CN109750173A - A kind of high-iron sphalerite zinc metallurgy and the system and technique for handling associated metal altogether - Google Patents
A kind of high-iron sphalerite zinc metallurgy and the system and technique for handling associated metal altogether Download PDFInfo
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- CN109750173A CN109750173A CN201711085318.4A CN201711085318A CN109750173A CN 109750173 A CN109750173 A CN 109750173A CN 201711085318 A CN201711085318 A CN 201711085318A CN 109750173 A CN109750173 A CN 109750173A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 93
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 82
- 229910052950 sphalerite Inorganic materials 0.000 title claims abstract description 45
- 238000009858 zinc metallurgy Methods 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 238000005188 flotation Methods 0.000 claims abstract description 135
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000001301 oxygen Substances 0.000 claims abstract description 84
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 83
- 239000011701 zinc Substances 0.000 claims abstract description 74
- 239000011133 lead Substances 0.000 claims abstract description 73
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 62
- 229910052802 copper Inorganic materials 0.000 claims abstract description 50
- 229910052738 indium Inorganic materials 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 14
- 238000006073 displacement reaction Methods 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 241001062472 Stokellia anisodon Species 0.000 claims abstract description 6
- 238000002386 leaching Methods 0.000 claims description 61
- 239000010949 copper Substances 0.000 claims description 59
- 239000012141 concentrate Substances 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 53
- 229910052717 sulfur Inorganic materials 0.000 claims description 52
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 51
- 229910052709 silver Inorganic materials 0.000 claims description 40
- 235000021110 pickles Nutrition 0.000 claims description 37
- 239000005864 Sulphur Substances 0.000 claims description 34
- 239000002893 slag Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052732 germanium Inorganic materials 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 15
- 238000003723 Smelting Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 8
- 239000002956 ash Substances 0.000 claims description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005363 electrowinning Methods 0.000 claims description 5
- SAZXSKLZZOUTCH-UHFFFAOYSA-N germanium indium Chemical compound [Ge].[In] SAZXSKLZZOUTCH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 abstract description 26
- 239000012943 hotmelt Substances 0.000 abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 15
- 239000011707 mineral Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 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 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- 239000005909 Kieselgur Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 239000011686 zinc sulphate Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 2
- 229910000367 silver sulfate Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- JKNZUZCGFROMAZ-UHFFFAOYSA-L [Ag+2].[O-]S([O-])(=O)=O Chemical group [Ag+2].[O-]S([O-])(=O)=O JKNZUZCGFROMAZ-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229940083025 silver preparation Drugs 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a kind of high-iron sphalerite zinc metallurgy and the systems for handling associated metal altogether, including the first surge tank, I sections of pulp pre-heating devices, I sections of oxygen pressure kettles, I sections of flash tanks, I sections of medial launders, I sections of filter presses, lead to smelt unit, neutralization chamber, displacement slot, purification tank, zinc electrolysis bath, the second surge tank, the first flotation device, third surge tank, II section of pulp pre-heating device, II section of oxygen pressure kettle, II section of flash tank, II section of medial launder, II section of filter press, the 4th surge tank, the second flotation device, hot melt filter.The invention also discloses a kind of high-iron sphalerite zinc metallurgy and the techniques for handling associated metal altogether, the present invention is sufficiently combined two sections of oxygen pressure acidleach with flotation, the high-iron sphalerite of total association can be effectively treated, and Cu, In, Ge, Ag, Pb, Fe are recycled, recovery efficiency is high.
Description
Technical field:
The present invention relates to a kind of high-iron sphalerite zinc metallurgy and the systems and technique of the total associated metal of processing, belong to non-ferrous metal
Field of hydrometallurgy.
Background technique:
Traditional zinc metallurgy mainly uses hydrometallurgical processes, i.e. roasting-leaching-purification-electrodeposition technique production, accounts for production capacity
90% or more.The technique is since there are the sulfur dioxide pollutions of baking flue gas, and can not achieve zinc and associated metal altogether
High-efficiency comprehensive utilization, handling the more metal zinc concentrates of association altogether just seems not largely effective, or even can not.
Currently, be total to the feature more than associated metal for high-iron sphalerite, oxygen pressure acid-hatching of young eggs smelting is used to it, advantage exists
In eliminating sulfur dioxide pollution, sulphur is with element morphology output；High-iron sphalerite resource can be effectively treated and complexity is difficult
Contain zinc concentrate.Although oxygen leaching technology compensates for existing roasting-leaching-purification-electrodeposition process technical deficiency, can
Realize the efficient synthetical recovery of zinc and part associated valuable metals, such as Cu, In, Ge by neutralizing heavy indium, displacement to a certain degree
Heavy copper and isolation of purified can obtain synthetical recovery, but the rate of recovery is relatively low, and still have part associated metal such as Ag, Pb,
Fe etc. cannot effectively realize synthetical recovery, wherein on the one hand the tailing after the pressure acidleach of high-iron sphalerite oxygen, which is directly stored up, causes ring
Border pollution, on the other hand, Ag, Pb, Fe, S etc. of association are a kind of important valuable resources, and stockpiling causes the wave of resource
Take.
Summary of the invention:
The system that first purpose of the invention is to provide a kind of high-iron sphalerite zinc metallurgy and handles associated metal altogether.
Second purpose of the invention is the technique developed a kind of high-iron sphalerite zinc metallurgy and handle associated metal altogether, should
Technique has valuable element comprehensive recovery height, without sulfur dioxide pollution, direct output lead smelting gas, easy to industrialized production, ring
The advantages that border is friendly, water recycling rate is high.
The first purpose of this invention is implemented by following technical solution, a kind of high-iron sphalerite zinc metallurgy and handles associated gold altogether
The system of category comprising sequentially connected first surge tank, I sections of pulp pre-heating devices, I sections of oxygen pressure kettles, I sections of flash tanks, I sections of centres
Slot and I sections of filter presses；
The entrance of the filtrate (liquid of the I sections of filter press and neutralization chamber connects, the outlet of the neutralization chamber and displacement slot
Entrance connection, the outlet of the displacement slot and the entrance of purification tank connect, the outlet of the purification tank and the entrance of zinc electrolysis bath
Connection；
The sludge outlet of the I sections of filter press is connect with the entrance of the second surge tank, the outlet of second surge tank with
The entrance of first flotation device connects, and the concentrate outlet of first flotation device is connect with the entrance of third surge tank, the third
The outlet of surge tank is connect with the entrance of II section of pulp pre-heating device, and outlet and the II section of oxygen of II section of pulp pre-heating device press kettle
The outlet of entrance connection, II section of oxygen pressure kettle is connect with the entrance of II section of flash tank, the outlet and II of II section of flash tank
The entrance connection of section medial launder, the outlet of II section of medial launder are connect with the entrance of II section of filter press, II section of filter press
Filtrate (liquid connect with the entrance of first surge tank, II section of sludge outlet of filter press and entering for the 4th surge tank
Mouthful connection, the outlet of the 4th surge tank connect with the entrance of the second flotation device, the concentrate of second flotation device export according to
It is secondary to be connect with sulfur melting kettle and hot melt filter；
The tailing outlet of first flotation device, the tailing outlet of second flotation device, the filter of the hot melt filter
Slag outlet smelts unit with lead and connect；
The electrolyte outlet of the zinc electrolysis bath is connect with the entrance of the third surge tank.
