CN117625956B - Efficient zinc extraction method for zinc calcine - Google Patents
Efficient zinc extraction method for zinc calcine Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 235
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 163
- 238000000605 extraction Methods 0.000 title claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 163
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000007788 liquid Substances 0.000 claims abstract description 122
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 120
- 230000007935 neutral effect Effects 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000011787 zinc oxide Substances 0.000 claims abstract description 58
- 239000012535 impurity Substances 0.000 claims abstract description 50
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 50
- 238000005406 washing Methods 0.000 claims abstract description 42
- 239000000779 smoke Substances 0.000 claims abstract description 41
- 239000007787 solid Substances 0.000 claims abstract description 40
- 238000000746 purification Methods 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 36
- 239000000428 dust Substances 0.000 claims abstract description 34
- 238000004070 electrodeposition Methods 0.000 claims abstract description 27
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims abstract description 18
- 230000002195 synergetic effect Effects 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 238000005266 casting Methods 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims description 75
- 239000006228 supernatant Substances 0.000 claims description 55
- 239000002699 waste material Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 239000003792 electrolyte Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008235 industrial water Substances 0.000 claims description 10
- 238000004537 pulping Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000001603 reducing effect Effects 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 24
- 238000001035 drying Methods 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 19
- 238000009826 distribution Methods 0.000 description 12
- 239000010865 sewage Substances 0.000 description 8
- 238000005363 electrowinning Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 241000695274 Processa Species 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a high-efficiency zinc extraction method for zinc calcine, and belongs to the technical field of nonferrous metal extraction. The method comprises 8 working procedures of zinc calcine neutral leaching, zinc oxide smoke neutral leaching, collaborative leaching, preneutralization, washing, GT superoxide body preparation impurity removal, deep purification, electrodeposition and casting; the zinc calcine is firstly neutral leached to realize a great amount of leaching of ZnO which is a main phase, the impurities are hardly leached, and the neutral leaching liquid can be directly purified without neutralization and iron removal; synergistic reduction leaching of refractory ZnFe in calcine by utilizing refractory ZnS in zinc oxide smoke 2 O 4 The leaching rate of zinc calcine and zinc oxide smoke dust can be improved simultaneously; the neutralization stage is realized by regulating and controlling Fe 3+ And Fe (Fe) 2+ The proportion of the GT super-oxygen body with magnetism and larger particles is generated, the filtering and separating time is shortened, meanwhile, the impurity removing efficiency of the GT super-oxygen body is high, and the subsequent purifying burden is lightened. The Zn direct yield of the invention reaches 98.37 percent, the liquid-solid separation time after neutralization is reduced to 10 minutes, the zinc powder purifying consumption per ton of zinc is reduced to 2.40kg, and the GT super-oxygen iron content after drying reaches 52.51 percent.
Description
Technical Field
The invention relates to a high-efficiency zinc extraction method for zinc calcine, and belongs to the technical field of nonferrous metal extraction.
Background
Zinc is an important nonferrous metal raw material, and at present, more than 80% of zinc adopts a hydrometallurgical method. At present, two production lines are commonly built in zinc smelting enterprises, namely zinc concentrate and calcine leaching slag are respectively used as raw materials, zinc concentrate is produced by the processes of oxidizing roasting, leaching, neutralizing, deironing, purifying and electrodepositing, the calcine leaching slag is produced by the processes of reducing roasting, leaching, neutralizing, deironing, purifying and electrodepositing, and zinc ferrite is easily produced in the oxidizing roasting process of the zinc concentrate, so that zinc leaching is influenced; in the reduction roasting process of the calcine leaching slag, the phase oxidation transformation degree of the zinc sulfide phase is not high, so that zinc leaching is affected; simultaneously, two materials are subjected to neutralization and iron removal processes by Fe 3+ The hydrolysis is colloid to absorb impurities and remove iron synchronously, but the iron slag obtained by filtration is slow, precipitation is low in grade and impurity absorption rate, and a large amount of zinc powder is needed to be supplemented to realize deep purification. The direct yield of zinc extraction from zinc calcine in the existing process is only 90%, the liquid-solid separation time of iron slag is more than 1h, the Fe content in the iron slag is less than 25%, and 55kg of purified zinc powder is consumed in production of zinc per ton.
Patent CN201110096566.5 discloses a method for separating iron and zinc in the traditional zinc hydrometallurgy process, which is characterized in that zinc calcine is reduced and roasted under the condition of low reducing atmosphere, so that zinc ferrite in the zinc calcine is decomposed into zinc oxide and magnetic ferroferric oxide, the reduced calcine is leached out of zinc by weak acid, separation of iron and zinc is realized, and iron concentrate is recovered by weak magnetic separation after grinding zinc leaching slag. However, zinc ferrite is leached at high cost by the pyrogenic process. Patent CN2015147096. X discloses a zinc hydrometallurgy process, wherein hot calcine obtained by fluidized bed roasting of zinc concentrate is directly introduced with mixed gas of sulfur dioxide and oxygen for heat preservation, and after heat preservation, a section of weak acid leaching is carried out to obtain zinc sulfate leaching solution, and after purification of the zinc sulfate leaching solution, electrowinning is carried out. But solving zinc ferrite by maintaining the temperature of the hot calcine also increases the processing cost.
Patent CN202210401366.4 discloses a method for removing iron from zinc hydrometallurgy leaching solution and application thereofSlowly dripping the zinc hydrometallurgy leaching solution into a closed container filled with a mixed solution of an oxidant and ammonia water, and stirring at normal temperature for reaction to obtain a zinc-ammonia complex solution and magnetite with low crystallinity; and heating and stirring to react after the dripping is finished to obtain zinc-containing solution and magnetite with high crystallinity, and separating solid from liquid, wherein the process is complex. Patent CN201410174685.1 discloses a method for removing iron from zinc solution by using an SO 2 /O 2 And (3) carrying out catalytic oxidation neutralization and iron removal on the (air) mixed gas. The method can reduce Fe 2+ Oxidation to Fe 3+ Thereby effectively accelerating Fe 2+ Oxidation rate. But the resulting iron slag is still in a colloidal form and is poorly filtered.
