CN102324592A - Method for recovering cadmium, ferrum, nickel and cobalt from used nickel-cadmium battery - Google Patents
Method for recovering cadmium, ferrum, nickel and cobalt from used nickel-cadmium battery Download PDFInfo
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- CN102324592A CN102324592A CN201110211546A CN201110211546A CN102324592A CN 102324592 A CN102324592 A CN 102324592A CN 201110211546 A CN201110211546 A CN 201110211546A CN 201110211546 A CN201110211546 A CN 201110211546A CN 102324592 A CN102324592 A CN 102324592A
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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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Abstract
The invention provides a method for recovering cadmium, ferrum, nickel and cobalt from a used nickel-cadmium battery. The method comprises the following steps: firstly crushing the used nickel-cadmium battery into a mixture with the particle size of 0.5mm-2mm; separating cadmium from the mixture by adopting a vacuum metallurgy separation method, wherein the cadmium recovery rate is above 98% and the purity of the recovered cadmium is above 99%; separating magnetic materials including ferrum, nickel and cobalt and the like from the used nickel-cadmium battery mixed metal subjected to the vacuum metallurgy treatment by preferably using a magnetic separation method, wherein the recovery rate of ferrum, nickel and cobalt is above 95%. The method provided by the invention has the advantages of low cost, high efficiency, simple structure and no pollution and the like, can overcome the heavy metal pollution problem caused by landfill and burning treatment and the like and reduce environmental pollution; meanwhile, the recovered products are metal simple substances instead of metallic compounds, thus the added value is higher.
Description
Technical field
The present invention relates to abandoned nickel and cadmium cell, cadmium in particularly a kind of abandoned nickel and cadmium cell, iron, nickel, cobalt recovery method.
Background technology
Along with the raising of China's national life level, national to electronics technology product demand also increase day by day, the use of battery more and more widely is deep in people's the sphere of life.China is nickel-cadmium cell production and use big country, and according to statistics, the nickel-cadmium cell that China scraps every year reaches 1.2 hundred million, and China in 2005 scraps nickel-cadmium cell and reaches 600,000,000.
Abandoned nickel and cadmium cell is a hazardous waste, and it contains a large amount of poisonous and harmful substances, and like heavy metal substance and acid, alkaline electrolytes etc. such as cadmium, nickel, in a single day these materials get into environment, can bring severe contamination.But there is not processing method preferably in China at present, and most of abandoned nickel and cadmium cells are often with house refuse landfill and burning disposal, and heavy metals such as the cadmium in the abandoned nickel and cadmium cell, nickel are not effectively reclaimed.
See that from the material angle these abandoned nickel and cadmium cells have just temporarily lost use value, its essential characteristic does not change.Therefore, see that old and useless battery also is a kind of resource from another angle.Data shows, nickeliferous 116-556 gram in every kilogram of abandoned nickel and cadmium cell, and cadmium 11-173 gram will be if reasonably development and utilization will economize on resources in a large number.
Present abandoned nickel and cadmium cell resource treatment technique mainly contains hydrometallurgy, pyrometallurgy, biological metallurgy method, physics method or several kinds of treatment technologies and combines.It is simple and practical that the old and useless battery process is handled in pyrometallurgy, easy realization of industrialization, and it is high to reclaim metal purity, thereby is extensively adopted.Patent " abandoned nickel and cadmium cell reclaim special-purpose vacuum distillation industrial device " (Zheng just, the patent No. 200720042088.9), this invention is reclaimed special-purpose vacuum distillation industrial device for the abandoned nickel and cadmium cell cadmium.Patent " a kind of method of recovering cadmium from waste nickel-cadmium battery " (Pan Dean; Application number 200910089687.X); Employing low temperature pyrogenic process oxidation-ammonia soaks the method for flotation, with abandoned nickel and cadmium cell fragmentation, roasting, screening and flotation, to reclaim the cadmium in the abandoned nickel and cadmium cell.Though above patent can realize the separation and the recovery of cadmium in the abandoned nickel and cadmium cell, all can not effectively reclaim another harmful substance nickel in the abandoned nickel and cadmium cell, reach the abandoned nickel and cadmium cell harmless treatment.
