CN106939377A - A kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled - Google Patents

A kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled Download PDF

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Publication number
CN106939377A
CN106939377A CN201710289361.6A CN201710289361A CN106939377A CN 106939377 A CN106939377 A CN 106939377A CN 201710289361 A CN201710289361 A CN 201710289361A CN 106939377 A CN106939377 A CN 106939377A
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China
Prior art keywords
lead
filtrate
liquid
sodium chloride
precipitation
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CN201710289361.6A
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Chinese (zh)
Inventor
郑雅杰
李伟
王欣欣
彭映林
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Central South University
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/04Obtaining lead by wet processes
    • C22B13/045Recovery from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/04Obtaining noble metals by wet processes
    • C22B11/042Recovery of noble metals from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/02Obtaining antimony
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/06Obtaining bismuth
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled, the present invention, which adds sulfur acid lead materials in sodium chloride solution, to be taken off lead and recycles de- lead liquid, sulfur acid lead materials are added in sodium chloride solution, the lower heating response of stirring is filtered while hot after for a period of time, obtains leached mud and leachate;By leachate cold filtration, lead-rich slag and de- lead filtrate are obtained;Lead powder removal of impurities is added into de- lead filtrate, it is 8.0~13.0 that the lower heating response of stirring adds alkali regulation pH value afterwards for a period of time, and filtering obtains filtrate after precipitation slag and precipitation;It is to add sodium chloride and recycle after 4.0~7.0 to add filtrate pH value after hydrochloric acid regulation precipitation.The present invention has technique simple, with low cost, and de- lead effect is good, takes off lead liquid reusable edible, greatly reduces wastewater discharge.

