CN101250720B - Method for electrolytic reduction and regeneration of lead resource in lead paste in waste lead acid accumulator - Google Patents
Method for electrolytic reduction and regeneration of lead resource in lead paste in waste lead acid accumulator Download PDFInfo
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- CN101250720B CN101250720B CN200710157084XA CN200710157084A CN101250720B CN 101250720 B CN101250720 B CN 101250720B CN 200710157084X A CN200710157084X A CN 200710157084XA CN 200710157084 A CN200710157084 A CN 200710157084A CN 101250720 B CN101250720 B CN 101250720B
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for electrolyzing and regenerating lead resources in leaded paste mud of waste lead-acid batteries under normal temperature through using a whole wet method, which comprises following steps: processing the waste lead-acid batteries to obtain the leaded paste mud, taking nitric acid as accelerant, reacting with sulfuric acid solution, completely transforming the component of lead in the leaded paste mud into lead sulfate, adding the lead sulfate into sulfuric acid solution and fully stirring, then, using a pump to input the lead sulfate into an electrolysis bath which works in a continuous mode, controlling the fluid velocity to be 0.1-0.4m/s, fluidizing lead sulfate particles in a cathode chamber, realizing sufficient contact between the lead sulfate particles and a cathode feedback electrode, and electrolyzing and reducing to obtain electrolytic lead. In the electrolysis process of the invention, lead dioxide is not precipitated on the surface of an anode, the electrolysis process does not have dendrite short circuit, and completely solves the problem that the lead dioxide is generated on the anode in the traditional electrolysis process, simultaneously, since the electrolysis bath which works in the continuous mode is adopted, the working efficiency is high, the investment and the operational cost are low, and the method is suitable for industrial production.
Description
(1) technical field
What the present invention relates to is a kind of method that full wet method normal temperature electrolytic regeneration lead-acid accumulator contains lead plaster mud lead resource that is used for.
(2) background technology is present, and pyrogenic process, fiery wet method coupling and full wet method electrolysis for production technology have been adopted in the recovery of lead resource in the lead-acid accumulator.In full wet method electrolysis for production technology, typical technological line has: (1) acid solubility lead salt electrodeposition technology; (2) liquid caustic soda-potassium sodium tartrate solution electrodeposition technology; (3) solid phase electrolysis tech.
Typical technology has the Rolla research centre patent U.S.Patent of U.S. mineral bureau 4,272,340 in the acid solubility lead salt electrodeposition technology; The Italy Engitec U.S.Patent4 of house journal, 769,116; The Italy Ginatta U.S.Patent of house journal 4,451,340.Above-mentioned technology has all adopted fluorine-containing silicofluoric acid or fluoroboric acid medium, the plumbum ion concentration height, and fluorine silicon (boron) hydrochlorate and free fluorine silicon (boron) acid concentration height, the lead ion of waste liquid is seriously polluted.In addition, the fluorochemicals solution of high density itself also is a kind of more serious pollutent.Moreover the possibility of separating out plumbic oxide on the anode is big, and separating out of plumbic oxide causes material to return the processing load greatly, is equivalent to partial material and is in idling conditions, reduced utilization rate of electrical and production efficiency significantly.Separate out plumbic oxide for reducing anode, taked some measures, but can not eliminate separating out of plumbic oxide on the anode at present.
The technology that Chen Wei equality has proposed a kind of " liquid caustic soda-potassium sodium tartrate solution electrodeposition lead " (Chen Weiping, Tian Yizhuan, Yang Xia etc. waste lead accumulator slurry recovery technology research [J]. non-ferrous metal, 1997,49 (4): 64-67.), in this technology, cathode current density is lower, is generally 150-250A/m
2, the space-time yield of electrochemical reactor is lower, and occupation area of equipment is big, fixed investment and working cost height.The lead that negative electrode is separated out in the electrolytic deposition process is the very high spongy lead of a kind of surface-area, forms dendrite easily, causes the anode and cathode short circuit.
Chemical Industry ﹠ Metallrygy Research Office of CAS developed the plumbous technology of a kind of solid phase electrolytic regeneration (Lu Keyuan. the new technology of solid phase electrolytic process---a kind of secondary lead [J]. non-ferrous metal regeneration with utilize, 2005,12,19-20.), its principle is to have utilized lead sulfate, plumbous oxide, the plumbic oxide cathodic reduction reaction in alkaline medium.Because lead-containing material through the desulfurization pre-treatment, can not generate sulfate ion in the electrolytic process simultaneously, causes the progressively accumulation of sulfate ion.The batch operation pattern has been adopted in production, needs after electrolytic reduction is finished to hang out negative plate and take out plumbous mud from electric groove, and the labor operation amount is excessive, and production efficiency is lower.Because the negative plate mud layer is thicker, current efficiency is relatively low, generally about 85%.
(3) summary of the invention
The technical problem to be solved in the present invention is: the novel process that proposes to contain in a kind of electrolytic process regeneration lead-acid accumulator lead resource in the lead plaster mud, adopt continuous operation mode, in the electrolytic process, anode surface is not separated out plumbic oxide, no dendrite short circuit, thoroughly solve the problem that generates plumbic oxide in traditional electrodeposition process on the anode, technology is simple, production efficiency is high.
The present invention solves the scheme that above technical problem adopts: lead-acid accumulator handle obtain contain lead plaster mud, be promotor with the salpeter solution, after the sulphuric acid soln reaction, the plumbous composition that will contain in the lead plaster mud all is converted into lead sulfate; Lead sulfate is handled with dilute sulphuric acid, fully stirred, and with the electrolyzer of pump input continuously-running duty, the controlling flow rate of flow of fluid makes the lead sulfate particle fluidized of cathode compartment, realizes that the lead sulfate particle fully contacts with the fixing negative electrode of presenting, and carries out electrolytic reduction and obtains electrolytic lead.