Patent " a kind of method for reclaiming and recycling of abandoned nickel and cadmium cell " (Lei Lixu; Application number 200810195082.4); Adopt the physics method that the nickel-cadmium cell all the components is separated earlier, the positive plate and the negative plate that then separation are obtained are handled through hydrometallurgical, obtain Ni (OH)
2And Cd (OH)
2Though patent can realize separating and recovery of cadmium and nickel in the abandoned nickel and cadmium cell simultaneously, the product that reclaims is a metal mixture, needs further processing.
Summary of the invention
The objective of the invention is to overcome the deficiency that above-mentioned prior art exists; The recovery method of cadmium, iron, nickel, cobalt in a kind of abandoned nickel and cadmium cell is provided, through magnetic materials such as the cadmium in fragmentation-vacuum metallurgy-magnetic force method for separating separating waste, worn nickel-cadmium cell and iron, nickel, cobalts.
Technical solution of the present invention is following:
The recovery method of cadmium, iron, nickel, cobalt in a kind of abandoned nickel and cadmium cell, its characteristics are that this method carries out under air-proof condition, comprise the steps:
At first described abandoned nickel and cadmium cell is carried out break process, be broken into the mixed material that granularity is 0.5mm-2mm;
Described then mixed material is put into the vacuum metallurgy stove, and after adding the 1wt%-5wt% activated carbon powder, carries out the vacuum metallurgy separating treatment, in order to the cadmium separation metallic particles;
To carry out the magnetic force sorting at last through the remaining hybrid metal after the said vacuum metallurgy separating treatment and handle, in order to separation of iron metallic particles, nickel metallic particles and cobalt metallic particles.
Described break process is to be the mixed material of 0.5mm-2mm with described abandoned nickel and cadmium cell broken dissociating to broken particle size range in disintegrating machine.
The particle diameter of described activated carbon powder is less than 0.15mm.
Described vacuum metallurgy separating treatment comprises the steps:
1. the sealed vacuum stove starts vacuum system and bleeds, and makes the pressure of vacuum furnace remain on 1 * 10
-2～1 * 10
2Pa;
2. start the vacuum furnace power supply, make the interior temperature of vacuum furnace be heated to 500～900 ℃, keep temperature-resistant then, make the cadmium evaporation in the raw material, evaporation time is 1～3 hour;
3. zinc fume condensation on condenser, condensing temperature are 100～400 ℃.
Magnetic flux density was 200～500mT during described magnetic force sorting was handled, and the magnetic separator rotating speed is 30～60rpm.
The principle of vacuum metallurgy is based on each component of abandoned nickel and cadmium cell and under same temperature, has different vapour pressures, in a vacuum through evaporation and condensation, realizes comprehensive utilization and reclaims thereby it is separated from each other under different temperatures respectively.Therefore, can the high vapour pressure metal of the low melting points such as cadmium in the abandoned nickel and cadmium cell be separated from hybrid metal through distillation or means such as distillation, then at a certain temperature, through after the condensation with metal recovery.
Based on the magnetic contrast of each metallic element in the abandoned nickel and cadmium cell, technical scheme of the present invention, is separated magnetic metals such as iron, nickel, cobalt after vacuum metallurgy in uneven magnetic field through the magnetic force sorting process the residue.Technical scheme of the present invention adopts magnetic separator that iron, nickel, cobalt are separated from hybrid metal, thereby realizes that magnetic flux density is 200～500mT in comprehensive utilization and the recovery magnetic separation process, and the magnetic separator rotating speed is 30～60rpm.
The concrete technical process of the present invention is following:
1. be transported to disintegrating machine to abandoned nickel and cadmium cell, carry out fragmentation, being crushed to particle diameter is 0.5mm-2mm.
2. be to add 1wt%-5wt% activated carbon powder (particle diameter is less than 0.15mm) in the 0.5mm-2mm abandoned nickel and cadmium cell as reducing agent, Separation and Recovery cadmium in the vacuum metallurgy stove in granularity.During the Separation and Recovery cadmium, the pressure of vacuum furnace remains on 1 * 10 in the vacuum metallurgy stove
-2～1 * 10
2Pa, heating-up temperature is 500～900 ℃.Be 1～3 hour heating time.
3. cadmium vapor is able to condensation on condenser, and condensing temperature is 100～400 ℃, and the cadmium rate of recovery reaches more than 98%, and purity reaches more than 99%, thus cadmium is separated from abandoned nickel and cadmium cell.
