CN106868306B - A kind of method of zinc leaching residue valuable metal high efficiente callback - Google Patents
A kind of method of zinc leaching residue valuable metal high efficiente callback Download PDFInfo
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- CN106868306B CN106868306B CN201611207776.6A CN201611207776A CN106868306B CN 106868306 B CN106868306 B CN 106868306B CN 201611207776 A CN201611207776 A CN 201611207776A CN 106868306 B CN106868306 B CN 106868306B
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- zinc
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- iron
- slag
- indium
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- 239000011701 zinc Substances 0.000 title claims abstract description 163
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 159
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 148
- 238000002386 leaching Methods 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 232
- 229910052742 iron Inorganic materials 0.000 claims abstract description 112
- 239000002893 slag Substances 0.000 claims abstract description 109
- 229910052738 indium Inorganic materials 0.000 claims abstract description 84
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 84
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052709 silver Inorganic materials 0.000 claims abstract description 41
- 239000004332 silver Substances 0.000 claims abstract description 41
- 238000004458 analytical method Methods 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 238000006073 displacement reaction Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000011946 reduction process Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 124
- 239000002253 acid Substances 0.000 claims description 101
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 238000005406 washing Methods 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000006210 lotion Substances 0.000 claims description 30
- 230000035484 reaction time Effects 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 19
- 239000010802 sludge Substances 0.000 claims description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000011656 manganese carbonate Substances 0.000 claims description 12
- 229940093474 manganese carbonate Drugs 0.000 claims description 12
- 235000006748 manganese carbonate Nutrition 0.000 claims description 12
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 12
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000004568 cement Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002956 ash Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 229910052595 hematite Inorganic materials 0.000 claims description 3
- 239000011019 hematite Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000004566 building material Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000009867 copper metallurgy Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- -1 For 30~50g/L Substances 0.000 claims 1
- 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 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000002075 main ingredient Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 4
- 229910052598 goethite Inorganic materials 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- QYHNIMDZIYANJH-UHFFFAOYSA-N diindium Chemical compound [In]#[In] QYHNIMDZIYANJH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/22—Iron ore cements ; Iron rich cements, e.g. Ferrari cements, Kühl cements
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Structural Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the zinc abstraction technical field technical fields of non-ferrous metal metallurgy industry, more particularly to a kind of method of zinc leaching residue valuable metal high efficiente callback, mainly including the use of the high silver-colored zinc phase analysis of high-copper and silver enrichment slag after mixing by preimpregnation process, middle sour process, peracid process, reduction process, neutralization step, displacement process, heavy indium process, bloodstone iron removal step；This method is suitable for the processing high silver-colored zinc phase analysis of high-copper and silver enrichment slag mixed material, the recovery rate of valuable metals such as indium, copper, silver, zinc are high, iron zinc separation process is short, energy conservation and environmental protection, remarkable in economical benefits, is the synthetical recovery of the high silver-colored zinc material of high-copper, opens the efficient new method of clean environment firendly.
Description
Technical field
The invention belongs to the zinc abstraction technical field technical field of non-ferrous metal metallurgy industry more particularly to a kind of zinc leaching residues
The method of valuable metal high efficiente callback.
Background technology
85% or more of the worlds zinc hydrometallurgy yield Yi Zhan zinc yield at present, mainly by roasting, leaching, purification, electrolysis, molten
The processes such as casting composition, wherein leaching residue treating method mainly have two kinds of the wet method and pyrogenic process, pyrogenic process to be mainly：Rotary Kiln volatility process and
Blast furnace fuming method, wet method are removed iron after mainly being leached zinc and iron using hot acid extract technology, and method for removing iron includes Huang
Krausite method, goethite process, hematite process etc..
Most domestic zinc hydrometallurgy factory uses Rotary Kiln volatility process.But this method is there is leaching that the quantity of slag is big, energy consumption
High, volatilization kiln exhaust gas contains SO2 high, and tail gas absorbing system is larger, operating cost is higher, and the rate of recovery of dissipated metal is low etc. asks
Topic；Hot Acid Leaching Jarosite Process is used in China part smeltery, and the technical maturity is reliable, and investment is relatively low.But
There are siderotil acid slags to need special cinder field stockpiling, and there are environmentally friendly potential problems.Use iron precipitation by goethite process technique can be with output iron content
Higher goethite slag, advantage are that comprehensive reutilization effect is good, but the utilization of goethite still has some problems, needle iron
Though slag amount is reduced but still needed to pyrogenic attack, the direct yield of zinc metal is relatively low, the valuable metals meeting such as copper-lead during heavy iron
It brings into slag, recovery process lengthens, cost increases or the rate of recovery reduces, and needs the Utilizing question for considering high acidic oils slag.
For above-mentioned zinc abstraction technique there are the problem of, the present invention provides that a kind of recovery rate of valuable metals is high, clean environment firendly
The method of the high-effect processing high silver-colored zinc phase analysis of high-copper and silver enrichment slag mixed material.The technique and existing conventional leaching-volatilization
Kiln treatment process is combined, it can be achieved that the valuable metals such as copper, silver, indium maximizing the benefits, moreover it is possible to keep the body of entire Zn system
Product balance and iron balance.
Invention content
It is an object of the invention to solve the metal synthetical recovery benefit in zinc abstraction technique in the prior art in leached mud
Low problem, and a kind of method of the zinc leaching residue valuable metal high efficiente callback provided.
