CN101586190B - Leaching method for anode material of waste nickel-hydrogen battery - Google Patents
Leaching method for anode material of waste nickel-hydrogen battery Download PDFInfo
- Publication number
- CN101586190B CN101586190B CN2009100596945A CN200910059694A CN101586190B CN 101586190 B CN101586190 B CN 101586190B CN 2009100596945 A CN2009100596945 A CN 2009100596945A CN 200910059694 A CN200910059694 A CN 200910059694A CN 101586190 B CN101586190 B CN 101586190B
- Authority
- CN
- China
- Prior art keywords
- leaching
- nitric acid
- positive electrode
- electrode material
- waste nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Abstract
A leaching method for the anode material of a waste nickel-hydrogen battery provided by the invention comprises the following steps: putting the anode 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 anode 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 1-4h; 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 anode 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 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, 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 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) 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 positive electrode material, carry out liquid-solid separation after leaching end, obtain required infusion solution.Temperature of reaction 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 1～4 hour, and leaching process stirs, and stirring velocity is 30～100r/min.The nitric acid add-on is in the positive electrode 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 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 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 positive electrode 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
When nitric 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 nitric acid:
NiO+2HNO
3＝Ni(NO
3)
2+H
2O
Under the condition of airtight pressurization and the existence of industrial pure oxygen, following chemical reaction takes place in the process that partial oxidation nickel generates nickelous nitrate:
NiO+4HNO
3＝Ni(NO
3)
3+NO
2+2H
2O
3NiO+10HNO
3＝3Ni(NO
3)
3+NO+5H
2O
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
Total reaction is:
4NiO+12HNO
3+O
2＝4Ni(NO
3)
3+6H
2O
In addition, when nitric acid leached the waste nickel-metal hydrogen batteries positive electrode material, following chemical reaction took place in the oxide compound of cobalt:
CoO+2HNO
3＝Co(NO
3)
2+H
2O
In excessive, the airtight pressurization of nitric acid with use under the leaching condition of industrial pure oxygen, most nickel and cobalt 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 to reduce the nitric acid consumption greatly, 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: with 100g waste nickel-metal hydrogen batteries positive electrode material (nickeliferous 56.4%, cobalt 5.9%) adding volume is in the stainless steel autoclave of 1L, the nitric acid 800ml that adds 3.0mol/L, feed the industrial pure oxygen of 0.2MPa, stirring (stirring velocity 80r/min) down at 40～50 ℃ leached 2.5 hours, carry out liquid-solid separation after leaching end, obtain 780ml infusion solution (not containing the leached mud washing water).The about 600ml of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 5.8mg/m
3The leaching yield of nickel and cobalt is respectively 98.7% and 97.8% (calculating by the nickel and the cobalt that enter in infusion solution and the leached mud washings).
Embodiment 2: with 500g waste nickel-metal hydrogen batteries positive electrode material (nickeliferous 56.4%, cobalt 5.9%) adding volume is in the stainless steel autoclave of 10L, the nitric acid 5.8L that adds 2.0mol/L, feed the industrial pure oxygen of 0.1MPa, stir (stirring velocity 80r/min) down at 50～60 ℃ and leached 3 hours, reaction is carried out liquid-solid separation after finishing, and obtains 5.6L infusion solution (not containing the leached mud washing water), the about 6.8L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 4.7mg/m
3The leaching yield of nickel and cobalt is respectively 98.9% and 98.1% (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 the corrosive of anti-nitric acid container by isolated positive electrode 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 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 nitric acid starting point concentration that leaches is 1～6mol/L, extraction time is 1～4 hour, leaching process stirs, and stirring velocity is 30～100r/min, and the nitric acid add-on is in the positive electrode 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 |
|---|---|---|---|
| CN2009100596945A CN101586190B (en) | 2009-06-23 | 2009-06-23 | Leaching method for anode material of waste nickel-hydrogen battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100596945A CN101586190B (en) | 2009-06-23 | 2009-06-23 | Leaching method for anode material of waste nickel-hydrogen battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101586190A CN101586190A (en) | 2009-11-25 |
| CN101586190B true CN101586190B (en) | 2011-11-30 |
Family
ID=41370616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100596945A Expired - Fee Related CN101586190B (en) | 2009-06-23 | 2009-06-23 | Leaching method for anode material of waste nickel-hydrogen battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101586190B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103667721A (en) * | 2013-12-29 | 2014-03-26 | 四川师范大学 | Leaching method for anode material of used nickel-hydrogen battery |
| CN107338357B (en) * | 2017-07-07 | 2019-01-22 | 金川集团股份有限公司 | A kind of nitric acid Selectively leaching method of the high iron alloy powder of low nickel |
-
2009
- 2009-06-23 CN CN2009100596945A patent/CN101586190B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101586190A (en) | 2009-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101624651B (en) | Method for leaching cathode materials from waste nickel-metal hydrogen batteries | |
| CN101619394B (en) | Method for leaching anode and cathode mixed material of waste lithium nickel manganese cobalt battery | |
| CN101586192B (en) | Leaching method for anode and cathode mixed materials of waste LiCoxNiyMnzO2 battery | |
| CN101629243A (en) | Infusion method of Ni-MH used battery anode and cathode mixed material | |
| CN101665872A (en) | Leaching method of anode material of used nickel cadmium battery | |
| CN101624653A (en) | Method for leaching mixed cathode and anode materials from waste nickel-cadmium batteries | |
| CN101624652B (en) | Method for leaching mixed cathode and anode materials from waste nickel-cadmium batteries | |
| CN101643851A (en) | Method for lixiviating anode materials of lithium nickel waste batteries | |
| CN101586189B (en) | Leaching method for anode material of waste LiCoO battery | |
| CN101586190B (en) | Leaching method for anode material of waste nickel-hydrogen battery | |
| CN101660049B (en) | Method for leaching cathode material of nickel-hydrogen used battery | |
| CN101586193B (en) | Leaching method for anode material of waste LiNiO2 battery | |
| CN101586194B (en) | Leaching method for anode and cathode mixed materials of waste nickel-hydrogen battery | |
| CN101665873A (en) | Leaching method of anode material of used nickel cadmium battery | |
| CN101586191B (en) | Leaching method for cathode material of waste nickel-hydrogen battery | |
| CN103757293A (en) | Method for leaching positive pole material of waste nickel-metal hydride battery | |
| CN103757407A (en) | Leaching method of nickel-metal hydride waste battery positive-negative electrode mixed material | |
| CN103757400A (en) | Leaching method of nickel-metal hydride waste battery positive-negative electrode mixed material | |
| CN103757254A (en) | Method for leaching positive pole material of waste nickel-metal hydride battery | |
| CN103757402A (en) | Leaching method of nickel-metal hydride waste battery positive electrode material | |
| CN103757406A (en) | Leaching method of nickel-metal hydride waste battery positive electrode material | |
| CN103757414A (en) | Leaching method of nickel-metal hydride waste battery negative electrode material | |
| CN103757284A (en) | Method for leaching positive pole material of waste nickel-metal hydride battery | |
| CN103757412A (en) | Leaching method of waste battery electrode mixed material | |
| CN103757311A (en) | Method for leaching positive-negative pole material mixture of waste nickel-metal hydride battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111130 Termination date: 20130623 |