CN105671589A - Low-copper-iron-lead zinc hydrometallurgy process - Google Patents

Low-copper-iron-lead zinc hydrometallurgy process Download PDF

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Publication number
CN105671589A
CN105671589A CN201610061381.3A CN201610061381A CN105671589A CN 105671589 A CN105671589 A CN 105671589A CN 201610061381 A CN201610061381 A CN 201610061381A CN 105671589 A CN105671589 A CN 105671589A
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zinc
low
copper
electrolytic solution
iron
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CN201610061381.3A
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Chinese (zh)
Inventor
刘野平
尹朝晖
吕伯康
叶军乔
欧阳全红
张超
黄月东
朱智祯
彭滔
罗振
伍文丙
叶龙泉
叶文洋
盛德梁
赵坤
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Shenzhen Zhongjin Lingnan Non-Ferrous Metal Co Ltd
DANXIA SMELTING PLANT SHENZHEN ZHONGJIN LINGNAN NONFEMET Co Ltd
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Shenzhen Zhongjin Lingnan Non-Ferrous Metal Co Ltd
DANXIA SMELTING PLANT SHENZHEN ZHONGJIN LINGNAN NONFEMET Co Ltd
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Application filed by Shenzhen Zhongjin Lingnan Non-Ferrous Metal Co Ltd, DANXIA SMELTING PLANT SHENZHEN ZHONGJIN LINGNAN NONFEMET Co Ltd filed Critical Shenzhen Zhongjin Lingnan Non-Ferrous Metal Co Ltd
Priority to CN201610061381.3A priority Critical patent/CN105671589A/en
Publication of CN105671589A publication Critical patent/CN105671589A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention discloses a low-copper-iron-lead zinc hydrometallurgy process and relates to the technical field of smelting. The low-copper-iron-lead zinc hydrometallurgy process comprises the steps that zinc ore is smashed and then added into an electrolytic solution, the temperature of the electrolytic solution is 35 DEG C-38 DEG C, and the electric current density between a cathode plate and an anode plate is 350-400 A/m<2>; the electrolytic solution comprises less than 5 mg/L of Fe<2+>, less than 0.2 mg/L of Cu, 180-195 g/L of H2SO4 and 55-65 g/L of Zn<2+>; the weight of a precipitated single zinc sheet is 75-80 kg. According to the low-copper-iron-lead zinc hydrometallurgy process, the three impurities of copper, iron and lead can be controlled in one process procedure, the method is simple, and the production cost is reduced; a zinc ingot with extra high quality can be produced, the zinc content is 99.995% or above, the copper content is 0.0001%, the iron content is 0.0001%, and the requirement for high-quality zinc can be met.

