CN103000968B - A kind of waste lead acid battery lead cream desulfurization and transformation method - Google Patents
A kind of waste lead acid battery lead cream desulfurization and transformation method Download PDFInfo
- Publication number
- CN103000968B CN103000968B CN201210424305.6A CN201210424305A CN103000968B CN 103000968 B CN103000968 B CN 103000968B CN 201210424305 A CN201210424305 A CN 201210424305A CN 103000968 B CN103000968 B CN 103000968B
- Authority
- CN
- China
- Prior art keywords
- lead
- desulfurization
- conversion
- lead plaster
- plaster
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of waste lead acid battery lead cream desulfurization and transformation method, belong to field of waste battery disposal.The steps include: prepared by (1) lead plaster former state: lead-acid accumulator resolution process is taken out grid alloy, lead plaster is taken off from grid, impurities removing, dries in the environment of 80 ~ 90 DEG C, grinds the lead plaster former state that 10 ~ 30min obtains granularity 50 ~ 300 μm in grinder; (2) desulfurization conversion agent is configured: desulfurization conversion agent is mixed with conversion fluid, with water bath with thermostatic control bed, desulfurization conversion liquid is heated to 20 ~ 90 DEG C; (3) fully react: load weighted lead plaster is added in the obtained conversion fluid of step (2), and stirring makes it fully react; (4) cooling after to be transformed, filters, and repeatedly rinses filter residue repeatedly with distilled water.This method determines the technological parameter of lead plaster desulfurization conversion in lead-acid accumulator, effectively by PbSO
4transform the PbCO for ease of decomposing
3, reduce energy consumption, alleviate environmental pollution.
Description
Technical field
The invention belongs to field of waste battery disposal, more particularly, relate to a kind of waste lead acid battery lead cream desulfurization and transformation method.
Background technology
In recent years, along with the day by day exhausted of lead ore resource and the plumbous continuous increase of measuring of lead acid accumulator consumption, from lead-acid accumulator, reclaiming lead becomes the important channel realizing lead resource sustainable development.But in China, immature due to technology, has plurality of heavy metal or SO in the process of plumbous regeneration
2be discharged in environment, pollute.The consumption lead amount of current China lead acid accumulator occupies about 70% of total value, but recycling waste lead batteries rate is less than 90%, and developed country's general warranty 100%; In addition, the lead recovery in China's secondary lead smelting process is generally about 80%, and Foreign Advanced Lerel can reach more than 98%.Therefore annual China about has the waste lead accumulator of about 30,000 tons to fail to be recycled utilization; cause China about to have the lead of about 4.5 ten thousand tons and lead compound to flow in air, soil and water every year because the rate of recovery is low simultaneously; cause the serious wasting of resources and environmental pollution (Li Jinhui etc.; China's recycling waste lead batteries utilizes present situation and management game; environmental protection, (2000) No.4:40-42).Simultaneously, according to the literature, according to the reserve-production ratio having verified lead ore resource at present, lead ore only enough exploits 25-30.Along with the mouth benefit of lead ore resource is exhausted, the recycling and reuse of lead metal has become the only way realizing plumbing sustainable development.The development of China's plumbing in the research carrying out the plumbous regenerative process of pollution-free or light pollution also direct relation.
