CN101629243A - Infusion method of Ni-MH used battery anode and cathode mixed material - Google Patents

Infusion method of Ni-MH used battery anode and cathode mixed material Download PDF

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Publication number
CN101629243A
CN101629243A CN200910059692A CN200910059692A CN101629243A CN 101629243 A CN101629243 A CN 101629243A CN 200910059692 A CN200910059692 A CN 200910059692A CN 200910059692 A CN200910059692 A CN 200910059692A CN 101629243 A CN101629243 A CN 101629243A
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Prior art keywords
sulfuric acid
cathode mixed
mixed material
leaching
anode
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CN200910059692A
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龙炳清
魏涛
龙怡
方绪坤
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Sichuan Normal University
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Sichuan Normal University
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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 introduces an infusion method of a Ni-MH used battery anode and cathode mixed material, which is implemented by putting the anode and cathode mixed material separated from Ni-MH used battery in a pressure-resistance, sulfuric acid and nitric acid resistance container, sealing the container and pumping sulfuric acid and nitric acid into the container, and injecting industrial pure oxygen to carry out infusion on the Ni-MH used battery anode and cathode mixed material. The infusion temperature is 20-100 DEG C, the infusion pressure is 0.05-0.5MPa, the sulfuric acid initial concentration of infusion is 1-5mol/L, the nitric acid initial concentration of infusion is 5-20g/L, the infusion time is 1-5h, and the speed of stirring in the process of infusion is 30-100r/min. The addition of sulfuric acid is 101-200% of nitric acid theoretic consumption infused by all metal in the anode and cathode mixed material added into the container.

Description

The leaching method of Ni-MH used battery anode and cathode mixed material
Technical field
The present invention relates to a kind of leaching method of Ni-MH used battery anode and cathode mixed 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 ni-mh anode and cathode mixed materials 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 Ni-MH used battery anode and cathode mixed 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 Ni-MH used battery anode and cathode mixed 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 Ni-MH used battery anode and cathode mixed material of basic non-environmental-pollution has big practical value.
Summary of the invention
Problem at present Ni-MH used battery anode and cathode mixed material leaching, the objective of the invention is to seek a kind of need not expensive oxygenant, the leaching method of the Ni-MH used battery anode and cathode mixed material that basic nitrogenfree oxide pollutes, it is characterized in that and from waste nickel-metal hydrogen batteries, (to comprise by isolated anode and cathode mixed materials by elementary anode and cathode mixed materials artificial or that mechanical separation goes out, the positive and negative electrode mixed powder material that elementary anode and cathode mixed materials obtains through broken and ball milling or rod milling, the more purified anode and cathode mixed materials that elementary anode and cathode mixed materials or positive and negative electrode mixed 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 Ni-MH used battery anode and cathode mixed 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 anode and cathode mixed materials 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 Ni-MH used battery anode and cathode mixed material, and (nickel in the material and cobalt are metal and two kinds of forms of oxide compound, rare earth is metal form substantially) 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 Ni-MH used battery anode and cathode mixed 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 Ni-MH used battery anode and cathode mixed 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 Ni-MH used battery anode and cathode mixed 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
Under the condition of industrial pure oxygen of pressurization and nitric acid existence, when sulfuric acid leached Ni-MH used battery anode and cathode mixed material, following chemical reaction took place in the process that cobalt metal generates rose vitriol:
Co+2HNO 3+H 2SO 4＝CoSO 4+2NO 2+2H 2O
3Co+2HNO 3+3H 2SO 4＝3CoSO 4+2NO+4H 2O
2NO+O 2＝2NO 2
3NO 2+H 2O＝2HNO 3+NO
Total reaction is:
2Co+O 2+2H 2SO 4＝2CoSO 4+2H 2O
When sulfuric acid leached Ni-MH used battery anode and cathode mixed material, following chemical reaction took place in the process that cobalt oxide generates rose vitriol:
CoO+H 2SO 4＝CoSO 4+H 2O
Under the condition of industrial pure oxygen of pressurization and nitric acid existence, when sulfuric acid leached Ni-MH used battery anode and cathode mixed material, following chemical reaction took place in the process that rare earth generates rare earth sulfate:
Re+2HNO 3+H 2SO 4＝ReSO 4+2NO 2+2H 2O
3Re+2HNO 3+3H 2SO 4＝3ReSO 4+2NO+4H 2O
2Re+6HNO 3+3H 2SO 4＝Re 2(SO 4) 3+6NO 2+6H 2O
2Re+2HNO 3+3H 2SO 4＝Re 2(SO 4) 3+2NO+4H 2O
2NO+O 2＝2NO 2
3NO 2+H 2O＝2HNO 3+NO
Total reaction is:
2Re+2H 2SO 4+O 2＝ReSO 4+2H 2O
4Re+6H 2SO 4+3O 2＝2Re 2(SO 4) 3+6H 2O
At nitric acid with the sulfuric acid total acid content is excessive and use under the leaching condition of the industrial pure oxygen of pressurization, most nickel, cobalt and small portion rare earth enter leach liquor with the trivalent form; Most of rare earth generates the rare earth sulfuric acid double salt precipitation and enters in the leached mud.
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 Ni-MH used battery anode and cathode mixed material (nickeliferous 57.5%, cobalt 6.1%, rare earth 13.2%) is added volume, adds the sulfuric acid 600ml of 3.0mol/L, adds nitric acid 9g (with HNO 3Count), the industrial pure oxygen of feeding 0.2MPa stirs (stirring velocity is 80r/min) down at 50～60 ℃ and leached 2 hours, carries out liquid-solid separation after the leaching end, obtains 580ml infusion solution (not containing the leached mud washing water).The about 1.2L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 2.6mg/m 3The leaching yield of nickel, cobalt and rare earth is respectively 98.6% and 97.2% and 6.4% (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 lining titanium autoclave of 5L that 500g Ni-MH used battery anode and cathode mixed material (nickeliferous 57.5%, cobalt 6.1%, rare earth 13.2%) is added volume, adds the sulfuric acid 4.5L of 2.0mol/L, adds nitric acid 70g (with HNO 3Meter), feed the industrial pure oxygen of 0.1MPa, stirring (stirring velocity is 80r/min) down at 60～70 ℃ leached 3 hours, carry out liquid-solid separation after leaching end, obtain 4.8L infusion solution (not comprising the leached mud washing water), the about 1L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 3.3mg/m 3The leaching yield of nickel, cobalt and rare earth is respectively 98.8%, 98.1% and 8.5% (calculating by the nickel, cobalt and the rare earth that enter in infusion solution and the leached mud washings).

