CN103757315A - Method for leaching positive pole material of waste nickel-metal hydride battery - Google Patents

Method for leaching positive pole material of waste nickel-metal hydride battery Download PDF

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Publication number
CN103757315A
CN103757315A CN201310736507.9A CN201310736507A CN103757315A CN 103757315 A CN103757315 A CN 103757315A CN 201310736507 A CN201310736507 A CN 201310736507A CN 103757315 A CN103757315 A CN 103757315A
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China
Prior art keywords
leaching
positive electrode
electrode material
sulfuric acid
nickel
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CN201310736507.9A
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龙炳清
曹攀
秦丹
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Sichuan Normal University
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Sichuan Normal University
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Priority to CN201310736507.9A priority Critical patent/CN103757315A/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The invention discloses a method for leaching a positive pole material of a waste nickel-metal hydride battery. The method comprises the steps of adding the positive pole material which is separated from the waste nickel-metal hydride battery and is subjected to roasting pretreatment, and cocoanut 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 waste nickel-metal hydrogen batteries positive electrode material
Technical field
The present invention relates to a kind of leaching method of waste nickel-metal hydrogen batteries positive electrode 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.The main nickeliferous and cobalt of waste nickel-metal hydrogen batteries positive electrode material, both total contents are up to 50~70%, have very much a recovery value.The technique that reclaims at present nickel, cobalt from waste nickel-metal hydrogen batteries positive electrode material 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 waste nickel-metal hydrogen batteries positive electrode 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 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 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 waste nickel-metal hydrogen batteries positive electrode material of basic non-environmental-pollution has larger practical value.
Summary of the invention
The problem leaching for current waste nickel-metal hydrogen batteries positive electrode 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, basic non-environmental-pollution the leaching method of waste nickel-metal hydrogen batteries positive electrode material, it is characterized in that by positive electrode material isolated from waste nickel-metal hydrogen 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, 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 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, the waste nickel-metal hydrogen batteries positive electrode material of sulfuric acid leaching after roasting pretreatment is when (nickel and cobalt in material are oxide form), and following main chemical reactions occurs 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
12nCo 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 waste nickel-metal hydrogen batteries positive electrode 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 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 to overflow and produce.
specific implementation method
embodiment 1: by 100g waste nickel-metal hydrogen batteries positive electrode material (nickeliferous 56.4%, cobalt 5.9%) and≤to add volume be in the lining titanium pressure reaction still of 2L to 1.5mm coconut shell powder 37.5g, adding sulfuric acid concentration is the mixed acid solution 850ml 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 820ml infusion solution (not containing leached mud washing water).The leaching yield of nickel and cobalt be respectively 98.7% and 98.4%(by entering nickel in infusion solution and leached mud washings and cobalt, calculate).
Embodiment 2: by 500g waste nickel-metal hydrogen batteries positive electrode material (nickeliferous 56.4%, cobalt 5.9%) and≤to add volume be in the lining titanium pressure reaction still of 5L to 1.5mm coconut shell powder 230g, adding sulfuric acid concentration is the mixed acid solution 2500ml 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 2300ml infusion solution (not containing leached mud washing water).The leaching yield of nickel and cobalt be respectively 99.6% and 99.4%(by entering nickel in infusion solution and leached mud washings and cobalt, calculate).

Claims (1)

1. the leaching method of a waste nickel-metal hydrogen batteries positive electrode material, it is characterized in that by positive electrode material isolated from waste nickel-metal hydrogen 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, 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 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.
CN201310736507.9A 2013-12-29 2013-12-29 Method for leaching positive pole material of waste nickel-metal hydride battery Pending CN103757315A (en)

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CN201310736507.9A CN103757315A (en) 2013-12-29 2013-12-29 Method for leaching positive pole material of waste nickel-metal hydride battery

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624651A (en) * 2009-06-23 2010-01-13 四川师范大学 Method for leaching cathode materials from waste nickel-metal hydrogen batteries
CN102030375A (en) * 2010-10-29 2011-04-27 北京矿冶研究总院 Method for preparing lithium cobaltate by directly using failed lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624651A (en) * 2009-06-23 2010-01-13 四川师范大学 Method for leaching cathode materials from waste nickel-metal hydrogen batteries
CN102030375A (en) * 2010-10-29 2011-04-27 北京矿冶研究总院 Method for preparing lithium cobaltate by directly using failed lithium ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张宏雷等: ""从生物质还原的氧化锰矿中回收钴镍的试验研究"", 《稀有金属》 *
李进中等: ""氧化锰矿还原浸出工艺技术研究进展"", 《中国锰业》 *

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Application publication date: 20140430