The technical solution adopted in the present invention is：
A kind of method of zinc leaching residue valuable metal high efficiente callback, mainly including the use of the high silver-colored zinc phase analysis of high-copper and silver enrichment slag
After mixing by preimpregnation process, middle sour process, peracid process, reduction process, neutralization step, displacement process, heavy indium process,
Bloodstone iron removal step：
Step 1）, preimpregnation process：The high silver-colored zinc phase analysis of high-copper and silver enrichment slag are mixed in proportion, by mixed material and sulfur-bearing
The waste electrolyte of acid obtains pre- phase analysis and prepreg solution through preimpregnation, and prepreg solution returns existing Zn system calcining and leaches process；
Step 2）, middle sour process：By step 1）In pre- phase analysis and sulfur acid waste electrolyte warp in during Ore Leaching obtains
Acid sludge and middle acid leaching liquor；
Step 3）, peracid process：By step 2）In middle acid sludge and the waste electrolyte of sulfur acid obtain height through high acidic oils
Acid sludge and high acid solution, high acid solution can return to step 2）The bottom liquid of the middle Ore Leaching as in, highly acid slag washing after obtain lead smelting gas and
Water lotion, wherein lead smelting gas can be used as the raw material of refining lead；
Step 4）, reduction process：By step 3）In middle acid leaching liquor after reducing agent restores to obtain reducing slag and reduction
Liquid, reducing slag return to existing Zn system calcining process dispensing and use；
Step 5）, neutralization step：By step 4）In reduction after neutralized dose of liquid neutralize obtain gypsum and neutralize after liquid, stone
Cream can be used as cement and the raw material of building materials plasterboard factory；
Step 6）, displacement process：By step 5）In neutralization after liquid obtain copper ashes and displaced liquid, copper ashes through zinc dust precipitation
It can be used as the raw material of copper metallurgy；
Step 7）, heavy indium process：By step 6）In displaced liquid and step 3）The washing obtained after middle highly acid slag washing
Liquid obtains liquid after indium enrichment slag and heavy indium after indium is sunk in heavy indium agent, and indium enrichment slag returns the existing smart smart indium of indium process production；
Step 8）, bloodstone iron removal step：By step 7）In heavy indium after liquid through hematite process except iron obtains bloodstone slag
With except liquid after iron, liquid returns step 1 after partly removing iron）As the pre- preserved material of preimpregnation, liquid returns existing Zn system roasting after remaining removes iron
Sand leaches the electric zinc of process production, and bloodstone slag obtains bloodstone and washing lotion after being washed with production water, wherein bloodstone can be used as water
The raw material of mud factory, washing lotion can return to step 3）Middle participation highly acid slag washing.
Further, it presoaks the high silver-colored zinc phase analysis of high-copper in process and contains zinc 10~25%, iron 15~40%, copper 0.5~3%, indium
0.01~0.05%, silver 0.005~0.06%, silver enrichment slag is containing zinc 20~25%, silver 0.15~1.0%, and the two is in following ratio
Mixing is with even：The high silver-colored zinc phase analysis of high-copper：50~95%, silver enrichment slag：5~50%, the preimpregnation process, middle sour process and height
The main component of the waste electrolyte used in sour process is 40~60g/l of zinc, 150~200g/l of sulfuric acid.
Further, it is generated in the bloodstone iron removal step except after liquid after iron, liquid can after iron is removed in part therein
Returning in preimpregnation process replaces expense electrolyte to be used as the pre- preserved material of preimpregnation, and bloodstone iron removal step output is removed after iron in liquid
Containing 80~100 g/l of zinc, 2~6 g/l of iron, 30~50 g/l of acid, 90~95 DEG C of temperature, and presoak process use remove iron after liquid as
It is 30~50g/l that the reaction condition of pre- preserved material, which is initial acidity, solvent and solute weight ratio 3~5 in reaction process:1, the reaction time 0.5
~1h.
Further, the reaction condition of the middle sour process is solvent and solute weight ratio 4~6 in reaction process:1, reaction temperature
65~75 DEG C, reaction time 6h of degree, acidity are 50~70g/l, and the middle acid sludge after reaction is containing zinc 8~16%, iron 8~15%, copper
0.2~0.4%, silver 0.05~0.5%, the middle acid leaching liquor after reaction contain 45~70 g/l of zinc, 50~70 g/l containing acid, contain trivalent
15~45 g/l of iron.
Further, the reaction condition of the peracid process is to be added to contain 40~60 g/l of zinc, 150~200 g/ of sulfuric acid
L waste electrolytes, solvent and solute weight ratio 6~8:1,85~95 DEG C, reaction time 6h of reaction temperature, terminal acidity be 110~
130g/l, highly acid slag after reaction after water lotion washs output containing zinc 2~5%, leaded 10~20%, silver-colored 0.1~1.5% lead silver
Slag and 30~50 g/l highly acid slag cleaning solutions containing zinc, wherein raw material of the lead smelting gas as refining lead, highly acid slag washing lotion enter heavy indium work
Sequence.