Disclosure of Invention
Aiming at the problems that zinc ferrite is difficult to leach, iron slag is difficult to filter, iron slag grade is low, zinc powder consumption is large and the like in the conventional zinc calcine wet zinc extraction process, the invention provides a high-efficiency zinc extraction method for zinc calcine, which comprises 8 working procedures of zinc calcine neutral leaching, zinc oxide smoke neutral leaching, collaborative leaching, preneutralization, washing, GT super-oxygen body preparation impurity removal, deep purification, electrodeposition and fusion casting: the zinc calcine is firstly neutral leached, a great amount of ZnO which is a main phase is leached, the impurities are hardly leached, the neutral leaching liquid can be directly purified without neutralization and iron removal, and the burden of the neutralization and iron removal process is reduced; synergistic leaching of refractory ZnFe in calcine by refractory ZnS in zinc oxide fume 2 O 4 S in ZnS 2- Has reducing effect and can reduce ZnFe 2 O 4 Fe of (B) 3+ Reduction to destroy ZnFe 2 O 4 The crystal lattice can simultaneously improve the leaching rate of zinc calcine and zinc oxide smoke dust; the neutralization stage is realized by regulating and controlling Fe 3+ And Fe (Fe) 2+ The proportion of the produced GT super-oxygen is magnetic, the particles are larger, the GT super-oxygen is easy to filter and separate, and meanwhile, different types of impurity ions can be combined in the GT super-oxygen crystal lattice, so that the impurity removal efficiency is high, and the subsequent purification burden is reduced. The method has the advantages that the Zn direct yield reaches 98.37 percent, the liquid-solid separation time is reduced to 10 minutes after neutralization, the consumption of zinc powder for zinc purification per ton is reduced to 2.40kg, and the GT super-oxygen iron content reaches 52.51 percent after drying.
The high-efficiency zinc extraction method for zinc calcine comprises the following specific steps:
(1) Neutral leaching of zinc calcine: mixing zinc calcine, sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I and underflow I;
(2) Neutral leaching of zinc oxide smoke dust: mixing zinc oxide smoke dust with washing liquid to obtain slurry, mixing the slurry with sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I 'and underflow I';
(3) Synergistic leaching: mixing the bottom flow I and the bottom flow I' to obtain a mixed bottom flow, adding sulfuric acid into the mixed bottom flow to perform synergistic leaching, and performing liquid-solid separation to obtain leaching liquid II and leaching residue II;
(4) Pre-neutralization: the zinc calcine is utilized to preneutralize the leaching solution II, the underflow III and the supernatant III are obtained through dense separation, and the underflow III returns to the collaborative leaching process of the step (3);
(5) Washing: washing leaching residue II by using industrial water to obtain washing liquid and lead slag, and returning the washing liquid to the pulp mixing procedure of the step (2);
(6) Preparing GT superoxide to remove impurities: splitting the supernatant III to obtain a first split flow liquid and a second split flow liquid, reducing the second split flow liquid iron powder, merging the reduced second split flow liquid iron powder with the first split flow liquid, and neutralizing the reduced second split flow liquid iron powder with an alkali reagent to obtain impurity GT superoxide and impurity-removed liquid;
(7) Deep purification: mixing the supernatant I and the supernatant I' with the impurity-removed liquid to carry out deep purification and impurity removal to obtain purified slag and deep purification liquid, wherein the purified slag returns to the cadmium smelting system;
(8) Electrodeposition and casting: and (3) carrying out electro-deposition on the deep purification liquid to obtain electro-deposited zinc and waste electro-deposition liquid, casting the electro-deposited zinc to obtain zinc ingots, and returning the waste electro-deposition liquid to the neutralization leaching process of the step (1) and the step (2).
The zinc calcine in the step (1) contains 50-65% of Zn, 1-3% of Pb, 6-12% of Fe and 1-3% of S by mass percent; 85-95% ZnO, 0.1-3% ZnS and ZnFe in Zn phase 2 O 4 3.9-8%, and 1-4% of other zinc phases; the acidity of the waste electrolyte is 100-160 g/L, the initial neutral leaching acidity is 113.17-219.82 g/L, the neutral leaching temperature is 40-65 ℃, the liquid-solid ratio is mL, the g is 3:1-8:1, and the time is prolongedThe pH of the neutral leaching end point is 4.5-5.3, and the concentration separation time is 10-20 min;
zn in the supernatant I 2+ The content of Pb is 75.68-139.08 g/L 2+ The content is 50-85 mg/L, fe 2+ The content of Fe is 3.17-26.34 mg/L 3+ The content is 0.16-1.29 g/L; the water content of the underflow I is 40-60%, the Zn content is 21.00-26.40%, the Pb content is 5.93-8.22%, the Fe content is 29.44-34.83%, and the S content is 2.96-4.11% based on the mass percentage of slag in the underflow I; znO accounts for 10.27-27.74%, znS accounts for 1.44-29.91%, and ZnFe in Zn phase in slag of underflow I 2 O 4 35.89-56.36%, and other zinc phases 14.45-23.93%.
The zinc oxide smoke dust in the step (2) contains 40-60% of Zn, 8-15% of Pb, 1-2% of Fe and 3-8% of S by mass percent; 82-91% ZnO, 8.8-17% ZnS and ZnFe in Zn phase 2 O 4 0.1-0.5%, and other zinc phases 0.1-0.5%; the liquid-solid ratio of the washing liquid to the zinc oxide smoke dust is mL, g is 2:1-4:1, and the pulping time of the pulping is 2-6 min; the acidity of the waste electrolyte is 100-160 g/L, the initial neutral leaching acidity is 101.84-128.69 g/L, the liquid-solid ratio mL of the waste electrolyte to zinc oxide smoke dust is 4:1-8:1, the neutral leaching temperature is 40-65 ℃, the leaching time is 5-30 min, the end pH of the neutral leaching is 4.5-5.3, and the dense separation time is 10-20 min.
Zn in the supernatant I' of the step (2) 2+ The content of Pb is 66.95-80.54 g/L 2+ The content is 50-85 mg/L, fe 2+ The content of Fe is 56.23mg/L to 0.15g/L 3+ The content is 1.15-3.10 mg/L; the water content of the bottom flow I 'is 40-60%, the Zn content is 17.99-25.58%, the Pb content is 31.79-34.67%, the Fe content is 2.23-5.20%, and the S content is 10.73-16.64% based on the mass percentage of slag in the bottom flow I'; 8.43-16.96% ZnO, 81.19-86.48% ZnS and ZnFe in Zn phase in slag of underflow I 2 O 4 0.92-2.54% and 0.92-2.54% of other zinc phases.