Current lead metal mainly consumes in the production of storage battery, and therefore plumbous regenerative process is mainly carried out reduction to the lead plaster slag mud in lead-acid accumulator and transformed with the process obtaining lead and lead alloy.The difficult point of this process is the smelting of lead plaster, its method can be divided at present pyrogenic process, wet method and dry wet combination method (Xiao Yongqing. market business opportunity unlimited [J] is produced in automobile-used waste lead acid battery reclaiming. the metal world, 2004 (2): 11-13; Hu Tao, Han Hong, Zhu Bin, wait recovery [J] plumbous in waste lead acid battery. battery, 2007,37 (6): 472-473; Straight China. pollution-free pyrometallurgical smelting reviver and alloy [J] from used and scrapped battery. Shanghai non-ferrous metal, 2002,23 (4): 156-163).Pyrometallurgical smelting also exists that metal recovery rate is low, energy consumption is high and seriously polluted three large problems.Dry wet combination method generally takes wet desulphurization, pyrometallurgical smelting, after namely carrying out cracking and sorting, synthetical recovery, lead plaster desulfurization conversion to waste lead accumulator, then carries out melting with rotary kiln or reverberatory furnace.This method, compared to pure pyrometallurgical smelting, significantly reduces SO
2discharge capacity, but later stage melting still have employed high-temperature service, therefore invariably cannot can cause lead dust pollution.The wet treatment of waste lead accumulator can be divided three classes: (1) lead plaster desulfurization conversion one leaches an electrodeposition method; (2) lead plaster directly leaches an electrodeposition method; (3) lead plaster direct electrowinning method.From the angle of environmental protection, the plumbous regeneration techniques of wet method eliminates SO
2with the important method of lead dust pollution, but due to hydrometallurgy for the solids in scrap battery not bonus point selection of land to carry out mixed smelting mixing, cause about having 10,000 tons of lead to run off in vain every year.
Summary of the invention
the technical problem solved
Low, the seriously polluted and problem that lead plaster pyrometallurgical smelting cost is high for the lead-acid accumulator recovery utilization rate existed in prior art, the invention provides a kind of waste lead acid battery lead cream desulfurization and transformation method, which provide a determination the technological parameter of lead plaster desulfurization conversion in lead-acid accumulator, effectively by PbSO
4transform the PbCO for ease of decomposing
3, after desulfurization, the pyrometallurgical smelting temperature of lead plaster is lower than smelting temperature before its desulfurization more than 150 DEG C, reduces energy consumption, alleviates environmental pollution.
technical scheme
Object of the present invention is achieved through the following technical solutions.
A kind of waste lead acid battery lead cream desulfurization and transformation method of the present invention, the steps include:
(1) lead plaster former state preparation
Lead-acid accumulator resolution process is taken out grid alloy, takes off lead plaster from grid, impurities removing, dry in the environment of 80 ~ 90 DEG C, in grinder, grind the lead plaster former state that 10 ~ 30min obtains granularity 50 ~ 300 μm;
(2) desulfurization conversion agent is configured
Desulfurization conversion agent is mixed with conversion fluid, with water bath with thermostatic control bed, desulfurization conversion liquid is heated to 20 ~ 90 DEG C;
(3) fully react
Load weighted lead plaster is added in the obtained conversion fluid of step (2), and stirring makes it fully react;
(4) cooling after to be transformed, filters, and repeatedly rinses filter residue repeatedly with distilled water.
Preferably, the desulfurization conversion agent in described step (2) is Na
2cO
3, NH
4hCO
3and K
2cO
3mixture, and Na
2cO
3: NH
4hCO
3: K
2cO
3=1:2 ~ 6:1(mass ratio).
Preferably, in described step (2), the temperature of conversion fluid is 60 ~ 70 DEG C.
Preferably, in described step (2), the pH value of conversion fluid is 6 ~ 9.5.
Further, in described step (2), the pH value of conversion fluid is 7.
Preferably, in described step (2), the CO in conversion fluid
3 2-concentration be 0.5 ~ 1.5mol/L.
Preferably, in described step (3), the stir speed (S.S.) of conversion fluid is 700 ~ 1300r/min.
Preferably, in described step (1), the granularity of lead plaster former state is 100 ~ 125 μm.