It is as follows that described lead-acid accumulator is handled the step that obtains containing lead plaster mud: lead-acid accumulator is carried out fragmentation, grinding, gravitational segregation, obtain containing lead plaster mud.Containing in the lead plaster mud of obtaining is plumbous with Pb, PbO, PbO
2, PbSO
4Form exists.
Particularly, the described full wet method electrolytic reduction regeneration lead-acid accumulator method that contains lead resource in the lead plaster mud may further comprise the steps:
(1) lead-acid accumulator handle obtain contain lead plaster mud, with the salpeter solution is promotor, in the aqueous solution, react with sulphuric acid soln A, described reaction is carried out according to following steps: add salpeter solution earlier in containing lead plaster mud, making concentration of nitric acid is 1～12mol/L, stirring reaction 0.5～5h, and then adding sulphuric acid soln A, stirring reaction 0.5～2h, obtain the sedimentary mixed solution of sulfur-bearing lead plumbate, filter, get filtrate and filter cake, filter cake is the lead sulfate precipitation, and filtrate is reusable handles containing lead plaster mud in this step; Describedly contain lead plaster mud and the vitriolic mass ratio is 3～8: 1.
(2) lead sulfate with step (1) gained adds among the sulphuric acid soln B, adjusting the vitriolic final concentration is 0.1～5.0%, the content of lead sulfate is 150～250g/L, fully stir continuously, and with the cathode compartment of pump input continuously-running duty electrolyzer as cathode compartment electrolytic solution, the controlling flow rate of flow of fluid is 0.1～0.4m/s, makes the lead sulfate particle fluidized of cathode compartment, obtains electrolytic lead at cathode compartment through electrolytic reduction; Initial stage at electrolytic reduction adds 30～50g/L lead powder in cathode compartment electrolytic solution, described negative electrode adopts the fluidized bed structure, by fixing feedback negative electrode conduction current; Described negative electrode and anode are separated with mechanical diaphragm, and described barrier film adopts mineral membrane, organic high molecular layer or inorganic organic polymer composite membrane; The control of electrolysis process condition is as follows: electrolyte temperature is 20～70 ℃, and sulfuric acid concentration is 0.1～5.0% in the maintenance cathode compartment electrolytic solution, and sulfuric acid concentration is 5～20% in the electrolytic solution of holding anode chamber, and fixing feedback negative electrode apparent current density is 100～400A/M
2, the anode apparent current density is 200～1000A/M
2
The anode of described electrolyzer is recommended as the pure lead pipe of plastic lining, and fixing feedback negative electrode is recommended as the lead plating stainless steel bar; Described barrier film preferably polyethylene, polypropylene porous film.
Particularly, the electrolyzer of described continuously-running duty comprises electrolyzer, be arranged on electrode and electrolysis material storage tank in the electrolyzer, described upper part of the electrolytic cell major trough body is a column structure, the bottom is an inverted pyramidal structures, column structure and inverted pyramidal structures junction are provided with fluid flow rate uniform distribution plate, vertically arrange the anode tube and the fixing feedback cathode bar that are parallel to each other in the major trough, described fixedly feedback cathode bar and anode tube staggered arrangement, separate with the porous mechanical membrane between fixing feedback cathode bar and the anode tube, bottom of electrolytic tank is provided with opening for feed, upper part of the electrolytic cell is provided with discharge port, described opening for feed is connected with electrolysis material storage tank by recycle pump, described discharge port is connected with electrolysis material storage tank, and described electrolysis material storage tank and electrolyzer can be formed electrolysis material circulation-supplied system by recycle pump.
Nitric acid is as promotor in step (1), and the lead that its role is to contain in the lead plaster mud is converted into lead, and after sulphuric acid soln replenished, the nitric acid amount kept constant substantially in the treatment solution.
Above-mentioned steps (2) lead sulfate adds among the sulphuric acid soln B, is a lasting process to electrolytic reaction, both mixtures to stir constantly and with the successive form with the cathode compartment of the electrolyzer of pump input continuously-running duty as cathode compartment electrolytic solution.
In step (2) electrolytic process, at the incunabulum of electrolytic reduction, need to add the lead powder of 30～50g/L in the cathode compartment electrolytic solution, preferred size is at 1～20 micron thin lead powder, to increase the electroconductibility of solids in the electrolytic solution when the present invention uses; After electrolytic reaction,, do not need to continue to add thin lead powder owing to produced increasing electrolysis lead powder.
Because the anolyte compartment has H+ to generate in the electrolytic process, for sulfuric acid concentration in the electrolytic solution of holding anode chamber in 5～20% scopes, when sulfuric acid concentration meets or exceeds 20%, electrolytic solution in the anolyte compartment need be extracted out, and benefit is gone into isopyknic deionized water simultaneously, sulfuric acid concentration in anolyte compartment's electrolytic solution is reduced to about 5%, and said process needs periodically to implement.The sulfuric acid of extracting out can contain lead plaster argillization material for refuse battery and transform, and realizes recycle.
Because understanding some, the hydrogen ion in the anolyte compartment sees through barrier film, enter cathode compartment, cause that acidity slowly increases in the cathode compartment, when sulfuric acid concentration in the cathode compartment electrolytic solution surpasses set processing range, in cathode compartment, need to add the 30-40% sodium hydroxide solution, sulfuric acid concentration is transferred in the processing range; In electrolytic process, will have sodium sulfate in the cathode compartment electrolytic solution and build up, can adopt the electrodialytic method desalination, the concentration of sodium sulfate is maintained below the 10g/L.The electrodialytic desalting method is as follows: when sodium sulfate concentration surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously, the treatment solution of being extracted out in the electrolysis material storage tank is filtered, filter residue returns electrolysis material storage tank again; Filtrate is stocked and is used for supply cathode compartment electrolyte circulation system through about electrodialysis unit desalination to 1%.Said process needs periodically to implement.For realizing control, electrolytic solution intermediate ion concentration is implemented regularly to detect in the above-mentioned electrolytic process to concentration.The detection of ionic concn can be adopted ordinary method.Detect usable acid alkali titration etc. such as sulfuric acid concentration, sodium sulfate concentration detects and can obtain the wherein concentration of sodium sulfate by detecting sulfate concentration and sulfuric acid concentration.
