CN103757324A - Method for leaching positive-negative pole material mixture of waste nickel-metal hydride battery - Google Patents

Method for leaching positive-negative pole material mixture of waste nickel-metal hydride battery Download PDF

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Publication number
CN103757324A
CN103757324A CN201310736516.8A CN201310736516A CN103757324A CN 103757324 A CN103757324 A CN 103757324A CN 201310736516 A CN201310736516 A CN 201310736516A CN 103757324 A CN103757324 A CN 103757324A
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leaching
sulfuric acid
add
anode
nitric acid
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龙炳清
万旭
陈俊
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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 discloses a method for leaching a positive-negative pole material mixture of a waste nickel-metal hydride battery. The method comprises the steps of adding the positive-negative pole material mixture which is separated from the waste nickel-metal hydride battery and is subjected to roasting pretreatment, and high-concentration organic wastewater which does not contain benzene-ring substances into a reaction kettle which is resistant to pressure and the corrosion of sulfuric acid and nitric acid, adding a mixed solution of sulfuric acid and nitric acid, and leaching while stirring under closed conditions.

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, if abandon into environment, will environment be produced to very large direct and potential hazard.Ni-MH used battery anode and cathode mixed material is nickeliferous, cobalt and rare earth mainly, and three's total content is up to 75～97%, has very much a recovery value.The technique 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 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 wet processing.The leaching method of Ni-MH used battery anode and cathode mixed material mainly contains hydrochloric acid leaching process, sulfuric acid leaching, nitric acid lixiviation process and nitration mixture (sulfuric acid adds nitric acid) lixiviation process at present.The equipment corrosion of hydrochloric acid leaching process is large, the large and contaminate environment of acid mist generation.The more expensive reductive agent of sulfuric acid leaching consumption (as hydrogen peroxide etc.), and leaching velocity is slower, and acid consumption is high.The nitric acid consumption of nitric acid lixiviation process is large, and can produce a large amount of oxynitride, contaminate environment.All there is the problem that improves how economically leaching velocity, raising metal leaching rate, reduces acid consumption and other supplementary product onsumption in all wet processings.Although nitric acid processing industry pure oxygen lixiviation process and nitration mixture processing industry pure oxygen lixiviation process have solved the problems referred to above preferably, but leaching plant is more complicated, and the required industrial pure oxygen amount of refuse battery leaching is little, refuse battery is processed enterprise, and manufacture pure oxygen is personal uneconomical on the spot, and storage, transportation and the use of industrial pure oxygen are cumbersome.Development equipment corrosion is little, leaching velocity is fast, leaching yield is high, acid consumes and other supplementary product onsumption is low, easy to use, the leaching method of the Ni-MH used battery anode and cathode mixed material of basic non-environmental-pollution has larger practical value.
Summary of the invention
The problem leaching for current Ni-MH used battery anode and cathode mixed material, the object of the invention is to find a kind of metal leaching rate high, easy to use, need not expensive reductive agent, the leaching method of the Ni-MH used battery anode and cathode mixed material that basic nitrogenfree oxide pollutes, it is characterized in that anode and cathode mixed materials isolated from waste nickel-metal hydrogen batteries and that obtain through roasting pretreatment and containing the high concentrated organic wastewater of benzene ring substance, do not add withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of sulfuric acid and nitric acid, and carry out in confined conditions agitation leach.After leaching finishes, carry out liquid-solid separation, obtain required infusion solution.Temperature of reaction is 50 ℃～80 ℃, and the sulfuric acid starting point concentration of leaching is 1mol/L～4mol/L, and the starting point concentration of nitric acid is 5g/L～10g/L.Be used for the COD of the high concentrated organic wastewater leaching crconcentration>=30000mg/L.Extraction time is 2h～4h, and leaching process stirs, and stirring velocity is 30r/min～120r/min.Sulphuric acid is to add 110%～140% of sulfuric acid theoretical consumption that in the anode and cathode mixed materials of reaction vessel, all metals leach.COD cradd-on be 17%～22% of nickel in anode and cathode mixed materials, cobalt total mass, the add-on of high concentrated organic wastewater adds by this calculating.
The object of the present invention is achieved like this: airtight and have under the condition that high concentrated organic wastewater and nitric acid exists, during the Ni-MH used battery anode and cathode mixed material (nickel, cobalt and rare earth in material be oxide form) of sulfuric acid leaching after roasting pretreatment, Ni in leaching process 2o 3and Co 2o 3redox reaction can represent with general formula below:
3(C-H xO y) m?+?4mHNO 3?=?4mNO?+?3mCO 2?+?zH 2O
3Ni 2O 3?+?6H 2SO 4?+?2NO?=?6NiSO 4?+?2HNO 3?+?5H 2O
3Co 2O 3?+?6H 2SO 4?+?2NO?=?6CoSO 4?+?2HNO 3?+?5H 2O
Total reaction is:
(C-H xO y) m?+?2mNi 2O 3?+?4mH +?=?4mNi 2+?+?mCO 2?+?zH 2O
(C-H xO y) m?+?2mCo 2O 3?+?4mH +?=?4mCo 2+?+?mCO 2?+?zH 2O
NiO, CoO and Re 2o 3there is following chemical reaction:
NiO?+?H 2SO 4?=?NiSO 4?+?H 2O
CoO?+?H 2SO 4?=?CoSO 4?+?H 2O
Re 2O 3?+?3H 2SO 4?=?Re 2(SO 4) 3?+?3H 2O
Because the organism speed of response in nitric acid and high concentrated organic wastewater is very fast, the NO of generation and Ni 2o 3and Co 2o 3reaction also very fast, accelerate thus whole leaching process, and realize nickel, cobalt and leach more completely.NO can thoroughly destroy the laminate structure of high oxide in anode and cathode mixed materials, improves the leaching yield of valuable metal.
With respect to existing method, outstanding advantages of the present invention is to adopt the not high concentrated organic wastewater reductive agent containing benzene ring substance, and nitric acid is made to leach accelerator and leached Ni-MH used battery anode and cathode mixed material, and speed of response is fast, such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little; In anode and cathode mixed materials, the laminate structure of high oxide is destroyed thoroughly, can improve metal leaching rate; Utilize high concentrated organic wastewater to make oxygenant, not only for the improvement of high concentrated organic wastewater opens up a new way, and can reduce the leaching cost of Ni-MH used battery anode and cathode mixed material, there is obvious economic benefit and environmental benefit; In leach liquor subsequent disposal, do not need to neutralize a large amount of acid, cost is lower; Process is carried out in confined conditions, the environmental pollution of having avoided NO effusion to produce.
specific implementation method
embodiment 1: by 100g through the Ni-MH used battery anode and cathode mixed material of roasting pretreatment (nickeliferous 55.3%, cobalt 6.2%, rare earth 12.5%) and 210mL Alcohol Production waste water (containing COD cr50000mg/L) adding volume with the sulfuric acid concentration of sulfuric acid and the nitric acid preparation 850ml that is 1.5mol/L, the concentration of nitric acid mixed acid solution that is 5g/L is in the lining titanium pressure reaction still of 2L, at 50 ℃～60 ℃, 4h is leached in airtight stirring (stirring velocity 80r/min), after leaching finishes, carry out liquid-solid separation, obtain 840ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt and rare earth be respectively 99.3%, 99.2% and 8.7 %(by entering nickel in infusion solution and leached mud washings, cobalt and rare earth, calculate).
Embodiment 2: by the 500g Ni-MH used battery anode and cathode mixed material through roasting pretreatment (nickeliferous 55.3%, cobalt 6.2%, rare earth 12.5%) and and the concentrated waste water of 750mL Starch Production (containing COD crbe 90000mg/L) that to add volume be in the lining titanium pressure reaction still of 5L for mixed acid solution 2700ml that 3.0mol/L, concentration of nitric acid are 10g/L with the sulfuric acid concentration of sulfuric acid and nitric acid preparation, at 70 ℃～80 ℃, 2.0h is leached in airtight stirring (stirring velocity 70r/min), after leaching finishes, carry out liquid-solid separation, obtain 2500ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt and rare earth be respectively 99.7%, 99.5% and 7.5 %(by entering nickel in infusion solution and leached mud washings, cobalt and rare earth, calculate).

