CN110042252A - A method of scrapping the recycling of nickel-metal hydride battery valuable metal element - Google Patents
A method of scrapping the recycling of nickel-metal hydride battery valuable metal element Download PDFInfo
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- CN110042252A CN110042252A CN201910459039.2A CN201910459039A CN110042252A CN 110042252 A CN110042252 A CN 110042252A CN 201910459039 A CN201910459039 A CN 201910459039A CN 110042252 A CN110042252 A CN 110042252A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention belongs to solid waste field of comprehensive utilization, and in particular to a method of scrap the recycling of nickel-metal hydride battery valuable metal element.Nickel, cobalt and rare earth element is separately recovered after sulfating roasting, water dissolution, extraction, back extraction, rare-earth precipitation after nickel-metal hydride battery pre-processes the method includes that will scrap.The method of the invention uses sulfating roasting waste nickel-hydrogen battery powder, then the sulfate of water dissolved cobalt nickel rare earth；With directly with sulfuric acid leaching waste nickel-hydrogen battery powder compared with, reduce water and acid consumption；Also, the method for the invention, which realizes, scraps nickel-metal hydride battery valuable metal full constituent green high-efficient recycling nickel, cobalt and rare earth element, and tail washings, which realizes, to be recycled, no discharge.
Description
Technical field
The invention belongs to solid waste field of comprehensive utilization, and in particular to a kind of to scrap what nickel-metal hydride battery valuable metal element recycled
Method.
Background technique
Nickel-metal hydride battery is a kind of new chemical battery to grow up the 1990s, and positive electrode is hydroxide
Nickel, negative electrode material contain the elements such as Co, Ni, rare earth, have the characteristics that the high-energy, long-life, pollution-free, are widely used in
Electronics and automobile industry, consumption increase year by year, while the nickel-metal hydride battery of scrapping generated is also gradually increasing, and such as handles it
It is improper, it will cause that environmental pollution is serious, the valuable metals such as Co, Ni and rare earth largely lose, therefore nickel-metal hydride battery is scrapped in recycling, no
Only there is significant environmental benefit, also there is certain economic benefit and social benefit.
The recovery method for scrapping nickel-metal hydride battery at present mainly has pyrogenic process and wet process.Wet process is mostly that acid medium leaches, and is passed through
Filter separation and Extraction different metal.Waste battery fragment is fired by pyrogenic process, is separated from the gas, flue gas, smelting slag of discharge
It purifies metals.Chinese invention patent (application number 201110173754.3) discloses one kind and recycles metal from waste nickel hydrogen battery
Method, nickel-metal hydride battery is discharged, is crushed, is sieved, magnetic separation, heat treatment and melting process, to obtain iron nickel base alloy, nickel
Based alloy and high-grade rare earth oxide, this method treating capacity is big, but it requires strictly calcination atmosphere, and equipment energy consumption
It is higher.Chinese invention patent (application number 201110304896.9) discloses metallic element recycling side in a kind of waste nickel hydrogen battery
Method, after waste nickel hydrogen battery reduction roasting, metal is recycled in the Oxidation Leaching in acid medium, extraction.This method nickel and cobalt recovery
Rate is high, but Extraction of rare eart process is cumbersome and the rate of recovery is low, and acid consumption is big, wastewater flow rate is big, and environmental pollution is serious.Chinese invention patent
A kind of method that (application number 201610708390.7) discloses the recovering rare earth from waste nickel hydrogen battery and make the transition, will be waste and old
Sulfuric acid leaching is carried out after nickel-metal hydride battery is broken, separation of solid and liquid, sodium sulphate precipitating, secondary is separated by solid-liquid separation, again through sulfuric acid rare earth double salt
Carbonated rare earth precipitating is obtained after processing, this method cooperates with leaching, recovering rare earth element with hydrogen peroxide using sulfuric acid, and every kg scraps nickel
Hydrogen battery powder needs 12-18 mol sulfuric acid dissolution, and acid consumption is big, and wastewater flow rate is big.Chinese invention patent (application number
201710097235.0) a kind of method that valuable metal is recycled from waste nickel hydrogen battery is disclosed, by nickel-metal hydride battery, reduction
Agent, vulcanizing agent and slag former mixing are roasted, and nickel, cobalt, iron is made to form sulfide, and rare earth element forms compound, this method
Without to nickel-metal hydride battery carry out pulverization process, but subsequent extracted metal sulfide separation and Extraction generate sulfur oxide contamination, cobalt,
The separation and Extractions such as nickel, rare earth are difficult.
