CN100362691C - Cyclic utilization method and apparatus of lead dioxide from storage cells - Google Patents

Cyclic utilization method and apparatus of lead dioxide from storage cells Download PDF

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Publication number
CN100362691C
CN100362691C CNB2006100003931A CN200610000393A CN100362691C CN 100362691 C CN100362691 C CN 100362691C CN B2006100003931 A CNB2006100003931 A CN B2006100003931A CN 200610000393 A CN200610000393 A CN 200610000393A CN 100362691 C CN100362691 C CN 100362691C
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lead
powder
pbo
stone roller
formula pulverizer
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CN1805208A (en
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赵恒祥
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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 relates to a cycle utilization method of lead dioxide of an accumulator and a device thereof. When the temperature is 80 DEG to 100DEG, an anode plate is parched; when moisture content is less than 10 wt%, the anode plate is extracted, and slab lattices and lead plaster are separated; the lead plaster is pulverized to PbO2 power through a roller pulverizer, air output of a positive pressure blower and a negative pressure fan is controlled, the air output passes through an air nozzle, micro negative pressure is formed in the roller pulverizer, and the PbO2 power is collected to be collected in a powder collector; when the lead plaster is stirred, the collected PbO2 power is added into the lead powder according to 4.5-5.0 wt% of the content of the lead power. The present invention utilizes electrode plates of the accumulator after the electrode plates of the accumulator are written-off. The present invention has the advantages of easy material fetching, easy formation and initial stage capacity improvement, and can improve the cyclic life of the accumulators.

