CN114149031A - Method for preparing ferrous sulfate from copper smelting slag - Google Patents
Method for preparing ferrous sulfate from copper smelting slag Download PDFInfo
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- CN114149031A CN114149031A CN202111484448.1A CN202111484448A CN114149031A CN 114149031 A CN114149031 A CN 114149031A CN 202111484448 A CN202111484448 A CN 202111484448A CN 114149031 A CN114149031 A CN 114149031A
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- leaching
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- copper smelting
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- 239000002893 slag Substances 0.000 title claims abstract description 113
- 239000010949 copper Substances 0.000 title claims abstract description 92
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000003723 Smelting Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 42
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 42
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 52
- 239000011575 calcium Substances 0.000 claims abstract description 43
- 239000011777 magnesium Substances 0.000 claims abstract description 42
- 238000002425 crystallisation Methods 0.000 claims abstract description 41
- 230000008025 crystallization Effects 0.000 claims abstract description 41
- 239000011701 zinc Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012452 mother liquor Substances 0.000 claims abstract description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012535 impurity Substances 0.000 claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 14
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 14
- 239000004571 lime Substances 0.000 claims abstract description 14
- 239000008267 milk Substances 0.000 claims abstract description 14
- 210000004080 milk Anatomy 0.000 claims abstract description 14
- 235000013336 milk Nutrition 0.000 claims abstract description 14
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 10
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 10
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 49
- 238000000926 separation method Methods 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 238000001953 recrystallisation Methods 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 105
- 229910052742 iron Inorganic materials 0.000 abstract description 44
- 239000000047 product Substances 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000005955 Ferric phosphate Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 229940032958 ferric phosphate Drugs 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 238000007885 magnetic separation Methods 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052840 fayalite Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 101800004637 Communis Proteins 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920001074 Tenite Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing ferrous sulfate from copper smelting slag, which comprises the steps of carrying out curing treatment on the copper smelting slag by adopting normal-temperature sulfuric acid, leaching iron in clinker by adopting clean water and/or crystallization mother liquor, directly adding lime milk into ore pulp after iron leaching for rapid neutralization, removing impurities such as silicon, titanium, aluminum, arsenic and the like by hydrolysis and coprecipitation, then removing calcium and magnesium by adopting fluoride, and precipitating zinc by a vulcanization method, so that a zinc sulfide byproduct can be obtained, and valuable metal recovery is realized; the purified iron-containing solution can be evaporated, concentrated and crystallized to prepare a ferrous sulfate product, and can also be used as an iron source material of a battery material of ferric phosphate/lithium iron phosphate.
Description
Technical Field
The invention relates to the technical field of comprehensive recycling of solid waste resources, in particular to a method for preparing ferrous sulfate from copper smelting slag.
Background
Copper smelting slag is a main solid waste of the copper pyrometallurgical process, and according to statistics, 2-3 tons of smelting slag can be generated when 1 ton of copper is produced. At present, the amount of copper smelting slag produced in China every year is more than 2000 million tons. Most of the copper smelting slag is still treated by stacking, and the accumulated stacking amount of the copper smelting slag reaches 1.5 hundred million tons so far.
The smelting slag is an oxide eutectic body formed by mutually melting furnace charges (including gangue, solvent, coke ash and the like) at high temperature. According to the production process steps, the copper slag can be divided into smelting slag, blowing slag and refining slag; according to different smelting equipment, the copper slag can be divided into bottom blowing smelting slag, Tenite slag, Isa slag, Mitsubishi flash smelting slag, converter slag, bottom blowing continuous blowing slag, Mitsubishi continuous blowing slag, flash blowing slag and the like. Regardless of the slag, the main components of the slag are magnetite, fayalite and vitreous, which are equal. Typical copper smelting slag composition is shown in Table 1, and its main components are Fe 29% -40%, SiO2 30％～40％、Al2O3≤10％、CaO≤11％、Cu 0.42％～4.6％。
TABLE 1
Note "-" indicates no detection.
