CN103014347A - 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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- CN103014347A CN103014347A CN2012105351541A CN201210535154A CN103014347A CN 103014347 A CN103014347 A CN 103014347A CN 2012105351541 A CN2012105351541 A CN 2012105351541A CN 201210535154 A CN201210535154 A CN 201210535154A CN 103014347 A CN103014347 A CN 103014347A
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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 plumbous hydrometallurgy field of processing.
Background technology
From 1859 by French slip-stick artist Pulan since the special invention lead-acid cell, lead-acid cell is widely used in the igniting of automobile and the fields such as 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, for example competition of lithium ion battery and nickel metal hydride battery, but lead-acid cell is keeping stable increase with the advantage of its unique cost performance and security always, and it has still occupied the output value of global secondary cell nearly 60%.Show that 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, wherein Lead for China consumption reaches more than 350 ten thousand tons, and the production of lead-acid cell has accounted for more than 85% of above-mentioned plumbous consumption.Because the explored lead resource of China is day by day poor, causes 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 the lead resource problem.The pyrogenic process that relatively falls behind at present reclaims plumbous technology and produced a large amount of leaded dust and lead skim thereof in high-temperature smelting process, has caused the generation of secondary lead pollution problem.
We find that in analysis the lead that current waste and old lead acid accumulator mainly obtains by pyrometallurgical smelting is mainly the lead-acid cell service of producing.Yet the lead that pyrometallurgical smelting obtains mainly is the lead bullion that contains 1-3% impurity, and people are referred to as reduction lead usually.This lead bullion can not directly be used for producing lead plaster, generally needs process lead bullion electrorefining and then becomes shot, and last ball milling oxidation obtains plumbous oxide.Plumbous oxide through and the accent cream of sulfuric acid and add various additives after, be coated in the active substance that becomes on the grid on the 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 with 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 the lead plaster transformed, and obtain at last the difficult point that pure plumbous oxide becomes regenerating oxidation splicer skill.
There is at present the investigator once to report to adopt its lead plaster to lead-acid cell effectively to reduce and the method for producing afterwards plumbous oxide is processed in desulfurization.Chinese patent 201210201272.9 has been reported waste lead acid battery has at first been carried out negative pole powder and the positive powder that independent fragmentation obtains.Positive powder and reductive agent carry out reduction reaction under 300 ℃ of high temperature, then add constitution controller and carbonate or oxyhydroxide and be not higher than 200 ℃ of lower reactions, and the solid that obtains obtains plumbous oxide 200-500 ℃ of lower heating after drying again.The negative pole powder at first with morphology control agent reacting by heating after, again 500 ℃ of following temperature heating, subsequently by behind nitric acid or the hot dissolving with hydrochloric acid, with alkali or ammoniacal liquor reaction, obtain plumbous oxide again.We think, this process not only needs 200-500 ℃ high temperature, 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 the 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) reported that the employing hydrogen peroxide decomposes plumbic oxide, and then dissolved with citric acid that then the technique that obtains plumbous oxide is processed in high-temperature roasting.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 300 ~ 450 ℃ of lower high temperature, be not the technique of an atom economy therefore.External also have the scholar such as R.Kumar to develop the technology that similar citric acid method reclaims the plumbous oxide in the lead-acid cell, its economy also exist same problem (Hydrometallurgy, 2009,95:53-60).
The above-mentioned up-to-date plumbous oxide preparation technology both domestic and external of analysis-by-synthesis finds that these methods can directly obtain plumbous oxide, but the problem that exists mainly contains:
(1) purity of plumbous oxide is not very desirable, usually is mingled with lead carbonate or lead;
(2) need 200-500 ℃ 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 purpose of this invention is to provide the novel process that under a kind of aqueous temperature waste lead acid battery is reclaimed the lead plaster direct production high-purity mangesium oxide lead that obtains.
First technical problem to be solved by this invention is to have avoided existing technique to need first the acid dissolving, 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 the shortcoming of existing arts demand high-temperature roasting, decrease produce raw material consumption and the energy consumption of plumbous oxide process, be the atom economy novel process of a green.
