CN101956214A - Method for recycling secondary lead by electrolyzing alkaline leaded solution - Google Patents

Method for recycling secondary lead by electrolyzing alkaline leaded solution Download PDF

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Publication number
CN101956214A
CN101956214A CN2010102975224A CN201010297522A CN101956214A CN 101956214 A CN101956214 A CN 101956214A CN 2010102975224 A CN2010102975224 A CN 2010102975224A CN 201010297522 A CN201010297522 A CN 201010297522A CN 101956214 A CN101956214 A CN 101956214A
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lead
electrolysis
waste
current density
naoh
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CN101956214B (en
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潘军青
孙艳芝
张超
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • 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
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

The invention relates to a method for recycling secondary lead by electrolyzing an alkaline leaded solution. Leaded alkaline electrolyte is directly obtained by prepositive catalytic conversion and alkalinity desulfuration leaching processes; and then the leaded alkaline electrolyte is subjected to fractional electrolysis in an ion film electrolyser, thus directly obtaining the high-purity metal lead and byproducts of oxygen gas and sodium sulfate decahydrate. The method in the invention is a novel technology which has the advantages of energy conservation and large-scale industrialization application prospect.

Description

The method of the leaded solution reclaiming lead of a kind of electrolysis alkalescence
Technical field
The present invention relates to the method that a kind of alkaline electrolysis contains lead solution reclaiming lead, belong to lead-containing material and waste lead acid battery are reclaimed plumbous hydrometallurgy field of handling.
Background technology
From 1859 by French slip-stick artist Pulan special lead-acid cell is proposed since, lead-acid cell is widely used in as in power truck, automobile, the uninterrupted ups power etc. as the rechargeable cell of a kind of low price and dependable performance.In recent years, though the competition of lithium ion battery and nickel metal hydride battery is arranged, lead-acid cell is in the first place of secondary cell always, has occupied the output value of global secondary cell nearly 60%.Show that according to the data statistics of power supply relevant industries association the plumbous consumption of China in 2009 reaches more than 350 ten thousand tons, accounts for plumbous more than 23% of total quantity consumed in the world.Contained a large amount of poisonous lead compound reclaims plumbous technology with the at present relative pyrogenic process that falls behind and has caused lead-acid cell serious Lead contamination to occur in removal process in the lead-acid cell, for example " blood lead " incident that occurred in the North China in 2009.Because lead-acid cell is the leading power supply of current automobile and electric bicycle, and will in the quite a long time from now on, exist, thereby how lead-acid cell is carried out high efficiente callback, thereby effectively realize the recycling utilization of lead resource and reduce plumbous pollution significantly having become problem demanding prompt solution to environment.
The lead of lead acid cell is mainly metallic lead on electrode plate grid and the lug and the lead plaster in the positive and negative electrode.Lead in grid and the lug is plumbous simple substance, can be by recovery such as ordinary method such as meltings.Lead plaster account for plumbous total amount in the battery more than 55% and complicated component.Lead plaster is mainly Pb, PbSO 4, PbO and PbO 2Mixture.How seeking a kind of effective means reduces to the lead in the lead plaster and becomes the difficult point of secondary lead technology to obtain purified metallic lead.
Method in common is a pyrometallurgical smelting at present, and wherein the most representative company in the whole world is gondola Encke Tyke (Engitec) company.Be easy to generate a large amount of sulfurous gas, lead powder dirt and lead containing sludge in the pyrometallurgical smelting process, this has not only reduced plumbous organic efficiency, and environment is caused serious Lead contamination.
Comparatively speaking, hydrometallurgy is as a kind of smelting mode of relative clean and effective, and Many researchers is attempting adopting its lead plaster to lead-acid cell effectively to reduce processing always.The hydrometallurgy of having reported at present can be divided into according to the different of technological line and treatment media: 1) acid solubility lead salt electro-deposition techniques; 2) liquid caustic soda-potassium sodium tartrate solution electro-deposition techniques; With 3) the solid phase electrolysis tech.
Acid solubility lead salt electro-deposition techniques can be referring to USBM technology (the Journal of Metals of report in 1985,1985,37 (2): 79-83), the U.S. Pat .Patent 4451340 of the U.S. Pat .Patent 4769116 of Italian Engitec company and Italian Ginatta company.The characteristics of above-mentioned technology are at first to utilize (NH 4) 2CO 3Perhaps Na 2CO 3Carry out desulfurization as sweetening agent and transform, add reductive agent subsequently and reduce PbO in the lead plaster 2The PbO and the PbCO that generate 3Use HBF 4Perhaps H 2SiF 6Dissolving obtains the dissoluble lead salt electrolyte.Because fluorine boron (silicon) lead plumbate and fluorine boron (silicon) acid concentration height, so the lead ion environmental pollution of waste liquid is serious, and fluorochemicals solution itself is the very high compound of toxicity, and is very big to operator's physical impairment.This technology is separated out a large amount of plumbic oxide by products at Yang Banshang in electrolytic process in addition, has reduced plumbous organic efficiency, causes the secondary treatment load very big.The electrolyzer of this technology is pressed and is 2.7-3.2V at present, and the energy consumption of lead per ton is generally 700-950KWh.Though this method is polluted big, the energy consumption height, owing to its secondary lead purity can reach more than 99.99%, thereby the domestic unit of still having is at the course of industrialization of this method of trial.
Aspect alkaline electrolysis, flat technology (Chen Weiping, a kind of new technology of hydrometallurgic recovery waste lead accumulator filler, Hunan University's journal, 1996,23 (6): 111-116) that proposed a kind of " liquid caustic soda-potassium sodium tartrate solution galvanic deposit lead " of the Chen Wei of Hunan University.The characteristics of this technology are a large amount of plumbic oxide of anode by-product, and cathode current density is lower simultaneously, generally has only 150~250A/m 2And the lead that electrolysis obtains is the very high spongy lead of a kind of specific surface area, and this causes the oxidation of anode and cathode short circuit and melting process easily.Owing to adopted Seignette salt to come complexing plumbous oxide, thereby needed to consume a large amount of tartrate lead plumbates in the electrolytic process.The introducing of Seignette salt has increased solution resistance and electrolyzer is pressed, and organo-lead compound waste liquid toxicity is high and intractability is big.These factors have caused this method space-time yield low, need higher occupation area of equipment and investment working cost.