As previously mentioned, contain in the lead plaster mud plumbous with Pb, PbO, PbO
2, PbSO
4Form exists, when above-mentioned material handling fully reacts back plumbic oxide surplus, mixed solution is brown, then step (1) contains in the sedimentary mixed solution of lead sulfate and needs to add the plumbic oxide transforming agent, in 25～65 ℃ of stirring reactions 0.5～2 hour, to the mixed solution gray, show that when the mixed solution gray the plumbous composition that contains in the lead plaster mud all is converted into lead sulfate; Described plumbic oxide transforming agent is for promoting to contain the compound that tetravalence lead in the lead plaster mud is converted into lead.
It is one of following that described plumbic oxide transforming agent can use: ammonium sulphite, S-WAT, hydrogen peroxide.
Further, step (1) to contain lead plaster mud and nitric acid, the vitriolic temperature of reaction does not have special requirement, below boiling temperature, all can react, but generally helping reaction under higher temperature carries out, preferred 20～65 ℃, more preferably 40～60, step (1) contains lead plaster mud and the salpeter solution reaction times is preferably 1～2h, then with preferred 1～2h of sulfuric acid reaction time.
The described sulphuric acid soln A of step (1) concentration is preferably 20～80%, and more preferably 30～60%, further preferred 40～50%.
Preferably, step (1) is described contains lead plaster mud and the vitriolic mass ratio is 6: 1.
The described electrolysis process condition optimization control of step (2) is as follows: electrolyte temperature is 25～45 ℃, sulfuric acid concentration is 0.1～1.0% in the maintenance cathode compartment electrolytic solution, sulfuric acid concentration is 5～10% in anolyte compartment's electrolytic solution, and fixing feedback negative electrode apparent current density is 150～250A/M
2, the anode apparent current density is 400～600A/M
2
All percentage concentrations of indication of the present invention are mass percentage concentration.
The described method of concrete recommendation is carried out according to following steps:
(1) lead-acid accumulator handle obtain contain lead plaster mud, with the salpeter solution is promotor, in the aqueous solution, react with sulphuric acid soln A, described reaction is carried out according to following steps: add salpeter solution earlier in containing lead plaster mud, making concentration of nitric acid is 3～8mol/L, and control reaction temperature is 40～60 ℃, stirring reaction 1～2h, and then add 30～60% sulphuric acid soln A, stirring reaction 1～2h.When the reaction solution gray, explanation reacts completely, and then with the reaction solution direct filtration, obtains lead sulfate; When reaction solution is brown, illustrate and also contain tetravalence lead in the reaction solution, then add the plumbic oxide transforming agent again, in 25～65 ℃ of stirring reactions 0.5～2 hour, to the mixed solution gray, filter, get filtrate and filter cake, filter cake is the lead sulfate throw out, and filtrate is re-used in this step and handles containing lead plaster mud; Describedly contain lead plaster mud and the vitriolic mass ratio is 6: 1.
(2) lead sulfate with step (1) gained adds among the sulphuric acid soln B, adjusting the vitriolic final concentration is 0.1～1.0%, the content of lead sulfate is 150～200g/L, fully stir continuously, import the cathode compartment of continuously-running duty electrolyzer as cathode compartment electrolytic solution with pump simultaneously, the controlling flow rate of flow of fluid is 0.2m/s, makes the lead sulfate particle fluidized of cathode compartment, obtains electrolytic lead through electrolytic reduction; In cathode compartment electrolytic solution, add 30～50/L lead powder at the electrolytic reduction initial stage, the control of electrolysis process condition is as follows: electrolyte temperature is 25～45 ℃, sulfuric acid concentration is 0.1～1.0% in the maintenance cathode compartment electrolytic solution, sulfuric acid concentration is 5～20% in anolyte compartment's electrolytic solution, and fixing feedback negative electrode apparent current density is 150～250A/M
2, the anode apparent current density is 400～600A/M
2In the electrolytic process when sulfuric acid concentration meets or exceeds 20% in anolyte compartment's electrolytic solution, need carry out anolyte compartment's electrolytic solution adjustment, described anolyte compartment electrolytic solution is adjusted into: the electrolytic solution in the anolyte compartment is extracted out, and benefit is gone into isopyknic deionized water simultaneously, sulfuric acid concentration in anolyte compartment's electrolytic solution is reduced to about 5%, said process needs periodically to implement, and is 5～20% with the sulfuric acid concentration that guarantees the anolyte compartment.When sulfuric acid concentration in the cathode compartment electrolytic solution surpasses 1.0%, in cathode compartment, need to add the 30-40% sodium hydroxide solution, sulfuric acid concentration is transferred in the processing range; When sodium sulfate concentration in the cathode compartment surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously, the treatment solution of being extracted out in the electrolysis material storage tank is filtered, filter residue returns electrolysis material storage tank again; Filtrate is stocked and is used for supply cathode compartment electrolyte circulation system through about electrodialysis unit desalination to 1%.The adjustment process of sulfuric acid concentration needs periodically to implement in above-mentioned cathode compartment electrolytic solution, the anolyte compartment's electrolytic solution.The water content that contains lead plaster mud of indication of the present invention is in 5～15% scopes.
Compare with existing technology, beneficial effect of the present invention is embodied in following aspect:
(1) in the electrolytic process, anode surface is not separated out plumbic oxide, and no dendrite short circuit has thoroughly solved the problem that generates plumbic oxide in traditional electrodeposition process on the anode.And the processing that contains lead plaster mud do not need to carry out desulfurization and transforms, and do not consume alkali; The dilution heat of sulfuric acid that produces in the electrolytic process can contain lead plaster argillization material cycle of treatment for refuse battery and use.