Because magnetite, fayalite phase and other amorphous phase materials are tightly combined together, the magnetite has fine crystal particle size, the traditional mineral processing technology is difficult to realize the high-efficiency separation of iron and silicon, and qualified iron ore concentrate is difficult to obtain. Aiming at the recovery of iron in copper slag, the currently adopted treatment methods mainly comprise a pyrogenic treatment method and a wet treatment method.
(1) High-temperature oxidation-magnetic separation process. And (3) carrying out high-temperature oxidation on the copper smelting slag to obtain a magnetite phase, and carrying out magnetic separation to obtain iron ore concentrate. Migration and precipitation behavior of iron component in copper smelting slag [ J]Proceedings of process engineering, 2009 (2): 284-288.) to study the migration and precipitation behavior of iron components in the slag, at the temperature of 1380 ℃ and under the condition of oxygen supply, the iron in the fayalite phase is converted into a magnetite phase, iron concentrate containing 54% of iron is obtained through magnetic separation, and the iron recovery rate is about 90%. Experimental study on the extraction of iron from molten copper slag by oxidation, Liu's class (Liu's class, Zhurong, Wangchang, etc.)]China nonferrous metallurgy, 2009 (1): 71-74.) researches on melting copper oxide slag at high temperature of 1350 ℃ and enriching and extracting iron are carried out, calcium oxide is added into a molten pool, oxygen is introduced into the copper oxide slag, and the iron component in fayalite is converted into Fe3O4And then obtaining iron ore concentrate through magnetic separation, wherein the grade of the iron ore concentrate is more than 61%.
(2) High-temperature reduction-magnetic separation process. And (3) obtaining an iron simple substance by adopting high-temperature reduction, and further carrying out magnetic separation to obtain iron powder/simple substance iron. Direct reduction and magnetic separation recovery of iron component from Populus communis Huifen (Populus communis Huifen, Jinglii, Dang Chun Ge.) copper slag [ J]Chinese non-ferrous metals, 2011, 21 (5): 1165 and 1170)) takes brown coal as a reducing agent to directly reduce iron in the copper slag at high temperature (1250 ℃), and the result shows that the Fe in the slag3O4、2FeO·SiO2The iron can be directly reduced into iron, the calcium oxide accounting for 10 percent of the mass of the copper slag can improve the reduction efficiency of the iron in the slag, and the reduced metallic iron is easy to dissociate and carry out magnetic separation to obtain iron powder with the iron mass fraction of 92.05 percent. Jensengon et al (research on modification of Osmant copper smelting slag and recovery of copper and iron [ D)]Wuhan-Wuhan university of science and technology 2015) recovering iron from the copper slag by roasting-leaching-magnetic separation. Adding 20% of sodium carbonate into copper slag by taking carbon powder as a reducing agent, roasting for 1.5 hours at the roasting temperature of 900 ℃, then grinding the roasted sand, leaching by using sulfuric acid with the concentration of 18.7%, and magnetically separating the leached slag to obtain 61.52% grade iron ore concentrate, wherein the recovery rate reaches 82.26%.
(3) Wet leaching-producing ironmaking raw materials. The wet leaching process comprises direct leaching, indirect leaching, microbial leaching and the like. Patent CN109136531 obtains hematite by using sulfuric acid leaching-pressure oxidation transformation. The specific operation is as follows: crushing the copper smelting slag, adding a dilute sulfuric acid solution with the concentration of 20-60g/L according to the solid-to-liquid ratio of 1:4-8, introducing oxygen, carrying out pressure leaching at the temperature of 150-. Similarly, patent CN109082533 crushes copper smelting slag, adds concentrated sulfuric acid according to the mass ratio of 100:20-50, mixes, then adds water to carry out acidolysis at 80-100 ℃, then adds water to the liquid-solid ratio of 3-7:1, moves ore pulp into a high-pressure kettle, controls the temperature at 150-. Korea seed Rong (separation of Fe and Si from water-quenched slag from copper smelting [ D)]Kunming: university of Kunming technology, 2012) adopts salt water pressure leaching to obtain SiO with higher purity2Slag, the slag is soaked after the leachate is neutralized by sodium hydroxide for dehydration treatment to obtain Fe2O3. The specific operation is as follows: crushing and grinding the copper smelting slag, adding hydrochloric acid (300mL hydrochloric acid/1000 mL) according to the ratio of L/S to 10, then placing the mixture into a high-pressure kettle, controlling the temperature to be 90 ℃, and reacting for 120min to obtain the SiO-containing material2Leaching slag and iron leaching liquid with the purity of 88.2 percent; neutralizing the iron leaching solution with sodium hydroxide to pH value of 8.0, drying and dehydrating a slag sample to obtain Fe with purity of 83.6%2O3. Sunjin et al (Sunjin, Huang Zi, Yangbao, et al. copper smelting slag test research on recovery of copper by sulfuric acid leaching [ J)]Comprehensive utilization of mineral products, 2017, 6: 102-107), crushing and grinding the copper smelting slag, leaching by adopting sulfuric acid, adding hydrogen peroxide in the process for oxidation, performing solid-liquid separation after leaching is finished, and performing magnetic separation on the leached slag to obtain iron ore concentrate with the grade of 53.15%.