Compare with in above-mentioned acid-base 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 always.German Patent in 1985 (DE3402338A) and English Patent (1368423 and 1428957) have reported that in succession employing lead-acid cell negative plate changes into principle, the scrap battery lead plaster is fixed on the metallic cathode, in dilution heat of sulfuric acid, carry out electrolytic reduction, obtain metallic lead and sulfuric acid as negative electrode.This method is subjected to the restriction of lead sulfate solubleness in diluted acid, and current density and pressure layer thickness are all less, cause plant factor low, makes 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.The plumbous mud that Chinese patent ZL200710157084.X (a kind of electrolytic reduction regeneration lead-acid accumulator contains the method for lead resource in the lead plaster mud) utilizes lead plaster to make pours into pump and contains the method that the vitriolic electrolyzer carries out continuous electrolysis, and this method can directly realize serialization production and obtain lead powder.Shortcoming is that electrolyzer is pressed up to 2.92~3.12V, makes direct electrolysis energy consumption up to 920KWh/t (Pb).Chinese patent ZL200810114308.3 subsequently (method of acid wet method electrolytic recovery waste lead acid battery lead) utilizes dual power supply and activator 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, can reclaim simultaneously concentration up to 30% sulfuric acid.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.
The alkaline process solid phase is coated with new technology (the non-ferrous metal regeneration and utilization, 2005, (12): 16-17) of cream secondary lead technology referring to the open CN88103531 of the Lu Keyuan researcher's of the Chinese Academy of Sciences Chinese patent and solid phase electrolytic process-a kind of secondary lead.This characteristic feature of an invention is at first positive and negative pole lead paste and water to be reconciled into the paste with viscosity, and is coated in and makes negative electrode on the wire netting, adopts the mode of batch operation that lead-containing material is carried out the lead powder that electrolysis obtains containing lead sulfate in alkaline medium.Shortcoming is this method complex process, needs to hang out negative plate and take out plumbous mud from electric groove after electrolytic reduction is finished, and causes the loading and unloading material loaded down with trivial details, and the labor operation amount is excessive.Coating has been thickeied in some new work in order to reduce the volume of goods loaded and unloaded, the problem of being brought is that current efficiency is relatively low, and generally about 85%, and reduction process is not thorough, is mingled with 2% abundant reductive lead sulfate.
The Chinese patent ZL02132647.9 of nearest 2004 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 in the mode of constant-potential electrolysis, show electrolytic terminal point with the variation of constant-potential electrolysis process electric current.The shortcoming of this method is because scrap lead material component complexity, 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, be difficult to drop to 15~35% of peak point current and judge the electrolysis terminal point with Faradaic current, so still have 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, lead loss electricity 547~880KWh per ton.Nearest work also comprises the Lei Lixu of Southeast China University professor's Chinese invention patent (ZL200910024467.9), and it adopts mechanical means to separate positive/negative plate, carries out the method that electrolysis respectively obtains plumbous and lead dioxide powder then in sulfuric acid or NaOH solution.The shortcoming of this method is to need a large amount of artificial separation processes, and is particularly difficult for the sorting of the remollescent positive plate that expands.This technology produces the lead and the lead dioxide powder of equivalent simultaneously in addition, causes the organic efficiency of actual lead to have only 50%.
Find that though wet processing has improved the plumbous rate of recovery to a certain extent at present, the problem that exists mainly contains in above-mentioned up-to-date wet processing both domestic and external of analysis-by-synthesis and the current sophisticated thermal process contrast:
(1) electrolytic recovery contains in the process of scrap lead, and the complexing process need of plumbous oxide uses complexing agent;
(2) direct current consumption of acidic electrolysis is higher, and secondary lead power consumption per ton is higher than pyrogenic process 550KWh up to 600~1000KWh;
(3) corrodibility of acidic electrolysis is big, makes that producer is difficult to accept;
(4) alkaline direct electrolysis method by product is many, as by product PbO 2, complex treatment process; With
(5) alkaline solid phase be coated with the cream method can't continuous mechanized operation, caused the difficulty of actual industrial production.
Summary of the invention
An object of the present invention is to provide the method for the leaded solution reclaiming lead of a kind of electrolysis alkalescence, this method need not to use complexing agent just can directly make plumbous oxide and basic solution complexing.
Another object of the present invention provides a kind of method of the leaded solution reclaiming lead of big electrolysis alkalescence that can significantly cut down the consumption of energy.
A further object of the present invention provides a kind of method that prevents at the leaded solution reclaiming lead of electrolysis alkalescence of anode place formation by product plumbic oxide, thereby puies forward the plumbic rate of recovery, and can generate the by product of industrial value.
Another object of the present invention provides a kind of method that part material can be carried out the leaded solution reclaiming lead of electrolysis alkalescence of cycling and reutilization.
According to an aspect of the present invention, the invention provides a kind of from contain scrap lead the method for reclaiming lead, comprising: lead and oxygenate conversion thereof that (1) will contain in the scrap lead are lead sulfate; (2) described lead sulfate and excess NaOH solution reaction are generated Na 2[Pb (OH) 4], or described lead sulfate contained the lead sulfate that exists in the scrap lead and the excess NaOH solution reaction generates Na with described 2[Pb (OH) 4], to obtain containing Na 2[Pb (OH) 4] and the mixing solutions of NaOH; (3) the described mixing solutions of selectivity ion electrolysis is to generate metallic lead and oxygen; Wherein, excess NaOH solution concentration is 3~10mol/L described in the step (2), and preferably 5.5mol/L, and the temperature of described reaction is 40~116 ℃, preferred 105 ℃.
In one embodiment, described scrap lead comprises lead plaster, PbO waste material, Pb waste material, the PbO of waste lead acid battery 2Waste material, Pb (SO) 4In waste material, the plumbiferous battery production other contains scrap lead, and other field contains scrap lead in producing.
In one embodiment, lead in the lead plaster of described waste lead acid battery and oxide compound thereof and ferrous perchlorate, perchloric acid and the reaction of vitriolic mixed solution are converted into lead sulfate.In this reaction process, utilization of the present invention inserts platinum wire electrode in reactor and the mercurous sulfate electrode carries out degree with monitoring reaction.Preferably, described ferrous perchlorate, perchloric acid and vitriolic concentration are respectively 0.05~1.5mol/L, 0.1~3mol/L and 0.5~12mol/L, and the temperature of reaction of described reaction is 30~95 ℃.
In one embodiment, described sulfuric acid is the mixture of sulfur waste acid, additional sulfuric acid or sulfur waste acid and additional sulfuric acid in the refuse battery.