Description

The recycling method and apparatus of lead dioxide from storage cells
Technical field
The present invention relates to a kind of recovery and reuse of scrapping brown lead oxide in the storage battery.
Technical background
At present, to scrapping the recovery and reuse of brown lead oxide in the storage battery, be by preparation lead orthoplumbate (Pb 3O 4, be commonly called as red lead) finish.Production procedure is as follows: electrolytic lead (raw material) is made lead powder (PbO) through Ba Dunshi or Tianjin, island formula ball mill, and the heating lead powder toasts it to 450-500 ℃, is ground to certain fineness at last and makes lead orthoplumbate (Pb 3O 4).
The shortcoming of this recycling method is:
(1) use electrolytic lead to produce red lead, the cost height as raw material.
(2) produce red lead and need add facilities such as ball mill, baking oven, pulverizing, need infusion of financial resources increase expense.
(3) red lead is produced occupied ground, increases to pollute.
Summary of the invention
The objective of the invention is to, a kind of recycling method and apparatus of lead dioxide from storage cells is provided.
For achieving the above object, the present invention takes following technical scheme:
Recycling method is: when 80～100 ℃ of temperature positive plate is dried, take out positive plate when treating moisture less than 10wt%, grid is separated with lead plaster; Again lead plaster is ground into PbO at stone roller formula pulverizer 2Powder is controlled positive pressure fan and the negative-pressure air fan air output by tuyere, makes to form little negative pressure in the stone roller formula pulverizer, with PbO 2Powder is received to powder collector and is collected; The PbO that with cream the time, collects 2Powder adds in the lead powder with 4.5～5.0wt% of lead powder amount.Thereby realized the recycling of battery brown lead oxide.
Recycling device is made up of positive pressure fan, negative-pressure air fan, stone roller formula pulverizer, powder collector, separator, air compressor and tuyere; Positive pressure fan directly links to each other with stone roller formula pulverizer, and negative-pressure air fan communicates with stone roller formula pulverizer by powder collector, pipeline and separator; The arm that described separator has a spindle body pipeline and draws from this body pipeline, the other end of this arm communicates with stone roller formula pulverizer.Outlet contraction the body pipeline is designed to spindle, owing to can prevent effectively that the excessive lead powder of granularity from entering pipeline.The excessive lead powder of granularity can be got back in the stone roller formula pulverizer from arm, and further pulverizes up to 300 purpose fineness, thereby can enter pipeline and powder collector with comparalive ease.
On powder collector, be provided with air compressor, on the air blast bucket that grinds the formula pulverizer, be provided with a plurality of tuyeres.Preferably, tuyere is 2～8.
Principle of the present invention is:
α-PbO 2And β-PbO 2Relative amount use circulation to change α-PbO in cyclic process with storage battery 2Gradate and be β-PbO 2Increase β-the PbO of cycle life is used in this conversion with battery 2Ratio increases.
Therefore at the end its waste battery positive plate main component is β-PbO to battery useful life 2, its content is greater than 95%, and processing back fineness is by 300 mesh sieves, and addition is 4.5-5.0% with positive cream the time, and is as follows at the function analysis of lead acid accumulator:
(1) shortens green plate curing time, improve the polar plate solidification quality
PbO in useless positive plate extraction 2In, the content of metallic lead is less than 1%, therefore, and PbO in the active material 2The percentage quality high more, the content of metallic lead is just low more in the whole active material.When green plate solidified, metallic lead did not drop to a certain degree (promptly plumbous oxidized), and grid and active material interfacial corrosion layer just are difficult for forming, and this is the most important stage of crystallization dynamic change in the lead plaster, contains PbO 2Positive plate can reach optimum value below 1% at the content of metallic lead after the curing, this explanation in lead plaster metallic lead and the oxidation reaction of oxygen be deep into the interface, corrosion layer forms.So its result has not only improved the curing quality but also can shorten curing time.
In solidification process, also can be by adjusting the α-PbO in the curing temperature adjustment lead plaster 2And β-PbO 2Mass ratio, will produce significant impact to the deep discharge performance of storage battery.
(2) shortening changes into the time
Useless positive plate PbO 2In formation process, become grey lead powder and be transformed into PbO 2Crystal seed.Changing into the incipient stage, owing in the lead plaster a large amount of PbO is arranged 2, PbOPbSO 4And 3PbOPbSO 4H 2O exists, and the sulfuric acid of consumption of chemical reaction is greater than sulfuric acid that electrochemical reaction generated.Therefore, the sulfuric acid concentration in electrode surface and the active material micropore is lower than the sulfuric acid concentration in the main body solution, causes the electrolyte in the pole plate micropore that higher pH value is arranged, and promptly there is more basic sulfatase pole plate inside.And polar board surface has more PbSO owing to pickling with near main body solution 4, these conditions make in the 7～8h that changes into after the beginning, reaction mainly takes place in that pole plate is inner, generation mainly be PbO 2Variant α-PbO 2During this period, sulfuric acid concentration reduces along with the continuity of time.Time continues again, and chemical reaction is tending towards finishing, and the sulfuric acid that electrochemical reaction generates begins greater than consumption, and the concentration of sulfuric acid begins to improve, and electrolytic bath is pressed also and raise, and anode potential is just becoming, PbSO 4The beginning oxidation generates PbO at polar board surface 2Another variant β-PbO 2Because useless positive plate PbO 2A certain amount of β-PbO has been arranged when solidifying 2The time of changing into that changes into behind about 8h generates, so can shorten.