To sum up, the existing technology that valuable metal is recycled from waste nickel hydrogen battery, complex procedures, material consumption energy consumption is high, ring
Border is seriously polluted.Therefore, the method that valuable metal element in nickel-metal hydride battery is scrapped in research and development green high-efficient recycling is needed.
Summary of the invention
In view of the above technical problems, the invention discloses it is a kind of scrap nickel-metal hydride battery valuable metal element recycling method,
This method will scrap the techniques such as nickel-metal hydride battery preprocessed (electric discharge is crushed), sulfating roasting, water dissolution and solve in the prior art
The problems such as metal recovery rate is low, and treatment process is seriously polluted, and sulfuric acid consumption is big, and energy consumption is higher.
The present invention is achieved by the following technical solutions:
A method of scrapping the recycling of nickel-metal hydride battery valuable metal element, which comprises
Scrap nickel-metal hydride battery pretreatment: will scrap more than nickel-metal hydride battery after discharge of electricity, disassembled, it is broken after obtain waste nickel-hydrogen battery powder
And steel shell；
Sulfating roasting: after the waste nickel-hydrogen battery powder and sulfuric acid are proportionally mixed, sulfating roasting is carried out；
Water dissolution: water dissolution, filtering are carried out to the product after sulfating roasting, obtain leached mud and leachate；
Extraction and back extraction: the leachate is extracted using extractant, nickel element and cobalt element is made to be enriched in organic phase
In, rare earth element is enriched in extraction extraction raffinate；Then the pregnant solution of nickeliferous cobalt element, extraction are obtained with acid solution back extraction organic phase
Agent is back to nickel cobalt extraction；
Rare earth element precipitating: oxalic rare earth precipitates and filtrate are obtained after oxalic acid precipitation, filtering is added into the extraction extraction raffinate；Filter
Liquid is back to water dissolution.
Further, the sulfating roasting are as follows: the concentrated sulfuric acid that dry waste nickel-hydrogen battery powder and concentration are 98wt% exists
10 ~ 120min is roasted at 150 DEG C ~ 800 DEG C, concentrated sulfuric acid additional amount is 1.0-1.1 times for chemically reacting stoichiometric number.
Further, the condition control of the water dissolution are as follows: sulfating roasting product, water and the sulfuric acid are dissolved using water
The liquid-solid ratio for changing product of roasting is 5 ~ 20 (L/kg), water-soluble 15 ~ 180min at 20 ~ 100 DEG C.
Further, in the step of rare earth element precipitates, oxalic acid precipitation rare earth, oxalic acid is added into extraction extraction raffinate
Additional amount is 1.1-1.5 times for chemically reacting stoichiometric number, and the reaction time is 5 ~ 90min, and oxalic rare earth precipitates are obtained after filtering, dilute
The earth elements rate of recovery is 99% or more.
The principle of the present invention is as follows:
(1) scrapping nickel-metal hydride battery sulfating roasting makes Ni (OH) in battery powder2、Co3O4, rare earth element (RE) etc. be converted into phase
The sulfate answered is conducive to subsequent Leach reaction；It reacts as follows:
Ni(OH)2+H2SO4=NiSO4+2H2O (1)
2Co3O4+6H2SO4=6CoSO4+O2↑+6H2O (2)
2RE(OH)3+3H2SO4=RE2(SO4)3+6H2O (3)
(2) with the sulfate of water dissolution nickel cobalt rare earth；
(3) nickel cobalt sulfate is enriched in organic phase with extractant, rare earth sulfate enters water phase extraction extraction raffinate；Organic phase warp
Back extraction obtains nickel cobalt pregnant solution；The method of the invention realizes nickel cobalt using extraction leachate and separates with the accurate of rare earth, instead
Extracting and enriching nickel cobalt element.
(4) oxalic acid is added into extraction extraction raffinate, precipitating rare earth, reaction equation is as follows:
2RE3++3H2C2O4+xH2O=RE2(C2O4)3·xH2O↓+6H+(4)
Wherein, the present invention uses oxalic acid precipitation rare earth, and rare earth yield is high, up to 99% or more.
Advantageous effects of the invention:
(1) the method for the invention uses sulfating roasting waste nickel-hydrogen battery powder, then the sulfate of water dissolved cobalt nickel rare earth；With
It is directly compared with sulfuric acid leaching waste nickel-hydrogen battery powder, reduces the consumption of water and acid；
(2) the method for the invention, which realizes, scraps the extraction of nickel-metal hydride battery valuable metal full constituent green high-efficient, and tail washings realizes
It recycles, no discharge；
(3) present invention has the advantages that simple process, at low cost, pollution-free, applicability is wide, is easy to industrialize.