In one embodiment, the electrolysis in the wherein said step (2) is electrolysis stage by stage, and described electrolysis stage by stage comprises constant-current electrolysis and pulse electrolysis subsequently, and the condition of wherein said constant-current electrolysis is: 60~120 ℃ of electrolyte temperatures; Cathode current density 150~3500A/m 2Anodic current density 400~5000A/m 2Ionic membrane apparent current density 300~4500A/m 2And the condition of described pulse electrolysis is: electrolyte temperature is 40~115 ℃; Cathode current density is 60~2000A/m 2Anodic current density is 100~2900A/m 2The ionic membrane apparent current density is 30~2000A/m 2Pulse duration is 0.01~1s; Dutycycle is 1: 1~1: 2.
In one embodiment, described electrolysis is stage by stage sequentially carried out in constant current mode cationic membrane electrolyzer and pulsed cationic membrane electrolyzer respectively, or sequentially carries out in same cationic membrane electrolyzer.
In one embodiment, further in step (3), add NaOH2H in the mixing solutions after the electrolysis 2O is to separate out Na 2SO 410H 2O is with Na 2SO 410H 2O separates, and the residue mixing solutions that will mainly comprise NaOH is circulated in the step (2).
According to another aspect of the present invention, provide a kind of from the PbO waste material method of reclaiming lead, comprising: (1) generates Na with PbO waste material and excess NaOH solution reaction 2[Pb (OH) 4], to obtain Na 2[Pb (OH) 4] and the mixing solutions of NaOH; (2) the described mixing solutions of electrolysis is to generate metallic lead, and wherein, excess NaOH solution concentration is 3~10mol/L described in the step (1), and the temperature of described reaction is 60~115 ℃.
In one embodiment, the concentration of described excess NaOH is 5.5mol/L, and the temperature of described reaction is 105 ℃.
In one embodiment, the electrolysis in the described step (2) is electrolysis stage by stage, and described electrolysis stage by stage comprises constant-current electrolysis and pulse electrolysis subsequently, and wherein, the condition of described constant-current electrolysis is: 60~120 ℃ of electrolyte temperatures; Cathode current density 150~3500A/m 2Anodic current density 400~5000A/m 2Ionic membrane apparent current density 300~4500A/m 2And the condition of described pulse electrolysis is: electrolyte temperature is 40~115 ℃; Cathode current density is 60~2000A/m 2Anodic current density is 100~2900A/m 2The ionic membrane apparent current density is 30~2000A/m 2Pulse duration is 0.01~1s; Dutycycle is 1: 1~1: 2.
In one embodiment, described electrolysis is stage by stage sequentially carried out in constant current mode cationic membrane electrolyzer and pulsed cationic membrane electrolyzer respectively, or sequentially carries out in same cationic membrane electrolyzer.
In one embodiment, comprise that further the residue mixing solutions that mainly comprises NaOH after the electrolysis is circulated in the step (2) in step (2).
The method that alkaline electrolysis of the present invention contains lead solution reclaiming lead can be converted into highly purified lead and not produce by product such as PbO containing scrap lead efficiently 2, obviously cut down the consumption of energy, avoid the use of hazardous and noxious substances in the removal process and the secondary pollution that causes thereof, and realized the totally-enclosed suitability for industrialized production of serialization.
Description of drawings
Fig. 1 is the method flow diagram of one embodiment of the present invention;
Fig. 2 is the synoptic diagram of ion-exchange membrane electrolyzer of the present invention.
Embodiment
Hereinafter come to describe in more detail illustrative embodiments with reference to the accompanying drawings.Described accompanying drawing is used to illustrate the present invention, but not limits it.
Fig. 1 is the method flow diagram of one embodiment of the present invention.With reference to Fig. 1, waste lead acid battery obtains sulfur waste acid, lead plaster and grid etc. through broken and screening.Lead plaster is converted into lead sulfate with sulfuric acid (sulfur waste acid and additional sulfuric acid) reaction under the katalysis of catalyzer ferrous perchlorate and perchloric acid, and lead sulfate is separated with the mother liquor that comprises ferrous perchlorate, Iron triperchlorate and perchloric acid.In this mother liquor, add iron powder or iron filings with reduction Iron triperchlorate wherein, mother liquor is reclaimed to be used for next circulation subsequently.In the gained lead sulfate, add sodium hydroxide solution, and the reaction generation contains Na under comparatively high temps 2[Pb (OH) 4], NaOH and Na 2SO 4Solution.After with this solution separating, order is carried out constant-current electrolysis and pulse electrolysis, obtaining plumbous at negative electrode and to obtain oxygen at anode, and NaOH in electrolytic solution and Na 2SO 4After the segmentation electrolytic process is finished, comprise in the electrolytic solution of NaOH and sodium sulfate and add NaOH2H 2O separates out the sodium sulfate in the electrolytic solution, and the sodium sulfate of separating out is filtered.To remain NaOH solution reclaims to be used for next circulation.
The invention provides the method for the leaded solution reclaiming lead of a kind of electrolysis alkalescence.Particularly, the invention provides a kind of from contain scrap lead the method for reclaiming lead.The described scrap lead that contains comprises lead plaster, PbO waste material, Pb waste material, PbO in the waste lead acid battery for example 2Waste material, Pb (SO) 4In waste material, the plumbiferous battery production other contains scrap lead, and other field contains scrap lead etc. in producing.Be that example describes the present invention in detail hereinafter with reclaiming lead from the lead plaster of waste lead acid battery.
In one embodiment, the invention provides a kind of from the lead plaster of waste lead acid battery the method for reclaiming lead, comprising: from waste lead acid battery, separate lead plaster process, with lead plaster carry out the process, alkalescence leaching scavenging process of catalyzed conversion, in ion-exchange membrane electrolyzer electrolytic process stage by stage and make the electrolysis mother liquor regeneration turn back to the working cycle of alkali leaching purifying step.
(1) process of separation lead plaster:
With waste lead acid battery with ordinary method as carrying out fragmentation by crusher, and separate by conventional separation method such as density difference and to obtain lead plaster, grid, dividing plate, shell, sulfur waste acid etc.Isolated lead plaster and sulfur waste acid is standby.
(2) catalytic conversion process:
The raw material of catalytic conversion process is a lead plaster, and wherein the lead in the lead plaster is with Pb, PbSO 4, PbO and PbO 2Form of mixtures exist.In this process, the Pb in the lead plaster, PbO and PbO 2Under the katalysis of catalyzer ferrous perchlorate and perchloric acid, be converted into lead sulfate with sulfuric acid reaction.
Catalytic conversion process may further comprise the steps:
(1) with lead plaster with contain ferrous perchlorate, perchloric acid and vitriolic mixing solutions and react so that the Pb in the lead plaster, PbO and PbO 2Generate lead sulfate, wherein ferrous perchlorate, perchloric acid and vitriolic concentration are respectively 0.05~1.5mol/L, 0.1~3mol/L and 0.5~12mol/L, and temperature of reaction is 30~95 ℃.Preferably, ferrous perchlorate, perchloric acid and vitriolic concentration are respectively 0.5mol/L, 0.5mol/L and 5mol/L, and temperature of reaction is 80 ℃.