(3) initial capacity of raising storage battery
Because β-PbO that useless positive plate forms 2Crystal grain is tiny, is α-PbO approximately 2Half, so β-PbO 2Crystallization than α-PbO 2It is long-pending to have bigger real surface.Work as PbO 2When quantity is identical, β-PbO 2The capacity that provides surpasses α-PbO 21.5～3.0 times of the capacity that provides.
From the crystalline structure of the two, they are different fully.α-PbO 2With PbSO 4Crystalline form is close, and β-PbO 2With PbSO 4Difference is very big.Discharging product PbSO 4Lattice grow up, it otherwise form new crystal seed, or at remaining PbSO 4On grow up.So at PbSO 4Between form many slits, these slits provide more sulfuric acid passage, and more sulfuric acid is diffused in the micropore of active material inside, thereby make pole plate that more capacity arranged.
Accumulator plate after utilization of the present invention is scrapped has the following advantages:
(1) raw material of Shi Yonging are useless pole plate, draw materials easily, cost is low, accomplishes that useless plate utilizes again.
(2) equipment, facility investment are few, and production capacity is big.
(3) add useless pole plate powder when positive plate and cream, make to be easy in the pole plate production solidify, change into, can improve the initial capacity and the cycle life of battery.
Description of drawings
Fig. 1 is the recycling equipment schematic diagram of lead dioxide from storage cells.
Fig. 2 is the structural representation of the air blast bucket on the stone roller formula pulverizer.
Fig. 3 is the structural representation of separator.
Embodiment
Embodiment 1
The waste battery pole plate is split out, after positive plate carefully separates with negative plate, the positive plate oven dry, 90 ℃ of bake out temperatures take out positive plate when treating moisture less than 10wt%, manually strike the lead plaster on the bottom crown, grid is separated with lead plaster, when collecting the titanium dioxide lead powder, pulverize with stone roller formula pulverizer, granularity is proposed for adding in the lead powder by the 5wt% with the lead powder amount behind powder of 300 mesh sieves and during cream.
As shown in Figure 1, device is made up of positive pressure fan 1, negative-pressure air fan 2, stone roller formula pulverizer 3, powder collector 4, air compressor 5, tuyere 6 and separator 8.Positive pressure fan 1 directly links to each other with stone roller formula pulverizer 3, and negative-pressure air fan communicates with stone roller formula pulverizer 3 by powder collector 4, pipeline and separator 8.On powder collector 4, be provided with air compressor 5, be provided with 8 tuyeres 6 (please refer to Fig. 2,5 tuyeres shown in the figure, other has 3 tuyeres not show) on the formula pulverizer 3 grinding.
Please refer to Fig. 3, the arm 10 that separator 8 has a spindle body pipeline 9 and draws from this body pipeline 9, the other end of this arm 10 communicates with stone roller formula pulverizer 3.Body pipeline 9 is designed to spindle, can prevents effectively that the excessive lead powder of granularity from entering pipeline.The excessive lead powder of granularity can be got back in the stone roller formula pulverizer 3 from arm 10.
During use, earlier lead or lead plaster are ground into PbO at stone roller formula pulverizer 3 2Powder is controlled positive pressure fan 1 and negative-pressure air fan 2 air output by tuyere 6, makes to form little negative pressure in the stone roller formula pulverizer 3, with PbO 2Powder is received to powder collector 4 and is collected; PbO with cream the time 2Powder adds in the lead powder with the 5.0wt% of lead powder amount.
For the calibrating positive plate adds the PbO that collects from powder collector 4 2The effect of powder, the spy makees following battery case and changes into test, PbO in the positive plate 2Content with change into the time, charge into electric weight and add PbO 2The relation of powder sees Table 1.
PbO in table 1 positive plate 2Content with change into the time, charge into electric weight and add PbO 2The relation of powder
Change into the time (h)/charge into electric weight (multiple) 9/2 14/3 18/4 21/4.7 24/5.5
Add PbO 20％ 38％ 49％ 54％ 60％ 65％
Add PbO 22％ 41％ 51％ 58％ 68％ 66％
Add PbO 24％ 44％ 54％ 60％ 63％ 67％
Add PbO 26％ 46％ 56％ 61％ 64％ 68％
Add PbO 28％ 48％ 57％ 62％ 66％ 73％
Practice shows that storage battery is when cyclic test, by adding useless pole plate PbO 2The storage battery that forms of positive plate can reach 100% or more capacity first, do not add useless pole plate PbO 2Will be through just reaching the capacity more than 95% after the circulation for several times, this is very tangible.
More than the recycling method and the device thereof of lead dioxide from storage cells provided by the present invention is described in detail, used specific case herein principle of the present invention and execution mode are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.