At present, iron ore concentrate is obtained by magnetic separation or pyrogenic process-magnetic separation basically or hematite is prepared by a wet method, the obtained iron products are basically used as iron making raw materials, and reports related to preparation of ferrous sulfate by using copper smelting slag are not seen.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing ferrous sulfate from copper smelting slag.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing ferrous sulfate from copper smelting slag specifically comprises the following steps:
s1, normal-temperature curing: adding concentrated sulfuric acid into the copper smelting slag, uniformly mixing, standing and curing;
s2, leaching: adding water and/or crystallization mother liquor into the cured material obtained in the step S1, and stirring and leaching;
s3, purifying and removing impurities: adding lime milk into the leached ore pulp obtained in the step S2 for neutralization and impurity removal, and performing liquid-solid separation after removing silicon, arsenic, aluminum and titanium to obtain neutralized liquid;
s4, concentration and crystallization: and (4) heating the neutralized liquid obtained in the step (S3), evaporating to remove part of water, freezing and crystallizing to obtain primary ferrous sulfate, and returning the crystallization mother liquor to the leaching step.
Further, the method also comprises a calcium and magnesium removing procedure, a zinc precipitation procedure and a recrystallization procedure; calcium and magnesium removal: dissolving the primary ferrous sulfate obtained in the step S4 by using recrystallization mother liquor, then adding fluoride to remove calcium and magnesium, carrying out solid-liquid separation after the reaction is finished, carrying out regeneration treatment on filter residues, and enabling the filtrate to enter a zinc removal process; a zinc removal procedure: adding sulfide into the filtrate for zinc precipitation, carrying out liquid-solid separation after the reaction is finished to obtain purified liquid and zinc sulfide slag, and carrying out recrystallization on the purified liquid; a recrystallization step: cooling and crystallizing the purified liquid, then carrying out centrifugal separation to obtain refined ferrous sulfate, and returning the recrystallized mother liquor to the calcium and magnesium removal process.
As a second embodiment, a method for preparing ferrous sulfate from copper smelting slag specifically comprises the following steps:
s1, normal-temperature curing: adding concentrated sulfuric acid into the copper smelting slag, uniformly mixing, standing and curing;
s2, leaching: adding water and/or crystallization mother liquor into the cured material obtained in the step S1, and stirring and leaching;
s3, purifying and removing impurities: adding lime milk into the leached ore pulp obtained in the step S2 for neutralization and impurity removal, and performing liquid-solid separation after removing silicon, arsenic, aluminum and titanium to obtain neutralized liquid; heating the obtained neutralized liquid, adding fluoride to remove calcium and magnesium, performing solid-liquid separation to obtain filter residue and filtrate, and performing regeneration treatment on the filter residue; the filtrate is subjected to step S4;
s4, concentration and crystallization: and (4) heating the filtrate obtained in the step S3, evaporating to remove part of water, then performing freeze crystallization to obtain primary ferrous sulfate, and returning crystallization mother liquor to the leaching step.
Further, the crystallization mother liquor is circulated for a plurality of times and then is treated by opening a circuit, sulfide is adopted to carry out zinc precipitation on the crystallization mother liquor, then evaporation and desalination are carried out, and water is returned to the leaching process for use.
