CN103667723A - Leaching method of cobalt acid lithium used battery anode material - Google Patents
Leaching method of cobalt acid lithium used battery anode material Download PDFInfo
- Publication number
- CN103667723A CN103667723A CN201310736635.3A CN201310736635A CN103667723A CN 103667723 A CN103667723 A CN 103667723A CN 201310736635 A CN201310736635 A CN 201310736635A CN 103667723 A CN103667723 A CN 103667723A
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- CN
- China
- Prior art keywords
- leaching
- nitric acid
- anode material
- pyrolusite
- positive electrode
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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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- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a leaching method of cobalt acid lithium used battery anode material. An anode material separated out from cobalt acid lithium used batteries and finely ground pyrolusite are placed into a pressure-proof and nitric acid etching resisting container, nitric acid is pumped into the container, then the container is sealed, and leaching of the cobalt acid lithium used battery anode material is performed.
Description
Technical field
The present invention relates to a kind of leaching method of anode material of waste LiCoO battery.
Background technology
Cobalt acid lithium battery is the widely used battery of a class, and this battery will produce a large amount of refuse batteries after using and scrapping.Because this class battery contains plurality of heavy metal, if abandon into environment, will environment be produced to very large direct and potential hazard.Anode material of waste LiCoO battery is mainly containing cobalt, lithium, copper and aluminium, and wherein cobalt, lithium and copper three's total content is greater than 60%, has very much a recovery value.The technique that reclaims at present cobalt, lithium and copper from anode material of waste LiCoO battery mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, cobalt, lithium and copper that very difficult acquisition is purer.Wet processing becomes more readily available purer cobalt, lithium and copper.Leaching is a requisite process in wet processing.The leaching method of anode material of waste LiCoO battery mainly contains hydrochloric acid leaching process, sulfuric acid leaching, nitric acid lixiviation process and nitration mixture (sulfuric acid adds nitric acid) lixiviation process at present.Hydrochloric acid leaching process, equipment corrosion is large, the large and contaminate environment of acid mist generation.The oxygenant (as hydrogen peroxide etc.) that sulfuric acid leaching consumption is more expensive.The nitric acid consumption of nitric acid lixiviation process is large, and can produce a large amount of oxynitride, contaminate environment.All wet processings all exist and eliminate how cost-effectively the package action of organic polymer to metal and metal oxide in this type of raw material, improve the problem of metal leaching rate.Although nitric acid processing industry pure oxygen lixiviation process and nitration mixture processing industry pure oxygen lixiviation process have solved the problems referred to above preferably, but leaching plant is more complicated, and the required industrial pure oxygen amount of refuse battery leaching is little, refuse battery is processed enterprise, and manufacture pure oxygen is personal uneconomical on the spot, and the storage of industrial pure oxygen, transportation and use are cumbersome.Development equipment corrosion is little, leaching yield is high, cost is low, the leaching method of the anode material of waste LiCoO battery of easy to use, basic non-environmental-pollution has larger practical value.
Summary of the invention
The problem leaching for current anode material of waste LiCoO battery, the object of the invention is to find a kind of nitric acid consumption low, the leaching method of the anode material of waste LiCoO battery that basic nitrogenfree oxide pollutes, it is characterized in that from waste LiCoO battery, (comprising by elementary positive electrode material artificial or that mechanical separation goes out by isolated positive electrode material, the positive pole powder material that elementary positive electrode material obtains through broken and ball milling or rod milling, the purer positive electrode material that elementary positive electrode material or positive pole powder material obtain through pre-treatment such as roastings) and levigate pyrolusite put into the container of withstand voltage and resistance to nitric acid corrosion, and nitric acid is pumped into this container, then sealed vessel, carry out the leaching of anode material of waste LiCoO battery, after finishing, leaching carries out liquid-solid separation, obtain required infusion solution.Extraction temperature is 40 ℃～80 ℃, and the nitric acid starting point concentration of leaching is 1mol/L～6mol/L, and extraction time is 1h～3h, and leaching process stirs, stirring velocity 30 r/min～100r/min.Nitric acid add-on is to add 101～130% of nitric acid theoretical consumption that in the positive electrode material of reaction vessel and pyrolusite, all metals leach.The MnO of pyrolusite used
2content>=40%, particle diameter≤180 order.The add-on of pyrolusite is with MnO
2count in oxidation positive electrode material all 100%～110% of the required theoretical amount of metallic state metal.
