SO4: 185g/L、Zn: 53g/L；
A germanium-rich zinc oxide smoke leaching method comprises the following specific steps:
(1) 1.4kg of germanium-rich zinc oxide smoke dust and a sulfur dispersing agent are uniformly mixed to obtain a mixture A, water is added for size mixing, and then wet grinding and activation are carried out to obtain fine grinding ore pulp with the smoke dust granularity not more than 0.074 mm; wherein the mass ratio of the germanium-rich zinc oxide smoke dust to the sulfur dispersant is 1:0.001, and the solid-to-liquid ratio kg/L of the germanium-rich zinc oxide smoke dust to water is 1: 2;
(2) adding 5.5L of zinc hydrometallurgy electrolytic waste liquid into the finely ground ore pulp in the step (1), uniformly mixing, introducing oxygen (the volume concentration of the oxygen is 99.9%), carrying out low-acid oxygen-controlled leaching reaction for 2 hours at the temperature of 85 ℃ under the stirring condition to obtain low-acid leachate A and low-acid underflow; wherein the solid-to-liquid ratio kg of the dry basis of the fine grinding ore pulp to the zinc hydrometallurgy electrolytic waste liquid is 1: 5.5; the low acid leaching solution A contains 1g/L ferric iron and 20g/L sulfuric acid; the low acid stream contains 20wt.% zinc;
(3) adding the finely ground ore pulp obtained in the step (1) into the low-acid leachate A obtained in the step (2), and carrying out neutralization reduction reaction for 1.5h at the temperature of 75 ℃ under the stirring condition to obtain leachate B and neutralized underflow; carrying out germanium precipitation treatment on the leaching solution B; wherein the solid-to-liquid ratio kg of the dry basis of the fine grinding ore pulp to the low-acid leaching liquid A is 0.40: 5.5; the leaching solution B contains less than 30mg/L of ferric iron, and the pH value is 3.5; the neutralized underflow contained 25 wt.% zinc and 10wt.% iron;
(4) uniformly mixing the neutralization bottom flow in the step (3), the low-acid bottom flow in the step (2) and the zinc hydrometallurgy electrolytic waste liquid, and performing a peracid synergistic leaching reaction for 3 hours at the temperature of 80 ℃ under the stirring condition to obtain a peracid leaching solution C and a peracid bottom flow; returning the high-acid leaching solution C to the step (2) to replace the zinc hydrometallurgy electrolysis waste liquid for carrying out low-acid oxygen control leaching reaction; filter-pressing the high-acid bottom flow to obtain filter-pressing residues, mixing the filter-pressing residues with water, pulping and washing at low temperature, centrifuging and filtering to obtain zinc-germanium-containing washing water and leaching final slag, returning the zinc-germanium washing water to the step (1) to replace water for size mixing, and obtaining the leaching final slag, namely the zinc-lead-silver slag smelted by the wet method; wherein the solid-to-liquid ratio kg: L of the dry basis of the neutralization underflow and the dry basis of the low-acid underflow to the wet zinc smelting electrolytic waste liquid is 0.30:0.45:5.5, and the solid-to-liquid ratio kg: L of the dry basis of the filter pressing residue to the water is 0.55: 2.5; the high-acid leaching solution C contains 1.5g/L of ferric iron and 80g/L of sulfuric acid, and the high-acid leaching solution C contains 10wt.% of zinc, 0.02wt.% of germanium and 1.5wt.% of iron;
in the embodiment, the leaching rate of zinc is 90.6%, and the leaching rate of germanium is 82.7%; the final leached slag contains 9.87 percent of zinc and 211g/t of germanium.
