CN101831668B - Clean wet-method solid-liquid two-phase electroreduction lead recovery method - Google Patents

Clean wet-method solid-liquid two-phase electroreduction lead recovery method Download PDF

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CN101831668B
CN101831668B CN2010101849582A CN201010184958A CN101831668B CN 101831668 B CN101831668 B CN 101831668B CN 2010101849582 A CN2010101849582 A CN 2010101849582A CN 201010184958 A CN201010184958 A CN 201010184958A CN 101831668 B CN101831668 B CN 101831668B
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lead
electrolysis
concentration
solid
naoh
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CN101831668A (en
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潘军青
岳希红
孙艳芝
唐路
万平玉
伊晓波
王子镐
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北京化工大学
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    • 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
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    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention relates to a wet-method electroreduction clean lead recovery method with closed circulation. In the method, based on an electrochemical principle, a solid-liquid two-phase one-step reduction reaction is performed by establishing a closed electrolyte circulation and by the lead-containing material activation of an active agent and the catalytic oxygen absorption action of a high-efficiency anode so as to convert waste lead storage batteries or the lead-containing waste material from lead storage battery production plants into metal lead directly. Thus, the method is a novel environmentally-friendly and energy-saving wet-method electroreduction lead recovery method, and is a novel technique that can be used for large-scale industrial production.

Description

A kind of method of clean wet-method solid-liquid two-phase electroreduction lead recovery

Technical field:

The present invention relates to a kind of method of clean wet-method solid-liquid two-phase electroreduction lead recovery, belong to scrap lead material secondary lead hydrometallurgy field.

Background technology:

Lead-acid cell is as the indispensable electric energy energy storage device of the vehicles such as automobile, and its consumption and learies are along with the consumption of automobile and power truck increases rapidly.Consumption plumbous in the lead-acid cell of China in 2002 reaches 64.5 ten thousand tons, has increased more than 150% than 2000.According to Chinese physics and chemical power source employer's organization relevant data statistics, Chinese plumbous consumption in 2008 will reach more than 200 ten thousand tons, account for plumbous more than 23% of total quantity consumed in the world.Because the contradiction between the demand of existing lead ore resource-constrained and increase has day by day caused raising up day by day of plumbous valency.How lead-acid cell is carried out high efficiente callback, not only help to extenuate the contradiction between the supply and demand significantly, and the more important thing is the recycling utilization that has realized lead resource, thereby reduced environmental pollution significantly, have important social economic value.

The lead of lead acid cell mainly is distributed in the grid and the lead plaster of positive/negative plate, and the plumbous connecting strip of inside battery (or lead joint line terminals).For lead-acid cell, the lead of its grid and plumbous connecting strip reclaims simple relatively, can directly obtain through high temperature melting.Wherein lead plaster has accounted for plumbous more than 55% of total amount of battery, is mainly PbSO 4, PbO, PbO 2And Pb, wherein PbSO 4And PbO 2Reduction process become the difficult point of whole lead-acid cell secondary lead technology.

At present method in common is a pyrometallurgical smelting, though this technology technical requirements is lower, flow process is more, causes the plumbous recovery generally between 80-85%, produces a large amount of SO simultaneously in process of production 2, lead powder dirt and lead containing sludge, environment is caused severe contamination, harm humans healthy, and product is lead bullion, can not directly use, and also will further handle.

Hydrometallurgy is as a kind of smelting mode of relative clean and effective, and Many researchers is attempting adopting wet method that the lead plaster of lead-acid cell is effectively reduced processing always.The wet reclamation lead base can be divided into acid system and two kinds of methods of alkaline process in the difference of electrolyte.

The USBM technology of report in 1985 (Joumal of Metals, 1985,37 (2): 79-83) with the same utilization of USP (US, 4769116 [P] .1988-9-6.) (NH 4) 2CO 3Perhaps Na 2CO 3Carry out desulfurization as sweetening agent and transform, adopt lead powder or H afterwards 2O 2Reduce the PbO in the lead plaster as reductive agent 2, the PbO of generation and PbCO 3Use H 2SiF 6Electrolytic solution is processed in dissolving.Electrolytic process is at current density 180A/m 2Condition under carry out 24h, gained lead powder purity is greater than 99.99%, current efficiency is 97%, energy consumption is plumbous 700kWh per ton.Problems such as above-mentioned technology exists the production current density little, and power consumption is high, equipment corrosion is big, and reagent expensive and toxicity are big.