beneficial effect
Compared to prior art, the invention has the advantages that:
(1) in the method for the invention, control the condition such as granularity size and certain temperature, time and mixing speed, lead plaster is fully reacted with desulfurization conversion agent in agitating device, generate sulfate, PbCO
3or PbO etc.For pyrometallurgical smelting, lead plaster is after desulfurization preliminary treatment, and plumbous grade gets a promotion, and decrease the inventory into stove, the lead metal rate of recovery effectively improves.Due to PbCO
3just PbO can be decomposed at about 340 DEG C, therefore lead plaster can carry out pyrometallurgical smelting at a lower temperature after desulfurization process, and the pyrometallurgical smelting temperature of lead plaster is lower than smelting temperature before its desulfurization more than 150 DEG C after desulfurization, thus reduce energy consumption, alleviate environmental pollution.Experimental configuration shows, adopts this technology that the sulfur content of furnace charge can be made to reduce by more than 90%, greatly reduces and smelt required flux amount and SO
2discharge capacity; Compared with before desulfurization, lead plaster is smelted ability and is improve 30%, and the metallic lead rate of recovery reaches more than 90%, and energy consumption reduction surpasses 10%, smelts discarded object and reduces 75%;
(2) because pH value affects the final form of converted product, therefore need in course of reaction to keep pH value in the scope of 6 ~ 9.5, under these circumstances, PbSO
4conversion ratio can reach more than 80%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
A kind of waste lead acid battery lead cream desulfurization and transformation method of the present invention, the steps include:
(1) lead plaster former state preparation
Lead-acid accumulator resolution process is taken out grid alloy, takes off lead plaster from grid, impurities removing, dry in the environment of 80 ~ 90 DEG C, in grinder, grind the lead plaster former state that 10 ~ 30min obtains granularity 50 ~ 300 μm;
(2) desulfurization conversion agent is configured
Desulfurization conversion agent is mixed with conversion fluid, with water bath with thermostatic control bed, desulfurization conversion liquid is heated to 20 ~ 90 DEG C;
(3) fully react
Load weighted lead plaster is added in the obtained conversion fluid of step (2), and stirring makes it fully react;
(4) cooling after to be transformed, filters, and repeatedly rinses filter residue repeatedly with distilled water.
embodiment 1
A kind of waste lead acid battery lead cream desulfurization and transformation method of the present embodiment 1, the steps include:
(1) lead plaster former state preparation
Lead-acid accumulator resolution process is taken out grid alloy, takes off lead plaster from grid, impurities removing, dry in the environment of 80 DEG C, in grinder, grind the lead plaster former state that 10min obtains granularity 50 μm;
(2) desulfurization conversion agent is configured
Desulfurization conversion agent is mixed with conversion fluid, and desulfurization conversion agent is Na
2cO
3, NH
4hCO
3and K
2cO
3mixture, and Na
2cO
3: NH
4hCO
3: K
2cO
3=1:2 ~ 3:1(mass ratio).The pH value of conversion fluid is 6.CO in conversion fluid
3 2-concentration be 0.5mol/L, with water bath with thermostatic control bed, desulfurization conversion liquid is heated to 20 DEG C;
(3) fully react
Load weighted lead plaster is added in the obtained conversion fluid of step (2), and stirring makes it fully react; The stir speed (S.S.) of conversion fluid is 700r/min.
(4) cooling after to be transformed, filters, and repeatedly rinses filter residue repeatedly with distilled water.
embodiment 2
A kind of waste lead acid battery lead cream desulfurization and transformation method of the present embodiment 2, the steps include:
(1) lead plaster former state preparation
Lead-acid accumulator resolution process is taken out grid alloy, takes off lead plaster from grid, impurities removing, dry in the environment of 85 DEG C, in grinder, grind the lead plaster former state that 20min obtains granularity 100 μm;
(2) desulfurization conversion agent is configured
Desulfurization conversion agent is mixed with conversion fluid, and desulfurization conversion agent is Na
2cO
3, NH
4hCO
3and K
2cO
3mixture, and Na
2cO
3: NH
4hCO
3: K
2cO
3=1:3 ~ 4:1(mass ratio).CO in conversion fluid
3 2-concentration be 1.0mol/L, the pH value of conversion fluid is 7.With water bath with thermostatic control bed, desulfurization conversion liquid is heated to 70 DEG C;
(3) fully react
Load weighted lead plaster is added in the obtained conversion fluid of step (2), and stirring makes it fully react; The stir speed (S.S.) of conversion fluid is 1000r/min.