In the reaction of step (1), H 2SO 4Can be the mixture of sulfur waste acid, additional sulfuric acid or sulfur waste acid and additional sulfuric acid in the refuse battery.The ferrous perchlorate is a Primary Catalysts, and perchloric acid then has been the effect of activation and promotor.Because the reaction of step (1) relates to insoluble PbSO 4Generation, and ferrous perchlorate and perchloric acid can be in reaction process and Pb, PbO and PbO 2Generate the Pb (ClO of high-dissolvability 4) 2But, thereby select for use ferrous perchlorate and perchloric acid as catalyzer accelerated reaction process.
Concrete reaction is as follows:
PbO 2+2Fe(ClO 4) 2+4HClO 4=Pb(ClO 4) 2+2Fe(ClO 4) 3+2H 2O (I)
Pb+2Fe(ClO 4) 3=Pb(ClO 4) 2+2Fe(ClO 4) 2 (II)
PbO+2HClO 4=Pb(ClO 4) 2+H 2O (III)
3Pb(ClO 4) 2+3H 2SO 4=3PbSO 4+6HClO 4 (IV)
Net reaction is:
Pb+PbO+PbO 2+3H 2SO 4=3PbSO 4+3H 2O (V)
In order to guarantee carrying out fully of said process, can after carrying out for some time, reaction in reactor, insert platinum wire electrode and mercurous sulfate electrode with the monitoring reaction process.When the current potential of two electrodes is higher than 0.30~0.35V, can in reaction solution, add a spot of ferrous perchlorate and perchloric acid solution to promote reaction.When current potential is reduced between 0.0~0.3V, show that reaction finishes substantially.
Residual Pb and PbO in lead plaster 2Coupling (is Pb: PbO fully 2Be 1: 1) time, Fe (ClO 4) 2And HClO 4Before and after reaction, do not consume.Since the singularity of refuse battery, residual Pb and PbO in the battery 2Be not lucky 1: 1, PbO normally 2Surplus 0~15%, thereby the ferrous perchlorate may be by the PbO of remnants 2Institute's oxidation generates the Iron triperchlorate.
Reaction soln in the reaction back step (1) comprises other impurity in lead sulfate, ferrous perchlorate, Iron triperchlorate, perchloric acid and the lead plaster, and the lead sulfate in the described reaction soln comprises the PbSO that is present in the lead plaster 4With the PbSO that generates in the described step (1) 4
(2) with process press filtration of the reaction soln in the step (1) or centrifugation, the mother liquor that obtains lead sulfate and comprise ferrous perchlorate, Iron triperchlorate and perchloric acid.The lead sulfate of gained is standby.
(3) in the mother liquor that comprises ferrous perchlorate, Iron triperchlorate and perchloric acid, add iron powder or iron filings so that the Iron triperchlorate is reduced to the ferrous perchlorate, behind additional sulfuric acid, turn back in the step (1) and recycle.
Concrete reaction is as follows:
Fe+2Fe(ClO 4) 3=3Fe(ClO 4) 2 (VI)
(3) alkalescence leaching scavenging process:
The raw material of alkalescence leaching scavenging process is the lead sulfate that obtains in the above catalytic conversion process.In this process, the sodium hydroxide solution of lead sulfate and adding reacts under comparatively high temps and generates Na 2[Pb (OH) 4].
Alkalescence leaching scavenging process may further comprise the steps: excessive NaOH solution reaction generates Na 2[Pb (OH) 4], thereby obtain Na 2[Pb (OH) 4] and the mixing solutions of NaOH
(1) lead sulfate and excessive NaOH solution reaction are generated Na 2[Pb (OH) 4] and Na 2SO 4Thereby, obtain containing Na 2[Pb (OH) 4], Na 2SO 4Mixing solutions with NaOH.Control NaOH concentration is 3~10mol/L in the reaction, and temperature of reaction is 40~116 ℃, and the reaction times is 2~7 hours.NaOH concentration is preferably 5~9mol/L, most preferably is 5.5mol/L.Temperature of reaction is preferably more than 80 ℃, most preferably is more than 105 ℃.Reaction times is preferably 4 hours.
In step (1), lead sulfate at first generates Pb (OH) with the NaOH solution reaction 2, Pb (OH) subsequently 2Generate Na with the NaOH complexing 2[Pb (OH) 4].Concrete reaction is as follows:
PbSO 4+2NaOH=Na 2SO 4+Pb(OH) 2 (VII)
Pb(OH) 2+2NaOH=Na 2[Pb(OH) 4] (VIII)
(2) with mixing solutions sedimentation, filtration and the purification of gained in the step (1), with further removal impurity wherein.Na after the purification 2[Pb (OH) 4], NaOH and Na 2SO 4Mixing solutions standby.
The present inventor finds NaOH and Pb (OH) 2The Na that (or PbO) complexing generates 2[Pb (OH) 4] under comparatively high temps (preferred more than 105 ℃) have very big solubleness, can reach the above concentration of 95g/L.This concentration has satisfied the demand of industrial electrolysis.Yet people study NaOH and Pb (OH) in the lesser temps temperature range usually before this 2The complexing of (or PbO).In this temperature range, Pb (OH) 2(or PbO) solubleness in NaOH solution is very low, maybe needs to add the complexing agent Seignette salt and comes electrolysis again behind the complexing PbO, as described in " liquid caustic soda-potassium sodium tartrate solution galvanic deposit lead " in the background technology.The present inventor finds to be controlled to be 3~10mol/L by the concentration with NaOH, particularly is controlled to be 5.5mol/L, can make NaOH under normal pressure even reach 122 ℃ and also do not seethe with excitement.Find PbO simultaneously behind boiling point, increase severely owing to overcritical effect makes PbO solubleness near water.
Therefore, the present invention adopts and make NaOH and Pb (OH) under comparatively high temps 2(or PbO) direct complexing is to form Na 2[Pb (OH) 4].The advantage of this method is:
(1) Na of Sheng Chenging 2[Pb (OH) 4] solubleness is very high under comparatively high temps, can be used for electrolytic process subsequently, therefore satisfies the demand of industrial electrolysis;
(2) overcome in the current non-selective electrolytic process at a large amount of plumbic oxide of anode by-product, reduced plumbous organic efficiency;
(3) this method need not to use complexing agent such as Seignette salt, therefore can not produce the problem that causes solution resistance increase and liquid waste disposal because of the complexing agent adding, the conservation cost;
(4) NaOH of high density has greatly improved specific conductivity, presses thereby reduce electrolyzer.