(2) electrolyzer of this process using continuously-running duty can be realized continuously feeding, the continuous operator scheme of discharging, and no cathode plate is safeguarded complicated problems, and the work workload is little, the production efficiency height.And this electric tank working electric current is big, the space-time yield height, and occupation area of equipment is little, and fixed investment and working cost are low.
(4) specific embodiment
Further set forth technical scheme of the present invention with specific embodiment below, but protection scope of the present invention is not limited thereto.
Embodiment 1
The electrolyzer of the continuously-running duty that present embodiment adopts comprises electrolyzer, be arranged on electrode and electrolysis material storage tank in the electrolyzer, described upper part of the electrolytic cell major trough body is a column structure, the bottom is an inverted pyramidal structures, column structure and inverted pyramidal structures junction are provided with fluid flow rate uniform distribution plate, vertically arrange the anode tube and the fixing feedback cathode bar that are parallel to each other in the major trough, described fixedly feedback cathode bar and anode tube staggered arrangement, separate with the porous mechanical membrane between fixing feedback cathode bar and the anode tube, bottom of electrolytic tank is provided with opening for feed, upper part of the electrolytic cell is provided with discharge port, described opening for feed is connected with electrolysis material storage tank by recycle pump, described discharge port is connected with electrolysis material storage tank, and described electrolysis material storage tank and electrolyzer can be formed electrolysis material circulation-supplied system by recycle pump.Anode tube is the pure lead pipe of plastic lining, and fixing feedback cathode bar is the lead plating stainless steel bar; Described barrier film adopts polyethylene, polypropylene porous film.
Get lead-acid accumulator handle obtain contain lead plaster mud (water content 12%) 200kg, put into reactor, add 7.5% salpeter solution 300kg, concentration of nitric acid is about 1.1mol/L in this moment treatment solution; Control treatment solution temperature is 60-65 ℃, and stirring reaction added 80% sulfuric acid 40kg after 3 hours, and further stirring reaction generated the lead sulfate precipitation after 1 hour; Because material handling is brown, the ammonium sulfite solution 60kg that adds plumbic oxide transforming agent 15%, stirring reaction 2 hours, until the mixed solution gray, the plumbous composition that will contain in the lead plaster mud all is converted into highly purified lead sulfate, filters, get filter residue, get highly purified lead sulfate throw out, weight is amounted to into the about 203kg of siccative, and filtrate is re-used in this step and handles containing lead plaster mud.
Get lead sulfate throw out 50kg, join in 300kg 0.5% sulphuric acid soln, fully stir continuously, import the electric tank cathode chamber as cathode compartment electrolytic solution with pump simultaneously, the controlling flow rate of flow of fluid is about 0.2m/s, make the lead sulfate particle fluidized of cathode compartment, realize that the lead sulfate particle fully contacts with fixing feedback negative electrode.In the electrolytic process, the lead sulfate throw out adds in the electrolytic solution storage tank with intermittent mode, and its add-on is for amounting to into about siccative 2.8kg/h.The control of electrolysis process condition is as follows: electrolyte temperature is 20～25 ℃, sulfuric acid concentration is 0.3～1.0% in the cathode compartment electrolytic solution, sulfuric acid concentration is 5～20% in anolyte compartment's electrolytic solution, when sulfuric acid concentration meets or exceeds 20%, electrolytic solution in the anolyte compartment need be extracted out, and mend isopyknic deionized water simultaneously, sulfuric acid concentration in anolyte compartment's electrolytic solution is reduced to about 5%; When sulfuric acid concentration in the cathode compartment electrolytic solution surpasses 1.0%, in cathode compartment, need to add the 30-40% sodium hydroxide solution, sulfuric acid concentration is transferred in the processing range; When sodium sulfate concentration in the cathode compartment surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously, the treatment solution of being extracted out in the electrolysis material storage tank is filtered, filter residue returns electrolysis material storage tank again; Filtrate is stocked and is used for supply cathode compartment electrolyte circulation system through about electrodialysis unit desalination to 1%.The adjustment process of sulfuric acid concentration needs periodically to implement in above-mentioned cathode compartment electrolytic solution, the anolyte compartment's electrolytic solution.
Fixing feedback negative electrode apparent current density is 150A/M
2, the anode apparent current density is 400A/M
2, the working current of electrochemical reactor is 500A.
In the above-mentioned electrolytic process, at the incunabulum of electrolytic reduction, add the thin lead powder of 150g in the cathode compartment electrolytic solution, to increase the electroconductibility of solids in the electrolytic solution; After electrolytic reaction,, need not to continue to add thin lead powder owing to produced increasing electrolysis lead powder.
Adopt present technique, electrolytic reduction 12h, electrolysis finishes the back separation and obtains the about 19.7kg of electrolysis lead powder; Bath voltage is the 2.92-3.15 volt, and current efficiency is about 84%, and direct current consumption is about the 950kWh/ ton, and electrolysis lead powder test purity behind the fusing blocking reaches more than 99.99%.
Embodiment 2
The electrolyzer of the continuously-running duty that present embodiment adopts is with embodiment 1.
Get lead-acid accumulator handle obtain contain lead plaster mud (water content 15%) 500kg, add in the reactor, add 20% salpeter solution 300kg, concentration of nitric acid is about 3.0mol/L in this moment treatment solution; Control treatment solution temperature is 50-55 ℃, and stirring reaction added 30% sulfuric acid 340kg after 1.5 hours, and further stirring reaction generated the lead sulfate precipitation after 1.5 hours; Because material handling is brown, the ammonium sulfite solution 200kg that adds plumbic oxide transforming agent 20%, stirring reaction 2 hours, the plumbous composition that will contain in the lead plaster mud all is converted into highly purified lead sulfate, filter, get filter residue, get highly purified lead sulfate throw out, weight is amounted to into the about 507kg of siccative, and filtrate is re-used in this step and handles containing lead plaster mud.