Compare with in acid solution, carrying out the complicated conversion reaction and then the wet processing of electrolytic reduction, utilize lead-acid cell to change into principle and directly in sulfuric acid electrolyte, carry out the wet method of electrolytic reduction report is also arranged.German Patent in 1985 (DE, 3402338A) and English Patent (1368423 and 1428957) reported that in succession employing lead-acid cell negative plate changes into principle, is fixed on the scrap battery lead plaster on one metal sheet or the wire basket; In dilution heat of sulfuric acid, carry out electrolytic reduction as negative electrode; Obtain metallic lead and sulfuric acid, but because of lead sulfate solubility limit in diluted acid, current density and pressure layer thickness are all less; Cause plant factor low, make that the cathodic reduction degree of depth is little, groove is pressed height, energy consumption is big; And reclaim(ed) sulfuric acid concentration only reaches about 10%, has therefore limited industrial popularization.Chinese patent ZL2008101114308.3 (method of acid wet method electrolytic recovery waste lead acid battery accumulator cell lead) utilizes dual power supply and acvator to increase substantially the reduction rate and the reduction efficiency of lead sulfate; Realized the direct reduction of lead-acid cell lead plaster and grid; Realized the power consumption of plumbous 600-700KWh per ton; Simultaneously can reclaim sulfuric acid up to 30%; Shortcoming is that this process need carry out independent electrolysis treatment to the monomer of lead-acid cell at electrolytic process, is not easy to realize large-scale industrial production.

At the plumbous technical elements of alkaline regeneration, Chinese patent CN88103531 has proposed the solid phase electrolytic process of electrolytic reduction paste spread type negative electrode in basic soln.This characteristic feature of an invention is at first positive and negative pole lead paste to be carried out plumbic prereduction in sour environment to handle; Adopt the net metal negative electrode then; With tackiness agents such as Z 150PH lead plaster and water are reconciled into the paste with viscosity; And be coated in and process negative electrode on the wire netting, subsequently with negative electrode, dividing plate and anode according to certain order stack addition pole plate crowd, be placed at last in the alkaline NaOH solution and carry out the lead powder that electrolysis obtains containing lead sulfate.Shortcoming is this method complex process, because coating is very thin, 3-5mm is only arranged, and makes the pole plate area very big; The very big and complex structure of electrode area, reduction process is not thorough, is mingled with 2% and is abundant reductive lead sulfate; Cause the loading and unloading material loaded down with trivial details, it is frequent to go out tankage, in industry, is difficult to use.The Chinese patent CN02132647.9 of nearest 2002 reports has overcome the thin shortcoming of the former windrow, has proposed to adopt the rectangular frame with grid structure as negative electrode, thereby has improved the cream amount that is coated with.Overcome the shortcoming of original single constant-current electrolysis with the mode of constant-potential electrolysis, show electrolytic terminal point with constant-potential electrolysis process change in current.The shortcoming of this method is because the scrap lead material component is complicated, thereby causes between each batch of material because Pb and PbO 2The resistance that the difference of composition causes being coated with cream self has significant difference; Thereby make actual electrolysis difference between current very not big in the constant-potential electrolysis condition; The 15-35% that is difficult to drop to Faradaic current peak point current judges the electrolysis terminal point; Thereby still having not electrolytic in a large number lead compound in the actual product, electrolyzing rate is 85-96% usually.Because the constant-potential electrolysis current floating changes, and causes electrolysis actual current in mid-term very big, voltage descends in the internal resistance of two polarization of electrodes and solution greatly, and this makes that this method actual power consumption is very uneconomical, the plumbous 547-880 degree that needs per ton.

Wet processing is compared with sophisticated thermal process; Though improved the plumbous recovery to a certain extent; But the power consumption up to the 600-1000 degree has increased production cost; It is high and corrodibility is big to add the energy consumption of acidic electrolysis, and alkaline solid phase is coated with the discontinuous mechanized operation of cream, causes being difficult at present be applied in actual industrialization.

