CN101586191B - Leaching method for cathode material of waste nickel-hydrogen battery - Google Patents
Leaching method for cathode material of waste nickel-hydrogen battery Download PDFInfo
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- CN101586191B CN101586191B CN200910059695XA CN200910059695A CN101586191B CN 101586191 B CN101586191 B CN 101586191B CN 200910059695X A CN200910059695X A CN 200910059695XA CN 200910059695 A CN200910059695 A CN 200910059695A CN 101586191 B CN101586191 B CN 101586191B
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- leaching
- nitric acid
- waste nickel
- negative material
- nickel
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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
A leaching method for the cathode material of a waste nickel-hydrogen battery provided by the invention comprises the following steps: putting the cathode material separated from the waste nickel-hydrogen battery into a pressure-resistant and nitric acid resistant container, and then sealing the container and pumping nitric acid into the container; leaching the cathode material of the waste nickel-hydrogen battery by adding industrial pure oxygen. The leaching temperature is 20-100 DEG C; the leaching pressure is 0.05-0.5MPa; the initial concentration of the leached nitric acid is 1-6mol/L; the leaching time is 1-5h; the leaching process needs stirring; and the stirring speed is 30-100r/min. The adding amount of nitric acid is 101-130% of the theoretical quantity of the nitric acid consuming by leaching all the metal out from the cathode material added in a reaction vessel.
Description
Technical field
The present invention relates to a kind of leaching method of waste nickel-metal hydrogen batteries negative 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.Nickel-hydrogen battery negative pole material is mainly nickeliferous, cobalt and rare earth, and three's total content is up to 85～97%, has very much a recovery value.The technology that reclaims at present nickel, cobalt and rare earth from the waste nickel-metal hydrogen batteries negative material mainly contains thermal process and wet processing.The product that thermal process obtains is an alloy material, nickel, cobalt and rare earth that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, cobalt and rare earth.Leaching is a requisite process in the wet processing.The leaching method of waste nickel-metal hydrogen batteries negative 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 negative material of basic non-environmental-pollution has big practical value.
Summary of the invention
Problem at present waste nickel-metal hydrogen batteries negative material leaching, it is low to the objective of the invention is to seek a kind of nitric acid consumption, the leaching method of the waste nickel-metal hydrogen batteries negative material that basic nitrogenfree oxide pollutes, it is characterized in that and from waste nickel-metal hydrogen batteries, (to comprise by isolated negative material by elementary negative material artificial or that mechanical separation goes out, the negative pole powder body material that elementary negative material obtains through broken and ball milling or rod milling, the more purified negative material that elementary negative material or negative pole powder body material obtain through pre-treatment such as alkali cleaning or roastings) put into withstand voltage and the corrosive of anti-nitric acid container, sealed vessel then, and nitric acid pumped into this container, feed industrial pure oxygen and carry out the leaching of waste nickel-metal hydrogen batteries negative 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 nitric acid starting point concentration of leaching is 1～6mol/L, and extraction time is 1～5 hour, and leaching process stirs, stirring velocity 30～100r/min.The nitric acid add-on is in the negative material that adds reaction vessel all 101～130% of the nitric acid theoretical consumption that leaches of metals.
The object of the present invention is achieved like this: under the condition of airtight pressurization and the existence of industrial pure oxygen, nitric acid leaches the waste nickel-metal hydrogen batteries negative material when (each metallic element in the material is metal form substantially), and following chemical reaction takes place the process that metallic nickel generates the inferior nickel of nitric acid:
Ni+4HNO
3＝Ni(NO
3)
2+2NO
2+2H
2O
3Ni+8HNO
3＝3Ni(NO
3)
2+2NO+4H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
2Ni+4HNO
3+O
2＝2Ni(NO
3)
2+2H
2O
Under the condition of airtight pressurization and the existence of industrial pure oxygen, when nitric acid leached the waste nickel-metal hydrogen batteries negative material, following chemical reaction took place in the process that metallic nickel generates nickelous nitrate:
Ni+6HNO
3＝Ni(NO
3)
3+3NO
2+3H
2O
Ni+4HNO
3＝Ni(NO
3)
3+NO+2H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
4Ni+12HNO
3+3O
2＝4Ni(NO
3)
3+6H
2O
Under the condition of airtight pressurization and the existence of industrial pure oxygen, when nitric acid leached the waste nickel-metal hydrogen batteries negative material, following chemical reaction took place in the process that cobalt metal generates Xiao Suangu:
Co+4HNO
3＝Co(NO
3)
2+2NO
2+2H
2O
3Co+8HNO
3＝3Co(NO
3)
2+2NO+4H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
2Co+4HNO
3+O
2＝2Co(NO
3)
2+2H
2O
Under the condition of airtight pressurization and the existence of industrial pure oxygen, when nitric acid leached the waste nickel-metal hydrogen batteries negative material, following chemical reaction took place in the process that rare earth generates rare earth nitrate:
Re+4HNO
3＝Re(NO
3)
2+2NO
2+2H
2O
3Re+8HNO
3＝3Re(NO
3)
2+2NO+4H
2O
Re+6HNO
3＝Re(NO
3)
3+3NO
2+3H
2O
Re+4HNO
3＝Re(NO
3)
3+NO+2H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
2Re+4HNO
3+O
2＝2Re(NO
3)
2+2H
2O
4Re+12HNO
3+3O
2＝4Re(NO
3)
3+6H
2O
In excessive, the airtight pressurization of nitric acid with use under the condition that industrial pure oxygen leaches, most nickel, cobalt and rare earth finally enter leach liquor with the trivalent form.
