CN105861842B - A kind of method that lead is reclaimed from lead-containing material - Google Patents

A kind of method that lead is reclaimed from lead-containing material Download PDF

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Publication number
CN105861842B
CN105861842B CN201610438890.3A CN201610438890A CN105861842B CN 105861842 B CN105861842 B CN 105861842B CN 201610438890 A CN201610438890 A CN 201610438890A CN 105861842 B CN105861842 B CN 105861842B
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lead
liquid
containing material
electrodeposition
solution
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CN105861842A (en
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王成彦
陈永强
邢鹏
马保中
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • 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
    • 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
    • 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
    • C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
    • 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

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

Abstract

The present invention provides a kind of method that lead is reclaimed from lead-containing material, belongs to technical field of wet metallurgy.Sulfuric acid lead skim caused by lead plaster or zinc abstraction is first added solution of ferrous chloride and leached in Ball-stirring mill by this method, lead therein is entered solution, and leachate obtains metallic lead by electrodeposition, and liquid, which returns, after lead electrodeposition continues leaching lead-containing material.This technique has the characteristics that flow is short, process is few, energy consumption cost is low, and meets the environmental requirement of clean manufacturing.

Description

A kind of method that lead is reclaimed from lead-containing material
Technical field
The present invention relates to technical field of wet metallurgy, particularly relates to a kind of method that lead is reclaimed from lead-containing material.
Background technology
The utilization of lead secondary resource have obtained increasing attention at present.Existing desulfurization conversion+pyrometallurgical smelting Method be applied to waste lead acid battery lead cream recovery.Fire metallurgy process processing lead plaster energy consumption cost is high, and can produce SO2, the atmosphere pollution such as volatility lead dust.
Another potential lead secondary resource, the sulfuric acid lead skim of zinc metallurgical process output, is not opened effectively also at present Send out, Pb contents are generally 20~50% in such slag.Lead content is relatively low in such slag and lead is mainly lead sulfate, pyrogenic process Metallurgical method handles same high energy consumption and easily produces atmosphere pollution.By contrast, sulfuric acid is handled using the method for hydrometallurgy Lead skim has clean manufacturing, the advantage of valuable metal high efficiency extraction.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of method that lead is reclaimed from lead-containing material, realize from lead plaster or Directly extraction obtains the metallic lead of high content in zinc metallurgical process output sulfuric acid lead skim.
The key step of this method is as follows：
(1) lead-containing material is leached by leaching agent of solution of ferrous chloride, is leached after the completion of leaching by solid-liquor separation Liquid and leached mud；
(2) liquid after metallic lead and electrodeposition is obtained by electrodeposition obtained by the step (1) in leachate；
(3) after adding metallic iron reduction in liquid after the electrodeposition that step (2) obtains, liquid after being reduced, liquid returns after reduction Return step (1) and be used as leaching agent；When sulfate ion concentration is more than 30g/L in liquid after reduction, reduction is made by freezing and crystallizing The partially crystallizable in the form of ferrous sulfate precipitates the sulfate ion accumulated afterwards in liquid with ferrous ion, obtains errous sulfate crystal；
(4) after the errous sulfate crystal dissolving obtained step (3), barium carbonate is added, barium salt is carried out and removes lead, after recrystallization Obtain pure ferrous sulfate product.
Wherein, the lead-containing material of processing is lead plaster or the sulfuric acid lead skim of zinc metallurgical process output, wherein lead plaster in step (1) Containing Pb 60~75%, sulfuric acid lead skim contains Pb 20~50%.
Leaching agent is solution of ferrous chloride in step (1), 20~90 DEG C, 0.5~3h of extraction time of extraction temperature, protochloride Liquid-solid ratio 20~40 in the mixed solution of ferrous solution 100~450g/L of concentration, solution of ferrous chloride and lead-containing material composition:1, leaching It is Ball-stirring mill to go out device therefor, and leaching process is with hydrochloric acid control solution pH in 0.5-1.5.
The anode of electrolytic deposition process is insoluble anode in step (2), 100~300A/m of cathode-current density2, electrodeposition temperature For room temperature.
Metallic iron is iron powder or iron plate in step (3), and the temperature of freezing and crystallizing is -10~0 DEG C.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
(1) with pyrometallurgic methods ratio, this method energy consumption is low, meets the environmental requirement of clean manufacturing.
(2) this method technological process is succinct, easy to operate, because frerrous chloride leaching agent can be recycled, puies forward lead process A small amount of metallic iron is only consumed, reagent consumption is few, and cost is low.In addition to it can directly obtain the metallic lead of high content, accumulation enters solution In sulfate ion can be crystallized with ferrous ion by freezing and crystallizing in the form of ferrous sulfate, the iron of reduction process consumption is also Regeneration is arrived.
Brief description of the drawings
Fig. 1 is the method process chart that lead is reclaimed from lead-containing material of the present invention.
Embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool Body embodiment is described in detail.
The present invention provides a kind of method that lead is reclaimed from lead-containing material, as shown in figure 1, the technological process for this method Figure, this method mainly include leaching, electrodeposition, reduction, freezing and crystallizing and barium salt except steps such as lead, given especially by embodiment Explanation.
Embodiment 1
Leach：1kg lead plasters (Pb 71.1%), leaching agent are 450g/L solution of ferrous chloride, leach pH 1.0, leach temperature 80 DEG C, extraction time 2h of degree, liquid-solid ratio 35:1.Lead leaching rate is up to 98.1%.
Lead electrodeposition：The above-mentioned leachates of 1.2L are taken, in cathode area 0.01m2, cathode-current density 150A/m2, room temperature condition Electrodeposition under (25 DEG C), electrodeposition 5h, tank voltage 2.9V, obtain electric lead 25.8g, electric lead leaded 98%, electrolytic deposition process current efficiency 87.2%, power consumption 860.4kwh/t.
Reduction and freezing and crystallizing：Reducing agent is made using iron powder, is ferrous iron by ferric iron back in liquid after electrodeposition.- 10 Under the conditions of~0 DEG C, ferrous sulfate crystallization precipitation is formed, is controlled in solution by freezing and crystallizing in liquid after the electrodeposition of circulation Sulfate concentration is within 30g/L.
Barium salt removes lead：After obtained errous sulfate crystal is dissolved, barium carbonate is added, barium salt is carried out and removes lead, after recrystallization Obtain pure ferrous sulfate product.
Embodiment 2
Leach：1kg sulfuric acid lead skim (Pb 45.7%), leaching agent are 450g/L solution of ferrous chloride, leach pH 1.0, leaching Go out temperature 70 C, extraction time 2h, liquid-solid ratio 29:1.Lead leaching rate is up to 96.4%.
Lead electrodeposition：The above-mentioned leachates of 1.2L are taken, in cathode area 0.01m2, cathode-current density 150A/m2, room temperature condition Electrodeposition under (25 DEG C), electrodeposition 5h, tank voltage 2.85V, obtain electric lead 25.9g, electric lead leaded 98.2%, electrolytic deposition process current efficiency 87.8%, power consumption 839.7kwh/t.
Reduction and freezing and crystallizing：Reducing agent is made using iron powder, is ferrous iron by ferric iron back in liquid after electrodeposition.- 10 Under the conditions of~0 DEG C, ferrous sulfate crystallization precipitation is formed, is controlled with this molten by freezing and crystallizing in liquid after the lead electrodeposition of circulation Sulfate concentration in liquid is within 30g/L.
Barium salt removes lead：After obtained errous sulfate crystal is dissolved, barium carbonate is added, barium salt is carried out and removes lead, after recrystallization Obtain pure ferrous sulfate product.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, on the premise of principle of the present invention is not departed from, some improvements and modifications can also be made, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims (2)