The 3rd technical problem to be solved by this invention provides a kind of plumbous oxide dissolves in alkaline medium-filters-method of purification of recrystallization, the method can farthest improve the purity of plumbous oxide, thereby for making the assurance of supplying raw materials of high-quality lead-acid cell.
The purpose that the present invention will realize is not limited to above-mentioned purpose, and those skilled in the art can be expressly understood other purpose from following detailed description.
For achieving the above object, the invention provides a kind of method from waste lead acid battery reclaiming plumbous oxide, may further comprise the steps:
(1) materials such as lead plaster, stereotype grid, plastics and dilute sulphuric acid that adopt conventional broken apart technique to obtain respectively waste lead acid battery;
(2) lead plaster, lead powder, catalyzer and sodium hydroxide solution are reacted obtain containing NaHPbO
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 (2) process, carried out again redox reaction;
(5) with the mixing solutions of (3) process in the sedimentation, filtration and the purification that keep carrying out under the original temperature again, with further removal impurity wherein, the NaHPbO after being purified
2, NaOH and Na
2SO
4Mixing solutions for subsequent use.
(6) mixing solutions of (5) process is cooled off and filter, obtain the PbO crystal, and contain Na
2SO
4With residual content NaHPbO
2Basic solution;
(7) NaOH is joined gradually (6) process and obtain in the basic solution, make that NaOH concentration reaches more than 15% gradually in the solution, cooling makes its sodium sulfate solid of separating out low solubility again, and obtains containing remaining NaHPbO
2NaOH solution;
What (8) should (7) process obtain contains remaining NaHPbO
2NaOH solution turn back to (2) process and again be used for reaction.
Aforesaid method, further comprising the steps of: the PbO that (9) obtain (6) process again dissolves in the NaOH of mass concentration 15-50%-filters-re-crystallization step, obtains purer plumbous oxide solid.
Wherein, NaOH strength of solution excessive described in the step (2) is 3 ~ 14mol/L, is preferably 4-7mol/L, perhaps adopts the basic solution of step (8) gained, and the temperature of described reaction is 30 ~ 110 ℃, is preferably 60-105 ℃.
The wherein said lead powder of step (2) is the lead powder that common lead powder or leaded grid fragmentation obtain, and the preferred 20-400 order of the size range of its lead powder, its dosage are 0.2-3 times of lead plaster weight.Catalyzer described in the step (2) refers to one or several the mixture in antimony, lead antimony alloy, weisspiessglanz, antimonic salt, antimonite or the 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.For carrying out fast of guaranteeing to react, best reaction conditions is under 30-110 ℃, keeps 20-600 rev/min stirring velocity, successive reaction 0.5-20 hour.
Above-mentioned steps (6) process of cooling adds the PbO solid as crystal seed.
Finish 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 the solution further to separate out, and the sodium sulfate of separating out is filtered.Gained filtrate is returned above-mentioned alkali leaching purification Cheng Jinhang to be recycled.
Method of the present invention can directly obtain purity up to the high-purity plumbous oxide more than 99.99%, thereby satisfy lead-acid cell to the needs of 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 saved the huge energy consumption of said process, and the shortening for the treatment of process, increased substantially plumbous organic efficiency.Experiment shows that the lead recovery of waste lead acid battery is generally between 98.5～99.2%, is higher than the level of present pyrometallurgical smelting 90-95%, thereby has significant environmental value, is a kind of secondary lead novel process of cleaning.
Description of drawings
Fig. 1 is the process flow sheet of one embodiment of the present invention.
Embodiment
Hereinafter come 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 limits it.
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 reacted under the katalysis of catalyzer be converted into plumbous oxide, plumbous oxide is dissolved in simultaneously in the NaOH solution and obtains NaHPbO
2(some document is also with NaHPbO
2Write as Na
2PbO
2Perhaps Na
2Pb (OH)
4).Add excessive lead powder and catalyzer in this mother liquor and reduce plumbic oxide in the lead plaster, and reaction generates and contains NaHPbO under comparatively high temps
2, NaOH and Na
2SO
4Solution, and residual lead powder and the battery material such as the additive that is mingled with of shattering process or clay in process of production in the reaction.After with this solution separating, cool off and stir, and add a small amount of PbO crystal seed and promote separating out of PbO.When treating that solution temperature drops to below 20 ℃, separate above-mentioned reaction solution and obtain the PbO solid and contain sodium sulfate and the NaOH mother liquor of a small amount of PbO.Replenish NaOH solid or NaOH solution in this NaOH mother liquor, improve the concentration of NaOH mother liquor, separate out sodium sulfate in electrolytic solution by common-ion effcet this moment, and the sodium sulfate of separating out is filtered.To remain NaOH solution and reclaim to be used for next circulation.
(1) process of separation lead plaster:
With waste lead acid battery with ordinary method as carrying out fragmentation by crusher, and separate by conventional separation method such as density difference and to obtain lead plaster, stereotype grid, dividing plate, shell, Waste Sulfuric Acid etc.Isolated lead plaster and stereotype grid is for subsequent use.
(2) catalytic conversion process:
The raw material of catalytic conversion process is lead plaster, and wherein the lead in the lead plaster is with Pb, PbSO
4, PbO and PbO
2Form of mixtures exist.In this process, the Pb in the lead plaster and PbO
2Redox reaction occurs under the katalysis of catalyzer obtain plumbous oxide, lead sulfate also is converted into plumbous oxide with NaOH generation desulphurization reaction simultaneously.
Catalytic conversion process may further comprise the steps:
(1) with lead plaster Pb and PbO
2Carry out redox reaction and obtain PbO in the NaOH medium, 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
As seen, Pb and PbO
2Can redox reaction occur spontaneously and obtain PbO, and can obtain the electromotive force of 0.956V.Yet because waste lead acid battery has normally used the used batteries after a lot of circulations, and also very long to the time in secondary lead workshop from scrapping, reclaim again, therefore the most of active substance in the lead-acid cell has been lost electrochemical activity, be difficult to have the same high response capacity with fresh electrode active material, add between them it is solid-affixed tactile reaction, this has caused electrode reaction speed slow.In order to accelerate speed of response between lead powder and the lead dioxide powder, suitable catalyzer is crucial.Second purpose of the present invention provides the catalystic material of the above-mentioned reaction needed of a kind of confession.The design philosophy of catalyzer is at Pb and PbO
2Provide one can carry out transfer transport and the liquid media of exchange between two solids, thereby with solid-solid reaction, Gu change solid-liquid-reaction into.Through a large amount of experimental exploring and contrasts, the present invention finds to drop into a small amount of metallic antimony, lead antimony alloy, weisspiessglanz, antimonic salt (SbCl in the NaOH medium
3, Sb (NO
3)
3Perhaps Sb
2(SO
4)
3Deng), antimonite or stibnate (Na for example
3SbO
4) have good catalytic effect, greatly accelerate Pb and PbO
2Redox reaction between two solids.Further further investigation finds that this effect is in fact finally by containing Na
3SbO
3Perhaps Na
3SbO
4Solution respectively with PbO
2Perhaps the redox reaction between the Pb realizes the transfer of catalytic process electronics.We are with Na
3SbO
3Be example, the catalytic reaction process of antimony catalyst is described.When we to containing Pb powder, PbO
2Drop into Na in the NaOH solution of powder
3SbO
3The time, SbO
3 3-First by PbO
2Oxidation generates PbO and SbO
4 3-, SbO then
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, find that also these materials have similar katalysis, and this is because the antimony in antimony powder or the 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 also be Sb
3+Reaction is created on the more stable SbO of alkalescence with NaOH
3 3-Ion reaches the effect of catalysis.
Because SbO
3 3-Ion does not consume before and after reaction, so the dosage of Sb or Sb compound is that the seldom part of NaOH solution weight can satisfy the catalysis requirement.Usually, in order to guarantee good catalytic effect, the dosage of antimony element is between the 0.1-10% of NaOH solution total amount in the antimony class catalyzer.
Finish 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 the solution further to separate out, and the sodium sulfate of separating out is filtered.Gained filtrate is returned above-mentioned alkali leaching purification Cheng Jinhang to be recycled.
Working cycle may further comprise the steps:
(1) adds NaOH solid or concentrated NaOH solution after the crystallization in the solution that contains NaOH and sodium sulfate of gained, and keep cooling conditions, make and progressively separate out Na in the solution
2SO
4Solid; With
(2) above-mentioned basic solution (being mainly NaOH) of separating out after filtration behind the sodium sulfate solid returns that initial alkali leaching purifies and reaction process recycles.
The present invention during the working cycle to add NaOH strong solution or NaOH solid can so that: (1) impels the sodium sulfate in the electrolytic solution to separate out under common-ion effcet, reaches the purpose of the direct reclaim(ed) sulfuric acid sodium of non-evaporation; (2) NaOH that adds directly comes complexing PbO to use as the raw material of next one circulation; (3) add dense NaOH solution and almost reduce exothermic phenomenon, more be conducive to sodium sulfate and separate out.
Embodiment 1
Getting the specification of buying on 2 markets is 12V, 12Ah common electrical motor-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 lead plaster, grid, Waste Sulfuric Acid, dividing plate and shell through conventional fragmentation with separating.
2) lead plaster that is press-filtered out is put into crusher successively and ball mill is pulverized, sieve with 60 purpose stainless steel meshs subsequently, larger lead plaster particle continues to change over 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 with 20 purpose stainless steel meshs subsequently, and larger plumbous particle continues to change over to pulverizer to be pulverized, until that all lead buttons all see through behind the screen cloth is for subsequent use.
4) configuration 40L weight percent concentration is 32% NaOH solution, solution is placed after as catalyzer 200 gram antimony trisulfate dissolution of solids for subsequent use in NaOH solution simultaneously.
5) with 2 kilograms of lead plasters of (2) process, and add the excessive lead button that 1.2 kilograms (3) obtain and put in the above-mentioned NaOH solution, make Pb and PbO
2, and PbSO
4And react between the NaOH, make their unifications change PbO into, and be dissolved in the NaOH solution.Between the reaction period, keeping temperature of reaction is 90 ℃, and stirring velocity is 100 rev/mins.
6) question response carries out filtering after 4 hours, the filtrate that obtains clarifying, a small amount of residual lead powder and the filter residue of impurity formation.
7) place crystallization kettle to cool off gradually filtrate, add simultaneously 200 gram PbO solids as crystal seed, keeping speed of cooling is 10 ℃/h, and stirring velocity is 60 rev/mins.Slowly separate out PbO solid in the solution this moment, when treating that solution temperature drops to below 20 ℃, separates said mixture, obtains filtrate and plumbous oxide solid.The plumbous oxide solid is for subsequent use as product after washing drying.
8) filtrate that (6) process is obtained is by replenishing the NaOH solid, the actual concentrations of NaOH is brought up to 32% again after, solution is cooled to below 20 ℃, gradually separate out sodium sulfate solid in the solution this moment.This mother liquor is carried out solid-liquid separation 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 the battery production processes such as a small amount of lead powder and barium sulfate add additive substantially, wherein lead powder can again turn back to step (5) and recycles, and perhaps the reselecting method by routine obtains lead powder by separating filter residue.Through Measurement and Computation, above-mentioned global cycle process has obtained 2.95 kilograms plumbous oxide at last, 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 (1), (2) and (3) process of embodiment 1, obtain lead plaster and grid after the fragmentation.
4) configuration 80L weight percent concentration is 30% NaOH solution, solution is placed after as catalyzer 300 gram weisspiessglanz dissolution of solids for subsequent use in NaOH solution simultaneously.
5) with 5 kilograms of lead plasters of (2) process, and add the excessive lead button that 3.5 kilograms (3) obtain and put in the above-mentioned NaOH solution, make Pb and PbO
2, and PbSO
4And react between the NaOH, make their unifications change PbO into, and be dissolved in the NaOH solution.Between the reaction period, keeping temperature of reaction is 100 ℃, and stirring velocity is 100 rev/mins.
4) question response carries out filtering after 2 hours, the filtrate that obtains clarifying, the filter residue that a small amount of residual lead powder and insoluble impurity consist of.
7) place crystallization kettle to cool off gradually filtrate, add simultaneously 0.5 kilogram of PbO solid as crystal seed, keeping speed of cooling is 5 ℃/h, and stirring velocity is 50 rev/mins.Slowly separate out PbO solid in the solution this moment, when treating that solution temperature drops to below 20 ℃, separates said mixture, obtains filtrate and plumbous oxide solid.The plumbous oxide solid is for subsequent use as product after washing drying.
8) filtrate that (6) process is obtained is by replenishing the NaOH solid, the actual concentrations of NaOH is brought up to 30% again after, solution is cooled to below 20 ℃, gradually separate out sodium sulfate solid in the solution this moment.This mother liquor is carried out solid-liquid separation 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 barium sulfate adds substantially substantially except excessive lead powder is residual.Through Measurement and Computation, above-mentioned global cycle process has obtained 7.45 kilograms plumbous oxide at last, and its purity is 99.991%, the rate of recovery 98.5%.
Embodiment 3
Get the identical junked-auto lead-acid cell of embodiment 2, and according to same (1), (2) and (3) process, obtain lead plaster and grid after the fragmentation.
4) configuration 75L weight percent concentration is that 28% NaOH solution is positioned in the sealing bucket for subsequent use.
5) with 5 kilograms of lead plasters of (2) process, and add the excessive lead button that 3.3 kilograms (3) obtain, and 200 commercially available antimony powders put in the above-mentioned NaOH solution as catalyzer, make Pb and PbO
2, and PbSO
4And react between the NaOH, make their unifications change PbO into, and be dissolved in the NaOH solution.Between the reaction period, keeping temperature of reaction is 105 ℃, and stirring velocity is 80 rev/mins.
4) question response carries out filtering after 2 hours, the filtrate that obtains clarifying, the filter residue that a small amount of residual lead powder and insoluble impurity consist of.
7) place crystallization kettle to cool off gradually filtrate, add simultaneously 0.4 kilogram of PbO solid as crystal seed, keeping speed of cooling is 10 ℃/h, and stirring velocity is 50 rev/mins.Slowly separate out PbO solid in the solution this moment, when treating that solution temperature drops to below 20 ℃, separates said mixture, obtains filtrate and plumbous oxide solid.The plumbous oxide solid is for subsequent use as product after washing drying.
8) filtrate that (6) process is obtained is by replenishing 40%NaOH solution, the actual concentrations of NaOH is brought up to 28% again after, electrolytic solution is cooled to below 20 ℃, gradually separate out sodium sulfate solid in the solution this moment.This mother liquor is carried out solid-liquid separation 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 processes such as the lead powder of excess residual in the reaction and a small amount of barium sulfate add basically.Through Measurement and Computation, above-mentioned global cycle process has obtained 7.50 kilograms plumbous oxide at last, and its purity is 99.991%, the rate of recovery 99.2%.
Embodiment 4
(1) gets 5 kilograms in the lead plaster powder that positive/negative plate separates of scrapping of certain lead-acid cell factory, and 2 kilograms contain the antimony amount and be about 0.3% lead antimony alloy grid particle, lead in this alloying pellet can be used as reductive agent, and contained metallic antimony had both been made reductive agent simultaneously, also is Pb and PbO simultaneously
2Catalyzer between the reaction.
(2) configuration 55L weight percent concentration is that 25% NaOH solution is stored in the bucket for subsequent use.
