CN103757307B - The leaching method of Ni-MH used battery anode and cathode mixed material - Google Patents

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

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CN103757307B
CN103757307B CN201310736498.3A CN201310736498A CN103757307B CN 103757307 B CN103757307 B CN 103757307B CN 201310736498 A CN201310736498 A CN 201310736498A CN 103757307 B CN103757307 B CN 103757307B
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cathode mixed
anode
leaching
sulfuric acid
nitric acid
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CN103757307A (en
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龙炳清
秦丹
曹攀
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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 Ni-MH used battery anode and cathode mixed material of introduction of the present invention is by isolated from waste nickel-metal hydrogen batteries and the anode and cathode mixed materials obtained through roasting pretreatment and walnut shell flour 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 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 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.Ni-MH used battery anode and cathode mixed material is nickeliferous, cobalt and rare earth mainly, and the total content of three, up to 75 ~ 97%, has a recovery value very much.The technique reclaiming nickel, cobalt and rare earth at present 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 current 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.The equipment corrosion of hydrochloric acid leaching process is large, and acid mist generation is contaminate environment greatly.Sulfuric acid leaching consumption reductive agent costly (as hydrogen peroxide etc.), and leaching velocity is comparatively slow, 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 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 Ni-MH used battery anode and cathode mixed material 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 Ni-MH used battery anode and cathode mixed material leaches, 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, isolated from waste nickel-metal hydrogen batteries and the anode and cathode mixed materials obtained through roasting pretreatment and≤1.5mm walnut shell flour is it is characterized in that to 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.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 anode and cathode mixed materials adding reaction vessel all metal leach 110% ~ 140% of sulfuric acid theoretical consumption.The add-on of walnut shell flour with butt count nickel in anode and cathode mixed materials, cobalt total mass 60% ~ 75%.
The object of the present invention is achieved like this: airtight and under having walnut shell flour and nitric acid existent condition, time the Ni-MH used battery anode and cathode mixed material of sulfuric acid leaching after roasting pretreatment (nickel in material, cobalt and rare earth are 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
Re 2O 3+3H 2SO 4=Re 2(SO 4) 3+3H 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 walnut shell flour 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 walnut shell flour 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 anode and cathode mixed materials, improves the leaching yield of valuable metal.
Relative to existing method, outstanding advantages of the present invention adopts walnut shell flour to make reductive agent, and nitric acid is done to leach accelerator and leached Ni-MH used battery anode and cathode mixed material, speed of response is fast, such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little, and walnut shell flour is cheap; In anode and cathode mixed materials, 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: it is in the lining titanium pressure reaction still of 2L that 100g is added volume through the Ni-MH used battery anode and cathode mixed material (nickeliferous 55.3%, cobalt 6.2%, rare earth 12.5%) of roasting pretreatment and≤1.5mm walnut shell flour 37g, add the mixed acid solution 870ml that sulfuric acid concentration is 1.5mol/L, concentration of nitric acid is 5g/L, at 50 DEG C ~ 60 DEG C, 4h is leached in airtight stirring (stirring velocity 80r/min), carry out solid-liquor separation after leaching terminates, obtain 840ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt and rare earth be respectively 99.0%, 98.5% and 8.7%(calculate by the nickel, cobalt and the rare earth that enter in infusion solution and leached mud washings).
Embodiment 2: be in the lining titanium pressure reaction still of 5L by adding volume through the 500g Ni-MH used battery anode and cathode mixed material (nickeliferous 55.3%, cobalt 6.2%, rare earth 12.5%) of roasting pretreatment and≤1.5mm walnut shell flour 230g, add the mixed acid solution 2700ml that sulfuric acid concentration is 3.0mol/L, concentration of nitric acid is 10g/L, at 70 DEG C ~ 80 DEG C, 2.0h is leached in airtight stirring (stirring velocity 70r/min), carry out solid-liquor separation after leaching terminates, obtain 2400ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt and rare earth be respectively 99.2%, 99.0% and 7.9%(calculate by the nickel, cobalt and the rare earth that enter in infusion solution and leached mud washings).

Claims (1)

1. the leaching method of a Ni-MH used battery anode and cathode mixed material, isolated from waste nickel-metal hydrogen batteries and the anode and cathode mixed materials obtained through roasting pretreatment and≤1.5mm walnut shell flour 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 anode and cathode mixed materials adding reaction vessel all metal leach 110% ~ 140% of sulfuric acid theoretical consumption, the add-on of walnut shell flour counts nickel in anode and cathode mixed materials with butt, 60% ~ 75% of cobalt total mass.
CN201310736498.3A 2013-12-29 2013-12-29 The leaching method of Ni-MH used battery anode and cathode mixed material Expired - Fee Related CN103757307B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1171171A (en) * 1994-12-20 1998-01-21 瓦尔达电池股份公司 Process for recovery of metals from used nickel-metal hydride accumulators
CN101383440A (en) * 2007-11-16 2009-03-11 佛山市邦普镍钴技术有限公司 Method for recycling and preparing superfine nickel powder from nickel-hydrogen cell
CN101629243A (en) * 2009-06-23 2010-01-20 四川师范大学 Infusion method of Ni-MH used battery anode and cathode mixed material
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
WO2012011205A1 (en) * 2010-07-21 2012-01-26 住友金属鉱山株式会社 Method for separating nikel and cobalt from active materials contained in spent nickel-hydrogen battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1171171A (en) * 1994-12-20 1998-01-21 瓦尔达电池股份公司 Process for recovery of metals from used nickel-metal hydride accumulators
CN101383440A (en) * 2007-11-16 2009-03-11 佛山市邦普镍钴技术有限公司 Method for recycling and preparing superfine nickel powder from nickel-hydrogen cell
CN101629243A (en) * 2009-06-23 2010-01-20 四川师范大学 Infusion method of Ni-MH used battery anode and cathode mixed material
WO2012011205A1 (en) * 2010-07-21 2012-01-26 住友金属鉱山株式会社 Method for separating nikel and cobalt from active materials contained in spent nickel-hydrogen 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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