CN103757401A - Leaching method of waste battery electrode mixed material - Google Patents

Abstract

The invention provides a leaching method of a waste battery electrode mixed material, which comprises the following steps: adding an electrode mixed material subjected to roasting pretreatment separated from waste batteries and bran coats 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 refuse battery electrode mixing material

Technical field

The present invention relates to a kind of leaching method of refuse battery electrode mixing material.

Background technology

Battery is widely used in the fields such as illumination, communication, traffic.Battery will produce a large amount of refuse batteries after using and scrapping.Owing to containing plurality of heavy metal in battery, if abandon into environment, will environment be produced to very large direct and potential hazard.Refuse battery electrode mixing material is nickeliferous, cobalt, lithium, copper, aluminium, cadmium, rare earth and Mn mainly, has very much a recovery value.The technique that reclaims at present the valuable metals such as nickel, cobalt, lithium, copper, cadmium and rare earth from refuse battery electrode mixing material mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, nickel, cobalt, lithium, copper, cadmium and rare earth etc. that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, cobalt, lithium, copper, cadmium and rare earth etc.Leaching is a requisite process in wet processing.The leaching method of refuse battery electrode mixing material 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 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 storage, transportation and the use of industrial pure oxygen 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 refuse battery electrode mixing material of basic non-environmental-pollution has larger practical value.

Summary of the invention

The problem leaching for current refuse battery electrode mixing material, 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 refuse battery electrode mixing material of basic non-environmental-pollution, it is characterized in that by electrode mixing material isolated from refuse battery and that obtain through roasting pretreatment and≤cavings of 1.5mm adds 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 in confined conditions agitation leach.After leaching finishes, carry out liquid-solid separation, obtain required infusion solution.Temperature of reaction is 50 ℃～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 110%～140% of sulfuric acid theoretical consumption that in the electrode mixing material of reaction vessel, all metals leach.The add-on of cavings is counted 60%～75% of nickel in electrode mixing material, cobalt and manganese total mass with butt.

The object of the present invention is achieved like this: airtight and have under the condition that cavings and nitric acid exists, during the refuse battery electrode mixing material (metallic element in material be oxide form) of sulfuric acid leaching after roasting pretreatment, 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

CoO?+?H ₂SO ₄?=?CoSO ₄?+?H ₂O

CdO?+?H ₂SO _4?=?CdSO 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

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 cavings also generates NO, CO with nitric acid reaction ₂and H ₂o, the NO of generation and Ni ₂o ₃, Co ₂o ₃and Mn ₂o ₃by previous reaction, generate NiSO ₄, CoSO ₄, MnSO ₄, HNO ₃and H ₂o.

Because the speed of response of nitric acid and cavings is very fast, the NO of generation and Ni ₂o ₃, Co ₂o ₃and Mn ₂o ₃reaction also very fast, accelerate thus whole leaching process, and realize Ni ₂o ₃, Co ₂o ₃and Mn ₂o ₃leach more completely.NO can thoroughly destroy the laminate structure of high oxide in electrode mixing material, improves the leaching yield of valuable metal.

With respect to existing method, outstanding advantages of the present invention is to adopt cavings to make reductive agent, and nitric acid is made to leach accelerator and leached refuse battery electrode mixing material, 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 cavings is cheap; In electrode mixing 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 effusion to produce.

specific implementation method

embodiment 1: by 100g refuse battery electrode mixing material (nickeliferous 20.5%, cobalt 20.3%, lithium 8.4%, aluminium 2.2%, copper 2.5%, cadmium 2.3%, manganese 4.9%, rare earth 5.7%) and≤to add volume be in the lining titanium pressure reaction still of 2L to 1.5mm cavings 27.5g, adding sulfuric acid concentration is the mixed acid solution 1170ml that 1.5mol/L, concentration of nitric acid are 5g/L, at 50 ℃～60 ℃, 4.0h is leached in airtight stirring (stirring velocity 80r/min), after leaching finishes, carry out liquid-solid separation, obtain 1100ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt, lithium, copper, cadmium, manganese, aluminium, rare earth be respectively 98.6%, 98.5%, 99.0%, 99.3%, 99.2%, 99.1%, 98.9% and 8.6%(by entering nickel in infusion solution and leached mud washings, cobalt, lithium, copper, cadmium, manganese, aluminium, rare earth, calculate).

Embodiment 2: by 500g refuse battery electrode mixing material (nickeliferous 20.5%, cobalt 20.3%, lithium 8.4%, aluminium 2.2%, copper 2.5%, cadmium 2.3%, manganese 4.9%, rare earth 5.7%) and≤to add volume be in the lining titanium pressure reaction still of 5L to 1.5mm cavings 170g, adding sulfuric acid concentration is the mixed acid solution 3500ml that 3.0mol/L, concentration of nitric acid are 10g/L, at 70 ℃～80 ℃, 2h is leached in airtight stirring (stirring velocity 60r/min), after leaching finishes, carry out liquid-solid separation, obtain 3200ml infusion solution (not comprising leached mud washing water).The leaching yield of nickel, cobalt, lithium, copper, cadmium, manganese, aluminium, rare earth be respectively 99.2%, 99.2%, 99.4%, 99.4%, 99.5%, 99.3%, 99.2% and 6.0%(by entering nickel in infusion solution and leached mud washings, cobalt, lithium, copper, cadmium, manganese, aluminium, rare earth, calculate).

Claims (1)

1. the leaching method of a refuse battery electrode mixing material, be characterised in that by electrode mixing material isolated from refuse battery and that obtain through roasting pretreatment and≤cavings of 1.5mm adds 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 in confined conditions agitation leach, after finishing, leaching carries out liquid-solid separation, obtain required infusion solution, temperature of reaction is 50 ℃～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 electrode mixing material of reaction vessel, all metals leach, the add-on of cavings is counted nickel in electrode mixing material with butt, 60%～75% of cobalt and manganese total mass.