CN1804062A - Crude indium and active zinc oxide co-production process - Google Patents
Crude indium and active zinc oxide co-production process Download PDFInfo
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- CN1804062A CN1804062A CN 200610031149 CN200610031149A CN1804062A CN 1804062 A CN1804062 A CN 1804062A CN 200610031149 CN200610031149 CN 200610031149 CN 200610031149 A CN200610031149 A CN 200610031149A CN 1804062 A CN1804062 A CN 1804062A
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- Prior art keywords
- press filtration
- zinc
- slag
- washing
- filter pressing
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 36
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000011787 zinc oxide Substances 0.000 title claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 26
- 239000002893 slag Substances 0.000 claims abstract description 24
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 9
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- 238000007670 refining Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 4
- 239000012141 concentrate Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000002411 adverse Effects 0.000 claims description 3
- 238000010564 aerobic fermentation Methods 0.000 claims description 3
- 150000004965 peroxy acids Chemical class 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000003472 neutralizing effect Effects 0.000 abstract 2
- 238000005266 casting Methods 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000007858 starting material Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The coproduction technique for coarse indium and active ZnO comprises: (1) curing In-contained hypo-ZnO or material contained both Zn and In; (2) leaching out with mother liquor; (3) filter pressing; (4) neutralizing; (5) filter pressing; (51) extracting neutralized slag; (52) cuing; (53) leaching out; (54) filter pressing; (55) displacing and reducing with Zinc concentrate; (56) filter pressing; (57) extracting; (58) back extracting; (59) displacing; (60) agglomerating; (61) fusing and casting; then, obtaining the coarse IN element; meanwhile, (4) neutralizing; (5) filter pressing; (6) removing Fe and Mn elements with KMnO4; (64) mixing reffinate; (7) filter pressing; (8) displacing with Zn powder; (9) filter pressing; (10) refining with KMnO4; (11) depositing with NH4HCO3; (12) cleaning, filter pressing; (13) drying and baking; (14) obtaining the active ZnO. Compared with the independent prior art, this invention produces little pollution, has small loss to valuable metal, makes full use to the source with low request, and needs low cost and investment.
Description
Technical field
The present invention relates to contain that indium secondary zinc oxide or other contain zinc and contain the indium material is raw material, produces thick indium and active zinc flower novel process.
Background technology
Indium belongs to dissipated metal, and the amount in the earth's crust is considerably less, is about 1 * 10 by mass percentage
-5%, it is dispersion state and is present in the various metal ore bodies, does not still find independent indium mineral deposit up to now in the world;
The most normal association of indium is in the pot zinc ore, and the raw material of at present thick indium production mainly is plumbous zinc calcination fume; Therefore plumbous, zinc and the master operation that is thick indium production separating of indium; Lead is insoluble to sulfuric acid, still stays after the leaching in the slag, and it separates with indium, and is just fairly simple; And zinc, indium all are soluble in sulfuric acid, and their separation is difficulty just; Traditional thick indium and active zinc flower production technique respectively have independently production unit and production technique for dividing presentation:
1, thick indium production: contain the low zinc material of indium → sulfuric acid leaching → iron powder reducing → extraction → back extraction → displacement → pressure group → founding → thick indium product;
2, active zinc flower production: secondary zinc oxide → deironing → zinc dust precipitation of sulfuric acid leaching → accent PH=5 → potassium permanganate → potassium permanganate secondary deironing → soda ash sinks zinc → zinc subcarbonate washing → drying → calcining → active zinc flower cooling → finished product crushing packing;
There is following drawback in traditional technology in actual production:
1, big for environment pollution: just there are two strands of independently discharge of wastewater in two separate systems, just the environmental pollution of twice; The raffinate that particularly thick cigarette is produced because the processing requirement excess sulfuric acid wherein not only has multiple heavy non-ferrous metal, and also has excessive acid; Some producer directly discharges, and base has just been well imagined the pollution of water body; Though some producer discharges through simple neutralization back, does not reach the standard of " qualified discharging " far away, it is also contaminate environment similarly;
2, valuable metal runs off serious: two separate systems, the serious situation that also causes two parts of valuable metals to run off; Because zinc, indium be vitriolization all, all in liquid phase, exist after the leaching, and two systems all are a kind of metals of only getting wherein, and another kind of metal causes serious waste in vain with discharging of waste liquid; It is estimated, every production one kg crude indium, the zinc metal loss is about 100 to 300 kilograms; And one ton of active zinc flower of every production, indium metal runs off about 50 to 150 grams; And with the metal of discharge of wastewater also one of metal of contaminate environment just;
3, starting material are required high: because the loss of valuable metal,, could reduce loss like this so selected starting material all are confined to the scope of " the metal content height of getting, and to give up metal content low " in producing; Also just dwindled manufacturer's starting material scope of application Just because of this; In other words, just limited the development of manufacturer; Limited resources can not get sufficient utilization;
4, investment is big, the cost height: build two separate production systems, because of no common part equipment, its fixed investment is higher relatively certainly; And two separate production systems, its production cost constitutes also correspondingly high; Such as thick indium production, its processing requirement excess sulfuric acid that is to say that dropping into superfluous one-tenth adapted to processing requirement originally; And this part superfluous sulfuric acid must neutralize it with lime again passively in the process of wastewater treatment, and this has increased a high production cost again; Such contradiction also has many in traditional technology.
