CN111235392A - Method for deep oxidation and harmless comprehensive recovery of valuable metals from zinc sulfite slag - Google Patents
Method for deep oxidation and harmless comprehensive recovery of valuable metals from zinc sulfite slag Download PDFInfo
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- CN111235392A CN111235392A CN202010187100.5A CN202010187100A CN111235392A CN 111235392 A CN111235392 A CN 111235392A CN 202010187100 A CN202010187100 A CN 202010187100A CN 111235392 A CN111235392 A CN 111235392A
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- germanium
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- lead
- sulfite
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- HSYFJDYGOJKZCL-UHFFFAOYSA-L zinc;sulfite Chemical compound [Zn+2].[O-]S([O-])=O HSYFJDYGOJKZCL-UHFFFAOYSA-L 0.000 title claims abstract description 102
- 239000002893 slag Substances 0.000 title claims abstract description 95
- 230000003647 oxidation Effects 0.000 title claims abstract description 78
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000011084 recovery Methods 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 title claims description 23
- 239000002184 metal Substances 0.000 title claims description 23
- 150000002739 metals Chemical class 0.000 title claims description 21
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 122
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 103
- 239000011701 zinc Substances 0.000 claims abstract description 103
- 229910052709 silver Inorganic materials 0.000 claims abstract description 49
- 239000004332 silver Substances 0.000 claims abstract description 49
- 239000012141 concentrate Substances 0.000 claims abstract description 38
- 238000002386 leaching Methods 0.000 claims abstract description 38
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 16
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 claims abstract description 15
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 13
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003546 flue gas Substances 0.000 claims abstract description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 68
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 41
- 239000000706 filtrate Substances 0.000 claims description 35
- 229910052742 iron Inorganic materials 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 239000012286 potassium permanganate Substances 0.000 claims description 16
- 239000008235 industrial water Substances 0.000 claims description 15
- 229920001864 tannin Polymers 0.000 claims description 15
- 239000001648 tannin Substances 0.000 claims description 15
- 235000018553 tannin Nutrition 0.000 claims description 15
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 12
- 239000001263 FEMA 3042 Substances 0.000 claims description 12
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 12
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 12
- 229940033123 tannic acid Drugs 0.000 claims description 12
- 235000015523 tannic acid Nutrition 0.000 claims description 12
- 229920002258 tannic acid Polymers 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 239000013055 pulp slurry Substances 0.000 claims description 5
- 238000009854 hydrometallurgy Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 44
- 235000010269 sulphur dioxide Nutrition 0.000 description 14
- 239000007789 gas Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 6
- 239000013049 sediment Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- LTVQIVFOQNASOU-UHFFFAOYSA-N sulfurous acid zinc Chemical compound [Zn].S(O)(O)=O LTVQIVFOQNASOU-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
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Classifications
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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
- C22B7/006—Wet processes
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
-
- 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
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- 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 discloses a method for carrying out deep oxidation and harmless comprehensive recovery treatment on zinc sulfite slag, which directly adopts zinc oxide powder produced by a zinc volatilization kiln to pulpify and absorb low-concentration sulfur dioxide flue gas produced by the zinc volatilization kiln to obtain the zinc sulfite slag as a raw material, pulpifies the zinc sulfite slag, then carries out air oxidation, then adds a mixed oxidant to carry out deep oxidation, heats and heats, and finally filters to obtain a zinc sulfate solution containing germanium and zinc oxide slag which are both wet zinc smelting raw materials, wherein the zinc sulfate solution contains high germanium and low zinc and ferric iron, and can directly recover germanium to obtain high-grade germanium concentrate, the zinc oxide slag is subjected to acid leaching to recover zinc, and the produced lead-silver concentrate is used for recovering lead and silver.
Description
Technical Field
The invention belongs to the technical field of nonferrous metallurgy, and particularly relates to a method for comprehensively recovering valuable metals by deep oxidation and harmlessness of zinc sulfite slag.
Background
The blue sky water is protected, and at present, green home is built together, the zinc hydrometallurgy industry adopts self-produced zinc oxide powder and smoke dust to absorb low-concentration sulfur dioxide flue gas so as to achieve the emission standard, and meanwhile, zinc sulfite slag is obtained, and the main component of the zinc sulfite slag is zinc sulfite. The following methods are currently mainly used for treating zinc sulfite: 1. the zinc sulfite is intensively analyzed by dilute sulfuric acid to generate high-concentration sulfur dioxide gas and zinc sulfate ore pulp solution for acid production, but part of sulfur dioxide overflows from an analyzing tank to worsen the operating environment, and more importantly, in the analyzing process, because the input of the zinc sulfite and the addition of the dilute sulfuric acid are difficult to control uniformly, the concentration fluctuation of the generated sulfur dioxide gas is large, the production of an acid production system is difficult to control, so that the tail gas is difficult to discharge after reaching the standard, and the environmental protection risk is increased. 2. The method has the disadvantages that zinc sulfite is not completely oxidized, the oxidation rate is not high and is only about 80 wt%, a large amount of sulfur dioxide gas is released during acid leaching in the next process, the operation environment is deteriorated, and great risk and pressure are caused to production. 3. Chinese patent CN109161691A discloses a method for comprehensively recovering and treating zinc sulfite slag, which adopts a fluidized bed roasting method, i.e. zinc sulfite slag is dried and crushed and then mixed with high-sulfur zinc concentrate to be fluidized bed roasted for recovering zinc, and the method has the disadvantages that: (1) the mixture is mixed with high-sulfur zinc concentrate, and then boiling roasting can be carried out; (2) the zinc sulfite is mixed with zinc concentrate, the grades of lead, germanium and silver are reduced, and valuable metal intermediate product zinc sulfite slag is depleted. (3) The zinc sulfite is decomposed to release sulfur dioxide in the baking process, so that the operation environment is deteriorated, and pressure is brought to environmental protection.