The object of the present invention is achieved like this: under condition airtight and that pyrolusite exists, nitric acid has leached anode material of waste LiCoO battery, and (cobalt in material and lithium exist with cobalt acid lithium form, copper and aluminium are mainly metal form) time, there is following chemical reaction in the process that metallic copper generates cupric nitrate:
Cu?+?4HNO
3?=?Cu(NO
3)
2?+?2NO
2?+?2H
2O
3Cu?+?8HNO
3?=?3Cu(HNO
3)
2?+?2NO?+?4H
2O
NO?+?MnO
2?+2HNO
3?=?NO
2?+?Mn(NO
3)
2?+H
2O
3NO
2?+?H
2O?=?2HNO
3?+?NO
2NO?+?3MnO
2?+?4HNO
3?=?3Mn(NO
3)
2?+?2H
2O
2NO
2?+?MnO
2?=?Mn(NO
3)
2
Total reaction is:
Cu?+?4HNO
3?+?MnO
2?=?Cu(NO
3)
2?+?Mn(NO
3)
2?+?2H
2O
Under condition airtight and that pyrolusite exists, when nitric acid has leached anode material of waste LiCoO battery, there is following chemical reaction in the process that metallic aluminium generates aluminum nitrate:
Al?+?4HNO
3?=?Al(NO
3)
3?+?NO?+?2H
2O
3NO
2?+?H
2O?=?2HNO
3?+?NO
2NO?+?3MnO
2?+?4HNO
3?=?3Mn(NO
3)
2?+?2H
2O
2NO
2?+?MnO
2?=?Mn(NO
3)
2
Total reaction is:
2Al?+?12HNO
3?+?3MnO
2?=?2Al(NO
3)
3?+?3Mn(NO
3)
2?+?6H
2O
When nitric acid leaches anode material of waste LiCoO battery, there is following chemical reaction in cobalt acid lithium:
4LiCoO
2?+?12HNO
3?=?4Co(NO
3)
2?+?4LiNO
3?+?6H
2O?+?O
2
The O producing
2the NO producing with previous reaction reacts and generates NO
2, finally generate nitric acid.
Utilize NO
2strong corrosion effect to organic polymer, eliminates the package action of organic polymer to metal and metal oxide in anode material of waste LiCoO battery, can fully react with nitric acid, has improved metal leaching rate.
Through above-mentioned series reaction, finally make anode material of waste LiCoO battery and pyrolusite leach simultaneously, saved pyrolusite and leached and need reducing roasting (reduction ratio is about 85%, unreduced MnO
2in nitric acid, can not leach) etc. preprocessing process, improved the utilization ratio of metal leaching rate and nitric acid, substantially avoided the generation of nitrogen oxides pollution thing, realized cleaning of technique.NO and NO that leaching process produces
2substantially regeneration nitric acid in slurry, the NO overflowing on a small quantity and NO
2by stirring, return to regeneration nitric acid in slurry, whole leaching process carries out under pressure-fired, is easy to engineering application.
specific implementation method
embodiment 1: by 100g anode material of waste LiCoO battery (containing cobalt 53.6%, lithium 5.3%, copper 8.2%, aluminium 3.4%) and levigate pyrolusite (particle diameter 200 orders, MnO
2content 55%, add-on be theoretical amount 105%) to add volume be in the stainless steel pressure reactor of 2L, the nitric acid 1800ml that adds 5.0mol/L, at 40～50 ℃, stirring (stirring velocity 80r/min) leaches 2.5 hours, after leaching finishes, carry out liquid-solid separation, obtain 1750ml infusion solution (not containing leached mud washing water).The about 200ml of reaction end gas, nitrous oxides concentration is 6.3mg/m
3.The leaching yield of cobalt, lithium, copper, aluminium and manganese be respectively 98.5%, 98.9%, 98.1%, 98.2% and 98.3%(by entering cobalt in infusion solution and leached mud washings, lithium, copper, aluminium and manganese, calculate).
Embodiment 2: by 400g anode material of waste LiCoO battery (containing cobalt 53.6%, lithium 5.3%, copper 8.2%, aluminium 3.4%) and levigate pyrolusite (particle diameter 180 orders, MnO
2content 45%, add-on be theoretical amount 103%) to add volume be in the stainless steel pressure reactor of 10L, the nitric acid 9.0L that adds 3.5mol/L, at 50～60 ℃, stirring (stirring velocity 70r/min) leaches 3 hours, after finishing, leaching carries out liquid-solid separation, obtain 8.7L infusion solution (not containing leached mud washing water), the about 1.3L of reaction end gas, nitrous oxides concentration is 4.7 mg/m
3.The leaching yield of cobalt, lithium, copper, aluminium and manganese be respectively 98.7%, 98.8%, 98.3%, 98.4% and 98.9%(by entering cobalt in infusion solution and leached mud washings, lithium, copper, aluminium and manganese, calculate).
