CN1477216A - Zinc sulfide concentrate calcines and zinc ide ore combined leaching process - Google Patents

Zinc sulfide concentrate calcines and zinc ide ore combined leaching process Download PDF

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Publication number
CN1477216A
CN1477216A CNA021336628A CN02133662A CN1477216A CN 1477216 A CN1477216 A CN 1477216A CN A021336628 A CNA021336628 A CN A021336628A CN 02133662 A CN02133662 A CN 02133662A CN 1477216 A CN1477216 A CN 1477216A
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leaching
zinc
zinc oxide
oxide ore
ore
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CN1303231C (en
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舒毓璋
宝国峰
张琦
杨龙
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Yunnan Xiangyun Feilong Recycling Technology Co ltd
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XIANGYUN FEILONG INDUSTRIAL Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The present invention belongs to the wet metallurgical technology, in particular, it relates to a combined leaching-out method of zinc sulfide ore and zinc oxide ore containing high iron and silicone content. It includes the following steps: (1). leaching-out of zinc sulfide concentrate calcines, the calcines and solution containing sulfuric acid are simultaneously added into leaching-out channel, stirred under the condition of high-temp. and high acid to make reaction; (2) neutral leaching out of zinc oxide ore, the zinc oxide ore powder and leached ore slurry are stirred, its pH value can be progressively raised from 3.0-3.5 to 5-5.2, the reacted neutral leach can be used for electrolysis, and the leached slag can be used for next releaching-out.

Description

Zinc sulfide concentrates calcining and zinc oxide ore combined leaching process
Technical field
The invention belongs to hydrometallurgical technology, the method that the zinc sulfide ore that particularly will contain high ferro, silicon and zinc oxide ore are connected and leached in same leaching operation.
Technical background
Zinc sulfide concentrates adopts the fluidizing reactor roasting usually, ZnS is converted into dissolve in the zinc oxide of dilute sulphuric acid, wherein contained iron cpd can become zinc ferrite under the high temperature of roasting simultaneously, and when leaching zinc oxide under higher acidity, the leaching of zinc ferrite is accompanied by iron and is leached.In iron removal, along with the removal meeting of iron ion produces acid simultaneously, for the deposition rate that improves iron must use neutralizing agent with these acid neutralizations again, the result makes and leaches quite complexity of operation, required equipment is also huger, invests greatlyyer, causes production cost to increase.
It is lower that zinc oxide ore contains the zinc rate usually, and complicated component, and zinc wherein is many to be existed with smithsonite and lapis calaminaris, and the iron in the ore deposit, silicon, calcium contents are many, cause the leaching of zinc oxide ore complicated.
In recent years Yunnan Lan Ping non-ferrous metal company obtains some progress with relevant research institution in the combination treatment technology of zinc sulphide calcining and zinc oxide concentrate, promptly earlier the zinc sulphide calcining is leached under the high temperature peracid, zinc in the calcining is thoroughly leached, and most iron and solvable silicon are also along with entering solution simultaneously; Adopt the very high above-mentioned ore pulp of acidity that zinc oxide ore is leached again, terminal point is controlled at PH1, and compositions such as zinc in the ore deposit, iron, silicon are entered in the solution in a large number, and then with limestone powder or lime neutralization, removes iron, silicon in the solution; When being neutralized to PH5.2, silicon and iron sink in the slag, output " desiliconization slag " and solution of zinc sulfate, remove impurity in the solution with zinc powder after, electrodeposition output electricity zinc." desiliconization slag " of this method output is quite loose, heavy clear poor-performing, and the water ratio that filters the back slag is very high, so zinc is also very big with the loss amount of slag; If reclaim zinc in the slag with washing methods, then water consumption is very big; Though the zinc leaching rate height of this method, but the iron, the silicon amount that enter solution are also high, in the hydrolysis of neutralization stage along with iron ion, can produce acid again, this needs this part acid that neutralizes of more neutralizing agent again, and the result is a large amount of gypsum of output again, have both increased the quantity of slag, also increased neutralizing agent and vitriolic consumption, so the zinc ore that this art breading is siliceous, iron is high also is uneconomic.Many metallargists both domestic and external think, zinc content is lower than 20% zinc oxide ore should not be handled with the wet method extract technology separately.