Second object of the present invention is implemented by following technical solution, a kind of high-iron sphalerite zinc metallurgy and handles associated gold altogether
The technique of category, process flow include:
Process (1): it sizes mixing
By high-iron sphalerite with water by solid-liquid mass ratio 1:(1~3) mix that be milled to granularity be -200~-400 mesh, it is added the
In one surge tank, dispersing agent is added and carries out processing of sizing mixing, obtain adjusting slurry, the additional amount of the dispersing agent is that the high-speed rail dodges zinc
0.1~5wt% of mine；
Process (2): I section of oxygen presses acidleach
After the adjusting slurry is preheating to 80~120 DEG C by I sections of pulp pre-heating devices, it is added in I sections of oxygen pressure kettles, with II section
Pickle liquor is by volume (1~5): 1 mixing is warming up to 140~180 DEG C, and is passed through oxygen pressing to 0.6~2.0MPa, carries out I
Section oxygen presses acidleach, 30~180min of reaction time, then by into I sections of medial launders, then passing through after I sections of flash tank flashed downs
I sections of filter presses obtain I section of pickle liquor and I section of acid leaching residue after being separated by solid-liquid separation；
II section of pickle liquor in process (1) and process (2) is configured when using first time using chemical reagent.
The purpose of the process is that zinc is selectively immersed to solution and realizes neutralization sour in II section of leachate, so that output is low
I section of pickle liquor of sour, low iron, high zinc ion.
By the processing of process (2), total accompanying element Cu, In, Ge in high-iron sphalerite are with Zn together with sulfate
Form be enriched in I section of pickle liquor, and Ag, Pb, Fe and S are then enriched in I section of acid leaching residue, wherein the enrichment of Zn, Fe and S
Shown in process such as equation [1]~[9].
There are following reactions in I section of oxygen pressure kettle:
When adjusting slurry is passed into II section of pickle liquor to be mixed in I sections of oxygen pressure kettles, temperature is sharply increased, and carries out at this time as follows
Reaction:
CaO+H2SO4=CaSO4+H2O [1]
MgO+H2SO4=MgSO4+H2O [2]
ZnS+H2SO4=ZnSO4+H2S [3]
ZnS+Fe2(SO4)3=ZnSO4+2FeSO4+S [4]
FeS2+Fe2(SO4)3=3FeSO4+2S [5]
2H2S+O2=2H2O+2S [6]
2ZnS+2H2SO4+ O2=2ZnSO4+S+H2O [7]
2FeS2+2H2SO4+O2=2FeSO4+4S+H2O [8]
FeSO4+H2O+O2=Fe2O3+H2SO4 [9]
I section of oxygen pressure is substantially carried out the neutralization of CaO and MgO, ZnS and FeS acidleach early period2Leach reaction formed ZnSO4Solution
And element S and FeSO4React to form Fe except iron2O3, element S and Fe2O3It is the solid product newly formed, and it is unreacted
High-iron sphalerite concentrate mixes.Pb and Ag is present in I section of acid leaching residue, exists in the form of Pb, Ag and AgS, thus real
The enrichment of Pb and Ag are showed.
Process (3): copper and indium germanium enrichment
I section of pickle liquor is successively discharged into neutralization chamber, purification tank and electrolytic cell, by neutralizing heavy indium, replacing heavy copper, separation
Purification and electrodeposition obtain respectively obtaining indium slag, copper ashes, germanium slag and electrowinning zinc；I section of acid leaching residue and cavitation agent press liquid and consolidate weight
Than (2~5): carrying out cavitation pretreatment after sizing mixing in 1 the second surge tank of addition, obtain I section of pretreatment ore pulp；It is pre- by described I section
Processing ore pulp be discharged into the first flotation device carry out flotation, obtain I section of flotation concentrate and I section of flotation tailing, wherein Zn and S flotation into
Enter I section of flotation concentrate, Fe, Pb and Ag enter I section of flotation tailing substantially；
In process (2), bloodstone, S, Pb mineral, Ag mineral and the unreacted high-speed rail of gangue, generation after reaction
Zincblende concentrate mixes, and the pretreated purpose of cavitation is to promote gangue, bloodstone, Ag mineral, S and other sulfide
Dissociation.
The pretreated principle of cavitation is: cavitation effect generation device can produce a large amount of stingy when acting on I section of acid leaching residue
Bubble.Locally there is tensile stress in one side liquid and form negative pressure, the reduction of pressure make the gas overflowing for being dissolved in liquid originally or
Solution boils become minute bubbles.On the other hand it is that powerful tensile stress is empty at one liquid " tearing ", is steamed in cavity for liquid
Gas or another gas for being dissolved in liquid, in some instances it may even be possible to be vacuum.Because the minute bubbles that cavitation is formed can be with surrounding medium
It vibrates and constantly moves, grows up or crumble and fall suddenly.Surrounding liquid pours bubble suddenly and generates high temperature, high pressure when crumbling and fall, simultaneously
Generate powerful shear stress.It is present in microbubble (cavitation nucleus) the partial Pressure peak value in liquid up to hundreds of or even thousands of atmosphere
The jet stream of pressure and speed per hour 400km/h, while generating moment upper 1000K temperature.
Due to during crumbling and fall partial Pressure peak value up to hundreds of or even upper kilo-atmospheric pressure and speed per hour 400km/h jet stream,
Generating powerful shear stress makes to be deposited on S, Pb mineral, Ag mineral, other sulfide on the bloodstone surface of gangue and generation etc.
Be stripped out, keep the bloodstone of the gangue wrapped up and generation exposed, promoted gangue, bloodstone, Ag mineral, sulphur and its
The dissociation of his sulfide, so that the flotation separating effect of S, sulfide, Pb mineral, Ag mineral, gangue and bloodstone is improved, into
And improve Pb, Ag, S, Zn comprehensive reutilization rate.
