CN103757353B - The leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery - Google Patents
The leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery Download PDFInfo
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- CN103757353B CN103757353B CN201310736548.8A CN201310736548A CN103757353B CN 103757353 B CN103757353 B CN 103757353B CN 201310736548 A CN201310736548 A CN 201310736548A CN 103757353 B CN103757353 B CN 103757353B
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Abstract
The leaching method of the anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of introduction of the present invention is by isolated from waste LiCoxNiyMnzO 2 battery and the anode and cathode mixed materials obtained through roasting pretreatment and rice straw 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
Technical field
The present invention relates to a kind of leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery.
Background technology
Nickle cobalt lithium manganate battery (main metal element that anode and cathode mixed materials contains is the battery of nickel, cobalt, manganese, lithium) is a class novel battery, 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.Nickle cobalt lithium manganate battery plus-negative plate mixing material is nickeliferous, cobalt, lithium, copper, aluminium and manganese mainly, and wherein the total content of nickel, cobalt and lithium is up to more than 50%, has very much a recovery value.From anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, the technique of Call Provision, lithium and copper mainly contains thermal process and wet processing at present.The product that thermal process obtains is alloy material, nickel, cobalt and lithium that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, cobalt and lithium.Leaching is a requisite process in wet processing.The leaching method of current anode and cathode mixed materials of waste LiCoxNiyMnzO 2 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 oxygenant 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 and cathode mixed materials of waste LiCoxNiyMnzO 2 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 and cathode mixed materials of waste LiCoxNiyMnzO 2 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 and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of basic non-environmental-pollution, isolated from waste LiCoxNiyMnzO 2 battery and the anode and cathode mixed materials obtained through roasting pretreatment and≤1.5mm rice straw 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 anode and cathode mixed materials adding reaction vessel all metal leach 110% ~ 140% of sulfuric acid theoretical consumption.The add-on of rice straw powder counts 60% ~ 75% of nickel in anode and cathode mixed materials, cobalt and manganese total mass with butt.
The object of the present invention is achieved like this: airtight and under having rice straw powder and nitric acid existent condition, time the anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of sulfuric acid leaching after roasting pretreatment (metallic element in material is oxide form), there is following main chemical reactions in leaching process:
NiO+H
2SO
4=NiSO
4+H
2O
CuO+H
2SO
4=CuSO
4+H
2O
Al
2O
3+3H
2SO
4=Al
2(SO
4)
3+3H
2O
Li
2O+H
2SO
4=Li
2SO
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
3Mn
2O
3+6H
2SO
4+2NO=6MnSO
4+2HNO
3+5H
2O
Ni
2o
3, Co
2o
3and Mn
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
12nMn
2O
3+nC
6H
10O
5+24nH
2SO
4=24nMnSO
4+6nCO
2+29nH
2O
Other organism in rice straw powder also generates NO, CO with nitric acid reaction
2and H
2o, NO and the Ni of generation
2o
3, Co
2o
3and Mn
2o
3niSO is generated by previous reaction
4, CoSO
4, MnSO
4, HNO
3and H
2o.
Because the speed of response of nitric acid and rice straw powder is very fast, NO and the Ni of generation
2o
3, Co
2o
3and Mn
2o
3reaction also very fast, accelerate whole leaching process thus, and realize Ni
2o
3, Co
2o
3and Mn
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 rice straw powder to make reductive agent, and nitric acid is done to leach accelerator and leached anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, speed of response is fast, such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little, and rice straw powder 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 anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery (nickeliferous 14.5%, cobalt 20.3%, lithium 17.5%, aluminium 2.2%, copper 2.5%, manganese 12.9%) and≤1.5mm rice straw powder 29g are added volume, add the mixed acid solution 1650ml 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 1600ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt, lithium, copper, aluminium and manganese be respectively 99.1%, 98.8%, 99.0%, 99.1%, 98.7% and 99.2%(calculate by the nickel, cobalt, lithium, copper, aluminium and the manganese that enter in infusion solution and leached mud washings).
Embodiment 2: it is in the lining titanium pressure reaction still of 5L that 300g anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery (nickeliferous 14.5%, cobalt 20.3%, lithium 17.5%, aluminium 2.2%, copper 2.5%, manganese 12.9%) and≤1.5mm rice straw powder 105g are added volume, add the mixed acid solution 3000ml that sulfuric acid concentration is 3mol/L, concentration of nitric acid is 10g/L, at 70 DEG C ~ 80 DEG C, 2h is leached in airtight stirring (stirring velocity 70r/min), carry out solid-liquor separation after leaching terminates, obtain 2800ml infusion solution (not comprising leached mud washing water).The leaching yield of nickel, cobalt, lithium, copper, aluminium and manganese be respectively 99.4%, 99.3%, 99.6%, 99.2%, 98.7% and 99.3%(calculate by the nickel, cobalt, lithium, copper, aluminium and the manganese that enter in infusion solution and leached mud washings).
Claims (1)
1.
a kind of leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, isolated from waste LiCoxNiyMnzO 2 battery and the anode and cathode mixed materials obtained through roasting pretreatment and≤1.5mm rice straw 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 anode and cathode mixed materials adding reaction vessel all metal leach 110% ~ 140% of sulfuric acid theoretical consumption, the add-on of rice straw powder counts nickel in anode and cathode mixed materials with butt, 60% ~ 75% of cobalt and manganese total mass.
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