The initial acidity of the synergistic leaching in the step (3) is 258.to 401.29g/L, the leaching temperature is 75 to 90 ℃, the liquid-solid ratio mL is 2:1 to 6:1, the leaching time is 90 to 180min, the acidity of the leaching end point is 20 to 40g/L, and the solid-liquid ratio in the synergistic leaching process is lower than that in the neutral leaching processA liquid ratio; zn in leaching solution II 2+ The content of Pb is 40.89-86.78 g/L 2+ The content is 60-95 mg/L, fe 2+ The content of Fe is 1.73-4.88 g/L 3+ The content is 15.55-43.93 g/L.
The pH of the end point of the pre-neutralization in the step (4) is 2-4, the pre-neutralization temperature is 50-70 ℃, and the pre-neutralization time is 15-45 min; zn in supernatant III 2+ The content of Pb is 57.90-81.36 g/L 2+ The content is 70-105 mg/L, fe 2+ The content of Fe is 1.73-4.87 g/L 3+ The content is 15.60-43.94 g/L; the water content of the bottom flow III is 25-35%, the Zn content is 21-26.40%, the Pb content is 5.93-8.22%, the Fe content is 29.44-34.83%, and the S content is 2.96-4.11% based on the mass percentage of slag in the bottom flow III.
The pH value of the industrial water in the step (5) is 4-5, the liquid-solid ratio mL in the washing process is 5.98:1-23.46:1, and the washing time is 5-15 min; the lead slag comprises, by mass, 6.71-7.77% of Zn, 52.78-54.35% of Pb, 15.97-22.62% of Fe and 5.63-7.80% of S; znO in Zn phase in lead slag accounts for 0.0062-0.018%, znS accounts for 34.17-39.95%, and ZnFe 2 O 4 26.12-38.80% and 21.34-35.92% of other zinc phases.
The volume ratio of the first split flow liquid to the second split flow liquid in the step (6) is 4.01-4.5:1, the liquid-solid ratio of the iron powder to the second split flow liquid is mL, g is 45.52:1-128.22:1, the alkaline agent is NaOH, KOH or ammonia water, the pH value in the neutralization process is 4.6-5.4, the neutralization temperature is 55-65 ℃, and the neutralization time is 60-120 min; zn in the solution after impurity removal 2+ The content of Pb is 55.00-77.29 g/L 2+ The content is 25-42 mg/L, fe 2+ The content of Fe is 34.85-70.23 mg/L 3+ The content is 69.69mg/L to 0.14g/L; the GT superoxide is 6.78-9.39% in Zn, 0.19-0.48% in Pb and 39.25-43.03% in Fe in percentage by mass, and can return to the sewage acid and sewage impurity removal system.
Zn in the mixed solution of the supernatant I, the supernatant I' and the impurity-removed liquid in the step (7) 2+ The content of Pb is 69.36-99.02 g/L 2+ The content is 39.72-73.82 mg/L, fe 2+ The content of Fe is 30.4-78.18 mg/L 3+ The content is 77.19mg/L to 0.46g/L; the temperature of deep purification and impurity removal is 55-65 ℃ and the time isThe pH value in the deep purification and impurity removal process is 5.2-5.5 for 120-180 min; zn in deep purifying liquid 2+ The content of Pb is 69.51-99.63 g/L 2+ The content of Fe is 0.40-0.74 mg/L 2+ The content of Fe is 0.30-0.78 mg/L 3+ The content is 0.77-4.57 mg/L; the purifying slag comprises, by mass, 6.32-7.75% of Zn, 2.49-15.76% of Pb and 22.98-32.71% of Fe.
And (3) the acidity of the waste electro-deposition liquid in the step (8) is 100-160 g/L.
The beneficial effects of the invention are as follows:
(1) The zinc calcine is subjected to neutral leaching to realize massive leaching of the main phase ZnO, the impurity Fe is hardly leached, the neutral leaching liquid can be directly purified without neutralization and deironing, the solution amount in the neutralization and deironing process is reduced, and the absorption loss of iron slag in the deironing process on zinc package can be reduced;
(2) The method utilizes the refractory ZnS in the zinc oxide smoke to cooperatively leach the refractory ZnFe in the calcine 2 O 4 S in ZnS 2- Has reducing effect and can reduce ZnFe 2 O 4 Fe of (B) 3+ Reduction to destroy ZnFe 2 O 4 The crystal lattice can simultaneously improve the leaching rate of zinc calcine and zinc oxide smoke dust, and the Zn direct yield reaches 98.37 percent;
(3) The invention regulates and controls Fe in the neutralization stage 3+ And Fe (Fe) 2+ The proportion of GT superoxide (Fe-like) 3 O 4 The structure of the (2) GT super-oxygen body has magnetism, larger particles, easy filtration and separation, the liquid-solid separation time is reduced to 10min after neutralization, and the iron content of the GT super-oxygen body reaches 52.51 percent after drying. Meanwhile, different types of impurity ions can be combined in the GT super-oxide crystal lattice, so that the impurity removal efficiency is high, the subsequent purification load is reduced, and the consumption of zinc powder for zinc purification per ton is reduced to 2.40kg.