Process (4): II section of oxygen presses acidleach
By the waste electrolyte generated in I section of flotation concentrate and the electrodeposition process by solvent and solute weight ratio (3~10): 1
Third surge tank is added to size mixing, after being preheating to 80~120 DEG C by II section of pulp pre-heating device, is added in II section of oxygen pressure kettle,
Oxygen pressing is passed through to 0.4~1.2MPa, and is warming up to 100~140 DEG C, carries out the pressure acidleach of II section of oxygen, the reaction time 80~
360min, then by entering II section of medial launder after II section of flash tank flashed down, then after being separated by solid-liquid separation by II section of filter press
Obtain II section of pickle liquor and II section of acid leaching residue；
The purpose of the process is that Zn, Cu, In, Ge in I section of flotation concentrate are enriched to II section of pickle liquor to the maximum extent,
Fe, S, Pb, Ag enrichment enter in II section of acid leaching residue, and II section of pickle liquor, which returns in process (2), continues I sections of oxygen pressure acid
Leaching, further realizes the enrichment and separation of Zn, Cu, In, Ge.
Process (5): cavitation flotation
By II section of acid leaching residue and the cavitation agent by solvent and solute weight ratio (2~5): 1 size mixing after the 4th surge tank of addition
It is interior to carry out the cavitation pretreatment, obtain II section of pretreatment ore pulp；By II section of pretreatment ore pulp be discharged into the second flotation device into
Row flotation obtains II section of flotation concentrate and II section of flotation tailing, wherein the S flotation in II section of acid leaching residue enters I section of flotation essence
Mine, Fe, Pb and Ag flotation enter II section of flotation tailing；
Process (6): molten sulphur is heated
S in II section of flotation concentrate00.3~1MPa of steam pressure, molten sulphur temperature are 120~160 in sulfur melting kettle
After melting under conditions of DEG C, filter aid, 120~160 DEG C of the item for accounting for that II section of flotation concentrate ratio is 1~30wt% is added
Under part, after hot melt filter filtering, molten sulphur and molten sulphur slag are obtained；
Molten sulphur is sulfur product (S0>=99.5%) it, melts sulphur slag and is mainly enriched with Ag, S and Pb.
Process (7): lead silver iron enrichment
Obtain being enriched with after I section of flotation tailing and II section of flotation tailing are mixed with the molten sulphur slag Ag, Pb,
The lead smelting gas of Fe, wherein Ag>400g/t, Pb>4wt%, Fe>27wt%, S<10% in the lead smelting gas are smelted single into lead
Member carries out lead silver recovery smelting.
Preferably, in the high-iron sphalerite, 7~30wt% of Fe, 30~60wt% of Zn, 10~50wt% of S, Ag 30
30~300g/t of~300g/t, In, 0.1~3wt% of Cu, 0.2~20wt% of Pb.
Preferably, the cavitation pretreatment is that ultrasonic cavitation pretreatment or jet flow cavitation pretreatment or propeller vortex are empty
Change pretreatment, 0~90 DEG C of cavitation temperature, 1~500KW of cavitation power, 18~30KHz of cavitation frequency, 10~30A of cavitation electric current,
5~300min of cavitation time.
Preferably, the flotation in the process (3) include: 1~3 roughing, scan for 1~4 time, 1~5 time it is selected.
Preferably, the flotation in the process (5) include: 1~3 roughing, scan for 1~4 time, 1~5 time it is selected.
Preferably, the dispersing agent is wooden calcium sulfonate or wooden sodium sulfonate.
Preferably, the filter aid is diatomite.
Preferably, the cavitation agent is I section of acid leaching residue washing water, II section of acid leaching residue washing water, any one in water.
Preferably, the cavitation agent is I section of acid leaching residue washing water, any two kinds or three in II section of acid leaching residue washing water, water
The mixed liquor of kind.
Advantages of the present invention:
A kind of high-iron sphalerite zinc metallurgy of the present invention and the system for handling associated metal altogether fill two sections of oxygen pressure acidleach with flotation
Divide and combine, the high-iron sphalerite of total association can be effectively treated, and recycled to Cu, In, Ge, Ag, Pb, Fe, recycles
It is high-efficient.
When the process high-iron sphalerite of a kind of high-iron sphalerite zinc metallurgy of the present invention and the total associated metal of processing, it is processed into
This is low, and Zn leaching rate is high, and Cu, In, Ge, Ag, Pb, Fe rate of recovery are high, wherein
(1) Zn leaching rate reaches 55% or more, S and is converted into SO in the pressure acidleach of I section of oxygen4 2-Conversion ratio < 8%, leachate
Free acid < 5g/L, the leachate 2g/L of < containing Fe, significantly reduces solution processing cost.I section of oxygen pressure acid leaching residue passes through pretreatment
Afterwards using roughing, scan, selected flotation flowsheet carries out flotation when, obtain I section of flotation concentrate of Zn grade 25~35%, zinc returns
Yield > 98%.I section of flotation tailing contains Zn < 2%, contains Ag about 70~100g/t, Ag rate of recovery > 90%, effectively realizes valuable member
The recycling of element.
(2) II sections of oxygen press conversion ratio < 5% of the leaching rate > 99% of acidleach Zn, sulphur.I section of oxygen pressure acid leaching residue carries out flotation
The rejecting for realizing gangue mineral in I section of leached mud reduces the relative quantity into II section of oxygen pressure acidleach, to reduce by II section of oxygen pressure
The treating capacity or cost of acidleach；II section of oxygen pressure acidleach is carried out in lower temperature and oxygen pressure, realizes that II section of oxygen pressure acidleach reduces energy
The purpose of consumption and amount of oxygen reduces by II section of oxygen pressure acidleach cost, also improves the safety etc. of II section of oxygen pressure pickling equipment.
(3) II sections of acid leaching residues by after pretreatment using roughing, scan, selected flotation flowsheet carries out flotation when, obtain
Iron concentrate contains S >=95%, element S content >=92%, concentrate yield 70~85%, the rate of recovery respectively >=90% of S and element S
With >=98%.The enrichment for effectively realizing elementary sulfur, is effectively reduced the cost of further element sulfur recovery.The iron concentrate heat that flotation obtains
Slag after molten merges with flotation tailing can be used as silver preparation concentrate, containing Ag in 1000~1500g/t.
In (4) I sections of acid leaching residues and II section of acid leaching residue floatation process, acidity, the concentration of zinc ion do not have any shadow to flotation
It rings, can directly carry out flotation, be conducive to technique simplification and reduce flotation cost.
Detailed description of the invention:
Fig. 1 is a kind of high-iron sphalerite zinc metallurgy of the present invention and the system diagram for handling associated metal altogether.
Fig. 2 is a kind of high-iron sphalerite zinc metallurgy of embodiment 2-4 and the process flow chart for handling associated metal altogether.
In figure: the first surge tank 1, I sections of pulp pre-heating devices 2, I sections of oxygen pressure kettles 3, I sections of flash tanks 4, I sections of medial launders 5, I sections
Filter press 6, lead smelt unit 7, neutralization chamber 8, purification tank 9, zinc electrolysis bath 10, the second surge tank 11, the first flotation device 12, third
Surge tank 13, II section of pulp pre-heating device 14, II section of oxygen press kettle 15, II section of flash tank 16, II section of medial launder 17, II section of filter press
18, the 4th surge tank 19, the second flotation device 20, sulfur melting system 21, displacement slot 22.