Description

The Zinc hydrometallurgy process of a kind of low copper low lead of low iron
Technical field
The present invention relates to technical field of smelting, particularly relate to a kind of method of zinc hydrometallurgy.
Background technology
Along with the continuous expansion of zinc purposes, the consumption of countries in the world zinc product increases year by year, and the smelting process of zinc is also constantly being modified. Along with the development of high-precision industry, also more coming also high to the specification of quality of zinc ingot, in low copper zinc, content requirement to copper is very low, need to reach 1ppm, meanwhile, iron and plumbous content requirement is also more and more harsher.
Chinese invention patent application (application publication number CN102876888A) discloses a kind of Zinc hydrometallurgy process, it is crossed and reducing leaching supernatant liquor is carried out pre-neutralization, add zinc dust precipitation indium again, after indium is removed in separation, lead to, in liquid after heavy indium, the oxygen being not less than 98% into concentration again, control temperature 160～200 DEG C, pressure 1000～2000kPa, after making heavy indium, the precipitation of the iron in liquid enters in slag. After the deironing that this invention obtains, the iron level of liquid is lower than 1.2g/L. But this invention has no to the report reducing copper and plumbous content in zinc ingot finished product. Report disclosed in other also has no the production of zinc ingot method of same control iron, copper and lead content.
Summary of the invention
For above-mentioned technical problem, the present invention provides the Zinc hydrometallurgy process of a kind of low copper low lead of low iron. Its processing method comprises the following steps:
(1). zinc ore concentrate adds in excess sulfuric acid after pulverizing, and is dissolved completely by zinc;
(2). in the solution that step (1) is obtained, add zinc powder, regulate each material concentration in solution to be Fe2+: < 5mg/L, Cu:< 0.2mg/L, H2SO4: 180～195g/L, Zn2+: 55～65g/L, obtained electrolytic solution;
(3). adding in electrolyzer by the electrolytic solution that step (2) is obtained, at 35～38 DEG C, between yin, yang pole plate, current density is 350～400A/m2Carry out electrolysis, until the weight of the single piece of zinc sheet of electrolysis precipitation is 75～80kg.
Add zinc powder after solving zinc concentrate and can displace iron excessive in electrolytic solution, copper and lead, it is also possible to reduce the acidity of electrolytic solution, the obtained electrolytic solution meeting electrolysis requirement.
Further, also comprising gelatine in described electrolytic solution, the add-on of described gelatine is 50～70g/t-zinc sheet. Gelatine can make precipitation zinc surface flat smooth, compact structure, can improve current efficiency, it is also possible to stops the microbattery effect of impurity on negative electrode and reduces the anti-molten of zinc, thus reduces the harmful effect of the impurity such as antimony, cobalt.
Further, also comprising Strontium carbonate powder in described electrolytic solution, the add-on of described Strontium carbonate powder is 2～3kg/t-zinc sheet. Strontium carbonate powder can reduce the lead content precipitating out zinc, but add-on is excessive, increases solution resistance, makes bath voltage increase, and its content must be made to keep how in certain limit.
Specifically, described electrolytic solution also comprise the Mn of 5～7g/L2+。Mn2+It is oxidized to MnO2Become the anode sludge sink to bottom of electrolytic tank or stick to anode surface; form film and effectively protect anode; and various metals ion can be adsorbed; such as Fe, Co, Cu, Sb alkaline-earth metal and other metal ions; thus make these ions adsorbed be sunken to bottom land, decrease the hazardness of these impurity. If Mn2+Lower than certain content, can not effectively form MnO2Film protection Pb-Ag anode, anode is corroded, and lead ion enters electrolytic solution, precipitates out on negative electrode, reduces the quality precipitating out zinc; If Mn2+Excessive concentration, then the amount of precipitation of the anode sludge is big, and the viscosity of electrolytic solution increases, and equally also reduces the quality precipitating out zinc.
Specifically, described electrolytic solution also comprise the Sn of Co and the < 0.2mg/L of Cd, < 0.2mg/L of < 0.2mg/L. Co appropriate in electrolytic solution can reduce anode potential, stops the corrosion of anode lead.
Specifically, described electrolytic solution also comprise the Ge of Sb and the < 0.01mg/L of As, < 0.01mg/L of Ni, < 0.01mg/L of < 0.01mg/L.
Specifically, described electrolytic solution also comprise≤the Cl of 400mg/L-With the F of < 10mg/L-。
Improve Zinc content in electrolyte amount and areal electric current, reduction electrolyte acidity and temperature, be conducive to reducing the lead tolerance precipitating out zinc, thus lead is controlled. In zinc hydrometallurgy, in finished product zinc ingot, the content of copper and iron derives from new electrolytic solution to a great extent, it is therefore necessary to reduce the content of impurity copper and iron in electrolytic solution and strict production control condition.