Further, the reaction condition of the reduction process is that middle acid leaching liquor is warming up to 65~85 DEG C, is added also
Former agent, reducing agent used are that zinc concentrate, lead concentrate or low iron vulcanize one or more of lead and zinc concentrate, reducing agent addition amount
For 1.0~1.6 times of Fe3+ theory of reduction amount, 2~6 hours recovery times, 65~85 DEG C of reaction temperature, reaction end is after restoring
Fe3+ is less than 3g/L in liquid, restores 45~65g/L of concentration of acid eventually, send neutralization step.
Further, the reducing agent used in the reduction process is that low iron vulcanizes lead and zinc concentrate.
Further, the reaction condition of the neutralization step be added neutralizer, neutralizer be white lime and carbide slag,
And white lime and carbide slag are formed according to following ratio by weight percentage：White lime：60~90%, carbide slag：10~40%, in
It is the 80%~110% of theoretical amount that weight, which is added, with agent, neutralizes time 10min, 10~35 DEG C of reaction process reaction temperature, terminal
Acidity is 5~15g/l.
Further, the displacement process is that displacement process will be added in liquid after neutralizing, and displacer zinc powder is added, zinc powder adds
Enter 1.5-2.5 times that amount is theoretical amount, 60-70 DEG C of reaction temperature, reaction time 2h, control displaced liquid copper is less than 0.1 g/L
Interior, displaced liquid send heavy indium process.
Further, the heavy indium agent used in the heavy indium process is sodium carbonate and manganese carbonate, and reaction condition is to react
60~75 DEG C of journey reaction temperature, 2~3 h of reaction time, terminal acidity is Ph value 3.5-4.5, and sodium carbonate is pressed with manganese carbonate
Weight percent is formed according to following ratio：Sodium carbonate：30~60%, manganese carbonate：40~70%, it is theory that weight, which is added, in indium agent of sinking
The 90%~160% of amount, indium obtained by reacting are enriched with liquid after slag and heavy indium, wherein indium is enriched with slag and is more than 0.6% containing indium, send smart indium system
It unites, liquid send bloodstone iron removal step after heavy indium.
Further, the reaction condition of the bloodstone iron removal step is that liquid after heavy indium is warming up to 150~220 DEG C, is added
Entering oxygen, oxygen is added 110%~200% that weight is theoretical amount, and control bloodstone iron removal kettle is pressed in 0.65~
2.8MPa reacts 3h, and except 3g/L is less than containing Fe in liquid after iron, except a liquid part returns to preimpregnation process after iron, remaining is except after iron
Liquid returns existing Zn system calcining and leaches the electric zinc of process production, and the bloodstone slag of output carries out multiple countercurrent washing with production water, with
It is washing terminal that the water lotion obtained after washing is less than 20g/l containing zinc, and highly acid slag washing is with after washing in the peracid process
The water lotion arrived containing zinc be less than 50g/l be washing terminal, bloodstone slag after washing output containing zinc 0.5~1.5%, iron content 55~
60% bloodstone can be used as the raw material in cement plant.
The beneficial effects of the present invention are：
1. from after the flash distillation of iron removal step autoclave except after iron liquid directly mixed with the high silver-colored zinc phase analysis of high-copper and silver enrichment slag
Material mixing is closed, because liquid temperature is up to 90~95 DEG C after removing iron, preimpregnation is not required to heat up when reacting, that is, saves the steaming needed for reaction
Vapour consumes, and cools and reduced except liquid after iron except the construction investment of liquid cooling equipment and production run cost after iron；Presoak mesh
Mainly zinc leaching residue and silver enrichment slag mixed material in sour molten zinc and water-soluble zinc enter prepreg solution, reduce it is follow-up in acid,
The leaching burden of peracid process and the zinc ion content except liquid before iron, and the iron etc. in mixed material stays in pre- phase analysis, the party
Method is suitable for the processing high silver-colored zinc phase analysis of high-copper and silver enrichment slag mixed material, and the recovery rate of valuable metals such as indium, copper, silver, zinc are high,
Iron-zinc separation process is short, energy conservation and environmental protection, remarkable in economical benefits, is the synthetical recovery of the high silver-colored zinc material of high-copper, opens wiper ring
Protect efficient new method；
2. reducing agent, which is low iron, vulcanizes lead and zinc concentrate, the reducing slag lead grade after reduction is enriched with, after zinc enters reduction
Liquid fully solves this kind of low iron vulcanization drawback that lead and zinc concentrate is difficult, cost recovery is high；
3. countercurrent washing determines the washing terminal of washing bloodstone slag according to bloodstone water lotion containing zinc less than 20g/l；
And apply repeatedly to this water lotion in highly acid slag water-washing process, it is washed less than 50g/l to determine containing zinc according to highly acid slag water lotion
The washing terminal for washing highly acid slag, the slag rate that bloodstone and lead smelting gas are optimal after being washed by the requirement, minimum slag contain zinc,
Saved industrial water, which enters sink indium process after not only recycled the zinc of water lotion, but also after adjustable heavy indium liquid zinc from
Sub- concentration is less than 100g/l, reaches bloodstone and removes requirement of the iron to solution zinc ion concentration；
4. neutralizer is arranged in pairs or groups uses in proportion using white lime and carbide slag, cost of supplementary product is not only saved, but also can output height
The product gypsum of quality；
5. heavy indium agent is arranged in pairs or groups use in proportion using sodium carbonate and manganese carbonate, the addition of manganese carbonate is according to manganese in Zn system
Ion concentration is adjusted, and both ensure that liquid is best after heavy indium indium recovery and indium enrichment slag indium grade, has been in turn ensured zinc system
System manganese ion content improves economic benefit to ensure that the electrolytic zinc of Zn system output high quality.
