CN108996481A - A kind of lead plaster doctor solution circulation utilization method - Google Patents
A kind of lead plaster doctor solution circulation utilization method Download PDFInfo
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- CN108996481A CN108996481A CN201810778845.1A CN201810778845A CN108996481A CN 108996481 A CN108996481 A CN 108996481A CN 201810778845 A CN201810778845 A CN 201810778845A CN 108996481 A CN108996481 A CN 108996481A
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- lead plaster
- filtrate
- lead
- desulfurization
- sodium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/775—Liquid phase contacting processes or wet catalysis processes
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention belongs to discard lead-acid battery processing technology field.The invention discloses a kind of lead plaster doctor solution circulation utilization methods, it includes the content for 1) detecting lead sulfate in scrap lead cream, and configure sodium hydroxide lye, 2) lead plaster is mixed with sodium hydroxide lye, then desulfurization is carried out, 3) desulfurization lead plaster mixture filters pressing is obtained into filtrate, 4) content of the sulfate and sodium hydroxide in filtrate is detected, calcium hydroxide or calcium oxide are added into desulfurization filtrate, 5) suspension is handled in colloid mill or cutter and causticization material is made, 6) causticization feed separation is obtained into calcium sulphate solid and causticization filtrate, 7) sodium hydroxide is supplemented in causticization filtrate to be recycled as lye, 8) calcium sulfate is roasted and calcium oxide and sulfur dioxide is made, calcium oxide is recycled, sulfur dioxide dilute sulfuric acid.Sodium sulfate crystal will not be generated by guaranteeing that doctor solution is recycled completely using the method in the present invention, can be avoided the processing sulfate crystal process that the time is long, energy consumption is high.
Description
Technical field
The present invention relates to discarded lead-acid battery processing technology fields, more particularly, to a kind of lead plaster doctor solution side of recycling
Method.
Background technique
Lead plaster desulfurization is an important procedure in atom economy method lead recycling project, technique be lead plaster and lye according to the ratio
Reaction in ball mill is put into, using processing lead plaster and filtrate is obtained by filtration, contains sodium sulphate, sodium hydroxide, water in filtrate.Mesh
The mode that filtrate is handled on preceding experiment line is the mode of crystallisation by cooling, allows sodium sulphate at low ambient temperatures with Na2SO4·10H2O's
Form forms crystal, leaves sodium sulphate, filtrate recycle using centrifuge.This low temperature crystallization mode, one energy consumption is high, handles
Time is long, secondly obtaining product sodium sulphate does not have good place to go.
Summary of the invention
To solve the above problems, the present invention provides it is a kind of can be sufficiently by doctor solution recycles in lead plaster desulfurization lead
Cream doctor solution circulation utilization method.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of lead plaster doctor solution circulation utilization method, comprising the following steps:
1) content of lead sulfate in scrap lead cream active material is detected, and configures sodium hydroxide lye；
2) lead plaster is mixed with sodium hydroxide lye, then carries out ball milling or shearing desulfurization, obtains desulfurization lead plaster mixture；This
The reaction equation of step are as follows: PbSO4+2NaOH---PbO+Na2SO4+H2O；
3) desulfurization lead plaster mixture filters pressing is obtained into filtrate, and filter residue is cleaned and obtains cleaning solution, filtrate and cleaning solution are merged
Obtain desulfurization filtrate；
4) sulphates content and sodium hydrate content in desulfurization filtrate are detected, and calcium hydroxide or oxygen are added into desulfurization filtrate
Change calcium, forms suspension；The reaction equation of this step are as follows: Na2SO4+CaO+H2O---CaSO4+2NaOH；
5) suspension is handled in colloid mill or cutter, causticization material is made；
6) causticization material is centrifugated, obtains calcium sulphate solid and the filtrate of causticization containing sodium hydroxide；
7) sodium hydrate content in causticization filtrate is detected, hydroxide is supplemented according to sodium hydroxide lye concentration needed for desulfurization link
Sodium replaces being recycled as the sodium hydroxide lye in step 1)；
8) calcium sulphate solid is roasted and calcium oxide and sulfur dioxide is made, be recycled in calcium oxide investment step 4), titanium dioxide
Sulphur is absorbed through absorption tower water spray is made dilute sulfuric acid；The reaction equation of this step are as follows: CaSO4---CaO+SO3(high-temperature calcination).
Carrying out desulfurization process using sodium hydroxide in the present invention can keep away because sodium hydrate aqueous solution is more stable
Exempt from the prior art using ammonium salt handled when because ammonium salt it is unstable it is readily volatilized caused by raw material dosage be difficult to definitely calculate
The problems such as, it can also influence to process to avoid using sodium bicarbonate that can generate carbon dioxide gas when being handled in the prior art
The problem of journey.
Preferably, sodium hydroxide lye is the sodium hydrate aqueous solution that content is 5~15wt% in step 1).
The concentration of sodium hydrate aqueous solution in step 1) is in fact not important, it is only necessary to can satisfy subsequent sodium hydroxide
With the molar ratio of lead sulfate, but concentration is too low, will affect efficiency, excessive concentration will increase cost again, or even cause wave
Take, therefore the weight percent of sodium hydroxide is proper within the scope of 5~15wt%.
Preferably, in step 2, after lead plaster is mixed with Strong oxdiative soda lye, lead sulfate and sodium hydroxide lye in lead plaster
The molar ratio of middle sodium hydroxide is 1:2.5~5.
Preferably, ball milling or shearing desulfurization carry out at 5~60 DEG C in step 2.
Preferably, passing through the content of lead sulfate in EDTA titrimetry lead plaster in sweetening process in step 2.
Preferably, in step 2, when sulfuric acid lead content is less than 0.5wt% sweetening process and terminates in sweetening process.
Preferably, in step 4), calcium hydroxide or calcium oxide are added into desulfurization filtrate, makes sodium sulphate and calcium ion
Molar ratio is 1:1.
Preferably, step 5) is to handle 5~30 minutes at 0~25 DEG C.
Preferably, detecting wherein sodium sulphate content in step 5), ended processing when sodium sulphate conversion ratio is greater than 80%.
Preferably, the naoh concentration in causticization filtrate is supplemented to 5~15wt% in step 7).
Therefore, the invention has the following advantages: using the present invention in method to discarded lead-acid accumulator lead plaster into
Row desulfurization process can guarantee that doctor solution is recycled completely without generating as generated the sulphur without suitable place to go in the prior art
Sour sodium crystal, and can be avoided the processing sodium sulfate crystal low temperature crystallization process that the time is long, energy consumption is high.
Specific embodiment
Further description of the technical solution of the present invention With reference to embodiment.
Obviously, the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, all other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
In the present invention, if not refering in particular to, all equipment and raw material is commercially available or the industry is common,
Method in following embodiments is unless otherwise instructed conventional method in that art.
Embodiment 1
A kind of lead plaster doctor solution circulation utilization method, comprising the following steps:
1) content for detecting lead sulfate in scrap lead cream active material, through being detected using EDTA titration, lead sulfate contains in scrap lead cream
Amount is 33wt%, and the sodium hydrate aqueous solution of 10wt% is configured with 900 grams of water and 100 grams of sodium hydroxides；
2) 300 grams of lead plasters are mixed with 523 grams of sodium hydrate aqueous solutions, at this time in lead plaster in lead sulfate and sodium hydrate aqueous solution
The molar ratio of sodium hydroxide is 1:4, then carries out carrying out ball milling desulfurization 30 minutes at 35 DEG C and detects sulphur through EDTA titration
The content of lead plumbate is 0.25wt%, and desulphurization reaction terminates, and obtains desulfurization lead plaster mixture；
3) desulfurization lead plaster mixture filters pressing is obtained into filtrate, and filter residue is cleaned and obtains cleaning solution, filtrate and cleaning solution are merged
Obtain 643 grams of desulfurization filtrates；
4) sulphates content and sodium hydrate content in detected 634 grams of desulfurization filtrate, the content of sodium sulphate are 52.64
Gram, the content of sodium hydroxide is 18.34 grams, and calcium oxide is added into desulfurization filtrate by sodium sulphate and calcium oxide molar ratio 1:1.5
32 grams, form suspension；
5) by suspension at milling treatment of colloid 30 minutes, processing detection wherein sodium hydroxide and sodium sulphate content, through detecting
Wherein the content of sodium hydroxide is 6.5wt%, and sodium sulphate conversion ratio is greater than 80%, and causticization material is made；
6) causticization material is centrifugated, obtains calcium sulphate solid and the filtrate of causticization containing sodium hydroxide；
7) sodium hydrate content in causticization filtrate is detected, 25 grams of sodium hydroxides, which are not added, to the filtrate of causticization containing sodium hydroxide reaches it
To the sodium hydrate aqueous solution in desulfurization lye (i.e. above-mentioned steps 1)) in sodium hydrate content requirement, followed as desulfurization lye
Ring uses；
8) calcium sulphate solid is roasted and calcium oxide and sulfur dioxide is made, be recycled in calcium oxide investment step 4), titanium dioxide
Sulphur absorbs the dilute sulfuric acid that 1.1g/ml is made through absorption tower water spray.
It should be understood that those skilled in the art, can be improved or be become according to the above description
It changes, and all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (10)
1. a kind of lead plaster doctor solution circulation utilization method, it is characterised in that the following steps are included:
1) content of lead sulfate in scrap lead cream active material is detected, and configures sodium hydroxide lye；
2) lead plaster is mixed with sodium hydroxide lye, then carries out ball milling or shearing desulfurization, obtains desulfurization lead plaster mixture；
3) desulfurization lead plaster mixture filters pressing is obtained into filtrate, and filter residue is cleaned and obtains cleaning solution, filtrate and cleaning solution are merged
Obtain desulfurization filtrate；
4) sulphates content and sodium hydrate content in desulfurization filtrate are detected, and calcium hydroxide or oxygen are added into desulfurization filtrate
Change calcium, forms suspension；
5) suspension is handled in colloid mill or cutter, causticization material is made；
6) causticization material is centrifugated, obtains calcium sulphate solid and the filtrate of causticization containing sodium hydroxide；
7) sodium hydrate content in causticization filtrate is detected, hydroxide is supplemented according to sodium hydroxide lye concentration needed for desulfurization link
Sodium replaces being recycled as the sodium hydroxide lye in step 1)；
8) calcium sulphate solid is roasted and calcium oxide and sulfur dioxide is made, be recycled in calcium oxide investment step 4), titanium dioxide
Sulphur is absorbed through absorption tower water spray is made dilute sulfuric acid.
2. lead plaster doctor solution circulation utilization method according to claim 1, it is characterised in that:
In the step 1), sodium hydroxide lye is the sodium hydrate aqueous solution that content is 5~15wt%.
3. lead plaster doctor solution circulation utilization method according to claim 1, it is characterised in that:
In the step 2, after lead plaster is mixed with Strong oxdiative soda lye, lead sulfate and hydroxide in sodium hydroxide lye in lead plaster
The molar ratio of sodium is 1:2.5~5.
4. lead plaster doctor solution circulation utilization method according to claim 1, it is characterised in that:
In the step 2, ball milling or shearing desulfurization carry out at 5~60 DEG C.
5. lead plaster doctor solution circulation utilization method according to claim 1 or 4, it is characterised in that:
In the step 2, pass through the content of lead sulfate in EDTA titrimetry lead plaster in sweetening process.
6. a kind of lead plaster doctor solution circulation utilization method according to claim 5, it is characterised in that:
In the step 2, when in sweetening process sulfuric acid lead content be less than 0.5wt% sweetening process terminate.
7. lead plaster doctor solution circulation utilization method according to claim 1, it is characterised in that:
In the step 4), calcium hydroxide or calcium oxide are added into desulfurization filtrate, makes the molar ratio of sodium sulphate and calcium ion
1:1.
8. lead plaster doctor solution circulation utilization method according to claim 1, it is characterised in that:
The step 5) is to handle 5~30 minutes at 0~25 DEG C.
9. lead plaster doctor solution circulation utilization method according to claim 1 or 8, it is characterised in that:
In the step 5), wherein sodium sulphate content is detected, is ended processing when sodium sulphate conversion ratio is greater than 80%.
10. lead plaster doctor solution circulation utilization method according to claim 1, it is characterised in that:
In the step 7), the naoh concentration in causticization filtrate is supplemented to 5~15wt%.
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| CN201810778845.1A CN108996481A (en) | 2018-07-16 | 2018-07-16 | A kind of lead plaster doctor solution circulation utilization method |
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| CN201810778845.1A CN108996481A (en) | 2018-07-16 | 2018-07-16 | A kind of lead plaster doctor solution circulation utilization method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694955A (en) * | 2019-02-20 | 2019-04-30 | 湘潭大学 | A kind of pre- sulfur method of lead plaster based on the double alkali of sodium calcium |
| CN110137588A (en) * | 2019-05-28 | 2019-08-16 | 超威电源有限公司 | A kind of waste and old lead acid accumulator circulation recovery method |
| CN113621812A (en) * | 2021-08-17 | 2021-11-09 | 太和县大华能源科技有限公司 | Lead oxide preparation process based on waste lead-acid storage battery lead plaster |
| CN114853212A (en) * | 2022-05-09 | 2022-08-05 | 纪宏轩 | Zero-emission recycling treatment method for magnesium sulfate wastewater |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694955A (en) * | 2019-02-20 | 2019-04-30 | 湘潭大学 | A kind of pre- sulfur method of lead plaster based on the double alkali of sodium calcium |
| CN110137588A (en) * | 2019-05-28 | 2019-08-16 | 超威电源有限公司 | A kind of waste and old lead acid accumulator circulation recovery method |
| CN113621812A (en) * | 2021-08-17 | 2021-11-09 | 太和县大华能源科技有限公司 | Lead oxide preparation process based on waste lead-acid storage battery lead plaster |
| CN113621812B (en) * | 2021-08-17 | 2022-11-08 | 太和县大华能源科技有限公司 | Lead oxide preparation process based on waste lead-acid storage battery lead plaster |
| CN114853212A (en) * | 2022-05-09 | 2022-08-05 | 纪宏轩 | Zero-emission recycling treatment method for magnesium sulfate wastewater |
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