Get lead sulfate throw out 50kg, join in 300kg 1.0% sulphuric acid soln, fully stir continuously, import the electric tank cathode chamber as cathode compartment electrolytic solution with pump simultaneously, the controlling flow rate of flow of fluid is 0.4m/s, make the lead sulfate particle fluidized of cathode compartment, realize that the lead sulfate particle fully contacts with fixing feedback negative electrode.In the electrolytic process, lead sulfate adds in the electrolytic solution storage tank with intermittent mode, and its add-on is for amounting to into siccative 4.2kg/h.The control of electrolysis process condition is as follows: temperature is 45-50 ℃, sulfuric acid concentration is 0.5-1.5% in the cathode compartment electrolytic solution, sulfuric acid concentration is 5-20% in anolyte compartment's electrolytic solution, when sulfuric acid concentration meets or exceeds 30%, electrolytic solution in the anolyte compartment need be extracted out, and mend isopyknic deionized water simultaneously, sulfuric acid concentration in anolyte compartment's electrolytic solution is reduced to about 5%; When sulfuric acid concentration in the cathode compartment electrolytic solution surpasses 1.5%, in cathode compartment, need to add the 30-40% sodium hydroxide solution, sulfuric acid concentration is transferred in the processing range; When sodium sulfate concentration in the cathode compartment surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously, the treatment solution of being extracted out in the electrolysis material storage tank is filtered, filter residue returns electrolysis material storage tank again; Filtrate is stocked and is used for supply cathode compartment electrolyte circulation system through about electrodialysis unit desalination to 1%.The adjustment process of sulfuric acid concentration needs periodically to implement in above-mentioned cathode compartment electrolytic solution, the anolyte compartment's electrolytic solution.
Fixing feedback negative electrode apparent current density is 225A/M
2, the anode apparent current density is 600A/M
2, the working current of electrochemical reactor is 750A.
In the above-mentioned electrolytic process, at the incunabulum of electrolytic reduction, add the thin lead powder of 90g in the cathode compartment electrolytic solution, to increase the electroconductibility of solids in the electrolytic solution; After electrolytic reaction,, need not to continue to add thin lead powder owing to produced increasing electrolysis lead powder.
Adopt present technique, electrolytic reduction 12h, electrolysis finishes the back separation and obtains the about 29.1kg of electrolysis lead powder; Bath voltage is the 2.90-3.10 volt, and current efficiency is about 83%, and direct current consumption is about the 960kWh/ ton; Electrolysis lead powder test purity behind the fusing blocking reaches more than 99.99%.
Embodiment 3
The electrolyzer of the continuously-running duty that present embodiment adopts is with embodiment 1.
Get lead-acid accumulator handle obtain contain lead plaster mud (water content 5%) 200kg, put into reactor, add 42% salpeter solution 60kg, concentration of nitric acid is about 7.5mol/L in this moment treatment solution; Control treatment solution temperature is 35-40 ℃, and stirring reaction added 60% sulfuric acid 90kg after 1.5 hours, and further stirring reaction generated the lead sulfate precipitation after 2 hours; Because material handling is brown, the ammonium sulfite solution 40kg that adds plumbic oxide transforming agent 25%, stirring reaction 1.5 hours, until the mixed solution gray, the plumbous composition that will contain in the lead plaster mud all is converted into highly purified lead sulfate, filters, get filter residue, get highly purified lead sulfate throw out, weight is amounted to into the about 233kg of siccative, and filtrate is re-used in this step and handles containing lead plaster mud.
Get lead sulfate throw out 50kg, join in 300kg 3% sulphuric acid soln, fully stir continuously, import the electric tank cathode chamber as cathode compartment electrolytic solution with pump simultaneously, the controlling flow rate of flow of fluid is about 0.2m/s, make the lead sulfate particle fluidized of cathode compartment, realize that the lead sulfate particle fully contacts with fixing feedback negative electrode.In the electrolytic process, the lead sulfate throw out adds in the electrolytic solution storage tank with intermittent mode, and its add-on is for amounting to into about siccative 2.8kg/h.The control of electrolysis process condition is as follows: electrolyte temperature is 30～35 ℃, sulfuric acid concentration is 2.5～3.5% in the cathode compartment electrolytic solution, sulfuric acid concentration is 5～20% in anolyte compartment's electrolytic solution, when sulfuric acid concentration meets or exceeds 20%, electrolytic solution in the anolyte compartment need be extracted out, and mend isopyknic deionized water simultaneously, sulfuric acid concentration in anolyte compartment's electrolytic solution is reduced to about 5%; When sulfuric acid concentration in the cathode compartment electrolytic solution surpasses 3.5%, in cathode compartment, need to add the 30-40% sodium hydroxide solution, sulfuric acid concentration is transferred in the processing range; When sodium sulfate concentration in the cathode compartment surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously, the treatment solution of being extracted out in the electrolysis material storage tank is filtered, filter residue returns electrolysis material storage tank again; Filtrate is stocked and is used for supply cathode compartment electrolyte circulation system through about electrodialysis unit desalination to 1%.The adjustment process of sulfuric acid concentration needs periodically to implement in above-mentioned cathode compartment electrolytic solution, the anolyte compartment's electrolytic solution.
Fixing feedback negative electrode apparent current density is 300A/M
2, the anode apparent current density is 800A/M
2, the working current of electrochemical reactor is 1000A.
In the above-mentioned electrolytic process, at the incunabulum of electrolytic reduction, add the thin lead powder of 135g in the cathode compartment electrolytic solution, to increase the electroconductibility of solids in the electrolytic solution; After electrolytic reaction,, need not to continue to add thin lead powder owing to produced increasing electrolysis lead powder.