Description of the drawings
Fig. 1 is a kind of process flow chart of the method for zinc leaching residue valuable metal high efficiente callback provided by the invention.
Specific implementation mode
The invention will be further described in the following with reference to the drawings and specific embodiments.
Embodiment 1
Contain zinc containing zinc 10%, iron 15%, copper 0.5%, indium 0.01%, the high silver-colored zinc phase analysis of high-copper of silver 0.005% and 1 ton by 19 tons
Sulfur acid 150g/l, the 40g/l containing zinc are taken electrolyte as pre- preserved material and mixture by 20%, silver-colored 0.15% silver medal enrichment slag mixing
Preimpregnation, liquid consolidate mass ratio 3:1,0.5h is reacted, obtains liquid after 17.6 tons of pre- phase analysis and preimpregnation, liquid enters main system calcining after preimpregnation
Leach process；It is sour in progress by the pre- phase analysis of sulfur acid 150g/l, the 40g/l containing zinc taken electrolyte and preimpregnation process output is added
It leaches, solvent and solute weight ratio 4:1,65 DEG C, reaction time 6h of reaction temperature, terminal acidity is 50g/l, and 9.16 are obtained after reaction
Acid sludge in ton, acid sludge is containing zinc 8%, iron 8%, copper 0.2%, silver 0.05% in these, middle 45 g/l of acid solution zinc obtained by the reaction, containing acid 50
G/l, 15 g/l containing ferric iron；Middle acid sludge enters high acidic oils process, is added containing 40 g/l of zinc, sour 150 g/l waste electrolytes, liquid
Gu mass ratio 6:1,85 DEG C, reaction time 6h of reaction temperature, terminal acidity is 110g/l, 5.5 tons of highly acid slags warp after reaction
After water lotion washing 4.12 tons of output containing zinc 2%, leaded 10%, silver-colored 0.1% lead gold and silver slag and containing 30 g/l highly acid slags cleaning solution of zinc into
Enter heavy indium process；The middle acid solution of middle Ore Leaching process is warming up to 65 DEG C, and 4.64 tons of reducing agent zinc concentrate is added, and reducing agent is added
Amount is 1 times of Fe3+ theory of reduction amounts, and 2 hours recovery times, Fe3+2.8g/L in liquid after reduction restores the concentration 45g/ of acid eventually
L send neutralization step；Liquid enters neutralization step after reduction, and 0.6 ton of the carbide slag that weight accounts for 10% is first added, adds weight and accounts for 85%
80% that weight is theoretical amount is added in 5.1 tons of white lime, neutralizer, neutralizes time 10min, 10 DEG C of reaction temperature, the concentration of whole acid
5g/L；Liquid enters displacement process after neutralization, and 300 kilograms of zinc powder is added, and zinc powder addition is the 150% of theoretical amount, reaction temperature 60
DEG C, reaction time 120min, displaced liquid copper is less than 0.1 g/L；Heavy indium agent is added in displaced liquid, and weight is first added and accounts for 30%
0.54 ton of sodium carbonate adds weight and accounts for 1.26 tons of 70% manganese carbonate, and it is the 90% of theoretical amount that weight, which is added, 60 DEG C of reaction temperature,
Reaction time 2h, terminal acidity pH value obtain indium enrichment slag and are more than 0.6% containing indium, indium enrichment slag send smart indium between 3.5-4.5
System, liquid send bloodstone iron removal step after heavy indium, and liquid after heavy indium is warming up to 150 DEG C, oxygen is added, oxygen addition is theory
110% measured, control bloodstone autoclave kettle press 0.65MPa, react 3h, are less than 3g/L except Fe is contained in liquid after iron；Except liquid after iron
A part returns to preimpregnation process, and liquid returns the electric zinc of existing Zn system calcining leaching process production, the red iron of output after remaining removes iron
Slag carries out multiple countercurrent washing with production water, and it is washing terminal to be less than 20g/l containing zinc with the water lotion obtained after washing, described
It is washing terminal that highly acid slag washing is less than 50g/l with the water lotion obtained after washing containing zinc in peracid process, and bloodstone slag is through water
Bloodstone of 6.4 tons of the rear output containing zinc 0.5%, iron content 55% is washed, these bloodstone can be as the raw material in cement plant；The embodiment
For the embodiment of initial situation, the embodiment that waste electrolyte is all added in process, middle sour process and peracid process is as presoaked.
