CN103482690A - Method for synthesizing tetrabasic lead sulfate by utilizing positive electrode waste lead plaster and application thereof - Google Patents
Method for synthesizing tetrabasic lead sulfate by utilizing positive electrode waste lead plaster and application thereof Download PDFInfo
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- CN103482690A CN103482690A CN201310381762.6A CN201310381762A CN103482690A CN 103482690 A CN103482690 A CN 103482690A CN 201310381762 A CN201310381762 A CN 201310381762A CN 103482690 A CN103482690 A CN 103482690A
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- lead
- sublimed
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- cream
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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 invention discloses a method for synthesizing tetrabasic lead sulfate by utilizing positive electrode waste lead plaster and application thereof. The method comprises the following steps of washing, filtering, separating, dehydrating, drying, sieving and purifying the positive electrode waste lead plaster, and then, carrying out chemical analysis on a treated mixture, thereby obtaining contents of various components of lead sulfate, lead oxide and free lead in the treated mixture according to chemical analysis, adding lead powder to carry out mixing, grinding and sieving, so that the molar ratio of the lead oxide to lead sulfate after hybrid reaction is (4-5):1; and preserving the heat and presintering the sieved mixture in a resistance furnace, and then heating up to sinter, cooling and drying to obtain the tetrabasic lead sulfate. The method can be used for a storage battery manufacturer to prepare according to convenient conditions of the manufacturer, is simple and easy to implement; the prepared tetrabasic lead sulfate can completely satisfy performance requirements while being applied to battery production, so that early capacity loss of a lead storage battery is restrained, various electrical performances of the battery and a cycle life of the storage battery are greatly improved and prolonged, respectively, thereby not only solving a treatment problem of lead-containing waste materials of the storage battery enterprises, but also lowering production cost of enterprises and changing waste into things of value.
Description
Technical field
the present invention relates to scrap lead cream recovery and utilization technology field, be specifically related to a kind of the utilize synthetic four sublimed lead methods of anodal scrap lead cream and the application in battery thereof.
Background technology
Lead storage battery is because of its powerful, abundant raw materials, and the advantage such as cheap all is widely used in a plurality of fields.But also can produce a large amount of scrap leads that contain in the lead storage battery production process, if discharge will cause serious environmental pollution.Most enterprises still do not form perfect recovery system, general treatment process or will directly be added back in lead plaster and be produced afterwards containing the scrap lead ovendry power is broken, or being sold to metal processing enterprise reclaims, virtually increased the cost of enterprise, therefore seeking the efficient utilization recovery of store battery producer self is research staff's purpose containing scrap lead.
There is early stage capacitance loss in lead storage battery in use and storage process, causes that electrical property descends rapidly, and four sublimed leads (4BS) are electrode active material plumbic oxide (PbO
2) presoma, if pole plate contains a large amount of four sublimed leads after solidifying, just can form the stabilization of bony shelf structure of satisfactory mechanical property when changing into, prevent the active substance obscission caused more greatly due to volume change in charge and discharge process, the early stage capacitance loss that suppresses lead storage battery, can improve every electrical property and the cycle life of battery greatly.
The more method of use is raising and cream temperature or carries out hot setting at present, but the how many and size of the generation content of four sublimed leads in more difficult control lead plaster, once in lead plaster, four sublimed lead too high levels, easily cause changing into difficulty, greatly reduces the battery initial capacity.
Certainly outsourcing 4BS adds in lead plaster and can address this problem, but at present more external companies have grasped the core technology of 4BS, domestic less production, so, if the higher 4BS of outsourcing purity adds in store battery production, can increase the production cost of battery manufacturers.If that can utilize battery manufacturers self makes four sublimed leads containing scrap lead, both solved the processing problem containing scrap lead, reduce again enterprise's production cost, turn waste into wealth.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind ofly utilizes anodal scrap lead cream to synthesize four sublimed lead methods, store battery producer is according to self convenience preparation, operation is simple, four sublimed leads that make are applied to satisfiability energy requirement fully in battery production, the early stage capacitance loss that suppresses lead storage battery, improve every electrical property and the cycle life of battery greatly; Both solved the processing problem of battery manufacturers containing scrap lead, reduced again enterprise's production cost, turned waste into wealth.
The present invention is achieved through the following technical solutions:
A kind ofly utilize anodal scrap lead cream to synthesize four sublimed lead methods, comprise the following steps:
(1) anodal scrap lead cream is washed, filtering separation, dewatered drying, crossed 200～300 mesh sieve purification processes, then the mixture after processing is carried out to chemical analysis;
(2) draw according to chemical analysis the various component contents of processing lead sulfate, plumbous oxide, free lead in rear mixture, add lead powder and carry out mixed grinding 2～3h, cross 200～300 mesh sieves, requiring plumbous oxide after hybrid reaction and the mol ratio of lead sulfate is 4～5:1;
(3) mixture after sieving first is incubated to pre-burning 1h at 100～120 ℃, then is warming up to 500～700 ℃ of sintering 5～8h, cooling drying, obtain four sublimed leads.
