CN103757298A - Method for leaching positive-negative pole material mixture of waste lithium nickel cobalt manganese oxide battery - Google Patents
Method for leaching positive-negative pole material mixture of waste lithium nickel cobalt manganese oxide battery Download PDFInfo
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- CN103757298A CN103757298A CN201310736485.6A CN201310736485A CN103757298A CN 103757298 A CN103757298 A CN 103757298A CN 201310736485 A CN201310736485 A CN 201310736485A CN 103757298 A CN103757298 A CN 103757298A
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- leaching
- anode
- sulfuric acid
- mixed materials
- battery
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for leaching a positive-negative pole material mixture of a waste lithium nickel cobalt manganese oxide battery. The method comprises the steps of adding the positive-negative pole material mixture which is separated from the waste lithium nickel cobalt manganese oxide battery and is subjected to roasting pretreatment, and high-concentration organic wastewater which does not contain benzene-ring substances 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
Technical field
The present invention relates to a kind of leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery.
Background technology
Nickle cobalt lithium manganate battery (the major metal element that anode and cathode mixed materials contains is the battery of nickel, cobalt, manganese, lithium) is a class novel battery, 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.Nickle cobalt lithium manganate battery plus-negative plate mixing material is nickeliferous, cobalt, lithium, copper, aluminium and manganese mainly, and wherein the total content of nickel, cobalt and lithium is up to more than 50%, has very much a recovery value.The technique that reclaims at present cobalt, lithium and copper from anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, nickel, cobalt and lithium that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, cobalt and lithium.Leaching is a requisite process in wet processing.The leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 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 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 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 anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of basic non-environmental-pollution has larger practical value.
?
Summary of the invention
The problem leaching for current anode and cathode mixed materials of waste LiCoxNiyMnzO 2 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 and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of basic non-environmental-pollution, it is characterized in that anode and cathode mixed materials isolated from waste LiCoxNiyMnzO 2 battery and that obtain through roasting pretreatment and containing the high concentrated organic wastewater of benzene ring substance, do not add 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 5g/L～10g/L.COD for the high concentrated organic wastewater that leaches
crconcentration>=30000mg/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.COD
cradd-on be 17%～22% of nickel in anode and cathode mixed materials, cobalt, manganese total mass, the add-on of high concentrated organic wastewater adds by this calculating.
The object of the present invention is achieved like this: airtight and have under the condition that high concentrated organic wastewater and nitric acid exists, the anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of sulfuric acid leaching after roasting pretreatment be when (metallic element in material is oxide form), Ni
2o
3, Co
2o
3and Mn
2o
3redox reaction can represent with general formula below:
3(C-H
xO
y)
m?+?4mHNO
3?=?4mNO?+?3mCO
2?+?zH
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
Total reaction is:
(C-H
xO
y)
m?+?2mNi
2O
3?+?4mH
+?=?4mNi
2+?+?mCO
2?+?zH
2O
(C-H
xO
y)
m?+?2mCo
2O
3?+?4mH
+?=?4mCo
2+?+?mCO
2?+?zH
2O
(C-H
xO
y)
m?+?2mMn
2O
3?+?4mH
+?=?4mMn
2+?+?mCO
2?+?zH
2O
There is following chemical reaction in other oxide compound:
NiO?+?H
2SO
4?=?NiSO
4?+?H
2O
CoO?+?H
2SO
4?=?CoSO
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
Because the organism speed of response in nitric acid and high concentrated organic wastewater 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 nickel, cobalt, manganese and leach 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 not containing the high concentrated organic wastewater reductive agent of benzene ring substance, and nitric acid is made to leach accelerator and leached anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, and speed of response is fast, such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little; In anode and cathode mixed materials, the laminate structure of high oxide is destroyed thoroughly, can improve metal leaching rate; Utilize high concentrated organic wastewater to make oxygenant, not only for the improvement of high concentrated organic wastewater opens up a new way, and can reduce the leaching cost of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, there is obvious economic benefit and environmental benefit; In leach liquor subsequent disposal, do not need to neutralize a large amount of acid, cost is lower; 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 anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery (nickeliferous 14.5%, cobalt 20.3%, lithium 17.5%, aluminium 2.2%, copper 2.5%, manganese 12.9%) and 165mL Alcohol Production waste water (containing COD
crbe 50000mg/L) that to add volume be in the lining titanium pressure reaction still of 2L for mixed acid solution 1650ml that 1.5mol/L, concentration of nitric acid are 5g/L with the sulfuric acid concentration of sulfuric acid and nitric acid preparation, at 50 ℃～60 ℃, 4h is leached in airtight stirring (stirring velocity 80r/min), after leaching finishes, carry out liquid-solid separation, obtain 1600ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt, lithium, copper, aluminium and manganese be respectively 99.4%, 99.2%, 99.4%, 99.0%, 98.6% and 99.2%(by entering nickel in infusion solution and leached mud washings, cobalt, lithium, copper, aluminium and manganese, calculate).
