CN1038315A - A kind of method that reclaims lead from scrap battery - Google Patents

A kind of method that reclaims lead from scrap battery Download PDF

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Publication number
CN1038315A
CN1038315A CN88103531A CN88103531A CN1038315A CN 1038315 A CN1038315 A CN 1038315A CN 88103531 A CN88103531 A CN 88103531A CN 88103531 A CN88103531 A CN 88103531A CN 1038315 A CN1038315 A CN 1038315A
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China
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scrap
plumbous
negative electrode
lead powder
paste
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CN88103531A
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CN1012909B (en
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易应文
郑克文
王如松
钟火坤
王信友
杨文秀
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Pla Wuhan Air Force Four Station Equipment Repair Shop
No712 Inst No7 Research Inst Chinese Shipbuilding Corp
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Pla Wuhan Air Force Four Station Equipment Repair Shop
No712 Inst No7 Research Inst Chinese Shipbuilding Corp
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Priority to CN88103531A priority Critical patent/CN1012909B/en
Publication of CN1038315A publication Critical patent/CN1038315A/en
Publication of CN1012909B publication Critical patent/CN1012909B/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The present invention is a kind of about reclaiming plumbous method from scrap battery, in the electrolyzer that is adopted, the paste spread type negative electrode that comprises electrolyzer, dilute alkaline electrolyte and the anode of arranging with tight assembly structure form, dividing plate and make with scrap lead powder, water and paste after the reduction processing, by the solid phase reduction electrolytic process, it is plumbous to make the paste spread type negative electrode form reduction.The present invention is except having free of contamination advantage, also because its electrolysis voltage is low, current density is big, current efficiency is high, so have the advantage that electrolysis time is short, energy consumption is low and production cost is low.