Summary of the invention
Technical problem to be solved by this invention provides a kind of zinc sulfide concentrates and zinc oxide ore is united the leaching extract technology, and its technology is simple, and production cost is low, and the sulfuric acid consumption is few, does not consume neutralizing agent, and leach liquor can be recycled, the leaching yield height of zinc.
Solving the scheme that technical problem of the present invention adopts is:
(1) leaching of zinc sulfide concentrates calcining adds in the leaching vat stirring reaction under the high temperature peracid simultaneously with calcining and vitriolated solution, and temperature is 85 ℃~95 ℃, and the whole acid concentration of last solution is 45 grams per liters~100 grams per liter H 2SO 4
(2) zinc oxide ore is neutral leaches, add in the leaching vat simultaneously the pulp slurry after zinc oxide breeze and the calcining leaching and stirring, the pH value of solution is 3.0~3.5 during beginning, pH value then gradually rises, finally reach PH5~5.2, reacted neutral leach liquor is made electrolysis usefulness for clean liquid, and leached mud carries out next step and leaches;
(3) the low acidleach of zinc oxide ore goes out, and adds to contain vitriolic solution and stir in leached mud, and the control pH value descends gradually, drops to PH1.5~3.0 by PH5~5.2 of beginning, leaches ore pulp and carries out liquid-solid separation;
(4) circulate soln, the neutrality of the isolating waste liquid that contains sulphuric leachate of last step being returned again zinc oxide ore leaches the stage.
In above-mentioned technological process, zinc sulfide concentrates can leach once with acidiferous zinc sulfate waste electrolyte is neutral earlier before the high temperature peracid leaches reaction, it is PH4.5~PH5.2 that solution leaches the terminal point pH value, solution after the leaching is done electrolysis for clean liquid and is used, the main component of the zinc oxide ore that is adopted is smithsonite and lapis calaminaris, and the zinc rate that contains in the ore is 15%~40%.
When the zinc sulfide concentrates calcining leaches at the high temperature peracid, reaction times is 120~240 minutes, 60~80 ℃ of the neutral extraction temperatures of zinc oxide ore, and leaching the reaction times is 120~240 minutes, the low acidleach of zinc oxide ore secondary goes out 60~80 ℃ of temperature, and the time is 120~240 minutes.
The neutral leaching of zinc oxide ore can adopt interruption leaching mode to carry out, also can adopt the mode of continuous leaching, but in continuously arranged leaching vat, carry out continuously, the most convenient and economical, leach the back solid-liquid separation and adopt thickener, the solid-liquid separation after the low acidleach of secondary goes out adopts filter.
The zinc sulfide concentrates calcining leaches by the high temperature peracid, zinc in the calcining is thoroughly leached, solvable silicon and iron in the calcining enter leach liquor, leach zinc oxide ore with this solution again, when carrying out the neutral leaching of zinc oxide ore, silicon in the solution and iron generate precipitation and enter in the zinc oxide ore leached mud, the precipitation of silicon in the high acid leaching liquor of calcining high temperature and iron and the neutrality leaching of zinc oxide ore are merged to get up, just can reach and reduce production costs, reduce the sulfuric acid consumption, need not use the purpose of neutralizing agent, the neutrality leaching of zinc oxide ore and low acidleach go out step makes that the zinc in the ore deposit is thoroughly leached.