Aiming at the problems, the invention is urgently needed to invent a method for deeply oxidizing the zinc sulfite slag and comprehensively recovering valuable metals.
Disclosure of Invention
The invention aims to provide a method for comprehensively recovering valuable metals by deeply oxidizing and harmlessly recovering zinc sulfite slag, so as to realize the harmless utilization of the whole-flow process of zinc sulfite and the comprehensive recovery of the valuable metals of zinc, germanium, lead and silver.
The method of the invention is realized as follows: directly pulping zinc oxide powder produced by a zinc volatilization kiln to absorb low-concentration sulfur dioxide flue gas produced by the zinc volatilization kiln to obtain zinc sulfite slag, pulping the zinc sulfite slag, then carrying out air oxidation, adding a mixed oxidant to carry out deep oxidation, heating to raise temperature, and finally filtering to obtain a zinc sulfate solution containing germanium and zinc oxide slag, wherein the products are zinc hydrometallurgy raw materials, the zinc sulfate solution contains high germanium and low zinc and ferric iron, and directly recovering germanium to obtain high-grade germanium concentrate; and (3) recovering zinc by acid leaching the zinc oxide slag, producing lead-silver concentrate to recover lead and silver, and comprehensively recovering valuable metals of zinc, germanium, lead and silver.
The zinc sulfite slag produced by absorbing low-concentration sulfur dioxide flue gas by adopting the company comprises the following main components: 25-40 wt% of zinc, 20-35 wt% of zinc sulfite, 1.0-4.0 wt% of iron, 0.02-0.04 wt% of germanium, 2.0-4.0 wt% of lead and 0.001-0.006 wt% of silver, wherein the method is realized by adopting the following steps:
1) slurrying of zinc sulfite slag: using the slurry to mix the zinc sulfite slag according to the weight ratio of 6-7: slurrying is carried out according to the liquid-solid ratio of 1, the slurrying time is 10 minutes, and the slurrying is uniformly stirred for standby.
2) Air oxidation of pulp slurry: introducing compressed air into the slurry after stirring and pulping uniformly by adopting a reverse method, adjusting the acidity by using 150g/l-200g/l sulfuric acid or acid-containing filtrate in the process, keeping the pH value in the process to be 3.5-4.0, stirring at normal temperature, and oxidizing for 2.0-2.5 hours by using air. Obtaining the liquid after air oxidation.
3) Deep oxidation of an oxidant: adding hydrogen peroxide in an amount which is 2 to 4 weight percent of the amount of the zinc sulfite slag and potassium permanganate in an amount which is 0.5 to 1.0 weight percent of the amount of the zinc sulfite slag into the air oxidized liquid, adjusting the acidity by using 150 to 200g/l of sulfuric acid or acid-containing filtrate, keeping the pH value in the process of 2.0 to 3.0, and then carrying out deep oxidation for 1.0 to 1.5 hours. And finally, heating to 40-50 ℃, filtering I to obtain No. 1 slag and No. 1 filtrate.
4) And (3) tannic acid germanium precipitation: heating the No. 1 filtrate to 70-80 ℃, adding 25-35 times of tannic acid, stirring for 15-20 minutes, filtering II to obtain No. 2 tannin germanium slag and No. 2 germanium precipitation liquid, and feeding the No. 2 germanium precipitation liquid to a zinc production system to serve as slurrying liquid to recover zinc. And sending the produced No. 2 tannin germanium slag to a germanium recovery workshop for firing to obtain germanium concentrate.
5) Slurry treatment of No. 1 slag: and (3) using the slurry to mix No. 1 slag according to the weight ratio of 3-4: slurrying is carried out according to the liquid-solid ratio of 1, the slurrying time is 10 minutes, and the slurrying is uniformly stirred for standby.
6) High-temperature high-acid leaching of No. 1 slag: leaching residue No. 1 after stirring and slurrying uniformly by adopting high-temperature high acid, adjusting the acidity by using sulfuric acid or zinc electrolysis waste liquid, controlling the initial acidity to be 60-80 g/l, controlling the temperature to be 85-90 ℃, stirring for 1.5-2.5 hours, filtering III, and filtering III to obtain filtrate No. 3 and filter residue No. 3.
7) No. 3 filter residue washing: and (3) using industrial water to remove residue according to the weight ratio of 4-5: slurrying the slurry according to the liquid-solid ratio of 1, stirring for 30 minutes, and filtering IV to obtain No. 4 washing water and No. 4 filter residue, wherein the No. 4 filter residue is the lead-silver concentrate.
The slurry in the step (1) is industrial water or No. 4 washing water.
The reverse method in the step (2) is that the direction of the air introduced into the stirring tank is opposite to the stirring direction.
And (3) the sulfuric acid in the steps (2, 3 and 6) is industrial concentrated sulfuric acid.
And (3) the acid-containing filtrate in the steps (2 and 3) is No. 3 filtrate.
The hydrogen peroxide in the step (3) is industrially used under the chemical name of hydrogen peroxide; potassium permanganate is used industrially.
The ratio of the tannin added in the step (4) refers to the ratio of the weight of the added tannin to the total germanium content of the germanium-precipitated solution.