Through above-mentioned series reaction, finally improved the utilization ratio of nitric acid, avoided the generation of nitrogen oxides pollution thing substantially, realized cleaning of technology.
With respect to existing method, outstanding advantage of the present invention is can reduce the nitric acid consumption more than 50%, has avoided the generation of pollutent oxynitride substantially, thereby does not need 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 stainless steel autoclave of 1L that 100g waste nickel-metal hydrogen batteries negative material (nickeliferous 58.5%, cobalt 6.2%, rare earth 29.5%) is added volume, the nitric acid 850ml that adds 4.0mol/L, feed the industrial pure oxygen of 0.2MPa, stirring (stirring velocity is 80r/min) down at 40～50 ℃ leached 2 hours, carry out liquid-solid separation after leaching end, obtain 820ml infusion solution (not containing the leached mud washing water).The about 450ml of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 6.1mg/m
3The leaching yield of nickel, cobalt and rare earth is respectively 98.6%, 97.8% and 96.9% (calculating by the nickel, cobalt and the rare earth that enter in infusion solution and the leached mud washings).
Embodiment 2: it is in the stainless steel autoclave of 5L that 500g waste nickel-metal hydrogen batteries negative material (nickeliferous 58.5%, cobalt 6.2%, rare earth 29.5%) is added volume, the nitric acid 4.8L that adds 3.5mol/L, feed the industrial pure oxygen of 0.1MPa, stirring (stirring velocity is 80r/min) down at 50～60 ℃ leached 2.5 hours, carry out liquid-solid separation after leaching end, obtain 5.6L infusion solution (not containing the leached mud washing water), the about 0.4L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 4.9mg/m
3The leaching yield of nickel, cobalt and rare earth is respectively 98.7% and 98.0% and 97.1% (calculating by the nickel, cobalt and the rare earth that enter in infusion solution and the leached mud washings).
Claims (1)
1. the leaching method of a waste nickel-metal hydrogen batteries negative material, it is characterized in that and from waste nickel-metal hydrogen batteries, to put into withstand voltage and the corrosive of anti-nitric acid container by isolated negative material, sealed vessel then, and nitric acid pumped into this container, feed industrial pure oxygen and carry out the leaching of waste nickel-metal hydrogen batteries negative 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 nitric acid starting point concentration that leaches is 1～6mol/L, extraction time is 1～5 hour, leaching process stirs, stirring velocity 30～100r/min, and the nitric acid add-on is in the negative material that adds reaction vessel all 101～130% of the nitric acid theoretical consumption that leaches of metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910059695XA CN101586191B (en) | 2009-06-23 | 2009-06-23 | Leaching method for cathode material of waste nickel-hydrogen battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910059695XA CN101586191B (en) | 2009-06-23 | 2009-06-23 | Leaching method for cathode material of waste nickel-hydrogen battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101586191A CN101586191A (en) | 2009-11-25 |
| CN101586191B true CN101586191B (en) | 2011-03-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910059695XA Expired - Fee Related CN101586191B (en) | 2009-06-23 | 2009-06-23 | Leaching method for cathode material of waste nickel-hydrogen battery |
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| CN (1) | CN101586191B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103667721A (en) * | 2013-12-29 | 2014-03-26 | 四川师范大学 | Leaching method for anode material of used nickel-hydrogen battery |
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2009
- 2009-06-23 CN CN200910059695XA patent/CN101586191B/en not_active Expired - Fee Related
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| CN101586191A (en) | 2009-11-25 |
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Granted publication date: 20110316 Termination date: 20110623 |