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: the main components of the zinc calcine of the embodiment are shown in table 1.1, the zinc phase distribution in the zinc calcine is shown in table 1.2, the main components of zinc oxide smoke dust are shown in table 2.1, the zinc phase distribution in the oxidized smoke dust is shown in table 2.2, and the acidity of the waste electrowinning liquid is 100g/L;
table 1.1 main component of zinc calcine (wt.%)
| Zn | Pb | Fe | S |
| 50% | 3% | 12% | 3% |
Table 1.2 zinc phase distribution (wt.%) in zinc calcine
| ZnO | ZnS | ZnFe 2 O 4 | Other zinc phases | Sum total |
| 85% | 3% | 8% | 4% | 100 |
TABLE 2.1 zinc oxide Smoke Main ingredient (wt.%)
| Zn | Pb | Fe | S |
| 40% | 15% | 1% | 8% |
Table 2 zinc phase distribution (wt.%) in zinc oxide fume
| ZnO | ZnS | ZnFe 2 O 4 | Other zinc phases | Sum total |
| 82% | 17% | 0.5% | 0.5% | 100 |
The method for efficiently extracting zinc from zinc calcine (see figure 1) comprises the following specific steps:
(1) Neutral leaching of zinc calcine: mixing zinc calcine, sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I and underflow I; wherein the initial acidity of neutral leaching is 219.82g/L, the temperature of neutral leaching is 40 ℃, the liquid-solid ratio is mL, g is 3:1, the time is 5min, and the final pH of neutral leaching is 4.5; the concentration separation time is 10min, and Zn in supernatant I 2+ The content of Pb is 139.08g/L 2+ The content is 50mg/L, fe 2+ The content of Fe is 26.34mg/L 3+ The content is 1.29g/L; the water content of the bottom flow I is 40%, the Zn content is 21.00%, the Pb content is 7.61%, the Fe content is 29.44% and the S content is 3.80% based on the mass percentage of slag in the bottom flow I; znO in Zn phase in slag of underflow I accounts for 10.27%, znS accounts for 29.91%, and ZnFe 2 O 4 35.89% and 23.93% of other zinc phases;
(2) Neutral leaching of zinc oxide smoke dust: mixing zinc oxide smoke dust with washing liquid to obtain slurry, mixing the slurry with sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I 'and underflow I'; wherein the solid ratio of the washing liquid to the zinc oxide smoke dust is mL, g is 2:1, and the pulping time of the pulping is 2min; the initial acidity of neutral leaching is 128.69g/L, the liquid-solid ratio mL of waste electrolyte to germanium-containing zinc oxide smoke dust is 4:1, the temperature of neutral leaching is 40 ℃, the leaching time is 5min, and the end pH of neutral leaching is4.5; the concentration separation time is 10min, zn in supernatant I' 2+ The content of Pb is 80.54g/L 2+ The content is 50mg/L, fe 2+ The content is 89.03mg/L, fe 3+ The content is 1.82mg/L; the water content of the bottom flow I 'is 40%, the Zn content is 17.99%, the Pb content is 34.67%, the Fe content is 2.23%, and the S content is 16.64% based on the mass percentage of slag in the bottom flow I'; 8.43% ZnO, 86.48% ZnS and ZnFe in Zn phase in slag of underflow I 2 O 4 2.54% and 2.54% of other zinc phases;
(3) Synergistic leaching: mixing the bottom flow I and the bottom flow I' to obtain a mixed bottom flow, adding sulfuric acid into the mixed bottom flow to perform synergistic leaching, and performing liquid-solid separation to obtain leaching liquid II and leaching residue II; the initial acidity of the collaborative leaching is 401.29g/L, the collaborative leaching temperature is 75 ℃, the solid ratio of the collaborative leaching solution is mL, g is 2:1, the collaborative leaching time is 90min, the final acidity of the collaborative leaching is 20g/L, and the solid-liquid ratio of the collaborative leaching process is lower than that of the neutral leaching process in the step (1) and the step (2); zn in leaching solution II 2+ The content of Pb is 86.78g/L 2+ The content is 60mg/L, fe 2+ The content of Fe is 4.88g/L 3+ The content is 43.93g/L;
(4) Pre-neutralization: the zinc calcine is utilized to preneutralize the leaching solution II, the underflow III and the supernatant III are obtained through dense separation, and the underflow III returns to the collaborative leaching process of the step (3); the pH of the endpoint of the pre-neutralization is 2, the pre-neutralization temperature is 50 ℃, and the pre-neutralization time is 15min; zn in supernatant III 2+ The content of Pb is 81.36g/L 2+ The content is 70mg/L, fe 2+ The content of Fe is 4.87g/L 3+ The content is 43.94g/L; the water content of the bottom flow III is 25%, the Zn content is 21.00%, the Pb content is 7.61%, the Fe content is 29.44% and the S content is 3.80% based on the mass percentage of slag in the bottom flow III;
(5) Washing: washing leaching residue II by using industrial water to obtain washing liquid and lead slag, and returning the washing liquid to the pulp mixing procedure of the step (2); the pH of the industrial water is 4, the liquid-solid ratio mL in the washing process is 5.98:1, and the washing time is 5min; in mass percent, the Zn content in the lead slag is 7.25%, the Pb content is 53.79%, the Fe content is 15.97%, and the S content is 7.80%; znO in Zn phase in lead slag accounts for 0.0062% and ZnS accounts for 37.60%、ZnFe 2 O 4 26.12% and 35.92% of other zinc phases;
(6) Preparing GT superoxide to remove impurities: splitting the supernatant III to obtain a first split flow liquid and a second split flow liquid, reducing the second split flow liquid iron powder, merging the second split flow liquid with the first split flow liquid, and neutralizing the first split flow liquid by using an alkali reagent NaOH to obtain impurity GT superoxide and impurity-removed liquid; the volume ratio of the first split flow liquid to the second split flow liquid is 4.01:1, and the liquid-solid ratio mL of the iron powder to the second split flow liquid is 45.52:1; the pH value in the neutralization process is 4.6, the neutralization temperature is 55 ℃, and the neutralization time is 60min; zn in the solution after impurity removal 2+ The content of Pb is 77.29g/L 2+ The content is 25mg/L, fe 2+ The content of Fe is 70.23mg/L 3+ The content is 0.14g/L; the GT superoxide has the Zn content of 6.78%, the Pb content of 0.19% and the Fe content of 43.03% in percentage by mass, and can return to the sewage acid and sewage impurity removal system;
(7) Deep purification: mixing the supernatant I and the supernatant I' with the impurity-removed liquid to carry out deep purification and impurity removal to obtain purified slag and deep purification liquid, wherein the purified slag returns to the cadmium smelting system; zn in the mixed solution of supernatant I, supernatant I' and the solution after impurity removal 2+ The content of Pb is 99.02g/L 2+ The content of Fe is 39.72mg/L 2+ The content of Fe is 64.13mg/L 3+ The content is 0.46g/L; the temperature of deep purification and impurity removal is 55 ℃, the time is 120min, and the pH value in the deep purification process is 5.2; zn in deep purifying liquid 2+ The content of Pb is 99.63g/L 2+ The content of Fe is 0.40mg/L 2+ The content of Fe is 0.64mg/L 3+ The content is 4.57mg/L; the purifying slag returns to the copper-cadmium smelting system in percentage by mass, wherein the content of Zn in the purifying slag is 7.75%, the content of Pb in the purifying slag is 2.49%, the content of Fe in the purifying slag is 32.71%;
(8) Electrodeposition and casting: electro-deposition is carried out on the deep purification and impurity removal liquid by adopting a conventional process to obtain electro-deposited zinc and waste electro-deposition liquid, zinc ingots are obtained by electro-deposition zinc casting, and the waste electro-deposition liquid is returned to the neutralization leaching process of the step (1); wherein the acidity of the waste electrowinning liquid is 100g/L;
in the embodiment, the total direct yield of Zn in the zinc calcine and the zinc oxide smoke dust is 92.13 percent, the consumption of zinc powder for purifying zinc per ton is 6.75kg, and the content of GT super-oxygen iron after drying reaches 53.45 percent.