Specific embodiment:
Embodiment 1:
As shown in Figure 1, a kind of high-iron sphalerite zinc metallurgy and the system for handling associated metal altogether, including sequentially connected first
Surge tank 1, I sections of pulp pre-heating devices 2, I sections of oxygen pressure kettles 3, I sections of flash tanks 4, I sections of medial launders 5 and I sections of filter presses 6；
The filtrate (liquid of I sections of filter presses 6 is connect with the entrance of neutralization chamber 8, the outlet of neutralization chamber 8 and the entrance of displacement slot 22
Connection, the outlet of displacement slot 22 are connect with the entrance of purification tank 9, and the outlet of purification tank 9 connect zinc with the entrance of zinc electrolysis bath 10
Electrolytic cell 10；
The sludge outlet of I sections of filter presses 6 is connect with the entrance of the second surge tank 11, the outlet and first of the second surge tank 11
The entrance of flotation device 12 connects, and the concentrate outlet of the first flotation device 12 is connect with the entrance of third surge tank 13, third surge tank
13 outlet is connect with the entrance of II section of pulp pre-heating device 14, and outlet and the II section of oxygen of II section of pulp pre-heating device 14 press entering for kettle 15
The outlet of mouth connection, II section of oxygen pressure kettle 15 is connect with the entrance of II section of flash tank 16, in the outlet of II section of flash tank 16 and II section
Between slot 17 entrance connection, the outlet of II section of medial launder 17 connect with the entrance of II section of filter press 18, the filter of II section of filter press 18
Liquid outlet is connect with the entrance of the first surge tank 1, and the sludge outlet of II section of filter press 18 is connect with the entrance of the 4th surge tank 19,
The outlet of 4th surge tank 19 is connect with the entrance of the second flotation device 20, concentrate outlet and the sulfur melting system 21 of the second flotation device 20
Connection；
The tailing outlet of first flotation device 12, the tailing of the second flotation device 20 export, heat the sludge outlet of filter 21
Unit 7 is smelted with lead to connect；
The electrolyte outlet of zinc electrolysis bath 10 is connect with the entrance of third surge tank 13.
Embodiment 2:
High-iron sphalerite zinc metallurgy is carried out using system described in embodiment 1 and prepares the technique of lead smelting gas, process flow packet
It includes:
Process (1): it sizes mixing
60kg 12.05wt% containing Fe, Zn 43.17wt%, S 30.05wt%, Pb 2.19wt%, As 2.32wt%,
Ag 269.7g/t, In 226.1g/t, Cu 2.85wt%, Ge251g/t high-iron sphalerite mixed with 60kg water, it is levigate to-
325 mesh account for 95%, are added in the first surge tank 1, and 0.6kg wooden calcium sulfonate is added and carries out processing of sizing mixing, obtains adjusting slurry.
Process (2): I section of oxygen presses acidleach
After adjusting slurry is preheating to 80 DEG C of set temperature by I sections of pulp pre-heating devices 2, it is added in I sections of oxygen pressure kettles 3, with II
5:1 is mixed by volume for section pickle liquor, and II section of pickle liquor prepares solution when being added first time；Oxygen pressing is passed through to arrive
0.6MPa is warming up to 180 DEG C, carries out the pressure acidleach of I section of oxygen, reaction time 30min, then by I sections of 4 flashed downs of flash tank after
Into I sections of medial launders 5.
I section of oxygen pressure acid leaching slurry in above-mentioned I sections of medial launder 5 is separated by solid-liquid separation to obtain I section by I sections of filter presses 6
Pickle liquor and I section of acid leaching residue.I section of pickle liquor component content are as follows: Fe2+0.42g/L、FeT 0.56g/L、H2SO4 3.95g/L、Zn2 +130.45g/L,Cu 2.42g/L,In 331.23mg/L,Ge39.78mg/L；I section of oxygen pressure acid leaching residue is 54.05kg, and ingredient contains
Amount are as follows: Fe 22.87wt%, Zn 30.42wt%, Cu 1.45wt%, Ag 193.5g/t, In 137.03g/t, Pb
1.35wt%, S 33.91wt%, S016.31wt%.Zn, Cu, In, Ge leaching rate or conversion ratio be respectively 59.95%,
58.73%, 70.34%, 50.45%.
Process (3): copper and indium germanium enrichment
I section of pickle liquor is successively discharged into neutralization chamber 8, displacement slot 22, purification tank 9 and zinc electrolysis bath 10, by neutralizing heavy indium, setting
It changes heavy copper, isolation of purified and electrodeposition and respectively obtains indium slag, copper ashes, germanium slag and electrowinning zinc, wherein In content is in indium slag
0.56wt%, Cu content is 69.95wt% in copper ashes, and the content of Ge is respectively 0.1wt% in germanium slag；I section of acid leaching residue and I section of acid
Phase analysis washing water obtains I section of pretreatment by cavitation pretreatment is carried out after sizing mixing in solvent and solute weight ratio 2:1 the second surge tank 11 of addition
Ore pulp, pretreatment condition are as follows: 0 DEG C of temperature, pretreatment mode is ultrasonic cavitation, and cavitation power is 500KW, cavitation frequency is
30KHz, cavitation electric current are 30A, the cavitation time is 5min；
I section of pretreatment ore pulp is discharged into the first flotation device 12 and carries out flotation, floatation process specifically includes that 1 roughing, 2 times
Scan, 5 times it is selected, obtain I section of flotation concentrate and I section of flotation tailing.
I section of flotation concentrate yield is 70.31%, component content are as follows: S 42.37wt%, Zn 31.78wt%, Fe
12.17wt%, Ag273.15g/t, In 195.41g/t, Pb 0.77wt%；Fe and mineral are mainly contained in I section of flotation tailing
Gangue, S 8.72%, Zn1.03%, Fe 37.56%, Ag 85.67g/t, In 85.36g/t, Pb 2.76%.