As a third embodiment, a method for preparing ferrous sulfate from copper smelting slag specifically comprises the following steps:
s1, normal-temperature curing: adding concentrated sulfuric acid into the copper smelting slag, uniformly mixing, standing and curing;
s2, leaching: adding water and/or crystallization mother liquor into the cured material obtained in the step S1, and stirring and leaching;
s3, purifying and removing impurities: adding lime milk into the leached ore pulp obtained in the step S2 for neutralization and impurity removal, and performing liquid-solid separation after removing silicon, arsenic, aluminum and titanium to obtain neutralized liquid; heating the obtained neutralized liquid, adding fluoride to remove calcium and magnesium, performing solid-liquid separation after the completion of the calcium and magnesium removal, obtaining fluoride slag and the calcium and magnesium removed liquid, and performing regeneration treatment on the fluoride slag; adding sulfide into the obtained calcium and magnesium removed solution for zinc precipitation, and then carrying out solid-liquid separation to obtain a purified solution and zinc sulfide slag;
s4, concentration and crystallization: and (4) heating the purified liquid obtained in the step (S3), evaporating to remove part of water, then performing freeze crystallization to obtain primary ferrous sulfate, and returning crystallization mother liquor to the leaching step.
Further, in step S1, the amount of concentrated sulfuric acid added is 0.2 to 1.0 times the mass of the copper smelting slag, and the aging is performed at normal temperature for 0.5 to 4 hours.
Further, in step S2, the amount of the added clear water and/or the crystallization mother liquor is 2-6 times of the mass of the copper smelting slag, and the leaching time is 0.5-4 hours.
Further, in step S3, when lime milk is added for neutralization, the end point pH value is controlled to be 4.0-5.5, and the reaction time is controlled to be 0.5-4 hours.
Further, in step S3, when calcium and magnesium are removed, the reaction temperature is 70-95 ℃, the addition amount of fluoride is 1.0-3.0 times of the theoretical amount, and the reaction time is 2-5 hours.
Furthermore, when the zinc is deposited, the reaction temperature is 20-50 ℃, the addition amount of the sulfide is 1.0-1.5 times of the theoretical amount, and the reaction time is 2-4 hours.
Further, in step S4, heating at 95-100 deg.C, evaporating to remove 30-70% of water, cooling and crystallizing the solution at 0-5 deg.C, and separating to obtain primary ferrous sulfate.
The invention has the beneficial effects that:
(1) the invention adopts the processes of normal-temperature curing, leaching, impurity removal, concentration and crystallization to prepare a ferrous sulfate product from the copper smelting slag, and simultaneously obtains the zinc sulfide slag to realize the comprehensive recovery of solid waste resources;
(2) the invention is based on the fact that the iron in the copper smelting slag is mainly Fe2+The method has the characteristics that a proper process and a target product are selected, the process is simple and flexible, and products of different grades can be obtained by adjusting according to market demands;
(3) according to the invention, the copper smelting slag is cured by adopting normal-temperature sulfuric acid, so that soluble silicon is converted into insoluble silicon dioxide, the dissolution of silicon in the leaching process is reduced, the solid-liquid separation performance is optimized, and the difficulty in subsequent impurity removal is reduced;
(4) according to the invention, the ore pulp after iron leaching is directly added into lime milk for rapid neutralization, impurities such as silicon, titanium, aluminum and arsenic are removed by hydrolysis and coprecipitation, the process is simple, and the impurity removal effect is good;
(5) the invention adopts a vulcanization method to precipitate zinc, obtains a zinc sulfide byproduct and realizes valuable metal recovery;
(6) in the invention, the purified iron-containing solution can be evaporated, concentrated and crystallized to prepare a ferrous sulfate product, and can also be used as an iron source material of a battery material of ferric phosphate/lithium iron phosphate;
(7) in the method, system water is circulated internally, so that zero discharge of waste water is realized; and realizing resource utilization of waste residues.
The method can obtain qualified ferrous sulfate products, realizes the resource recycling of solid wastes, has important economic, social and environmental benefits, and provides a new method for the resource recycling of the copper smelting slag.