Adopt present technique, electrolytic reduction 12h, electrolysis finishes the back separation and obtains the about 37.9kg of electrolysis lead powder; Bath voltage is the 3.0-3.20 volt, and current efficiency is about 80%, and direct current consumption is about the 970kWh/ ton; Electrolysis lead powder test purity behind the fusing blocking reaches more than 99.99%.
Embodiment 4
The electrolyzer of the continuously-running duty that present embodiment adopts is with embodiment 1.
Get lead-acid accumulator handle obtain contain lead plaster mud (water content 10%) 200kg, put into reactor, add 57% salpeter solution 40kg, concentration of nitric acid is about 8.2mol/L in this moment treatment solution; Control treatment solution temperature is 20-30 ℃, and stirring reaction added 50% sulfuric acid 80kg after 0.5 hour, and further stirring reaction generated the lead sulfate precipitation after 1 hour; Because material handling is brown, the ammonium sulfite solution 75kg that adds plumbic oxide transforming agent 20%, stirring reaction 2 hours, until the mixed solution gray, the plumbous composition that will contain in the lead plaster mud all is converted into highly purified lead sulfate, filters, get filter residue, get highly purified lead sulfate throw out, weight is amounted to into the about 213kg of siccative, and filtrate is re-used in this step and handles containing lead plaster mud.
Get lead sulfate throw out 50kg, join in 300kg 5% sulphuric acid soln, fully stir continuously, import the electric tank cathode chamber as cathode compartment electrolytic solution with pump simultaneously, the controlling flow rate of flow of fluid is about 0.3m/s, make the lead sulfate particle fluidized of cathode compartment, realize that the lead sulfate particle fully contacts with fixing feedback negative electrode.In the electrolytic process, the lead sulfate throw out adds in the electrolytic solution storage tank with intermittent mode, and its add-on is for amounting to into about siccative 2.8kg/h.The control of electrolysis process condition is as follows: electrolyte temperature is 55～60 ℃, sulfuric acid concentration is 4.5-5% in the cathode compartment electrolytic solution, sulfuric acid concentration is 5～20% in anolyte compartment's electrolytic solution, when sulfuric acid concentration meets or exceeds 20%, electrolytic solution in the anolyte compartment need be extracted out, and mend isopyknic deionized water simultaneously, sulfuric acid concentration in anolyte compartment's electrolytic solution is reduced to about 5%; When sulfuric acid concentration in the cathode compartment electrolytic solution surpasses 5%, in cathode compartment, need to add the 30-40% sodium hydroxide solution, sulfuric acid concentration is transferred in the processing range; When sodium sulfate concentration in the cathode compartment surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously, the treatment solution of being extracted out in the electrolysis material storage tank is filtered, filter residue returns electrolysis material storage tank again; Filtrate is stocked and is used for supply cathode compartment electrolyte circulation system through about electrodialysis unit desalination to 1%.The adjustment process of sulfuric acid concentration needs periodically to implement in above-mentioned cathode compartment electrolytic solution, the anolyte compartment's electrolytic solution.
Fixing feedback negative electrode apparent current density is 100A/M
2, the anode apparent current density is 267A/M
2, the working current of electrochemical reactor is 333A.
In the above-mentioned electrolytic process, at the incunabulum of electrolytic reduction, add the thin lead powder of 140g in the cathode compartment electrolytic solution, to increase the electroconductibility of solids in the electrolytic solution; After electrolytic reaction,, need not to continue to add thin lead powder owing to produced increasing electrolysis lead powder.
Adopt present technique, electrolytic reduction 12h, electrolysis finishes the back separation and obtains the about 12.5kg of electrolysis lead powder; Bath voltage is the 2.85-3.05 volt, and current efficiency is about 82%, and direct current consumption is about the 940kWh/ ton; Electrolysis lead powder test purity behind the fusing blocking reaches more than 99.99%.
Embodiment 5
The electrolyzer of the continuously-running duty that present embodiment adopts is with embodiment 1.
Get lead-acid accumulator handle obtain contain lead plaster mud (water content 12%) 200kg, put into reactor, add 25% salpeter solution 85kg, concentration of nitric acid is about 3.7mol/L in this moment treatment solution; Control treatment solution temperature is 40-45 ℃, and stirring reaction added 25% sulfuric acid 160kg after 2 hours, and further stirring reaction generated the lead sulfate precipitation after 1 hour; Because material handling is brown, the ammonium sulfite solution 90kg that adds plumbic oxide transforming agent 18%, stirring reaction 2 hours, until the mixed solution gray, the plumbous composition that will contain in the lead plaster mud all is converted into highly purified lead sulfate, filters, get filter residue, get highly purified lead sulfate throw out, weight is amounted to into the about 208kg of siccative, and filtrate is re-used in this step and handles containing lead plaster mud.
Get lead sulfate throw out 50kg, join in 300kg 0.1% sulphuric acid soln, fully stir continuously, import the electric tank cathode chamber as cathode compartment electrolytic solution with pump simultaneously, the controlling flow rate of flow of fluid is about 0.2m/s, make the lead sulfate particle fluidized of cathode compartment, realize that the lead sulfate particle fully contacts with fixing feedback negative electrode.In the electrolytic process, the lead sulfate throw out adds in the electrolytic solution storage tank with intermittent mode, and its add-on is for amounting to into about siccative 3.4kg/h.The control of electrolysis process condition is as follows: electrolyte temperature is 65～70 ℃, sulfuric acid concentration is 0.1～0.5% in the cathode compartment electrolytic solution, sulfuric acid concentration is 5～20% in anolyte compartment's electrolytic solution, when sulfuric acid concentration meets or exceeds 20%, electrolytic solution in the anolyte compartment need be extracted out, and mend isopyknic deionized water simultaneously, sulfuric acid concentration in anolyte compartment's electrolytic solution is reduced to about 5%; When sulfuric acid concentration in the cathode compartment electrolytic solution surpasses 0.5%, in cathode compartment, need to add the 30-40% sodium hydroxide solution, sulfuric acid concentration is transferred in the processing range; When sodium sulfate concentration in the cathode compartment surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously, the treatment solution of being extracted out in the electrolysis material storage tank is filtered, filter residue returns electrolysis material storage tank again; Filtrate is stocked and is used for supply cathode compartment electrolyte circulation system through about electrodialysis unit desalination to 1%.The adjustment process of sulfuric acid concentration needs periodically to implement in above-mentioned cathode compartment electrolytic solution, the anolyte compartment's electrolytic solution.