Compared with prior art, copper, iron and plumbous three kinds of impurity can be controlled by the Zinc hydrometallurgy process of the low copper low lead of low iron of the present invention in a technical process, method is simple, reduce production cost, special Higher quality zinc ingot can be produced, containing zinc more than 99.995, containing copper 0.0001%, iron content 0.0001%, it is possible to meet the requirement to high-quality zinc.
In order to understand better and implement, the following detailed description of the present invention.
Embodiment
Embodiment 1
It is dissolved in 53L sulfuric acid after 10kg zinc ore is pulverized, adds zinc powder, regulate in electrolytic solution and contain: the Fe of 4mg/L2+, 0.15mg/L the H of Cu, 180g/L2SO4, 55g/L Zn2+, 5g/L Mn2+, 0.15mg/L the Cl of Ge, 400mg/L of Sb and 0.008mg/L of As, 0.008mg/L of Ni, 0.008mg/L of Sn, 0.008mg/L of Co and 0.15mg/L of Cd, 0.15mg/L-With the F of 9mg/L-. Elimination insolubles, adds the gelatine of 0.25g and the Strontium carbonate powder of 10000g, and setting electrolyte temperature is 35 DEG C, and between yin, yang pole plate, current density is 350A/m2, cathode-anode plate is all perpendicular to bottom surface, and the precipitation cycle is 48h; The weight of the single piece of zinc sheet precipitated out is 75kg. After testing, in the zinc sheet of precipitation institute's iron content and copper be all less than 0.0001%, lead be less than 0.002%, zinc content is greater than 99.995%.
Embodiment 2
Add in 51L sulfuric acid after 10kg zinc ore is pulverized, add zinc powder, regulate in electrolytic solution and contain: the Fe of 3mg/L2+, 0.12mg/L the H of Cu, 195g/L2SO4, 65g/L Zn2+, 7g/L Mn2+, 0.12mg/L the Cl of Ge, 300mg/L of Sb and 0.005mg/L of As, 0.005mg/L of Ni, 0.005mg/L of Sn, 0.005mg/L of Co and 0.12mg/L of Cd, 0.12mg/L-With the F of 6mg/L-. Elimination insolubles, adds the gelatine of 0.3g and the Strontium carbonate powder of 11000g, and setting electrolyte temperature is 38 DEG C, and between yin, yang pole plate, current density is 400A/m2, cathode-anode plate is all perpendicular to bottom surface, and the precipitation cycle is 48h; The weight of the single piece of zinc sheet precipitated out is 80kg. After testing, after testing, in the zinc sheet of precipitation institute's iron content and copper be all less than 0.0001%, lead be less than 0.002%, zinc content is greater than 99.995%.
Embodiment 3
Add in 52L sulfuric acid after 10kg zinc ore is pulverized, add zinc powder, regulate in electrolytic solution and contain: the Fe of 4.5mg/L2+, 0.16mg/L the H of Cu, 190g/L2SO4, 60g/L Zn2+, 6g/L Mn2+, 0.16mg/L the Cl of Ge, 200mg/L of Sb and 0.003mg/L of As, 0.003mg/L of Ni, 0.003mg/L of Sn, 0.003mg/L of Co and 0.16mg/L of Cd, 0.16mg/L-With the F of 9mg/L-. Elimination insolubles, adds the gelatine of 0.3g and the Strontium carbonate powder of 12000g, and setting electrolyte temperature is 36 DEG C, and between yin, yang pole plate, current density is 360A/m2, cathode-anode plate is all perpendicular to bottom surface, and the precipitation cycle is 48h; The weight of the single piece of zinc sheet precipitated out is 76kg. After testing, after testing, in the zinc sheet of precipitation institute's iron content and copper be all less than 0.0001%, lead be less than 0.002%, zinc content is greater than 99.995%.
Embodiment 4
Add in 53L sulfuric acid after 10kg zinc ore is pulverized, add zinc powder, regulate in electrolytic solution and contain: the Fe of 4.2mg/L2+, 0.14mg/L the H of Cu, 185g/L2SO4, 58g/L Zn2+, 6.5g/L Mn2+, 0.14mg/L the Cl of Ge, 320mg/L of Sb and 0.007mg/L of As, 0.007mg/L of Ni, 0.007mg/L of Sn, 0.007mg/L of Co and 0.14mg/L of Cd, 0.14mg/L-With the F of 8mg/L-. Elimination insolubles, adds the gelatine of 0.35g and the Strontium carbonate powder of 15000g, and setting electrolyte temperature is 37 DEG C, and between yin, yang pole plate, current density is 390A/m2, cathode-anode plate is all perpendicular to bottom surface, and the precipitation cycle is 48h; The weight of the single piece of zinc sheet precipitated out is 77kg. After testing, after testing, in the zinc sheet of precipitation institute's iron content and copper be all less than 0.0001%, lead be less than 0.002%, zinc content is greater than 99.995%.
Embodiment 5 (comparative example)
Add in 70L sulfuric acid after 10kg zinc ore is pulverized, add zinc powder, regulate in electrolytic solution and contain: the Fe of 5mg/L2+, 0.2mg/L the H of Cu, 180g/L2SO4, 55g/L Zn2+, 5g/L Mn2+, 0.2mg/L the Cl of Ge, 400mg/L of Sb and 0.01mg/L of As, 0.01mg/L of Ni, 0.01mg/L of Sn, 0.01mg/L of Co and < 0.2mg/L of Cd, 0.2mg/L-With the F of 10mg/L-. Elimination insolubles, adds the gelatine of 20g and the Strontium carbonate powder of 900g, and setting electrolyte temperature is 35 DEG C, and between yin, yang pole plate, current density is 350A/m2, cathode-anode plate is all perpendicular to bottom surface, and the precipitation cycle is 48h; The weight of the single piece of zinc sheet precipitated out is 72kg. After testing, in the zinc sheet of precipitation institute's iron content be 0.00015%, copper be 0.00023%, lead be 0.0035%, zinc content is 99.99%.
The present invention is not limited to above-mentioned enforcement mode, if various change or distortion to the present invention do not depart from the spirit and scope of the present invention, if these are changed and are out of shape within the claim and equivalent technologies scope that belong to the present invention, then the present invention also is intended to comprise these changes and distortion.