Drawings
FIG. 1 is a flow chart of a method according to examples 1 to 3 of the present invention;
FIG. 2 is a flowchart of a method according to embodiment 4 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
Example 1
In the method for preparing ferrous sulfate from copper smelting slag provided by this embodiment, the copper smelting slag is copper smelting flash smelting slag, and contains 40.7% of Fe, 14.5% of Si, 1.1% of Cu, 3.5% of Zn, 1.5% of Al, 1.3% of Ca, and 0.3% of Mg. As shown in fig. 1, the method specifically comprises the following steps:
curing at normal temperature: adding concentrated sulfuric acid into the copper smelting slag according to the addition amount of 0.4 time of the weight of the copper smelting slag, uniformly mixing, standing and curing for 1 hour;
leaching: adding clear water into the cured material, which is 3 times the weight of the copper smelting slag, stirring and leaching, wherein the water leaching time is 1 hour;
purifying and removing impurities: adding lime milk with the mass concentration of 20% into the leached ore pulp for neutralization and impurity removal, controlling the end point pH value to be 5.0, reacting for 2 hours, then carrying out liquid-solid separation, and feeding neutralized liquid (Fe 40.32g/L, Zn 4.32g/L, Cu 0.15Mg/L, Si 38.1Mg/L, Al 0.32Mg/L, As <0.1Mg/L, Ca 560Mg/L and Mg 988Mg/L) into the next working procedure; heating the neutralized solution to 80 ℃, adding sodium fluoride with the amount 3.0 times of the theoretical amount of calcium and magnesium precipitation into the neutralized solution for precipitation, reacting for 2 hours, performing solid-liquid separation, regenerating filter residues, and allowing the solution (3.4 Mg/L of Ca and 7.8Mg/L of Mg) after calcium and magnesium removal to enter a zinc precipitation process; adding sodium hydrosulfide into the solution after calcium and magnesium removal, wherein the dosage is 1.1 times of the theoretical amount, controlling the temperature at 40 ℃, reacting for 2 hours, and then carrying out liquid-solid separation to obtain a purified solution (Fe 39.78g/L, Zn 3.22Mg/L, Cu <0.1Mg/L, Si 18.3Mg/L, Al 0.25Mg/L, As <0.1Mg/L, Ca 3.7Mg/L, Mg 7.6Mg/L) and zinc sulfide slag (Zn 35.3%);
concentration and crystallization: heating the purified liquid to boil, evaporating 50% of water, cooling the solution, crystallizing at 0-5 ℃, and performing centrifugal separation to obtain ferrous sulfate; the mother liquid is back soaked in water and if necessary, is treated by open circuit.
Example 2
In the method for preparing ferrous sulfate from copper smelting slag provided by the embodiment, the copper smelting slag is copper smelting slag and comprises the components of 50.1% of Fe, 12.3% of Si, 2.0% of Cu, 1.3% of Zn, 3.0% of Al, 3.2% of Ca and 1.0% of Mg1.0%.
Curing: adding concentrated sulfuric acid into the copper smelting slag according to the mass of 1.0 time of the copper smelting slag, uniformly mixing, standing and curing for 0.5 hour;
leaching: adding backwater which is 2 times of the weight of the copper smelting slag into the cured material, and stirring and leaching for 4 hours;
purifying and removing impurities: adding lime milk with 20% mass concentration into the leached ore pulp for neutralization and impurity removal, controlling the end point pH value to be 5.5, reacting for 0.5 hour, then carrying out liquid-solid separation, and feeding the neutralized liquid (Fe 74.54g/L, Zn 1.83g/L, Cu <0.1Mg/L, Si 15.3Mg/L, Al 0.18Mg/L, As <0.1Mg/L, Ca 583Mg/L and Mg 4835Mg/L) into the next working procedure; heating the neutralized solution to 70 ℃, adding ammonium fluoride with the temperature 1.5 times of the theoretical amount of calcium and magnesium precipitation for precipitation, reacting for 3 hours, performing solid-liquid separation, regenerating filter residues, and allowing the filtrate (Ca 33.1Mg/L and Mg 27.9Mg/L) to enter a zinc precipitation process; adding ammonium sulfide into the filtrate, controlling the temperature at 20 ℃ and reacting for 2 hours, and then carrying out liquid-solid separation to obtain purified liquid (Fe 71.28g/L, Zn 0.52Mg/L, Cu <0.1Mg/L, Si 18.3Mg/L, Al 0.25Mg/L, As <0.1Mg/L, Ca 34.5Mg/L and Mg 8.6Mg/L) and zinc sulfide slag (Zn 32.6%) filtrate to enter a crystallization process;
concentration and crystallization: heating the purified liquid to boil, evaporating 30% of water, cooling the solution, crystallizing at 0-5 deg.C, centrifuging to obtain primary ferrous sulfate, and returning the crystallized mother liquid to leaching step.
