CN101624651B - Method for leaching cathode materials from waste nickel-metal hydrogen batteries - Google Patents
Method for leaching cathode materials from waste nickel-metal hydrogen batteries Download PDFInfo
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- CN101624651B CN101624651B CN2009100596979A CN200910059697A CN101624651B CN 101624651 B CN101624651 B CN 101624651B CN 2009100596979 A CN2009100596979 A CN 2009100596979A CN 200910059697 A CN200910059697 A CN 200910059697A CN 101624651 B CN101624651 B CN 101624651B
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- leaching
- sulfuric acid
- metal hydrogen
- hydrogen batteries
- 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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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for leaching cathode materials from waste nickel-metal hydrogen batteries, which is introduced by the invention, comprises the following steps: placing the cathode materials separated from the waste nickel-metal hydrogen batteries into a container which is resistant to pressure and sulfuric acid and nitric acid corrosion, sealing the container, pumping the sulfuric acid and nitric acid into the container and filling industrial pure oxygen to leach the cathode materials from the waste nickel-metal hydrogen batteries. The leaching temperature is 20-100 DEG C; the leaching pressure is 0.05-0.5MPa; the initial concentration of the sulfuric acid for leaching is 1-5mol/L and that of the nitric acid is 5-20g/L; the leaching time is 1-5h; stirring is carried out at a speed of 30-100r/min in the process of leaching. The addition of the sulfuric acid is 101-200% of the theoretical consumption of the sulfuric acid leaching all the metals in the cathode materials added into the reaction container.
Description
Technical field
The present invention relates to a kind of leaching method of waste nickel-metal hydrogen batteries positive electrode material.
Background technology
Nickel metal hydride 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 main nickeliferous and cobalt of nickel-hydrogen battery positive pole material, both total contents be up to 50～70%, has very much a recovery value.The technology that reclaims at present nickel, cobalt from the waste nickel-metal hydrogen batteries positive electrode material mainly contains thermal process and wet processing.The product that thermal process obtains is an alloy material, nickel that very difficult acquisition is purer and cobalt.Wet processing becomes more readily available purer nickel and cobalt.Leaching is a requisite process in the wet processing.The leaching method of waste nickel-metal hydrogen batteries positive electrode material 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 waste nickel-metal hydrogen batteries positive electrode material of basic non-environmental-pollution has big practical value.
Summary of the invention
Problem at present waste nickel-metal hydrogen batteries positive electrode material leaching, the objective of the invention is to seek a kind of need not expensive oxygenant, the leaching method of the waste nickel-metal hydrogen batteries positive electrode material that basic nitrogenfree oxide pollutes, it is characterized in that and from waste nickel-metal hydrogen batteries, (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 alkali cleaning or 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 waste nickel-metal hydrogen batteries positive electrode material, 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 the waste nickel-metal hydrogen batteries positive electrode material, and (nickel in the material is metal and two kinds of forms of oxide compound, cobalt is oxide form) time, following chemical reaction takes place in the process that metallic nickel generates the inferior nickel of sulfuric acid:
Ni+2HNO
3+H
2SO
4＝NiSO
4+2NO
2+2H
2O
3Ni+2HNO
3+3H
2SO
4＝3NiSO
4+2NO+4H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
2Ni+2H
2SO
4+O
2＝2NiSO
4+2H
2O
Under the condition of industrial pure oxygen of pressurization and nitric acid existence, when sulfuric acid leached the waste nickel-metal hydrogen batteries positive electrode material, following chemical reaction took place in the process that metallic nickel generates single nickel salt:
2Ni+6HNO
3+3H
2SO
4＝Ni
2(SO
4)
3+6NO
2+6H
2O
2Ni+2HNO
3+3H
2SO
4＝Ni
2(SO
4)
3+2NO+4H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
4Ni+6H
2SO
4+3O
2＝2Ni
2(SO
4)
3+6H
2O
When sulfuric acid leached the waste nickel-metal hydrogen batteries positive electrode material, following chemical reaction took place in the process that partial oxidation nickel generates the inferior nickel of sulfuric acid:
NiO+H
2SO
4＝NiSO
4+H
2O
Under the condition of industrial pure oxygen of pressurization and nitric acid existence, when sulfuric acid leached the waste nickel-metal hydrogen batteries positive electrode material, following chemical reaction took place in the process that partial oxidation nickel generates single nickel salt:
2NiO+2HNO
3+3H
2SO
4＝Ni
2(SO
4)
3+2NO
2+4H
2O
6NiO+2HNO
3+9H
2SO
4＝3Ni
2(SO
4)
3+2NO+10H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
4NiO+6H
2SO
4+O
2＝2Ni
2(SO
4)
3+6H
2O
When sulfuric acid leached the waste nickel-metal hydrogen batteries positive electrode material, following chemical reaction took place in the process that cobalt oxide generates rose vitriol:
CoO+H
2SO
4＝CoSO
4+H
2O
Excessive and use under the leaching condition of the industrial pure oxygen of pressurization at nitric acid and sulfuric acid total acid content, most nickel and cobalt finally enter leach liquor with the trivalent form.