(4) electrolytic process stage by stage:
The raw material of electrolytic process (being electrolytic solution) leaches the Na that contains that obtains in the scavenging process for alkalescence stage by stage 2[Pb (OH) 4], NaOH and Na 2SO 4Mixing solutions.The segmentation electrolytic process carries out in ion-exchange membrane electrolyzer, and sequentially comprises constant-current electrolysis and pulse electrolysis.Can carry out constant-current electrolysis earlier in an ion-exchange membrane electrolyzer, be transferred to subsequently and carry out pulse electrolysis in another electrolyzer again, the difference of described two ion-exchange membrane electrolyzers is the power supply difference.By changing power supply, also can in same electrolyzer, sequentially carry out constant-current electrolysis and pulse electrolysis.The electrolysis result obtains lead at negative electrode, obtains oxygen at anode.
Fig. 2 is the synoptic diagram of ion-exchange membrane electrolyzer of the present invention.With reference to Fig. 2, ion-exchange membrane electrolyzer of the present invention comprises direct current (or pulse) power supply 1; Contain Na 2[Pb (OH) 4], NaOH and Na 2SO 4Electrolyte entrance 2; Lead electrode sheet 3; Galvanic deposit lead 4; Lead concentration transmitter 5; Contain NaOH and Na 2SO 4Electrolyte outlet 6; Cationic membrane 7 (as the Nafion cationic membrane); Nickel plating anode 8; NaOH storage tank 9; Crystallization NaOH storage tank 10.
Electrolytic process may further comprise the steps stage by stage:
(being example) to use constant current mode cationic membrane electrolyzer and pulsed cationic membrane electrolyzer respectively
(1) will contain Na 2[Pb (OH) 4], NaOH and Na 2SO 4Electrolytic solution inject constant current mode cationic membrane electrolyzer and carry out constant-current electrolysis, wherein the condition of constant-current electrolysis is: electrolyte temperature is 60~120 ℃, preferred 65~105 ℃, more preferably 75~100 ℃; Cathode current density is 150~3500A/m 2, preferred 300~1000A/m 2, more preferably 400A/m 2Anodic current density is 400~5000A/m 2, preferred 500~4000A/m 2The ionic membrane apparent current density is 300~4500A/m 2
(2) as Pb (OH) 4 2-When concentration is reduced to 20~35g/L (in plumbous oxide), will contain Na 2[Pb (OH) 4], NaOH and Na 2SO 4Electrolytic solution be injected into and carry out pulse electrolysis in the pulsed electrolyzer, until Pb (OH) 4 2-Concentration is less than 3~5g/L (in plumbous oxide), and wherein the condition of pulse electrolysis is: electrolyte temperature is 40~115 ℃, preferred 65~105 ℃, and more preferably 85~100 ℃; Cathode current density is 60~2000A/m 2, preferred 300~1500A/m 2Anodic current density is 100~2900A/m 2, preferred 500~2500A/m 2The ionic membrane apparent current density is 30~2000A/m 2, preferred 50~1500A/m 2Pulse duration is 0.01~1s; Dutycycle is 1: 1~1: 2.
Under electric field action, Pb (OH) 4 2-Formation of deposits galvanic deposit lead 4 on lead electrode sheet 3, OH -The (not shown) that produces oxygen at nickel plating anode 8 places, Na +Move to negative electrode from anode by the selectivity cationic membrane.Adding NaOH at positive terminal in the electrolytic process stage by stage.When the NaOH in the NaOH storage tank too much consumes, in the NaOH storage tank, add crystallization NaOH.Comprise NaOH and sodium sulfate in the electrolytic solution after electrolysis is finished stage by stage.
Concrete reaction is as follows:
Negative electrode: [Pb (OH) 4] 2-+ 2e=Pb+4OH -(IX)
Ionic membrane: 2Na + (anode)→ 2Na + (negative electrode)(X)
Anode: 2OH --2e=1/2O 2+ H 2O (XI)
Total reaction: Na 2[Pb (OH) 4]=Pb+1/2O 2+ 2NaOH (XII)
The present invention utilizes the selective permeation principle of cationic membrane, and promptly cationic membrane allows Na +To cathodic migration, thereby improve the NaOH concentration at negative electrode place from anode, and stop [Pb (OH) 4] 2-From the migration of negative electrode anode, thereby prevent that the anode place generates the by product plumbic oxide in the electrolytic process, and the anode place can generate industrial useful byproducts oxygen.
The electrolysis stage by stage that the present invention adopts can improve electrolytic efficiency and reduce power consumption.Electrolytic deposition is most of plumbous apace during constant-current electrolysis.During pulse electrolysis, adopt the short period of time (0.1s) large-current electric to separate, and then rest for some time (0.5s), the electrolytic solution around the electrode can be enriched to electrode surface like this, then in next cycle electrolysis again.By the pulse electrolysis mode, in the lead ion solution of lower concentration, realize being energy-conservation and electrolysis completely.Because pulse electrolysis is the discontinuity electric current, thereby it has guaranteed electrolytic efficient on the one hand, has guaranteed the electrolysis degree of depth on the other hand.If continue big electric current constant-current electrolysis, certainly will in electrolytic process, be reduced and a large amount of by-product hydrogen by the water of negative electrode, cause lowering efficiency.
The present invention adds NaOH at positive terminal can make holding anode end Na +Concentration, and then keep carrying out continuously of electrolytic reaction, and the NaOH that adds can directly come complexing PbO to use as next round-robin raw material.
The present invention is adding the concentration that crystallization NaOH not only can improve NaOH in the NaOH storage tank during the electrolysis stage by stage in the NaOH storage tank, and can prevent that direct NaOH solid from adding heat release and the boiling phenomenon that causes.Crystallization NaOH (NaOH2H 2O) for example handling the NaOH solid with frozen water obtains.
(5) working cycle:
By adding NaOH2H in the electrolytic solution that after the segmentation electrolytic process is finished, comprises NaOH and sodium sulfate 2O further separates out the sodium sulfate in the electrolytic solution, and the sodium sulfate of separating out is filtered.To remain NaOH solution returns the leaching of above-mentioned alkali and purifies Cheng Jinhang and recycle.
Working cycle may further comprise the steps:
(1) adds crystallization NaOH in the electrolytic solution that contains NaOH and sodium sulfate after electrolysis, progressively separate out Na 2SO 410H 2The O crystal;
(2) electrolytic solution is after filtration behind this sodium sulfate crystal, electrolytic solution (being mainly NaOH) returned above-mentioned alkali leaching purify Cheng Jinhang and recycle.