Embodiment 2
Contain zinc containing zinc 25%, iron 40%, copper 3%, indium 0.05%, the high silver-colored zinc phase analysis of high-copper of silver 0.06% and 10 tons by 10 tons
25%, silver-colored 1% silver medal enrichment slag mixing, using sulfur acid 200g/l, the 60g/l containing zinc to take electrolyte pre- as pre- preserved material and mixture
Leaching, liquid consolidate mass ratio 5:1,1h is reacted, liquid after 17 tons of pre- phase analysis and preimpregnation is obtained, liquid enters main system calcining leaching work after preimpregnation
Sequence；By the pre- phase analysis of sulfur acid 200g/l, the 60g/l containing zinc taken electrolyte and preimpregnation process output is added, Ore Leaching in progress, liquid
Gu weight ratio 6:1,75 DEG C, reaction time 6h of reaction temperature, terminal acidity is 70g/l, and acid sludge in 8.5 tons is obtained after reaction,
In these middle 70 g/l of acid solution zinc obtained by the reaction, acid sludge 70 g/l containing acid, contains containing zinc 16%, iron 15%, copper 0.4%, silver 0. 5%
45 g/l of ferric iron；Middle acid sludge enters high acidic oils process, is added containing 60 g/l of zinc, sour 200 g/l waste electrolytes, liquid stereoplasm amount
Than 8:1,95 DEG C, reaction time 6h of reaction temperature, terminal acidity is 130g/l, and 5.2 tons of highly acid slags after reaction are through water lotion
3.9 tons of output enters containing zinc 5%, leaded 20%, silver-colored 1.5% lead gold and silver slag and containing 50 g/l highly acid slag cleaning solutions of zinc after washing sinks indium
Process；The middle acid solution of middle Ore Leaching process is warming up to 85 DEG C, and 5.24 tons of reducing agent zinc concentrate, reducing agent addition amount Fe3 is added
1.6 times of+theory of reduction amount, 6 hours recovery times, Fe3+1.6g/L in liquid after reduction, during the whole sour concentration 65g/L of reduction is sent
And process；Liquid enters neutralization step after reduction, and 1.92 tons of the carbide slag that weight accounts for 40% is first added, adds weight and accounts for 60% ripe stone
110% that weight is theoretical amount is added in 4.48 tons of ash, neutralizer, neutralizes time 10min, 35 DEG C of reaction temperature, the concentration of whole acid
15g/L；Liquid enters displacement process after neutralization, and 460 kilograms of zinc powder is added, and zinc powder addition is the 250% of theoretical amount, reaction temperature
70 DEG C, reaction time 120min, displaced liquid copper is less than 0.1 g/L；Heavy indium agent is added in displaced liquid, and weight is first added and accounts for 60%
1.2 tons of sodium carbonate, add weight and account for 0.8 ton of 40% manganese carbonate, be added 160% that weight is theoretical amount, 75 DEG C of reaction temperature,
Reaction time 3h, terminal acidity pH value obtain indium enrichment slag and are more than 0.6% containing indium, indium enrichment slag send smart indium between 3.5-4.5
System, liquid send bloodstone iron removal step after heavy indium, and liquid after heavy indium is warming up to 220 DEG C, oxygen is added, oxygen addition is theory
200% measured, control bloodstone autoclave kettle press 2.8MPa, react 3h, are less than 3g/L except Fe is contained in liquid after iron；Except liquid one after iron
Part returns to preimpregnation process, and liquid returns the electric zinc of existing Zn system calcining leaching process production, the bloodstone of output after remaining removes iron
Slag carries out multiple countercurrent washing with production water, and it is washing terminal, peracid work to be less than 20g/l containing zinc with the water lotion obtained after washing
It is washing terminal that highly acid slag washing is less than 50g/l with the water lotion obtained after washing containing zinc in sequence, and bloodstone slag produces after washing
Go out 7 tons of bloodstone containing zinc 1.5%, iron content 60%, these bloodstone can be as the raw material in cement plant；The embodiment is initial feelings
The embodiment of condition as presoaks the embodiment that waste electrolyte is all added in process, middle sour process and peracid process.
Embodiment 3
By bloodstone iron removal step output except in liquid after iron containing 95 g/l of zinc, 3.5 g/l of iron, acid 42 g/l, temperature
93.5 DEG C, be added containing zinc 18.5%, iron 22.5%, copper 0.9%, indium 0.032%, silver 0.032% weight account for 80% 8 tons of zinc leaching residue and
Weight containing zinc 23.8%, silver 0.42% accounts for 20% silver 2 tons of slag of enrichment, liquid-solid ratio 3:1, react 1h, obtain 8.8 tons of pre- phase analysis and
Liquid after preimpregnation, liquid enters main system calcining leaching process after preimpregnation, and being added containing sour 128 g/l high acid solutions for high acidic oils process is pre-
Soak the pre- phase analysis of process output, Ore Leaching in progress, liquid-solid ratio 4:1,75 DEG C, reaction time 6h of reaction temperature, terminal acidity
For 66g/l, acid sludge is containing zinc 8.2%, iron 8.5%, copper 0.23%, silver 0.17% in 4.58 tons after reaction；Middle acid sludge enters high acidleach
Go out process, is added containing 55 g/l of zinc, sour 192 g/l waste electrolytes, liquid-solid ratio 6:1,94 DEG C of reaction temperature, the reaction time
6h, terminal acidity are 128g/l, the bloodstone water lotion of 2.75 tons of highly acid slags and bloodstone iron removal step output after reaction
2.06 tons of output is containing zinc 2.2%, leaded 15.8%, silver-colored 0.35% lead gold and silver slag after washing.Containing 48.5 g/l of zinc, bis- highly acid slag washings
Liquid enters heavy indium process, and middle Ore Leaching process contains 48.9 g/l of zinc, 66 g/l containing acid, acid solution in 19.5 g/l of ferric iron, rises
2.32 tons of zinc concentrate is added to 76 DEG C in temperature, and addition is 1.05 times of Fe3+ theory of reduction amount, 5 hours recovery times, liquid after reduction
Middle Fe3+ 2.8g/L, the concentration 62g/L for restoring acid eventually send neutralization step, and liquid enters neutralization step after reduction, and weight is first added and accounts for