(3) lead plaster and the antimonial lead grain of (1) process are put in the above-mentioned NaOH solution, made Pb and PbO
2, and PbSO
4And react between the NaOH, make their unifications change PbO into, and be dissolved in the NaOH solution.Between the reaction period, keeping temperature of reaction is 105 ℃, and stirring velocity is 50 rev/mins.
4) question response carries out filtering after 3 hours, the filtrate that obtains clarifying, the filter residue that a small amount of residual lead powder and insoluble impurity consist of.
5) place crystallization kettle to cool off gradually filtrate, add simultaneously 0.3 kilogram of PbO solid as crystal seed, keeping speed of cooling is 5 ℃/h, and stirring velocity is 50 rev/mins.Slowly separate out PbO solid in the solution this moment, when treating that solution temperature drops to below 20 ℃, separates said mixture, obtains filtrate and plumbous oxide solid.The plumbous oxide solid is for subsequent use as product after washing drying.
6) filtrate that (6) process is obtained is by replenishing 35%NaOH solution, the actual concentrations of NaOH is brought up to 25% again after, again electrolytic solution is cooled to 10 ℃, separate out gradually the sodium sulfate solid in the solution.This mother liquor is carried out solid-liquid separation 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 basically.Through Measurement and Computation, above-mentioned global cycle process has obtained 5.2 kilograms plumbous oxide at last, and its purity is 99.992%, the rate of recovery 98.9%.
Claims (10)
1. a method that reclaims waste lead acid battery direct production plumbous oxide is characterized in that, may further comprise the 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 and sodium hydroxide solution are reacted obtain containing NaHPbO
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) step (3) filter residue is put into (2) process again, carry out again redox reaction;
(5) with the mixing solutions of (3) process in the sedimentation, filtration and the purification that keep carrying out under the original temperature again, with further removal impurity wherein, the NaHPbO after being purified
2, NaOH and Na
2SO
4Mixing solutions for subsequent use;
(6) mixing solutions of (5) process is cooled off and filter, obtain the PbO crystal, and contain Na
2SO
4With residual content NaHPbO
2Basic solution;
(7) NaOH is joined gradually (6) process and obtain in the basic solution, make that NaOH concentration reaches more than 15% gradually in the solution, cooling makes its sodium sulfate solid of separating out low solubility again, and obtains containing remaining NaHPbO
2NaOH solution;
What (8) should (7) process obtain contains remaining NaHPbO
2NaOH solution turn back to (2) process and again be used for reaction.
2. according to the method for claim 1, it is characterized in that the concentration of sodium hydroxide solution described in the step (2) is 3 ~ 14mol/L or the basic solution that adopts step (8) gained, the sodium hydroxide amount of substance is 2-10 times of the contained lead sulfate amount of substance of lead plaster.
3. according to the method for claim 1, it is characterized in that the concentration of sodium hydroxide solution described in the step (2) is 4-7mol/L.
4. according to the method for claim 1, it is characterized in that, reaction described in the step (2), temperature is 30 ~ 110 ℃.
5. according to the method for claim 1, it is characterized in that the wherein said lead powder of step (2) is the lead powder that common lead powder or leaded grid fragmentation obtain, the size range of its lead powder is the 20-400 order, and its dosage is 0.2-3 times of lead plaster weight.
6. according to the method for claim 1, it is characterized in that the catalyzer described in the step (2) refers to refer to one or several the mixture in antimony, lead antimony alloy, weisspiessglanz, antimonic salt, antimonite or the stibnate.
7. according to the method for claim 1, it is characterized in that the antimony element in the step (2) in the catalyzer is the 0.01-10% of NaOH solution weight.
8. according to the method for claim 1, it is characterized in that step (6) process of cooling adds the PbO solid as crystal seed.
9. 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.
10. according to the method for claim 1, it is characterized in that further comprising the steps of: the PbO that (6) process is obtained again dissolves-filters-re-crystallization step in the NaOH of mass concentration 15-50%, obtain pure plumbous oxide solid.
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