The present invention can make to adding crystallization NaOH during the working cycle: (1) impels the sodium sulfate in the electrolytic solution to separate out under common-ion effcet, reaches the purpose of the direct reclaim(ed) sulfuric acid sodium of non-evaporation; (2) NaOH that adds directly comes complexing PbO to use as next round-robin raw material; (3) add crystallization NaOH and produce heat release and boiling phenomenon hardly, more help sodium sulfate than noncrystalline NaOH and separate out.
In another embodiment, the invention provides a kind of from the scrap lead that mainly contains PbO the method for reclaiming lead, comprising: alkalescence leaching scavenging process, the electrolytic process stage by stage in ion-exchange membrane electrolyzer and make the electrolysis mother liquor regeneration turn back to the working cycle of alkali leaching purifying step.
(1) alkalescence leaching scavenging process:
Alkalescence leaching scavenging process may further comprise the steps:
(1) directly will mainly contain the scrap lead of PbO and excessive NaOH solution reaction and generate Na 2[Pb (OH) 4], thereby obtain Na 2[Pb (OH) 4] and the mixing solutions of NaOH.Control NaOH concentration is 3~10mol/L in the reaction, and temperature of reaction is 60~115 ℃, and the reaction times is 3~8 hours.NaOH concentration is preferably 5~9mol/L, most preferably is 5.5mol/L.Temperature of reaction is preferably 80~110 ℃, most preferably is 105 ℃.Reaction times is preferably 4 hours.
Concrete reaction is as follows:
PbO+H 2O+2NaOH=Na 2[Pb(OH) 4]
(2) with mixing solutions sedimentation, filtration and the purification of gained in the step (1), with further removal impurity wherein.Na after the purification 2[Pb (OH) 4] and the mixing solutions of NaOH standby.
(2) electrolytic process stage by stage:
Electrolytic process may further comprise the steps stage by stage:
(being example) with the same ion membrane electrolyser that uses different electrical power
(1) with Na 2[Pb (OH) 4] and the mixing solutions of NaOH inject ion-exchange membrane electrolyzer and carry out constant-current electrolysis, wherein the condition of constant-current electrolysis is: electrolyte temperature is 60~120 ℃, preferred 65~105 ℃, more preferably 75~100 ℃; Cathode current density is 150~3500A/m 2, preferred 300~1000A/m 2, more preferably 400A/m 2Anodic current density is 400~5000A/m 2, preferred 500~4000A/m 2The ionic membrane apparent current density is 300~4500A/m 2
(2) as Pb (OH) 4 2-When concentration is reduced to 20~35g/L (in plumbous oxide), constant current power supply is replaced by the pulse power to proceed pulse electrolysis, until Pb (OH) 4 2-Concentration is less than 3~5g/L (in plumbous oxide), and wherein the condition of pulse electrolysis is: electrolyte temperature is 40~115 ℃, preferred 65~105 ℃, and more preferably 85~100 ℃; Cathode current density is 60~2000A/m 2, preferred 300~1500A/m 2Anodic current density is 100~2900A/m 2, preferred 500~2500A/m 2The ionic membrane apparent current density is 30~2000A/m 2, preferred 50~1500A/m 2Pulse duration is 0.01~1s; Dutycycle is 1: 1~1: 2.
Under electric field action, Pb (OH) 4 2-Formation of deposits lead on negative electrode, OH -The place produces oxygen at anode.Comprise NaOH in the electrolytic solution after electrolysis is finished stage by stage.
(3) working cycle:
Working cycle may further comprise the steps:
The electrolyte solution that will comprise NaOH returns above-mentioned alkali leaching purification Cheng Jinhang and recycles.
Embodiment:
Below further specify method of the present invention by specific embodiment.
Embodiment 1
Getting the specification of buying on 10 markets is 12V, 12Ah power truck waste lead acid battery, 45.5 kilograms of series of cells gross weights.Specific implementation process is as follows:
1) with after 10 batteries elder generation process discharge process, puts into crusher in crushing, 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 crusher and ball mill is pulverized successively, sieves with 60 purpose stainless steel meshs subsequently, and bigger lead plaster particle continues to change over to pulverizer to be pulverized, and all sees through screen cloth until all lead plasters.
3) getting sulfur waste acid that 40L (1) process obtains can be through after replenishing a small amount of vitriol oil, it is adjusted to comprise 5mol/L H 2SO 4, 0.5mol/L Fe (ClO 4) 2With 0.5mol/L HClO 4(2) process of getting is sieved 26 kilograms lead plaster powder and waste sulfuric acid solution obtaining and is mixed, and stirs 5 hours down at 80 ℃.In this process, lead, plumbous oxide and plumbic oxide progressively are converted into lead sulfate in the lead plaster under the catalysis of ferrous perchlorate and perchloric acid.Current potential detected and to be 0.42V this moment, showed that a small amount of plumbic oxide is arranged in the reaction solution is residual, added and comprised 3mol/L HClO 4With 0.5mol/L Fe (ClO 4) 2Mixed solution 2L, be reduced to 0.29V until detecting current potential.
4) lead sulfate that obtains after the reaction solution process centrifugation with (3) process, and the mother liquor that contains ferrous perchlorate, Iron triperchlorate and perchloric acid.Obtain regeneration after mother liquor and 1.9 kilograms of iron filings reactions, after replenishing sulfuric acid, turn back to (3) process and recycle.
Reacted lead plaster is separated in whizzer and wash, add 32% the NaOH solution of 280L in the product that press filtration obtains, under 110 ℃, make lead sulfate and sodium hydroxide carry out the engaging sulphate reaction, and complexing leaching reaction takes place simultaneously.In this process, the PbSO of lead plaster 4Almost all change into Na with NaOH 2[Pb (OH) 4].
5) reaction solution that (4) process is obtained carries out the press filtration separation, and obtaining lead tolerance is alkaline electrolysis mother liquor and 0.5 kilogram of residue of 82g/L.By analysis, residue is battery production process adding additives such as barium sulfate substantially.Leaded mother liquor through leaving standstill and deep purifying (promptly after the leaving standstill of routine, using the method for charcoal absorption impurity and micro-filtrate membrane filtration to remove impurity in the solution) after enter and carry out electrolysis in the electrolyzer.Simultaneously for the pattern of the galvanic deposit lead that improves negative electrode, in the electrolysis mother liquor, add weight percent and be 0.15% gelatin and 0.2% DPE-III (electroplating additive is available from Wuhan Yuancheng Technology Development Co., Ltd.) and improve the slickness on plumbous electrolytic process surface.