4. after the vacuum metallurgy, adopt magnetic materials such as the iron in the abandoned nickel and cadmium cell hybrid metal, nickel, cobalt behind the magnetic force method for separating separate vacuum metallurgy.In the magnetic separation process, magnetic flux density is 200～500mT, and the magnetic separator rotating speed is 30～60rpm, and iron, nickel, the cobalt rate of recovery reach more than 95% in the abandoned nickel and cadmium cell.
The present invention has characteristics such as cost is low, efficient, simple in structure, pollution-free.Overcome the problem of method heavy metal pollutions such as landfill and burning disposal, reduced environmental pollution.Simultaneously, reclaim product and be metal simple-substance and nonmetallic compound, added value is higher.
Description of drawings
Fig. 1 is the recovery method flow chart of cadmium, iron, nickel, cobalt in the abandoned nickel and cadmium cell of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is further described, but should not limit protection scope of the present invention with this.
Please consult Fig. 1 earlier, Fig. 1 is the recovery method flow chart of cadmium, iron, nickel, cobalt in the abandoned nickel and cadmium cell of the present invention.As scheme said, the recovery method of cadmium, iron, nickel, cobalt in a kind of abandoned nickel and cadmium cell, this method is carried out under air-proof condition, comprises the steps:
At first described abandoned nickel and cadmium cell is carried out break process, be broken into the mixed material that granularity is 0.5mm-2mm;
Described then mixed material is put into the vacuum metallurgy stove, and after adding the 1wt%-5wt% activated carbon powder, carries out the vacuum metallurgy separating treatment, in order to the cadmium separation metallic particles;
To carry out the magnetic force sorting at last through the remaining hybrid metal after the said vacuum metallurgy separating treatment and handle, in order to separation of iron metallic particles, nickel metallic particles and cobalt metallic particles.
During processing, at first send into disintegrating machine to abandoned nickel and cadmium cell through conveyer belt and carry out fragmentation, granularity is the fragment of 0.5mm-2mm; Send into the vacuum metallurgy separation equipment to the fragment of granularity 0.5mm-2mm through conveyer belt then, and the activated carbon powder (particle diameter is less than 0.15mm) of adding 2wt% carries out the separation of cadmium metal as reducing agent; Send into the magnetic force sorting unit through the residue of conveyer belt after again and carry out separating of magnetisable material and namagnetic substance vacuum metallurgy; Isolate metals such as metallic particles such as namagnetic substance copper, potassium and magnetisable material iron, nickel, cobalt.
Embodiment 1
At first abandoned nickel and cadmium cell is broken into the mixed material that particle diameter is 0.5-1mm; Then; Material after the fragmentation is put into the vacuum metallurgy stove; The activated carbon powder (particle diameter is less than 0.15mm) that adds 1wt% is as reducing agent, and vacuum furnace sealing back starts vacuum system bleeds, and makes the vacuum degree of vacuum furnace be in 0.01Pa.Temperature is heated to 500 ℃ in the vacuum furnace.Keep temperature-resistant then, make the cadmium evaporation, evaporation time is 1 hour.Cadmium vapor is able to condensation on condenser, condensing temperature is 100 ℃, and the cadmium rate of recovery is 98.5%, and purity is 99.6%, and the hybrid metal that evaporates carries out the magnetic force sorting and continues the separation of purifying.In the magnetic separation process, magnetic flux density is 200m T, and the magnetic separator rotating speed is 30rpm, and iron, nickel, the cobalt rate of recovery reach more than 98.3%.
Embodiment 2
At first abandoned nickel and cadmium cell is broken into the mixed material that particle diameter is 1-2mm; Then; Material after the fragmentation is put into the vacuum metallurgy stove; The activated carbon powder (particle diameter is less than 0.15mm) that adds 3wt% is as reducing agent, and vacuum furnace sealing back starts vacuum system bleeds, and makes the vacuum degree of vacuum furnace be in 10Pa.Temperature is heated to 750 ℃ in the vacuum furnace.Keep temperature-resistant then, make cadmium evaporation in the raw material, evaporation time is 2 hours.Cadmium vapor is able to condensation on condenser, condensing temperature is 200 ℃, and the cadmium rate of recovery is 99.5%, and purity is 99.4%, and the hybrid metal that evaporates carries out the magnetic force sorting and continues the separation of purifying.In the magnetic separation process, magnetic flux density is 350mT, and the magnetic separator rotating speed is 40rpm, and iron, nickel, the cobalt rate of recovery reach 96.1%.