0.45 ton of 15% carbide slag adds weight and accounts for 2.55 tons of 85% white lime, and 99% that weight is theoretical amount is added, neutralizes the time
10min, 32 DEG C of temperature, the concentration 11g/L of whole acid；Liquid enters displacement process after neutralization, and 150 kilograms of zinc powder is added, and zinc powder is added
Amount is the 155% of theoretical amount, 65 DEG C, reaction time 120min, 0.02 g/L of displaced liquid copper of reaction temperature, displaced liquid addition
0.45 ton of the sodium carbonate that weight accounts for 50% is first added in heavy indium agent, adds weight and accounts for 0.45 ton of 50% manganese carbonate, it is reason that weight, which is added,
The 106% of stoichiometric, 72 DEG C, reaction time 3h of reaction temperature, indium are enriched with slag and contain indium 0.85%, except liquid enters after the i.e. heavy indium of liquid before iron
Bloodstone iron removal step is warming up to 185 DEG C, and oxygen is added, and oxygen addition is the 160% of theoretical amount, bloodstone autoclave kettle
1.35MPa is pressed, 3h is reacted, except 2.8g/L containing Fe in liquid after iron, except a liquid part returns to preimpregnation process after iron, remaining removes iron
Liquid returns existing Zn system calcining and leaches the electric zinc of process production afterwards, and the bloodstone slag of output carries out multiple countercurrent washing with production water,
It is washing terminal to be less than 20g/l containing zinc with the water lotion that is obtained after washing, and highly acid slag washing is to obtain after washing in peracid process
Water lotion to be less than 50g/l containing zinc be washing terminal, bloodstone slag after washing 3.2 tons of output containing zinc 0.78%, iron content 59%
Bloodstone, the embodiment be presoak use in process output in iron removal step except after iron liquid as pre- preserved material, middle acid process use
The case where embodiment of high acidic oils liquid, i.e. waste liquid reuse.
Embodiment 4
By bloodstone iron removal step output except in liquid after iron containing 82 g/l of zinc, 2.5 g/l of iron, acid 35 g/l, temperature 91
DEG C, the weight containing zinc 19.5%, iron 20.8%, copper 1.2%, indium 0.025%, silver 0.025% is added and accounts for 50% 5 tons of zinc leaching residue and containing zinc
22.5%, the weight of silver 0.28% accounts for 50% silver 5 tons of slag of enrichment, liquid-solid ratio 5:1,0.5h is reacted, 8.5 tons of pre- phase analysis and pre- is obtained
Liquid after leaching, liquid enters main system calcining leaching process after preimpregnation, and being added containing sour 108.5 g/l high acid solutions for high acidic oils process is pre-
Soak the pre- phase analysis of process output, Ore Leaching in progress, liquid-solid ratio 6:1,68 DEG C, reaction time 6h of reaction temperature, terminal acidity
For 56.5g/l, acid sludge is containing zinc 12.5%, iron 12.6%, copper 0.25%, silver 0.22% in 4.25 tons after reaction；Middle acid sludge enters height
Ore Leaching process is added containing 45 g/l of zinc, sour 185 g/l waste electrolytes, liquid-solid ratio 8:1,91 DEG C of reaction temperature, reaction
Time 6h, terminal acidity are 111.5g/l, water of bloodstone of highly acid slag and bloodstone iron removal step output after reaction
Output is containing zinc 4.9%, leaded 12.8%, silver-colored 0.91% 1.95 tons of lead gold and silver slag after wash liquid.Containing zinc highly acid slag of 35.6 g/l
Cleaning solution enters heavy indium process, and middle Ore Leaching process contains 48 g/l of zinc, 56.5 g/l containing acid, acid in 28.6 g/l of ferric iron
Liquid is warming up to 75 DEG C, and 2.62 tons of zinc concentrate is added, and addition is 1.2 times of Fe3+ theory of reduction amount, 4 hours recovery times, reduction
Fe3+1.6g/L in liquid afterwards, the concentration 53.2g/L for restoring acid eventually send neutralization step, and liquid enters neutralization step after reduction, is first added
Weight accounts for 30% 0.96 ton of carbide slag, adds weight and accounts for 2.24 tons of 70% white lime, and 102% that weight is theoretical amount is added, in
With time 10min, 32 DEG C of temperature, the concentration 9.5g/L of whole acid；Liquid enters displacement process after neutralization, and 230 kilograms of zinc powder, zinc is added
Powder addition is the 180% of theoretical amount, 68 DEG C, reaction time 120min of reaction temperature, 0.06 g/L of displaced liquid copper；After displacement
Heavy indium agent is added in liquid, and 0.3 ton of the sodium carbonate that weight accounts for 30% is first added, and adds weight and accounts for 0.7 ton of 70% manganese carbonate, weight is added
It is the 108% of theoretical amount, 68 DEG C, reaction time 2.5h of reaction temperature, indium is enriched with slag indium containing I 0.72%, except liquid enters red iron before iron
Mine iron removal step is warming up to 170 DEG C, and oxygen is added, and oxygen addition is the 120% of theoretical amount, bloodstone autoclave kettle pressure
1.05MPa reacts 3h, and except 2.2g/L containing Fe in liquid after iron, except a liquid part returns to preimpregnation process after iron, remaining is except after iron
Liquid returns existing Zn system calcining and leaches the electric zinc of process production, and the bloodstone slag of output carries out multiple countercurrent washing with production water, with
It is washing terminal that the water lotion obtained after washing is less than 20g/l containing zinc, and highly acid slag washing is to obtain after washing in peracid process
It is washing terminal, bloodstone slag red iron of 3.5 tons of the output containing zinc 0.8%, iron content 56% after washing that water lotion is less than 50g/l containing zinc
Mine, the embodiment be presoak use in process output in iron removal step except after iron liquid as pre- preserved material, middle sour process peracid
The case where embodiment of leachate, i.e. waste liquid reuse.
