CN107164636B - A kind of method that high-purity lead oxide is recycled in waste lead acid battery processing - Google Patents
A kind of method that high-purity lead oxide is recycled in waste lead acid battery processing Download PDFInfo
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- CN107164636B CN107164636B CN201710388054.3A CN201710388054A CN107164636B CN 107164636 B CN107164636 B CN 107164636B CN 201710388054 A CN201710388054 A CN 201710388054A CN 107164636 B CN107164636 B CN 107164636B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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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- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The present invention relates to the methods that high-purity lead oxide is recycled in a kind of processing of waste lead acid battery.The method of the present invention includes the PbO used in nitrate reductase lead plaster under 1. acid condition2；2. lead powder restores the recycling that nitrate realizes nitrate reductase agent at nitrite；3. the lead sulfate in lead plaster is extracted in obtained reduction lead plaster mixture salt dissolution；4. lead solution is added carbonate deposition and generates ceruse heat resolve at high-purity mangesium oxide lead or directly reinforcement alkali direct preparation of high-purity lead oxide.Present invention process is simple, obtains lead oxide purity is high, and reducing agent can be recycled.
Description
Technical field
The invention belongs to resource reclaim and technique is utilized, in particular to the lead plaster after a kind of waste lead acid battery is broken apart
The method of the high-purity lead oxide obtained after processing, which can realize the regeneration and circulation of reducing agent, so that the technique
With good economy.
Background technique
Lead-acid accumulator is widely applied in occasions such as automobile, electric vehicle, submarine, mobile communication base stations, according to incompletely statistics,
Lead storage battery manufacturing firm, China has reached 1500 or so, and about 1.1 hundred million lead-acid accumulators generate every year, leaded
Amount of metal be about 2,000,000 tons, when estimating 2015, metallic lead amount contained by used and scrapped battery is up to 3,000,000 tons.Production
Amount is average to be grown at top speed with every year about 20% speed, and lead storage battery yield accounts for about the 1/3 of world wide production.Lead in the coming years
Acid accumulator regenerative system market demand is up to 80-100 production line, is roughly equal to the hundred million market output value of 6-10.
Lead becomes great technical need in how efficient, clean recycling lead-acid accumulator.The wet reclamation of lead plaster
It is considered as more environmentally friendly next-generation reviver technology.
PbSO is mainly contained in the lead plaster after waste lead acid battery is broken apart4(50~60%)、PbO2 (20~30%)、
PbO (10 ~ 20%), a small amount of metallic lead (3% or less) and a small amount of impurity.If the high price lead economy in lead plaster can be converted
The ceruse that high-purity is prepared for plumbeous compound, then decomposing generation again can high pure oxygen of the direct reuse in battery production
Change lead (purity > 97%), then can generate very important meaning.
Summary of the invention
The purpose of the present invention is to provide the method that high-purity lead oxide is recycled in a kind of processing of waste lead acid battery, the present invention is related to
And waste lead acid battery it is broken apart after the lead plaster method and technique of the lead oxide that obtain after processing.Method packet of the invention
It includes under 1. acid condition with the PbO in nitrate reductase lead plaster2；2. lead powder, which restores nitrate, realizes nitrous acid at nitrite
The recycling of salt reducing agent；3. the lead sulfate in lead plaster is extracted in obtained reduction lead plaster mixture salt dissolution；4. lead solution
Carbonate deposition generation ceruse heat resolve is added and reinforces the oxidation of alkali direct preparation of high-purity at high-purity mangesium oxide lead or directly
Lead and etc..The characteristics of present invention has simple process, obtains lead oxide purity is high, and reducing agent can be recycled.
It prepares in lead oxide technique in wet process by the PbO in lead plaster2It is reduced to divalent lead at low cost, is the technology key
The step of, the reduction reaction that this law is related to has:
(1) PbO2 + MNO2 + H2SO4 = PbSO4 + MNO3
(2) MNO3 + Pb = PbO + MNO2
It can be seen that reducing agent nitrite itself does not consume from reaction equation above, consumption is lead powder, and lead powder exists
In reaction can conversion cost technique target product PbO, therefore this is an Atom economy process.
