CN103757343A

CN103757343A - Leaching method of nickel-cadmium waste battery positive-negative electrode mixed material

Info

Publication number: CN103757343A
Application number: CN201310736536.5A
Authority: CN
Inventors: 龙炳清; 舒曼; 曾伟
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-negative electrode mixed material, which comprises the following steps: adding a positive-negative electrode mixed material subjected to roasting pretreatment and separated from nickel-cadmium waste batteries and reed 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 waste nickel-cadmium batteries anode and cathode mixed materials

Technical field

The present invention relates to a kind of leaching method of waste nickel-cadmium batteries anode and cathode mixed materials.

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.Waste nickel-cadmium batteries anode and cathode mixed materials is nickeliferous, cobalt and cadmium mainly, and three's total content is up to 60% left and right, has very much a recovery value.Have very much a recovery value.The technique that reclaims at present nickel, cobalt and cadmium from waste nickel-cadmium batteries anode and cathode mixed materials mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, nickel, cobalt and cadmium that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, cobalt and cadmium.Leaching is a requisite process in wet processing.The leaching method of waste nickel-cadmium batteries anode and cathode mixed materials 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 oxygenant (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 waste nickel-cadmium batteries anode and cathode mixed materials of basic non-environmental-pollution has larger practical value.

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Summary of the invention

The problem leaching for current waste nickel-cadmium batteries anode and cathode mixed materials, 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 waste nickel-cadmium batteries anode and cathode mixed materials of basic non-environmental-pollution, it is characterized in that by anode and cathode mixed materials isolated from waste nickel-cadmium batteries and that obtain through roasting pretreatment and≤reed 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 anode and cathode mixed materials of reaction vessel, all metals leach.The add-on of reed powder 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 reed powder and nitric acid exists, during the waste nickel-cadmium batteries anode and cathode mixed materials (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

CdO?+?H ₂SO ₄?=?CdSO 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 reed 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 reed 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 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 reed powder to make reductive agent, and nitric acid is made to leach accelerator and leached waste nickel-cadmium batteries anode and cathode mixed materials, speed of response is fast, such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little, and reed powder 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 waste nickel-cadmium batteries anode and cathode mixed materials (nickeliferous 30.5%, cobalt 1.6%, cadmium 28.1%) and≤to add volume be in the lining titanium pressure reaction still of 1L to 1.5mm reed powder 19.5g, adding sulfuric acid concentration is the mixed acid solution 590ml 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 560ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt and cadmium be respectively 99.1%, 98.5% and 99.4%(by entering nickel in infusion solution and leached mud washings, cobalt and cadmium, calculate).

Embodiment 2: by 500g waste nickel-cadmium batteries anode and cathode mixed materials (nickeliferous 30.5%, cobalt 1.6%, cadmium 28.1%) to add volume be in the lining titanium pressure reaction still of 5L to≤1.5mm reed powder 120g, adding sulfuric acid concentration is 2.5mol/L, concentration of nitric acid is the mixed acid solution 2200ml of 10g/L, , at 70 ℃～80 ℃, stir (stirring velocity is 70r/min) and leach 2h, after finishing, leaching carries out liquid-solid separation, obtain 2000ml infusion solution (not containing leached mud washing water), nickel, the leaching yield of cobalt and cadmium is respectively 99.4%, 99.2% and 99.6%(by the nickel entering in infusion solution and leached mud washings, cobalt and cadmium calculate).

Claims

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