Summary of the invention
The object of the present invention is to provide a kind of thick indium and active zinc oxide co-production process that can overcome above-mentioned drawback.
This technology comprises following content:
1, raw material contains the indium secondary zinc oxide (this technology is example to contain the indium secondary zinc oxide, and being applicable to that major part contains zinc and contains the indium material) water is sized mixing in aerobic fermentation tank, join the vitriol oil on request and carry out the slaking of high temperature peracid, the filtrate (also claiming " mother liquor ") that adds the zinc subcarbonate washing and recycling is leached; Slag after the press filtration washing goes refining plumbous;
2, leach liquor, slag washing liquid import in the neutralization tank with the secondary zinc oxide neutralization, and heating, drum atmospheric oxidation, hydrolysis removal of impurities, after the press filtration in and slag, neutralizer;
3, in above-mentioned and slag add the vitriol oil through slaking once more, add mother liquor and leach, press filtration, and with after the zinc ore concentrate displacement reduction, press filtration again, last extraction tank extracts, and makes thick indium again after back extraction, displacement, pressure group, founding.
4, A: raffinate heats, rouses atmospheric oxidation, hydrolysis removal of impurities with not containing the neutralization of indium secondary zinc oxide, and press filtration adds behind potassium permanganate deironing, the demanganization and above-mentioned neutralizer converges press filtration after heating, adding potassium permanganate deironing, demanganization, gets mixed solution;
B: mixed solution adds zinc dust precipitation, purification, press filtration, and its slag is the zinc dust precipitation slag;
C: it is refining that its liquid secondary adds potassium permanganate.
D: add the heavy zinc of bicarbonate of ammonia.
E: reacted zinc subcarbonate through repeatedly wash, clarify, filtration, washings adverse current use, final stage adds " pure water of condensation " washing back press filtration.
F: one filtrate is advanced the ammonium sulfate recovery system;
G: in ammonium sulfate reclaimed, evaporated liquor and the steam condensate that condensation is got off can be described as " pure water of condensation " and uses for the final stage washing;
H: other filtrate of recovery is for leaching, washing usefulness, and having more part can stock or efflux.
I: the zinc subcarbonate drying after the washing, roasting become active zinc flower, and packaging final prod after the cooling, fine grinding.
Characteristics of the present invention: the one, environmental pollution is little; The 2nd, valuable metal runs off few; The 3rd, low to the starting material requirement, resource can be fully used; The 4th, this process using equipment component is shared, the technology parallel connection, and the mode of mutual supplement with each other's advantages, less investment, cost is low.
Description of drawings:
Accompanying drawing is this process flow diagram.
