CN103757226A

CN103757226A - Method for leaching positive pole material of waste lithium nickelate battery

Info

Publication number: CN103757226A
Application number: CN201310736448.5A
Authority: CN
Inventors: 龙炳清; 秦丹; 曹攀
Original assignee: Sichuan Normal University
Current assignee: Sichuan Normal University
Priority date: 2013-12-29
Filing date: 2013-12-29
Publication date: 2014-04-30

Abstract

The invention discloses a method for leaching a positive pole material of a waste lithium nickelate battery. The method comprises the steps of adding the positive pole material which is separated from the waste lithium nickelate 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 anode material of waste LiNiO 2 battery

Technical field

The present invention relates to a kind of leaching method of anode material of waste LiNiO 2 battery.

Background technology

Lithium nickelate 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.Anode material of waste LiNiO 2 battery is nickeliferous, lithium, copper and aluminium mainly, and wherein nickel, lithium and copper three's total content is greater than 60%, has very much a recovery value.The technique that reclaims at present nickel, lithium and copper from anode material of waste LiNiO 2 battery mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, nickel, lithium and copper that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, lithium and copper.Leaching is a requisite process in wet processing.The leaching method of anode material of waste LiNiO 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 at present.Hydrochloric acid leaching process, equipment corrosion 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 the storage of industrial pure oxygen, transportation and use 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 anode material of waste LiNiO 2 battery of basic non-environmental-pollution has larger practical value.

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Summary of the invention

The problem leaching for current anode material of waste LiNiO 2 battery, 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 and other supplementary product onsumption are low, easy to use, need not expensive reductive agent, the leaching method of the anode material of waste LiNiO 2 battery of basic non-environmental-pollution, it is characterized in that positive electrode material isolated from waste LiNiO 2 battery 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, the mixing solutions that adds 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 60 ℃～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.COD for the high concentrated organic wastewater that leaches _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 positive electrode material of reaction vessel, all metals leach.The add-on of high concentrated organic wastewater is with per kilogram LiNiO in positive electrode material ₂add COD _cr0.13 kilogram～0.15 kilogram calculating adds.

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, (cobalt in material and lithium exist with lithium nickelate form the anode material of waste LiNiO 2 battery of sulfuric acid leaching after roasting pretreatment, copper and aluminium are mainly metal oxide form) time, 6LiNiO in leaching process ₂redox reaction can represent with general formula below:

3(C-H _xO _y) _m?+?4mHNO ₃?=?4mNO?+?3mCO ₂?+?zH ₂O

6LiNiO ₂?+?9H ₂SO ₄?+?2NO?=?6NiSO ₄?+?3Li ₂SO ₄?+?2HNO ₃?+?8H ₂O

Total reaction is:

(C-H _xO _y) _m?+?4mLiNiO ₂?+?6mH ⁺?=?4mNi ²⁺?+?4mLi ⁺?+?mCO ₂?+?zH ₂O

CuO and Al ₂o ₃there is following chemical reaction:

CuO?+?H ₂SO ₄?=?CuSO ₄?+?H ₂O

Al ₂O ₃?+?3H ₂SO ₄?=?3Al 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 LiCoO ₂reaction also very fast, accelerate thus whole leaching process, and realize LiCoO ₂leach more completely.NO can thoroughly destroy the laminate structure of high oxide in positive electrode material, improves the leaching yield of valuable metal.

With respect to existing method, outstanding advantages of the present invention is to adopt not containing the high concentrated organic wastewater reductive agent of phenyl ring material, and nitric acid is made to leach accelerator and leached anode material of waste LiNiO 2 battery, and speed of response is fast, such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little; In positive electrode material, 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 anode material of waste LiNiO 2 battery, 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 to overflow and produce.

specific implementation method

embodiment 1: by 100g anode material of waste LiNiO 2 battery (nickeliferous 54.3%, lithium 5.5%, copper 7.8%, aluminium 3.1%) and 235mL brewing wastewater (containing COD _crbe 50000mg/L) that to add volume be in the lining titanium pressure reaction still of 2L for mixed acid solution 1300ml that 1.5mol/L, concentration of nitric acid are 5g/L with the sulfuric acid concentration of sulfuric acid and nitric acid preparation, at 60 ℃～70 ℃, stir (stirring velocity 80r/min) and leach 4.0h, after leaching finishes, carry out liquid-solid separation, obtain 1250ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, lithium, copper and aluminium be respectively 99.1%, 99.1%, 98.5% and 98.3%(by entering nickel in infusion solution and leached mud washings, lithium, copper and aluminium, calculate).

Embodiment 2: by 500g anode material of waste LiNiO 2 battery (nickeliferous 54.3%, lithium 5.5%, copper 7.8%, aluminium 3.1%) 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 3200ml that 3.5mol/L, concentration of nitric acid are 10g/L with the sulfuric acid concentration of sulfuric acid and nitric acid preparation, at 70 ℃～80 ℃, stir (stirring velocity 70r/min) and leach 2.0h, after leaching finishes, carry out liquid-solid separation, obtain 3000 ml infusion solutions (not containing leached mud washing water).The leaching yield of nickel, lithium, copper and aluminium be respectively 99.4%, 99.6%, 99.1% and 98.5%(by entering nickel in infusion solution and leached mud washings, lithium, copper and aluminium, calculate).

Claims

1. the leaching method of an anode material of waste LiNiO 2 battery, it is characterized in that positive electrode material isolated from waste LiNiO 2 battery 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, the mixing solutions that adds 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 60 ℃～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, COD for the high concentrated organic wastewater that leaches _crconcentration>=30000mg/L, extraction time is 2h～4h, leaching process stirs, stirring velocity is 30r/min～120r/min, sulphuric acid is to add 110%～140% of sulfuric acid theoretical consumption that in the positive electrode material of reaction vessel, all metals leach, and the add-on of high concentrated organic wastewater is with per kilogram LiNiO in positive electrode material ₂add COD _cr0.13 kilogram～0.15 kilogram calculating adds.