Claims (7)

1. the Zinc hydrometallurgy process of the low copper low lead of low iron, it is characterised in that comprise the following steps:
(1). zinc ore concentrate adds in excess sulfuric acid after pulverizing, and is dissolved in completely in sulfuric acid by zinc;
(2). in the solution that step (1) is obtained, add zinc powder, regulate each material concentration in solution to be Fe2+: < 5mg/L, Cu:< 0.2mg/L, H2SO4: 180～195g/L, Zn2+: 55～65g/L, obtained electrolytic solution;
(3). adding in electrolyzer by the electrolytic solution that step (2) is obtained, at 35～38 DEG C, between yin, yang pole plate, current density is 350～400A/m2Carry out electrolysis, until the weight of the single piece of zinc sheet of electrolysis precipitation is 75～80kg.
2. the Zinc hydrometallurgy process of the low copper according to claim 1 low lead of low iron, it is characterised in that: also comprising gelatine in described electrolytic solution, the weight of the gelatine added required for producing every ton of zinc sheet is 50～70g.
3. the Zinc hydrometallurgy process of the low copper according to claim 1 low lead of low iron, it is characterised in that: also comprising Strontium carbonate powder in described electrolytic solution, the weight of the Strontium carbonate powder added required for producing every ton of zinc sheet is 2～3kg.
4. the Zinc hydrometallurgy process of the low copper low lead of low iron according to Claims 2 or 3, it is characterised in that: the Mn also comprising 5～7g/L in described electrolytic solution2+。
5. the Zinc hydrometallurgy process of the low copper low lead of low iron according to Claims 2 or 3, it is characterised in that: the Sn also comprising Co and the < 0.2mg/L of Cd, < 0.2mg/L of < 0.2mg/L in described electrolytic solution.
6. the Zinc hydrometallurgy process of the low copper low lead of low iron according to Claims 2 or 3, it is characterised in that: the Ge also comprising Sb and the < 0.01mg/L of As, < 0.01mg/L of Ni, < 0.01mg/L of < 0.01mg/L in described electrolytic solution.
7. the Zinc hydrometallurgy process of the low copper low lead of low iron according to Claims 2 or 3, it is characterised in that: described electrolytic solution also comprises≤the Cl of 400mg/L-With the F of < 10mg/L-。
CN201610061381.3A 2016-01-28 2016-01-28 Low-copper-iron-lead zinc hydrometallurgy process Pending CN105671589A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105937040A (en) * 2016-06-24 2016-09-14 白银有色集团股份有限公司 Process for reducing cathode zinc direct-current current unit loss in zinc wet method smelting for processing high mixed ore
CN114134538A (en) * 2021-12-08 2022-03-04 昆明理工恒达科技股份有限公司 Zinc electrodeposition system suitable for high current density
CN114808042A (en) * 2022-06-07 2022-07-29 赵坤 Cation membrane continuous electrolysis device and use method thereof

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Publication number Priority date Publication date Assignee Title
CN102876888A (en) * 2012-10-18 2013-01-16 广西华锡集团股份有限公司 Zinc hydrometallurgy production process
CN103695657A (en) * 2013-12-24 2014-04-02 广西博士海意信息科技有限公司 Method for enriching and recovering gallium and germanium from zinc hydrometallurgy waste residues
CN104131174A (en) * 2014-07-29 2014-11-05 广西金山铟锗冶金化工有限公司 Smelting method for comprehensive recovery of tin lead antimony silver zinc indium in bulk concentrate from ore dressing
CN104711423A (en) * 2015-02-03 2015-06-17 贵州宏达环保科技有限公司 Method for reducing content of Cu, Cd, Ni, Co and Sb in zinc hydrometallurgy zinc sulfate solution

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Publication number Priority date Publication date Assignee Title
CN102876888A (en) * 2012-10-18 2013-01-16 广西华锡集团股份有限公司 Zinc hydrometallurgy production process
CN103695657A (en) * 2013-12-24 2014-04-02 广西博士海意信息科技有限公司 Method for enriching and recovering gallium and germanium from zinc hydrometallurgy waste residues
CN104131174A (en) * 2014-07-29 2014-11-05 广西金山铟锗冶金化工有限公司 Smelting method for comprehensive recovery of tin lead antimony silver zinc indium in bulk concentrate from ore dressing
CN104711423A (en) * 2015-02-03 2015-06-17 贵州宏达环保科技有限公司 Method for reducing content of Cu, Cd, Ni, Co and Sb in zinc hydrometallurgy zinc sulfate solution

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邱竹贤 等: "《有色金属冶金学》", 31 May 1988 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105937040A (en) * 2016-06-24 2016-09-14 白银有色集团股份有限公司 Process for reducing cathode zinc direct-current current unit loss in zinc wet method smelting for processing high mixed ore
CN105937040B (en) * 2016-06-24 2018-05-25 白银有色集团股份有限公司 It is a kind of to handle the technique that cathode zinc unit dc consumption is reduced in high miscellaneous ore deposit zinc hydrometallurgy
CN114134538A (en) * 2021-12-08 2022-03-04 昆明理工恒达科技股份有限公司 Zinc electrodeposition system suitable for high current density
CN114134538B (en) * 2021-12-08 2024-03-26 昆明理工恒达科技股份有限公司 Zinc electrowinning system suitable for high current density
CN114808042A (en) * 2022-06-07 2022-07-29 赵坤 Cation membrane continuous electrolysis device and use method thereof

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Application publication date: 20160615