In the step (4), the No. 5 germanium concentrate contains 25 wt% -30 wt% of zinc, 1.0 wt% -3.0 wt% of iron, 14.0 wt% -20.0 wt% of germanium and 2.0 wt% -5.0 wt% of lead.
And (5) the slurry liquid is zinc electrolysis waste liquid and No. 4 washing water or industrial water.
In the step (7), the No. 4 filter residue is lead-silver concentrate, and the lead-silver concentrate contains 2.0 wt% -5.0 wt% of zinc, 10.0 wt% -20.0 wt% of lead and 0.0160 wt% -0.040 wt% of silver.
The mechanism of the invention is as follows: this application directly uses the produced zinc oxide powder pulpifying of zinc volatilization kiln to absorb the produced low concentration sulfur dioxide flue gas of zinc volatilization kiln and obtain intermediate product zinc sulfite sediment, in the earlier stage that raw materials for production obtained, the earlier stage does not produce secondary pollution like this, because zinc sulfite is slightly soluble in cold water, we turn into zinc sulfite can carry out wet-method zinc smelting, the zinc sulfate raw materials of easy soluble in water, reduce the sulphuric acid quantity when subsequent handling zinc leaches, reduce production safety and environmental protection pressure, obtain from the raw materials and just reduced manufacturing cost.
The intermediate product zinc sulfite slag is firstly subjected to air oxidation, and then the mixed oxidant is added for deep oxidation, after the deep oxidation is carried out by the mixed oxidant, the zinc sulfite is completely oxidized, the oxidation rate is up to more than 98.7 wt%, the zinc sulfite is oxidized into zinc sulfate and directly enters the solution, the sulfuric acid dosage during zinc leaching can be greatly reduced, so that the safety and environmental protection pressure is reduced, and the production cost is reduced; meanwhile, after deep oxidation, the zinc and ferric iron in the oxidation liquid are lower, and the germanium content is high; below 1.0 g/L, the germanium content is up to more than 40 mg/L, the zinc content is 25-40 g/L, the pH value is 2.0-3.0, the germanium can be directly precipitated by using the germanium precipitation front liquid, and the subsequent comprehensive recovery of valuable metals such as zinc, germanium, lead and silver is facilitated. This is also a phenomenon that we have found after actually conducting deep oxidation experiments and an unexpected technical effect.
The properties of the zinc sulfite: (1) zinc sulfite loses two crystal waters at 100 ℃; decomposing at 200 deg.C, and dissolving in sulfuric acid; the hot water fractionally explains the evolution of sulphur dioxide gas.
(2) The zinc sulfite has reducibility, and is easy to generate oxidation-reduction reaction with oxygen, potassium permanganate and hydrogen peroxide with oxidability.
(a) The zinc sulfite reacts with oxygen in the air, equation: 2ZnSO3+O2＝2ZnSO4；
(b) The zinc sulfite reacts with potassium permanganate, and the equation is as follows: 2KMnO4+3ZnSO3+H2O＝2MnO2+3ZnSO4+2KOH；
(c) Reacting zinc sulfite with hydrogen peroxide, and obtaining an equation: h2O2+ZnSO3＝ZnSO4+H2O；
The invention has the advantages that:
1. the air oxidation process of the zinc sulfite slag is simple and short, the equipment is simple, the operation is simple and convenient, the production cost is low, and the method is a harmless comprehensive utilization technology of the oxidation desulfurization product with industrial prospect;
2. after air oxidation, hydrogen peroxide and potassium permanganate are added, zinc sulfite is completely oxidized, the oxidation rate is up to more than 98.7 wt%, and the zinc sulfite is oxidized into zinc sulfate and directly enters a solution, so that the sulfuric acid dosage during zinc leaching can be greatly reduced, the safety and environmental protection pressure is reduced, and the production cost is reduced;
3. the recovery rate of valuable metals of zinc, germanium, lead and silver is high, and is respectively 97.9%, 81.8%, 98.5% and 98.6%;
4. the oxidized liquid of the method has low ferric iron content below 1.0 g/L, the germanium content is higher than 40 mg/L, the zinc content is 25-40 g/L, and the pH value is 2.0-3.0, so the liquid before germanium precipitation can be directly used for germanium precipitation. Directly recovering germanium due to low zinc and ferric iron content to obtain high-grade germanium concentrate; thereby realizing the harmless utilization of the zinc sulfite and the comprehensive recovery of valuable metal germanium;
5. the method does not produce waste water, waste gas and waste residue, beautifies the operating environment, realizes green production, and meets the requirements of national environmental protection, comprehensive cyclic utilization of limited resources and sustainable development.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
As is known, sulfur dioxide (formula SO)2) Is a gas with pungent odor, one of the main pollutants of the atmosphere. This application adopts the zinc oxide powder pulpifying of zinc volatilization kiln production to absorb the produced sulfurous acid zinc sediment that low concentration sulfur dioxide flue gas of zinc volatilization kiln is obtained as the raw materials, carry out the pulpifying earlier with the sulfurous acid zinc sediment, then carry out air oxidation, add mixed oxidant and carry out the degree of depth oxidation, the heating intensifies, at last filter, the zinc sulfate solution and the zinc oxide sediment of output germanic, wherein it is high to contain germanium among the zinc sulfate solution, contain zinc, the ferric iron is low, can directly retrieve germanium, obtain the germanium concentrate of high-grade, zinc is retrieved in zinc oxide sediment acid leaching, and lead silver is retrieved to output lead silver concentrate. So that the products are the raw materials of the zinc hydrometallurgy.