In above-mentioned leaching, can directly carry out the high temperature peracid once the step and leach the zinc sulfide concentrates calcining; Also can be earlier carry out neutrality to calcining and leach, neutrality leaches routinely technology carries out, and neutral leach liquor send cleaning section, and leached mud carries out the high temperature peracid again and leaches; Calcining can also be carried out that neutrality leaches and after low acidleach goes out, low acidleach is slagged tap and is carried out the high temperature peracid again and leach.No matter calcining with which kind of mode leaches, the neutrality that all the highly acid leach liquor of high temperature or ore pulp is used for zinc oxide ore leaches.The high acid leaching liquor of calcining high temperature does not need common siderotil method to sink operations such as iron, separation of iron in goethite form, and the solution silica removal does not need special neutralization to sink the silicon operation yet.
Embodiment
Embodiment 1: the zinc sulphide raw material is from the zinc sulfide concentrates calcining of certain factory and the mixture of flue dust, and its composition is Zn53.01%, Fe5.82%, Pb1.95%.Zinc oxide ore contains Zn22.80% from another mine, and the zinc oxidation ratio is 90%.At first the waste electrolyte with zinc sulfate leaches above-mentioned zinc sulfide concentrates calcining is neutral, and the pH value of terminal point is 5.0, and ore pulp enters thickener, and the zinc sulfate supernatant liquor that output is qualified send clean liquid electrolysis; The underflow of thickener adds waste electrolyte and sulfuric acid, carries out the high temperature peracid and leaches, and the beginning acid concentration is 150~180 grams per liter .H 2SO 4, 85 ℃~95 ℃ of temperature of reaction, whole acid concentration 60~65 grams per liter .H 2SO 4, pickling liquor contains zinc 110~115 grams per liters, iron 18~20 grams per liters, measures slag rate 20.02%, zinc leaching rate 97.48%, iron leaching yield 82.4%.Behind the zinc oxide ore pulverizing and jevigating, the zinc sulphide ore pulp that leaches with above-mentioned peracid stirs with adding in the neutral leaching vat, the initial value PH3 of solution, and leached after 120 minutes terminal point PH5.0~5.2, carries out solid-liquid separation; Leach liquor is made electrolysis usefulness for clean liquid, adds in the leached mud to contain acid waste liquid and hang down acidleach and go out, and pH value drops to PH2.0 gradually by the PH5.2 of beginning, and again with solid-liquid separation on ore pulp, supernatant liquor returns neutral extracting stage and recycles, leached mud washing back stacking.
Total leaching yield of two kinds of ore zinc is 89.9%, total slag rate 56.1%.
The qualified solution of zinc sulfate composition of output is as follows: Zn147.5 grams per liter, Fe6.4 mg/litre, Cd0.73 grams per liter, SiO 20.2 grams per liter, the As0.06 mg/litre.Slag adopts box filter to filter, and filtration velocity is 58 kilograms/meter 2. the time.
Embodiment 2: choose the zinc sulfide concentrates calcining, its chemical ingredients is:
Zn?58.8%、 Fe?7.42%、 SiO 2?5.88%,
Thing coordinates and is divided into:
Zn (total zinc) 58.8%
Zn(ZnSO 4) 0.53%
Zn(ZnS) 0.27%
Zn(ZnO) 47.94%
Zn(ZnO.SiO 2) 6.6%
Zn(ZnO.Fe 2O 3)3.47%
Leaching condition: 90 ℃ of temperature, extraction time 4 hours, sour 150 grams per liter .H begin 2SO 4, whole sour 60 grams per liter .H 2SO 4
Zn, Fe, Si leaching yield:
Zn98.54%, Fe74.78%, SiO 236.70%, slag rate 20.06%.
