CN103014347B - Method for recycling waste lead-acid cells to directly produce lead oxide - Google Patents
Method for recycling waste lead-acid cells to directly produce lead oxide Download PDFInfo
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- CN103014347B CN103014347B CN201210535154.1A CN201210535154A CN103014347B CN 103014347 B CN103014347 B CN 103014347B CN 201210535154 A CN201210535154 A CN 201210535154A CN 103014347 B CN103014347 B CN 103014347B
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Abstract
The invention discloses a method for recycling waste lead-acid cells to directly produce lead oxide, belonging to the wet-process metallurgical field of recycling lead from lead-containing materials and waste lead-acid cells. The method for recycling waste lead-acid cells to directly produce lead oxide comprises the following steps of: carrying out a reaction on diachylum, lead powder and sodium hydroxide solution in the presence of catalyst to obtain a mixed solution containing NaHPbO2, sodium sulfate and sodium hydroxide, and un-reacted lead powder and impurities, and separating the mixed solution; cooling and filtering the mixed solution to obtain PbO crystals, and an alkaline solution containing Na2SO4 and the residual NaHPbO2; adding the NaOH to the solution, re-cooling the mixture to separate out sodium sulfate solid and obtain the NaOH solution containing the residual NaHPbO2; and carrying out re-dissolving-filtering-re-crystallizing to the PbO in the NaOH solution with mass concentration of 15-50% to obtain the pure lead oxide solid. The lead recovery ratio is generally between 98.5% and 99.2%, and the purity of the lead oxide is as high as 99.99% or higher.
Description
Technical field
The present invention relates to a kind of method that reclaims the high-purity plumbous oxide of waste lead acid battery direct production, belong to lead-containing material and waste lead acid battery are reclaimed to plumbous hydrometallurgy field of processing.
Background technology
From 1859 by the special invention lead-acid cell in French slip-stick artist Pulan since, lead-acid cell is widely used in the field such as the igniting of automobile and the ups power of telecommunications as the secondary cell of a kind of low price and stable performance.In recent years, the secondary cell that some are emerging, the competition of for example lithium ion battery and nickel metal hydride battery, but lead-acid cell is with the advantage of its unique cost performance and security, is keeping stable increase always, and it has still occupied the output value of global secondary cell nearly 60%.Show according to the data statistics of power supply relevant industries association, the consumption of global lead bullion in 2010 reaches more than 9,300,000 tons, and wherein Lead for China consumption reaches more than 350 ten thousand tons, and the production of lead-acid cell has accounted for the more than 85% of above-mentioned plumbous consumption.Because the explored lead resource of China is day by day poor, cause a large amount of lead and lead ore dependence on import thereof, the recycling of carrying out waste lead accumulator becomes the important channel that solves lead resource problem.Relatively backward pyrogenic process reclaims plumbous technology and in high-temperature smelting process, has produced a large amount of leaded dust and lead skim thereof at present, has caused the generation of secondary lead pollution problem.
We find in analysis, and the lead that current waste and old lead acid accumulator mainly obtains by pyrometallurgical smelting is mainly the lead-acid cell service of producing.But the lead that pyrometallurgical smelting obtains is mainly the lead bullion that contains 1-3% impurity, people are referred to as reduction lead conventionally.This lead bullion can not directly be used for producing lead plaster, generally need to and then become shot through lead bullion electrorefining, and last ball milling oxidation obtains plumbous oxide.Plumbous oxide is through with the tune cream of sulfuric acid and add after various additives, is coated in and on grid, becomes the active substance on lead-acid cell pole plate.From the process of above-mentioned lead plaster-lead bullion-lead bullion-shot-ball milling-plumbous oxide, we see if by the highly purified plumbous oxide of lead plaster direct production of waste lead acid battery, can omit the energy consumption of pyrometallurgical smelting, electrorefining and ball milling oxidising process, and the leaded dust of these processes generations.Because lead plaster mainly contains Pb, PbSO
4, PbO and PbO
2mixture, therefore study a kind of effective means the lead compound of the various forms in lead plaster transformed, and finally obtain pure plumbous oxide and become the difficult point of regenerating oxidation splicer skill.