Summary of the invention:

The purpose of this invention is to provide a kind of have the wet method electrolytic reduction lead-acid accumulator of closed circulation or the cleaning and reclaiming method that contains lead in the scrap lead of lead storage battery factory; Utilize electrochemical principle, through circulation of elecrolyte, the acvator of setting up sealing the activation of lead-containing material is analysed oxygen with efficient anodic catalysis and be used for realizing that solid-liquid two one goes on foot contain a kind of method that scrap lead be converted into metallic lead of reduction reaction with waste lead accumulator or lead storage battery factory mutually.

The method of a kind of clean wet-method solid-liquid two-phase electroreduction lead recovery of the present invention; React with the sulphuric acid soln that adds stannous sulfate earlier containing scrap lead; After NaOH solution complexometric extraction obtains plumbiferous basic soln, again through electrolysis, obtain lead, anode obtains plumbic oxide at negative electrode; Add solid NaOH then in the electrolysis mother liquor after electrolysis, separate out and remove Na 2SO 4Crystal returns NaOH solution to complexation extraction and recycles.

Concrete grammar and step are following:

1) containing scrap lead, to carry out wet pulverization levigate, sieves with 40-300 purpose screen cloth; Pulverizing levigate process can carry out in the kibbler of routine and ball mill.

The described scrap lead that contains is after lead-acid accumulator carries out conventional discharge process, through Mechanical Crushing, to carry out the lead plaster that aqueous phase separation obtains then, perhaps is the scrap lead that contains of lead storage battery factory.

2) the scrap lead powder that contains that screening is obtained is respectively with mass percent with the sulphuric acid soln that adds stannous sulfate: the mixed of 20-95%, 5-80% is even, under 20-105 ℃ of temperature stirring reaction 1-24 hour; The concentration of wherein adding vitriolic concentration in the sulphuric acid soln of stannous sulfate and be 1.5-7.0mol/L, SnSO4 is 0.05-2.0mol/L; The waste sulfuric acid solution that sulphuric acid soln can obtain with step 1).

In this process, redox reaction takes place under the catalysis of stannous sulfate, reaction formula is shown in (1):

Pb+PbO 2+2H 2SO 4＝2PbSO 4+2H 2O (1)

3) isolate step 2) solid substance that obtains after the reaction, add the NaOH solution submergence solid substance of mass percentage concentration 20-45%, carry out the complexometric extraction reaction at 30-120 ℃; After complexation extraction reaches capacity, through filtering, isolate residual solid substance and leaded electrolysis mother liquor, residual solid substance continues and new NaOH solution reacts;

In this process, the complexometric extraction reaction takes place in lead-containing material in the lead plaster and NaOH, and suitably elevated temperature helps to obtain the lead solution that contains of higher concentration, and the reaction that is taken place is shown in reaction formula (2), (3), (4) and (5):

PbSO 4+2NaOH＝Na 2SO 4+Pb(OH) 2 (2)

Pb(OH) 2+2NaOH＝Na 2[Pb(OH) 4] (3)

PbO+2NaOH+H 2O＝Na 2[Pb(OH) 4] (4)

PbO 2+2NaOH+H 2O＝Na 2PbO 3 (5)

In said process, PbSO 4Desulphurization reaction takes place earlier, together with among the NaOH complex solution process takes place with PbO subsequently.General N a 2[Pb (OH) 4] having higher solubleness, the lead tolerance of this part accounts for higher ratio, in addition, residual PbO in the lead plaster 2The reaction process of (5) also takes place.In order suitably to increase plumbous effective concentration, be added with complexing-aid agent in the above-mentioned NaOH solution, the amount of adding is controlled at 0.1-3.0mol/L, and described complexing-aid agent is a kind of in nitrilotriacetic acid(NTA), EDTA, the potassium sodium citrate or their mixture.