Detailed description of the invention
Fig. 1 is a kind of process signal for the method for scrapping the recycling of nickel-metal hydride battery valuable metal element in the embodiment of the present invention
Figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is explained in further detail.It should be appreciated that described herein, the specific embodiments are only for explaining the present invention, not
For limiting the present invention.
On the contrary, the present invention covers any substitution done on the essence and scope of the present invention being defined by the claims, repairs
Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to of the invention thin
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
The present invention can also be understood completely in description.
Embodiment 1
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 350 DEG C of roasting 98min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 8(L/kg by liquid-solid ratio) nickel is obtained in 100 DEG C of water dissolution 18min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.1 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 90min, passes through
Filter obtains rare earth oxalate and filtrate, and rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 2
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 800 DEG C of roasting 10min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 5(L/kg by liquid-solid ratio) dissolving 30min in 98 DEG C of water, to obtain nickel cobalt dilute
The sulfate liquor of soil；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth be enriched in extraction extraction raffinate in；So
It is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid afterwards, extractant is back to extraction process；Grass is added into extraction extraction raffinate
Acid obtains oxalic rare earth precipitates, and consumption of oxalic acid is 1.12 times that sulfuric acid rare earth chemically reacts stoichiometric number, 85min is reacted, through filtering
Obtain rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 3
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 750 DEG C of roasting 15min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.02 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 6(L/kg by liquid-solid ratio) nickel is obtained in 95 DEG C of water dissolution 40min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.16 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 70min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 4
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 700 DEG C of roasting 20min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.03 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 7(L/kg by liquid-solid ratio) nickel is obtained in 90 DEG C of water dissolution 50min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.2 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 60min, passes through
Filter obtains rare earth oxalate and filtrate, and rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 5
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 650 DEG C of roasting 25min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.04 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 9(L/kg by liquid-solid ratio) nickel is obtained in 50 DEG C of water dissolution 120min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.22 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 55min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 6
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 600 DEG C of roasting 35min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.05 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 12(L/kg by liquid-solid ratio) nickel is obtained in 85 DEG C of water dissolution 20min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.24 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 48min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 7
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 550 DEG C of roasting 40min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.06 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 13(L/kg by liquid-solid ratio) nickel is obtained in 80 DEG C of water dissolution 25min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.18 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 75min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 8
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 150 DEG C of roasting 120min after mixing, sulfuric acid dosage is the chemical reaction metering of waste nickel-hydrogen battery powder
Several 1.1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 14(L/kg by liquid-solid ratio) it is obtained in 20 DEG C of water dissolution 180min
The sulfate liquor of nickel cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in more than extraction
In liquid；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Into extraction extraction raffinate
Oxalic acid is added and obtains oxalic rare earth precipitates, consumption of oxalic acid is 1.28 times that sulfuric acid rare earth chemically reacts stoichiometric number, 45min is reacted,
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 9
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 200 DEG C of roasting 115min after mixing, sulfuric acid dosage is the chemical reaction metering of waste nickel-hydrogen battery powder
Several 1.08 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 20(L/kg by liquid-solid ratio) 170min is dissolved in 25 DEG C of water
Obtain the sulfate liquor of nickel cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction
In extraction raffinate；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；To extraction extraction raffinate
Middle addition oxalic acid obtains oxalic rare earth precipitates, and consumption of oxalic acid is 1.3 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 43min,
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 10
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 250 DEG C of roasting 110min after mixing, sulfuric acid dosage is the chemical reaction metering of waste nickel-hydrogen battery powder
Several 1.09 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 15(L/kg by liquid-solid ratio) 160min is dissolved in 30 DEG C of water
Obtain the sulfate liquor of nickel cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction
In extraction raffinate；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；To extraction extraction raffinate
Middle addition oxalic acid obtains oxalic rare earth precipitates, and consumption of oxalic acid is 1.35 times that sulfuric acid rare earth chemically reacts stoichiometric number, reaction
40min, is obtained by filtration rare earth oxalate and filtrate, and rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 11
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 300 DEG C of roasting 105min after mixing, sulfuric acid dosage is the chemical reaction metering of waste nickel-hydrogen battery powder
Several 1.07 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 19(L/kg by liquid-solid ratio) it is obtained in 99 DEG C of water dissolution 15min
The sulfate liquor of nickel cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in more than extraction
In liquid；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Into extraction extraction raffinate
Oxalic acid is added and obtains oxalic rare earth precipitates, consumption of oxalic acid is 1.38 times that sulfuric acid rare earth chemically reacts stoichiometric number, 37min is reacted,