(4) cooling after to be transformed, filters, and repeatedly rinses filter residue repeatedly with distilled water.
embodiment 3
A kind of waste lead acid battery lead cream desulfurization and transformation method of the present embodiment 3, the steps include:
(1) lead plaster former state preparation
Lead-acid accumulator resolution process is taken out grid alloy, takes off lead plaster from grid, impurities removing, dry in the environment of 90 DEG C, in grinder, grind the lead plaster former state that 30min obtains granularity 300 μm;
(2) desulfurization conversion agent is configured
Desulfurization conversion agent is mixed with conversion fluid, and desulfurization conversion agent is Na
2cO
3, NH
4hCO
3and K
2cO
3mixture, and Na
2cO
3: NH
4hCO
3: K
2cO
3=1:5 ~ 6:1(mass ratio).CO in conversion fluid
3 2-concentration be 1.5mol/L, the pH value of conversion fluid is 9.5, with water bath with thermostatic control bed, desulfurization conversion liquid is heated to 90 DEG C;
(3) fully react
Load weighted lead plaster is added in the obtained conversion fluid of step (2), and stirring makes it fully react; The stir speed (S.S.) of conversion fluid is 1300r/min.
(4) cooling after to be transformed, filters, and repeatedly rinses filter residue repeatedly with distilled water.
Below be schematically described the invention and execution mode thereof, this description is not restricted.So, if those of ordinary skill in the art enlightens by it, when not departing from this creation aim, designing the technical scheme similar to this technical scheme and embodiment without creationary, the protection range of this patent all should be belonged to.
Claims (2)
1. a waste lead acid battery lead cream desulfurization and transformation method, the steps include:
(1) lead plaster former state preparation
Lead-acid accumulator resolution process is taken out grid alloy, takes off lead plaster from grid, impurities removing, dry in the environment of 80 ~ 90 DEG C, in grinder, grind the lead plaster former state that 10 ~ 30min obtains granularity 50 ~ 300 μm;
(2) desulfurization conversion agent is configured
Desulfurization conversion agent is mixed with conversion fluid, with water bath with thermostatic control bed, desulfurization conversion liquid is heated to 60 ~ 70 DEG C;
(3) fully react
Load weighted lead plaster is added in the obtained conversion fluid of step (2), and stirring makes it fully react;
(4) cooling after to be transformed, filters, and repeatedly rinses filter residue repeatedly with distilled water;
Wherein, the desulfurization conversion agent in described step (2) is Na
2cO
3, NH
4hCO
3and K
2cO
3mixture, and Na
2cO
3: NH
4hCO
3: K
2cO
3=1:2 ~ 6:1 (mass ratio);
Wherein, in described step (2), the pH value of conversion fluid is 7;
Wherein, in described step (2), the CO in conversion fluid
3 2-concentration be 0.5 ~ 1.5mol/L;
In wherein said step (3), the stir speed (S.S.) of conversion fluid is 700 ~ 1300r/min.
2. waste lead acid battery lead cream desulfurization and transformation method according to claim 1, is characterized in that, in described step (1), the granularity of lead plaster former state is 100 ~ 125 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210424305.6A CN103000968B (en) | 2012-10-31 | 2012-10-31 | A kind of waste lead acid battery lead cream desulfurization and transformation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210424305.6A CN103000968B (en) | 2012-10-31 | 2012-10-31 | A kind of waste lead acid battery lead cream desulfurization and transformation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103000968A CN103000968A (en) | 2013-03-27 |
| CN103000968B true CN103000968B (en) | 2015-10-07 |
Family
ID=47929271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210424305.6A Expired - Fee Related CN103000968B (en) | 2012-10-31 | 2012-10-31 | A kind of waste lead acid battery lead cream desulfurization and transformation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103000968B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468970A (en) * | 2013-09-03 | 2013-12-25 | 四川景星环境科技有限公司 | Lead plaster desulfurizer and desulphurization method for secondary lead industry |
| CN103540741B (en) * | 2013-11-05 | 2015-11-04 | 湖南江冶机电科技股份有限公司 | A kind of lead plaster wet method forces sulfur removal technology |
| 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 |