And (3) recrystallization: dissolving the primary product ferrous sulfate by using recrystallization mother liquor, controlling the temperature at 50 ℃, controlling the dissolved iron concentration at 110-.
Example 3
In the method for preparing ferrous sulfate from copper smelting slag provided by the embodiment, the copper smelting slag is copper smelting slag and comprises the components of 30.9% of FeC, 16.9% of Si, 0.4% of Cu, 5.7% of ZnC, 3.6% of Al, 4.87% of CaC and 0.8% of MgC.
Curing: adding concentrated sulfuric acid into the copper smelting slag according to 0.2 time of the mass of the copper smelting slag, uniformly mixing, standing and curing for 4 hours;
leaching: adding returned crystallization mother liquor (Fe58g/L) with the mass 6 times that of the copper smelting slag into the cured material, and stirring and leaching for 0.5 hour;
purifying and removing impurities: adding lime milk with the mass concentration of 20% into the leached ore pulp for neutralization and impurity removal, controlling the end point pH value to be 4.0, reacting for 4 hours, then carrying out liquid-solid separation, and feeding neutralized liquid (Fe 88.37g/L, Zn 2.76g/L, Cu 0.12Mg/L, Si 27.3Mg/L, Al 0.42Mg/L, As <0.1Mg/L, Ca 573Mg/L and Mg 1288Mg/L) into the next working procedure; heating the neutralized solution to 95 ℃, adding sodium fluoride with 2.5 times of the theoretical amount of calcium and magnesium precipitates for precipitation, reacting for 5 hours, then carrying out solid-liquid separation, carrying out regeneration treatment on filter residues, and enabling filtrate (Fe 91.33g/L, Zn 0.67Mg/L, Cu <0.1Mg/L, Si 28.3Mg/L, Al 0.21Mg/L, As <0.1Mg/L, Ca 21.7Mg/L and Mg 12.6Mg/L) to enter a concentration and crystallization process;
concentration and crystallization: heating the filtrate to boil, evaporating 40% of water, cooling the solution, crystallizing at 0-5 deg.C, centrifuging to obtain ferrous sulfate, and returning the crystallized mother liquor to leaching process.
After the crystallization mother liquor is circulated for 5 times (Fe 57.8g/L, Zn 27.5g/L, Ca 3.7Mg/L, Mg 7.6Mg/L and Na 46.8g/L), open-circuit treatment is carried out, zinc is deposited by adopting sodium sulfide (the dosage is 1.0 time of the theoretical amount, the temperature is controlled at 30 ℃, the reaction is carried out for 2 hours, then liquid-solid separation is carried out), and then desalination (sodium sulfate) is evaporated, and water is returned for use.