Example 2: the main components of the germanium-rich zinc oxide smoke dust provided by a certain factory are as follows: 47.17wt.% of Zn, 4.03 wt.% of Fe, 6.45 wt.% of S, 11.96 wt.% of Pb11, 721g/t of Ge, and the main components of the wet-process zinc-smelting electrolytic waste liquid are as follows: h2SO4: 165g/L、Zn: 49g/L；
A germanium-rich zinc oxide smoke leaching method comprises the following specific steps:
(1) 1.45kg of germanium-rich zinc oxide smoke dust and a sulfur dispersing agent are uniformly mixed to obtain a mixture A, water is added for size mixing, and then wet grinding and activation are carried out to obtain fine grinding ore pulp with the smoke dust granularity not more than 0.074 mm; wherein the mass ratio of the germanium-rich zinc oxide smoke dust to the sulfur dispersant is 1:0.002, and the solid-to-liquid ratio kg of the germanium-rich zinc oxide smoke dust to water and L are 1: 1.52;
(2) adding 6L of zinc hydrometallurgy electrolytic waste liquid into the fine grinding ore pulp in the step (1), uniformly mixing, introducing oxygen (the volume concentration of the oxygen is 80%), carrying out low-acid oxygen-controlled leaching reaction for 1.5h at the temperature of 90 ℃ under the stirring condition to obtain low-acid leachate A and low-acid underflow; wherein the solid-to-liquid ratio kg of the dry basis of the fine grinding ore pulp to the zinc hydrometallurgy electrolytic waste liquid is 1: 6; the low acid leaching solution A contains 0.6g/L ferric iron and 30g/L sulfuric acid; the low acid stream contains 16wt.% zinc;
(3) adding the finely ground ore pulp in the step (1) into the low-acid leaching solution A in the step (2), and carrying out neutralization reduction reaction for 1.0h at the temperature of 80 ℃ under the stirring condition to obtain a leaching solution B and a neutralization underflow; carrying out germanium precipitation treatment on the leaching solution B; wherein the solid-to-liquid ratio kg of the dry basis of the fine grinding ore pulp to the low-acid leaching liquid A is 0.45: 6; the leaching solution B contains ferric iron less than 30mg/L, and the pH value is 3.0; the neutralized underflow contained 21 wt.% zinc and 7wt.% iron;
(4) uniformly mixing the neutralization bottom flow in the step (3), the low-acid bottom flow in the step (2) and the zinc hydrometallurgy electrolytic waste liquid, and performing a peracid synergistic leaching reaction for 2.5 hours at the temperature of 90 ℃ under the stirring condition to obtain a peracid leaching solution C and a peracid bottom flow; returning the high-acid leaching solution C to the step (2) to replace the zinc hydrometallurgy electrolysis waste liquid for carrying out low-acid oxygen control leaching reaction; filter-pressing the high-acid bottom flow to obtain filter-pressing residues, mixing the filter-pressing residues with water, pulping and washing at low temperature, centrifuging and filtering to obtain zinc-germanium-containing washing water and leaching final slag, returning the zinc-germanium washing water to the step (1) to replace water for size mixing, and obtaining the leaching final slag, namely the zinc-lead-silver slag smelted by the wet method; wherein the solid-to-liquid ratio kg: L of the dry basis of the neutralization underflow and the dry basis of the low-acid underflow to the wet zinc smelting electrolytic waste liquid is 0.25:0.40:6, and the solid-to-liquid ratio kg: L of the dry basis of the press filtration residue to the water is 0.61: 2.2; the high-acid leaching solution C contains 1.1g/L of ferric iron and 105g/L of sulfuric acid, the high-acid bottom flow contains 8.6wt.% of zinc, 0.028wt.% of germanium and 1.2wt.% of iron;
in the embodiment, the leaching rate of zinc is 91.6 percent, and the leaching rate of germanium is 84.2 percent; the final leached slag contains 8.57 percent of zinc and 281g/t of germanium.
Example 3: the main components of the germanium-rich zinc oxide smoke dust provided by a certain factory are as follows: 45.33wt.% of Zn, 3.22 wt.% of Fe, 2.05 wt.% of S, 13.89 wt.% of Pb13, 1972g/t of Ge, and the electrolytic waste liquid of zinc hydrometallurgy comprises the following main components: h2SO4: 155g/L、Zn: 46g/L；
A germanium-rich zinc oxide smoke leaching method comprises the following specific steps:
(1) 1.5kg of germanium-rich zinc oxide smoke dust and a sulfur dispersing agent are uniformly mixed to obtain a mixture A, water is added for size mixing, and then wet grinding and activation are carried out to obtain fine grinding ore pulp with the smoke dust granularity not more than 0.074 mm; wherein the mass ratio of the germanium-rich zinc oxide smoke dust to the sulfur dispersant is 1:0.003, and the solid-to-liquid ratio kg of the germanium-rich zinc oxide smoke dust to water and L are 1: 1;
(2) adding 7.5L of zinc hydrometallurgy electrolytic waste liquid into the finely ground ore pulp in the step (1), uniformly mixing, introducing oxygen (the volume concentration of the oxygen is 92%), carrying out low-acid oxygen-control leaching reaction for 2.5h at the temperature of 80 ℃ under the stirring condition to obtain low-acid leachate A and low-acid underflow; wherein the solid-to-liquid ratio kg of the dry basis of the fine grinding ore pulp to the zinc hydrometallurgy electrolytic waste liquid is 1: 7.5; the low acid leaching solution A contains 0.3g/L ferric iron and 40g/L sulfuric acid; the low acid stream contained 10wt.% zinc;