The further improvement project of the present invention is that in the mixture after described step (1) is processed, the total content of lead sulfate, plumbous oxide, free lead is greater than 95%.The four sublimed lead purity that make are higher.
The present invention further improvement project is that described chemical analysis method adopts complexometric titration.Lead sulfate in mixture after Check processing, plumbous oxide, free lead content are accurate.
The application of four sublimed leads in battery that the synthetic four sublimed lead methods of the anodal scrap lead cream of the described utilization of claims 1 to 3 make.Current more battery manufacturers is by raising and cream temperature or carry out the hot setting method, how many and the size of the generation content of four sublimed leads in more difficult control lead plaster, once in lead plaster, four sublimed lead too high levels, easily cause changing into difficulty, greatly reduces the battery initial capacity.Application of the present invention, add-on is controlled, satisfiability energy requirement fully, and add the shared lead powder ratio of four sublimed leads in lead plaster seldom, can change fully and cream technique, do not affect production efficiency.Without outsourcing, both solved the processing problem of battery manufacturers containing scrap lead simultaneously, reduced again enterprise's production cost, turned waste into wealth.
Embodiment
Embodiment 1
(1) collect anodal scrap lead cream, anodal scrap lead cream is carried out to purification processes, comprise washing, filtering separation, remove soluble impurity, as carbon black, xylogen and so on, then dewatered drying, mistake 200 mesh sieves, remove large particulate matter.Then the mixture after processing is adopted to the complexometric titration chemical analysis, measured the wherein various component contents of lead sulfate, plumbous oxide, free lead, be respectively that lead sulfate accounts for 61.5%, plumbous oxide accounts for 29.1%, free lead accounts for 7.4%, total content 98%;
(2) requirement that is 4～5:1 according to scrap lead cream after processing and the mol ratio of adding plumbous oxide after the lead powder hybrid reaction and lead sulfate, take the anodal scrap lead cream after 10g processes, wherein: lead sulfate is that 0.020 mole, plumbous oxide are that 0.013 mole, free lead are 0.0036 mole, separately take 0.065 mole, lead powder, carry out mixed grinding 2h, cross 300 mesh sieves;
(3) mixture after sieving first is incubated to pre-burning 1h at 100 ℃, then is warming up to 500 ℃ of sintering 8h, cooling drying, obtain four sublimed leads, and purity is 90%.
Embodiment 2
(1) collect anodal scrap lead cream, anodal scrap lead cream is carried out to purification processes, comprise washing, filtering separation, remove soluble impurity, as carbon black, xylogen and so on, then dewatered drying, mistake 250 mesh sieves, remove large particulate matter.Then the mixture after processing is adopted to the complexometric titration chemical analysis, measured the wherein various component contents of lead sulfate, plumbous oxide, free lead, be respectively that lead sulfate accounts for 56.1%, plumbous oxide accounts for 36.4%, free lead accounts for 5.8%, total content 98.3%;
(2) requirement that is 4～5:1 according to scrap lead cream after processing and the mol ratio of adding plumbous oxide after the lead powder hybrid reaction and lead sulfate, take the anodal scrap lead cream after 10g processes, wherein: lead sulfate is that 0.0185 mole, plumbous oxide are that 0.016 mole, free lead are 0.0028 mole, separately take 0.060 mole, lead powder, carry out mixed grinding 2.5h, cross 250 mesh sieves;
(3) mixture after sieving first is incubated to pre-burning 1h at 110 ℃, then is warming up to 600 ℃ of sintering 6h, cooling drying, obtain four sublimed leads, and purity is 92.0%.
Embodiment 3
(1) collect anodal scrap lead cream, anodal scrap lead cream is carried out to purification processes, comprise washing, filtering separation, remove soluble impurity, as carbon black, xylogen and so on, then dewatered drying, mistake 300 mesh sieves, remove large particulate matter.Then the mixture after processing is adopted to the complexometric titration chemical analysis, measured the wherein various component contents of lead sulfate, plumbous oxide, free lead, be respectively that lead sulfate accounts for 63.1%, plumbous oxide accounts for 30.7%, free lead accounts for 6.0%, total content 99.8%;
(2) requirement that is 4～5:1 according to scrap lead cream after processing and the mol ratio of adding plumbous oxide after the lead powder hybrid reaction and lead sulfate, take the anodal scrap lead cream after 10g processes, wherein: lead sulfate is that 0.021 mole, plumbous oxide are that 0.0138 mole, free lead are 0.0029 mole, separately take 0.069 mole, lead powder, carry out mixed grinding 3h, cross 300 mesh sieves;
(3) mixture after sieving first is incubated to pre-burning 1h at 120 ℃, then is warming up to 700 ℃ of sintering 5h, cooling drying, obtain four sublimed leads, and purity is 91.5%.
Claims (4)
1. one kind is utilized anodal scrap lead cream to synthesize four sublimed lead methods, it is characterized in that comprising the following steps:
(1) anodal scrap lead cream is washed, filtering separation, dewatered drying, crossed 200～300 mesh sieve purification processes, then the mixture after processing is carried out to chemical analysis;
(2) draw according to chemical analysis the various component contents of processing lead sulfate, plumbous oxide, free lead in rear mixture, add lead powder and carry out mixed grinding 2～3h, cross 200～300 mesh sieves, the mol ratio that requires mixed plumbous oxide and lead sulfate is 4～5:1;
(3) mixture after sieving first is incubated to pre-burning 1h at 100～120 ℃, then is warming up to 500～700 ℃ of sintering 5～8h, cooling drying, obtain four sublimed leads.
2. the anodal scrap lead cream of utilization according to claim 1 synthesizes four sublimed lead methods, it is characterized in that: in the mixture after described step (1) is processed, the total content of lead sulfate, plumbous oxide, free lead is greater than 95%.
3. the synthetic four sublimed lead methods of the anodal scrap lead cream of utilization according to claim 1 and 2, is characterized in that: described chemical analysis method employing complexometric titration.
4. the application of four sublimed leads in battery made by the synthetic four sublimed lead methods of the anodal scrap lead cream of the described utilization of claims 1 to 3.
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| CN201310381762.6A CN103482690A (en) | 2013-08-29 | 2013-08-29 | Method for synthesizing tetrabasic lead sulfate by utilizing positive electrode waste lead plaster and application thereof |
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| CN201310381762.6A CN103482690A (en) | 2013-08-29 | 2013-08-29 | Method for synthesizing tetrabasic lead sulfate by utilizing positive electrode waste lead plaster and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271375A (en) * | 2015-10-20 | 2016-01-27 | 深圳市雄韬电源科技股份有限公司 | Method for preparing tetrabasic lead sulfate |
| CN105390763A (en) * | 2015-11-06 | 2016-03-09 | 天能电池集团（安徽）有限公司 | Method for preparing tetrabasic lead sulfate from waste lead plaster |
| CN106587142A (en) * | 2016-11-23 | 2017-04-26 | 超威电源有限公司 | Method for preparing 4BS through waste lead-acid battery |
| 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 |
| CN109052458A (en) * | 2018-10-19 | 2018-12-21 | 阳煤集团山西吉天利科技有限公司 | The preparation process of four basic lead sulphate crystal seed of nanoscale is prepared using waste lead accumulator |
| CN110444829A (en) * | 2018-05-04 | 2019-11-12 | 东南大学 | A method of basic lead sulphate and its electrode are prepared with lead sulfate and lead oxide |
Citations (3)
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|---|---|---|---|---|
| JPS5310827A (en) * | 1976-07-19 | 1978-01-31 | Raika Kk | Method of regenerating lead battery with organic acid |
| US7309478B2 (en) * | 2004-03-19 | 2007-12-18 | Ges Technologies Ip Gmbh | Production of tetrabasic lead sulfate from solid state reactions for the preparation of active plates to be used in lead-acid batteries |
| CN103022594A (en) * | 2011-09-26 | 2013-04-03 | 深圳市雄韬电源科技股份有限公司 | Method for preparing tetrabasic lead sulfate from waste batteries and application of tetrabasic lead sulfate |
-
2013
- 2013-08-29 CN CN201310381762.6A patent/CN103482690A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5310827A (en) * | 1976-07-19 | 1978-01-31 | Raika Kk | Method of regenerating lead battery with organic acid |
| US7309478B2 (en) * | 2004-03-19 | 2007-12-18 | Ges Technologies Ip Gmbh | Production of tetrabasic lead sulfate from solid state reactions for the preparation of active plates to be used in lead-acid batteries |
| CN103022594A (en) * | 2011-09-26 | 2013-04-03 | 深圳市雄韬电源科技股份有限公司 | Method for preparing tetrabasic lead sulfate from waste batteries and application of tetrabasic lead sulfate |
Non-Patent Citations (1)
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| 吴战宇: ""用铅酸蓄电池极板生产过程中废料制备四碱式硫酸铅"", 《蓄电池》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271375A (en) * | 2015-10-20 | 2016-01-27 | 深圳市雄韬电源科技股份有限公司 | Method for preparing tetrabasic lead sulfate |
| CN105390763A (en) * | 2015-11-06 | 2016-03-09 | 天能电池集团（安徽）有限公司 | Method for preparing tetrabasic lead sulfate from waste lead plaster |
| CN105390763B (en) * | 2015-11-06 | 2018-06-29 | 天能电池集团（安徽）有限公司 | The method that scrap lead cream prepares four basic lead sulphates |
| 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 |
| CN106587142A (en) * | 2016-11-23 | 2017-04-26 | 超威电源有限公司 | Method for preparing 4BS through waste lead-acid battery |
| CN106587142B (en) * | 2016-11-23 | 2017-12-29 | 超威电源有限公司 | A kind of method that 4BS is prepared using waste lead acid battery lead cream |
| CN110444829A (en) * | 2018-05-04 | 2019-11-12 | 东南大学 | A method of basic lead sulphate and its electrode are prepared with lead sulfate and lead oxide |
| CN109052458A (en) * | 2018-10-19 | 2018-12-21 | 阳煤集团山西吉天利科技有限公司 | The preparation process of four basic lead sulphate crystal seed of nanoscale is prepared using waste lead accumulator |
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Application publication date: 20140101 |