Embodiment 2: by 300g anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery (nickeliferous 14.5%, cobalt 20.3%, lithium 17.5%, aluminium 2.2%, copper 2.5%, manganese 12.9%) and the concentrated waste water of 340mL Starch Production (containing COD
crbe 90000mg/L) that to add volume be in the lining titanium pressure reaction still of 5L for mixed acid solution 3000ml that 3mol/L, concentration of nitric acid are 10g/L with the sulfuric acid concentration of sulfuric acid and nitric acid preparation, at 70 ℃～80 ℃, 2h is leached in airtight stirring (stirring velocity 70r/min), after leaching finishes, carry out liquid-solid separation, obtain 2800ml infusion solution (not comprising leached mud washing water).The leaching yield of nickel, cobalt, lithium, copper, aluminium and manganese be respectively 99.6%, 99.4%, 99.7%, 99.1%, 98.5% and 99.4%(by entering nickel in infusion solution and leached mud washings, cobalt, lithium, copper, aluminium and manganese, calculate).
Claims (1)
1. the leaching method of an anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, it is characterized in that anode and cathode mixed materials isolated from waste LiCoxNiyMnzO 2 battery and that obtain through roasting pretreatment and containing the high concentrated organic wastewater of benzene ring substance, do not add 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 5g/L～10g/L, COD for the high concentrated organic wastewater that leaches
crconcentration>=30000mg/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, COD
cradd-on be 17%～22% of nickel in anode and cathode mixed materials, cobalt, manganese total mass, the add-on of high concentrated organic wastewater adds by this calculating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736485.6A CN103757298A (en) | 2013-12-29 | 2013-12-29 | Method for leaching positive-negative pole material mixture of waste lithium nickel cobalt manganese oxide battery |
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|---|---|---|---|
| CN201310736485.6A CN103757298A (en) | 2013-12-29 | 2013-12-29 | Method for leaching positive-negative pole material mixture of waste lithium nickel cobalt manganese oxide battery |
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| Publication Number | Publication Date |
|---|---|
| CN103757298A true CN103757298A (en) | 2014-04-30 |
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|---|---|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619394A (en) * | 2009-06-23 | 2010-01-06 | 四川师范大学 | Method for leaching anode and cathode mixed material of waste lithium nickel manganese cobalt battery |
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2013
- 2013-12-29 CN CN201310736485.6A patent/CN103757298A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619394A (en) * | 2009-06-23 | 2010-01-06 | 四川师范大学 | Method for leaching anode and cathode mixed material of waste lithium nickel manganese cobalt battery |
Non-Patent Citations (1)
| Title |
|---|
| 粟海锋等: "硫酸-糖蜜酒精废液浸出锰矿的工艺研究", 《高校化学工程学报》 * |
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Application publication date: 20140430 |