(3) adding the finely ground ore pulp obtained in the step (1) into the low-acid leachate A obtained in the step (2), and carrying out neutralization reduction reaction for 2.0h at the temperature of 70 ℃ under the stirring condition to obtain leachate B and neutralized underflow; carrying out germanium precipitation treatment on the leaching solution B; wherein the solid-to-liquid ratio kg of the dry basis of the fine grinding ore pulp to the low-acid leaching liquid A is 0.50: 7.5; the leaching solution B contains less than 30mg/L of ferric iron, and the pH value is 2.5; the neutralized underflow contained 15 wt.% zinc, 5wt.% iron;
(4) uniformly mixing the neutralization bottom flow in the step (3), the low-acid bottom flow in the step (2) and the zinc hydrometallurgy electrolytic waste liquid, and performing a peracid synergistic leaching reaction for 2 hours at the temperature of 85 ℃ under the stirring condition to obtain a peracid leaching solution C and a peracid bottom flow; returning the high-acid leaching solution C to the step (2) to replace the zinc hydrometallurgy electrolysis waste liquid for carrying out low-acid oxygen control leaching reaction; filter-pressing the high-acid bottom flow to obtain filter-pressing residues, mixing the filter-pressing residues with water, pulping and washing at low temperature, centrifuging and filtering to obtain zinc-germanium-containing washing water and leaching final slag, returning the zinc-germanium washing water to the step (1) to replace water for size mixing, and obtaining the leaching final slag, namely the zinc-lead-silver slag smelted by the wet method; wherein the solid-to-liquid ratio kg: L of the dry basis of the neutralization underflow and the dry basis of the low-acid underflow to the wet zinc smelting electrolytic waste liquid is 0.20:0.35:7.5, and the solid-to-liquid ratio kg: L of the dry basis of the filter pressing residue to the water is 0.65: 1.5; the high-acid leaching solution C contains 0.5g/L of ferric iron and 120g/L of sulfuric acid, and the high-acid leaching solution C contains 5wt.% of zinc, 0.03wt.% of germanium and 0.5wt.% of iron;
in the embodiment, the leaching rate of zinc is 95.1%, and the leaching rate of germanium is 93.4%; the final leached slag contains 5.17 percent of zinc and 298g/t of germanium.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (4)
1. A germanium-rich zinc oxide smoke leaching method is characterized by comprising the following specific steps:
(1) uniformly mixing germanium-rich zinc oxide smoke dust with a sulfur dispersant to obtain a mixture A, adding water for size mixing, and performing wet grinding and activation to obtain fine grinding ore pulp with the smoke dust particle size not more than 0.074 mm;
(2) adding the zinc hydrometallurgy electrolytic waste liquid into the finely ground ore pulp obtained in the step (1), uniformly mixing, introducing oxygen, and carrying out low-acid oxygen-controlled leaching reaction for 1.5-2.5 h under the conditions of stirring and 80-90 ℃ to obtain low-acid leachate A and low-acid bottom flow; wherein the solid-to-liquid ratio kg of the dry basis of the finely ground ore pulp to the zinc hydrometallurgy electrolytic waste liquid is 1 (5.5-7.5);
(3) adding the finely ground ore pulp obtained in the step (1) into the low-acid leaching solution A obtained in the step (2), and carrying out neutralization reduction reaction for 1.0-2.0 h at the temperature of 70-80 ℃ under the stirring condition to obtain a leaching solution B and a neutralization underflow; carrying out germanium precipitation treatment on the leaching solution B; wherein the solid-to-liquid ratio kg of the dry basis of the fine grinding ore pulp to the low-acid leaching liquid A is that L is (0.40-0.50) to (5.5-7.5);
(4) uniformly mixing the neutralization underflow obtained in the step (3), the low-acid underflow obtained in the step (2) and the wet-process zinc smelting electrolytic waste liquid, and performing a high-acid synergistic leaching reaction for 2-3 hours at the temperature of 80-90 ℃ under the stirring condition to obtain a high-acid leachate C and a high-acid underflow, wherein the solid-to-liquid ratio kg of the dry basis of the neutralization underflow and the dry basis of the low-acid underflow to the wet-process zinc smelting electrolytic waste liquid is that kg, L is (0.20-0.30), 0.35-0.45 and (5.5-7.5); returning the high-acid leaching solution C to the step (2) to replace the zinc hydrometallurgy electrolysis waste liquid for carrying out low-acid oxygen control leaching reaction; and (3) performing filter pressing on the high acid bottom flow to obtain filter pressing residues, mixing the filter pressing residues with water, performing slurrying washing and centrifugal filtering to obtain zinc and germanium containing washing water and leaching final slag, returning the zinc and germanium washing water to the step (1) to replace water for size mixing, and obtaining the leaching final slag, namely the zinc-lead-silver slag smelted by the wet method.
2. The germanium-rich zinc oxide soot leaching method of claim 1, wherein: the mass ratio of the germanium-rich zinc oxide smoke dust to the sulfur dispersant in the step (1) is 1 (0.001-0.003).
3. The germanium-rich zinc oxide soot leaching method of claim 1, wherein: in the step (1), the solid-to-liquid ratio kg of the germanium-rich zinc oxide smoke dust to water, L, is 1 (1-2).
4. The germanium-rich zinc oxide soot leaching method of claim 1, wherein: in the step (4), the solid-liquid ratio kg of the dry basis of the filter residue to water is (0.55-0.65) to (1.5-2.5).
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