Example 4
In the method for preparing ferrous sulfate from copper smelting slag provided by the embodiment, the copper smelting slag is copper smelting slag and comprises 46.3% of Fe, 14.8% of Si, 0.2% of Cu, 3.14% of Zn, 1.8% of Al, 1.24% of Ca and 0.62% of Mg0.8%. As shown in fig. 2, the method specifically includes the following steps:
curing: adding concentrated sulfuric acid into the copper smelting slag according to the amount of the copper smelting slag which is 0.5 time of the amount of the copper smelting slag, uniformly mixing, standing and curing for 1 hour;
leaching: adding 2 times of backwater and 2 times of crystallization mother liquor (Fe 56g/L) of the weight of the copper smelting slag into the cured material, and stirring and leaching for 1 hour;
purifying and removing impurities: adding lime milk with the mass concentration of 20% into the leached ore pulp for neutralization and impurity removal, controlling the end point pH value to be 4.5, reacting for 1 hour, then carrying out liquid-solid separation, and enabling neutralized liquid (Fe 63.32g/L, Zn 0.81g/L, Cu <0.1Mg/L, Si 21.4Mg/L, Al 0.23Mg/L, As <0.1Mg/L, Ca 563Mg/L and Mg 943Mg/L) to enter a concentration and crystallization process;
concentration and crystallization: heating the neutralized solution to boil, evaporating 70% of water, cooling the solution, crystallizing at 0-5 deg.C, performing solid-liquid separation to obtain primary ferrous sulfate, and soaking the mother solution in water.
Removing calcium and magnesium: controlling the temperature to be 70 ℃, dissolving the primary ferrous sulfate by using recrystallization mother liquor (Fe58g/L), wherein the concentration of iron in the solution is 110-120g/L, then adding sodium fluoride which is 1.0 time of the theoretical amount of calcium and magnesium precipitation for precipitation, reacting for 2 hours, then carrying out solid-liquid separation, carrying out regeneration treatment on filter residues, and enabling the filtrate (Ca 5.1Mg/L and Mg 0.9Mg/L) to enter a zinc precipitation process. Adding sodium hydrosulfide into the filtrate, controlling the dosage to be 1.2 times of the theoretical amount, controlling the temperature to be 50 ℃, reacting for 4 hours, and then carrying out liquid-solid separation to obtain purified liquid (Fe 117.8g/L, Zn 0.3Mg/L, Cu <0.1Mg/L, Si 1.2Mg/L, Al <0.1Mg/L, As <0.1Mg/L, Ca 4.5Mg/L, Mg0.8 Mg/L) and zinc sulfide slag (Zn 43.8%) filtrate to enter a recrystallization process;
and (3) recrystallization: cooling the purified solution, controlling the temperature to be 0-5 ℃ for recrystallization, then carrying out centrifugal separation to obtain refined ferrous sulfate, and returning the recrystallization mother liquor to dissolve the primary ferrous sulfate.
The analysis results of the ferrous sulfate product obtained in each of the above examples are shown in table 1. As can be seen from Table 1, the ferrous sulfate products prepared in the examples meet the I-type water purifying agent standard (GB/T10531-2016) and the feed additive standard (GB34465-2017) specified by the national standard, and the purity can be improved by recrystallization to reach the food additive standard.
TABLE 1
Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.
Claims (11)
1. A method for preparing ferrous sulfate from copper smelting slag is characterized by comprising the following steps:
s1, normal-temperature curing: adding concentrated sulfuric acid into the copper smelting slag, uniformly mixing, standing and curing;
s2, leaching: adding water and/or crystallization mother liquor into the cured material obtained in the step S1, and stirring and leaching;
s3, purifying and removing impurities: adding lime milk into the leached ore pulp obtained in the step S2 for neutralization and impurity removal, and performing liquid-solid separation after removing silicon, arsenic, aluminum and titanium to obtain neutralized liquid;
s4, concentration and crystallization: and (4) heating the neutralized liquid obtained in the step (S3), evaporating to remove part of water, freezing and crystallizing to obtain primary ferrous sulfate, and returning the crystallization mother liquor to the leaching step.
2. The method according to claim 1, further comprising a calcium and magnesium removing step, a zinc precipitating step, and a recrystallization step; calcium and magnesium removal: dissolving the primary ferrous sulfate obtained in the step S4 by using recrystallization mother liquor, then adding fluoride to remove calcium and magnesium, carrying out solid-liquid separation after the reaction is finished, carrying out regeneration treatment on filter residues, and enabling the filtrate to enter a zinc removal process; a zinc removal procedure: adding sulfide into the filtrate for zinc precipitation, carrying out liquid-solid separation after the reaction is finished to obtain purified liquid and zinc sulfide slag, and carrying out recrystallization on the purified liquid; a recrystallization step: cooling and crystallizing the purified liquid, then carrying out centrifugal separation to obtain refined ferrous sulfate, and returning the recrystallized mother liquor to the calcium and magnesium removal process.