Embodiment 3
At first abandoned nickel and cadmium cell is broken into the mixed material that particle diameter is 0.75-1.5mm; Then; Material after the fragmentation is put into the vacuum metallurgy stove; The activated carbon powder (particle diameter is less than 0.15mm) that adds 5wt% is as reducing agent, and vacuum furnace sealing back starts vacuum system bleeds, and makes the vacuum degree of vacuum furnace be in 100Pa.Temperature is heated to 900 ℃ in the vacuum furnace.Keep temperature-resistant then, make cadmium evaporation in the raw material, evaporation time is 3 hours.Cadmium vapor is able to condensation on condenser, condensing temperature is 400 ℃, and the cadmium rate of recovery is 99.7%, and purity is 99.2%, and the hybrid metal that evaporates carries out the magnetic force sorting and continues the separation of purifying.In the magnetic separation process, magnetic flux density is 500mT, and the magnetic separator rotating speed is 60rpm, and iron, nickel, the cobalt rate of recovery reach 95.5%.
Embodiment 4
At first abandoned nickel and cadmium cell is broken into the mixed material that particle diameter is 0.8-1.2mm; Then; Material after the fragmentation is put into the vacuum metallurgy stove; The activated carbon powder (particle diameter is less than 0.15mm) that adds 2.5wt% is as reducing agent, and vacuum furnace sealing back starts vacuum system bleeds, and makes the vacuum degree of vacuum furnace be in 1.5Pa.Temperature is heated to 650 ℃ in the vacuum furnace.Keep temperature-resistant then, make cadmium evaporation in the raw material, evaporation time is 2.5 hours.Cadmium vapor is able to condensation on condenser, condensing temperature is 300 ℃, and the cadmium rate of recovery is 99.6%, and purity is 99.3%, and the hybrid metal that evaporates carries out the magnetic force sorting and continues the separation of purifying.In the magnetic separation process, magnetic flux density is 320mT, and the magnetic separator rotating speed is 45rpm, and iron, nickel, the cobalt rate of recovery reach 95.4%.
Embodiment 5
At first abandoned nickel and cadmium cell is broken into the mixed material that particle diameter is 0.75-1.5mm; Then; Material after the fragmentation is put into the vacuum metallurgy stove; The activated carbon powder (particle diameter is less than 0.15mm) that adds 1.8wt% is as reducing agent, and vacuum furnace sealing back starts vacuum system bleeds, and makes the vacuum degree of vacuum furnace be in 38Pa.Temperature is heated to 840 ℃ in the vacuum furnace.Keep temperature-resistant then, make cadmium evaporation in the raw material, evaporation time is 2.5 hours.Cadmium vapor is able to condensation on condenser, condensing temperature is 230 ℃, and the cadmium rate of recovery is 98.9%, and purity is 99.4%, and the hybrid metal that evaporates carries out the magnetic force sorting and continues the separation of purifying.In the magnetic separation process, magnetic flux density is 460mT, and the magnetic separator rotating speed is 35rpm, and iron, nickel, the cobalt rate of recovery reach 95.6%.
Claims (5)
1. the recovery method of cadmium, iron, nickel, cobalt in the abandoned nickel and cadmium cell is characterized in that this method carries out under air-proof condition, comprise the steps:
At first described abandoned nickel and cadmium cell is carried out break process, be broken into the mixed material that granularity is 0.5mm-2mm;
Described then mixed material is put into the vacuum metallurgy stove, and after adding the 1wt%-5wt% activated carbon powder, carries out the vacuum metallurgy separating treatment, in order to the cadmium separation metallic particles;
To carry out the magnetic force sorting at last through the remaining hybrid metal after the said vacuum metallurgy separating treatment and handle, in order to separation of iron metallic particles, nickel metallic particles and cobalt metallic particles.
2. the recovery method of cadmium, iron, nickel, cobalt in a kind of abandoned nickel and cadmium cell as claimed in claim 1 is characterized in that described break process is is the mixed material of 0.5mm-2mm with described abandoned nickel and cadmium cell broken dissociating to broken particle size range in disintegrating machine.