Process (4): II section of oxygen presses acidleach
Third surge tank is added by solvent and solute weight ratio 3:1 in the waste electrolyte generated in I section of flotation concentrate and electrodeposition process
13 size mixing, and Zn is contained in waste electrolyte2+Concentration 40g/L, H2SO4140g/L；80 are preheating to by II section of pulp pre-heating device 14
It after DEG C, is added in II section of oxygen pressure kettle 15, is passed through oxygen pressing to 0.4MPa, and be warming up to 140 DEG C, carry out II section of oxygen pressure acidleach,
Reaction time 80min, then by entering II section of medial launder 17 after II section of 16 flashed down of flash tank, the purpose of the process is to make
Zn, Cu, In in I section of flotation concentrate etc. enter solution to the maximum extent, and Fe, S, Pb, Ag are respectively with bloodstone, elemental sulfur, sulphur
Lead plumbate, silver sulfate form enter in slag, to realize the separation of Zn, Cu, In and Fe, S, Pb, Ag；
II section of oxygen pressure acid leaching slurry in above-mentioned II section of medial launder 17 is separated by solid-liquid separation to obtain by II section of filter press
II section of pickle liquor and II section of acid leaching residue.II section of pickle liquor directly returns to I section of oxygen pressure acidleach process.II section of pickle liquor component content
Are as follows: Fe2+2.15g/L、FeT 19.23g/L、H2SO4 39.56g/L、Zn2+103.23g/L、Cu 1.76g/L、In
143.26mg/L,Ge 45.31mg/L；II section of acid leaching residue is 15.67kg, component content are as follows: Fe 7.56wt%, Zn
1.03wt%, Cu 0.19wt%, Ag 368.21g/t, In 20.6g/t, Pb 1.53wt%, S 88.56wt%, S0
80.13wt%.Two sections of Zn, Cu, In, Ge total leaching rates are respectively 98.13%, 95.36%, 94.73%, 86.72%.
Process (5): cavitation flotation
It is added in the 4th surge tank 19 after II section of acid leaching residue and II section of acid leaching residue washing water are sized mixing by solvent and solute weight ratio 2:1
Cavitation pretreatment is carried out, II section of pretreatment ore pulp is obtained；Pretreatment condition are as follows: 0 DEG C of temperature, pretreatment mode is ultrasonic cavitation,
Cavitation power is 500KW, cavitation frequency is 30KHz, cavitation electric current is 30A, the cavitation time is 5min；
By II section of pretreatment ore pulp be discharged into the second flotation device 20 carry out flotation, scanned by 1 roughing, 2 times, 5 times it is selected
After obtain II section of flotation concentrate and II section of flotation tailing；II section of flotation concentrate component content are as follows: S 95.16wt%, Zn
1.07wt%, Fe 2.17wt%, Ag 417.1g/t, In 10.5g/t, Pb 0.12wt%；Mainly contain in II section of flotation tailing
There are Fe and mineral gangue, yield 26.30%, S 43.12wt%, Zn 0.92wt%, Fe 29.13wt%, Ag 245.63g/
T, In 28.9g/t, Pb 2.16wt%.
Process (6): molten sulphur is heated
S, Ag, Cu, Zn etc., II section of flotation concentrate S are mainly contained in II section of flotation concentrate0The vapour pressure in sulfur melting kettle
After power 0.5MPa, molten sulphur temperature melt under conditions of being 130 DEG C, the silicon for accounting for that II section of flotation concentrate ratio is 1wt% is added
Diatomaceous earth under conditions of 120 DEG C, after hot melt filter filtering, obtains molten sulphur and molten sulphur slag；Molten sulphur is sulfur product, S product
Position is 99.61%.
Process (7): lead silver iron enrichment
Lead smelting gas is obtained after I section of flotation tailing and II section of flotation tailing are mixed with molten sulphur slag, wherein wherein Ag
413.25g/t, Pb 4.13wt%, Fe 27.16wt%, S 9.32wt% can enter lead and smelt the progress lead silver recovery of unit 7.
Embodiment 3:
High-iron sphalerite zinc metallurgy is carried out using system described in embodiment 1 and prepares the technique of lead smelting gas, process flow packet
It includes:
Process (1): it sizes mixing
By 80kg 15.01wt% containing Fe, Zn 40.31wt%, S 32.03wt%, Pb 0.89wt%, As
0.75wt%, Ag 154.6g/t, In223.2g/t, Cu 1.43wt%, the high-iron sphalerite of Ge245g/t and 160kg water are mixed
It closes, it is levigate to account for 98% to -325 mesh, it is added in the first surge tank 1,1.6kg wooden calcium sulfonate is added and carries out processing of sizing mixing, obtains
Adjusting slurry.
Process (2): I section of oxygen presses acidleach
After adjusting slurry is preheating to 100 DEG C of set temperature by I sections of pulp pre-heating devices 2, it is added in I sections of oxygen pressure kettles 3, with II
3:1 is mixed by volume for section pickle liquor, and II section of pickle liquor prepares solution when being added first time；Oxygen pressing is passed through to arrive
1.2MPa is warming up to 160 DEG C, carries out I section of oxygen pressure acidleach, then reaction time 100min passes through I sections of 4 flashed downs of flash tank
Enter I sections of medial launders 5 afterwards.
I section of oxygen pressure acid leaching slurry in above-mentioned I sections of medial launder 5 is separated by solid-liquid separation to obtain I section by I sections of filter presses 6
Pickle liquor and I section of acid leaching residue.I section of pickle liquor component content are as follows: Fe2+1.05g/L、FeT 1.44g/L、H2SO4 5.63g/L、Zn2 +128.31g/L,Cu 1.89g/L,In 215.55mg/L,Ge38.31mg/L；I section of acid leaching residue is 71.91kg, component content
Are as follows: Fe 25.39wt%, Zn 29.11wt%, Cu 0.97wt%, Ag 167.2g/t, In 95.55g/t, Pb 1.01wt%,
S 35.26wt%, S020.03wt%.Zn, Cu, In leaching rate or conversion ratio are respectively 58.32%, 59.45%, 72.13%.
Process (3): copper and indium germanium enrichment
I section of pickle liquor is successively discharged into neutralization chamber 8, displacement slot 22, purification tank 9 and zinc electrolysis bath 10, by neutralizing heavy indium, setting
It changes heavy copper, isolation of purified and electrodeposition and respectively obtains indium slag, copper ashes, germanium slag and electrowinning zinc, wherein In content is in indium slag
0.35wt%, Cu content is 75.12wt% in copper ashes, and the content of Ge is 0.15wt% in germanium slag；I section of acid leaching residue and II section of acidleach
Slag washing water obtains I section of pretreatment by cavitation pretreatment is carried out after sizing mixing in solvent and solute weight ratio 3.5:1 the second surge tank 11 of addition
Ore pulp, pretreatment condition are as follows: temperature 50 C, pretreatment mode are ultrasonic cavitation, and cavitation power is 200KW, cavitation frequency is
25KHz, cavitation electric current are 20A, the cavitation time is 200min；
I section of pretreatment ore pulp is discharged into the first flotation device 12 and carries out flotation, floatation process specifically includes that 2 roughings, 4 times
Scan, 1 time it is selected, obtain I section of flotation concentrate and I section of flotation tailing.
