CN101643851A - Method for lixiviating anode materials of lithium nickel waste batteries - Google Patents
Method for lixiviating anode materials of lithium nickel waste batteries Download PDFInfo
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- CN101643851A CN101643851A CN200910059703A CN200910059703A CN101643851A CN 101643851 A CN101643851 A CN 101643851A CN 200910059703 A CN200910059703 A CN 200910059703A CN 200910059703 A CN200910059703 A CN 200910059703A CN 101643851 A CN101643851 A CN 101643851A
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- sulfuric acid
- leaching
- lixiviated
- battery
- nitric acid
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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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Abstract
The invention relates to a method for lixiviating anode materials of lithium nickel waste batteries. In the invention, the anode materials separated from the lithium nickel waste batteries are put ina container which resists pressure and resists corrosion of sulfuric acid and nitric acid; then the container is sealed; the sulfuric acid and the nitric acid are pumped into the container; and industrial pure oxygen is led in for lixiviating the anode materials of the lithium nickel waste batteries. The lixiviated temperature is 20 to 100 DEG C, the lixiviated pressure is 0.05 to 0.5 MPa, the initial concentration of the lixiviated sulfuric acid is 1 to 5 mol/L, the initial concentration of the nitric acid is 5 to 20 g/L, the lixiviated time is 1 to 5 hours, stirring is carried out on the lixiviated process, and the stirring speed is 30 to 100 r/min. The quality of the added sulfuric acid is 101 to 200 % of the theoretical consumption of the sulfuric acid lixiviated from all of metal of the anode materials added into the container.
Description
Technical field
The present invention relates to a kind of leaching method of anode material of waste LiNiO 2 battery.
Background technology
The lithium nickelate 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,, will produce very big direct and potential hazard to environment if abandon into environment.The lithium nickelate cell positive material is mainly nickeliferous, lithium, copper and aluminium, and wherein nickel, lithium and copper three's total content is greater than 60%, has very much a recovery value.The technology that reclaims at present nickel, nickel from anode material of waste LiNiO 2 battery mainly contains thermal process and wet processing.The product that thermal process obtains is an alloy material, nickel, lithium and copper that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, lithium and copper.Leaching is a requisite process in the wet processing.The leaching method of anode material of waste LiNiO 2 battery mainly contains salt acid leaching process, sulfuric acid leaching and nitric acid lixiviation process at present.The salt acid leaching process, equipment corrosion is big, the big and contaminate environment of acid mist generation.The expensive oxygenant of sulfuric acid leaching consumption (as hydrogen peroxide etc.).The nitric acid consumption of nitric acid lixiviation process is big, and can produce a large amount of oxynitride, contaminate environment.The development equipment corrosion is little, cost is low, the leaching method of the anode material of waste LiNiO 2 battery of basic non-environmental-pollution has big practical value.
Summary of the invention
Problem at present anode material of waste LiNiO 2 battery leaching, the objective of the invention is to seek a kind of need not expensive oxygenant, the leaching method of the anode material of waste LiNiO 2 battery that basic nitrogenfree oxide pollutes, it is characterized in that and from waste LiNiO 2 battery, (to comprise by isolated positive electrode material by elementary positive electrode material artificial or that mechanical separation goes out, the positive pole powder material that elementary positive electrode material obtains through broken and ball milling or rod milling, the more purified positive electrode material that elementary positive electrode material or positive pole powder material obtain through pre-treatment such as roastings) puts into withstand voltage and anti-sulfuric acid and nitric acid corrosive container, sealed vessel then, and sulfuric acid and nitric acid pumped into this container, feed industrial pure oxygen and carry out the leaching of anode material of waste LiNiO 2 battery, carry out liquid-solid separation after leaching end, obtain required infusion solution.Extraction temperature is 20～100 ℃, and leaching pressure is 0.05～0.5MPa, and the sulfuric acid starting point concentration of leaching is 1～5mol/L, and the nitric acid starting point concentration is 5～20g/L, and extraction time is 1～5 hour, and leaching process stirs, stirring velocity 30～100r/min.The sulfuric acid add-on is in the positive electrode material that adds reaction vessel all 101～200% of the sulfuric acid theoretical consumption that leaches of metals.