6) the electrolysis mother liquor is incorporated into secondary lead ion electrolyzer () and carries out electrolysis.Electrolyzer is of a size of: volume is 96 (length) * 22 (wide) * 150 (height) cm 3, the 60W electric blender stirs.Adopting thickness is that the pure stereotype of 1mm and 304 stainless steel plates of nickel plating are respectively negative electrode and anode, and the F4602 of Asahi Chemical Industry ionic membrane is a barrier film, and cell construction is 1 positive 1 negative electrode structure, places the sealed electrolytic cell of lead ion meter and import and export.At first carry out constant-current electrolysis in this electrolyzer, control cathode and anodic current density are 750A/m 2, electrolysis temperature is 95 ℃, electrolysis voltage is 1.53V.After electrolysis time reaches 80min, when this moment, lead concentration was 25g/L after testing, is transferred to electrolyzer (two) and proceeds pulse electrolysis.This moment, pulse duration was 0.02s, and dutycycle is 1: 1, and electrolysis temperature is 95 ℃, and peak impulse voltage is 1.93V.The concentration of plumbous oxide is reduced to below the 4g/L in the electrolysis mother liquor.Electrolysis mother liquor after the electrolysis is cooled to 5 ℃ with electrolytic solution after by additional crystallization NaOH the actual concentrations of NaOH being brought up to 32% once more, and separate out Disodium sulfate decahydrate crystal in the solution this moment.This mother liquor is carried out solid-liquid separation obtain 32% NaOH solution and sodium sulfate crystal, this plumbiferous NaOH mother liquor turns back in the extraction tank again and recycles.
Through test and calculating, negative electrode lead has obtained 20.92 kilograms lead, its purity is 99.991%, current efficiency is 98.9%, the energy consumption of the direct electrolytic process of lead plaster is 595kWh/t (Pb), separate stereotype grid and the lug that obtains in conjunction with shattering process, the comprehensive recovery of battery is 97.2%, all plumbous electrolysis energy consumption 443KWh/t.
Embodiment 2
Getting 1 block specifications is 12V, 54Ah junked-auto lead-acid cell, and 15.5 kilograms of series of cells gross weights, concrete removal process is as follows:
According to (1) and (2) process of embodiment 1, isolate lead plaster, grid, dividing plate and plastics etc.
3) get the sulfur waste acid that the 12L said process obtains it is adjusted the mixing solutions that acidity contains 4.0mol/L sulfuric acid, 1mol/L ferrous perchlorate and 1mol/L perchloric acid.Get 6 kilograms lead plaster powder and waste sulfuric acid solution that the screening of (2) process obtains, the two is mixed, add the mixing solutions of 4.0mol/L sulfuric acid, 0.8mol/L ferrous perchlorate and 0.8mol/L perchloric acid simultaneously, reaction is 4 hours under 85 ℃ of temperature.Stopped reaction when the detection current potential is reduced to 0.25V.
4) lead sulfate that obtains after the reaction solution process centrifugation with (3) process, and the mother liquor that contains ferrous perchlorate, Iron triperchlorate and perchloric acid.Obtain regeneration after mother liquor and 0.39 kilogram of iron filings reaction, after the additional vitriol oil makes concentration be raised to 4mol/L, turn back to (3) process and recycle.
After reacted lead plaster separated and washing, add 35% the NaOH solution of 65L in pressure filter, carry out engaging sulphate and extractive reaction at 112 ℃.In this process, the PbSO of lead plaster 4With NaOH complex reaction taking place, and almost all changes into Na 2[Pb (OH) 4].
5) reaction solution that (4) process is obtained carries out the press filtration separation, and obtaining lead tolerance is alkaline electrolysis mother liquor and 0.2 kilogram of residue of 95g/L.By analysis, residue is the non-plumbous additive that battery production process such as barium sulfate adds substantially.Leaded mother liquor through leaving standstill with deep purifying after enter among electrolyzer () among the embodiment 1 and (two) and carry out electrolysis successively.Simultaneously for the pattern of the galvanic deposit lead that improves negative electrode, in the electrolysis mother liquor, still add weight percent and be 0.2% gelatin and 0.2% DPE-III and improve cathodic process as the galvanic deposit additive.
Control cathode and anodic current density are 200A/m in the electrolytic process 2, electrolysis temperature is 95 ℃, electrolysis voltage is 1.47V.After electrolysis time reaches 2 hours, when this moment, lead concentration was 24g/L after testing, is transferred to electrolyzer (two) and proceeds pulse electrolysis.This moment, pulse duration was 0.017s, and dutycycle is 1: 1, and electrolysis temperature is elevated to 105 ℃, and peak impulse voltage is 2.05V.The concentration of plumbous oxide is reduced to below the 3.5g/L in the electrolysis mother liquor.Electrolysis mother liquor after the electrolysis is cooled to 10 ℃ with electrolytic solution after by additional crystallization NaOH the actual concentrations of NaOH being brought up to 35% once more, and separate out Disodium sulfate decahydrate crystal in the solution this moment.This mother liquor is carried out solid-liquid separation obtain 35% NaOH solution and sodium sulfate crystal, this plumbiferous NaOH mother liquor turns back in the extraction tank again and recycles.
Through test and calculating, negative electrode lead has obtained 4.05 kilograms lead, and its purity is 99.992%, and current efficiency is 99.0%, and the energy consumption of dc electrolysis process is 573kWh/t (Pb), and plumbous comprehensive recovery is 98.5%.Separate stereotype grid and the lug that obtains, the electrolysis energy consumption 425KWh/t of lead per ton in conjunction with shattering process.
Embodiment 3
Get the scrap lead that contains of 2 kilograms of Hebei company lead-acid cell production plants, be ground into powder, after measured for being mainly 95% plumbous oxide (PbO), 3% plumbous and a small amount of clay through ball mill.The secondary lead process is as follows:
1) the above-mentioned scrap lead powder that contains is carried out ball milling after 3 hours in air atmosphere, utilize 60 eye mesh screens to sieve and obtain fine powder, add 29% the NaOH solution of 20L then, under 100 ℃, leach reaction.In this process, complex reaction takes place and generates Na in plumbous oxide that the plumbous oxide in the waste material and a small amount of plumbous oxidation are newly-generated and NaOH 2[Pb (OH) 4].Measure Na through the EDTA chemistry titration 2[Pb (OH) 4] lead tolerance of part is 99g/L, filters the remaining about 0.05 kilogram of argillaceous precipitation in back.