4) leaded electrolysis mother liquor carries out electrolysis through leaving standstill in the galvanic deposit additive entering electrolyzer that purifies back adding 1-20g/L; The adding of galvanic deposit additive can improve the plumbous pattern of galvanic deposit of negative electrode; Described galvanic deposit additive is gelatin, gelatine or DPE-III (trade(brand)name belongs to the aldehyde ketone polymkeric substance); Used electrolyzer is for including the sealed electrolytic cell of pure lead electrode plate, inert anode (inert anode can be nickel, stainless steel, titanium alloy or Graphite Electrodes), constant temperature heating device, lead concentration transmitter, whisking appliance and import and export; Electrolytic process divides constant current and two stages of constant voltage, when lead concentration during greater than 20g/L, adopts with respect to cathode area current density 10-400mA/cm 2Continuous current carry out electrolysis; When lead concentration is 12-20g/L, 8-12g/L, 4-8g/L, adopt the constant voltage of 1.1V, 1.2V, 1.3V to carry out electrolysis respectively, obtain electrolytic lead at negative electrode after the electrolysis, anode obtains plumbic oxide;

Through analyzing, the plumbous purity of negative electrode is generally more than the 98.5-99.9%, and impurity is mainly plumbous oxide, water and the NaOH that oxygen produces in the air, thus can direct fusion for obtaining electrolytic lead No. two, anodic product is the α-PbO of densification 2, can be used as the anodal raw material of lead-acid cell or the energy consumption that additive reduces formation process through after levigate.

5) replenishing the NaOH solid in the electrolysis mother liquor after electrolysis makes concentration bring up to mass percentage concentration to be 20-45%, subsequently electrolytic solution to be cooled to 0-20 ℃, leave standstill, separate out sodium sulfate crystal in the solution.After solid-liquid separation, NaOH solution is returned step 3), be used for complexometric extraction and recycle.

Experiment shows that method of the present invention is generally 97.0-98.6% for the lead recovery of automobile lead-acid cell, and the recovery of power truck fully-closed battery reaches 97.1-99.3%.According to the current density of the situation of scrapping, duration of service and the electrolytic process of lead-acid cell, the power consumption of producing secondary lead per ton is 230-410KWh.Compared with prior art, can obviously cut down the consumption of energy, avoid the use of hazardous and noxious substances in the removal process, be a kind of lead recovery method of clean environment firendly.

Description of drawings:

Fig. 1 is a schematic flow sheet of the present invention.

Among the figure: the 1-lead-acid cell; 2-is broken; The 3-ball milling; 4-mixed lead mud; The acid of 5-sulfur waste; The 6-plastic waste; 7-stereotype grid; The 8-vulcanization reaction; The 9-NaOH solid; 10-lead sulfide mud; The 11-extraction; The 12-electrolyzer; The 13-galvanic deposit is plumbous; The 14-plumbic oxide; 15-electrolysis mother liquor; The 16-NaOH solid; The 17-crystallisation by cooling; 18-electrolytic solution; The 19-sodium sulfate crystal.

Embodiment:

Embodiment 1

Get 12V, the 10Ah power truck waste lead acid battery of blue sky, 10 Tianjin Gao Ke company, 42.6 kilograms of series of cells gross weights.The practical implementation process is following:

1) with 10 batteries earlier through after the discharge process, put into crusher in crushing then after, utilize density difference to separate at water and obtain lead plaster, grid, sulfur waste acid, dividing plate and shell.

2) lead plaster that press filtration is gone out is put into ball mill and is carried out the levigate back of wet method and sieve with 60 purpose stainless steel meshs, and bigger lead plaster particle continues to change over to kibbler to be pulverized, and all sees through screen cloth until all lead plasters.

3) get the H that sulfur waste acid that 60L 1 process obtains contains its adjustment acidity 3mol/L 2SO 4SnSO with 0.1mol/L 4, subsequently with step 2) and screening 20 kilograms lead plaster powder and waste sulfuric acid solution obtaining mix, and keep constant temperature and stirring 4 hours at 75 ℃.In this process, the lead powder of lead plaster Central Plains anodal plumbic oxide and former negative pole progressively is converted into lead sulfate under the catalysis of stannous sulfate.

4) reacted lead plaster is separated in pressure filter, 30% of adding 260L NaOH solution carries out desulfurization and extractive reaction at 100 ℃ in the product that separation obtains.In order suitably to increase plumbous solubleness, containing 0.2mol/L nitrilotriacetic acid(NTA) and 0.15mol/L EDTA in this 30%NaOH solution is complexing-aid agent.In this process, complexometric extraction reaction, wherein PbSO take place in the lead-containing material of lead plaster and NaOH 4, Pb (OH) 2All generate Na with PbO with NaOH 2[Pb (OH) 4], in addition, residual PbO in the lead plaster 2Reaction generates Na with NaOH 2PbO 3Through measuring Na 2[Pb (OH) 4] part lead tolerance be 77g/L.PbO 2The about 4g/L of lead of part.