Claims (5)

1. the recycling method of a lead dioxide from storage cells is characterized in that, when 80～100 ℃ of temperature positive plate is dried, and takes out positive plate when treating moisture less than 10wt%, and grid is separated with lead plaster; Again lead plaster is ground into PbO at stone roller formula pulverizer 2Powder is controlled positive pressure fan and the negative-pressure air fan air output by tuyere, makes to form little negative pressure in the stone roller formula pulverizer, with PbO 2Powder is received to powder collector and is collected; The PbO that with cream the time, collects 2Powder adds in the lead powder with 4.5～5.0wt% of lead powder amount.
2. the recycling device of a lead dioxide from storage cells is characterized in that, is made up of positive pressure fan, negative-pressure air fan, stone roller formula pulverizer, powder collector, separator, air compressor and tuyere; Positive pressure fan directly links to each other with stone roller formula pulverizer, and negative-pressure air fan communicates with stone roller formula pulverizer by powder collector, pipeline and separator; The arm that described separator has a spindle body pipeline and draws from this body pipeline, the other end of this arm communicates with stone roller formula pulverizer.
3. the recycling device of lead dioxide from storage cells according to claim 2 is characterized in that, is provided with air compressor on powder collector.
4. the recycling device of lead dioxide from storage cells according to claim 2 is characterized in that, is provided with a plurality of tuyeres on the air blast bucket that grinds the formula pulverizer.
5. the recycling device of lead dioxide from storage cells according to claim 4 is characterized in that, described tuyere is 8.
CNB2006100003931A 2006-01-10 2006-01-10 Cyclic utilization method and apparatus of lead dioxide from storage cells Expired - Fee Related CN100362691C (en)

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103128289A (en) * 2013-01-29 2013-06-05 超威电源有限公司 Process for producing lead powder by utilizing lead slag produced by lead smelting furnace
CN103296335B (en) * 2013-05-03 2015-05-13 超威电源有限公司 Method for recycling discarded pole plates of storage battery
CN104409782A (en) * 2014-10-23 2015-03-11 山东瑞宇蓄电池有限公司 Storage battery formation device and hydrogen and oxygen mixture guided-discharge device
CN105161683B (en) * 2015-08-31 2019-03-08 无锡市嘉邦电力管道厂 Cell positive material, preparation method and battery
CN106229578A (en) * 2016-08-23 2016-12-14 超威电源有限公司 A kind of method scrapping green plate recycling
CN106252700B (en) * 2016-08-29 2018-12-04 天能电池(芜湖)有限公司 The receipts powder device of environmentally friendly meal outlet between battery car
CN108832218A (en) * 2018-06-27 2018-11-16 湘潭大学 A kind of lead plaster fluidisation method for separating and device
CN113604668A (en) * 2021-07-12 2021-11-05 江苏海宝电池科技有限公司 Waste polar plate recycling method convenient for improving product production rate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2100278U (en) * 1990-11-16 1992-04-01 张茂成 Lapping machine
US5348713A (en) * 1989-12-15 1994-09-20 Sherritt Gordon Limited Recovery of metal values from zinc plant residues
CN2207225Y (en) * 1994-08-01 1995-09-13 林协中 Explosion-proof dustless universal pulverizer
JPH07290446A (en) * 1994-04-20 1995-11-07 Hosokawa Micron Corp Granulation of polymeric compound
CN1165866A (en) * 1997-02-25 1997-11-26 沈阳环境科学研究所 Pb cleaning and reclaiming method from waste storage battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5348713A (en) * 1989-12-15 1994-09-20 Sherritt Gordon Limited Recovery of metal values from zinc plant residues
CN2100278U (en) * 1990-11-16 1992-04-01 张茂成 Lapping machine
JPH07290446A (en) * 1994-04-20 1995-11-07 Hosokawa Micron Corp Granulation of polymeric compound
CN2207225Y (en) * 1994-08-01 1995-09-13 林协中 Explosion-proof dustless universal pulverizer
CN1165866A (en) * 1997-02-25 1997-11-26 沈阳环境科学研究所 Pb cleaning and reclaiming method from waste storage battery

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GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Assignee: Shandong Ruiyu Battery Co., Ltd.

Assignor: Zhao Hengxiang

Contract fulfillment period: 2009.3.6 to 2026.1.10 contract change

Contract record no.: 2009370000505

Denomination of invention: Cyclic utilization method and apparatus of lead dioxide from storage cells

Granted publication date: 20080116

License type: Exclusive license

Record date: 2009.12.7

LIC Patent licence contract for exploitation submitted for record

Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.3.6 TO 2026.1.10; CHANGE OF CONTRACT

Name of requester: SHANDONG RUIYU ACCUMULATOR CO., LTD.

Effective date: 20091207

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Granted publication date: 20080116

Termination date: 20140110