CN101660049A - Method for leaching cathode material of nickel-hydrogen used battery - Google Patents

Method for leaching cathode material of nickel-hydrogen used battery Download PDF

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Publication number
CN101660049A
CN101660049A CN200910059698A CN200910059698A CN101660049A CN 101660049 A CN101660049 A CN 101660049A CN 200910059698 A CN200910059698 A CN 200910059698A CN 200910059698 A CN200910059698 A CN 200910059698A CN 101660049 A CN101660049 A CN 101660049A
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China
Prior art keywords
leaching
nickel
sulfuric acid
negative material
nitric acid
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CN200910059698A
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CN101660049B (en
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龙炳清
魏涛
龙怡
姜鹏飞
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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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention discloses a method for leaching a cathode material of a nickel-hydrogen used battery, comprising the following steps: putting a cathode material separated from a nickel-hydrogen used battery in a vessel resisting the corrosion of the pressure, sulphuric acid and nitric acid; then sealing the vessel, pumping sulphuric acid and nitric acid in the vessel; and introducing industrial pureoxygen for leaching the cathode material of the nickel-hydrogen used battery. The leaching temperature is between 20 DEG C and 100 DEG C, the leaching pressure is between 0.05Mpa and 0. 5Mpa, the initial concentration of the leached sulphuric acid is between 1 mol/L and 5 mol/L, the initial concentration of the nitric acid is between 5g/L and 20 g/L, the leaching time is 1-5 hours, the stirring is carried out in the leaching process and the stirring speed is 30-100r/min. The addition quantity of the sulphuric acid is 101-200 percent of the theoretical consumption of the sulphuric acid which is added in the cathode material of a reaction vessel and leached with all metals.

Description

Method for leaching cathode material of nickel-hydrogen used battery
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, 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 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) 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 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 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 negative 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 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 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 negative 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
Under the condition of industrial pure oxygen of pressurization and nitric acid existence, when sulfuric acid leached the waste nickel-metal hydrogen batteries negative 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
Under the condition of industrial pure oxygen of pressurization and nitric acid existence, when sulfuric acid leached the waste nickel-metal hydrogen batteries negative 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+NO+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
Excessive and use the industrial pure oxygen of pressurization at nitric acid and sulfuric acid total acid content, most nickel, cobalt and small portion rare earth finally 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 waste nickel-metal hydrogen batteries negative material (nickeliferous 58.5%, cobalt 6.2%, rare earth 29.5%) is added volume, adds the sulfuric acid 700ml of 3.0mol/L, adds nitric acid 11g (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 680ml infusion solution (not containing the leached mud washing water).The about 0.6L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 3.1mg/m 3The leaching yield of nickel, cobalt and rare earth is respectively 98.3% and 97.4% and 7.3% (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 waste nickel-metal hydrogen batteries negative material (nickeliferous 58.5%, cobalt 6.2%, rare earth 29.5%) is added volume, adds the sulfuric acid 4.9L of 2.0mol/L, adds nitric acid 75g (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 0.2L of reaction end gas (amounting to into the volume of absolute pressure 0.1MPa), nitrous oxides concentration is 3.6mg/m 3The leaching yield of nickel, cobalt and rare earth is respectively 98.4%, 97.6% and 8.8% (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 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 anti-sulfuric acid and nitric acid corrosive container by isolated negative 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 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 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 negative material that adds reaction vessel all 101～200% of the sulfuric acid theoretical consumption that leaches of metals.
CN2009100596983A 2009-06-23 2009-06-23 Method for leaching cathode material of nickel-hydrogen used battery Expired - Fee Related CN101660049B (en)

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CN101660049B CN101660049B (en) 2011-03-16

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Cited By (4)

* 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
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
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
CN105742746A (en) * 2016-04-20 2016-07-06 昆明理工大学 Method for preparing Ni/NiO/C nanometer composite powder material by using waste nickel-hydrogen battery

Cited By (4)

* 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
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
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
CN105742746A (en) * 2016-04-20 2016-07-06 昆明理工大学 Method for preparing Ni/NiO/C nanometer composite powder material by using waste nickel-hydrogen battery

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