5) after extractive reaction reaches balance, alkalescence is contained lead solution through press filtration, isolate residual lead plaster and leaded electrolysis mother liquor.Residual lead plaster continues and new NaOH solution reacts, and leaded mother liquor carries out electrolysis through leaving standstill to purify in the back entering electrolyzer.The plumbous pattern of galvanic deposit in order to improve negative electrode simultaneously adds mass percent and is 0.15% gelatin and 0.2% DPE-III and improves cathodic process as the galvanic deposit additive in the electrolysis mother liquor.

6) adopting thickness is that pure stereotype and 304 stainless steel plates of 1mm are respectively negative electrode and anode, and cell construction is 3 positive 2 negative electrode structures, and volume is 96 (length) * 22 (wide) * 150 (height) cm 3, the 30W electric blender stirs, and places the sealed electrolytic cell of lead concentration transmitter and import and export.At first in this electrolyzer, carry out constant-current electrolysis, control current density is 400A/m 2, after electrolysis time reaches 42min, when detecting that this moment, lead concentration was 20g/L, change the constant-potential electrolysis pattern of 1.1V over to, thereafter according to lead concentration be reduced to 8-12 and 4-8g/L the time, adopt the constant voltage mode of 1.2V and 1.3V respectively.Whole electrolysis time is about 3h, and plumbous concentration is reduced to below the 4g/L in the electrolysis this moment mother liquor.Through test; Negative electrode lead has obtained 10.15 kilograms lead, and its purity is 99.1%, and anode has obtained 9.62 kilograms of plumbic oxide; Purity is 95%; Residual 0.65 kilogram red lead sesquioxide in the electrolytic solution, from the dropping and transforming of anode part plumbic oxide, this part is transferred in the truck for vulcanlzing pan again and recycles.Through calculating, the energy consumption of electrolytic process is 335kWh/t (Pb), and comprehensive recovery is 97.3%.

7) the NaOH alkali concn of the electrolysis mother liquor after the electrolysis is through traditional chemical titration analysis 13.5% (mass percent); Through after replenishing the NaOH solid actual concentrations of NaOH being brought up to 30% once more; Electrolytic solution is cooled to 10 ℃; In taking off the sodium sulfate groove, carry out crystallization, separate out sodium sulfate crystal in the solution this moment.This solution carries out solid-liquid separation and obtains 30% NaOH solution and sodium sulfate crystal then, and this NaOH solution turns back in the extraction tank again and recycles.

Embodiment 2

Get the 12V of 1 Baoding sail company, 45Ah junked-auto lead-acid cell, 13.5 kilograms of series of cells gross weights.Concrete removal process is following:

1) with this battery earlier through after discharge process, put into crusher in crushing then after, utilize density difference to separate at water and obtain lead plaster, grid, sulfur waste acid, dividing plate and shell.

2) lead plaster that press filtration is gone out is put into ball mill and is carried out the levigate back of wet method and sieve with 80 purpose stainless steel meshs, and bigger lead plaster particle continues to change over to kibbler to be pulverized, and all sees through screen cloth until all lead plasters.

3) get the H that sulfur waste acid that 10L 1 process obtains contains its adjustment acidity 4.2mol/L 2SO 4SnSO with 0.2mol/L 4, 5.5 kilograms lead plaster powder and waste sulfuric acid solution subsequently the screening of 2 processes being obtained mix, and keep constant temperature and stirred 6 hours at 75 ℃.In this process, the lead powder of lead plaster Central Plains anodal plumbic oxide and former negative pole progressively is converted into lead sulfate under the catalysis of stannous sulfate.

4) reacted lead plaster is separated in pressure filter, 35% of adding 63L NaOH solution carries out desulfurization and extractive reaction at 110 ℃ in the product that separation obtains.In order suitably to increase plumbous solubleness, containing 0.2mol/L nitrilotriacetic acid(NTA) and 0.3mol/L potassium sodium citrate in this 30%NaOH solution is complexing-aid agent.In this process, complexing solubilizing reaction, wherein PbSO take place in the lead-containing material of lead plaster and NaOH 4, Pb (OH) 2All generate Na with PbO with NaOH 2[Pb (OH) 4], in addition, residual PbO in the lead plaster 2Reaction generates Na with NaOH 2PbO 3Through measuring Na 2[Pb (OH) 4" part lead tolerance be 82g/L.PbO 2The about 5g/L of lead of part.