Example 2: the main components of zinc calcine of the embodiment are shown in table 3.1, the zinc phase distribution in the zinc calcine is shown in table 3.2, the main components of zinc oxide smoke dust are shown in table 4.1, the zinc phase distribution in the oxidized smoke dust is shown in table 4.2, and the acidity of the waste electrowinning liquid is 140g/L;
table 3.1 main component of zinc calcine (wt.%)
| Zn | Pb | Fe | S |
| 55% | 2% | 8% | 2% |
Table 3.2 zinc phase distribution (wt.%) in zinc calcine
| ZnO | ZnS | ZnFe 2 O 4 | Other zinc phases | Sum total |
| 92% | 0.3% | 5.5% | 2.2% | 100 |
TABLE 4.1 zinc oxide Smoke Main ingredient (wt.%)
| Zn | Pb | Fe | S |
| 50% | 12% | 2% | 6% |
Table 4.2 zinc phase distribution (wt.%) in zinc oxide fume
| ZnO | ZnS | ZnFe 2 O 4 | Other zinc phases | Sum total |
| 88% | 11.6% | 0.2% | 0.2% | 100 |
The method for efficiently extracting zinc from zinc calcine (see figure 1) comprises the following specific steps:
(1) Neutral leaching of zinc calcine: mixing zinc calcine, sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I and underflow I; wherein the initial acidity of neutral leaching is 150.53g/L, the temperature of neutral leaching is 55 ℃, the liquid-solid ratio is mL, g is 5:1, the time is 15min, and the end pH of neutral leaching is 5; the concentration separation time is 15min, and Zn in supernatant I 2+ The content of Pb is 99.26g/L 2+ The content is 60mg/L, fe 2+ The content of Fe is 7.74mg/L 3+ The content is 0.38g/L; the water content of the bottom flow I is 50%, the Zn content is 22.06%, the Pb content is 8.22%, the Fe content is 32.08%, and the S content is 4.11% based on the mass percentage of slag in the bottom flow I; 18.85% ZnO, 3.04% ZnS and ZnFe in Zn phase in slag of underflow I 2 O 4 55.79% and 22.32% of other zinc phases;
(2) Neutral leaching of zinc oxide smoke dust: mixing zinc oxide smoke dust with washing liquid to obtain slurry, mixing the slurry with sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I 'and underflow I'; wherein the solid ratio of the washing liquid to the zinc oxide smoke dust is 3:1, and the pulping time of the pulping is 4min; the initial acidity of neutral leaching is 112.64g/L, the liquid-solid ratio mL of waste electrolyte to germanium-containing zinc oxide smoke dust is 6:1, and the neutral leaching is carried outThe temperature is 55 ℃, the leaching time is 15min, and the end point pH of neutral leaching is 5; the concentration separation time is 15min, and Zn in supernatant I' 2+ The content of Pb is 71.97g/L 2+ The content is 60mg/L, fe 2+ The content of Fe is 0.15g/L 3+ The content is 3.10mg/L; the water content of the bottom flow I 'is 50%, the Zn content is 18.61%, the Pb content is 32.74%, the Fe content is 5.20% and the S content is 14.73% based on the mass percentage of slag in the bottom flow I'; 12.90% of ZnO, 84.19% of ZnS and ZnFe in Zn phase in slag of underflow I 2 O 4 1.45% and other zinc phases 1.45%;
(3) Synergistic leaching: mixing the bottom flow I and the bottom flow I' to obtain a mixed bottom flow, adding sulfuric acid into the mixed bottom flow to perform synergistic leaching, and performing liquid-solid separation to obtain leaching liquid II and leaching residue II; the initial acidity of the collaborative leaching is 258.33g/L, the collaborative leaching temperature is 85 ℃, the solid ratio of the collaborative leaching solution is mL, g is 4:1, the collaborative leaching time is 150min, the final acidity of the collaborative leaching is 30g/L, and the solid-liquid ratio of the collaborative leaching process is lower than that of the neutral leaching process in the step (1) and the step (2); zn in leaching solution II 2+ The content of Pb is 47.32g/L 2+ The content is 70mg/L, fe 2+ The content of Fe is 2.34g/L 3+ The content is 21.01g/L;
(4) Pre-neutralization: the zinc calcine is utilized to preneutralize the leaching solution II, the underflow III and the supernatant III are obtained through dense separation, and the underflow III returns to the collaborative leaching process of the step (3); the pH of the endpoint of the pre-neutralization is 3, the pre-neutralization temperature is 60 ℃, and the pre-neutralization time is 30min; zn in supernatant III 2+ The content of Pb is 57.90g/L 2+ The content is 80mg/L, fe 2+ The content of Fe is 2.33g/L 3+ The content is 21.07g/L; the water content of the bottom flow III is 30%, the Zn content is 22.06%, the Pb content is 8.22%, the Fe content is 32.08%, and the S content is 4.11% based on the mass percentage of slag in the bottom flow III;
(5) Washing: washing leaching residue II by using industrial water to obtain washing liquid and lead slag, and returning the washing liquid to the pulp mixing procedure of the step (2); the pH of the industrial water is 4.5, the liquid-solid ratio mL in the washing process is 11.65:1, and the washing time is 10min; in mass percent, the Zn content in the lead slag is 6.71 percent, the Pb content is 54.35 percent, and the Fe content is 18.85 percentS content is 7.45%; znO in Zn phase in lead slag accounts for 0.01%, znS accounts for 34.17%, and ZnFe 2 O 4 35.80% and 30.01% of other zinc phases;
(6) Preparing GT superoxide to remove impurities: splitting the supernatant III to obtain a first split flow liquid and a second split flow liquid, reducing the second split flow liquid iron powder, merging the second split flow liquid with the first split flow liquid, and neutralizing the first split flow liquid by using an alkaline reagent KOH to obtain impurity GT superoxide and impurity-removed liquid; the volume ratio of the first split flow liquid to the second split flow liquid is 4.13:1, and the liquid-solid ratio of the iron powder to the second split flow liquid, namely, the g, is 94.93:1; the pH value in the neutralization process is 5.2, the neutralization temperature is 60 ℃, and the neutralization time is 90min; zn in the solution after impurity removal 2+ The content of Pb is 55.00g/L 2+ The content is 35mg/L, fe 2+ The content of Fe is 46.56mg/L 3+ The content is 93.13mg/L; the GT superoxide has the Zn content of 7.17%, the Pb content of 0.28% and the Fe content of 42.42% in percentage by mass, and can return to the sewage acid and sewage impurity removal system;