Example 1
15000 g of zinc sulfite slag produced by the company is dried for standby, and the zinc sulfite slag contains 24.63 wt% of zinc, 22.79 wt% of zinc sulfite, 2.17 wt% of iron, 0.0299 wt% of germanium, 1.95 wt% of lead, 0.0056 wt% of silver and 9.5 wt% of water.
1) Slurrying of zinc sulfite slag: taking 60 liters of industrial water, adding 10000 grams of zinc sulfite slag for slurrying, wherein the slurrying time is 10 minutes, and stirring and slurrying uniformly for later use.
2) Air oxidation of pulp slurry: introducing compressed air into the slurry after stirring and pulping uniformly by adopting a reverse method, adjusting the acidity by using 150g/l-200g/l sulfuric acid or acid-containing filtrate in the process, keeping the pH value in the process to be 3.5-4.0, stirring at normal temperature, and oxidizing for 2.0-2.5 hours by using air. Obtaining the liquid after air oxidation.
3) Deep oxidation by using an oxidant: 200g of hydrogen peroxide and 50g of potassium permanganate are added into the intermediate solution after air oxidation, 150g/L of sulfuric acid or acid-containing filtrate is used for adjusting the acidity, the PH value is kept between 2.0 and 3.0 in the process, and then deep oxidation is carried out for 1.0 hour. Finally, heating to 40-50 ℃, filtering I to obtain 3950 g of No. 1 slag and 58 l of No. 1 filtrate. The No. 1 slag contains 8.1 wt% of water, 14.96 wt% of zinc, 0.95 wt% of zinc sulfite, 0.009 wt% of germanium, 4.85 wt% of lead, 0.0140 wt% of silver and 1.9 wt% of iron. No. 1 filtrate contains 33.10 g/L of zinc, 0.0459 g/L of germanium, 0.01 g/L of lead, trace silver, 2.50 g/L of total iron and 0.05 g/L of ferric iron.
4) And (3) tannic acid germanium precipitation: taking 55 liters of No. 1 filtrate, heating to 70-80 ℃, adding 63 grams of tannic acid, stirring for 15-20 minutes, filtering II to obtain 135 grams of No. 2 tannin germanium residue and 52 liters of No. 2 germanium precipitation solution, wherein the No. 2 tannin germanium residue contains 32.5 wt% of water, 4.20 wt% of zinc, 2.64 wt% of germanium, 0.56 wt% of lead, trace amount of silver and 0.22 wt% of iron. After No. 2 germanium deposition, the liquid contains 34.92 g/L of zinc, 0.0021 g/L of germanium, 0.0008 g/L of lead, trace silver and 2.64 g/L of iron. And feeding the liquid after the No. 2 germanium precipitation into a zinc production system to be used as slurry to recover the zinc. 120 g of the produced No. 2 tannin germanium slag is sent to a germanium recovery workshop for burning, so that 12.15 g of germanium concentrate is obtained, and the germanium concentrate contains 27.72 wt% of zinc, 17.25 wt% of germanium, 3.71 wt% of lead, trace of silver and 1.46 wt% of iron.
5) Slurry treatment of No. 1 slag: adding 3000 g of No. 1 slag into 9L of industrial water for slurrying, wherein the slurrying time is 10 minutes, and stirring and slurrying uniformly for later use.
6) High-temperature high-acid leaching of No. 1 slag: and (3) leaching the residue No. 1 after stirring and slurrying uniformly by adopting high-temperature high acid, adjusting the acidity by using sulfuric acid or zinc electrolysis waste liquid, controlling the initial acidity to be 60-80 g/l, controlling the temperature to be 85-90 ℃, stirring for 1.5-2.5 hours, filtering III, and filtering III to obtain 7.5 liters of filtrate No. 3 and 1350 grams of residue No. 3. No. 3 filtrate contains 63.33 g/L zinc, 0.0268 g/L germanium, 0.001 lead, trace silver, 6.64 g/L total iron and trace ferric iron. The No. 3 filter residue contains 10.5 wt% of water, 5.65 wt% of zinc, 0.0051 wt% of germanium, 10.94 wt% of lead, 0.0315 wt% of silver and 1.42 wt% of iron.
7) No. 3 filter residue washing: adding 1250 g of No. 3 filter residue into 5 l of industrial water for slurrying, stirring for 30 minutes, filtering IV, and filtering 4 to obtain 4.5 l of No. 4 washing water and 1100 g of No. 4 filter residue, wherein the No. 4 washing water contains 4.65 g/l of zinc, 0.0001 g/l of germanium, trace of lead, trace of silver, 0.95 g/l of total iron and trace of ferric iron. The No. 4 filter residue is 8.5 wt% of lead and silver concentrate, 4.2 wt% of zinc, 0.0057 wt% of germanium, 12.30 wt% of lead, 0.0350 wt% of silver and 1.14 wt% of iron.
The economic indexes obtained by calculation are as follows:
1. and (3) oxidation process of the zinc sulfite slag: the oxidation rate of zinc sulfite is 98.3 wt%, the leaching rate of zinc is 77.9 wt%, and the leaching rate of germanium is 89.0 wt%.
2. From zinc sulfite slag to lead-silver concentrate: the lead recovery rate is 99.7 wt%, and the silver recovery rate is 98.8 wt%.
3. From zinc sulfite slag to germanium concentrate: the recovery rate of germanium is 83.0 wt%.
Example 2
15000 g of zinc sulfite slag produced by the company is taken by calculation and dried for standby, and the zinc sulfite slag contains 27.56 wt% of zinc, 25.45 wt% of zinc sulfite, 3.22 wt% of iron, 0.0276 wt% of germanium, 2.96 wt% of lead, 0.0026 wt% of silver and 8.8 wt% of water.