Choose zinc oxide ore, its chemical ingredients is Zn26.55%, Fe18.20%, SiO 27.94%, wherein the zinc thing coordinates and is divided into, zinc carbonate 24.23%, zinc silicate 1.25%, zinc sulphide 0.73%, automolite 0.34%, behind the mineral pulverizing and jevigating, carry out neutrality with waste electrolyte and leach, promptly condition is that initial value is PH3, terminal point PH5.2 evenly stirs minute~minute; Carry out solid-liquid separation, leach liquor is made electrolysis usefulness for clean liquid, adds sulfur acid solution in the leached mud and hang down acidleach and goes out, and pH value drops to PH1.5 gradually by the PH5.2 that begins, solid-liquid separation again, and supernatant liquor returns neutral extracting stage and recycles.Each leading indicator is as follows:
Zinc leaches the rate of recovery: 91.88%
Cadmium leaches the rate of recovery: 95.86%
Slag rate: 55.45%
Slag contains zinc: 3.89%
Slag filtration velocity: 52.5kg/m 2h
Embodiment 3: choose the zinc sulfide concentrates calcining, its chemical ingredients is:
Zn?57.8%、Fe?8.4%、SiO 2?4.5%
Choose zinc oxide concentrate, take from certain dressing-works, its chemical ingredients is:
Zn?32.40%、?Pb?1.67%、Fe?5.79%、SiO 2?18.94%
Cd?0.38%、CaO?4.16%、MgO?0.16%
Soluble zinc rate 93.2%.
At first with waste electrolyte calcining is carried out neutrality and leach, neutral leach liquor send clean liquid, and leached mud is added H with useless electrolysis 2SO 4Carry out the high temperature peracid and leach, 95 ℃ of extraction temperatures, 2 hours time, whole acid concentration 65 grams per liter sulfuric acid are measured zinc leaching rate 98.5%, iron leaching yield 83%, silicon leaching yield 35%.Above-mentioned ore pulp is continuously flowed into the zinc oxide concentrate leaching vat, and first groove control PH3.0 leaches terminal point PH5.2.Neutrality is leached ore pulp clarify, supernatant contains zinc 140 grams per liters, send clean liquid leached mud to leach with waste electrolyte again, leaches PH and drops to PH1.5 gradually by 5.2, carries out liquid-solid separation, clarification low stream vacuum filtration, filtration velocity 65kg/m 2.h.Measure two kinds of material zinc and always leach the rate of recovery 95.3%.

Claims (4)

1, a kind of zinc sulfide concentrates calcining and zinc oxide ore combined leaching process is characterized in that processing step is as follows:
(1) leaching of zinc sulfide concentrates calcining adds calcining and vitriolated solution in the leaching vat simultaneously, stirring reaction under the high temperature peracid, and temperature is 85 ℃~95 ℃, the whole acid concentration of last solution is 45 grams per liters~100 grams per liter H 2SO 4
(2) zinc oxide ore is neutral leaches, add in the leaching vat simultaneously the pulp slurry after zinc oxide ore after levigate and the leaching of above-mentioned high temperature peracid and stirring, the pH value of solution is 2.7~3.5 during beginning, pH value then gradually rises, finally reach PH5.0~5.2, reacted neutral leach liquor is made electrolysis usefulness for clean liquid, and leached mud carries out next step leaching again;
(3) the low acidleach of zinc oxide ore goes out, and adds to contain vitriolic solution and stir in leached mud, and the control pH value descends gradually, drops to PH1.5~3.0 by PH5.0~5.2 of beginning;
(4) circulate soln leaches ore pulp to secondary and carries out solid-liquid separation, contains the neutrality leaching stage that the vitriolic leach liquor returns zinc oxide ore again.
2, by described zinc sulfide concentrates calcining of claim 1 and zinc oxide ore combined leaching process, it is characterized in that before the high temperature peracid of zinc sulfide concentrates leaches reaction, leaching once with acidiferous zinc sulfate waste electrolyte is neutral earlier, it is PH4.5~PH5.2 that solution leaches the terminal point pH value, solution after the leaching is done electrolysis for clean liquid and is used, the main component of the zinc oxide ore that is adopted is smithsonite and lapis calaminaris, and the zinc rate that contains in the ore is 15%~40%.
3, unite the leaching extract technology by described zinc sulfide concentrates calcining of claim 2 and zinc oxide ore, the leaching reaction times that it is characterized in that the zinc sulfide concentrates calcining is 120~240 minutes, 60~80 ℃ of the neutral extraction temperatures of zinc oxide ore, leaching the reaction times is 120~240 minutes, the low acidleach of zinc oxide ore secondary goes out 60~80 ℃ of temperature, and the time is 120~240 minutes.
