CN103757263B - The leaching method of anode material of used nickel cadmium battery - Google Patents

The leaching method of anode material of used nickel cadmium battery Download PDF

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CN103757263B
CN103757263B CN201310736381.5A CN201310736381A CN103757263B CN 103757263 B CN103757263 B CN 103757263B CN 201310736381 A CN201310736381 A CN 201310736381A CN 103757263 B CN103757263 B CN 103757263B
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leaching
sulfuric acid
nitric acid
add
acid
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CN103757263A (en
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龙炳清
陈建文
邓国海
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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 leaching method of the anode material of used nickel cadmium battery of introduction of the present invention is by isolated from waste nickel-cadmium batteries and the positive electrode material obtained through roasting pretreatment and napier grass powder add in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions.

Description

The leaching method of anode material of used nickel cadmium battery
Technical field
The present invention relates to a kind of leaching method of anode material of used nickel cadmium battery.
Background technology
Nickel-cadmium cell is the widely used battery of a class, and this battery will produce a large amount of refuse battery after using and scrapping.Because this kind of battery contains plurality of heavy metal, if abandon into environment, very large direct and potential hazard will be produced to environment.Anode material of used nickel cadmium battery is nickeliferous and cobalt mainly, and both total contents, up to about 60%, have a recovery value very much.From anode material of used nickel cadmium battery, reclaim nickel at present, the technique of cobalt mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, the 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 wet processing.The leaching method of current anode material of used nickel cadmium battery mainly contains hydrochloric acid leaching process, sulfuric acid leaching, nitric acid lixiviation process and nitration mixture (sulfuric acid adds nitric acid) lixiviation process.Hydrochloric acid leaching process, equipment corrosion is large, and acid mist generation is contaminate environment greatly.Sulfuric acid leaching consumption reductive agent costly (as hydrogen peroxide etc.).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 improving leaching velocity how economically, improve metal leaching rate, reduce 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 solve the problems referred to above preferably, but leaching plant is more complicated, and the required technical pure oxygen amount of refuse battery leaching is little, refuse battery process enterprise on the spot manufacture pure oxygen uses by oneself uneconomical, and the storage of industrial pure oxygen, transport and use are cumbersome.Development equipment corrosion is little, leaching velocity is fast, leaching yield is high, acid consumes and the leaching method of the anode material of used nickel cadmium battery of low, easy to use, the basic non-environmental-pollution of other supplementary product onsumption has larger practical value.
Summary of the invention
For the problem that current anode material of used nickel cadmium battery leaches, the object of the invention is to find a kind of metal leaching rate high, leaching velocity is fast, leaching yield is high, acid consumption is low with other supplementary product onsumption, easy to use, need not expensive reductive agent, the leaching method of the anode material of used nickel cadmium battery of basic non-environmental-pollution, isolated from waste nickel-cadmium batteries and the positive electrode material obtained through roasting pretreatment and≤1.5mm napier grass powder is it is characterized in that to 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 agitation leach in confined conditions.Carry out solid-liquor separation after leaching terminates, obtain required infusion solution.Temperature of reaction is 50 DEG C ~ 80 DEG C, 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 extraction time is 2h ~ 4h, and leaching process stirs, and stirring velocity is 30r/min ~ 120r/min.Sulphuric acid be in the positive electrode material adding reaction vessel all metal leach 110% ~ 140% of sulfuric acid theoretical consumption.The add-on of napier grass powder with butt count nickel in positive electrode material, cobalt total mass 60% ~ 75%.
The object of the present invention is achieved like this: airtight and under having napier grass powder and nitric acid existent condition, time the anode material of used nickel cadmium battery of sulfuric acid leaching after roasting pretreatment (nickel in material and cobalt are metal oxide form), there is following main chemical reactions in leaching process:
NiO+H 2SO 4=NiSO 4+H 2O
CoO+H 2SO 4=CoSO 4+H 2O
nC 6H 10O 5+nH 2SO 4=n(C 5H 11O 5)HSO 4
n(C 5H 11O 5)HSO 4+nH 2O=nC 6H 12O 6+nH 2SO 4
C 6H 12O 6+8HNO 3=8NO+6CO 2+10H 2O
nC 6H 10O 5+8nHNO 3=8nNO+6nCO 2+9nH 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
Ni 2o 3and Co 2o 3total reaction be:
12nNi 2O 3+nC 6H 10O 5+24nH 2SO 4=24nNiSO 4+6nCO 2+29nH 2O
12nCo 2O 3+nC 6H 10O 5+24nH 2SO 4=24nCoSO 4+6nCO 2+29nH 2O
Other organism in napier grass powder also generates NO, CO with nitric acid reaction 2and H 2o, NO and the Ni of generation 2o 3and Co 2o 3niSO is generated by previous reaction 4, CoSO 4, HNO 3and H 2o.
Because the speed of response of nitric acid and napier grass powder is very fast, NO and the Ni of generation 2o 3and Co 2o 3reaction also very fast, accelerate whole leaching process thus, and realize Ni 2o 3and Co 2o 3leach more completely.NO thoroughly can destroy the laminate structure of high oxide in positive electrode material, improves the leaching yield of valuable metal.
Relative to existing method, outstanding advantages of the present invention adopts napier grass powder to make reductive agent, and nitric acid is done to leach accelerator and leached anode material of used nickel cadmium battery, and speed of response is fast, and such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little, and napier grass powder is cheap; In positive electrode material, the laminate structure of high oxide is destroyed thoroughly, can improve metal leaching rate; Do not need in leach liquor subsequent disposal to neutralize a large amount of acid, cost is lower; The waste amount produced in leach liquor subsequent disposal is few, reduces pollution abatement costs, has obvious economic benefit and environmental benefit; Process is carried out in confined conditions, avoids the environmental pollution that NO effusion produces.
specific implementation method
Embodiment 1: by the anode material of used nickel cadmium battery (nickeliferous 55.2% of 100g through roasting pretreatment, cobalt 3.8%) and≤1.5mm napier grass powder 35.5g to add volume be in the lining titanium pressure reaction still of 2L, add the mixed acid solution 800ml that sulfuric acid concentration is 1.5mol/L, concentration of nitric acid is 5g/L, at 50 DEG C ~ 60 DEG C, stir (stirring velocity 80r/min) leach 4h, carry out solid-liquor separation after leaching terminates, obtain 770ml infusion solution (not containing leached mud washing water).The leaching yield of nickel and cobalt be respectively 99.2% and 99.0%(calculate by the nickel entered in infusion solution and leached mud washings and cobalt).
Embodiment 2: by the anode material of used nickel cadmium battery (nickeliferous 55.2% of 500g through roasting pretreatment, cobalt 3.8%) to add volume be in the lining titanium pressure reaction still of 5L to≤1.5mm napier grass powder 220g, add the mixed acid solution 2500ml that sulfuric acid concentration is 3.0mol/L, concentration of nitric acid is 10g/L, at 70 DEG C ~ 80 DEG C, stir (stirring velocity 70r/min) leach 2h, carry out solid-liquor separation after leaching terminates, obtain 2300ml infusion solution (not containing leached mud washing water).The leaching yield of nickel and cobalt be respectively 99.6% and 99.3%(calculate by the nickel entered in infusion solution and leached mud washings and cobalt).