1) Slurrying of zinc sulfite slag: taking 65 liters of industrial water, adding 10000 grams of zinc sulfite slag for slurrying, wherein the slurrying time is 10 minutes, and stirring and slurrying uniformly for later use.
2) Air oxidation of pulp slurry: introducing compressed air into the slurry after stirring and pulping uniformly by adopting a reverse method, adjusting the acidity by using 150g/l-200g/l sulfuric acid or acid-containing filtrate in the process, keeping the pH value in the process to be 3.5-4.0, stirring at normal temperature, and oxidizing for 2.0-2.5 hours by using air. Obtaining the liquid after air oxidation.
3) Deep oxidation by using an oxidant: 300 g of hydrogen peroxide and 70 g of potassium permanganate are added into the liquid after air oxidation, 150g/l of sulfuric acid or acid-containing filtrate is used for adjusting the acidity, the PH value is kept between 2.0 and 3.0 in the process, and then deep oxidation is carried out for 1.0 hour. Finally, the temperature is raised to 40-50 ℃, and then I is filtered to obtain 3890 g of No. 1 slag and 64L of No. 1 filtrate. The No. 1 slag contains 9.4 wt% of water, 16.11 wt% of zinc, 0.83 wt% of zinc sulfite, 0.0063 wt% of germanium, 7.64 wt% of lead, 0.0067 wt% of silver and 2.99 wt% of iron. No. 1 filtrate contains 35.2 g/L of zinc, 0.040 g/L of germanium, 0.012 g/L of lead, trace silver, 2.94 g/L of total iron and 0.07 g/L of ferric iron.
4) And (3) tannic acid germanium precipitation: taking 63 liters of No. 1 filtrate, heating to 70-80 ℃, adding 75.6 grams of tannic acid, stirring for 15-20 minutes, filtering II to obtain 141 grams of No. 2 tannin germanium residue and 62.5 liters of No. 2 germanium precipitation solution, wherein the No. 2 tannin germanium residue contains 29.5 wt% of water, 4.80 wt% of zinc, 2.37 wt% of germanium, 0.72 wt% of lead, trace silver and 0.31 wt% of iron. After No. 2 germanium precipitation, the liquid contains 35.3 g/L of zinc, 0.0026 g/L of germanium, 0.0007 g/L of lead, trace silver and 2.96 g/L of iron, and the liquid after No. 2 germanium precipitation is sent to a zinc production system to be used as slurry liquid to recover the zinc. 130 g of the produced No. 2 tannin germanium slag is sent to a germanium recovery workshop for burning, so that 14.7 g of germanium concentrate is obtained, and the germanium concentrate contains 29.30 wt% of zinc, 14.55 wt% of germanium, 4.40 wt% of lead, trace silver and 1.91 wt% of iron.
5) Slurry treatment of No. 1 slag: adding 3000 g of No. 1 slag into 10.5L of industrial water for slurrying, wherein the slurrying time is 10 minutes, and stirring and slurrying uniformly for later use.
6) High-temperature high-acid leaching of No. 1 slag: leaching residue No. 1 after stirring and slurrying uniformly by adopting high-temperature high acid, adjusting the acidity by using sulfuric acid or zinc electrolysis waste liquid, controlling the initial acidity to be 60-80 g/l, controlling the temperature to be 85-90 ℃, stirring for 1.5-2.5 hours, filtering III, and filtering III to obtain 9.5 liters of filtrate No. 3 and 1310 grams of filter residue No. 3. The filtrate 3 contains 40.10 g/L zinc, 0.0128 g/L germanium, 0.001 lead, trace silver, 7.24 g/L total iron and trace ferric iron. The No. 3 filter residue contains 9.5 wt% of water, 4.80 wt% of zinc, 0.0042 wt% of germanium, 17.51 wt% of lead, 0.0154 wt% of silver and 1.05 wt% of iron.
7) No. 3 filter residue washing: adding 1225 g of No. 3 filter residue into 5.5L of industrial water for slurrying, stirring for 30 minutes, filtering IV, and filtering 4 to obtain 5.2L of No. 4 washing water and 1050 g of No. 4 filter residue, wherein the No. 4 washing water contains 4.95 g/L of zinc, 0.0001 g/L of germanium, trace of lead, trace of silver, 1.05 g/L of total iron and trace of ferric iron. The No. 4 filter residue is 8.5 wt% of lead and silver concentrate, 2.86 wt% of zinc, 0.0048 wt% of germanium, 20.20 wt% of lead, 0.0177 wt% of silver and 0.64 wt% of iron.
The economic indexes obtained by calculation are as follows:
1. and (3) oxidation process of the zinc sulfite slag: the oxidation rate of zinc sulfite is 98.7 wt%, the leaching rate of zinc is 81.7 wt%, and the leaching rate of germanium is 92.7 wt%.
2. From zinc sulfite slag to lead-silver concentrate: the lead recovery rate is 99.7 wt%, and the silver recovery rate is 99.5 wt%.
3. From zinc sulfite slag to germanium concentrate: the recovery rate of germanium is 84.8 wt%.
Example 3
15000 g of zinc sulfite slag produced by the company is dried for standby, and the zinc sulfite slag contains 32.56 wt% of zinc, 29.89 wt% of zinc sulfite, 4.35 wt% of iron, 0.0338 wt% of germanium, 3.35 wt% of lead, 0.0047 wt% of silver and 8.5 wt% of water.
1) Slurrying of zinc sulfite slag: taking 70 liters of industrial water, adding 10000 grams of zinc sulfite slag for slurrying, wherein the slurrying time is 10 minutes, and stirring and slurrying uniformly for later use.