Claims (1)

1. the leaching method of a Ni-MH used battery anode and cathode mixed material, it is characterized in that anode and cathode mixed materials isolated from waste nickel-metal hydrogen batteries and that obtain through roasting pretreatment and containing the high concentrated organic wastewater of benzene ring substance, do not add withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of sulfuric acid and nitric acid, and carry out in confined conditions agitation leach, after finishing, leaching carries out liquid-solid separation, obtain required infusion solution, temperature of reaction is 50 ℃～80 ℃, the sulfuric acid starting point concentration leaching is 1mol/L～4mol/L, the starting point concentration of nitric acid is 5g/L～10g/L, be used for the COD of the high concentrated organic wastewater leaching crconcentration>=30000mg/L, extraction time is 2h～4h, and leaching process stirs, and stirring velocity is 30r/min～120r/min, sulphuric acid is to add 110%～140% of sulfuric acid theoretical consumption that in the anode and cathode mixed materials of reaction vessel, all metals leach, COD cradd-on be 17%～22% of nickel in anode and cathode mixed materials, cobalt total mass, the add-on of high concentrated organic wastewater adds by this calculating.
CN201310736516.8A 2013-12-29 2013-12-29 Method for leaching positive-negative pole material mixture of waste nickel-metal hydride battery Pending CN103757324A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1940098A (en) * 2006-09-21 2007-04-04 广西大学 Gray manganese ore leaching out process
CN101619394A (en) * 2009-06-23 2010-01-06 四川师范大学 Method for leaching anode and cathode mixed material of waste lithium nickel manganese cobalt battery
CN102030375A (en) * 2010-10-29 2011-04-27 北京矿冶研究总院 Method for preparing lithium cobaltate by directly using failed lithium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1940098A (en) * 2006-09-21 2007-04-04 广西大学 Gray manganese ore leaching out process
CN101619394A (en) * 2009-06-23 2010-01-06 四川师范大学 Method for leaching anode and cathode mixed material of waste lithium nickel manganese cobalt battery
CN102030375A (en) * 2010-10-29 2011-04-27 北京矿冶研究总院 Method for preparing lithium cobaltate by directly using failed lithium ion battery

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Application publication date: 20140430