Description

A kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled
Technical field
It is particularly effectively free of contamination to recycle the de- lead liquid of chlorination the present invention relates to hydrometallurgy process in field of metallurgy Wet-process metallurgy method.
Background technology
The application of lead is quite varied, is the indispensable metal material of national economy.The purposes of lead is mainly manifested in:Lead stores Battery, carrier lead makees the acoustic material in bearing metal, building trade, the shielding material of Z X-ray room X, chemistry and metallurgy Anti-corrosion, leakproof and solution storage equipment in industry etc..
Whole world major part lead yield derives from the recovery of lead.At present, the method for processing lead-containing material has pyrogenic process and wet method Two classes, pyrogenic process lead smelts to sinter-blast furnace traditional handicraft based on, pyrogenic attack lead-containing material have smelt speed, it is right The low advantage of ingredient requirement, but produce in pyrolytic semlting a large amount of SO2, volatilize and produce lead powder dirt and lead containing sludge, environment is made Into severe contamination, the harm mankind's is healthy.The method of wet-treating lead-containing material mainly has villaumite method, alkaline process, carbonate Conversion-the acid-hatching of young eggs.Carbonate conversion-acid-hatching of young eggs is that lead sulfate is changed into ceruse, carbonic acid with carbonate solution at normal temperatures Lead nitric acid or silicofluoric acid etc. dissolve, and the advantage of carbonate conversion-acid-hatching of young eggs is a cancellation SO2Pollution, leaching equipment requirement It is low, but the method energy consumption is higher, and production cost is higher, complex process.Alkaline process is ceruse, sulphur in the NaOH solution of high concentration Lead plumbate etc., which can dissolve, to be usually added into sugar or glycerine to promote the dissolving of lead in the soluble lead salt of formation, leaching process, alkaline process it is excellent Point is that noble metal is not leached in leaching process, but requires that leachate NaOH concentration is higher when leaching, and glycerine and sugar cause Solution viscosity is difficult to filter greatly.Villaumite method is to leach PbSO under lead, certain condition with chloride solution4It can turn with sodium chloride effect It is melted into PbCl2, the PbCl in the presence of having excessive chlorion in solution2It can be coordinated to form soluble PbCl with chlorion4 2-、 PbCl3 -And entering solution, villaumite method technique is simple, and production cost is low, and leaching lead effect is good, but the liquid processing of leaching lead is difficult, and meeting Produce the dangerous solid waste of a large amount of leaded gypsum.Wang Chengyan, CHEN YONGQIANG et al. invention " one kind reclaim from lead sulfate lead, The method of silver "(Patent No. CN106086432A), it is 20~90 DEG C in extraction temperature, extraction time is using lead sulfate as raw material 0.5~3h, leaching process pH be 0.5~3 under, by liquor alumini chloridi leach sulfuric acid lead skim, leaching lead liquid in add metallic lead Displacement silver, metallic aluminium is added into silver-colored displaced liquid, and lead is replaced with metallic aluminium, by lead displaced liquid circulation leaching lead, treats gained lead When sulfate ion concentration is more than 20g/L in displaced liquid, amine sulfate is added in the solution, make solution sulfate ion and aluminium from Subdivision crystalline deposit, will add barium carbonate after Exsiccated Ammonium Alum dissolution of crystals, progress barium salt, which is removed, obtains bright sulfur acid after lead, recrystallization Aluminium amine product.Although this method is avoided that a large amount of discharge of wastewater, but the liquid processing of leaching lead is complicated, and consumption metallic aluminium, amine sulfate, carbon Sour barium etc., cost is higher.
The content of the invention
It is an object of the invention to overcome the waste liquid discharging amount in the presence of the de- lead technology of existing chlorination big, and pass through lead powder Reduction reclaims noble metal and non-ferrous metal in de- lead liquid and takes off lead liquid there is provided a kind of chlorination that can effectively handle sulfur acid lead materials Method, particularly can it is more succinct, more effectively recycle de- lead liquid.
The inventive method operation is as follows:
Sulfur acid lead materials and sodium chloride solution are pressed into liquid-solid ratio(mL:g)5~20:1 mixing, concentration of sodium chloride solution be 4~ Filtered while hot after 50 DEG C~100 DEG C, reaction 20min~120min are heated under 6mol/L, stirring, obtain leached mud and leachate. Leachate is cooled to after 0 DEG C~30 DEG C and filtered, lead-rich slag and de- lead filtrate is obtained.Lead powder removal of impurities, lead are added into de- lead filtrate Powder consumption is 2g/L ~ 7.5g/L, is heated under stirring after 50 DEG C~100 DEG C, reaction 30min~120min, adds alkali regulation pH It is worth for 8.0~13.0, filtering, filtrate after obtaining precipitation slag and precipitating.It is 4.0~7.0 to add filtrate pH value after hydrochloric acid regulation precipitation After add sodium chloride and recycle.
Advantages of the present invention is:
(1)Present invention process flow is succinct, and only consumption sodium chloride, a small amount of lead powder and alkali, with low cost, environment-friendly and do not draw Enter new impurity;
(2)Chlorination takes off lead liquid processing method simplicity, and can effectively be recycled, and reduces the discharge of a large amount of waste water and contains The generation of lead gypsum danger solid waste;
(3)Filtrate reduces removal of impurities through lead powder after de- lead, and noble metal and other non-ferrous metals have been separately recovered.
Embodiment
Embodiment 1
5.8mol/L sodium chloride solutions 800mL is taken to add in reactor, by liquid-solid ratio 8:1 add 100g it is leaded be 11.9% it is de- It is heated to filtering while hot after 55 DEG C of reaction 30min under copper anode mud, stirring, washs, obtains leachate 842mL and leaded 0.9% leaching Slagged tap 76.2g, and lead leaching rate is 94.2%, and leachate is cooled to after 10 DEG C and filtered, lead-rich slag and de- lead filtrate 830mL is obtained.To Lead powder 6.3g removal of impurities is added in de- lead filtrate, is heated under stirring after 60 DEG C of reaction 1h, it is 10.0, mistake to add alkali regulation pH value Filter, obtains filtrate 840mL after precipitation slag and precipitation, the silver-colored rate of recovery is 99.8%, and lead, antimony, the rate of deposition of bismuth are 100%.Add Filtrate pH value is 6.0 after hydrochloric acid regulation precipitation.
It is 5.8mol/L to add sodium chloride to chlorine ion concentration in filtrate after the precipitation that regulation pH value is 6, obtains circulation fluid.Take Circulation fluid 800mL, by liquid-solid ratio 8:1 add 100g it is leaded be 11.9% the decopper(ing) earth of positive pole, reaction temperature be 55 DEG C, reaction Time, the leaching rate for obtaining lead was 90.2% to leach lead under 30nin.
Embodiment 2
5.5mol/L sodium chloride solutions 1600mL is taken to add in reactor, by liquid-solid ratio 16:1 to add 100g leaded be 34.9% It is heated to filtering while hot after 55 DEG C of reaction 30min under the decopper(ing) earth of positive pole, stirring, washs, obtains leachate 1660mL and leaded 2.0% Leached mud 53.1g, lead leaching rate be 96.9%.Leachate is cooled to after 15 DEG C and filtered, lead-rich slag and de- lead filtrate is obtained 1645mL.Lead powder 3.27g removal of impurities is added into de- lead filtrate, is heated under stirring after 60 DEG C of reaction 1h, alkali regulation pH value is added For 10.0, filtering obtains filtrate 1650mL after precipitation slag and precipitation, the silver-colored rate of recovery is 99.5%, and lead, antimony, the rate of deposition of bismuth are 100%.It is 7.0 to add filtrate pH value after hydrochloric acid regulation precipitation.
It is 5.5mol/L to add sodium chloride to chlorine ion concentration in filtrate after the precipitation that regulation pH value is 7, obtains circulation fluid.Take Circulation fluid 1600mL, by liquid-solid ratio 16:1 add 100g it is leaded be 34.9% the decopper(ing) earth of positive pole, reaction temperature be 55 DEG C, instead To soak lead under 30nin between seasonable, the leaching rate for obtaining lead is 96.5%.
Embodiment 3
The L of 5.8mol/L sodium chloride solutions 3.6 is taken to add in reactor, by liquid-solid ratio 12:1 adds 300g leaded 13.78% point Be heated under silver-colored slag, stirring 55 DEG C reaction 30min after filter while hot, obtain the L of leachate 3.95 and it is leaded be 1.95% leached mud 219.8g, lead leaching rate is 89.6%, and leachate is cooled to after 10 DEG C and filtered, lead-rich slag and the de- L of lead filtrate 3.87 is obtained.To de- Lead powder 12.1g removal of impurities is added in lead filtrate, is heated under stirring after 60 DEG C of reaction 1h, it is 10.0 to add alkali regulation pH value, filtering, Filtrate 3.90L after precipitation slag and precipitation is obtained, the silver-colored rate of recovery is 99.8%, and lead, antimony, the rate of deposition of bismuth are 100%.Add hydrochloric acid Filtrate pH value is 7.0 after regulation precipitation.
It is 5.8mol/L to add sodium chloride to chlorine ion concentration in filtrate after the precipitation that regulation pH value is 7, obtains circulation fluid.Take Circulation fluid 3.6L, is 12 by liquid-solid ratio:1 add 300g it is leaded be 13.78% silver separating residues, reaction temperature be 55 DEG C, during reaction Between be 30nin under leach lead, obtain lead leaching rate be 82.6%.