4, unite the leaching extract technology by described zinc sulfide concentrates of claim 3 and zinc oxide ore, it is characterized in that neutral leaching of zinc oxide ore carry out continuously in continuously arranged leaching vat, leach the back solid-liquid separation and adopt thickener, the solid-liquid separation after the low acidleach of secondary goes out adopts filter.
CNB021336628A 2002-08-24 2002-08-24 Zinc sulfide concentrate calcines and zinc ide ore combined leaching process Expired - Lifetime CN1303231C (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1303232C (en) * 2004-08-10 2007-03-07 兰坪金鼎锌业有限公司 Zinc oxide raw ore fluidization leaching process
CN101591733B (en) * 2009-06-22 2011-01-05 云南永昌铅锌股份有限公司 Method for jarosite precipitation and deironization by pressure acid leaching of high-iron zinc-sulphide concentrate in kettle
CN101748289B (en) * 2008-12-15 2012-04-18 汉中八一锌业有限责任公司 Neutral leaching method of zinc metallurgy in wet method
CN102952949A (en) * 2012-09-17 2013-03-06 株洲市兴民科技有限公司 Ultrasonic smelting method and system device for treating zinc leaching residue, and use of ultrasonic smelting method
CN103290214A (en) * 2013-05-28 2013-09-11 中国恩菲工程技术有限公司 Method for depositing iron from ferruginous zinc sulfate solution
CN103627911A (en) * 2013-12-09 2014-03-12 株洲冶炼集团股份有限公司 Treatment process for high-iron zinc oxide
CN103911518A (en) * 2012-12-31 2014-07-09 北京有色金属研究总院 Method for efficiently fully leaching zinc from dust caused by making steel from waste galvanized plates
CN104004923A (en) * 2014-06-11 2014-08-27 长沙有色冶金设计研究院有限公司 Method for extracting zinc by combination of roasting leaching and direct leaching of zinc sulfide concentrate
CN104073648A (en) * 2014-07-15 2014-10-01 吉首大学 Method for preparing high purity zinc through calamine vacuum carbothermic reduction
CN107217146A (en) * 2017-04-20 2017-09-29 云南永昌铅锌股份有限公司 The method containing Zn scrap returns of processing
CN109295320A (en) * 2018-11-14 2019-02-01 云南祥云飞龙再生科技股份有限公司 A method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material
CN111020185A (en) * 2019-12-25 2020-04-17 昆明冶金研究院有限公司 Zinc oxide concentrate curing and leaching method
CN111519040A (en) * 2020-05-12 2020-08-11 云南金鼎锌业有限公司 Zinc oxide concentrate leaching equipment and leaching mode thereof
CN113025815A (en) * 2021-03-04 2021-06-25 万宝矿产有限公司 Combined extraction method of complex copper-cobalt raw material
CN113667834A (en) * 2021-08-20 2021-11-19 云南金鼎锌业有限公司 Method for leaching zinc sulfide in calcine dust under normal pressure by using oxygen oxidation
CN114107656A (en) * 2021-11-24 2022-03-01 白银有色集团股份有限公司 Method for reducing consumption of zinc-manganese ore powder produced by wet smelting
CN115478172A (en) * 2022-09-30 2022-12-16 云南金鼎锌业有限公司 Method for reducing leaching oxidant in zinc hydrometallurgy
CN115612860A (en) * 2022-10-26 2023-01-17 云南驰宏资源综合利用有限公司 Leaching method of high-silicon zinc roasted ore

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CA1176853A (en) * 1981-08-05 1984-10-30 Gerald L. Bolton Process for recovering zinc from zinc ferrite material
CA1195846A (en) * 1982-06-03 1985-10-29 Donald R. Weir Recovery of zinc from zinc-containing sulphidic material
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US4778520A (en) * 1987-03-26 1988-10-18 University Of Waterloo Process for leaching zinc from partially desulfurized zinc concentrates by sulfuric acid