(7) Deep purification: mixing the supernatant I and the supernatant I' with the impurity-removed liquid to carry out deep purification and impurity removal to obtain purified slag and deep purification liquid, wherein the purified slag returns to the cadmium smelting system; zn in the mixed solution of supernatant I, supernatant I' and the solution after impurity removal 2+ The content of Pb is 78.41g/L 2+ The content is 50.99mg/L, fe 2+ The content of Fe is 78.18mg/L 3+ The content is 0.16g/L; the temperature of deep purification and impurity removal is 60 ℃, the time is 150min, and the pH value in the deep purification process is 5.3; zn in deep purifying liquid 2+ The content of Pb is 78.70g/L 2+ The content of Fe is 0.51mg/L 2+ The content of Fe is 0.78mg/L 3+ The content is 1.58mg/L; the purifying slag returns to the copper-cadmium smelting system in percentage by mass, wherein the content of Zn in the purifying slag is 7.20%, the content of Pb in the purifying slag is 6.33%, the content of Fe in the purifying slag is 29.31%;
(8) Electrodeposition and casting: electro-deposition is carried out on the deep purification and impurity removal liquid by adopting a conventional process to obtain electro-deposited zinc and waste electro-deposition liquid, zinc ingots are obtained by electro-deposition zinc casting, and the waste electro-deposition liquid is returned to the neutralization leaching process of the step (1); wherein the acidity of the waste electrowinning liquid is 140g/L;
in the embodiment, the total direct yield of Zn in the zinc calcine and the zinc oxide smoke dust is 95.08 percent, the consumption of zinc powder for zinc purification per ton is 4.16kg, and the content of GT super-oxygen iron after drying reaches 52.51 percent.
Example 3: the main components of zinc calcine of the embodiment are shown in table 5.1, the zinc phase distribution in the zinc calcine is shown in table 5.2, the main components of zinc oxide smoke dust are shown in table 6.1, the zinc phase distribution in the oxidized smoke dust is shown in table 6.2, and the acidity of the waste electrowinning liquid is 160g/L;
table 5.1 main component of zinc calcine (wt.%)
| Zn | Pb | Fe | S |
| 65% | 1% | 6% | 1% |
Table 5.2 zinc phase distribution (wt.%) in zinc calcine
| ZnO | ZnS | ZnFe 2 O 4 | Other zinc phases | Sum total |
| 95% | 0.1% | 3.9% | 1% | 100 |
TABLE 6.1 zinc oxide Smoke Main ingredient (wt.%)
| Zn | Pb | Fe | S |
| 60% | 8% | 1% | 3% |
Table 6.2 zinc phase distribution (wt.%) in zinc oxide fume
| ZnO | ZnS | ZnFe 2 O 4 | Other zinc phases | Sum total |
| 91% | 8.8% | 0.1% | 0.1% | 100 |
The method for efficiently extracting zinc from zinc calcine (see figure 1) comprises the following specific steps:
(1) Neutral leaching of zinc calcine: mixing zinc calcine, sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I and underflow I; wherein the initial acidity of neutral leaching is 113.17g/L, the temperature of neutral leaching is 65 ℃, the liquid-solid ratio is mL, g is 8:1, the time is 30min, and the final pH of neutral leaching is 5.3; the concentration separation time is 20min, and Zn in supernatant I 2+ The content of Pb is 75.68g/L 2+ The content is 85mg/L, fe 2+ The content of Fe is 3.17mg/L 3+ The content is 0.16g/L; the water content of the bottom flow I is 60%, the Zn content is 26.40%, the Pb content is 5.93%, the Fe content is 34.83% and the S content is 2.96% based on the mass percentage of slag in the bottom flow I; znO in Zn phase in slag of underflow I accounts for 27.74%, znS accounts for 1.44%, znFe 2 O 4 56.36% and 14.45% of other zinc phases;
(2) Neutral leaching of zinc oxide smoke dust: mixing zinc oxide smoke dust with washing liquid to obtain slurry, mixing the slurry with sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I 'and underflow I'; wherein the solid ratio of the washing liquid to the zinc oxide smoke dust is mL, g is 4:1, and the pulping time of the pulping is 6min; neutral leaching initial acidity is 101.84g/L, and waste electrolysisThe liquid-solid ratio of the liquid to the germanium-containing zinc oxide smoke dust is mL, g is 8:1, the neutral leaching temperature is 65 ℃, the leaching time is 30min, and the end point pH of the neutral leaching is 5.3; the concentration separation time is 20min, and Zn in supernatant I' 2+ The content of Pb is 66.95g/L 2+ The content is 85mg/L, fe 2+ The content is 56.23mg/L, fe 3+ The content is 1.15mg/L; the water content of the bottom flow I 'is 60%, the Zn content is 25.58%, the Pb content is 31.79%, the Fe content is 3.79% and the S content is 10.73% based on the mass percentage of slag in the bottom flow I'; 16.96% ZnO, 81.19% ZnS and ZnFe in Zn phase in slag of underflow I 2 O 4 0.92% and other zinc phases 0.92%;
(3) Synergistic leaching: mixing the bottom flow I and the bottom flow I' to obtain a mixed bottom flow, adding sulfuric acid into the mixed bottom flow to perform synergistic leaching, and performing liquid-solid separation to obtain leaching liquid II and leaching residue II; the initial acidity of the collaborative leaching is 266.23g/L, the collaborative leaching temperature is 90 ℃, the solid ratio of the collaborative leaching solution is mL, g is 6:1, the collaborative leaching time is 180min, the final acidity of the collaborative leaching is 40g/L, and the solid-liquid ratio of the collaborative leaching process is lower than that of the neutral leaching process in the step (1) and the step (2); zn in leaching solution II 2+ The content of Pb is 40.89g/L 2+ The content is 95mg/L, fe 2+ The content of Fe is 1.73g/L 3+ The content is 15.55g/L;
(4) Pre-neutralization: the zinc calcine is utilized to preneutralize the leaching solution II, the underflow III and the supernatant III are obtained through dense separation, and the underflow III returns to the collaborative leaching process of the step (3); the pH of the terminal point of the preneutralization is 4, the preneutralization temperature is 70 ℃, and the preneutralization time is 45min; zn in supernatant III 2+ The content of Pb is 61.24g/L 2+ The content is 105mg/L, fe 2+ The content of Fe is 1.73g/L 3+ The content is 15.60g/L; the water content of the bottom flow III is 35%, the Zn content is 26.40%, the Pb content is 5.93%, the Fe content is 34.83% and the S content is 2.96% based on the mass percentage of slag in the bottom flow III;
(5) Washing: washing leaching residue II by using industrial water to obtain washing liquid and lead slag, and returning the washing liquid to the pulp mixing procedure of the step (2); the pH of the industrial water is 5, the liquid-solid ratio mL in the washing process is 23.46:1, and the washing time is 15min; in mass percentThe Zn content in the lead slag is 7.77%, the Pb content is 52.78%, the Fe content is 22.62% and the S content is 5.63%; znO in Zn phase in lead slag accounts for 0.018%, znS accounts for 39.95%, and ZnFe 2 O 4 38.80% and 21.23% of other zinc phases;
(6) Preparing GT superoxide to remove impurities: splitting the supernatant III to obtain a first split flow liquid and a second split flow liquid, reducing the second split flow liquid iron powder, merging with the first split flow liquid, and neutralizing by an alkali reagent (ammonia water) to obtain impurity GT superoxide and impurity-removed liquid; the volume ratio of the first split flow liquid to the second split flow liquid is 4.5:1, and the liquid-solid ratio mg of the iron powder to the second split flow liquid is 128.22:1; the pH value in the neutralization process is 5.4, the neutralization temperature is 65 ℃, and the neutralization time is 120min; zn in the solution after impurity removal 2+ The content of Pb is 58.18g/L 2+ The content is 42mg/L, fe 2+ The content of Fe is 34.85mg/L 3+ The content is 69.69mg/L; the GT superoxide has the Zn content of 9.39%, the Pb content of 0.48% and the Fe content of 39.25% in percentage by mass, and can return to a sewage acid and sewage impurity removal system;
(7) Deep purification: mixing the supernatant I and the supernatant I' with the impurity-removed liquid to carry out deep purification and impurity removal to obtain purified slag and deep purification liquid, wherein the purified slag returns to the cadmium smelting system; zn in the mixed solution of supernatant I, supernatant I' and the solution after impurity removal 2+ The content of Pb is 69.36g/L 2+ The content is 73.82mg/L, fe 2+ The content of Fe is 30.4mg/L 3+ The content is 77.19mg/L; the temperature of deep purification and impurity removal is 65 ℃, the time is 180min, and the pH value in the deep purification process is 5.5; zn in deep purifying liquid 2+ The content of Pb is 69.51g/L 2+ The content is 0.74mg/L, fe 2+ The content of Fe is 0.30mg/L 3+ The content is 0.77mg/L; the purifying slag returns to the copper-cadmium smelting system in terms of mass percent, wherein the content of Zn in the purifying slag is 6.32%, the content of Pb in the purifying slag is 15.76%, the content of Fe in the purifying slag is 22.98%;
(8) Electrodeposition and casting: electro-deposition is carried out on the deep purification and impurity removal liquid by adopting a conventional process to obtain electro-deposited zinc and waste electro-deposition liquid, zinc ingots are obtained by electro-deposition zinc casting, and the waste electro-deposition liquid is returned to the neutralization leaching process of the step (1); wherein the acidity of the waste electrowinning liquid is 160g/L;
in the embodiment, the total direct yield of Zn in the zinc calcine and the zinc oxide smoke dust is 98.37 percent, the consumption of zinc powder for purifying zinc per ton is 2.40kg, and the content of GT superoxide body iron after drying reaches 47.73 percent.
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 (10)
1. The efficient zinc extraction method for zinc calcine is characterized by comprising the following specific steps of:
(1) Neutral leaching of zinc calcine: mixing zinc calcine, sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I and underflow I;
(2) Neutral leaching of zinc oxide smoke dust: mixing zinc oxide smoke dust with washing liquid to obtain slurry, mixing the slurry with sulfuric acid and waste electrolyte to perform neutral leaching, and performing dense separation to obtain supernatant I 'and underflow I';
(3) Synergistic leaching: mixing the bottom flow I and the bottom flow I' to obtain a mixed bottom flow, adding sulfuric acid into the mixed bottom flow to perform synergistic leaching, and performing liquid-solid separation to obtain leaching liquid II and leaching residue II;
(4) Pre-neutralization: the zinc calcine is utilized to preneutralize the leaching solution II, the underflow III and the supernatant III are obtained through dense separation, and the underflow III returns to the collaborative leaching process of the step (3);
(5) Washing: washing leaching residue II by using industrial water to obtain washing liquid and lead slag, and returning the washing liquid to the pulp mixing procedure of the step (2);
(6) Preparing GT superoxide to remove impurities: splitting the supernatant III to obtain a first split flow liquid and a second split flow liquid, reducing the second split flow liquid iron powder, merging the reduced second split flow liquid iron powder with the first split flow liquid, and neutralizing the reduced second split flow liquid iron powder with an alkali reagent to obtain impurity GT superoxide and impurity-removed liquid;
(7) Deep purification: mixing the supernatant I and the supernatant I' with the impurity-removed liquid to carry out deep purification and impurity removal to obtain purified slag and deep purification liquid, wherein the purified slag returns to the cadmium smelting system;
(8) Electrodeposition and casting: and (3) carrying out electro-deposition on the deep purification liquid to obtain electro-deposited zinc and waste electro-deposition liquid, casting the electro-deposited zinc to obtain zinc ingots, and returning the waste electro-deposition liquid to the neutralization leaching process of the step (1) and the step (2).
2. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: the zinc calcine in the step (1) contains 50-65% of Zn, 1-3% of Pb, 6-12% of Fe and 1-3% of S by mass percent; 85-95% ZnO, 0.1-3% ZnS and ZnFe in Zn phase 2 O 4 3.9-8%, and 1-4% of other zinc phases; the acidity of the waste electrolyte is 100-160 g/L, the initial neutral leaching acidity is 113.17-219.82 g/L, the neutral leaching temperature is 40-65 ℃, the liquid-solid ratio is mL, g is 3:1-8:1, the time is 5-35 min, the pH of the end point of the neutral leaching is 4.5-5.3, and the concentration separation time is 10-20 min;
zn in supernatant I 2+ The content of Pb is 75.68-139.08 g/L 2+ The content is 50-85 mg/L, fe 2+ The content of Fe is 3.17-26.34 mg/L 3+ The content is 0.16-1.29 g/L; the water content of the underflow I is 40-60%, the Zn content is 21.00-26.40%, the Pb content is 5.93-8.22%, the Fe content is 29.44-34.83%, and the S content is 2.96-4.11% based on the mass percentage of slag in the underflow I; znO accounts for 10.27-27.74%, znS accounts for 1.44-29.91%, and ZnFe in Zn phase in slag of underflow I 2 O 4 35.89-56.36%, and other zinc phases 14.45-23.93%.
3. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: the zinc oxide smoke dust in the step (2) contains 40-60% of Zn, 8-15% of Pb, 1-2% of Fe and 3-8% of S by mass percent; 82-91% ZnO, 8.8-17% ZnS and ZnFe in Zn phase 2 O 4 0.1-0.5%, and other zinc phases 0.1-0.5%; the liquid-solid ratio of the washing liquid to the zinc oxide smoke dust is mL, g is 2:1-4:1, and the pulping time of the pulping is 2-6 min; the acidity of the waste electrolyte is 100-160 g/L, the initial neutral leaching acidity is 101.84-128.69 g/L, the liquid-solid ratio mL of the waste electrolyte to zinc oxide smoke dust is 4:1-8:1, the neutral leaching temperature is 40-65 ℃, the leaching time is 5-30 min, the end pH of the neutral leaching is 4.5-5.3, and the dense separation time is 10-20 min.
4. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: zn in supernatant I' of step (2) 2+ The content of Pb is 66.95-80.54 g/L 2+ The content is 50-85 mg/L, fe 2+ The content of Fe is 56.23mg/L to 0.15g/L 3+ The content is 1.15-3.10 mg/L; the water content of the bottom flow I 'is 40-60%, the Zn content is 17.99-25.58%, the Pb content is 31.79-34.67%, the Fe content is 2.23-5.20%, and the S content is 10.73-16.64% based on the mass percentage of slag in the bottom flow I'; 8.43-16.96% ZnO, 81.19-86.48% ZnS and ZnFe in Zn phase in slag of underflow I 2 O 4 0.92-2.54% and 0.92-2.54% of other zinc phases.
5. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: the initial acidity of the synergistic leaching is 258.33-401.29 g/L, the leaching temperature is 75-90 ℃, the liquid-solid ratio mL is 2:1-6:1, the leaching time is 90-180 min, the final acidity of the leaching is 20-40 g/L, and the solid-liquid ratio in the synergistic leaching process is lower than that in the neutral leaching process; zn in leaching solution II 2+ The content of Pb is 40.89-86.78 g/L 2+ The content is 60-95 mg/L, fe 2+ The content of Fe is 1.73-4.88 g/L 3+ The content is 15.55-43.93 g/L.
6. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: the pH of the endpoint of the pre-neutralization in the step (4) is 2-4, the pre-neutralization temperature is 50-70 ℃, and the pre-neutralization time is 15-45 min; zn in supernatant III 2+ The content of Pb is 57.90-81.36 g/L 2+ The content is 70-105 mg/L, fe 2+ The content of Fe is 1.73-4.87 g/L 3+ The content is 15.60-43.94 g/L; the water content of the bottom flow III is 25-35%, the Zn content is 21-26.40%, the Pb content is 5.93-8.22%, the Fe content is 29.44-34.83%, and the S content is 2.96-4.11% based on the mass percentage of slag in the bottom flow III.
7. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: the pH value of the industrial water in the step (5) is 4-5, and the liquid-solid ratio mL in the washing process is g5.98:1-23.46:1, and the washing time is 5-15 min; the lead slag comprises, by mass, 6.71-7.77% of Zn, 52.78-54.35% of Pb, 15.97-22.62% of Fe and 5.63-7.80% of S; znO in Zn phase in lead slag accounts for 0.0062-0.018%, znS accounts for 34.17-39.95%, and ZnFe 2 O 4 26.12-38.80% and 21.34-35.92% of other zinc phases.
8. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: the volume ratio of the first diversion liquid to the second diversion liquid is 4.01-4.5:1, the liquid-solid ratio of the iron powder to the second diversion liquid is mL, g is 45.52:1-128.22:1, the alkaline agent is NaOH, KOH or ammonia water, the pH value in the neutralization process is 4.6-5.4, the neutralization temperature is 55-65 ℃, and the neutralization time is 60-120 min; zn in the solution after impurity removal 2+ The content of Pb is 55.00-77.29 g/L 2+ The content is 25-42 mg/L, fe 2+ The content of Fe is 34.85-70.23 mg/L 3+ The content is 69.69mg/L to 0.14g/L; the GT super-oxygen body comprises, by mass, 6.78-9.39% of Zn, 0.19-0.48% of Pb and 39.25-43.03% of Fe.
9. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: zn in the mixed solution of the supernatant I and the supernatant I' in the step (7) and the solution after impurity removal 2+ The content of Pb is 69.36-99.02 g/L 2+ The content is 39.72-73.82 mg/L, fe 2+ The content of Fe is 30.4-78.18 mg/L 3+ The content is 77.19mg/L to 0.46g/L; the temperature of the deep purification and impurity removal is 55-65 ℃, the time is 120-180 min, and the pH value of the deep purification and impurity removal process is 5.2-5.5; zn in deep purifying liquid 2+ The content of Pb is 69.51-99.63 g/L 2+ The content of Fe is 0.40-0.74 mg/L 2+ The content of Fe is 0.30-0.78 mg/L 3+ The content is 0.77-4.57 mg/L; the purifying slag comprises, by mass, 6.32-7.75% of Zn, 2.49-15.76% of Pb and 22.98-32.71% of Fe.
10. The efficient zinc extraction method of zinc calcine according to claim 1, characterized in that: the acidity of the waste electro-deposition solution in the step (8) is 100-160 g/L.
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