The technical solution of the present invention is as follows:
A kind of method that high-purity lead oxide is recycled in waste lead acid battery processing, includes the following steps:
(1) lead plaster restores: lead plaster of the waste lead acid battery after broken apart and nitrite solution being modulated into slurries, so
After dilute sulfuric acid is added, be separated by filtration after being stirred to react, obtain filtrate and lead sulfate filter cake；
(2) nitrite regenerates: by filtrate recycle obtained by step (1) in the slurries of step (1), when nitrate is in filtrate
Mass fraction reach 20% or more and be evaporated or freezing and crystallizing, nitrate solid is precipitated；Obtained nitrate and lead powder heat together
It generates lead oxide and nitrite, product is back to use step (1)；
(3) lead salt dissolution-precipitating: by lead sulfate filter cake obtained by step (1), be added after salt solution be added carbonate into
Row reaction generates ceruse precipitating, gained precipitation and separation, drying；
(4) it decomposes: ceruse solid heat resolve obtained by step (3) is obtained into high-purity mangesium oxide lead.
Further, in step (1), the nitrite is the alkali or alkaline earth metal salt of nitrous acid, is added
Amount and PbO in lead plaster2Molar ratio be preferably 0.9 ~ 1.1:1, more preferably 1:1；The solid-to-liquid ratio of nitrite solution and lead plaster
(volume: weight) is preferably 1 ~ 10:1, more preferable 2:1；The molar ratio of sulfuric acid and nitrite is preferably 0.2 ~ 1:1, more preferably
For 0.5:1.
Further, in step (2), the heat together, temperature is 100 ~ 400 DEG C, and the time is 0.1 ~ 3 hour；Nitrate
It is 1:1 with the ratio between the amount of substance of lead powder.
Further, in step (3), the salt is alkali metal salt, ammonium salt or the sodium chloride of acetic acid, additional amount and lead
The ratio between amount of substance of Pb element is 3 ~ 10:1, preferably 5:1 in cream；The solid-to-liquid ratio (volume: weight) of salting liquid and lead plaster be 3 ~
10:1, preferably 6:1；Reaction temperature is 20 ~ 100 DEG C, and the time is 0.5 ~ 2 hour；The alkali metal salt or ammonium of the preferred carbonic acid of carbonate
The ratio between amount of substance of lead element is 0.9 ~ 1.2:1, preferably 1:1 in salt, additional amount and lysate.
Further, in step (4), decomposition temperature is 300 ~ 750 DEG C, and the time is 0.5 ~ 6 hour.
The beneficial effects of the present invention are:
Technique of the invention has Atom economy, simple process, and reducing agent nitrite is formed in using and generating
Circulation, enables nitrite to be constantly recycled in the reduction of brown lead oxide, gained lead oxide purity is very high, highest
Direct reuse can be fully achieved to the quality requirement of lead-acid accumulator, therefore the present invention is not only able to achieve waste and old lead close to 100%
The resource utilization of sour battery, and preparation cost is low, it is good in economic efficiency, there is extraordinary industrial application value.
Specific embodiment
The present invention is described in further details combined with specific embodiments below, but the present invention is not limited thereto.