2) Air oxidation of pulp slurry: introducing compressed air into the slurry after stirring and pulping uniformly by adopting a reverse method, adjusting the acidity by using 150g/l-200g/l sulfuric acid or acid-containing filtrate in the process, keeping the pH value in the process to be 3.5-4.0, stirring at normal temperature, and oxidizing for 2.0-2.5 hours by using air. Obtaining the liquid after air oxidation.
3) Deep oxidation by using an oxidant: 400 g of hydrogen peroxide and 100 g of potassium permanganate are added into the solution after air oxidation, 150g/l of sulfuric acid or acid-containing filtrate is used for adjusting the acidity, the PH value is kept between 2.0 and 3.0 in the process, and then deep oxidation is carried out for 1.0 hour. Finally, after the temperature is raised to 40-50 ℃, filtering I to obtain 3900 g of No. 1 slag and 68L of No. 1 filtrate. The No. 1 slag contains 8.8 wt% of water, 20.66 wt% of zinc, 0.78 wt% of zinc sulfite, 0.006 wt% of germanium, 8.58 wt% of lead, 0.0.0121 wt% of silver and 2.23 wt% of iron. No. 1 filtrate contains 37.0 g/L of zinc, 0.0465 g/L of germanium, 0.015 g/L of lead, trace silver, 4.60 g/L of total iron and 0.08 g/L of ferric iron.
4) And (3) tannic acid germanium precipitation: taking 65 liters of No. 1 filtrate, heating to 70-80 ℃, adding 105 grams of tannic acid, stirring for 15-20 minutes, filtering II to obtain 152 grams of No. 2 tannin germanium residue and 64 liters of No. 2 germanium precipitation solution, wherein the No. 2 tannin germanium residue contains 31.5 wt% of water, 4.90 wt% of zinc, 2.73 wt% of germanium, 0.51 wt% of lead, trace amount of silver and 0.36 wt% of iron. After No. 2 germanium precipitation, the liquid contains 37.43 g/L zinc, 0.0028 g/L germanium, 0.0007 g/L lead, trace silver and 4.74 g/L iron. And feeding the liquid after the No. 2 germanium precipitation into a zinc production system to be used as slurry to recover the zinc. 140 g of the produced No. 2 tannin germanium slag is sent to a germanium recovery workshop for burning, and 16.3 g of germanium concentrate is obtained, wherein the germanium concentrate contains 28.25 wt% of zinc, 16.04 wt% of germanium, 2.94 wt% of lead and 2.07 wt% of trace iron of silver.
5) Slurry treatment of No. 1 slag: adding 3000 g of No. 1 slag into 12L of industrial water for slurrying, wherein the slurrying time is 10 minutes, and stirring and slurrying uniformly for later use.
6) High-temperature high-acid leaching of No. 1 slag: and (3) leaching the residue No. 1 after stirring and slurrying uniformly by adopting high-temperature high acid, adjusting the acidity by using sulfuric acid or zinc electrolysis waste liquid, controlling the initial acidity to be 60-80 g/l, controlling the temperature to be 85-90 ℃, stirring for 1.5-2.5 hours, filtering III, and filtering III to obtain 11 liters of filtrate No. 3 and 1370 g of residue No. 3. No. 3 filtrate contains 46.03 g/L zinc, 0.0106 g/L germanium, 0.001 lead, trace silver, 4.53 g/L total iron and trace ferric iron. The No. 3 filter residue contains 9.5 wt% of water, 4.75 wt% of zinc, 0.0038 wt% of germanium, 18.93 wt% of lead, 0.0267 wt% of silver and 1.12 wt% of iron.
7) No. 3 filter residue washing: adding 1200 g of No. 3 filter residue into 6L of industrial water for slurrying, stirring for 30 minutes, filtering IV, and filtering 4 to obtain 5.5L of No. 4 washing water and 1140 g of No. 4 filter residue. No. 4 washing water contains 3.95 g/L of zinc, 0.0001 g/L of germanium, trace lead and silver, 0.76 g/L of total iron and trace ferric iron. The residue No. 4 is the lead-silver concentrate with the components of 8.0 wt% of water, 2.84 wt% of zinc, 0.0039 wt% of germanium, 19.60 wt% of lead, 0.0276 wt% of silver and 0.76 wt% of iron.
The economic indexes obtained by calculation are as follows:
1. and (3) oxidation process of the zinc sulfite slag: 99.0 wt% of zinc sulfite oxidation rate, 77.3 wt% of zinc leaching rate and 93.5 wt% of germanium leaching rate.
2. From zinc sulfite slag to lead-silver concentrate: the lead recovery rate is 98.6 wt%, and the silver recovery rate is 99.0 wt%.
3. From zinc sulfite slag to germanium concentrate: the recovery rate of germanium is 87.7 wt%.
As can be seen from table 1 comparison of the test data for several different oxidation methods:
1. the oxidation rate of zinc sulfite is not as high as about 80%, the leaching rate of zinc is about 61%, and the leaching rate of germanium is about 59% by pure air oxidation. The germanium leaching rate is very low, so the germanium recovery rate is not high.
2. Air oxidation and hydrogen peroxide, wherein the oxidation rate of zinc sulfite is about 89%, the leaching rate of zinc is about 71%, and the leaching rate of germanium is about 73%;
3. air oxidation and potassium permanganate, wherein the oxidation rate of zinc sulfite is about 90%, the leaching rate of zinc is about 73%, and the leaching rate of germanium is about 80%;
4. air oxidation + (hydrogen peroxide and potassium permanganate), wherein the hydrogen peroxide and potassium permanganate are not equal to 2-4:1 (weight ratio), the oxidation rate of zinc sulfite is about 88%, the leaching rate of zinc is about 72%, and the leaching rate of germanium is about 80%.
