CN103757362A

CN103757362A - Leaching method of nickel-cadmium waste battery positive electrode material

Info

Publication number: CN103757362A
Application number: CN201310736559.6A
Authority: CN
Inventors: 龙炳清; 林春; 李贵
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 provides a leaching method of a nickel-cadmium waste battery positive electrode material, which comprises the following steps: adding a positive electrode material subjected to roasting pretreatment separated from nickel-cadmium waste batteries and cocoanut shell flour 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 used nickel cadmium battery

Technical field

The present invention relates to a kind of leaching method of anode material of used nickel cadmium battery.

Background technology

Nickel-cadmium cell 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.The main nickeliferous and cobalt of anode material of used nickel cadmium battery, both total contents are up to 60% left and right, have very much a recovery value.The technique that reclaims at present nickel, cobalt from anode material of used nickel cadmium battery mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, the nickel that very difficult acquisition is purer and cobalt.Wet processing becomes more readily available purer nickel and cobalt.Leaching is a requisite process in wet processing.The leaching method of anode material of used nickel cadmium 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 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 anode material of used nickel cadmium 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 used nickel cadmium 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 used nickel cadmium battery of basic non-environmental-pollution, it is characterized in that by positive electrode material isolated from waste nickel-cadmium batteries and that obtain through roasting pretreatment and≤coconut shell powder 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 positive electrode material of reaction vessel, all metals leach.The add-on of coconut shell powder is counted 60%～75% of nickel in positive electrode material, cobalt total mass with butt.

The object of the present invention is achieved like this: airtight and have under the condition that coconut shell powder and nitric acid exists, during the anode material of used nickel cadmium battery (nickel in material and cobalt be metal 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

CoO?+?H ₂SO ₄?=?CoSO 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

Ni ₂o ₃and Co ₂o ₃total reaction be:

12nNi ₂O ₃?+?nC ₆H ₁₀O ₅?+?24nH ₂SO ₄?=?24nNiSO ₄?+?6nCO ₂?+?29nH ₂O

12n?Co ₂O ₃?+?nC ₆H ₁₀O ₅?+?24nH ₂SO ₄?=?24nCoSO ₄?+?6nCO ₂?+?29nH ₂O

Other organism in coconut shell powder also generates NO, CO with nitric acid reaction ₂and H ₂o, the NO of generation and Ni ₂o ₃and Co ₂o ₃by previous reaction, generate NiSO ₄, CoSO ₄, HNO ₃and H ₂o.

Because the speed of response of nitric acid and coconut shell powder is very fast, the NO of generation and Ni ₂o ₃and Co ₂o ₃reaction also very fast, accelerate thus whole leaching process, and realize Ni ₂o ₃and Co ₂o ₃leach 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 coconut shell powder to make reductive agent, and nitric acid is made to leach accelerator and leached anode material of used nickel cadmium 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 coconut shell powder 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 effusion to produce.

specific implementation method

embodiment 1: the anode material of used nickel cadmium battery (nickeliferous 55.2% by 100g through roasting pretreatment, cobalt 3.8%) and≤to add volume be in the lining titanium pressure reaction still of 2L to 1.5mm coconut shell powder 35.5g, adding sulfuric acid concentration is the mixed acid solution 800ml that 1.5mol/L, concentration of nitric acid are 5g/L, at 50 ℃～60 ℃, stir (stirring velocity 80r/min) and leach 4h, after leaching finishes, carry out liquid-solid separation, obtain 770ml infusion solution (not containing leached mud washing water).The leaching yield of nickel and cobalt be respectively 99.2% and 99.0%(by entering nickel in infusion solution and leached mud washings and cobalt, calculate).

Embodiment 2: the anode material of used nickel cadmium battery (nickeliferous 55.2% by 500g through roasting pretreatment, cobalt 3.8%) to add volume be in the lining titanium pressure reaction still of 5L to≤1.5mm coconut shell powder 220g, adding sulfuric acid concentration is mixed acid solution 2500 ml that 3.0mol/L, concentration of nitric acid are 10g/L, at 70 ℃～80 ℃, stir (stirring velocity 70r/min) and leach 2h, after leaching finishes, carry out liquid-solid separation, obtain 2300 ml infusion solutions (not containing leached mud washing water).The leaching yield of nickel and cobalt be respectively 99.6% and 99.3%(by entering nickel in infusion solution and leached mud washings and cobalt, calculate).

Claims

1. the leaching method of a nickel anode material of used nickel cadmium battery, it is characterized in that by positive electrode material isolated from waste nickel-cadmium batteries and that obtain through roasting pretreatment and≤coconut shell powder 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 positive electrode material of reaction vessel, all metals leach, the add-on of coconut shell powder is counted nickel in positive electrode material with butt, 60%～75% of cobalt total mass.