2) the leaded mother liquor that (1) process is obtained carries out electrolysis through entering after purifying in the electrolyzer.For the pattern of the galvanic deposit lead that improves negative electrode, in the electrolysis mother liquor, add weight percent and be 0.2% DPE-III and improve cathodic process as the galvanic deposit additive.
3) carry out electrolysis in electrolyzer, electrolysis temperature is adjusted into 110 ℃, and other condition is carried out electrolysis step by step with embodiment 2, and negative electrode lead has obtained 1.92 kilograms lead, and its purity is 99.992%, and antianode is separated out a large amount of oxygen and carried out emptying process.Electrolytic solution after the electrolysis shows through titrimetry.The residual lead of 2.5g/L.This part is transferred to again in the leaching groove and recycles once more.As calculated, the energy consumption of electrolytic process is 560kWh/t (Pb), and plumbous comprehensive recovery is 97.6%.
Method of the present invention can be directly obtains purity up to the high purity lead more than 99.99% obtaining negative electrode, and the oxygen of industrial value is arranged at the anode by-product simultaneously.Lead recovery for the automobile lead-acid cell is generally 97.2~98.9%, and the lead recovery of power truck fully-closed battery reaches 97.1~99.2%.According to the current density of the situation of scrapping, duration of service, lead paste formula and the electrolytic process of lead-acid cell, the power consumption of producing secondary lead per ton is 380~490KWh.Compared with prior art, can obviously cut down the consumption of energy, avoid the use of hazardous and noxious substances in the removal process and the secondary pollution that causes thereof, be a kind of secondary lead method of cleaning.
More than describe the present invention in detail by preferred implementation and specific embodiment, yet it will be understood by those skilled in the art that scope of the present invention is not limited thereto, anyly do not deviate from modification of the present invention or change all within the scope of the invention.

Claims (10)

1. the method for a reclaiming lead from contain scrap lead comprises:
(1) plumbous and/or its oxygenate conversion that will contain in the scrap lead is a lead sulfate;
(2) lead sulfate and the excess NaOH solution reaction that is transformed generated Na 2[Pb (OH) 4], or the lead sulfate that transformed contained the lead sulfate and the excess NaOH solution reaction that exist in the scrap lead and generate Na with described 2[Pb (OH) 4], obtain containing Na 2[Pb (OH) 4] and the mixing solutions of NaOH; With
(3) the described mixing solutions of selectivity ion electrolysis to be generating metallic lead and oxygen,
Wherein, excess NaOH solution concentration is 3~10mol/L described in the step (2), is preferably 5.5mol/L, and the temperature of described reaction is 40~116 ℃, is preferably 105 ℃.
2. as claimed in claim 1 from contain scrap lead the method for reclaiming lead, the wherein said scrap lead that contains comprises lead plaster, PbO waste material, Pb waste material, the PbO that obtains from waste lead acid battery 2Waste material, Pb (SO) 4In waste material and the leaded battery production other contains at least a in the scrap lead.
3. as claimed in claim 2 from contain scrap lead the method for reclaiming lead, wherein in step (1), with lead in the described lead plaster and oxide compound thereof and contain ferrous perchlorate, perchloric acid and the reaction of vitriolic mixed solution is converted into lead sulfate, wherein said ferrous perchlorate, perchloric acid and vitriolic concentration are respectively 0.05~1.5mol/L, 0.1~3mol/L and 0.5~12mol/L, wherein said sulfuric acid is the sulfur waste acid that obtains from described waste lead acid battery, or is the mixture of described sulfur waste acid and additional sulfuric acid.
As in the claim 1 to 3 each described from contain scrap lead the method for reclaiming lead, wherein the described selectivity ion electrolysis in the step (3) is the electrolysis stage by stage that comprises constant-current electrolysis and pulse electrolysis subsequently, wherein,
The condition of described constant-current electrolysis is: 60~120 ℃ of electrolyte temperatures; Cathode current density 150~3500A/m 2Anodic current density 400~5000A/m 2Ionic membrane apparent current density 300~4500A/m 2And
The condition of described pulse electrolysis is: electrolyte temperature is 40~115 ℃; Cathode current density is 60~2000A/m 2Anodic current density is 100~2900A/m 2The ionic membrane apparent current density is 30~2000A/m 2Pulse duration is 0.01~1s; Dutycycle is 1: 1~1: 2.
5. as claimed in claim 4 from contain scrap lead the method for reclaiming lead, described electrolysis is stage by stage sequentially carried out in constant current mode cationic membrane electrolyzer and pulsed cationic membrane electrolyzer, or sequentially carries out in same cationic membrane electrolyzer.
As claim 1 or 5 described from contain scrap lead the method for reclaiming lead, further comprise in step (3) adding NaOH2H in the mixing solutions after the electrolysis 2O is to separate out Na 2SO 410H 2O is with Na 2SO 410H 2O separates, and the residue mixing solutions that will mainly comprise NaOH is circulated in the step (2).
7. the method for a reclaiming lead from the PbO waste material comprises:
(1) PbO waste material and excess NaOH solution reaction are generated Na 2[Pb (OH) 4], obtain containing Na 2[Pb (OH) 4] and the mixing solutions of NaOH;
(2) the described mixing solutions of selectivity ion electrolysis is to generate metallic lead;
Wherein, excess NaOH solution concentration is 3~10mol/L described in the step (1), and preferably 5.5mol/L, and the temperature of described reaction is 60~115 ℃, preferred 105 ℃.
8. the method that from the PbO waste material, reclaims metallic lead as claimed in claim 7, wherein the described selectivity ion electrolysis in the step (2) is the electrolysis stage by stage that comprises constant-current electrolysis and pulse electrolysis subsequently,
Wherein, the condition of described constant-current electrolysis is: 60~120 ℃ of electrolyte temperatures; Cathode current density 150~3500A/m 2Anodic current density 400~5000A/m 2Ionic membrane apparent current density 300~4500A/m 2And
The condition of described pulse electrolysis is: electrolyte temperature is 40~115 ℃; Cathode current density is 60~2000A/m 2Anodic current density is 100~2900A/m 2The ionic membrane apparent current density is 30~2000A/m 2Pulse duration is 0.01~1s; Dutycycle is 1: 1~1: 2.
9. the method that reclaims metallic lead from the PbO waste material as claimed in claim 8, wherein said electrolysis is stage by stage sequentially carried out in constant current mode cationic membrane electrolyzer and pulsed cationic membrane electrolyzer, or sequentially carries out in same cationic membrane electrolyzer.
10. as claim 7 or the 9 described methods that from the PbO waste material, reclaim metallic lead, further comprise the residue mixing solutions that mainly comprises NaOH after the electrolysis in the step (2) is circulated in the step (2).
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