Fixing feedback negative electrode apparent current density is 180A/M
2, the anode apparent current density is 480A/M
2, the working current of electrochemical reactor is 600A.
In the above-mentioned electrolytic process, at the incunabulum of electrolytic reduction, add the thin lead powder of 95g in the cathode compartment electrolytic solution, to increase the electroconductibility of solids in the electrolytic solution; After electrolytic reaction,, need not to continue to add thin lead powder owing to produced increasing electrolysis lead powder.
Adopt present technique, electrolytic reduction 12h, electrolysis finishes the back separation and obtains the about 19.6kg of electrolysis lead powder; Bath voltage is the 3.01-3.2 volt, and current efficiency is about 85%, and direct current consumption is about the 920kWh/ ton; Electrolysis lead powder test purity behind the fusing blocking reaches more than 99.99%.
Embodiment 6
The electrolyzer of the continuously-running duty that present embodiment adopts is with embodiment 1.
Get lead-acid accumulator handle obtain contain lead plaster mud (water content 8%) 200kg, put into reactor, add 15% salpeter solution 140kg, concentration of nitric acid is about 2.5mol/L in this moment treatment solution; Control treatment solution temperature is 35-40 ℃, and stirring reaction added 30% sulfuric acid 130kg after 1 hour, and further stirring reaction generated the lead sulfate precipitation after 1 hour; Because material handling is brown, the ammonium sulfite solution 70kg that adds plumbic oxide transforming agent 22%, stirring reaction 2 hours, until the mixed solution gray, the plumbous composition that will contain in the lead plaster mud all is converted into highly purified lead sulfate, filters, get filter residue, get highly purified lead sulfate throw out, weight is amounted to into the about 216kg of siccative, and filtrate is re-used in this step and handles containing lead plaster mud.
Get lead sulfate throw out 50kg, join in 300kg 0.6% sulphuric acid soln, fully stir continuously, import the electric tank cathode chamber as cathode compartment electrolytic solution with pump simultaneously, the controlling flow rate of flow of fluid is about 0.4m/s, make the lead sulfate particle fluidized of cathode compartment, realize that the lead sulfate particle fully contacts with fixing feedback negative electrode.In the electrolytic process, the lead sulfate throw out adds in the electrolytic solution storage tank with intermittent mode, and its add-on is for amounting to into about siccative 2.8kg/h.The control of electrolysis process condition is as follows: electrolyte temperature is 30～35 ℃, sulfuric acid concentration is 0.3～0.9% in the cathode compartment electrolytic solution, sulfuric acid concentration is 5～20% in anolyte compartment's electrolytic solution, when sulfuric acid concentration meets or exceeds 20%, electrolytic solution in the anolyte compartment need be extracted out, and mend isopyknic deionized water simultaneously, sulfuric acid concentration in anolyte compartment's electrolytic solution is reduced to about 5%; When sulfuric acid concentration in the cathode compartment electrolytic solution surpasses 0.9%, in cathode compartment, need to add the 30-40% sodium hydroxide solution, sulfuric acid concentration is transferred in the processing range; When sodium sulfate concentration in the cathode compartment surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously, the treatment solution of being extracted out in the electrolysis material storage tank is filtered, filter residue returns electrolysis material storage tank again; Filtrate is stocked and is used for supply cathode compartment electrolyte circulation system through about electrodialysis unit desalination to 1%.The adjustment process of sulfuric acid concentration needs periodically to implement in above-mentioned cathode compartment electrolytic solution, the anolyte compartment's electrolytic solution.
Fixing feedback negative electrode apparent current density is 150A/M
2, the anode apparent current density is 400A/M
2, the working current of electrochemical reactor is 500A.
In the above-mentioned electrolytic process, at the incunabulum of electrolytic reduction, add the thin lead powder of 150g in the cathode compartment electrolytic solution, to increase the electroconductibility of solids in the electrolytic solution; After electrolytic reaction,, need not to continue to add thin lead powder owing to produced increasing electrolysis lead powder.
Adopt present technique, electrolytic reduction 12h obtains the about 19.8kg of electrolysis lead powder; Bath voltage is the 2.92-3.12 volt, and current efficiency is about 85%, and direct current consumption is about the 920kWh/ ton; Electrolysis lead powder test purity behind the fusing blocking reaches more than 99.99%.