Claims (3)

1. a kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled, it is characterised in that:
Sulfur acid lead materials and sodium chloride solution are pressed into liquid-solid ratio 5~20:1 mixing, unit is mL/g, and concentration of sodium chloride solution is Filtered while hot after 50 DEG C~100 DEG C, reaction 20min~120min are heated under 4~6mol/L, stirring, obtain leached mud and leaching Liquid, leachate is cooled to after 0 DEG C~30 DEG C and filtered, lead-rich slag and de- lead filtrate is obtained, lead powder removal of impurities is added into de- lead filtrate, Lead powder consumption is the g/L of 2 g/L ~ 7.5, is heated under stirring after 50 DEG C~100 DEG C, reaction 30min~120min, adds alkali and adjust Save pH value be 8.0~13.0, filtering, obtain precipitation slag and precipitation after filtrate, add hydrochloric acid regulation precipitation after filtrate pH value be 4.0~ Sodium chloride is added after 7.0 to recycle.
2. a kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled according to claim 1, it is characterised in that: Described alkali is NaOH.
3. a kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled according to claim 1, it is characterised in that: It is described regulation precipitation after filtrate pH value be 4.0~7.0 after add after sodium chloride to heavy lead, in filtrate sodium chloride concentration be 4~ 6mol/L。
CN201710289361.6A 2017-04-27 2017-04-27 A kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled Pending CN106939377A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107447112A (en) * 2017-08-10 2017-12-08 云南龙蕴科技环保股份有限公司 A kind of method of the enriched lead from low-grade lead skim
CN115504439A (en) * 2022-09-07 2022-12-23 金川集团股份有限公司 Method for removing lead from high-lead tellurium powder

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1199780A (en) * 1997-05-15 1998-11-25 昆明贵金属研究所 Ag and Au extracting and Sb, Bi, Cu and Pb recovering process from lead slime
CN101343691A (en) * 2008-09-01 2009-01-14 中南大学 Pollution-free separation method for plumbum and silver
CN101994007A (en) * 2009-08-28 2011-03-30 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
CN103290225A (en) * 2013-06-20 2013-09-11 长沙华明复合材料科技有限公司 Method for recovering lead from lead-containing solid wastes
CN103966456A (en) * 2014-05-23 2014-08-06 江西理工大学 Method for comprehensively recovering valuable metals from copper anode sludge silver separating slag
CN104445380A (en) * 2014-12-12 2015-03-25 郴州市金贵银业股份有限公司 Preparation method of lead sulfate tribasic

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1199780A (en) * 1997-05-15 1998-11-25 昆明贵金属研究所 Ag and Au extracting and Sb, Bi, Cu and Pb recovering process from lead slime
CN101343691A (en) * 2008-09-01 2009-01-14 中南大学 Pollution-free separation method for plumbum and silver
CN101994007A (en) * 2009-08-28 2011-03-30 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
CN103290225A (en) * 2013-06-20 2013-09-11 长沙华明复合材料科技有限公司 Method for recovering lead from lead-containing solid wastes
CN103966456A (en) * 2014-05-23 2014-08-06 江西理工大学 Method for comprehensively recovering valuable metals from copper anode sludge silver separating slag
CN104445380A (en) * 2014-12-12 2015-03-25 郴州市金贵银业股份有限公司 Preparation method of lead sulfate tribasic

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107447112A (en) * 2017-08-10 2017-12-08 云南龙蕴科技环保股份有限公司 A kind of method of the enriched lead from low-grade lead skim
CN107447112B (en) * 2017-08-10 2019-03-01 云南龙蕴科技环保股份有限公司 A method of the enriched lead from low-grade lead skim
CN115504439A (en) * 2022-09-07 2022-12-23 金川集团股份有限公司 Method for removing lead from high-lead tellurium powder
CN115504439B (en) * 2022-09-07 2023-09-29 金川集团股份有限公司 Method for removing lead from high-lead tellurium powder

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Application publication date: 20170711

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