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Cited By (23)

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Publication number Priority date Publication date Assignee Title
CN1303232C (en) * 2004-08-10 2007-03-07 兰坪金鼎锌业有限公司 Zinc oxide raw ore fluidization leaching process
CN101748289B (en) * 2008-12-15 2012-04-18 汉中八一锌业有限责任公司 Neutral leaching method of zinc metallurgy in wet method
CN101591733B (en) * 2009-06-22 2011-01-05 云南永昌铅锌股份有限公司 Method for jarosite precipitation and deironization by pressure acid leaching of high-iron zinc-sulphide concentrate in kettle
CN102952949A (en) * 2012-09-17 2013-03-06 株洲市兴民科技有限公司 Ultrasonic smelting method and system device for treating zinc leaching residue, and use of ultrasonic smelting method
CN102952949B (en) * 2012-09-17 2014-04-16 株洲市兴民科技有限公司 Ultrasonic smelting method and system device for treating zinc leaching residue, and use of ultrasonic smelting method
CN103911518B (en) * 2012-12-31 2016-03-30 北京有色金属研究总院 A kind of efficient method fully leaching zinc in waste galvanized plate fume from steel making
CN103911518A (en) * 2012-12-31 2014-07-09 北京有色金属研究总院 Method for efficiently fully leaching zinc from dust caused by making steel from waste galvanized plates
CN103290214A (en) * 2013-05-28 2013-09-11 中国恩菲工程技术有限公司 Method for depositing iron from ferruginous zinc sulfate solution
CN103627911B (en) * 2013-12-09 2015-01-14 株洲冶炼集团股份有限公司 Treatment process for high-iron zinc oxide
CN103627911A (en) * 2013-12-09 2014-03-12 株洲冶炼集团股份有限公司 Treatment process for high-iron zinc oxide
CN104004923A (en) * 2014-06-11 2014-08-27 长沙有色冶金设计研究院有限公司 Method for extracting zinc by combination of roasting leaching and direct leaching of zinc sulfide concentrate
CN104073648A (en) * 2014-07-15 2014-10-01 吉首大学 Method for preparing high purity zinc through calamine vacuum carbothermic reduction
CN107217146A (en) * 2017-04-20 2017-09-29 云南永昌铅锌股份有限公司 The method containing Zn scrap returns of processing
CN109295320A (en) * 2018-11-14 2019-02-01 云南祥云飞龙再生科技股份有限公司 A method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material
CN111020185A (en) * 2019-12-25 2020-04-17 昆明冶金研究院有限公司 Zinc oxide concentrate curing and leaching method
CN111519040A (en) * 2020-05-12 2020-08-11 云南金鼎锌业有限公司 Zinc oxide concentrate leaching equipment and leaching mode thereof
CN113025815A (en) * 2021-03-04 2021-06-25 万宝矿产有限公司 Combined extraction method of complex copper-cobalt raw material
CN113025815B (en) * 2021-03-04 2022-05-17 万宝矿产有限公司 Combined extraction method of complex copper-cobalt raw material
CN113667834A (en) * 2021-08-20 2021-11-19 云南金鼎锌业有限公司 Method for leaching zinc sulfide in calcine dust under normal pressure by using oxygen oxidation
CN114107656A (en) * 2021-11-24 2022-03-01 白银有色集团股份有限公司 Method for reducing consumption of zinc-manganese ore powder produced by wet smelting
CN115478172A (en) * 2022-09-30 2022-12-16 云南金鼎锌业有限公司 Method for reducing leaching oxidant in zinc hydrometallurgy
CN115612860A (en) * 2022-10-26 2023-01-17 云南驰宏资源综合利用有限公司 Leaching method of high-silicon zinc roasted ore
CN115612860B (en) * 2022-10-26 2023-09-19 云南驰宏资源综合利用有限公司 Leaching method of high-silicon zinc roasted ore

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