Claims (1)
1. the leaching method of an anode material of waste LiCoO battery, it is characterized in that isolated positive electrode material from waste LiCoO battery and levigate pyrolusite to put into the container of withstand voltage and resistance to nitric acid corrosion, and nitric acid is pumped into this container, then sealed vessel, carry out the leaching of anode material of waste LiCoO battery, after finishing, leaching carries out liquid-solid separation, obtain required infusion solution, extraction temperature is 40 ℃～80 ℃, the nitric acid starting point concentration leaching is 1mol/L～6mol/L, extraction time is 1h～3h, leaching process stirs, stirring velocity 30 r/min～100r/min, nitric acid add-on is to add 101～130% of nitric acid theoretical consumption that in the positive electrode material of reaction vessel and pyrolusite, all metals leach, the MnO of pyrolusite used
2content>=40%, particle diameter≤180 order, the add-on of pyrolusite is with MnO
2count in oxidation positive electrode material all 100%～110% of the required theoretical amount of metallic state metal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736635.3A CN103667723A (en) | 2013-12-29 | 2013-12-29 | Leaching method of cobalt acid lithium used battery anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736635.3A CN103667723A (en) | 2013-12-29 | 2013-12-29 | Leaching method of cobalt acid lithium used battery anode material |
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| Publication Number | Publication Date |
|---|---|
| CN103667723A true CN103667723A (en) | 2014-03-26 |
Family
ID=50306493
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310736635.3A Pending CN103667723A (en) | 2013-12-29 | 2013-12-29 | Leaching method of cobalt acid lithium used battery anode material |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018538445A (en) * | 2015-12-22 | 2018-12-27 | ハンウィック リチャード ジェイ | Recovery of lithium from silicate minerals |
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|---|---|---|---|---|
| CN101280357A (en) * | 2008-01-16 | 2008-10-08 | 中南大学 | Environment-friendly acid leaching-extraction process in waste lithium battery recovery |
| CN101586189A (en) * | 2009-06-23 | 2009-11-25 | 四川师范大学 | Leaching method for anode material of waste LiCoO battery |
| CN101928831A (en) * | 2009-06-23 | 2010-12-29 | 四川师范大学 | Leaching method of anode material of lithium cobalt oxide waste battery |
| CN102703706A (en) * | 2012-06-01 | 2012-10-03 | 奇瑞汽车股份有限公司 | Method for recovering valued metals from waste lithium cobaltate batteries |
| CN103305698A (en) * | 2013-06-09 | 2013-09-18 | 南康市恒源循环科技有限公司 | Method for recovering gold, silver, tin and copper from industrial wastes |
-
2013
- 2013-12-29 CN CN201310736635.3A patent/CN103667723A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280357A (en) * | 2008-01-16 | 2008-10-08 | 中南大学 | Environment-friendly acid leaching-extraction process in waste lithium battery recovery |
| CN101586189A (en) * | 2009-06-23 | 2009-11-25 | 四川师范大学 | Leaching method for anode material of waste LiCoO battery |
| CN101928831A (en) * | 2009-06-23 | 2010-12-29 | 四川师范大学 | Leaching method of anode material of lithium cobalt oxide waste battery |
| CN102703706A (en) * | 2012-06-01 | 2012-10-03 | 奇瑞汽车股份有限公司 | Method for recovering valued metals from waste lithium cobaltate batteries |
| CN103305698A (en) * | 2013-06-09 | 2013-09-18 | 南康市恒源循环科技有限公司 | Method for recovering gold, silver, tin and copper from industrial wastes |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018538445A (en) * | 2015-12-22 | 2018-12-27 | ハンウィック リチャード ジェイ | Recovery of lithium from silicate minerals |
| JP2021193216A (en) * | 2015-12-22 | 2021-12-23 | アイシーエスアイピー プロプライエタリ リミテッド | Recovery of lithium from silicate mineral |
| JP7258093B2 (en) | 2015-12-22 | 2023-04-14 | アイシーエスアイピー プロプライエタリ リミテッド | Recovery of lithium from silicate minerals |
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Application publication date: 20140326 |