CN103022594B - The application of four basic lead sulphate methods and four basic lead sulphates is prepared from old and useless battery - Google Patents
The application of four basic lead sulphate methods and four basic lead sulphates is prepared from old and useless battery Download PDFInfo
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- CN103022594B CN103022594B CN201110287936.3A CN201110287936A CN103022594B CN 103022594 B CN103022594 B CN 103022594B CN 201110287936 A CN201110287936 A CN 201110287936A CN 103022594 B CN103022594 B CN 103022594B
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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
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Abstract
The present invention is applicable to waste processing arts, provides a kind of from preparing four basic lead sulphate methods and prepared four basic lead sulphates application in the battery from old and useless battery.Four basic lead sulphate methods should be prepared from old and useless battery to comprise process old and useless battery lead plaster, prepare lead citrate or lead oxalate; The content of lead sulfate lead mixture, the content determining lead sulfate in filter residue, lead citrate or lead oxalate, prepare the steps such as four basic lead sulphates.The present invention is by reclaiming from old and useless battery lead plaster, prepare four basic lead sulphates, battery recycling process is made to have huge economic benefit, and do not produce the material of contaminated environment, environmentally friendly, the present invention prepares four basic lead sulphate methods from old and useless battery, simple to operate, with low cost, be very suitable for suitability for industrialized production.
Description
Technical field
The invention belongs to waste processing arts, particularly relate to a kind of from preparing four basic lead sulphate methods and prepared four basic lead sulphates application in the battery from old and useless battery.
Background technology
Four basic lead sulphates (hereinafter referred to as 4BS) exist as intermediate forms in positive pole, and capacity of lead acid battery can be avoided to decay in early days.At present usually with to improve and cream or curing temperature improve 4BS content in lead plaster, in battery forming process, can there is oxidation reaction and be converted into a large amount of compact grained PbO in 4BS
2, be linked to be porous PbO
2fine grain aggregation. this aggregation viewed from configuration with 4BS original plesiomorphism.The PbO that this process obtains
2structural strength is than the PbO come by 3BS inversion of phases
2much bigger, the pole plate mechanical strength of formation increases, thus extends battery.In addition, application 4BS adds in anode diachylon as additive by a certain amount of, can realize not only increasing battery capacity but also the effect of extending battery life.
The recovery of lead-acid battery, relates to the process of lead-acid battery lead plaster to isolate lead from old and useless battery.Often adopt some physical separation and chemical treatment method, such as hydrometallurgical, electrowinning and melting (pyrometallurgical smelting method) etc.
In conventional method, battery lead plaster is put into smelting furnace, and fusion and decomposition obtains metallic lead at a certain temperature.The type of furnace of melting mainly contains the professional type of furnaces such as reverberatory furnace, rotary furnace, blast furnace.And PbSO in waste diachylon
4fusing point is high, and the temperature of decomposing completely more than 1000 DEG C, will can produce a large amount of SO in smelting process under high temperature
2, also can form a large amount of lead volatility and lead dust.Therefore, PbSO
4pyrometallurgical method have many shortcomings, need specific step to prevent SO
2be discharged in external environment condition, high-temperature process can produce and a large amount of harmful carry plumbous smog, dust and waste residue, has a strong impact on the healthy of surrounding environment and people.Hydrometallurgical has been used to, with soluble metal sulfate to remove the element sulphur in battery scrap lead cream, be separated by soluble metal sulfate from the insoluble plumbous product that recycling process produces.But due to desulfurization conversion efficiency, the plumbous product collected often retains a large amount of sulphur of some forms, if the product of collection is placed in smelting furnace, some special methods still must be taked to guarantee SO
2discharge fully processed, difficulty and expend all larger.Some scholar introduces electrowinning, solves the SO in lead plaster pyrometallurgical smelting process
2discharge and volatilization problems plumbous under high temperature.But need complicated chemicals lead to be dissolved into the form being applicable to process in the battery, itself also belong to energy intensive.This technology investment is large, difficult control, and the cycle is long, and power consumption is high, and alkaline consumption is large, is difficult to large-scale production.
Therefore, at present, from old and useless battery, reclaim the product obtained be essentially plumbous or lead monoxide, brown lead oxide, economic benefit is low, and seriously polluted.
Summary of the invention
In view of this, the object of the present invention is to provide one to prepare four basic lead sulphate methods from old and useless battery, solve old and useless battery in prior art and reclaim the technical problem that economic benefit is low, contaminated environment is serious.
