CN103757391A - Leaching method of lithium cobaltate waste battery positive electrode material - Google Patents

Abstract

The invention provides a leaching method of a lithium cobaltate waste battery positive electrode material, which comprises the following steps: adding a positive electrode material subjected to roasting pretreatment separated from lithium cobaltate waste batteries and ryegrass powder into a pressure-resistant sulfuric-acid/nitric-acid-corrosion-resistant reaction kettle, adding a sulfuric acid-nitric acid mixed solution, and carrying out agitation leaching under sealed conditions.

Description

The leaching method of anode material of waste LiCoO battery

Technical field

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

Background technology

Cobalt acid lithium 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 LiCoO battery is mainly containing cobalt, lithium, copper and aluminium, and wherein cobalt, lithium and copper three's total content is greater than 60%, has very much a recovery value.The technique that reclaims at present cobalt, lithium and copper from anode material of waste LiCoO battery mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, cobalt, lithium and copper that very difficult acquisition is purer.Wet processing becomes more readily available purer cobalt, lithium and copper.Leaching is a requisite process in wet processing.The leaching method of anode material of waste LiCoO 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 reductive agent (as hydrogen peroxide etc.) that sulfuric acid leaching consumption is more expensive.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 LiCoO 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 LiCoO 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 LiCoO battery of basic non-environmental-pollution, it is characterized in that by positive electrode material isolated from waste LiCoO battery and that obtain through roasting pretreatment and≤barley seeding food of 1.5mm adds 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 that 5g/L～10g/L extraction time is 2h～4h, and leaching process stirs, and stirring velocity is 30r/min～120r/min.Sulphuric acid is to add 101%～140% of sulfuric acid theoretical consumption that in the positive electrode material of reaction vessel, all metals leach.The add-on of barley seeding food is counted LiCoO in positive electrode material with butt ₂90%～120% of quality.

The object of the present invention is achieved like this: airtight and have under the condition that barley seeding food and nitric acid exists, (cobalt in material and lithium exist with cobalt acid lithium form the anode material of waste LiCoO battery of sulfuric acid leaching after roasting pretreatment, copper and aluminium are mainly metal oxide form) time, there is following main chemical reactions in leaching process:

CuO?+?H ₂SO ₄?=?CuSO ₄?+?H ₂O

Al ₂O ₃?+?3H ₂SO ₄?=?3Al 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

6LiCoO ₂?+?9H ₂SO ₄?+?2NO?=?6CoSO ₄?+?3Li ₂SO ₄?+?2HNO ₃?+?8H ₂O

The total reaction of cobalt acid lithium is:

24nLiCoO ₂?+?nC ₆H ₁₀O ₅?+?36nH ₂SO ₄?=?24nCoSO ₄?+?12nLi ₂SO ₄?+?6nCO ₂?+?41nH ₂O

Other organism in barley seeding food also generates NO, CO with nitric acid reaction ₂and H ₂o, the NO of generation and LiCoO ₂and H ₂sO ₄by previous reaction, generate CoSO ₄, Li ₂sO ₄, HNO ₃and H ₂o.

Because the speed of response of nitric acid and barley seeding food 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 barley seeding food to make reductive agent, and nitric acid is made to leach accelerator and leached anode material of waste LiCoO 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 barley seeding food is cheap; In positive electrode material, the laminate structure of high oxide is destroyed thoroughly, can improve metal leaching rate; In leach liquor subsequent disposal, do not need to neutralize a large amount of acid, cost is lower; The waste amount producing in leach liquor subsequent disposal is few, has reduced pollution abatement costs, has obvious economic benefit and environmental benefit; Process is carried out in confined conditions, the environmental pollution of having avoided NO to overflow and produce.

specific implementation method

embodiment 1: 100g anode material of waste LiCoO battery (is contained to cobalt 53.6%, lithium 5.3%, copper 8.2%, aluminium 3.4%) and≤to add volume be in the lining titanium pressure reaction still of 2L to 1.5mm barley seeding food 30g, adding sulfuric acid concentration is the mixed acid solution 1180ml that 1.5mol/L, concentration of nitric acid are 5g/L, at 60 ℃～70 ℃, 4.0h is leached in airtight stirring (stirring velocity 80r/min), after leaching finishes, carry out liquid-solid separation, obtain 1150ml infusion solution (not containing leached mud washing water).The leaching yield of cobalt, lithium, copper and aluminium be respectively 98.9%, 99.1%, 98.8% and 99.0%(by entering cobalt in infusion solution and leached mud washings, lithium, copper and aluminium, calculate).

Embodiment 2: 500g anode material of waste LiCoO battery (is contained to cobalt 53.6%, lithium 5.3%, copper 8.2%, aluminium 3.4%) it is in the lining titanium pressure reaction still of 5L that≤1.5mm barley seeding food 190g adds volume, adding sulfuric acid concentration is 3.0mol/L, concentration of nitric acid is the mixed acid solution 3500ml of 10g/L, at 70 ℃～80 ℃, 2h is leached in airtight stirring (stirring velocity 70r/min), after finishing, leaching carries out liquid-solid separation, obtain 3300ml infusion solution (not containing leached mud washing water), cobalt, lithium, the leaching yield of copper and aluminium is respectively 99.2%, 99.2%, 99.0% and 98.6%(by the cobalt entering in infusion solution and leached mud washings, lithium, copper and aluminium calculate).

Claims (1)

1. the leaching method of an anode material of waste LiCoO battery, it is characterized in that by positive electrode material isolated from waste LiCoO battery and that obtain through roasting pretreatment and≤barley seeding food of 1.5mm adds 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 that 5g/L～10g/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, the add-on of barley seeding food is counted LiCoO in positive electrode material with butt ₂90%～120% of quality.