Claims (10)
1. a kind of method of zinc leaching residue valuable metal high efficiente callback, it is characterised in that：Mainly including the use of the high silver-colored zinc phase analysis of high-copper
With silver enrichment slag after mixing by preimpregnation process, middle sour process, peracid process, reduction process, neutralization step, displacement work
Sequence, heavy indium process, bloodstone iron removal step：
Step 1）, preimpregnation process：The high silver-colored zinc phase analysis of high-copper and silver enrichment slag are mixed in proportion, by mixed material and sulfur acid
Waste electrolyte obtains pre- phase analysis and prepreg solution through preimpregnation, and prepreg solution returns existing Zn system calcining and leaches process；
Step 2）, middle sour process：By step 1）In pre- phase analysis and sulfur acid waste electrolyte warp in Ore Leaching obtain middle acid sludge
With middle acid leaching liquor；
Step 3）, peracid process：By step 2）In middle acid sludge and the waste electrolyte of sulfur acid obtain highly acid slag through high acidic oils
With high acid solution, high acid solution returns to step 2）The bottom liquid of the middle Ore Leaching as in obtains lead smelting gas and water lotion after highly acid slag washing,
Wherein, raw material of the lead smelting gas as refining lead；
Step 4）, reduction process：By step 2）In middle acid leaching liquor after reducing agent restores to obtain reducing slag and reduction liquid, also
Former slag returns to existing Zn system calcining process dispensing and uses；
Step 5）, neutralization step：By step 4）In reduction after neutralized dose of liquid neutralize obtain gypsum and neutralize after liquid, gypsum makees
For cement and the raw material of building materials plasterboard factory；
Step 6）, displacement process：By step 5）In neutralization after liquid obtain copper ashes and displaced liquid, copper ashes conduct through zinc dust precipitation
The raw material of copper metallurgy；
Step 7）, heavy indium process：By step 6）In displaced liquid and step 3）The water lotion warp obtained after middle highly acid slag washing
Liquid after indium enrichment slag and heavy indium is obtained after the heavy heavy indium of indium agent, indium enrichment slag returns existing smart indium process production essence indium；
Step 8）, bloodstone iron removal step：By step 7）In heavy indium after liquid through hematite process except iron obtains bloodstone slag and removes
Liquid after iron, liquid returns step 1 after partly removing iron）As the pre- preserved material of preimpregnation, liquid returns existing Zn system calcining leaching after remaining removes iron
Go out the electric zinc of process production, bloodstone slag obtains bloodstone and washing lotion after being washed with production water, wherein bloodstone is as cement plant
Raw material, washing lotion return to step 3）Middle participation highly acid slag washing.
2. a kind of method of zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：Presoak process
The middle high silver-colored zinc phase analysis of high-copper contains zinc 10~25%, iron 15~40%, copper 0.5~3%, indium 0.01~0.05%, silver 0.005~0.06%,
Silver enrichment slag is containing zinc 20~25%, silver 0.15~1.0%, and the two in the mixing of following ratio with even：The high silver-colored zinc phase analysis of high-copper：50~
95%, silver enrichment slag：5~50%；The waste electrolyte used in the preimpregnation process, middle sour process and peracid process it is main
Ingredient is 40~60g/L of zinc, 150~200g/L of sulfuric acid.
3. a kind of method of zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：Described is red
It is generated in iron ore iron removal step except after liquid after iron, liquid returns in preimpregnation process instead of waste electrolyte conduct after iron is removed in part therein
The pre- preserved material of preimpregnation uses, and bloodstone iron removal step output except in liquid after iron containing 80~100 g/L of zinc, 2~6 g/L of iron,
It is initial acidity that 30~50 g/L of acid, 90~95 DEG C of temperature, and preimpregnation process, which use the reaction condition of liquid as pre- preserved material after removing iron,
For 30~50g/L, solvent and solute weight ratio 3~5 in reaction process:1,0.5~1h of reaction time.
4. a kind of method of zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：In described
The reaction condition of sour process is solvent and solute weight ratio 4~6 in reaction process:1,65~75 DEG C, reaction time 6h of reaction temperature,
Acidity is 50~70g/L, and the middle acid sludge after reaction is containing zinc 8~16%, iron 8~15%, copper 0.2~0.4%, silver 0.05~0.5%, instead
Middle acid leaching liquor after answering is containing 45~70 g/L of zinc, 50~70 g/L containing acid, 15~45 g/L containing ferric iron.