Claims (10)
1. a full wet method electrolytic reduction regeneration lead-acid accumulator contains the method for lead resource in the lead plaster mud, it is characterized in that said method comprising the steps of:
(1) lead-acid accumulator handle obtain contain lead plaster mud, be promotor with nitric acid, react with sulphuric acid soln A, described reaction is carried out according to following steps: add salpeter solution earlier in containing lead plaster mud, making concentration of nitric acid is 1～12mol/L, stirring reaction 0.5～5h, and then add sulphuric acid soln A, stirring reaction 0.5～2h, obtain the sedimentary mixed solution of sulfur-bearing lead plumbate, filter, get filtrate and filter cake, filter cake is a lead sulfate precipitation, describedly contains lead plaster mud and the vitriolic mass ratio is 3～8: 1;
(2) lead sulfate with step (1) gained joins among the sulphuric acid soln B, adjusting the vitriolic final concentration is 0.1～5.0%, the content of lead sulfate is 150～250g/L, fully stir continuously, and with the cathode compartment of pump input continuously-running duty electrolyzer as cathode compartment electrolytic solution, the controlling flow rate of flow of fluid is 0.1～0.4m/s, makes the lead sulfate particle fluidized of cathode compartment, obtains electrolytic lead at cathode compartment through electrolytic reduction; Add 30～50g/L lead powder at the electrolytic reduction initial stage in cathode compartment electrolytic solution, negative electrode adopts fluidized bed structure, and by fixing feedback negative electrode conduction current, described fixedly feedback negative electrode is the lead plating stainless steel bar; Negative electrode and anode are separated with mechanical diaphragm, and described mechanical diaphragm adopts mineral membrane, organic high molecular layer or inorganic organic polymer composite membrane; The control of electrolysis process condition is as follows: electrolyte temperature is 20～70 ℃, and sulfuric acid concentration is 0.1～5.0% in the maintenance cathode compartment electrolytic solution, and sulfuric acid concentration is 5～20% in the electrolytic solution of holding anode chamber, and fixing feedback negative electrode apparent current density is 100A/M
2～400A/M
2, the anode apparent current density is 200A/M
2～1000A/M
2
2. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 1 contains the method for lead resource in the lead plaster mud, and it is characterized in that: the anode of described electrolyzer is the pure lead pipe of plastic lining.
3. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 1 contains the method for lead resource in the lead plaster mud, it is characterized in that: the electrolyzer of described continuously-running duty comprises electrolyzer, be arranged on electrode and electrolysis material storage tank in the electrolyzer, described upper part of the electrolytic cell major trough body is a column structure, the bottom is an inverted pyramidal structures, column structure and inverted pyramidal structures junction are provided with fluid flow rate uniform distribution plate, vertically arrange the anode tube and the fixing feedback cathode bar that are parallel to each other in the major trough, described fixedly feedback cathode bar and anode tube staggered arrangement, separate with the porous mechanical membrane between fixing feedback cathode bar and the anode tube, bottom of electrolytic tank is provided with opening for feed, upper part of the electrolytic cell is provided with discharge port, described opening for feed is connected with electrolysis material storage tank by recycle pump, described discharge port is connected with electrolysis material storage tank, and described electrolysis material storage tank and electrolyzer can be formed electrolysis material circulation-supplied system by recycle pump.
4. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 1 contains the method for lead resource in the lead plaster mud, it is characterized in that: in step (2) electrolytic process, when sulfuric acid concentration meets or exceeds 20% in anolyte compartment's electrolytic solution, carry out anolyte compartment's electrolytic solution adjustment, described anolyte compartment electrolytic solution is adjusted into: the electrolytic solution in the anolyte compartment is extracted out, mend isopyknic deionized water simultaneously, sulfuric acid concentration is reduced to 5% in anolyte compartment's electrolytic solution.
5. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 1 contains the method for lead resource in the lead plaster mud, it is characterized in that: in step (2) electrolytic process, when sulfuric acid concentration meets or exceeds 5% in the cathode compartment electrolytic solution, sodium hydroxide solution with 30～40% is adjusted in sulfuric acid concentration to 0.1～5.0% scope, and the concentration of controlling sodium sulfate simultaneously is below 10g/L.
6. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 5 contains the method for lead resource in the lead plaster mud, it is characterized in that: the control sodium sulfate concentration adopts following method: when sodium sulfate concentration surpasses 10g/L, extract the treatment solution in the electrolysis material storage tank out half, mend the deionized water of Extract volume about 80% simultaneously; The treatment solution of being extracted out in the electrolysis material storage tank is filtered, and filter residue returns electrolysis material storage tank again, and filtrate is stocked and is used for supply catholyte fluid circulation through about electrodialysis unit desalination to 1%.
7. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 1 contains the method for lead resource in the lead plaster mud, it is characterized in that: when the sedimentary mixed solution of step (1) gained sulfur-bearing lead plumbate is brown, in described mixed solution, add the plumbic oxide transforming agent, in 25～65 ℃ of reactions 0.5～2 hour, until the reaction solution gray, described plumbic oxide transforming agent is converted into plumbous compound for the tetravalence lead that can promote to contain in the lead plaster mud, and one of described plumbic oxide transforming agent use is following: ammonium sulphite, S-WAT, hydrogen peroxide.
8. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 1 contains the method for lead resource in the lead plaster mud, and it is characterized in that: the described temperature of reaction of step (1) is controlled at 20～65 ℃.
9. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 1 contains the method for lead resource in the lead plaster mud, and it is characterized in that: the concentration of the described sulphuric acid soln A of step (1) is 20～80%.
10. full wet method electrolytic reduction regeneration lead-acid accumulator as claimed in claim 1 contains the method for lead resource in the lead plaster mud, it is characterized in that: the described electrolysis process condition control of step (2) is as follows: electrolyte temperature is 25～45 ℃, sulfuric acid concentration is 0.1～1.0% in the maintenance cathode compartment electrolytic solution, and fixing feedback negative electrode apparent current density is 150～250A/M
2, the anode apparent current density is 400～600A/M
2
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| CN101899575B (en) * | 2010-08-17 | 2012-01-04 | 苏文峰 | Waste lead storage battery acid type wet method process |
| CN102433570B (en) * | 2011-12-08 | 2014-01-22 | 浙江汇同电源有限公司 | Wet-process lead refining technology |
| KR101739414B1 (en) * | 2013-11-19 | 2017-05-24 | 아쿠아 메탈스 인크. | Devices and method for smelterless recycling of lead acid batteries |
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| CN113390751A (en) * | 2021-05-24 | 2021-09-14 | 超威电源集团有限公司 | Method for measuring content of lead sulfate in lead paste of storage battery |
| CN113897489A (en) * | 2021-10-08 | 2022-01-07 | 太和县大华能源科技有限公司 | Sectional type desulfurization process for waste lead plaster for recycling lead-acid batteries |
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