The object of the present invention is achieved like this: under the condition of industrial pure oxygen of pressurization and nitric acid existence, sulfuric acid leaches anode material of waste LiNiO 2 battery, and (nickel in the material and lithium exist with the lithium nickelate form, copper and aluminium mainly are metal form) time, following chemical reaction takes place in the process that metallic copper generates copper sulfate:
Cu+2HNO
3+H
2SO
4＝GuSO
4+2NO
2+2H
2O
3Cu+2HNO
3+3H
2SO
4＝3CuSO
4+2NO+4H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
2Cu+2H
2SO
4+O
2＝2CuSO
4+2H
2O
Under the condition of industrial pure oxygen of pressurization and nitric acid existence, when sulfuric acid leached anode material of waste LiNiO 2 battery, following chemical reaction took place in the process that metallic aluminium generates Tai-Ace S 150:
2Al+6HNO
3+3H
2SO
4＝Al
2(SO
4)
3+6NO
2+6H
2O
2Al+2HNO
3+3H
2SO
4＝Al
2(SO
4)
3+2NO+4H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
4Al+6H
2SO
4+3O
2＝2Al
2(SO
4)
3+6H
2O
When sulfuric acid leached anode material of waste LiNiO 2 battery, following chemical reaction took place in lithium nickelate:
2LiNiO
2+4H
2SO
4＝Ni
2(SO
4)
3+Li
2SO
4+4H
2O
Through above-mentioned series reaction, finally avoid using expensive oxygenant, do not produce nitrogen oxides pollution substantially yet, realized cleaning of technology.
With respect to existing method, outstanding advantage of the present invention is not use expensive oxygenant, has avoided the generation of pollutent oxynitride substantially, thereby has not needed the Pollution abatement of oxynitride, save pollution abatement costs, had tangible economic benefit and environmental benefit.
Specific implementation method
Embodiment 1: it is in the lining titanium autoclave of 1L that 100g anode material of waste LiNiO 2 battery (nickeliferous 54.3%, lithium 5.5%, copper 7.8%, aluminium 3.1%) is added volume, adds the sulfuric acid 880ml of 3.5mol/L, adds nitric acid 13g (with HNO
3Count), the industrial pure oxygen of feeding 0.2MPa stirs (stirring velocity 80r/min) down at 50～60 ℃ and leached 2.0 hours, carries out liquid-solid separation after the leaching end, obtains 840ml infusion solution (not containing the leached mud washing water).The about 0.36L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 2.4mg/m
3The leaching yield of nickel, lithium and copper is respectively 98.2% and 98.3% and 97.1% (calculating by the nickel, lithium and the copper that enter in infusion solution and the leached mud washings).
Embodiment 2: it is in the lining titanium autoclave of 5L that 400g anode material of waste LiNiO 2 battery (nickeliferous 54.3%, lithium 5.5%, copper 7.8%, aluminium 3.1%) is added volume, adds the sulfuric acid 4.1L of 3.0mol/L, adds nitric acid 60g (with HNO
3Meter), feeds the industrial pure oxygen of 0.1MPa, 60～70 ℃ of following stirring reactions 3 hours, reaction is carried out liquid-solid separation after finishing, obtain 3.9L infusion solution (not comprising the leached mud washing water), the about 1.8L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 2.1mg/m
3The leaching yield of nickel, lithium and copper is respectively 98.3%, 98.6% and 97.3% (calculating by the nickel, lithium and the copper that enter in infusion solution and the leached mud washings).
Claims (1)
1, a kind of leaching method of anode material of waste LiNiO 2 battery, it is characterized in that and from waste LiNiO 2 battery, to put into withstand voltage and anti-sulfuric acid and nitric acid corrosive container by isolated positive electrode material, sealed vessel then, and sulfuric acid and nitric acid pumped into this container, feed industrial pure oxygen and carry out the leaching of anode material of waste LiNiO 2 battery, carry out liquid-solid separation after leaching end, obtain required infusion solution, extraction temperature is 20～100 ℃, leaching pressure is 0.05～0.5MPa, the sulfuric acid starting point concentration that leaches is 1～5mol/L, the nitric acid starting point concentration is 5～20g/L, and extraction time is 1～5 hour, and leaching process stirs, stirring velocity 30～100r/min, the sulfuric acid add-on is in the positive electrode material that adds reaction vessel all 101～200% of the sulfuric acid theoretical consumption that leaches of metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910059703A CN101643851A (en) | 2009-06-23 | 2009-06-23 | Method for lixiviating anode materials of lithium nickel waste batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910059703A CN101643851A (en) | 2009-06-23 | 2009-06-23 | Method for lixiviating anode materials of lithium nickel waste batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101643851A true CN101643851A (en) | 2010-02-10 |
Family
ID=41655912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910059703A Pending CN101643851A (en) | 2009-06-23 | 2009-06-23 | Method for lixiviating anode materials of lithium nickel waste batteries |
Country Status (1)
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757404A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Leaching method of lithium nickelate waste battery positive electrode material |
| CN103757287A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757281A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757283A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757289A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757286A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757220A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757290A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757292A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757251A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757280A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757294A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757288A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757282A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
-
2009
- 2009-06-23 CN CN200910059703A patent/CN101643851A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757404A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Leaching method of lithium nickelate waste battery positive electrode material |
| CN103757287A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757281A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757283A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757289A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757286A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757220A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757290A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757292A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757251A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757280A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757294A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757288A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
| CN103757282A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste lithium nickelate battery |
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Open date: 20100210 |