I section of flotation concentrate yield is 67.71%, component content are as follows: S 43.19wt%, Zn 30.65wt%, Fe
13.20wt%, Ag183.36g/t, In 123.37g/t, Pb 0.53wt%；Fe and mineral are mainly contained in I section of flotation tailing
Gangue, S 7.98wt%, Zn 1.35wt%, Fe 39.54wt%, Ag 73.69g/t, In75.88g/t, Pb 1.79wt%.
Process (4): II section of oxygen presses acidleach
Third surge tank is added by solvent and solute weight ratio 6:1 in the waste electrolyte generated in I section of flotation concentrate and electrodeposition process
13 size mixing, and Zn is contained in waste electrolyte2+Concentration 65g/L, H2SO4120g/L；After being preheating to 100 DEG C, II section of oxygen pressure kettle is added
In 15, oxygen pressing is passed through to 0.8MPa, and is warming up to 120 DEG C, carries out the pressure acidleach of II section of oxygen, reaction time 200min, then
By entering II section of medial launder 17 after II section of 16 flashed down of flash tank, the purpose of the process be make Zn in I section of flotation concentrate,
Cu, In etc. to the maximum extent enter solution, Fe, S, Pb, Ag respectively in the form of bloodstone, elemental sulfur, lead sulfate, silver sulfate into
Enter in slag, to realize the separation of Zn, Cu, In and Fe, S, Pb, Ag；
II section of oxygen pressure acid leaching slurry in above-mentioned II section of medial launder 17 be separated by solid-liquid separation by II section of filter press 18
To II section of pickle liquor and II section of acid leaching residue.II section of pickle liquor directly returns to I section of oxygen pressure acidleach process.II section of pickle liquor component content
Are as follows: Fe2+1.83g/L、FeT 20.69g/L、H2SO4 41.26g/L、Zn2+107.51g/L、Cu 1.55g/L、In
138.97mg/L,Ge40.01mg/L；II section of acid leaching residue is 18.63kg, component content are as follows: Fe 8.44wt%, Zn
1.42wt%, Cu 0.23wt%, Ag 306.97g/t, In 30.1g/t, Pb 1.02wt%, S 86.99wt%, S0
78.36wt%.Two sections of Zn, Cu, In, Ge total leaching rates are respectively 98.56%, 94.31%, 93.33%, 84.93%.
Process (5): cavitation flotation
The 4th surge tank 19 is added after II section of acid leaching residue and II section of acid leaching residue washing water are sized mixing by solvent and solute weight ratio 3.5:1
Interior progress cavitation pretreatment obtains II section of pretreatment ore pulp；Pretreatment condition are as follows: temperature 50 C, pretreatment mode are that ultrasound is empty
Change, cavitation power is 200KW, cavitation frequency is 25KHz, cavitation electric current is 20A, the cavitation time is 200min；
By II section of pretreatment ore pulp be discharged into the second flotation device 20 carry out flotation, scanned by 2 roughings, 4 times, 1 time it is selected
After obtain II section of flotation concentrate and II section of flotation tailing；II section of flotation concentrate component content are as follows: S 93.02wt%, Zn
1.65wt%, Fe 3.02wt%, Ag 397.5g/t, In 18.8g/t, Pb 0.15wt%；Mainly contain in II section of flotation tailing
There are Fe and mineral gangue, yield 34.59%, S42.10wt%, Zn 0.82wt%, Fe 30.61wt%, Ag 191.05g/
T, In 36.9g/t, Pb 3.06wt%.
Process (6): molten sulphur is heated
S, Ag, Cu, Zn etc., II section of flotation concentrate S are mainly contained in II section of flotation concentrate0The vapour pressure in sulfur melting kettle
After power 0.6MPa, molten sulphur temperature melt under conditions of being 150 DEG C, the silicon for accounting for that II section of flotation concentrate ratio is 10wt% is added
Diatomaceous earth under conditions of 140 DEG C, after hot melt filter filtering, obtains molten sulphur and molten sulphur slag；Molten sulphur is sulfur product, S product
Position is 99.75%.
Process (7): lead silver iron enrichment
Lead smelting gas is obtained after I section of flotation tailing and II section of flotation tailing are mixed with molten sulphur slag, wherein wherein Ag
502.69g/t, Pb 4.88wt%, Fe29.35wt%, S 8.77wt% can enter lead and smelt the progress lead silver recovery of unit 7.
Embodiment 4:
High-iron sphalerite zinc metallurgy is carried out using system described in embodiment 1 and prepares the technique of lead smelting gas, process flow packet
It includes:
Process (1): it sizes mixing
By 80kg 18.54wt% containing Fe, Zn 45.21wt%, S 35.03wt%, Pb 1.02wt%, As0.65wt%,
Ag 144.3g/t, In243.2g/t, Cu2.43wt%, Ge320g/t high-iron sphalerite mixed with 240kg water, it is levigate to-
325 mesh account for 98%, are added in the first surge tank 1, and 4kg wooden sodium sulfonate is added and carries out processing of sizing mixing, obtains adjusting slurry.
Process (2): I section of oxygen presses acidleach
After adjusting slurry is preheating to 120 DEG C of set temperature by I sections of pulp pre-heating devices 2, it is added in I sections of oxygen pressure kettles 3, with II
1:1 is mixed by volume for section pickle liquor, and II section of pickle liquor prepares solution when being added first time；Oxygen pressing is passed through to arrive
2MPa is warming up to 140 DEG C, carries out the pressure acidleach of I section of oxygen, reaction time 180min, then by I sections of 4 flashed downs of flash tank after
Into I sections of medial launders 5.
I section of oxygen pressure acid leaching slurry in above-mentioned I sections of medial launder 5 is separated by solid-liquid separation to obtain I section by I sections of filter presses 6
Pickle liquor and I section of acid leaching residue.I section of pickle liquor component content are as follows: Fe2+1.15g/L、FeT 1.46g/L、H2SO4 4.63g/L、Zn2 +130.35g/L,Cu 1.91g/L,In 215.06mg/L,Ge 45.34mg/L；I section of acid leaching residue is 70.43kg, component content
Are as follows: Fe 24.34wt%, Zn 28.15wt%, Cu 0.87wt%, Ag 177.8g/t, In 98.53g/t, Pb 1.58wt%,
S 33.28wt%, S021.03wt%.Zn, Cu, In, Ge leaching rate or conversion ratio be respectively 60.97%, 63.21%,
7.65%, 57.81%.