5) after extractive reaction reaches balance, alkalescence is contained lead solution through press filtration, isolate residual about 0.2 kilogram of lead plaster and leaded electrolysis mother liquor.Residual lead plaster continues and new NaOH solution reacts, and leaded mother liquor carries out electrolysis through purifying in the back entering electrolyzer.For the plumbous pattern of the galvanic deposit that improves negative electrode, in the electrolysis mother liquor, add mass percent and be 0.15% gelatine and 0.2% DPE-III and improve cathodic process as the galvanic deposit additive.

6) adopting thickness is that pure stereotype and the pure nickel plate of 1mm is respectively negative electrode and anode, and cell construction is 3 positive 2 negative electrode structures, and volume is 50 (length) * 22 (wide) * 75 (height) cm 3, the 20W electric blender stirs, and places the sealed electrolytic cell of lead concentration transmitter and import and export.At first in this electrolyzer, carry out constant-current electrolysis; Control current density is 350A/m2; After electrolysis time reached 55min, warp detected when this moment, lead concentration was 20g/L, changed the constant-potential electrolysis pattern of 1.1V over to; Thereafter according to lead concentration be reduced to 8-12 and 4-8g/L the time, in the constant voltage mode that gets into 1.2V and 1.3V respectively.Whole electrolysis time is about 2.9h, and plumbous concentration is reduced to below the 4g/L in the electrolysis this moment mother liquor.Through test; Negative electrode lead has obtained 2.7 kilograms lead, and its purity is 99.3%, and anode has obtained 2.9 kilograms of plumbic oxide; Purity is 95%; Residual 0.31 kilogram red lead sesquioxide in the electrolytic solution, from the dropping and transforming of anode part plumbic oxide, this part is transferred in the truck for vulcanlzing pan again and recycles.Through calculating, the energy consumption of electrolytic process is 295kWh/t (Pb), and comprehensive recovery is 97.5%.

7) the NaOH alkali concn of the electrolysis mother liquor after the electrolysis is through traditional chemical titration analysis 15.5% (mass percent); Through after replenishing the NaOH solid actual concentrations of NaOH being brought up to 35% once more; Electrolytic solution is cooled to 10 ℃; In taking off the sodium sulfate groove, carry out crystallization, separate out sodium sulfate crystal in the solution this moment.This solution carries out solid-liquid separation and obtains 35% NaOH solution and sodium sulfate crystal then, and this NaOH solution turns back in the extraction tank again and recycles.

Embodiment 3

Get the scrap lead that contains of 5 kilograms of Jiangsu, three ring company lead-acid cell production plants, be ground into powder, carry out following lead successively and reclaim through ball mill:

1) will contain the scrap lead powder and carry out ball milling after, utilize 60 eye mesh screens to sieve and obtain fine powder, add 27% the NaOH solution of 90L then, carry out extractive reaction at 90 ℃.In order suitably to increase plumbous solubleness, contain 0.2mol/L nitrilotriacetic acid(NTA) and 0.2mol/L EDTA in this 27%NaOH solution as complexing-aid agent.In this process, complexing solubilizing reaction, wherein Pb (OH) take place in the lead-containing material of fine powder and NaOH 2All generate Na with PbO with NaOH 2[Pb (OH) 4], through measuring Na 2[Pb (OH) 4] lead tolerance of part is 53g/L, remaining about 0.3 kilogram of earthy deposition is mainly the soil profile that contains silicate through analyzing.

2) after extractive reaction reaches completion, the leaded electrolysis mother liquor that obtains is carried out electrolysis through purifying in the back entering electrolyzer.For the plumbous pattern of the galvanic deposit that improves negative electrode, in the electrolysis mother liquor, add mass percent and be 0.2% DPE-III and improve cathodic process as the galvanic deposit additive.