Embodiment 1
(1) lead plaster by waste lead acid battery after broken apart and contain and PbO in lead plaster2The sodium nitrite of equimolar amounts
The molar ratio of solution modulation pulp, addition sulfuric acid solution, sulfuric acid and sodium nitrite is 0.5:1, at this time linen lead sulfate
Intermediate products are separated by filtration；Filtrate recycles as with the adjusting slurry of lead plaster；
(2) when the sodium nitrate mass fraction accumulation in step (1) to 40%, nitre of the heating evaporation concentration until in solution 80%
Sour sodium is precipitated, and the solid that this is filtered out is put into molten-bath, the lead powder of equimolar amounts is added, is heated to 200 DEG C, reaction starts
It is unlikely to excessively fierce by cooling device regulation reaction afterwards, cooling is dissolved in water after 1 hour, and solid is lead oxide, solution
For the solution containing sodium nitrite, it is back in step (1)；
(3) it is molten that the ammonium acetate that the mass fraction that solid-to-liquid ratio is 10:1 is 50% is added in lead sulfate product obtained in step (1)
Liquid, after 0.5 hour time, adds molten with ammonium carbonate that the molar ratio of lead element in lysate is 1:1 by 80 DEG C of reaction temperature
Liquid obtains the white precipitate of ceruse, washs, drying；
(4) ceruse that step (3) obtains is decomposed at 500 DEG C, and time 2 h obtains yellow lead oxide product, purity
99.96%。
Embodiment 2
(1) lead plaster by waste lead acid battery after broken apart and contain and PbO in lead plaster2The sodium nitrite of equimolar amounts
The molar ratio of solution modulation pulp, addition sulfuric acid solution, sulfuric acid and sodium nitrite is 0.8:1, at this time linen lead sulfate
Intermediate products are separated by filtration；Filtrate recycles as with the adjusting slurry of lead plaster；
(2) when the sodium nitrate mass fraction accumulation in step (1) to 30%, nitre of the heating evaporation concentration until in solution 85%
Sour sodium is precipitated, and the solid that this is filtered out is put into molten-bath, the lead powder of equimolar amounts is added, is heated to 300 DEG C, reaction starts
It is unlikely to excessively fierce by cooling device regulation reaction afterwards, cooling is dissolved in water after 0.5 hour, and solid is lead oxide, molten
Liquid is the solution containing sodium nitrite, is back in step (1)；
(3) it is molten that the sodium chloride that the mass fraction that solid-to-liquid ratio is 8:1 is 30% is added in lead sulfate product obtained in step (1)
Liquid, after 1 hour time, adds molten with sodium carbonate that the molar ratio of lead element in lysate is 1.2:1 by 70 DEG C of reaction temperature
Liquid obtains the white precipitate of ceruse, washs, drying；
(4) ceruse that step (3) obtains is decomposed at 600 DEG C, the time 1 hour, obtains yellow lead oxide product, purity
99.85%。
Embodiment 3
(1) lead plaster by waste lead acid battery after broken apart and contain and PbO in lead plaster2The sodium nitrite of equimolar amounts
The molar ratio of solution modulation pulp, addition sulfuric acid solution, sulfuric acid and sodium nitrite is 0.8:1, at this time linen lead sulfate
Intermediate products are separated by filtration；Filtrate recycles as with the adjusting slurry of lead plaster；
(2) when the sodium nitrate mass fraction accumulation in step (1) to 50%, sodium nitrate of the freezing and crystallizing until in solution 90%
It is precipitated, the solid that this is filtered out is put into molten-bath, and the lead powder of equimolar amounts is added, and is heated to 400 DEG C, reaction is led to after starting
Apparatus for supercooling regulation reaction is unlikely to excessively fierce, and cooling is dissolved in water after 3 hours, and solid is lead oxide, solution be containing
The solution of sodium nitrite is back in step (1)；
(3) it is molten that the sodium acetate that the mass fraction that solid-to-liquid ratio is 8:1 is 40% is added in lead sulfate product obtained in step (1)
Liquid, after 1.5 hours time, adds the sodium carbonate for being 1.1:1 with the molar ratio of lead element in lysate by 100 DEG C of reaction temperature
Solution obtains the white precipitate of ceruse, washs, drying；
(4) ceruse that step (3) obtains is decomposed at 550 DEG C, the time 3 hours, obtains yellow lead oxide product, purity
99.97 %。
Claims (3)
1. a kind of method that high-purity lead oxide is recycled in waste lead acid battery processing, which comprises the steps of:
(1) lead plaster restores: lead plaster of the waste lead acid battery after broken apart and nitrite solution are modulated into slurries, then plus
Enter dilute sulfuric acid, be separated by filtration after being stirred to react, obtains filtrate and lead sulfate filter cake；
(2) nitrite regenerates: by filtrate recycle obtained by step (1) in the slurries of step (1), when matter of the nitrate in filtrate
Amount score reaches 20% or more and is evaporated or freezing and crystallizing, and nitrate solid is precipitated；Obtained nitrate and lead powder heat together generates
Lead oxide and nitrite, product are back to use step (1)；
(3) lead salt dissolution-precipitating: by lead sulfate filter cake obtained by step (1), be added after sodium chloride solution dissolution be added carbonate into
Row reaction generates ceruse precipitating, gained precipitation and separation, drying；
(4) it decomposes: ceruse solid heat resolve obtained by step (3) is obtained into high-purity mangesium oxide lead；
In step (1), the nitrite is the alkali or alkaline earth metal salt of nitrous acid, PbO in additional amount and lead plaster2
Molar ratio be 0.9 ~ 1.1:1；The solid-to-liquid ratio of nitrite solution and lead plaster is 1 ~ 10:1；The molar ratio of sulfuric acid and nitrite
For 0.2 ~ 1:1；
In step (2), the heat together, temperature is 100 ~ 400 DEG C, and the time is 0.1 ~ 3 hour；The substance of nitrate and lead powder
The ratio between amount is 1:1；
In step (3), the ratio between amount of substance of Pb element is 3 ~ 10:1 in the additional amount and lead plaster of sodium chloride；Sodium chloride solution with
The solid-to-liquid ratio of lead plaster is 3 ~ 10:1；
In step (3), reaction temperature is 20 ~ 100 DEG C, and the time is 0.5 ~ 2 hour.