There is at present investigator once to report to adopt it to carry out effectively reduction to the lead plaster of lead-acid cell and the method for producing afterwards plumbous oxide is processed in desulfurization.Chinese patent 201210201272.9 has been reported first waste lead acid battery has been carried out to negative pole powder and the positive powder that independent fragmentation obtains.Positive powder and reductive agent carry out reduction reaction under 300 DEG C of high temperature, then add the reaction at not higher than 200 DEG C of constitution controller and carbonate or oxyhydroxide, and after drying, then heating obtains plumbous oxide to the solid obtaining at 200-500 DEG C.Negative pole powder first with morphology control agent reacting by heating after, then 500 DEG C of following temperature heating, subsequently by after nitric acid or hot dissolving with hydrochloric acid, then with alkali or ammoniacal liquor reaction, obtain plumbous oxide.We think, this process not only needs the high temperature of 200-500 DEG C, and consumes the toxic substances such as a large amount of methyl alcohol, formaldehyde, nitrite, has also increased aftertreatment complicacy and production cost simultaneously, therefore from atom angle, this is not the technique of an atom economy.The Central China University of Science and Technology (China YouSe metal, 2010,20 (1): 132-136) has reported that employing hydrogen peroxide decomposes plumbic oxide, and then with citric acid dissolve, then high-temperature roasting processing obtains the technique of plumbous oxide.This processes expend a large amount of soda acids, add that the price of hydrogen peroxide and citric acid is more expensive, and the thermal treatment process of high temperature at 300 ~ 450 DEG C, be not therefore the technique of an atom economy.The external technology that also has the scholars such as R.Kumar to develop the plumbous oxide in similar citric acid method recovery lead-acid cell, also there is same problem (Hydrometallurgy, 2009,95:53-60) in its economy.
Comprehensive analysis is above-mentioned up-to-date plumbous oxide preparation technology both domestic and external find, these methods can directly obtain plumbous oxide, but the problem existing mainly contains:
(1) purity of plumbous oxide is not very desirable, is conventionally mingled with lead carbonate or lead;
(2) need 200-500 DEG C of high-temperature heat treatment;
(3) the conversion process time long, flow process is many, simultaneously the consumption of bronsted lowry acids and bases bronsted lowry is large;
Therefore the novel process of developing a kind of atom economy becomes a difficult problem that solves waste lead acid battery remanufacture plumbous oxide technique.
Summary of the invention
The object of this invention is to provide the novel process that under a kind of aqueous temperature, waste lead acid battery is reclaimed to the lead plaster direct production high-purity mangesium oxide lead obtaining.
First technical problem to be solved by this invention is to have avoided existing technique first to need acid-soluble solution, and then by a large amount of alkali N-process, causes reaction process need to consume the shortcoming of a large amount of bronsted lowry acids and bases bronsted lowries;
Second technical problem to be solved by this invention is to have avoided existing technique to need the shortcoming of high-temperature roasting, significantly reduced raw material consumption and the energy consumption of producing plumbous oxide process, is a green atom economy novel process.
The 3rd technical problem to be solved by this invention is to provide a kind of plumbous oxide dissolves-filters in alkaline medium-method of purification of recrystallization, the method can farthest improve the purity of plumbous oxide, thereby for manufacturing the guarantee of supplying raw materials of the lead-acid cell of high-quality.
The object that the present invention will realize is not limited to above-mentioned purpose, and those skilled in the art can be expressly understood other object from following detailed description.
For achieving the above object, the invention provides a kind of method from waste lead acid battery reclaiming plumbous oxide, comprise the following steps:
(1) materials such as lead plaster, stereotype grid, plastics and the dilute sulphuric acid conventional broken apart technique of waste lead acid battery employing being obtained respectively;
(2) lead plaster, lead powder, catalyzer are reacted and obtain containing NaHPbO with sodium hydroxide solution
2, sodium sulfate and sodium hydroxide mixing solutions, and contain residual unreacted lead powder and the solid mixture of impurity;
(3) separate the reaction product that (2) process obtains, obtain containing NaHPbO
2, sodium sulfate and sodium hydroxide mixing solutions and filter residue;
(4) above-mentioned filter residue is put into again to (2) process, carried out redox reaction again;
(5) mixing solutions of (3) process is carried out to sedimentation, filtration and purification again under maintenance original temperature, further to remove impurity wherein, the NaHPbO after being purified
2, NaOH and Na
2sO
4mixing solutions for subsequent use.