Description

A kind of method that reclaims lead from scrap battery
The present invention a kind ofly reclaims about scrap metal, particularly a kind of in electrolyzer about reclaiming plumbous method from scrap battery.
Reclaim plumbous method from scrap battery, existing " pyrogenic process " and " wet method " two kinds." pyrogenic process " domestic manufacturer adopts, and this method technology falls behind (as: removal process must be carried out), low, the contaminate environment-can produce lead fume and poison gas (as: sulfurous gas, chlorine etc.) in fusion process of the rate of recovery about 1000 ℃." wet method " is the plumbous method of a kind of free of contamination recovery, can be divided into " alkaline process " and " acid system " by its used electrolyte medium kind.Two method technologies can be respectively referring to U.S. Pat 4107007 and US4597841 document: the former be a kind of " suspension electrolysis method ", be characterized in the lead thing behind the high alkali liquid dissolving mechanical treatment scrap battery of the 8-12N of 4-6 times of theoretical amount, this leaded alkali lye of electrolysis in the electrolyzer of non-tight assembly structure then, reclaim plumbous with buoyant spongy lead form, except that electrolyzer, also has agitator in the used electrolyzer, optional equipments such as recycle pump, the latter is a kind of " two steps reduction electrolytic process ", be characterized in making being pressed into formula negative electrode solid phase reduction in 0-36% sulfuric acid and being electrolyzed to produce lead, use electrolyzer and optional equipment oil press.Because These characteristics, it is plumbous to determine them to reclaim with little electric current, high electrolysis voltage (reaching 3.5 volts), cause pair react many, energy consumption is big, electrolysis time is long and production cost is high.
The objective of the invention is at above-mentioned deficiency, provide a kind of that a kind of electrolysis time is short, energy consumption is low to reclaim plumbous method from scrap battery.
The object of the present invention is achieved like this: behind the scrap battery mechanical treatment, obtain the plumbous parts of sulfur waste bulk sour and leaded and plumbousization thing, scrap lead powder, it is characterized in that electrolyzer 1 contains the dilute alkaline electrolyte 2 of 0.5-4N and is anode 3, dividing plate 4 and the paste spread type negative electrode 5 that tight assembly structure form is arranged, by the solid phase reduction electrolytic process, it is plumbous to make paste spread type negative electrode 5 form reduction, electrolysis temperature is 20-80 ℃, and best sig water concentration is 2N.
Purpose of the present invention can also realize like this: paste spread type negative electrode 5 can be formulated in proportion by the low price scrap lead powder after water and paste and the reduction processing, and it can form reduction under the electrolysis voltage of 1.3-2 volt plumbous.The scrap lead powder can be reduced in sulfur waste acid by the scrap lead powder and make at a low price, the weight ratio of scrap lead powder and sulfur waste acid can be 1: 1.051: 1.15, temperature of reaction can be 100-200 ℃, with 110-140 ℃ for well, lead in the scrap lead powder and plumbic oxide and the sulfur waste acid mechanism of action mainly are:
Because reaction (1) is equivalent to short circuit microbattery and reaction (2) by H 2SO 4Produced hydrogen in statu nascendi, so above-mentioned reduction reaction is abundant, promptly the plumbous transformation efficiency of high price can reach 99%.
The present invention is except the advantage with wet method, owing to adopted new operational path and electrolysis process, promptly machinery is handled scrap battery and is obtained the scrap lead powder earlier, after utilize sulfuric acid and plumbous high price leadization thing in the scrap lead powder is reduced in the scrap battery to be converted into low price leadization thing, again with water, make the paste spread type negative electrode with paste, it is plumbous to make it to obtain reduction with " solid phase reduction electrolytic process " at last in diluted alkaline, so with existing wet method (hereinafter to be referred as old method) ratio, advantage is more outstanding: Faradaic current can reach 30-50 ampere/kilogram waste material, than the big approximately 1-2 of old method doubly, so electrolysis time short (only needing 4-5 hour), the production efficiency height.Current efficiency can reach 90-95%, and higher by about 20% than old method, electrolysis voltage is low, than low 1 volt approximately of old method, pays and reacts less and power saving 300-400 degree/ton lead; The less residual and alkali lye of leadization thing can be handled by inexpensive liming and upgrade reuse in the electrolytic solution, and energy consumption is low as from the foregoing.In addition, the present invention is owing to having adopted tight assembly structure and not needed optional equipment, so reaction compartment is compact and production cost is low.
Description of drawings:
Fig. 1 is an electrolyzer synoptic diagram of the present invention.
Fig. 2 is a technical process block diagram of the present invention.
Below in conjunction with drawings and Examples the present invention is made and to further specify.
As shown in Figure 1, electrolyzer 1 is arranged, dilute alkaline electrolyte 2, anode 3, dividing plate 4, paste spread type negative electrode 5, locking end plate 6, tie down screw 7 etc.
Dilute alkaline electrolyte 2 used alkali can be alkali metal hydroxide, alkaline carbonate, ammonium hydroxide, volatile salt.Anode 3 can select for use materials such as nickel, stainless steel to make.Paste spread type negative electrode 5 is scrap lead powder, water and the paste mixing furnishing negative electrode cream after being handled by reduction, cream is applied on the wire netting (as: drawing in the net of doing such as copper, lead, iron, titanium, netting, punching net) makes the paste spread type negative electrode, the porosity of negative electrode is 45-70%, thickness is 2-10mm, press waste material weight (%), the consumption of institute's water and paste is respectively that 5-15,0.1-2 and paste can be selected materials such as polyvinyl alcohol, carboxymethyl cellulose rope for use.
During electrolysis, as long as multi-disc paste spread type negative electrode, dividing plate, anode are deposited in together according to the order of sequence, clamping is made and is pressed Lu formula electrolysis heap, negative electrode is close to assembling and is supported on voluntarily in the electrolysis heap, again electrolysis is stacked in the dilute alkaline soln electrolyzer of 0.5-4N, at 20-80 ℃ of following electrolytic reduction, this moment, anode produced oxygen, and negative electrode obtains spongy lead.Voltage rises in 1.3-2 volt gradually in electrolytic process, if be lower than 1.3 volts, electrolysis effectiveness is poor, and as if being higher than 2 volts, then cathode hydrogen evolution is paid reaction and can be enlarged markedly.
Embodiment one: waste lead accumulator obtains leaded useless powder behind mechanical treatment, and its composition is a plumbous oxide 7.80%, lead sulfate 51.74%, metallic lead 6.59%, plumbic oxide 33.79%.The scrap lead powder is put into the sulfur waste acid that obtains from waste lead accumulator, heat 140 ℃, make plumbic oxide be reduced into leadization thing at a low price, at a low price leadization thing and 0.1% polyvinyl alcohol and 10% water are modulated into cream and are coated in and does the thick paste spread type negative electrode 5 into about 3mm on the wire netting again, then with paste spread type negative electrode 5, dividing plate 4, anode 3 is assembled into electrolysis heap as shown in Figure 1, and make it at room temperature with in the 2N sodium hydroxide solution carry out electrolysis, current density is 50-30 ampere/kilogram waste material, electrolysis voltage is the 1.5-2 volt, finish through electrolysis in 4-5 hour, negative electrode becomes the spongy lead pole plate, wherein contain the lead sulfate of 2% impurity approximately, electrolytic cathode efficiency is greater than 92%.
Embodiment two: waste material to be recycled is the scrap lead ash of lead storage battery factory, and composition mainly is the lead sulfate of plumbous oxide and about 15%, and surplus is little metal lead.This kind waste material does not need mechanical treatment and reduction to handle, and directly makes the paste spread type negative electrode of thick about 3mm as example 1 and is assembled into the electrolysis heap, carries out electrolysis in 2N sodium hydroxide under room temperature.Electrolysis voltage is the 1.4-2 volt, and cathode current density is 50-40 ampere/kilogram waste material, finishes through electrolysis in 4 hours approximately.Negative electrode obtains the spongy lead electrode, sulfur-bearing lead plumbate 2-1.5% wherein, and plumbous 97-98%, cathode efficiency is 94%.
The resulting leaded parts of spongy lead pole plate in the foregoing description and mechanical treatment scrap battery, their aftertreatment are it to be dropped in the lead smelting furnace melt ingot casting.
Fig. 1 is a Figure of abstract of the present invention

Claims (4)

1, a kind ofly reclaims about scrap metal, particularly a kind of about reclaiming plumbous method from scrap battery, behind the scrap battery mechanical treatment, obtain the plumbous parts of sulfur waste bulk sour and leaded and plumbousization thing, scrap lead powder, it is characterized in that electrolyzer 1 contains the dilute alkaline electrolyte 2 of 0.5-4N and is anode 3, dividing plate 4 and the paste spread type negative electrode 5 that tight assembly structure form is arranged, by the solid phase reduction electrolytic process, it is plumbous to make paste spread type negative electrode 5 form reduction, electrolysis temperature is 20-80 ℃, and best sig water concentration is 2N.
2, the plumbous method of recovery according to claim 1, the plumbous electrolysis voltage that is adopted that it is characterized in that reducing is the 1.3-2 volt.
3, the plumbous method of recovery according to claim 1 is characterized in that paste spread type negative electrode 5 is to be mixed with in proportion by the low price scrap lead powder after water and paste and the reduction processing.
4, according to claim 1 or the plumbous method of 3 described recovery, it is characterized in that the scrap lead powder is to be reduced in sulfur waste acid by the scrap lead powder to make at a low price, the weight ratio of scrap lead powder and sulfur waste acid is 1: 1.05-1: 1.15, temperature of reaction is 100-200 ℃, with 110-140 ℃ for well.
CN88103531A 1988-06-08 1988-06-08 Process for recovering lead from exhuasted accumulator Expired CN1012909B (en)

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Application Number Priority Date Filing Date Title
CN88103531A CN1012909B (en) 1988-06-08 1988-06-08 Process for recovering lead from exhuasted accumulator

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Application Number Priority Date Filing Date Title
CN88103531A CN1012909B (en) 1988-06-08 1988-06-08 Process for recovering lead from exhuasted accumulator

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CN1038315A true CN1038315A (en) 1989-12-27
CN1012909B CN1012909B (en) 1991-06-19

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101748277A (en) * 2008-12-03 2010-06-23 江苏航虹电源有限公司 Method for recovering lead from waste lead acid batteries
CN1891841B (en) * 2005-07-04 2011-04-20 赵庭义 Regenerative lead processing method and apparatus
CN102420344A (en) * 2011-12-02 2012-04-18 浙江汇同电源有限公司 Technology for reclaiming lead from waste lead storage batteries by using pulse power supply
CN102437397A (en) * 2011-12-16 2012-05-02 浙江汇同电源有限公司 Device for recovering lead in lea-acid storage battery by pulse power supply
CN103782899A (en) * 2014-01-26 2014-05-14 山东省潍坊市农业科学院 Method of preventing field mung beans from degenerative mildew
CN107268028A (en) * 2017-06-30 2017-10-20 湘潭大学 A kind of method that lead bullion is prepared from waste lead acid battery lead plaster

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101250720B (en) * 2007-11-30 2010-06-02 浙江工业大学 Method for electrolytic reduction and regeneration of lead resource in lead paste in waste lead acid accumulator

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1891841B (en) * 2005-07-04 2011-04-20 赵庭义 Regenerative lead processing method and apparatus
CN101748277A (en) * 2008-12-03 2010-06-23 江苏航虹电源有限公司 Method for recovering lead from waste lead acid batteries
CN102420344A (en) * 2011-12-02 2012-04-18 浙江汇同电源有限公司 Technology for reclaiming lead from waste lead storage batteries by using pulse power supply
CN102437397A (en) * 2011-12-16 2012-05-02 浙江汇同电源有限公司 Device for recovering lead in lea-acid storage battery by pulse power supply
CN103782899A (en) * 2014-01-26 2014-05-14 山东省潍坊市农业科学院 Method of preventing field mung beans from degenerative mildew
CN103782899B (en) * 2014-01-26 2016-02-24 山东省潍坊市农业科学院 A kind of field mung bean that prevents goes bad mildew and rot method
CN107268028A (en) * 2017-06-30 2017-10-20 湘潭大学 A kind of method that lead bullion is prepared from waste lead acid battery lead plaster

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