3. A method for preparing ferrous sulfate from copper smelting slag is characterized by comprising the following steps:
s1, normal-temperature curing: adding concentrated sulfuric acid into the copper smelting slag, uniformly mixing, standing and curing;
s2, leaching: adding water and/or crystallization mother liquor into the cured material obtained in the step S1, and stirring and leaching;
s3, purifying and removing impurities: adding lime milk into the leached ore pulp obtained in the step S2 for neutralization and impurity removal, and performing liquid-solid separation after removing silicon, arsenic, aluminum and titanium to obtain neutralized liquid; heating the obtained neutralized liquid, adding fluoride to remove calcium and magnesium, performing solid-liquid separation to obtain filter residue and filtrate, and performing regeneration treatment on the filter residue; the filtrate is subjected to step S4;
s4, concentration and crystallization: and (4) heating the filtrate obtained in the step S3, evaporating to remove part of water, then performing freeze crystallization to obtain primary ferrous sulfate, and returning crystallization mother liquor to the leaching step.
4. The method as claimed in claim 3, characterized in that the crystallization mother liquor is recycled for several times and then treated by opening the circuit, the crystallization mother liquor is subjected to zinc precipitation by sulfide, and then is evaporated for desalination, and the water is returned to the leaching process for use.
5. A method for preparing ferrous sulfate from copper smelting slag is characterized by comprising the following steps:
s1, normal-temperature curing: adding concentrated sulfuric acid into the copper smelting slag, uniformly mixing, standing and curing;
s2, leaching: adding water and/or crystallization mother liquor into the cured material obtained in the step S1, and stirring and leaching;
s3, purifying and removing impurities: adding lime milk into the leached ore pulp obtained in the step S2 for neutralization and impurity removal, and performing liquid-solid separation after removing silicon, arsenic, aluminum and titanium to obtain neutralized liquid; heating the obtained neutralized liquid, adding fluoride to remove calcium and magnesium, performing solid-liquid separation after the completion of the calcium and magnesium removal, obtaining fluoride slag and the calcium and magnesium removed liquid, and performing regeneration treatment on the fluoride slag; adding sulfide into the obtained calcium and magnesium removed solution for zinc precipitation, and then carrying out solid-liquid separation to obtain a purified solution and zinc sulfide slag;
s4, concentration and crystallization: and (4) heating the purified liquid obtained in the step (S3), evaporating to remove part of water, then performing freeze crystallization to obtain primary ferrous sulfate, and returning crystallization mother liquor to the leaching step.
6. The method according to claim 1, 3 or 5, wherein in step S1, the concentrated sulfuric acid is added in an amount of 0.2-1.0 times the mass of the copper smelting slag, and the aging is performed at normal temperature for 0.5-4 hours.
7. The method according to claim 1, 3 or 5, characterized in that in step S2, the amount of added clean water and/or crystallization mother liquor is 2-6 times the mass of the copper smelting slag, and the leaching time is 0.5-4 hours.
8. The method of claim 1, 3 or 5, wherein in step S3, when lime milk is added for neutralization, the end point pH value is controlled to be 4.0-5.5, and the reaction time is controlled to be 0.5-4 hours.
9. The method according to claim 2, 3 or 5, wherein in the step S3, when removing calcium and magnesium, the reaction temperature is 70-95 ℃, the addition amount of fluoride is 1.0-3.0 times of the theoretical amount, and the reaction time is 2-5 hours.
10. The method according to claim 2 or 5, wherein the reaction temperature is 20-50 ℃, the addition amount of the sulfide is 1.0-1.5 times of the theoretical amount, and the reaction time is 2-4 hours during zinc precipitation.
11. The method according to claim 1, 3 or 5, wherein in step S4, the heating temperature is 95-100 ℃, 30-70% of water is evaporated and removed, and then the solution is placed in the environment of 0-5 ℃ for cooling crystallization, and primary ferrous sulfate is separated.
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