3) in electrolyzer (with embodiment 2), carry out electrolysis, electrolytic condition is with embodiment 2, and negative electrode lead has obtained 2.1 kilograms lead; Its purity is 99.95%; Anode has obtained 2.2 kilograms of plumbic oxide, and purity is 95.5%, residual 0.14 kilogram red lead sesquioxide in the electrolytic solution; From the lead dioxide powder that drops on the anode, this part is transferred in the truck for vulcanlzing pan again and recycles.Through calculating, the energy consumption of electrolytic process is 335kWh/t (Pb), and comprehensive recovery is 97.9%.

Embodiment 4

Get the old and useless battery pole plate of 7.5 kilograms of Hangzhou Nan Dou company lead-acid cell production plants, water carries out gravity separation after crusher is pulverized, and obtains waste and old grid and lead plaster powder, carries out following lead successively and reclaims:

1) will contain the scrap lead powder and carry out ball milling after, utilize 60 eye mesh screens to sieve and obtain fine powder, add 27% the NaOH solution of 150L then, carry out extractive reaction at 60 ℃.In order suitably to increase plumbous solubleness, contain 0.10mol/L nitrilotriacetic acid(NTA) and 0.10mol/L sodium-potassium tartrate in this 27%NaOH solution as complexing-aid agent.In this process, complexing solubilizing reaction, wherein Pb (OH) take place in the lead-containing material of fine powder and NaOH 2All generate Na with PbO with NaOH 2[Pb (OH) 4], through measuring Na 2[Pb (OH) 4] lead tolerance of part is 48g/L, remaining about 0.3 kilogram of brown shape deposition is mainly the composition that contains plumbic oxide and humic acids through analyzing.

2) after extractive reaction reaches completion, the leaded electrolysis mother liquor that obtains is carried out electrolysis through purifying in the back entering electrolyzer.For the plumbous pattern of the galvanic deposit that improves negative electrode, the DPE-III that in the electrolysis mother liquor, adds mass percent and be 0.2% (340ml) improves cathodic process as the galvanic deposit additive.

3) in electrolyzer (with embodiment 2), carry out electrolysis, electrolytic condition is with embodiment 2, and negative electrode lead has obtained 3.4 kilograms lead; Its purity is 99.95%; Anode has obtained 2.9 kilograms of plumbic oxide, and purity is 95.5%, residual 0.2 kilogram red lead sesquioxide in the electrolytic solution; From the lead dioxide powder that drops on the anode, this part is transferred in the truck for vulcanlzing pan again and recycles.Through calculating, the energy consumption of electrolytic process is 350kWh/t (Pb), and comprehensive recovery is 97.9%.

Claims (3)