Embodiment
With reference to accompanying drawing, this technology comprises:
1.: raw material contains indium secondary zinc oxide water in aerobic fermentation tank and sizes mixing, join the vitriol oil on request and carry out high temperature peracid slaking (1), the filtrate (being mother liquor) that adds the zinc subcarbonate washing and recycling is leached (2), after the press filtration (3), its slag after washing (31), press filtration (32), goes refining plumbous with mother liquor;
2.: through leach liquor (2) after the press filtration (3) and after press filtration (32) slag washing liquid (31) enter in the neutralization tank with secondary zinc oxide neutralization (4), and heating, drum atmospheric oxidation, hydrolysis removal of impurities, after press filtration (5) in and slag (51) and neutralizer;
3.: in above-mentioned and slag (51) add the vitriol oil through slaking once more (52), add mother liquor and leach (53), press filtration (54) liquid with zinc ore concentrate displacement reduction (55), press filtration again (56), its slag is a replacement slag, extraction tank extraction (57) on its liquid, through back extraction (58), displacement (59), the group of pressure (60), founding make thick indium after (61) again;
4.: A: raffinate with do not contain indium secondary zinc oxide neutralization (62), heating, drum atmospheric oxidation, hydrolysis removal of impurities, through press filtration (63), add behind potassium permanganate deironing, the demanganization (64) and above-mentioned neutralizer after heating adds potassium permanganate deferrization and demanganization (6), converge through press filtration (7) mixed solution;
B: mixed solution adds zinc dust precipitation (8), purification, press filtration (9), and its slag is the zinc dust precipitation slag;
C: its liquid adds potassium permanganate refining (10) again;
D: add the heavy zinc (11) of bicarbonate of ammonia;
E: the zinc subcarbonate that adverse current is used through repeatedly wash, clarify, filter, level does not add pure water of condensation washing and filter pressing (12);
F: one filtrate is advanced the ammonium sulfate recovery system;
G: evaporated liquor and the steam condensate in the recovery of ammonium sulfate under the condensation can be described as " pure water of condensation ", uses for the final stage washing;
H: other filtrate of recovery is for leaching, washing usefulness, and having more part can stock or efflux;
I: the zinc subcarbonate drying after the washing, roasting (13), active zinc flower (14), through the cooling abrasive dust (15), can pack dispatch from the factory (16).
Claims (1)
- A kind of thick indium and active zinc oxide co-production process is characterized in that this technology comprises:1.: raw material contains indium secondary zinc oxide water in aerobic fermentation tank and sizes mixing, join the vitriol oil on request and carry out high temperature peracid slaking (1), the filtrate (being mother liquor) that adds the zinc subcarbonate washing and recycling is leached (2), after the press filtration (3), its slag after washing (31), press filtration (32), goes refining plumbous with mother liquor;2.: through leach liquor (2) after the press filtration (3) and after press filtration (32) slag washing liquid (31) enter in the neutralization tank with secondary zinc oxide neutralization (4), and heating, drum atmospheric oxidation, hydrolysis removal of impurities, after press filtration (5) in and slag (51) and neutralizer;3.: in above-mentioned and slag (51) add the vitriol oil through slaking once more (52), add mother liquor and leach (53), press filtration (54) liquid with zinc ore concentrate displacement reduction (55), press filtration again (56), its slag is a replacement slag, extraction tank extraction (57) on its liquid, through back extraction (58), displacement (59), the group of pressure (60), founding make thick indium after (61) again;4.: A: raffinate with do not contain indium secondary zinc oxide neutralization (62), heating, drum atmospheric oxidation, hydrolysis removal of impurities, through press filtration (63), add behind potassium permanganate deironing, the demanganization (64) and above-mentioned neutralizer after heating adds potassium permanganate deferrization and demanganization (6), converge through press filtration (7) mixed solution;B: mixed solution adds zinc dust precipitation (8), purification, press filtration (9), and its slag is the zinc dust precipitation slag;C: its liquid adds potassium permanganate refining (10) again;D: add the heavy zinc (11) of bicarbonate of ammonia;E: the zinc subcarbonate that adverse current is used through repeatedly wash, clarify, filter, level does not add pure water of condensation washing and filter pressing (12);F: one filtrate is advanced the ammonium sulfate recovery system;G: evaporated liquor and the steam condensate in the recovery of ammonium sulfate under the condensation can be described as " pure water of condensation ", uses for the final stage washing;H: other filtrate of recovery is for leaching, washing usefulness, and having more part can stock or efflux;I: the zinc subcarbonate drying after the washing, roasting (13), active zinc flower (14), through the cooling abrasive dust (15), can pack dispatch from the factory (16).