Claims (1)

1. the leaching method of an anode material of used nickel cadmium battery, isolated from waste nickel-cadmium batteries and the positive electrode material obtained through roasting pretreatment and≤1.5mm napier grass powder is it is characterized in that to 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 agitation leach in confined conditions, solid-liquor separation is carried out after leaching terminates, obtain required infusion solution, temperature of reaction is 50 DEG C ~ 80 DEG C, the sulfuric acid starting point concentration leached is 1mol/L ~ 4mol/L, the starting point concentration of nitric acid is 5g/L ~ 10g/L extraction time is 2h ~ 4h, leaching process stirs, stirring velocity is 30r/min ~ 120r/min, sulphuric acid be in the positive electrode material adding reaction vessel all metal leach 110% ~ 140% of sulfuric acid theoretical consumption, the add-on of napier grass powder counts nickel in positive electrode material with butt, 60% ~ 75% of cobalt total mass.
CN201310736381.5A 2013-12-29 2013-12-29 The leaching method of anode material of used nickel cadmium battery Expired - Fee Related CN103757263B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1705152A (en) * 2004-05-28 2005-12-07 北京化工大学 Laminar vanadium-manganese oxide as positive electrode material of lithium ion cell and preparation method thereof
CN101255495A (en) * 2008-04-08 2008-09-03 上海电力学院 Leaching method for recycling waste zinc-manganese alkaline dry batteries
CN101624653A (en) * 2009-06-23 2010-01-13 四川师范大学 Method for leaching mixed cathode and anode materials from waste nickel-cadmium batteries
CN101665872A (en) * 2009-06-23 2010-03-10 四川师范大学 Leaching method of anode material of used nickel cadmium battery
JP2010174366A (en) * 2009-02-02 2010-08-12 Sumitomo Metal Mining Co Ltd Method of recovering metal from used nickel-metal hydride 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 (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1705152A (en) * 2004-05-28 2005-12-07 北京化工大学 Laminar vanadium-manganese oxide as positive electrode material of lithium ion cell and preparation method thereof
CN101255495A (en) * 2008-04-08 2008-09-03 上海电力学院 Leaching method for recycling waste zinc-manganese alkaline dry batteries
JP2010174366A (en) * 2009-02-02 2010-08-12 Sumitomo Metal Mining Co Ltd Method of recovering metal from used nickel-metal hydride battery
CN101624653A (en) * 2009-06-23 2010-01-13 四川师范大学 Method for leaching mixed cathode and anode materials from waste nickel-cadmium batteries
CN101665872A (en) * 2009-06-23 2010-03-10 四川师范大学 Leaching method of anode material of used nickel cadmium 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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