1. the method for a clean wet-method solid-liquid two-phase electroreduction lead recovery; React with the sulphuric acid soln that adds stannous sulfate earlier containing scrap lead; After NaOH solution complexometric extraction obtains plumbiferous basic soln, again through electrolysis, obtain lead, anode obtains plumbic oxide at negative electrode; Add solid NaOH then in the electrolysis mother liquor after electrolysis, separate out and remove Na 2SO 4Crystal returns NaOH solution to complexation extraction and recycles;
It is characterized in that: concrete grammar and step are following:
1) containing scrap lead, to carry out wet pulverization levigate, sieves with 40-300 purpose screen cloth;
2) the scrap lead powder that contains that screening is obtained is respectively with mass percent with the sulphuric acid soln that adds stannous sulfate: the mixed of 20-95%, 5-80% is even, under 20-105 ℃ of temperature stirring reaction 1-24 hour; Add wherein that vitriolic concentration is 1.5-7.0mol/L, SnSO in the sulphuric acid soln of stannous sulfate 4Concentration be 0.05-2.0mol/L;
3) isolate step 2) solid substance that obtains after the reaction, add the NaOH solution submergence solid substance of mass percentage concentration 20-45%, carry out the complexometric extraction reaction at 30-120 ℃; After complexation extraction reaches capacity, through filtering, isolate residual solid substance and leaded electrolysis mother liquor, residual solid substance continues and new NaOH solution reacts;
Be added with complexing-aid agent in the above-mentioned NaOH solution, the amount of adding is controlled at 0.1-3.0mol/L, and described complexing-aid agent is a kind of in nitrilotriacetic acid(NTA), EDTA, the potassium sodium citrate or their mixture;
4) leaded electrolysis mother liquor carries out electrolysis through leaving standstill in the galvanic deposit additive entering electrolyzer that purifies back adding 1-20g/L, and described galvanic deposit additive is gelatin, gelatine or DPE-III; Used electrolyzer is the sealed electrolytic cell that includes pure lead electrode plate, inert anode, constant temperature heating device, lead concentration transmitter, whisking appliance and import and export; Electrolytic process divides constant current and two stages of constant voltage, when lead concentration during greater than 20g/L, adopts with respect to cathode area current density 10-400mA/cm 2Continuous current carry out electrolysis; When lead concentration is 12-20g/L, 8-12g/L, 4-8g/L, adopt the constant voltage of 1.1V, 1.2V, 1.3V to carry out electrolysis respectively, obtain electrolytic lead at negative electrode after the electrolysis, anode obtains plumbic oxide;
5) replenishing the NaOH solid in the electrolysis mother liquor after electrolysis makes concentration bring up to mass percentage concentration to be 20-45%, subsequently the electrolysis mother liquor to be cooled to 0-20 ℃, leave standstill; Separate out sodium sulfate crystal in the solution; After solid-liquid separation, NaOH solution is returned step 3), be used for complexometric extraction and recycle.
2. according to claims 1 described method that reclaims lead; It is characterized in that: the described scrap lead that contains is after lead-acid accumulator carries out conventional discharge process; Through Mechanical Crushing, carry out the lead plaster that aqueous phase separation obtains then, perhaps be the scrap lead that contains of lead storage battery factory.
3. according to claims 1 described method that reclaims lead, it is characterized in that: said electrolyzer inert anode is nickel, stainless steel, titanium alloy or Graphite Electrodes.
CN2010101849582A 2010-05-21 2010-05-21 Clean wet-method solid-liquid two-phase electroreduction lead recovery method CN101831668B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US9555386B2 (en) 2014-06-20 2017-01-31 Johnson Controls Technology Company Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US9670565B2 (en) 2014-06-20 2017-06-06 Johnson Controls Technology Company Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries
US10062933B2 (en) 2015-12-14 2018-08-28 Johnson Controls Technology Company Hydrometallurgical electrowinning of lead from spent lead-acid batteries
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CN108914158B (en) * 2018-07-27 2019-09-24 湖南省金翼有色金属综合回收有限公司 A kind of method and device thereof recycling lead from battery waste
CN109273712A (en) * 2018-10-25 2019-01-25 天能电池集团有限公司 A kind of positive electode of lead battery lead plaster and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5211818A (en) * 1991-04-09 1993-05-18 Moure Jr William B Method for recovering lead from batteries
JP3934685B2 (en) * 1993-08-12 2007-06-20 エコケム アクチェンゲゼルシャフトＥｃｏｃｈｅｍ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ Lead recycling method by continuous electrochemical lead refining
CN101335370A (en) * 2008-07-11 2008-12-31 东莞市松山科技集团有限公司 Process implement full cycle regeneration of lead acid battery
CN101615707A (en) * 2008-06-24 2009-12-30 邹寿汉 Lead-acid accumulator recycles and reclaims plumbous method
CN101613803A (en) * 2009-07-28 2009-12-30 北京科技大学 A kind of method of recovering lead from lead paste of waste lead-acid battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5211818A (en) * 1991-04-09 1993-05-18 Moure Jr William B Method for recovering lead from batteries
JP3934685B2 (en) * 1993-08-12 2007-06-20 エコケム アクチェンゲゼルシャフトＥｃｏｃｈｅｍ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ Lead recycling method by continuous electrochemical lead refining
CN101615707A (en) * 2008-06-24 2009-12-30 邹寿汉 Lead-acid accumulator recycles and reclaims plumbous method
CN101335370A (en) * 2008-07-11 2008-12-31 东莞市松山科技集团有限公司 Process implement full cycle regeneration of lead acid battery
CN101613803A (en) * 2009-07-28 2009-12-30 北京科技大学 A kind of method of recovering lead from lead paste of waste lead-acid battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
E、R、Cole等.电解法回收废蓄电池中的铅.《中国资源综合利用》.1984,(第02期), *
陆克源,于红.铅渣回收新工艺.《中国资源综合利用》.1994,(第01期), *

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