Claims (1)

1, a kind of leaching method of Ni-MH used battery anode and cathode mixed 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 anode and cathode mixed materials, sealed vessel then, and sulfuric acid and nitric acid pumped into this container, feed industrial pure oxygen and carry out the leaching of Ni-MH used battery anode and cathode mixed 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 anode and cathode mixed materials that adds reaction vessel all 101～200% of the sulfuric acid theoretical consumption that leaches of metals.
CN200910059692A 2009-06-23 2009-06-23 Infusion method of Ni-MH used battery anode and cathode mixed material Pending CN101629243A (en)

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Cited By (23)

* Cited by examiner, † Cited by third party
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CN103667721A (en) * 2013-12-29 2014-03-26 四川师范大学 Leaching method for anode material of used nickel-hydrogen battery
CN103757384A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of waste battery electrode mixed 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
CN103757237A (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
CN103757295A (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
CN103757311A (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
CN103757244A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of waste battery electrode mixed material
CN103757308A (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
CN103757309A (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
CN103757312A (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
CN103757310A (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
CN103757400A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of nickel-metal hydride waste battery positive-negative electrode mixed material
CN103757235A (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
CN103757265A (en) * 2013-12-29 2014-04-30 四川师范大学 Method for leaching waste battery electrode mixed material
CN103757395A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of waste battery electrode mixed material
CN103757307A (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
CN103757318A (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
CN103757301A (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
CN103757239A (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
CN103757306A (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
CN103757296A (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
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
CN107312944A (en) * 2017-07-10 2017-11-03 山东理工大学 Utilize the method for asymmetric capacitor type Ni-MH battery recovering rare earth

Cited By (24)

* Cited by examiner, † Cited by third party
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
CN103757384A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of waste battery electrode mixed 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
CN103757237A (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
CN103757295A (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
CN103757311A (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
CN103757244A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of waste battery electrode mixed material
CN103757308A (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
CN103757309A (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
CN103757312A (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
CN103757310A (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
CN103757400A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of nickel-metal hydride waste battery positive-negative electrode mixed material
CN103757235A (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
CN103757265A (en) * 2013-12-29 2014-04-30 四川师范大学 Method for leaching waste battery electrode mixed material
CN103757395A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of waste battery electrode mixed material
CN103757307A (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
CN103757318A (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
CN103757301A (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
CN103757239A (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
CN103757306A (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
CN103757296A (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
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
CN103757307B (en) * 2013-12-29 2016-01-20 四川师范大学 The leaching method of Ni-MH used battery anode and cathode mixed material
CN107312944A (en) * 2017-07-10 2017-11-03 山东理工大学 Utilize the method for asymmetric capacitor type Ni-MH battery recovering rare earth

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