2. the method that high-purity lead oxide is recycled in waste lead acid battery processing according to claim 1, which is characterized in that step
(3) in, carbonate is the alkali metal salts or ammonium salt of carbonic acid, and the ratio between additional amount and the amount of substance of lead element in lysate are
0.9~1.2:1。
3. the method that high-purity lead oxide is recycled in waste lead acid battery processing according to claim 1, which is characterized in that step
(4) in, decomposition temperature is 300 ~ 750 DEG C, and the time is 0.5 ~ 6 hour.
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| CN201710388054.3A CN107164636B (en) | 2017-05-27 | 2017-05-27 | A kind of method that high-purity lead oxide is recycled in waste lead acid battery processing |
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| CN107164636B true CN107164636B (en) | 2019-03-26 |
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| CN110453077A (en) * | 2019-08-26 | 2019-11-15 | 湘潭大学 | A kind of method that scrap lead cream recycles |
| CN112359219A (en) * | 2020-11-09 | 2021-02-12 | 汨罗市锦胜科技有限公司 | Method for recovering lead oxide from waste lead-acid storage battery |
| CN112614972B (en) * | 2020-12-15 | 2022-05-06 | 湘潭大学 | Preparation method of negative plate of lead-acid battery and lead-acid battery |
Citations (5)
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|---|---|---|---|---|
| CN102747227A (en) * | 2012-06-18 | 2012-10-24 | 东南大学 | Method for preparing superfine lead oxide by using electrode active materials of wasted lead acid batteries |
| CN103014347A (en) * | 2012-12-12 | 2013-04-03 | 北京化工大学 | Method for recycling waste lead-acid cells to directly produce lead oxide |
| CN103773972A (en) * | 2014-01-10 | 2014-05-07 | 张超 | Processing method for lead-bearing raw material |
| CN104789776A (en) * | 2014-01-16 | 2015-07-22 | 北京化工大学 | Method for recovering lead oxide from waste containing lead oxide |
| CN105441686A (en) * | 2016-01-06 | 2016-03-30 | 湘潭大学 | Reducing method for lead dioxide in waste lead plaster |
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- 2017-05-27 CN CN201710388054.3A patent/CN107164636B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102747227A (en) * | 2012-06-18 | 2012-10-24 | 东南大学 | Method for preparing superfine lead oxide by using electrode active materials of wasted lead acid batteries |
| CN103014347A (en) * | 2012-12-12 | 2013-04-03 | 北京化工大学 | Method for recycling waste lead-acid cells to directly produce lead oxide |
| CN103773972A (en) * | 2014-01-10 | 2014-05-07 | 张超 | Processing method for lead-bearing raw material |
| CN104789776A (en) * | 2014-01-16 | 2015-07-22 | 北京化工大学 | Method for recovering lead oxide from waste containing lead oxide |
| CN105441686A (en) * | 2016-01-06 | 2016-03-30 | 湘潭大学 | Reducing method for lead dioxide in waste lead plaster |
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