3. the recovery method of cadmium, iron, nickel, cobalt in a kind of abandoned nickel and cadmium cell as claimed in claim 1, the particle diameter that it is characterized in that described activated carbon powder is less than 0.15mm.
4. the recovery method of cadmium, iron, nickel, cobalt in a kind of abandoned nickel and cadmium cell as claimed in claim 1 is characterized in that described vacuum metallurgy separating treatment comprises the steps:
1. the sealed vacuum stove starts vacuum system and bleeds, and makes the pressure of vacuum furnace remain on 1 * 10
-2～1 * 10
2Pa;
2. start the vacuum furnace power supply, make the interior temperature of vacuum furnace be heated to 500～900 ℃, keep temperature-resistant then, make the cadmium evaporation in the raw material, evaporation time is 1～3 hour;
3. zinc fume condensation on condenser, condensing temperature are 100～400 ℃.
5. the recovery method of cadmium, iron, nickel, cobalt in a kind of abandoned nickel and cadmium cell as claimed in claim 1 is characterized in that magnetic flux density is 200～500mT in the described magnetic force sorting processing, and the magnetic separator rotating speed is 30～6 () rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110211546A CN102324592A (en) | 2011-07-27 | 2011-07-27 | Method for recovering cadmium, ferrum, nickel and cobalt from used nickel-cadmium battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110211546A CN102324592A (en) | 2011-07-27 | 2011-07-27 | Method for recovering cadmium, ferrum, nickel and cobalt from used nickel-cadmium battery |
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| CN102324592A true CN102324592A (en) | 2012-01-18 |
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| CN201110211546A Pending CN102324592A (en) | 2011-07-27 | 2011-07-27 | Method for recovering cadmium, ferrum, nickel and cobalt from used nickel-cadmium battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450549A (en) * | 2016-10-24 | 2017-02-22 | 中国科学院过程工程研究所 | Method for cleanly recycling nickel and/or cobalt from positive electrode material |
| CN112680592A (en) * | 2019-10-17 | 2021-04-20 | 株式会社神户制钢所 | Pretreatment method for Ni/Co recovery |
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| CN101054631A (en) * | 2007-05-18 | 2007-10-17 | 北京矿冶研究总院 | Method for recovering valuable metal in invalid lithium ion battery |
| CN101069893A (en) * | 2007-03-29 | 2007-11-14 | 吴德余 | Waste zinc-manganese dry cell separation apparatus and separation method |
| CN101188323A (en) * | 2007-12-07 | 2008-05-28 | 南京大学 | Vacuum distillation industrial device special for recycling abandoned nickel and cadmium cell |
| CN101886178A (en) * | 2010-07-28 | 2010-11-17 | 江门市长优实业有限公司 | Comprehensive recovery method for nickel-hydrogen waste battery |
-
2011
- 2011-07-27 CN CN201110211546A patent/CN102324592A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1357938A (en) * | 2000-12-08 | 2002-07-10 | 同济大学 | Comprehensive recovery and utilization method of waste NiCd battery |
| CN101069893A (en) * | 2007-03-29 | 2007-11-14 | 吴德余 | Waste zinc-manganese dry cell separation apparatus and separation method |
| CN101054631A (en) * | 2007-05-18 | 2007-10-17 | 北京矿冶研究总院 | Method for recovering valuable metal in invalid lithium ion battery |
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| CN101886178A (en) * | 2010-07-28 | 2010-11-17 | 江门市长优实业有限公司 | Comprehensive recovery method for nickel-hydrogen waste battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450549A (en) * | 2016-10-24 | 2017-02-22 | 中国科学院过程工程研究所 | Method for cleanly recycling nickel and/or cobalt from positive electrode material |
| CN106450549B (en) * | 2016-10-24 | 2019-07-19 | 中国科学院过程工程研究所 | A method of nickel and/or cobalt in cleaning recycling positive electrode |
| CN112680592A (en) * | 2019-10-17 | 2021-04-20 | 株式会社神户制钢所 | Pretreatment method for Ni/Co recovery |
| CN112680592B (en) * | 2019-10-17 | 2023-03-21 | 株式会社神户制钢所 | Pretreatment method for Ni/Co recovery |
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Application publication date: 20120118 |