| CN105950872B (en) * | 2016-06-30 | 2017-12-12 | 中南大学 | A kind of method of waste lead acid battery lead cream hydrothermal reduction dual conversion |
| CN106816662A (en) * | 2016-12-24 | 2017-06-09 | 骆驼集团蓄电池研究院有限公司 | A kind of waste diachylon high-efficiency desulfurization technique |
| CN111170351A (en) * | 2018-11-13 | 2020-05-19 | 湖南省金翼有色金属综合回收有限公司 | Lead sulfate waste material desulfurization device and process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318692A (en) * | 2007-06-04 | 2008-12-10 | 湖南大学 | Method for preparing high quality lead dioxide with plumbum mud in waste lead acid accumulator |
| CN101518711A (en) * | 2009-04-03 | 2009-09-02 | 武汉工程大学 | Process and device for continuous ultrasound desulfurization of scrapped lead paste |
-
2012
- 2012-10-31 CN CN201210424305.6A patent/CN103000968B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318692A (en) * | 2007-06-04 | 2008-12-10 | 湖南大学 | Method for preparing high quality lead dioxide with plumbum mud in waste lead acid accumulator |
| CN101518711A (en) * | 2009-04-03 | 2009-09-02 | 武汉工程大学 | Process and device for continuous ultrasound desulfurization of scrapped lead paste |
Non-Patent Citations (1)
| Title |
|---|
| 唱鹤鸣 et al.废铅酸电池铅膏处理新工艺.《废铅酸电池铅膏处理新工艺(自然科学版)》.2011,第10卷第37-40页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103000968A (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103000968B (en) | A kind of waste lead acid battery lead cream desulfurization and transformation method | |
| EP2312686B1 (en) | Method for implementing full cycle regeneration of waste lead acid battery | |
| CN105506294B (en) | A kind of method of manganese and lead in synthetical recovery electrolytic manganese anode mud | |
| CN100583548C (en) | Method of recycling waste lead acid battery lead by electrolyzing with acid-wet method | |
| CN107083483A (en) | A kind of method for strengthening waste and old lithium ion battery metal recovery | |
| CN108486376A (en) | A method of leaching metal in waste lithium ion cell anode material | |
| CN109881008A (en) | A kind of method that reduction roasting-water quenching recycles lithium in waste and old lithium ion battery | |
| CN107083488B (en) | A kind of waste lead acid battery lead cream bath smelting processing method | |
| CN103184340B (en) | Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster | |
| CN104393364A (en) | Method for preparing PbO from waste lead-acid battery by using direct wet method | |
| CN105420489B (en) | A kind of diachylon desulphurization method based on throttling self collision | |
| CN201345398Y (en) | Regeneration and utilization system for waste lead-acid storage batteries and lead-containing waste | |
| CN105197987B (en) | PbO, PbSO4, PbO2the separation method of mixture | |
| CN108796230A (en) | A kind of method of lead-acid accumulator dismantling cream mud Whote-wet method recycling lead | |
| CN105226344A (en) | The recovery method of a kind of cobalt in waste lithium ion batteries acid lithium and graphite | |
| CN113912033A (en) | Method for recycling anode and cathode mixed powder of waste lithium iron phosphate battery with pre-positioned lithium extraction | |
| Zakiyya et al. | A review of spent lead-acid battery recycling technology in indonesia: comparison and recommendation of environment-friendly process | |
| CN110551899A (en) | High-efficiency energy-saving secondary lead smelting process | |
| CN111170358A (en) | Device and process for preparing lead oxide from waste lead-acid storage battery lead paste | |
| CN1808761A (en) | Clean recovery method of lead from waste storage cells by acidic electrolyzing and in-situ deoxidation in solid phase through wet process | |
| CN106222425A (en) | The sulfur method of lead plaster in a kind of waste and old lead acid accumulator | |
| CN105200241B (en) | The method that waste lead accumulator lead plaster separation prepares lead monoxide, lead sulfate, brown lead oxide | |
| CN101871045A (en) | Method for producing zinc by utilizing sulphate process titanium dioxide waste acid | |
| CN103280612A (en) | Energy-saving and environment-friendly method for recycling waste acid storage batteries | |
| CN106086414A (en) | A kind of method reclaiming lead from waste lead acid battery lead cream |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151007 Termination date: 20161031 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |