CN106222425A - The sulfur method of lead plaster in a kind of waste and old lead acid accumulator - Google Patents
The sulfur method of lead plaster in a kind of waste and old lead acid accumulator Download PDFInfo
- Publication number
- CN106222425A CN106222425A CN201610789958.2A CN201610789958A CN106222425A CN 106222425 A CN106222425 A CN 106222425A CN 201610789958 A CN201610789958 A CN 201610789958A CN 106222425 A CN106222425 A CN 106222425A
- Authority
- CN
- China
- Prior art keywords
- lead
- lead plaster
- serosity
- plaster
- waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C22B7/007—Wet processes by acid leaching
-
- 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
-
- 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
Abstract
The invention discloses the sulfur method of lead plaster in a kind of waste and old lead acid accumulator, stereotype grid and plastic sheet will be isolated after pending waste and old lead acid accumulator break process, and the lead plaster sub-elected introducing oxygen-enriched combusting stove will carry out heat treatment；Lead plaster after Overheating Treatment is introduced in agitator tank the stirring pulping that adds water, prepares lead plaster serosity；Hydrogen peroxide, dilute sulfuric acid are joined and carry out reduction reaction in the agitator tank containing lead plaster serosity；Desulfurizing agent is joined in described agitator tank with the form of powder or solution, and described lead plaster serosity is sufficiently stirred for described desulfurizing agent in described agitator tank；Send into grind in desulfurizer by the mixed serum after stirring again and carry out desulphurization reaction；Serosity after desulfurization is obtained filter cake after pressure filter filter pressing processes, obtained filter cake is carried out melting process.The reaction efficiency that said method can overcome existing Wet technique to exist is low, the halfway problem of desulfurization, and technology stability is strong, it is easy to industrialization.
Description
Technical field
The present invention relates to waste and old lead acid accumulator technical field of regeneration, particularly relate to lead plaster in a kind of waste and old lead acid accumulator
Sulfur method.
Background technology
At present, in waste and old lead acid accumulator, scrap lead cream is mixed by more than 1350 DEG C by the desulfurization of lead sulfate with coke
Lead sulfate is reduced to metallic lead by high temperature, but easily produces SO during the high temperature desulfurizing of whole lead sulfate2, lead dust and
The poisonous and harmful flue gases such as lead fume, can cause serious harm to the ecological environment of periphery and residents ' health.
" the reviver industry cleaner production apprasement index system " jointly formulated by the Committee of Development and Reform, Chinese Ministry of Environmental Protection and Ministry of Industry and Information pushes away
Recommending the recovery process method using cleaning, prior art proposes to leach, by leachate and sulphuric acid lead mud nitric acid oxidation
Reaction, makes the composition of lead mud be completely converted into lead sulfate, then reacts with lead sulfate with sodium carbonate and obtain ceruse, so far completes
The desulfurization of lead sulfate and the leaching of lead in lead mud, but said method does not has organic miscellaneous to the fiber contained in lead mud, barrier film etc.
Matter processes, and the most lead mud desulfurization is not carried out effective intensive treatment so that the response time is longer, leaches desulfuration efficiency relatively
Low.
Summary of the invention
It is an object of the invention to provide the sulfur method of lead plaster in a kind of waste and old lead acid accumulator, the method can overcome existing
Low, the halfway problem of desulfurization with the presence of the reaction efficiency of Wet technique, and technology stability is strong, it is easy to industrialization.
The sulfur method of lead plaster in a kind of waste and old lead acid accumulator, described method includes:
Stereotype grid and plastic sheet, and the lead that will sub-elect is isolated by after pending waste and old lead acid accumulator break process
Cream introduces in oxygen-enriched combusting stove and carries out heat treatment；
Lead plaster after Overheating Treatment is introduced in agitator tank the stirring pulping that adds water, prepares lead plaster serosity；
Hydrogen peroxide, dilute sulfuric acid are joined and carry out reduction reaction in the agitator tank containing lead plaster serosity；
Desulfurizing agent is joined in described agitator tank with the form of powder or solution, and described lead plaster serosity is de-with described
Sulfur agent is sufficiently stirred in described agitator tank；
Send into grind in desulfurizer by the mixed serum after stirring again and carry out desulphurization reaction, the most described agitator tank and institute
State and form closed circuit between grinding desulfurizer；
Serosity after desulfurization is obtained filter cake after pressure filter filter pressing processes, obtained filter cake is carried out melting process,
Sodium sulfate, ammonium sulfate product is obtained again after obtained sodium sulfate, the purified crystallization treatment of ammonium sulfate.
The temperature carrying out heat treatment in described oxygen-enriched combusting stove controls: 300～700 DEG C.
The mass fraction scope of obtained lead plaster serosity is 10～50%.
Described hydrogen peroxide and Lead oxide brown PbO in described lead plaster serosity2The ratio of amount of material be 1～1.5:1；
Described dilute sulfuric acid is 1～1.5:1 with the ratio of the amount of the material of lead oxide PbO in described lead plaster serosity, and described dilute
The concentration of sulphuric acid is 10～30wt.%.
Described desulfurizing agent is one or more in sodium carbonate, sodium bicarbonate or ammonium hydrogen carbonate；
And described desulfurizing agent and lead sulfate PbSO in described lead plaster serosity4The ratio of amount of material be 1.5～3:1.
Described desulphurization reaction specifically reacts 1～2.5h at 25～75 DEG C.
The lead plaster sub-elected is lead, lead oxide, Lead oxide brown, lead sulfate and the mixture of a small amount of organic impurities；
Wherein, after additive fiber during described organic impurities is battery pole plates and the sorting of membrane fibers material fragmentation
Residue.
As seen from the above technical solution provided by the invention, said method can overcome existing Wet technique to exist
Reaction efficiency is low, the halfway problem of desulfurization, and technology stability is strong, it is easy to industrialization.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, required use in embodiment being described below
Accompanying drawing be briefly described, it should be apparent that, below describe in accompanying drawing be only some embodiments of the present invention, for this
From the point of view of the those of ordinary skill in field, on the premise of not paying creative work, it is also possible to obtain other according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the sulfur method schematic flow sheet of lead plaster in the provided waste and old lead acid accumulator of the embodiment of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground describes, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on this
Inventive embodiment, the every other enforcement that those of ordinary skill in the art are obtained under not making creative work premise
Example, broadly falls into protection scope of the present invention.
Below in conjunction with accompanying drawing, the embodiment of the present invention is described in further detail, is illustrated in figure 1 the present invention and implements
The sulfur method schematic flow sheet of lead plaster in the provided waste and old lead acid accumulator of example, described method includes:
Step 11: stereotype grid and plastic sheet will be isolated after pending waste and old lead acid accumulator break process, and will divide
The lead plaster selected introduces in oxygen-enriched combusting stove and carries out heat treatment；
In this step, the lead plaster sub-elected is that lead, lead oxide, Lead oxide brown, lead sulfate and a small amount of Organic substance are miscellaneous
The mixture of matter；Wherein, additive fiber and membrane fibers material fragmentation during described organic impurities is battery pole plates divide
Residue after choosing.
In implementing, the temperature carrying out heat treatment in described oxygen-enriched combusting stove controls: 300～700 DEG C.
Step 12: the lead plaster after Overheating Treatment is introduced in agitator tank the stirring pulping that adds water, prepares lead plaster serosity；
In this step, the mass fraction scope of obtained lead plaster serosity is 10～50%.
Step 13: hydrogen peroxide, dilute sulfuric acid are joined and carry out reduction reaction in the agitator tank containing lead plaster serosity；
In this step, described hydrogen peroxide and Lead oxide brown PbO in described lead plaster serosity2The ratio of amount of material be 1～
1.5:1；
Described dilute sulfuric acid is 1～1.5:1 with the ratio of the amount of the material of lead oxide PbO in described lead plaster serosity, and described dilute
The concentration of sulphuric acid is 10～30wt.%.
Step 14: desulfurizing agent is joined in described agitator tank with the form of powder or solution, and by described lead plaster serosity
It is sufficiently stirred in described agitator tank with described desulfurizing agent；
In this step, one or more during described desulfurizing agent is sodium carbonate, sodium bicarbonate or ammonium hydrogen carbonate；
And described desulfurizing agent and lead sulfate PbSO in described lead plaster serosity4The ratio of amount of material be 1.5～3:1.
Above-mentioned desulphurization reaction specifically reacts 1～2.5h at 25～75 DEG C.
Step 15: send into grind in desulfurizer by the mixed serum after stirring again and carry out desulphurization reaction, simultaneously described in stir
Mix formation closed circuit between tank and described grinding desulfurizer；
Step 16: the serosity after desulfurization is obtained filter cake after pressure filter filter pressing processes, obtained filter cake is melted
Refining processes, then obtains sodium sulfate, ammonium sulfate product after obtained sodium sulfate, the purified crystallization treatment of ammonium sulfate.
With concrete example, said method is implemented process below to be described in detail:
Example 1, first the lead plaster of waste and old lead acid accumulator cracking and sorting gained is delivered to carry out in oxygen-enriched combusting stove fiber
The burning of the organic impurities such as barrier film, introduces pressed powder agitator tank and carries out adding water stirring pulping, make matter after burning 1.0h
Amount mark is the lead plaster serosity of 15%；
Add ammonium hydrogen carbonate (NH4HCO3) desulfurizing agent, according to the amount of lead sulfate in agitator tank, according to the ratio 2:1 of the amount of material
Being added, then heating lead plaster serosity to 50 DEG C and carries out desulfurization stirring；
While desulfurization is stirred, the lead plaster serosity in agitator tank is introduced and grinds in desulfurizer, grind desulfurizer
Use a large amount of zirconium ball to carry out lead plaster grinding, break particles coat, improve desulphurization reaction efficiency；In desulfurization agitator tank and grinding desulfurization
Lead plaster serosity flowing capable of circulation between device, desulfurization time is 1.5h, by the sulfur-bearing of lead plaster after carbon and sulfur analytical instrument mensuration desulfurization
Amount, after desulfurization, lead plaster sulfur-bearing rate is 0.45%.
Example 2, first the lead plaster of waste and old lead acid accumulator cracking and sorting gained is delivered to carry out in oxygen-enriched combusting stove fiber
The burning of the organic impurities such as barrier film, introduces pressed powder agitator tank and carries out adding water stirring pulping, make matter after burning 1.0h
Amount mark is the lead plaster serosity of 15%；
Add ammonium hydrogen carbonate (NH4HCO3) desulfurizing agent, according to the amount of lead sulfate in agitator tank, according to the ratio of the amount of material
2.2:1 is added, and then heating lead plaster serosity to 50 DEG C and carries out desulfurization stirring；
While desulfurization is stirred, the lead plaster serosity in agitator tank is introduced and grinds in desulfurizer, grind desulfurizer
Use a large amount of zirconium ball to carry out lead plaster grinding, break particles coat, improve desulphurization reaction efficiency；In desulfurization agitator tank and grinding desulfurization
Lead plaster serosity flowing capable of circulation between device, desulfurization time is 1.5h, by the sulfur-bearing of lead plaster after carbon and sulfur analytical instrument mensuration desulfurization
Amount, after desulfurization, lead plaster sulfur-bearing rate is 0.41%.
In sum, in the provided waste and old lead acid accumulator of the embodiment of the present invention, the sulfur method of lead plaster has the most excellent
Point:
1) before slurrying, lead plaster has been carried out heat treatment, removed the organic impurities such as fibre diaphragm therein, it is possible to effectively
Stop the reunion between lead plaster granule, hence it is evident that improve the desulfuration efficiency of lead plaster；
2) taking the process route of first slurrying desulfurization again, lead plaster enters back into desulfurizer after slurrying and carries out desulfurization, energy
Enough guarantee the scattered uniformity of lead plaster slurry；
3) during desulphurization reaction, add corresponding desulfurizing agent, use lead plaster forced circulation devulcanizer simultaneously, it is ensured that
Lead plaster circulates in retort up and down, is provided with lead plaster slurry abrasive device, breaks particle encapsulation inside forced circulation devulcanizer, with
Time lead plaster be fully contacted with desulfurizing agent, make desulfurization carry out more completely；
4) using the techniques such as pyrolysis-slurrying-grinding-desulfurization, the reaction efficiency overcoming the existence of existing Wet technique is low, de-
The problems such as sulfur is the most thorough, and technology stability is strong, it is easy to industrialization.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope of present disclosure, the change that can readily occur in or replacement,
All should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be as the criterion.
Claims (7)
1. the sulfur method of lead plaster in a waste and old lead acid accumulator, it is characterised in that described method includes:
Isolate stereotype grid and plastic sheet by after pending waste and old lead acid accumulator break process, and the lead plaster sub-elected is drawn
Enter and oxygen-enriched combusting stove carries out heat treatment；
Lead plaster after Overheating Treatment is introduced in agitator tank the stirring pulping that adds water, prepares lead plaster serosity；
Hydrogen peroxide, dilute sulfuric acid are joined and carry out reduction reaction in the agitator tank containing lead plaster serosity；
Desulfurizing agent is joined in described agitator tank with the form of powder or solution, and by described lead plaster serosity and described desulfurizing agent
Described agitator tank is sufficiently stirred for；
Sending into grind in desulfurizer by the mixed serum after stirring again and carry out desulphurization reaction, the most described agitator tank grinds with described
Closed circuit is formed between mill desulfurizer；
Serosity after desulfurization is obtained filter cake after pressure filter filter pressing processes, obtained filter cake is carried out melting process, then will
Obtained by sodium sulfate, obtain sodium sulfate, ammonium sulfate product after the purified crystallization treatment of ammonium sulfate.
The sulfur method of lead plaster in waste and old lead acid accumulator the most according to claim 1, it is characterised in that
The temperature carrying out heat treatment in described oxygen-enriched combusting stove controls: 300～700 DEG C.
The sulfur method of lead plaster in waste and old lead acid accumulator the most according to claim 1, it is characterised in that
The mass fraction scope of obtained lead plaster serosity is 10～50%.
The sulfur method of lead plaster in waste and old lead acid accumulator the most according to claim 1, it is characterised in that
Described hydrogen peroxide and Lead oxide brown PbO in described lead plaster serosity2The ratio of amount of material be 1～1.5:1；
Described dilute sulfuric acid is 1～1.5:1 with the ratio of the amount of the material of lead oxide PbO in described lead plaster serosity, and described dilute sulfuric acid
Concentration be 10～30wt.%.
The sulfur method of lead plaster in waste and old lead acid accumulator the most according to claim 1, it is characterised in that
Described desulfurizing agent is one or more in sodium carbonate, sodium bicarbonate or ammonium hydrogen carbonate；
And described desulfurizing agent and lead sulfate PbSO in described lead plaster serosity4The ratio of amount of material be 1.5～3:1.
The sulfur method of lead plaster in waste and old lead acid accumulator the most according to claim 1, it is characterised in that
Described desulphurization reaction specifically reacts 1～2.5h at 25～75 DEG C.
The sulfur method of lead plaster in waste and old lead acid accumulator the most according to claim 1, it is characterised in that
The lead plaster sub-elected is lead, lead oxide, Lead oxide brown, lead sulfate and the mixture of a small amount of organic impurities；
Wherein, residual after additive fiber during described organic impurities is battery pole plates and the sorting of membrane fibers material fragmentation
Stay thing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610789958.2A CN106222425A (en) | 2016-08-31 | 2016-08-31 | The sulfur method of lead plaster in a kind of waste and old lead acid accumulator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610789958.2A CN106222425A (en) | 2016-08-31 | 2016-08-31 | The sulfur method of lead plaster in a kind of waste and old lead acid accumulator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106222425A true CN106222425A (en) | 2016-12-14 |
Family
ID=58075125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610789958.2A Pending CN106222425A (en) | 2016-08-31 | 2016-08-31 | The sulfur method of lead plaster in a kind of waste and old lead acid accumulator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106222425A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245581A (en) * | 2017-05-17 | 2017-10-13 | 超威电源有限公司 | A kind of reuse method for drenching lead plumbate mud |
| CN108306070A (en) * | 2017-12-26 | 2018-07-20 | 浙江天能动力能源有限公司 | A kind of method that lead-acid accumulator leaching lead plumbate mud processing recycles |
| CN112442603A (en) * | 2020-10-09 | 2021-03-05 | 超威电源集团有限公司 | Method for desulfurizing lead waste |
| CN113957258A (en) * | 2021-10-23 | 2022-01-21 | 安徽省华鑫铅业集团有限公司 | Lead plaster smelting process based on oxygen-enriched side blowing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248801A (en) * | 1999-08-31 | 2000-03-29 | 沈阳环境科学研究所 | Technology for cleaning and recovering lead from waste accumulator |
| CN103436702A (en) * | 2013-08-30 | 2013-12-11 | 湖北骆驼蓄电池研究院有限公司 | Method for preparing highly oxidized lead powder from waste battery lead plaster |
| CN104263944A (en) * | 2014-09-29 | 2015-01-07 | 湖南江冶机电科技股份有限公司 | Lead paste desulfurization method based on grinding mechanism |
-
2016
- 2016-08-31 CN CN201610789958.2A patent/CN106222425A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248801A (en) * | 1999-08-31 | 2000-03-29 | 沈阳环境科学研究所 | Technology for cleaning and recovering lead from waste accumulator |
| CN103436702A (en) * | 2013-08-30 | 2013-12-11 | 湖北骆驼蓄电池研究院有限公司 | Method for preparing highly oxidized lead powder from waste battery lead plaster |
| CN104263944A (en) * | 2014-09-29 | 2015-01-07 | 湖南江冶机电科技股份有限公司 | Lead paste desulfurization method based on grinding mechanism |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245581A (en) * | 2017-05-17 | 2017-10-13 | 超威电源有限公司 | A kind of reuse method for drenching lead plumbate mud |
| CN108306070A (en) * | 2017-12-26 | 2018-07-20 | 浙江天能动力能源有限公司 | A kind of method that lead-acid accumulator leaching lead plumbate mud processing recycles |
| CN112442603A (en) * | 2020-10-09 | 2021-03-05 | 超威电源集团有限公司 | Method for desulfurizing lead waste |
| CN113957258A (en) * | 2021-10-23 | 2022-01-21 | 安徽省华鑫铅业集团有限公司 | Lead plaster smelting process based on oxygen-enriched side blowing |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1094816A (en) | Process for recycling junk lead-acid batteries | |
| CN105280976A (en) | Environmental-friendly and high-efficiency processing method of waste lead-acid storage battery | |
| CN105506294B (en) | A kind of method of manganese and lead in synthetical recovery electrolytic manganese anode mud | |
| CN106222425A (en) | The sulfur method of lead plaster in a kind of waste and old lead acid accumulator | |
| CN100583548C (en) | Method of recycling waste lead acid battery lead by electrolyzing with acid-wet method | |
| CN108486376A (en) | A method of leaching metal in waste lithium ion cell anode material | |
| CN107083488B (en) | A kind of waste lead acid battery lead cream bath smelting processing method | |
| WO2016049994A1 (en) | Lead paste desulfurization method based on grinding mechanism | |
| CN105374988B (en) | The method of waste lead accumulator comprehensive utilization of resources | |
| CN103526017A (en) | Extraction method of valuable elements from acid mud produced in sulfuric acid production by copper smelting flue gas | |
| CN105420489B (en) | A kind of diachylon desulphurization method based on throttling self collision | |
| CN108134150A (en) | The method of valuable element in hydro-thermal synthetical recovery waste lithium iron phosphate positive electrode | |
| CN105197987B (en) | PbO, PbSO4, PbO2the separation method of mixture | |
| CN107394300A (en) | A kind of sulfur method of waste lead acid battery lead cream | |
| CN108085481A (en) | A kind of low cost, the waste diachylon desulphurization method of high desulfurization rate | |
| CN103000968B (en) | A kind of waste lead acid battery lead cream desulfurization and transformation method | |
| CN107376594A (en) | A kind of method that sulfur dioxide is reclaimed from flue gas | |
| CN106756056A (en) | A kind of method of Copper making white cigarette dirt dearsenification | |
| CN103633394A (en) | Waste diachylon desulphurization method | |
| CN108796230A (en) | A kind of method of lead-acid accumulator dismantling cream mud Whote-wet method recycling lead | |
| CN106521180A (en) | Lead paste desulfurization method using ammonium bicarbonate as desulfurizing agent | |
| CN114421044A (en) | Purification treatment method and system for phosphorus-iron slag mixture containing Al and Cu impurities | |
| CN106450540A (en) | Lead paste recycling method by atomic economic method | |
| CN109467261A (en) | Waste lithium cell electrolyte wastewater treatment method | |
| CN105200241B (en) | The method that waste lead accumulator lead plaster separation prepares lead monoxide, lead sulfate, brown lead oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161214 |