CN103757307A

CN103757307A - Method for leaching positive-negative pole material mixture of waste nickel-metal hydride battery

Info

Publication number: CN103757307A
Application number: CN201310736498.3A
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
Anticipated expiration: 2033-12-29
Also published as: CN103757307B

Abstract

The invention discloses a method for leaching a positive-negative pole material mixture of a waste nickel-metal hydride battery. The method comprises the steps of adding the positive-negative pole material mixture which is separated from the waste nickel-metal hydride battery and is subjected to roasting pretreatment, and walnut shell powder 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 Ni-MH used battery anode and cathode mixed material

Technical field

The present invention relates to a kind of leaching method of Ni-MH used battery anode and cathode mixed material.

Background technology

Nickel metal hydride 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.Ni-MH used battery anode and cathode mixed material is nickeliferous, cobalt and rare earth mainly, and three's total content is up to 75～97%, has very much a recovery value.The technique that reclaims at present nickel, cobalt and rare earth from Ni-MH used battery anode and cathode mixed material mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, nickel, cobalt and rare earth that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, cobalt and rare earth.Leaching is a requisite process in wet processing.The leaching method of Ni-MH used battery anode and cathode mixed 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.The equipment corrosion of hydrochloric acid leaching process 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 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 Ni-MH used battery anode and cathode mixed material of basic non-environmental-pollution has larger practical value.

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Summary of the invention

The problem leaching for current Ni-MH used battery anode and cathode mixed material, the object of the invention is to find a kind of metal leaching rate high, easy to use, need not expensive reductive agent, the leaching method of the Ni-MH used battery anode and cathode mixed material that basic nitrogenfree oxide pollutes, it is characterized in that by anode and cathode mixed materials isolated from waste nickel-metal hydrogen batteries and that obtain through roasting pretreatment and≤walnut shell flour of 1.5mm adds 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.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 anode and cathode mixed materials of reaction vessel, all metals leach.The add-on of walnut shell flour is counted 60%～75% of nickel in anode and cathode mixed materials, cobalt total mass with butt.

The object of the present invention is achieved like this: airtight and have under the condition that walnut shell flour and nitric acid exists, during the Ni-MH used battery anode and cathode mixed material (nickel, cobalt and rare earth 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

CoO?+?H ₂SO ₄?=?CoSO 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

Ni ₂o ₃and Co 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

Other organism in walnut shell flour 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 walnut shell flour 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 anode and cathode mixed materials, improves the leaching yield of valuable metal.

With respect to existing method, outstanding advantages of the present invention is to adopt walnut shell flour to make reductive agent, and nitric acid is made to leach accelerator and leached Ni-MH used battery anode and cathode mixed material, speed of response is fast, such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little, and walnut shell flour is cheap; In anode and cathode mixed materials, 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 through the Ni-MH used battery anode and cathode mixed material of roasting pretreatment (nickeliferous 55.3%, cobalt 6.2%, rare earth 12.5%) and≤to add volume be in the lining titanium pressure reaction still of 2L to 1.5mm walnut shell flour 37g, adding sulfuric acid concentration is the mixed acid solution 870ml that 1.5mol/L, concentration of nitric acid are 5g/L, at 50 ℃～60 ℃, 4h is leached in airtight stirring (stirring velocity 80r/min), after leaching finishes, carry out liquid-solid separation, obtain 840ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt and rare earth be respectively 99.0%, 98.5% and 8.7 %(by entering nickel in infusion solution and leached mud washings, cobalt and rare earth, calculate).

Embodiment 2: by through the 500g of roasting pretreatment Ni-MH used battery anode and cathode mixed material (nickeliferous 55.3%, cobalt 6.2%, rare earth 12.5%) and≤to add volume be in the lining titanium pressure reaction still of 5L to 1.5mm walnut shell flour 230g, adding sulfuric acid concentration is the mixed acid solution 2700ml that 3.0mol/L, concentration of nitric acid are 10g/L, at 70 ℃～80 ℃, 2.0h is leached in airtight stirring (stirring velocity 70r/min), after leaching finishes, carry out liquid-solid separation, obtain 2400ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt and rare earth be respectively 99.2%, 99.0% and 7.9 %(by entering nickel in infusion solution and leached mud washings, cobalt and rare earth, calculate).

Claims

1. the leaching method of a Ni-MH used battery anode and cathode mixed material, it is characterized in that by anode and cathode mixed materials isolated from waste nickel-metal hydrogen batteries and that obtain through roasting pretreatment and≤walnut shell flour 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 anode and cathode mixed materials of reaction vessel, all metals leach, the add-on of walnut shell flour is counted nickel in anode and cathode mixed materials with butt, 60%～75% of cobalt total mass.