5. Air oxidation + (hydrogen peroxide and potassium permanganate), and the weight ratio of the double water to the potassium permanganate is 2-4:1, the oxidation rate of the zinc sulfite is up to more than 98.9%, the leaching rate of the zinc is more than 81%, and the leaching rate of the germanium is more than 93%.
The method can be used by installing the air pipe in the leaching tank of the original equipment without adding new equipment, so the method has the advantages of short process, simple equipment, simple and convenient operation, stable effect, low cost and practical application value; (2) the key point of the method is that the weight ratio of the double water to the potassium permanganate is 2-4:1, and the strong oxidation effect can be generated only in the ratio, so that the oxidation rate of the zinc sulfite can reach more than 98.9 percent, the leaching rate of the zinc is more than 81 percent, and the leaching rate of the germanium is more than 93 percent. (3) The method has high oxidation rate of the zinc sulfite slag, does not generate a large amount of sulfur dioxide gas in the sulfuric acid leaching of the next procedure, can reduce the absorption treatment cost of the sulfur dioxide gas, reduces the safe and environment-friendly cost, and can achieve the purposes of safety, environment protection and comprehensive utilization of resources of the zinc sulfite slag; (4) the method does not produce waste gas, waste water and waste residue, beautifies the operating environment and realizes green production; (5) the method has high recovery rate of valuable metals of zinc, germanium, lead and silver, and the produced germanium concentrate has high grade, thus being a comprehensive utilization technology of zinc oxide desulfurization products with better industrialized prospect.
Claims (10)
1. A method for comprehensively recovering valuable metals by deep oxidation and harmlessness of zinc sulfite slag is characterized in that zinc oxide powder produced by a zinc volatilization kiln is directly used for slurrying and absorbing low-concentration sulfur dioxide flue gas produced by the zinc volatilization kiln to obtain zinc sulfite slag, the zinc sulfite slag is slurried, then air oxidation is carried out, then mixed oxidant is added for deep oxidation, heating and temperature rise are carried out, and finally filtration is carried out to produce zinc sulfate solution containing germanium and zinc oxide slag, products are zinc hydrometallurgy raw materials, the zinc sulfate solution is high in germanium content and low in zinc and ferric iron, and the germanium is directly recovered to obtain high-grade germanium concentrate; and (3) recovering zinc by acid leaching the zinc oxide slag, producing lead-silver concentrate to recover lead and silver, and comprehensively recovering valuable metals of zinc, germanium, lead and silver.
2. The method for comprehensively recovering valuable metals from zinc sulfite slag through deep oxidation and harmlessness according to claim 1, characterized in that the comprehensive recovery method is realized by adopting the following steps:
1) slurrying of zinc sulfite slag: using the slurry to mix the zinc sulfite slag according to the weight ratio of 6-7: pulping at the liquid-solid ratio of 1 for 10 minutes, and stirring uniformly for later use;
2) air oxidation of pulp slurry: introducing compressed air into the uniformly stirred and pulped ore pulp by adopting a reverse method, adjusting the acidity by using 150g/l-200g/l sulfuric acid or other acid-containing filtrate in the process, keeping the pH value in the process to be 3.5-4.0, stirring at normal temperature, and carrying out air oxidation for 2.0-2.5 hours to obtain an air oxidation solution;
3) deep oxidation of mixed oxidant: adding hydrogen peroxide in an amount which is 2 to 4 weight percent of the amount of the zinc sulfite slag into the air oxidized liquid and potassium permanganate in an amount which is 0.5 to 1.0 weight percent of the amount of the zinc sulfite slag, adjusting the acidity by using 150 to 200g/l of sulfuric acid or other acid-containing filtrate, keeping the pH value in the process between 2.0 and 3.0, carrying out deep oxidation for 1.0 to 1.5 hours, finally heating to 40 to 50 ℃, filtering I, and filtering I to obtain No. 1 slag and No. 1 filtrate;
4) and (3) tannic acid germanium precipitation: heating the No. 1 filtrate to 70-80 ℃, adding tannic acid according to the multiplying power of 25-35, stirring for 15-20 minutes, filtering II to obtain No. 2 tannin germanium slag and No. 2 germanium-precipitated liquid, feeding the produced No. 2 germanium-precipitated liquid into a zinc production system to be pulped to recover zinc, and feeding the produced No. 2 tannin germanium slag to a germanium recovery workshop to be burned to obtain No. 5 germanium concentrate;
5) slurry treatment of No. 1 slag: and (3) using the slurry to mix No. 1 slag according to the weight ratio of 3-4: pulping at the liquid-solid ratio of 1 for 10 minutes, and stirring uniformly for later use;
6) high-temperature high-acid leaching of No. 1 slag: leaching residue No. 1 after stirring and slurrying uniformly by adopting high-temperature high acid, adjusting the acidity by using sulfuric acid or zinc electrolysis waste liquid, controlling the initial acidity to be 60-80 g/l, controlling the temperature to be 85-90 ℃, stirring for 1.5-2.5 hours, filtering III, and filtering III to obtain filtrate No. 3 and residue No. 3;
7) no. 3 filter residue washing: and (3) using industrial water to remove residue according to the weight ratio of 4-5: slurrying the slurry according to the liquid-solid ratio of 1, stirring for 30 minutes, and filtering IV to obtain No. 4 washing water and No. 4 filter residue, wherein the No. 4 filter residue is the lead-silver concentrate.
3. The method for comprehensively recovering valuable metals from zinc sulfite slag through deep oxidation and harmlessness according to claim 1, characterized in that the slurry in the step (1) is industrial water or No. 4 washing water.
4. The method for comprehensively recovering valuable metals from zinc sulfite slag through deep oxidation and harmlessness according to claim 1, characterized in that the reverse method in the step (2) is that the direction of air introduced into the stirring tank is opposite to the stirring direction;
the sulfuric acid in the step (2), the step (3) and the step (6) is industrial concentrated sulfuric acid;
and (3) the other acid-containing filtrate in the step (2) and the step (3) is No. 3 filtrate.
5. The method for comprehensively recovering valuable metals from the zinc sulfite slag through deep oxidation and harmlessness according to claim 1, wherein the hydrogen peroxide chemical name in the step (3) is hydrogen peroxide for industrial use; potassium permanganate is used industrially.
6. The method for comprehensively recovering valuable metals from zinc sulfite slag through deep oxidation and harmlessness according to claim 1, wherein the ratio of the added tannic acid in the step (4) is the ratio of the weight of the added tannic acid to the total germanium content of the germanium precipitation solution.
7. The method for comprehensively recovering valuable metals from the deep oxidation and the harmlessness of the zinc sulfite residue according to claim 1, wherein 25 to 30 weight percent of zinc, 1.0 to 3.0 weight percent of iron, 14.0 to 20.0 weight percent of germanium and 2.0 to 5.0 weight percent of lead are contained in the germanium concentrate No. 5 in the step (4).
8. The method for comprehensively recovering valuable metals from the zinc sulfite residue through deep oxidation and harmlessness according to claim 1, characterized in that the slurry in the step (5) is zinc electrolysis waste liquid and No. 4 washing water or industrial water.
9. The method for comprehensively recovering valuable metals from the deep oxidation and the harmlessness of the zinc sulfite residue according to claim 1, wherein the residue No. 4 in the step (7) is a lead-silver concentrate, and the lead-silver concentrate contains 2.0 wt% -5.0 wt% of zinc, 10.0 wt% -20.0 wt% of lead and 0.0160 wt% -0.040 wt% of silver.
10. The method for comprehensively recovering valuable metals from the zinc sulfite slag through deep oxidation and harmlessness according to claim 1, wherein the zinc sulfite slag mainly comprises the following components: 25 to 40 weight percent of zinc, 20 to 35 weight percent of zinc sulfite, 1.0 to 4.0 weight percent of iron, 0.02 to 0.04 weight percent of germanium, 2.0 to 4.0 weight percent of lead and 0.001 to 0.006 weight percent of silver.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174496A (en) * | 2021-04-22 | 2021-07-27 | 甘肃厂坝有色金属有限责任公司 | Method and system for supplementing manganese in zinc hydrometallurgy |
| CN113528816A (en) * | 2021-07-23 | 2021-10-22 | 昆明冶金研究院有限公司 | Method for directly acid-leaching and floating zinc oxide concentrate |
| CN115304095A (en) * | 2022-08-25 | 2022-11-08 | 萍乡宝海锌营养科技有限公司 | Method for oxidizing zinc sulfite into zinc sulfate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996002679A1 (en) * | 1994-07-19 | 1996-02-01 | Metals Recycling Technologies Corp. | Method for the reclamation of metallic compounds |
| CN106916945A (en) * | 2017-03-14 | 2017-07-04 | 云南罗平锌电股份有限公司 | The method that valuable metal is reclaimed in the integrated treatment of a kind of low germanium zinc-oxide calcine of high ferro and zinc sulfite |
| CN107983136A (en) * | 2017-12-21 | 2018-05-04 | 双盾环境科技有限公司 | A kind of technique of ash-laden gas recycling Sulphur ressource using after zinc calcine or zinc roasting |
| CN110184482A (en) * | 2019-05-29 | 2019-08-30 | 昆明理工大学 | A kind of germanic Second-rate zinc oxide powder extract technology |
-
2020
- 2020-03-17 CN CN202010187100.5A patent/CN111235392A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996002679A1 (en) * | 1994-07-19 | 1996-02-01 | Metals Recycling Technologies Corp. | Method for the reclamation of metallic compounds |
| CN106916945A (en) * | 2017-03-14 | 2017-07-04 | 云南罗平锌电股份有限公司 | The method that valuable metal is reclaimed in the integrated treatment of a kind of low germanium zinc-oxide calcine of high ferro and zinc sulfite |
| CN107983136A (en) * | 2017-12-21 | 2018-05-04 | 双盾环境科技有限公司 | A kind of technique of ash-laden gas recycling Sulphur ressource using after zinc calcine or zinc roasting |
| CN110184482A (en) * | 2019-05-29 | 2019-08-30 | 昆明理工大学 | A kind of germanic Second-rate zinc oxide powder extract technology |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174496A (en) * | 2021-04-22 | 2021-07-27 | 甘肃厂坝有色金属有限责任公司 | Method and system for supplementing manganese in zinc hydrometallurgy |
| CN113528816A (en) * | 2021-07-23 | 2021-10-22 | 昆明冶金研究院有限公司 | Method for directly acid-leaching and floating zinc oxide concentrate |
| CN115304095A (en) * | 2022-08-25 | 2022-11-08 | 萍乡宝海锌营养科技有限公司 | Method for oxidizing zinc sulfite into zinc sulfate |
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Application publication date: 20200605 |