Process (3): copper and indium germanium enrichment
I section of pickle liquor is successively discharged into neutralization chamber 8, displacement slot 22, purification tank 9 and zinc electrolysis bath 10, by neutralizing heavy indium, setting
It changes heavy copper, isolation of purified and electrodeposition and respectively obtains indium slag, copper ashes, germanium slag and electrowinning zinc, wherein In content is in indium slag
0.46wt%, Cu content is 65.14wt% in copper ashes, and the content of Ge is 0.2wt% and * * in germanium slag；I section of acid leaching residue is pressed with water
Cavitation pretreatment is carried out after sizing mixing in solvent and solute weight ratio 5:1 the second surge tank 11 of addition, I section of pretreatment ore pulp is obtained, pre-processes
Condition are as follows: 90 DEG C of temperature, pretreatment mode is ultrasonic cavitation, and cavitation power is 1KW, cavitation frequency is 30KHz, cavitation electric current is
30A, cavitation time are 300min；
I section of pretreatment ore pulp is discharged into the first flotation device 12 and carries out flotation, floatation process specifically includes that 3 roughings, 1 time
Scan, 1 time it is selected, obtain I section of flotation concentrate and I section of flotation tailing.
I section of flotation concentrate yield is 68.77%, component content are as follows: S 44.19wt%, Zn 32.61wt%, Fe
15.25wt%, Ag 181.34g/t, In 125.37g/t, Pb 0.57wt%；Fe and mineral are mainly contained in I section of flotation tailing
Gangue, S7.95%, Zn1.34%, Fe 38.55%, Ag 74.56g/t, In74.89g/t, Pb 1.72%.
Process (4): II section of oxygen presses acidleach
Third surge tank is added by solvent and solute weight ratio 10:1 in the waste electrolyte generated in I section of flotation concentrate and electrodeposition process
13 size mixing, and Zn is contained in waste electrolyte2+Concentration 63g/L, H2SO4122g/L；It is preheating to by II section of pulp pre-heating device 14
It after 120 DEG C, is added in II section of oxygen pressure kettle 15, is kept the temperature after being passed through oxygen pressing to 1.2MPa, carry out II section of oxygen pressure acidleach, when reaction
Between 360min, then by entering II section of medial launder 17 after II section of 16 flashed down of flash tank, the purpose of the process be make I section it is floating
Zn, Cu, In in concentrate selection etc. to the maximum extent enter solution, Fe, S, Pb, Ag respectively with bloodstone, elemental sulfur, lead sulfate,
The form of silver sulfate enters in slag, to realize the separation of Zn, Cu, In and Fe, S, Pb, Ag；
II section of oxygen pressure acid leaching slurry in above-mentioned II section of medial launder 17 be separated by solid-liquid separation by II section of filter press 18
To II section of pickle liquor and II section of acid leaching residue.II section of pickle liquor directly returns to I section of oxygen pressure acidleach process.II section of pickle liquor component content
Are as follows: Fe2+1.82g/L、FeT 21.69g/L、H2SO4 41.35g/L、Zn2+105.54g/L、Cu 1.58g/L、In
134.88mg/L,Ge45.01mg/L；II section of acid leaching residue is 17.69kg, component content are as follows: Fe 8.32wt%, Zn
1.48wt%, Cu 0.28wt%, Ag 315.92g/t, In 28.7g/t, Pb 1.15wt%, S 86.54wt%, S0
78.78wt%.Two sections of Zn, Cu, In, Ge total leaching rates are respectively 98.76%, 95.35%, 93.98%, 85.72%.
Process (5): cavitation flotation
Progress cavitation in the 4th surge tank 19 is added after II section of acid leaching residue and water are sized mixing by solvent and solute weight ratio 5:1 to locate in advance
Reason, obtains II section of pretreatment ore pulp；Pretreatment condition are as follows: 90 DEG C of temperature, pretreatment mode is ultrasonic cavitation, and cavitation power is
1KW, cavitation frequency are 30KHz, cavitation electric current is 30A, the cavitation time is 300min；
By II section of pretreatment ore pulp be discharged into the second flotation device 20 carry out flotation, scanned by 1 roughing, 2 times, 3 times it is selected
After obtain II section of flotation concentrate and II section of flotation tailing；II section of flotation concentrate component content are as follows: S 94.02wt%, Zn
1.57wt%, Fe 3.32wt%, Ag 387.5g/t, In 18.5g/t, Pb 0.14wt%；Mainly contain in II section of flotation tailing
There are Fe and mineral gangue, yield 32.59%, S 45.10wt%, Zn 0.82wt%, Fe 30.61wt%, Ag 193.25g/
T, In 38.9g/t, Pb 3.16wt%.
Process (6): molten sulphur is heated
S, Ag, Cu, Zn etc., II section of flotation concentrate S are mainly contained in II section of flotation concentrate0The vapour pressure in sulfur melting kettle
After power 0.8MPa, molten sulphur temperature melt under conditions of being 160 DEG C, the silicon for accounting for that II section of flotation concentrate ratio is 30wt% is added
Diatomaceous earth under conditions of 160 DEG C, after hot melt filter filtering, obtains molten sulphur and molten sulphur slag, molten sulphur is sulfur product, S product
Position is 99.75%.
Process (7): lead silver iron enrichment
Obtain lead smelting gas after I section of flotation tailing and II section of flotation tailing are mixed with molten sulphur slag, wherein Ag 504.69g/t,
Pb 4.78wt%, Fe29.56wt%, S 8.52wt% can enter lead and smelt the progress lead silver recovery of unit 7.
Claims (9)
1. a kind of high-iron sphalerite zinc metallurgy and the system for handling associated metal altogether, which is characterized in that it includes sequentially connected the
One surge tank, I sections of pulp pre-heating devices, I sections of oxygen pressure kettles, I sections of flash tanks, I sections of medial launders and I sections of filter presses；
The filtrate (liquid of the I sections of filter press and the entrance of neutralization chamber connect, the outlet of the neutralization chamber and the entrance of displacement slot
Connection, the outlet of the displacement slot and the entrance of purification tank connect, and the outlet of the purification tank and the entrance of zinc electrolysis bath connect；
The sludge outlet of the I sections of filter press is connect with the entrance of the second surge tank, the outlet and first of second surge tank
The entrance of flotation device connects, and the concentrate outlet of first flotation device is connect with the entrance of third surge tank, and the third is sized mixing
The outlet of slot is connect with the entrance of II section of pulp pre-heating device, the entrance of the outlet of II section of pulp pre-heating device and II section of oxygen pressure kettle
The outlet of connection, II section of oxygen pressure kettle is connect with the entrance of II section of flash tank, in the outlet of II section of flash tank and II section
Between slot entrance connection, the outlet of II section of medial launder connect with the entrance of II section of filter press, the filter of II section of filter press
Liquid outlet is connect with the entrance of first surge tank, and the sludge outlet of II section of filter press and the entrance of the 4th surge tank connect
It connects, the outlet of the 4th surge tank is connect with the entrance of the second flotation device, concentrate outlet and the molten sulphur of second flotation device
System connection；
The tailing outlet of first flotation device, the tailing outlet of second flotation device, the filter residue for heating filter go out
Mouth is smelted unit with lead and is connect；
The electrolyte outlet of the zinc electrolysis bath is connect with the entrance of the third surge tank.