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610031149 CN1804062A (en) | 2006-01-11 | 2006-01-11 | Crude indium and active zinc oxide co-production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610031149 CN1804062A (en) | 2006-01-11 | 2006-01-11 | Crude indium and active zinc oxide co-production process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1804062A true CN1804062A (en) | 2006-07-19 |
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| CN 200610031149 Pending CN1804062A (en) | 2006-01-11 | 2006-01-11 | Crude indium and active zinc oxide co-production process |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525696B (en) * | 2009-04-21 | 2011-04-27 | 中南大学 | A method for leaching indium from indium-containing leaching slag |
| CN102515252A (en) * | 2011-12-28 | 2012-06-27 | 韶关凯鸿纳米材料有限公司 | Film-coating production technology for nano zinc oxide |
| CN102586622A (en) * | 2012-03-20 | 2012-07-18 | 广西成源矿冶有限公司 | Method for producing electrolytic zinc by comprehensively recycling high-chlorine high-fluorine lead and antimony smelting waste residue |
| CN102653824A (en) * | 2011-03-02 | 2012-09-05 | 荆门市格林美新材料有限公司 | Copper electrolysis barren solution demanganization method and continuous demanganization process and equipment |
| CN102776384A (en) * | 2012-08-08 | 2012-11-14 | 汉源县广超有色金属综合回收有限责任公司 | Method for extracting zinc from non-ferrous metal waste residue |
| CN104404568A (en) * | 2014-12-15 | 2015-03-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for producing electrolytic manganese metal with manganese carbonate ore |
| CN104451206A (en) * | 2014-12-13 | 2015-03-25 | 株洲冶炼集团股份有限公司 | Process for increasing reclamation rate of indium in zinc concentrate |
| CN105624426A (en) * | 2015-12-30 | 2016-06-01 | 河南豫光锌业有限公司 | High-acid filtrate reduction method for zinc hydrometallurgy |
| CN105692683A (en) * | 2016-03-17 | 2016-06-22 | 安徽颖达锌业发展有限公司 | Ultra-fine zinc oxide production technology |
| CN111020185A (en) * | 2019-12-25 | 2020-04-17 | 昆明冶金研究院有限公司 | A kind of zinc oxide concentrate aging leaching method |
| CN114480874A (en) * | 2022-02-11 | 2022-05-13 | 长沙有色冶金设计研究院有限公司 | Method for removing manganese ions in high manganese zinc concentrate leaching solution and application thereof |
-
2006
- 2006-01-11 CN CN 200610031149 patent/CN1804062A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525696B (en) * | 2009-04-21 | 2011-04-27 | 中南大学 | A method for leaching indium from indium-containing leaching slag |
| CN102653824A (en) * | 2011-03-02 | 2012-09-05 | 荆门市格林美新材料有限公司 | Copper electrolysis barren solution demanganization method and continuous demanganization process and equipment |
| CN102515252A (en) * | 2011-12-28 | 2012-06-27 | 韶关凯鸿纳米材料有限公司 | Film-coating production technology for nano zinc oxide |
| CN102515252B (en) * | 2011-12-28 | 2013-06-05 | 韶关凯鸿纳米材料有限公司 | Film-coating production technology for nano zinc oxide |
| CN102586622A (en) * | 2012-03-20 | 2012-07-18 | 广西成源矿冶有限公司 | Method for producing electrolytic zinc by comprehensively recycling high-chlorine high-fluorine lead and antimony smelting waste residue |
| CN102776384A (en) * | 2012-08-08 | 2012-11-14 | 汉源县广超有色金属综合回收有限责任公司 | Method for extracting zinc from non-ferrous metal waste residue |
| CN104451206A (en) * | 2014-12-13 | 2015-03-25 | 株洲冶炼集团股份有限公司 | Process for increasing reclamation rate of indium in zinc concentrate |
| CN104404568A (en) * | 2014-12-15 | 2015-03-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for producing electrolytic manganese metal with manganese carbonate ore |
| CN105624426A (en) * | 2015-12-30 | 2016-06-01 | 河南豫光锌业有限公司 | High-acid filtrate reduction method for zinc hydrometallurgy |
| CN105624426B (en) * | 2015-12-30 | 2018-06-15 | 河南豫光锌业有限公司 | A kind of peracid filtrate restoring method of zinc hydrometallurgy |
| CN105692683A (en) * | 2016-03-17 | 2016-06-22 | 安徽颖达锌业发展有限公司 | Ultra-fine zinc oxide production technology |
| CN111020185A (en) * | 2019-12-25 | 2020-04-17 | 昆明冶金研究院有限公司 | A kind of zinc oxide concentrate aging leaching method |
| CN114480874A (en) * | 2022-02-11 | 2022-05-13 | 长沙有色冶金设计研究院有限公司 | Method for removing manganese ions in high manganese zinc concentrate leaching solution and application thereof |
| CN114480874B (en) * | 2022-02-11 | 2023-09-26 | 长沙有色冶金设计研究院有限公司 | Method for removing manganese ions in high-manganese zinc concentrate leaching solution and application thereof |
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