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 waste nickel-metal hydrogen batteries positive electrode material (nickeliferous 56.4%, cobalt 5.9%) is added volume, adds the sulfuric acid 500ml of 3.0mol/L, adds nitric acid 7.5g (with HNO
3Count), the industrial pure oxygen of feeding 0.2MPa stirs (stirring velocity 80r/min) down at 50～60 ℃ and leached 2.5 hours, carries out liquid-solid separation after the leaching end, obtains 495ml infusion solution (not containing the leached mud washing water).The about 1.5L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 2.9mg/m
3The leaching yield of nickel and cobalt is respectively 98.9% and 97.5% (calculating by the nickel and the cobalt that enter in infusion solution and the leached mud washings).
Embodiment 2: it is in the lining titanium autoclave of 5L that 500g waste nickel-metal hydrogen batteries positive electrode material (nickeliferous 56.4%, cobalt 5.9%) is added volume, adds the sulfuric acid 4.0L of 2.0mol/L, adds nitric acid 70g (with HNO
3Meter), feed the industrial pure oxygen of 0.1MPa, stirring (stirring velocity 80r/min) down at 60～70 ℃ leached 3 hours, carry out liquid-solid separation after leaching end, obtain 3.9L infusion solution (not comprising the leached mud washing water), the about 2L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 3.7mg/m
3The leaching yield of nickel and cobalt is respectively 98.8% and 97.9% (calculating by the nickel and the cobalt that enter in infusion solution and the leached mud washings).
Claims (1)
1. the leaching method of a waste nickel-metal hydrogen batteries positive electrode material, it is characterized in that and from waste nickel-metal hydrogen batteries, 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 waste nickel-metal hydrogen batteries positive electrode material, 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 |
|---|---|---|---|
| CN2009100596979A CN101624651B (en) | 2009-06-23 | 2009-06-23 | Method for leaching cathode materials from waste nickel-metal hydrogen batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100596979A CN101624651B (en) | 2009-06-23 | 2009-06-23 | Method for leaching cathode materials from waste nickel-metal hydrogen batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101624651A CN101624651A (en) | 2010-01-13 |
| CN101624651B true CN101624651B (en) | 2011-07-27 |
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ID=41520642
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100596979A Expired - Fee Related CN101624651B (en) | 2009-06-23 | 2009-06-23 | Method for leaching cathode materials from waste nickel-metal hydrogen batteries |
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|---|---|
| CN (1) | CN101624651B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757406A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Leaching method of nickel-metal hydride waste battery positive electrode material |
| CN103757326A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757304A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757305A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757314A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757315A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103667721A (en) * | 2013-12-29 | 2014-03-26 | 四川师范大学 | Leaching method for anode material of used nickel-hydrogen battery |
| CN103757394A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Leaching method of lithium cobaltate waste battery positive electrode material |
| CN103757240A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive-negative pole material mixture of waste nickel-metal hydride battery |
| CN103757284A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757300A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757293A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757316A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757327A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757238A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757402A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Leaching method of nickel-metal hydride waste battery positive electrode material |
| CN103757254A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757303A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757291A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757317A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757322A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
| CN103757328A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching positive pole material of waste nickel-metal hydride battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171171A (en) * | 1994-12-20 | 1998-01-21 | 瓦尔达电池股份公司 | Process for recovery of metals from used nickel-metal hydride accumulators |
| US5858061A (en) * | 1994-12-20 | 1999-01-12 | Varta Batterie Atkiengesellschaft | Process for the recovery of metals from used nickel/metal hydride storage batteries |
-
2009
- 2009-06-23 CN CN2009100596979A patent/CN101624651B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171171A (en) * | 1994-12-20 | 1998-01-21 | 瓦尔达电池股份公司 | Process for recovery of metals from used nickel-metal hydride accumulators |
| US5858061A (en) * | 1994-12-20 | 1999-01-12 | Varta Batterie Atkiengesellschaft | Process for the recovery of metals from used nickel/metal hydride storage batteries |
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| Publication number | Publication date |
|---|---|
| CN101624651A (en) | 2010-01-13 |
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Granted publication date: 20110727 Termination date: 20130623 |