(6) mixing solutions of (5) process carried out cooling and filter, obtaining PbO crystal, and contain Na
2sO
4with residual content NaHPbO
2basic solution;
(7) NaOH is joined gradually to (6) process and obtain in basic solution, NaOH concentration in solution is reached more than 15% gradually, again coolingly make its sodium sulfate solid of separating out low solubility, and obtain containing remaining NaHPbO
2naOH solution;
(8) what (7) process of being somebody's turn to do obtained contains remaining NaHPbO
2naOH solution turn back to (2) process again for reaction.
Aforesaid method, further comprising the steps of: again dissolve in the NaOH of mass concentration 15-50%-filtration-re-crystallization step of PbO that (9) obtain (6) process, obtains purer plumbous oxide solid.
Wherein, NaOH strength of solution excessive described in step (2) is 3 ~ 14mol/L, is preferably 4-7mol/L, or adopts the basic solution of step (8) gained, and the temperature of described reaction is 30 ~ 110 DEG C, is preferably 60-105 DEG C.
The wherein said lead powder of step (2) is the lead powder that common lead powder or leaded grid fragmentation obtain, the preferred 20-400 order of size range of its lead powder, and its dosage is 0.2-3 times of lead plaster weight.Catalyzer described in step (2) refers to one or several the mixture in antimony, lead antimony alloy, weisspiessglanz, antimonic salt, antimonite or stibnate, and the antimony element in its catalyzer is the 0.01-10% of NaOH solution weight.The concentration of step (2) sodium hydroxide is respectively 3-14mol/L simultaneously, and its amount of substance is 2-10 times of the contained lead sulfate amount of substance of lead plaster.In order to ensure carrying out fast of reaction, best reaction conditions is at 30-110 DEG C, keeps the stirring velocity of 20-600 rev/min, successive reaction 0.5-20 hour.
Above-mentioned steps (6) process of cooling adds PbO solid as crystal seed.
Complete the backward NaOH of comprising and Na by crystallization
2sO
4solution in add 25% or NaOH solution or the NaOH solid of greater concn impel the sodium sulfate in solution further to separate out, and the sodium sulfate of separating out is filtered.Gained filtrate is returned to above-mentioned alkali leaching purification Cheng Jinhang to be recycled.
Method of the present invention can directly obtain purity up to more than 99.99% high-purity plumbous oxide, thereby meet the needs of lead-acid cell to high-purity PbO, this has been avoided existing recovery lead to need pyrotic smelting to become lead bullion, the techniques such as the refining of lead bullion and shot reoxidize, thereby not only save the huge energy consumption of said process, and the shortening for the treatment of process, increase substantially plumbous organic efficiency.Experiment shows, the lead recovery of waste lead acid battery is generally between 98.5～99.2%, higher than the level of pyrometallurgical smelting 90-95% now, thereby has significant environmental value, is a kind of clean secondary lead novel process.
Brief description of the drawings
Fig. 1 is the process flow sheet of one embodiment of the present invention.
Embodiment
Hereinafter carry out with reference to the accompanying drawings to describe in more detail illustrative embodiments.Described accompanying drawing is used for illustrating the present invention, but not is limited.
With reference to Fig. 1, waste lead acid battery obtains Waste Sulfuric Acid, lead plaster and grid etc. through broken and screening.Lead plaster, lead powder and NaOH are reacted and are converted into plumbous oxide under the katalysis of catalyzer, and plumbous oxide is dissolved in NaOH solution simultaneously and obtains NaHPbO
2(some document is also by NaHPbO
2write as Na
2pbO
2or Na
2pb (OH)
4).To the plumbic oxide that adds excessive lead powder and catalyzer to reduce in lead plaster in this mother liquor, and reaction generates containing NaHPbO under comparatively high temps
2, NaOH and Na
2sO
4solution, and reaction in residual lead powder and the battery material such as additive or clay that shattering process is mingled with in process of production.By after this solution separating, carry out cooling and stir, and adding a small amount of PbO crystal seed to promote separating out of PbO.In the time that solution temperature drops to below 20 DEG C, separate above-mentioned reaction solution and obtain PbO solid and contain sodium sulfate and the NaOH mother liquor of a small amount of PbO.In this NaOH mother liquor, supplement NaOH solid or NaOH solution, improve the concentration of NaOH mother liquor, now by common-ion effcet, the sodium sulfate in electrolytic solution is separated out, and the sodium sulfate of separating out is filtered.To remain the recovery of NaOH solution circulates for the next one.
(1) process of separation lead plaster:
By waste lead acid battery by ordinary method as carried out fragmentation by crusher, and obtain lead plaster, stereotype grid, dividing plate, shell, Waste Sulfuric Acid etc. by conventional separation method as density difference separates.By for subsequent use to isolated lead plaster and stereotype grid.
(2) catalytic conversion process:
The raw material of catalytic conversion process is lead plaster, and wherein the lead in lead plaster is with Pb, PbSO
4, PbO and PbO
2form of mixtures exist.In this process, the Pb in lead plaster and PbO
2under the katalysis of catalyzer, redox reaction occurs and obtain plumbous oxide, lead sulfate is also converted into plumbous oxide with NaOH generation desulphurization reaction simultaneously.
Catalytic conversion process comprises the following steps:
(1) by lead plaster Pb and PbO
2in NaOH medium, carry out redox reaction and obtain PbO, its reaction formula can be expressed as follows:
Pb+PbO
2=2PbO
We know, in alkaline medium, and Pb and PbO
2half-cell reaction and standard potential are:
Pb-2e+2OH
-=PbO+H
2O E
B 0=-0.576V
PbO
2+2e+H
2O=PbO+2OH
-E
B 0=0.28V
Total reaction: Pb+PbO
2=2PbO E=0.956V
Visible, Pb and PbO
2can spontaneously there is redox reaction and obtain PbO, and can obtain the electromotive force of 0.956V.But because waste lead acid battery has normally used the used batteries after a lot of circulations, and also very long from scrapping, reclaim again the time to secondary lead workshop, therefore the most of active substance in lead-acid cell has been lost electrochemical activity, be difficult to have high response capacity the same as fresh electrode active material, Gu add between them it is solid-contact reacts, this has caused electrode reaction speed slow.In order to accelerate speed of response between lead powder and lead dioxide powder, suitable catalyzer is crucial.Second object of the present invention is to provide the catalystic material of the above-mentioned reaction needed of a kind of confession.The design philosophy of catalyzer is at Pb and PbO
2between two solids, provide one can carry out transfer transport and the liquid media of exchange, thereby by solid-solid reaction, Gu change solid-liquid-reaction into.Through a large amount of experimental exploring and contrast, the present invention finds to drop into a small amount of metallic antimony, lead antimony alloy, weisspiessglanz, antimonic salt (SbCl in NaOH medium
3, Sb (NO
3)
3or Sb
2(SO
4)
3deng), antimonite or stibnate (for example Na
3sbO
4) there is good catalytic effect, greatly accelerate Pb and PbO
2redox reaction between two solids.Further further investigation is found, this effect is in fact finally by containing Na
3sbO
3or Na
3sbO
4solution respectively with PbO
2or the redox reaction between Pb realizes the transfer of catalytic process electronics.We are with Na
3sbO
3for example, the catalytic reaction process of antimony catalyst is described.When we are to containing Pb powder, PbO
2in the NaOH solution of powder, drop into Na
3sbO
3time, SbO
3 3-first by PbO
2oxidation, generates PbO and SbO
4 3-, then SbO
4 3-and then oxidation Pb forms PbO and SbO
3 3-thereby, SbO
3 3-at Pb and PbO
2between played the part of liquid transfer transport medium, in NaOH solution, can recycle, reach quick catalysis Pb and PbO
2effect.Above-mentioned reaction formula can be expressed as follows:
PbO
2+SbO
3 3-=PbO+SbO
4 3-
Pb+SbO
4 3-=PbO+SbO
3 3-
Total reaction: Pb+PbO
2=2PbO
Similarly, in one embodiment of the invention, we drop into a small amount of antimony powder, lead antimony alloy in solution, also find that these materials have similar katalysis, and this is because the antimony in antimony powder or lead antimony alloy can be by PbO or PbO in alkaline medium
2oxidation generates SbO
3 3-due to, concrete reaction formula is as follows:
2Sb+3PbO+6OH
-=2SbO
3 3-+3Pb+3H
2O
4Sb+3PbO
2+12OH-=4SbO
3 3-+3Pb+6H
2O
In one embodiment of the invention, in solution, drop into Sb
2(SO
4)
3catalysis essence be also Sb
3+reaction is created on the SbO that alkalescence is more stable with NaOH
3 3-ion, reaches the effect of catalysis.
Due to SbO
3 3-ion does not consume before and after reaction, and therefore the dosage of Sb or Sb compound is that the little part of NaOH solution weight can meet catalysis requirement.Usually, in order to ensure good catalytic effect, in antimony class catalyzer, the dosage of antimony element is between the 0.1-10% of NaOH solution total amount.
Complete the backward NaOH of comprising and Na by crystallization
2sO
4solution in add 25% or NaOH solution or the NaOH solid of greater concn impel the sodium sulfate in solution further to separate out, and the sodium sulfate of separating out is filtered.Gained filtrate is returned to above-mentioned alkali leaching purification Cheng Jinhang to be recycled.
Working cycle comprises the following steps:
(1) in the solution containing NaOH and sodium sulfate of gained after crystallization, add NaOH solid or concentrated NaOH solution, and keep cooling conditions, make progressively to separate out in solution Na
2sO
4solid; With
(2) above-mentioned basic solution (being mainly NaOH) of separating out after filtration after sodium sulfate solid returns to that the leaching of initial alkali purifies and reaction process recycles.
The present invention during working cycle to adding NaOH strong solution or NaOH solid to make: (1), under common-ion effcet, impels the sodium sulfate in electrolytic solution to separate out, and reaches the object of the direct reclaim(ed) sulfuric acid sodium of non-evaporation; (2) NaOH adding directly carrys out complexing PbO as the raw material of next one circulation and uses; (3) add dense NaOH solution almost to reduce exothermic phenomenon, be more conducive to sodium sulfate and separate out.
Embodiment 1
Getting the specification of buying on 2 markets is 12V, 12Ah common electric car waste lead acid battery, 9.2 kilograms of series of cells gross weights.Specific implementation process is as follows:
1) waste lead acid battery is obtained to lead plaster, grid, Waste Sulfuric Acid, dividing plate and shell through conventional fragmentation with separating.
2) lead plaster being press-filtered out is put into crusher successively and ball mill is pulverized, sieve subsequently with 60 object stainless steel meshs, larger lead plaster particle continues to proceed to pulverizer to be pulverized, until all lead plasters all see through screen cloth.
3) grid is put into crusher and ball mill is pulverized successively, sieves subsequently with 20 object stainless steel meshs, and larger plumbous particle continues to proceed to pulverizer to be pulverized, until that all lead buttons all see through after screen cloth is for subsequent use.
4) the NaOH solution that configuration 40L weight percent concentration is 32% is placed solution for subsequent use using 200 grams of antimony trisulfate dissolution of solids simultaneously in NaOH solution after catalyzer.
5) by 2 kilograms of lead plasters of (2) process, and the excessive lead button that adds 1.2 kilograms (3) to obtain puts in above-mentioned NaOH solution, makes Pb and PbO
2, and PbSO
4and react between NaOH, make their unifications change PbO into, and be dissolved in NaOH solution.Between the reaction period, keeping temperature of reaction is 90 DEG C, and stirring velocity is 100 revs/min.
6) question response carries out filtering after 4 hours, obtains the filtrate of clarification, the filter residue that a small amount of residual lead powder and impurity form.
7) filtrate is placed in to crystallization kettle and carries out coolingly gradually, add 200 grams of PbO solids as crystal seed simultaneously, keeping speed of cooling is 10 DEG C/h, and stirring velocity is 60 revs/min.Now in solution, slowly separate out PbO solid, in the time that solution temperature drops to below 20 DEG C, separate said mixture, obtain filtrate and plumbous oxide solid.Plumbous oxide solid is for subsequent use as product through washing after dry.
8) filtrate (6) process being obtained, by supplementing NaOH solid, after the actual concentrations of NaOH is brought up to 32% again, is cooled to solution below 20 DEG C, now in solution, separates out gradually sodium sulfate solid.This mother liquor is carried out to solid-liquid separation and obtain NaOH mother liquor and sodium sulfate solid, this NaOH mother liquor returns to step (5) and recycles.
By analysis, the residue of step (6) is that a small amount of battery production such as lead powder and barium sulfate process adds additive substantially, wherein lead powder can again turn back to step (5) and recycles, or obtains lead powder by conventional reselecting method by separating filter residue.Through Measurement and Computation, above-mentioned global cycle process has finally obtained the plumbous oxide of 2.95 kilograms, and its purity is 99.991%, the rate of recovery 98.2%.
Embodiment 2
Getting 1 block specifications is 12V, 45Ah junked-auto lead-acid cell, and 13.2 kilograms of series of cells gross weights, concrete removal process is as follows:
According to embodiment 1 (1), (2) and (3) process, obtain lead plaster and grid after fragmentation.
4) the NaOH solution that configuration 80L weight percent concentration is 30% is placed solution for subsequent use using 300 grams of weisspiessglanz dissolution of solids simultaneously in NaOH solution after catalyzer.
5) by 5 kilograms of lead plasters of (2) process, and the excessive lead button that adds 3.5 kilograms (3) to obtain puts in above-mentioned NaOH solution, makes Pb and PbO
2, and PbSO
4and react between NaOH, make their unifications change PbO into, and be dissolved in NaOH solution.Between the reaction period, keeping temperature of reaction is 100 DEG C, and stirring velocity is 100 revs/min.
4) question response carries out filtering after 2 hours, obtains the filtrate of clarification, the filter residue that a small amount of residual lead powder and insoluble impurity form.
7) filtrate is placed in to crystallization kettle and carries out coolingly gradually, add 0.5 kilogram of PbO solid as crystal seed simultaneously, keeping speed of cooling is 5 DEG C/h, and stirring velocity is 50 revs/min.Now in solution, slowly separate out PbO solid, in the time that solution temperature drops to below 20 DEG C, separate said mixture, obtain filtrate and plumbous oxide solid.Plumbous oxide solid is for subsequent use as product through washing after dry.
8) filtrate (6) process being obtained, by supplementing NaOH solid, after the actual concentrations of NaOH is brought up to 30% again, is cooled to solution below 20 DEG C, now in solution, separates out gradually sodium sulfate solid.This mother liquor is carried out to solid-liquid separation and obtain NaOH solution and sodium sulfate solid, this NaOH mother liquor returns to step (5) and recycles.
By analysis, the residue of step (6) except excessive lead powder is residual, is the non-plumbous additive that the battery production processes such as barium sulfate add substantially substantially.Through Measurement and Computation, above-mentioned global cycle process has finally obtained the plumbous oxide of 7.45 kilograms, and its purity is 99.991%, the rate of recovery 98.5%.
Embodiment 3
Get the junked-auto lead-acid cell that embodiment 2 is identical, and according to same (1), (2) and (3) process, obtain lead plaster and grid after fragmentation.
4) the NaOH solution that configuration 75L weight percent concentration is 28% is positioned in sealing bucket for subsequent use.
5) by 5 kilograms of lead plasters of (2) process, and the excessive lead button that adds 3.3 kilograms (3) to obtain, and 200 commercially available antimony powders put in above-mentioned NaOH solution as catalyzer, make Pb and PbO
2, and PbSO
4and react between NaOH, make their unifications change PbO into, and be dissolved in NaOH solution.Between the reaction period, keeping temperature of reaction is 105 DEG C, and stirring velocity is 80 revs/min.
4) question response carries out filtering after 2 hours, obtains the filtrate of clarification, the filter residue that a small amount of residual lead powder and insoluble impurity form.
7) filtrate is placed in to crystallization kettle and carries out coolingly gradually, add 0.4 kilogram of PbO solid as crystal seed simultaneously, keeping speed of cooling is 10 DEG C/h, and stirring velocity is 50 revs/min.Now in solution, slowly separate out PbO solid, in the time that solution temperature drops to below 20 DEG C, separate said mixture, obtain filtrate and plumbous oxide solid.Plumbous oxide solid is for subsequent use as product through washing after dry.
8) filtrate (6) process being obtained, by supplementing 40%NaOH solution, after the actual concentrations of NaOH is brought up to 28% again, is cooled to electrolytic solution below 20 DEG C, now in solution, separates out gradually sodium sulfate solid.This mother liquor is carried out to solid-liquid separation and obtain NaOH solution and sodium sulfate solid, this NaOH mother liquor returns to step (5) and recycles.
By analysis, the residue of step (6) is the non-plumbous additive that the battery production process such as lead powder and a small amount of barium sulfate of excess residual in reaction adds substantially.Through Measurement and Computation, above-mentioned global cycle process has finally obtained the plumbous oxide of 7.50 kilograms, and its purity is 99.991%, the rate of recovery 99.2%.
Embodiment 4
(1) Qu Mou lead-acid cell factory scrap 5 kilograms, the lead plaster powder that positive/negative plate separates, and 2 kilograms be about 0.3% lead antimony alloy grid particle containing antimony amount, lead in this alloying pellet can be used as reductive agent, and contained metallic antimony had both been made reductive agent simultaneously, is also Pb and PbO simultaneously
2catalyzer between reaction.
(2) the NaOH solution that configuration 55L weight percent concentration is 25% is stored in bucket for subsequent use.
(3) lead plaster of (1) process and antimonial lead grain are put in above-mentioned NaOH solution, made Pb and PbO
2, and PbSO
4and react between NaOH, make their unifications change PbO into, and be dissolved in NaOH solution.Between the reaction period, keeping temperature of reaction is 105 DEG C, and stirring velocity is 50 revs/min.
4) question response carries out filtering after 3 hours, obtains the filtrate of clarification, the filter residue that a small amount of residual lead powder and insoluble impurity form.
5) filtrate is placed in to crystallization kettle and carries out coolingly gradually, add 0.3 kilogram of PbO solid as crystal seed simultaneously, keeping speed of cooling is 5 DEG C/h, and stirring velocity is 50 revs/min.Now in solution, slowly separate out PbO solid, in the time that solution temperature drops to below 20 DEG C, separate said mixture, obtain filtrate and plumbous oxide solid.Plumbous oxide solid is for subsequent use as product through washing after dry.
6) filtrate (6) process being obtained, by supplementing 35%NaOH solution, after the actual concentrations of NaOH is brought up to 25% again, is cooled to electrolytic solution 10 DEG C again, separates out gradually sodium sulfate solid in solution.This mother liquor is carried out to solid-liquid separation and obtain NaOH solution and sodium sulfate solid, this NaOH mother liquor returns to step (3) and recycles.
By analysis, the residue of step (5) is except excessive lead powder is residual and the non-plumbous additive that adds of the battery production process such as minute quantity barium sulfate substantially.Through Measurement and Computation, above-mentioned global cycle process has finally obtained the plumbous oxide of 5.2 kilograms, and its purity is 99.992%, the rate of recovery 98.9%.
Claims (6)
1. a method that reclaims waste lead acid battery direct production plumbous oxide, is characterized in that, comprises the following steps:
(1) lead plaster, stereotype grid, plastics and the dilute sulphuric acid material that adopt conventional broken apart technique to obtain respectively waste lead acid battery;
(2) lead plaster, lead powder, catalyzer are reacted and obtain containing NaHPbO with sodium hydroxide solution
2, sodium sulfate and sodium hydroxide mixing solutions, and contain residual unreacted lead powder and the solid mixture of impurity; Described catalyzer refers to one or several the mixture in antimony, lead antimony alloy, weisspiessglanz, antimonic salt;
(3) separate the reaction product that (2) process obtains, obtain the mixing solutions and the filter residue that contain NaHPbO2, sodium sulfate and sodium hydroxide;
(4) step (3) filter residue is put into (2) process again, carry out redox reaction again;
(5) mixing solutions of (3) process is carried out to sedimentation, filtration and purification again under maintenance original temperature, further to remove impurity wherein, the NaHPbO after being purified
2, NaOH and Na
2sO
4mixing solutions for subsequent use;
(6) mixing solutions of (5) process carried out cooling and filter, obtaining PbO crystal, and contain Na
2sO
4with residual content NaHPbO
2basic solution;
(7) NaOH is joined gradually to (6) process and obtain in basic solution, NaOH concentration in solution is reached more than 15% gradually, again coolingly make its sodium sulfate solid of separating out low solubility, and obtain containing remaining NaHPbO
2naOH solution;
(8) what (7) process of being somebody's turn to do obtained contains remaining NaHPbO
2naOH solution turn back to (2) process again for reaction;
Concentration of sodium hydroxide solution described in step (2) is 3～14mol/L or the basic solution that adopts step (8) gained, and sodium hydroxide amount of substance is 2-10 times of the contained lead sulfate amount of substance of lead plaster; Reaction described in step (2), temperature is 30～110 DEG C; The wherein said lead powder of step (2) is the lead powder that common lead powder or leaded grid fragmentation obtain, and the size range of its lead powder is 20-400 order, and its dosage is 0.2-3 times of lead plaster weight; Antimony element in step (2) in catalyzer is the 0.01-10% of NaOH solution weight.
2. according to the method for claim 1, it is characterized in that, the concentration of sodium hydroxide solution described in step (2) is 4-7mol/L.
3. according to the method for claim 1, it is characterized in that, step (6) process of cooling adds PbO solid as crystal seed.
4. according to the method for claim 1, it is characterized in that, step (7) NaOH adds gradually to refer to and adds mass concentration 25% or higher NaOH solution or NaOH solid.
5. according to the method for claim 1, it is characterized in that, further comprising the steps of: again dissolve in the NaOH of mass concentration 15-50%-filtration-re-crystallization step of PbO that (6) process is obtained, obtains pure plumbous oxide solid.
6. according to the method for claim 1, it is characterized in that, antimonic salt comprises antimonite or stibnate.
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| CN103723761B (en) * | 2013-12-09 | 2015-06-17 | 东南大学 | Preparing method for nano micron lead sulfate with electrochemical activity and method adopting lead sulfate to prepare lead-acid cell |
| CN103771459B (en) * | 2014-01-16 | 2016-01-13 | 北京化工大学 | A kind of method of reclaim(ed) sulfuric acid sodium from leaded desulfurization waste liquor |
| CN104862481A (en) * | 2014-02-21 | 2015-08-26 | 超威电源有限公司 | Recycling method of waste material containing lead oxide |
| CN104868187B (en) * | 2014-02-21 | 2017-06-06 | 北京化工大学 | A kind of method that lead-acid battery cathode lead oxide is directly reclaimed in the cream from scrap lead |
| CN104141045B (en) | 2014-08-20 | 2017-04-12 | 北京化工大学 | Method for recovering lead oxide from waste lead plaster |
| CN106757114B (en) * | 2015-11-22 | 2019-05-14 | 北京化工大学 | A method of lead oxide is prepared using fuel cell method |
| CN107302118B (en) * | 2016-04-15 | 2020-03-20 | 北京化工大学 | High-performance lead-acid storage battery with recovered lead oxide as active substance |
| CN106299521A (en) * | 2016-08-20 | 2017-01-04 | 超威电源有限公司 | A kind of lead-acid accumulator drenches acid scrap lead mud direct circulation and reclaims the method utilized |
| CN107164636B (en) * | 2017-05-27 | 2019-03-26 | 湘潭大学 | A kind of method that high-purity lead oxide is recycled in waste lead acid battery processing |
| JP7047492B2 (en) * | 2018-03-13 | 2022-04-05 | 住友金属鉱山株式会社 | Method for removing lead compound and method for recovering selenium or tellurium having it |
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