  1. A kind of 1. method that lead is reclaimed from lead-containing material, it is characterised in that：Comprise the following steps：
    (1) using solution of ferrous chloride as leaching agent leach lead-containing material, after the completion of leaching by solid-liquor separation obtain leachate and Leached mud；
    (2) liquid after metallic lead and electrodeposition is obtained by electrodeposition obtained by the step (1) in leachate；
    (3) after adding metallic iron reduction in liquid after the electrodeposition that step (2) obtains, liquid after being reduced, liquid returns to step after reduction Suddenly (1) is used as leaching agent；When sulfate ion concentration is more than 30g/L in liquid after reduction, liquid after reduction is made by freezing and crystallizing The partially crystallizable in the form of ferrous sulfate precipitates the sulfate ion of middle accumulation with ferrous ion, obtains errous sulfate crystal；
    (4) after the errous sulfate crystal dissolving obtained step (3), barium carbonate is added, barium salt is carried out and removes lead, obtained after recrystallization Pure ferrous sulfate product；
    Wherein, leaching agent is solution of ferrous chloride in step (1), 20~90 DEG C, 0.5~3h of extraction time of extraction temperature, chlorination Liquid-solid ratio 20~40 in the mixed solution of ferrous iron solution 100~450g/L of concentration, solution of ferrous chloride and lead-containing material composition:1, Leaching device therefor is Ball-stirring mill, and leaching process is with hydrochloric acid control solution pH in 0.5-1.5；
    The anode of electrolytic deposition process is insoluble anode in step (2), 100~300A/m of cathode-current density2, electrodeposition temperature is room Temperature；
    The temperature of freezing and crystallizing is -10~0 DEG C in step (3)；
    The lead-containing material of processing contains Pb for lead plaster or the sulfuric acid lead skim of zinc metallurgical process output, wherein lead plaster in the step (1) 60~75%, sulfuric acid lead skim contains Pb 20~50%.
  2. 2. the method according to claim 1 that lead is reclaimed from lead-containing material, it is characterised in that：It is golden in the step (3) It is iron powder or iron plate to belong to iron.
CN201610438890.3A 2016-06-17 2016-06-17 A kind of method that lead is reclaimed from lead-containing material Active CN105861842B (en)

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CN108754137A (en) * 2018-08-02 2018-11-06 桐乡市思远环保科技有限公司 The method that metallic lead is produced using solvent extraction electrodeposition process
CN110777394A (en) * 2019-10-24 2020-02-11 北京矿冶科技集团有限公司 Method for electrolyzing and recovering lead from lead-containing slag by using chlorination diaphragm

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CN101994007B (en) * 2009-08-28 2012-08-15 沈阳有色金属研究院 Method for removing sulfur from waste lead-acid storage battery gypsum mud by using magnesium chloride
CN102206750A (en) * 2011-05-04 2011-10-05 中南大学 Method for recovering lead from lead-containing material by matching leaching-electrowinning method
CN103194615B (en) * 2013-03-27 2014-06-04 云南祥云飞龙有色金属股份有限公司 Lead hydrometallurgical technology through utilizing lead sulfate
CN103757420B (en) * 2014-01-20 2016-09-21 北京矿冶研究总院 Method for recovering lead and silver from zinc leaching residues

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