The present invention is achieved in that
Old and useless battery lead plaster is dry, grinding, obtains grinding rear old and useless battery lead plaster;
Be added to by old and useless battery lead plaster after this grinding containing in the citric acid of hydrogen peroxide or oxalic acid solution, Separation of Solid and Liquid after reaction, collects filter residue;
Determine the content of the content of lead sulfate in filter residue, lead citrate or lead oxalate;
Be 4-4.5: 1 filter residue and lead monoxide to be mixed by lead citrate or lead oxalate mole and the mole sum of lead monoxide and the ratio of lead sulfate mole, roasting 2-16 hour under temperature is 350-600 DEG C of condition, grinding obtains four basic lead sulphates.
The present invention is by reclaiming from old and useless battery lead plaster, prepare four basic lead sulphates, battery recycling process is made to have huge economic benefit, and do not produce the material of contaminated environment, environmentally friendly, the present invention prepares four basic lead sulphate methods from old and useless battery, simple to operate, with low cost, be very suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention prepares four basic lead sulphate method flow diagrams from old and useless battery.
Fig. 2 is the XRD figure of four basic lead sulphate powder prepared by the embodiment of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Refer to Fig. 1, Fig. 1 shows the embodiment of the present invention and prepares four basic lead sulphate method flow diagrams from old and useless battery, comprises the steps:
Step S01, process old and useless battery lead plaster
Old and useless battery lead plaster is dry, grinding, obtains grinding rear old and useless battery lead plaster;
Step S02, prepares lead citrate or lead oxalate, lead sulfate mixture
Be added to by old and useless battery lead plaster after described grinding containing in the citric acid of hydrogen peroxide or oxalic acid solution, Separation of Solid and Liquid after reaction, collects filter residue;
Step S03, determines the content of the content of lead sulfate in filter residue, lead citrate or lead oxalate;
Step S04, prepares four basic lead sulphates
Be 4-4.5: 1 filter residue and lead monoxide to be mixed by lead citrate or lead oxalate mole and the mole sum of lead monoxide and the ratio of lead sulfate mole, roasting 2-16 hour under temperature is 350-600 DEG C of condition, grinding obtains four basic lead sulphates.
Particularly, the embodiment of the present invention prepares four basic lead sulphate methods from old and useless battery, by lead monoxide, brown lead oxide and citric acid in old and useless battery lead plaster or oxalic acid are reacted, generate lead citrate or lead oxalate, lead monoxide is resolved into again by high-temperature roasting lead citrate or lead oxalate, by lead monoxide and lead sulfate pyroreaction, generate four basic lead sulphates; Achieve preparation from old and useless battery and there are four basic lead sulphates of significant application value, substantially increase the economic benefit of old and useless battery treatment, in whole production technology, do not produce the material of contaminated environment simultaneously, environmentally friendly.
Particularly, before step S01, also comprise the step of old and useless battery being carried out discharge process.Old and useless battery is carried out discharge process, makes the voltage of single old and useless battery between 0-1V, be preferably 0V.By being discharged by old and useless battery, the active material major part in battery is made to be converted into PbSO
4, greatly reduce the existence of impurity in old and useless battery lead plaster, make follow-up four prepared basic lead sulphates have higher purity.In old and useless battery lead plaster after discharge process, main component is PbSO
4, PbO
2, PbO and Pb
After old and useless battery discharge process, adopt machinery to disassemble or the method (as battery pole plates rotary collision or conical hopper vibrations) of cracking and sorting, lead plaster is isolated from battery (stereotype grid can directly melt down use or use through other cycle for the treatment of); Again by old and useless battery lead plaster after vacuumize or the drying of roller-way method, baking temperature is 50 ~ 100 DEG C, then carries out grinding or pulverizing, and makes the particle diameter of old and useless battery lead plaster be preferably 50-200 order; By grinding, the old and useless battery lead plaster of reunion is broken up and smashes, destroy PbSO fine and close in lead plaster
4salinization layer, makes reaction more abundant, make the lead citrate that draws or lead oxalate predecessor thinner, in old and useless battery lead plaster, plumbous utilance is higher.
Particularly, before step S02, also comprise the step of determining to grind lead monoxide, brown lead oxide content in rear old and useless battery lead plaster, defining method does not limit, such as, and XRD diffraction or chemistry titration etc.
Particularly, in step S02, by citric acid or oxalic acid soluble in water, preparation citric acid or oxalic acid solution, the mass fraction of this citric acid or oxalic acid is 20% ~ 60%.Old and useless battery lead plaster after the grinding obtained in step S01 is added in this citric acid or oxalic acid solution, add hydrogen peroxide simultaneously, obtain mixed solution, mixed solution pH value is regulated to be preferably 3-7, under temperature is preferably 15-30 DEG C of condition, preferred stirring reaction 3-8 hour, makes the brown lead oxide in lead plaster, lead monoxide all be generated lead citrate or lead oxalate by reaction by the citric acid or oxalic acid using above-mentioned pH value.
The mol ratio of this brown lead oxide and hydrogen peroxide is preferably 1: 3-6, by using hydrogen peroxide as reducing agent, achieve the reduction of tetravalence lead ion on the one hand, on the other hand, hydrogen peroxide can send out decomposition in subsequent steps, form water and oxygen, do not produce and anyly obtain impurity, achieve the high-purity of finally prepd four basic lead sulphates.Meanwhile, by using excessive hydrogen peroxide, tetravalence lead ion in old and useless battery lead plaster is completely reduced.
In this old and useless battery lead plaster, the ratio of integral molar quantity and the citric acid of brown lead oxide and lead monoxide or the mole of oxalic acid is preferably 1: 5-8, by using excessive citric acid or oxalic acid, lead oxide in old and useless battery lead plaster and brown lead oxide are all reacted, generate lead citrate or lead oxalate, plumbous utilance is promoted greatly, decreases the content of impurity in four basic lead sulphates finally prepared simultaneously.
In this step, lead, lead monoxide and citric acid or oxalic acid react, and generate lead citrate or lead oxalate; Brown lead oxide is under the effect of hydrogen peroxide, and tetravalence lead ion is reduced to lead（II） ion, then generates lead citrate or lead oxalate with citric acid or oxalic acid reaction; Lead sulfate does not then participate in reaction.This step reaction formula is expressed as:
Pb+PbO+PbO
2+C
6H
8O
7·H
2O+H
2O
2→PbC
6H
6O
7·H
2O+H
2+H
2O+O
2
Or Pb+PbO+PbO
2+ H
2c
2o
42H
2o+H
2o
2→ PbC
2o
4+ H
2+ H
2o+O
2
After the reacting completely of step S02, solution after reaction is carried out Separation of Solid and Liquid, preferably adopts filtration, collect filter residue, the main component in filter residue is lead sulfate; Lead citrate or lead oxalate.Regather filtrate, in filtrate, main component is citric acid or oxalic acid solution, can directly reuse.
Step S03, by the content of the content of lead sulfate in the method determination filter residues such as XRD diffraction or chemistry titration, lead citrate or lead oxalate.
Particularly, in step S04, the filter residue that step S03 collects is carried out drying, and then grinds.In the filter residue after grinding, add lead monoxide (yellow lead PbO), use the lead monoxide Homogeneous phase mixing that mixer etc. stirs the filter residue after making grinding and adds.The addition of this lead monoxide is 1: 4-4.5 than the mole of lead citrate or lead oxalate in upper filter residue with the lead monoxide mole sum added for making lead sulfate mole in filter residue; Such as, lead sulfate mole: lead monoxide mole+lead citrate or lead oxalate mole are 1: 4.
Be added in reactor by the mixture of above-mentioned filter residue and lead monoxide, temperature is adjusted to 350-600 DEG C, roasting 2-16 hour, in roasting process, lead citrate or lead oxalate decompose, and generate lead monoxide; The lead monoxide be decomposed to form and the lead monoxide added react with lead sulfate together, generate four basic lead sulphates; This step reaction temperature is 350-600 DEG C, is preferably 360-440 DEG C; Further, in reactor, air or oxygen is passed in course of reaction.By passing into air or oxygen in reactor, and react at 360-440 DEG C, lead citrate or lead oxalate complete reaction is made to generate lead monoxide on the one hand, simultaneously, lead monoxide and lead sulfate are reacted fully, realizes preparation-obtained four basic lead sulphates and there is higher purity.
Further, after step S04, by the grinding altogether under 40 ~ 70 DEG C of conditions of preparation-obtained four basic lead sulphates, can be prepared into the powder that ultra-fine 4BS is main component, in this step, grinding uses Raymond machine or vibrations mill equipment to carry out.
The embodiment of the present invention provides above-mentioned further and prepares four basic lead sulphates application in the battery prepared by four basic lead sulphate methods from old and useless battery.
Refer to Fig. 2, Fig. 2 shows the XRD figure of four basic lead sulphate powder prepared by the embodiment of the present invention, and Fig. 2 can find out, the preparation-obtained four basic lead sulphate crystal formations of the embodiment of the present invention four basic lead sulphate preparation method are complete, and purity is high.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. prepare a method for four basic lead sulphates from old and useless battery, comprise the steps:
Old and useless battery is carried out discharge process, makes the voltage of single described old and useless battery be 0-1 volt;
The lead plaster of old and useless battery is dry, grinding, obtains grinding rear old and useless battery lead plaster;
Be added to by old and useless battery lead plaster after described grinding containing in the citric acid of hydrogen peroxide or oxalic acid solution, adjust ph is 3-7, and Separation of Solid and Liquid after reaction collects filter residue;
Determine the content of the content of lead sulfate in filter residue, lead citrate or lead oxalate;
Be that filter residue and lead monoxide mix by 4-4.5:1 by lead citrate or lead oxalate mole with the mole sum of lead monoxide and the ratio of lead sulfate mole, roasting 2-16 hour under temperature is 350-600 DEG C of condition, grinding obtains four basic lead sulphates.
2. the method preparing four basic lead sulphates from old and useless battery as claimed in claim 1, it is characterized in that, after described grinding, old and useless battery lead plaster particle diameter is 50 ~ 200 orders.
3. the method preparing four basic lead sulphates from old and useless battery as claimed in claim 1, it is characterized in that, described old and useless battery lead plaster after grinding to be added to containing before the step in the citric acid of hydrogen peroxide or oxalic acid solution, also to comprise the step determining brown lead oxide and lead oxide mole in old and useless battery lead plaster after described grinding.
4. the method preparing four basic lead sulphates from old and useless battery as claimed in claim 3, is characterized in that, described hydrogen peroxide is 1:3-6 with the mol ratio of brown lead oxide in the rear old and useless battery lead plaster of grinding.
5. the method preparing four basic lead sulphates from old and useless battery as claimed in claim 3, it is characterized in that, after described grinding, in old and useless battery lead plaster, brown lead oxide and lead oxide integral molar quantity are 1:5-8 with the ratio of described citric acid or oxalic acid mole.
6. the as claimed in claim 1 method preparing four basic lead sulphates from old and useless battery, is characterized in that, is describedly added to by old and useless battery lead plaster after grinding containing in the step in the citric acid of hydrogen peroxide or oxalic acid solution, and reaction temperature is 10-60 DEG C.
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| CN104178631A (en) * | 2013-07-22 | 2014-12-03 | 天能电池(芜湖)有限公司 | Lead recycling technology of lead pollution for storage battery |
| CN103413937B (en) * | 2013-08-29 | 2015-06-17 | 天能集团江苏特种电源有限公司 | Method for synthesizing high-purity four-basic lead sulfate and application thereof |
| CN103482690A (en) * | 2013-08-29 | 2014-01-01 | 天能集团江苏特种电源有限公司 | Method for synthesizing tetrabasic lead sulfate by utilizing positive electrode waste lead plaster and application thereof |
| CN104651616A (en) * | 2015-02-15 | 2015-05-27 | 天能集团江苏科技有限公司 | Method for desulfurizing scrap lead paste of lead-acid storage battery at low temperature |
| CN105958077B (en) * | 2016-07-06 | 2019-01-04 | 渤海大学 | A kind of method of sol-gal process preparation four basic lead sulphate of little crystallite size |
| CN106684463A (en) * | 2016-07-14 | 2017-05-17 | 安徽轰达电源有限公司 | Method for preparing 4BS seed crystal of lead-acid battery employing grinding method |
| GB201812664D0 (en) | 2018-08-03 | 2018-09-19 | Imperial Innovations Ltd | Recycling of lead-and tin-based materials |
| CN109052458B (en) * | 2018-10-19 | 2020-06-19 | 阳煤集团山西吉天利科技有限公司 | Preparation process for preparing nanoscale tetrabasic lead sulfate crystal seeds by using waste lead storage batteries |
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| CN101573461A (en) * | 2006-11-08 | 2009-11-04 | 剑桥企业有限公司 | Lead recycling |
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| CN101573461A (en) * | 2006-11-08 | 2009-11-04 | 剑桥企业有限公司 | Lead recycling |
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| Title |
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| 《用铅酸蓄电池极板生产过程中的废料制备四碱式硫酸铅》;吴战宇等;《蓄电池》;20110228;第49卷(第2期);74-76页 * |
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