5. a kind of method of zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：The height
The reaction condition of sour process is to be added containing 40~60 g/L of zinc, 150~200 g/L waste electrolytes of sulfuric acid, solvent and solute weight ratio 6~8:
1,85~95 DEG C, reaction time 6h of reaction temperature, terminal acidity is 110~130g/L, and the highly acid slag after reaction is through water lotion
Output is washed containing zinc 2~5%, leaded 10~20%, silver-colored 0.1~1.5% lead smelting gas and containing 30~50 g/L highly acid slags of zinc after washing
Liquid, wherein raw material of the lead smelting gas as refining lead, highly acid slag washing lotion enter heavy indium process.
6. a kind of method of zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：Described goes back
The reaction condition of former process is that middle acid leaching liquor is warming up to 65~85 DEG C, is added reducing agent, reducing agent used be zinc concentrate,
One or more of lead concentrate or low iron vulcanization lead and zinc concentrate, reducing agent addition amount Fe3+1.0~1.6 times of theory of reduction amount,
2~6 hours recovery times, 65~85 DEG C of reaction temperature, reaction end are Fe in liquid after reduction3+Less than 3g/L, whole acid is restored
45~65g/L of concentration, send neutralization step.
7. a kind of method of zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：In described
It is that neutralizer is added with the reaction condition of process, neutralizer is white lime and carbide slag, and white lime and carbide slag by weight hundred
Divide than being formed according to following ratio：White lime：60~90%, carbide slag：10~40%, it is theoretical amount that weight, which is added, in neutralizer
80%~110%, time 10min, 10~35 DEG C of reaction process reaction temperature are neutralized, terminal acidity is 5~15g/L.
8. a kind of method of zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：Described sets
It is that displacement process will be added in liquid after neutralizing to change process, and displacer zinc powder is added, and zinc powder addition is 1.5-2.5 times of theoretical amount,
60-70 DEG C of reaction temperature, reaction time 2h, control displaced liquid copper are less than in 0.1 g/L, and displaced liquid send heavy indium process.
9. the method for zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：The heavy indium work
Heavy indium agent used in sequence is sodium carbonate and manganese carbonate, and reaction condition is 60~75 DEG C of reaction process reaction temperature, reaction time 2
~3 h, terminal acidity is pH value 3.5-4.5, and sodium carbonate and manganese carbonate are formed according to following ratio by weight percentage：Carbon
Sour sodium：30~60%, manganese carbonate：40~70%, 90%~160% that weight is theoretical amount is added in indium agent of sinking, and indium obtained by reacting is rich
Liquid after collection slag and heavy indium, wherein indium is enriched with slag and is more than 0.6% containing indium, send smart indium system, and liquid send bloodstone iron removal step after heavy indium.
10. the method for zinc leaching residue valuable metal high efficiente callback according to claim 1, it is characterised in that：The bloodstone
The reaction condition of iron removal step is that liquid after heavy indium is warming up to 150~220 DEG C, oxygen is added, it is theoretical amount that weight, which is added, in oxygen
110%~200%, control bloodstone iron removal kettle is pressed in 0.65~2.8MPa, reacts 3h, except being less than containing Fe in liquid after iron
3g/L, except a liquid part returns to preimpregnation process after iron, liquid returns existing Zn system calcining leaching process production electricity after remaining removes iron
The bloodstone slag of zinc, output carries out multiple countercurrent washing with production water, is less than 20g/L containing zinc with the water lotion obtained after washing
Terminal is washed, it is washing terminal that highly acid slag washing is less than 50g/L with the water lotion obtained after washing containing zinc in the peracid process,
Bloodstone slag bloodstone of the output containing zinc 0.5~1.5%, iron content 55~60% after washing, the raw material as cement plant.
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| CN115109920B (en) * | 2022-06-20 | 2023-09-22 | 云锡文山锌铟冶炼有限公司 | Method for reducing zinc and sulfur in hematite by zinc hydrometallurgy system |
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| JP4765062B2 (en) * | 2005-03-23 | 2011-09-07 | Ｄｏｗａメタルマイン株式会社 | Wet treatment method for zinc leaching residue |
| CN102409180B (en) * | 2011-11-02 | 2013-07-17 | 郴州丰越环保科技股份有限公司 | Metallurgical process for recovering metal copper, lead, zinc and tin from copper refining waste slag |
| CN102766768A (en) * | 2012-07-28 | 2012-11-07 | 花垣县永诚矿业有限责任公司 | Method for separating valuable metal from zinc smelting acid leaching slags |
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| CN103409621A (en) * | 2013-07-22 | 2013-11-27 | 昆明理工大学科技产业经营管理有限公司 | Combined leaching method for high-iron zinc sulfide concentrate and high-iron zinc calcine leaching slag |
| CN103409622B (en) * | 2013-07-22 | 2016-01-20 | 昆明理工大学科技产业经营管理有限公司 | A kind of method of individual curing high-iron zinc sulfide concentrate |
| CN103484670A (en) * | 2013-10-12 | 2014-01-01 | 河南豫光锌业有限公司 | Process for comprehensively recovering valuable metal from floatation silver concentrates of zinc hydrometallurgy system |
| CN103667720B (en) * | 2013-12-26 | 2015-07-22 | 河南豫光锌业有限公司 | Method for recovering zinc, indium, iron, and lead from high-iron zinc oxide mixture smelted with zinc |
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