2. using a kind of high-iron sphalerite zinc metallurgy of claim 1 and handling the system zinc metallurgy of associated metal altogether and handling associated gold altogether
The technique of category, which is characterized in that its process flow includes:
Process (1): it sizes mixing
By high-iron sphalerite with water by solid-liquid mass ratio 1:(1~3) mix be milled to granularity be -200~-400 mesh, be added first adjust
In stock tank, dispersing agent being added and carries out processing of sizing mixing, the additional amount of the dispersing agent is 0.1~5wt% of the high-iron sphalerite,
Obtain adjusting slurry；
Process (2): I section of oxygen presses acidleach
After the adjusting slurry is preheating to 80~120 DEG C by I sections of pulp pre-heating devices, it is added in I sections of oxygen pressure kettles, with II section of acidleach
Liquid is by volume (1~5): 1 mixing is warming up to 140~180 DEG C, and be passed through oxygen pressing to 0.6~2.0MPa, carries out I section of oxygen
Press acidleach, 30~180min of reaction time, then by into I sections of medial launders, then passing through I sections after I sections of flash tank flashed downs
Filter press obtains I section of pickle liquor and I section of acid leaching residue after being separated by solid-liquid separation；
Process (3): copper and indium germanium enrichment
I section of pickle liquor sequentially enters neutralization chamber, purification tank and electrolytic cell, by neutralizing heavy indium, replacing heavy copper, isolation of purified
Indium slag, copper ashes, germanium slag and electrowinning zinc are respectively obtained with electrodeposition；Solvent and solute weight ratio (2~5) are pressed in I section of acid leaching residue and cavitation agent:
Cavitation pretreatment is carried out after sizing mixing in 1 the second surge tank of addition, obtains I section of pretreatment ore pulp；I section of pretreatment ore pulp is arranged
Enter the first flotation device and carry out flotation, obtains I section of flotation concentrate and I section of flotation tailing；
Process (4): II section of oxygen presses acidleach
By the waste electrolyte generated in I section of flotation concentrate and the electrodeposition process by solvent and solute weight ratio (3~10): 1 is added
Third surge tank is sized mixing, and after being preheating to 80~120 DEG C by II section of pulp pre-heating device, is added in II section of oxygen pressure kettle, is passed through
Oxygen pressing is warming up to 100~140 DEG C to 0.4~1.2MPa, carries out the pressure acidleach of II section of oxygen, 80~360min of reaction time,
Then by entering II section of medial launder after II section of flash tank flashed down, then it is described by being obtained after II section of filter press separation of solid and liquid
II section of pickle liquor and II section of acid leaching residue；
Process (5): cavitation flotation
By II section of acid leaching residue and the cavitation agent by solvent and solute weight ratio (2~5): 1 size mixing after be added the 4th surge tank it is interior into
The row cavitation pretreatment, obtains II section of pretreatment ore pulp；II section of pretreatment ore pulp is discharged into the second flotation device to float
Choosing, obtains II section of flotation concentrate and II section of flotation tailing；
Process (6): molten sulphur is heated
The filter aid for accounting for that II section of flotation concentrate ratio is 1~30wt% is added in II section of flotation concentrate, 120~
Under conditions of 160 DEG C, molten sulphur is heated by sulfur melting system, obtains molten sulphur and molten sulphur slag；
Process (7): lead silver iron enrichment
Lead smelting gas is obtained after I section of flotation tailing and II section of flotation tailing are mixed with the molten sulphur slag, wherein described
Ag>400g/t, Pb>4wt%, S<10% in lead smelting gas smelt unit into lead and carry out lead silver recovery smelting.
3. a kind of high-iron sphalerite zinc metallurgy and the technique for handling associated metal altogether according to claim 2, which is characterized in that institute
It states in high-iron sphalerite, 7~30wt% of Fe, 30~60wt% of Zn, 10~50wt% of S, 30~300g/t of Ag, In 30~
0.1~3wt% of 300g/t, Cu, 0.2~20wt% of Pb.
4. a kind of high-iron sphalerite zinc metallurgy and the technique for handling associated metal altogether according to claim 2, which is characterized in that institute
Stating cavitation pretreatment is ultrasonic cavitation pretreatment or jet flow cavitation pretreatment or the pretreatment of propeller convolution cavitation, cavitation temperature
0~90 DEG C, 1~500KW of cavitation power, 18~30KHz of cavitation frequency, 10~30A of cavitation electric current, 5~300min of cavitation time.
5. a kind of high-iron sphalerite zinc metallurgy and the technique for handling associated metal altogether according to claim 2, which is characterized in that institute
State the flotation in process (3) include: 1~3 roughing, scan for 1~4 time, 1~5 time it is selected.
6. a kind of high-iron sphalerite zinc metallurgy and the technique for handling associated metal altogether according to claim 2, which is characterized in that institute
State the flotation in process (5) include: 1~3 roughing, scan for 1~4 time, 1~5 time it is selected.
7. a kind of high-iron sphalerite zinc metallurgy and the technique for handling associated metal altogether according to claim 2, which is characterized in that institute
Stating dispersing agent is wooden calcium sulfonate or wooden sodium sulfonate.
8. a kind of high-iron sphalerite zinc metallurgy and the technique for handling associated metal altogether according to claim 2, which is characterized in that institute
Stating filter aid is diatomite.
9. a kind of high-iron sphalerite zinc metallurgy and the technique for handling associated metal altogether according to claim 2, which is characterized in that institute
Cavitation agent is stated as any one or more in I section of acid leaching residue washing water, II section of acid leaching residue washing water, water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114956008A (en) * | 2022-05-16 | 2022-08-30 | 中南大学 | Method for separating zinc smelting leaching slag by monomer cavitation dissociation technology |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114956008A (en) * | 2022-05-16 | 2022-08-30 | 中南大学 | Method for separating zinc smelting leaching slag by monomer cavitation dissociation technology |
| CN114956008B (en) * | 2022-05-16 | 2023-12-26 | 中南大学 | Method for separating zinc smelting leaching residues by adopting monomer emptying dissociation technology |
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Address after: 021008 Technology Department, No. 9, Chuangye Street, Hulunbeier Economic Development Zone, Inner Mongolia Autonomous Region Applicant after: HULUN BUIR CHIHONG MINING INDUSTRY Co.,Ltd. Applicant after: Kunming Metallurgical Research Institute Co.,Ltd. Address before: 021008 Technology Department, No. 9, Chuangye Street, Hulunbeier Economic Development Zone, Inner Mongolia Autonomous Region Applicant before: HULUN BUIR CHIHONG MINING INDUSTRY Co.,Ltd. Applicant before: KUNMING METALLURGICAL Research Institute |