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 12
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 350 DEG C of roasting 100min after mixing, sulfuric acid dosage is the chemical reaction metering of waste nickel-hydrogen battery powder
Several 1.06 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 16(L/kg by liquid-solid ratio) 150min is dissolved in 40 DEG C of water
Obtain the sulfate liquor of nickel cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction
In extraction raffinate；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；To extraction extraction raffinate
Middle addition oxalic acid obtains oxalic rare earth precipitates, and consumption of oxalic acid is 1.4 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 34min,
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 13
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 400 DEG C of roasting 96min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.05 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 17(L/kg by liquid-solid ratio) it is obtained in 35 DEG C of water dissolution 175min
The sulfate liquor of nickel cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in more than extraction
In liquid；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Into extraction extraction raffinate
Oxalic acid is added and obtains oxalic rare earth precipitates, consumption of oxalic acid is 1.41 times that sulfuric acid rare earth chemically reacts stoichiometric number, 30min is reacted,
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 14
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 450 DEG C of roasting 95min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 18(L/kg by liquid-solid ratio) nickel is obtained in 45 DEG C of water dissolution 140min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.42 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 24min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 15
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 500 DEG C of roasting 44min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.04 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 20(L/kg by liquid-solid ratio) nickel is obtained in 48 DEG C of water dissolution 80min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.43 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 20min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 16
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 480 DEG C of roasting 50min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.06 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 11(L/kg by liquid-solid ratio) nickel is obtained in 70 DEG C of water dissolution 60min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.44 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 18min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 17
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 420 DEG C of roasting 90min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 17(L/kg by liquid-solid ratio) nickel is obtained in 55 DEG C of water dissolution 160min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.45 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 14min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 18
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 470 DEG C of roasting 80min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.06 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 13(L/kg by liquid-solid ratio) nickel is obtained in 60 DEG C of water dissolution 70min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.46 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 13min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 19
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 475 DEG C of roasting 70min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1.07 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 20(L/kg by liquid-solid ratio) nickel is obtained in 47 DEG C of water dissolution 90min
The sulfate liquor of cobalt rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth is enriched in extraction extraction raffinate
In；Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；Add into extraction extraction raffinate
Enter oxalic acid and obtain oxalic rare earth precipitates, consumption of oxalic acid is 1.47 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 10min, warp
It is obtained by filtration rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 20
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 510 DEG C of roasting 60min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 20(L/kg by liquid-solid ratio) nickel cobalt is obtained in 55 DEG C of water dissolution 110min
The sulfate liquor of rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth be enriched in extraction extraction raffinate in；
Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；It is added into extraction extraction raffinate
Oxalic acid obtains oxalic rare earth precipitates, and consumption of oxalic acid is 1.48 times that sulfuric acid rare earth chemically reacts stoichiometric number, 8min is reacted, through filtering
Obtain rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 21
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 530 DEG C of roasting 55min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 8(L/kg by liquid-solid ratio) nickel cobalt is obtained in 50 DEG C of water dissolution 130min
The sulfate liquor of rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth be enriched in extraction extraction raffinate in；
Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；It is added into extraction extraction raffinate
Oxalic acid obtains oxalic rare earth precipitates, and consumption of oxalic acid is 1.49 times that sulfuric acid rare earth chemically reacts stoichiometric number, 6min is reacted, through filtering
Obtain rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 22
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 600 DEG C of roasting 45min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 6(L/kg by liquid-solid ratio) nickel cobalt is obtained in 60 DEG C of water dissolution 100min
The sulfate liquor of rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth be enriched in extraction extraction raffinate in；
Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；It is added into extraction extraction raffinate
Oxalic acid obtains oxalic rare earth precipitates, and consumption of oxalic acid is 1.5 times that sulfuric acid rare earth chemically reacts stoichiometric number, 5min is reacted, through filtering
Obtain rare earth oxalate and filtrate, rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Embodiment 23
By discharge of electricity more than waste nickel hydrogen battery, disassemble, pulverize and sieve after obtain waste nickel-hydrogen battery powder and steel shell；By the dense sulphur of 98wt%
Acid and waste nickel-hydrogen battery powder carry out 650 DEG C of roasting 30min after mixing, sulfuric acid dosage is that waste nickel-hydrogen battery powder chemically reacts stoichiometric number
1 times；The sulfating roasting product of nickel cobalt rare earth is obtained, is 11(L/kg by liquid-solid ratio) nickel cobalt is obtained in 75 DEG C of water dissolution 58min
The sulfate liquor of rare earth；Using extractant by nickel cobalt ion enrichment in organic phase, sulfuric acid rare earth be enriched in extraction extraction raffinate in；
Then it is stripped to obtain nickel cobalt pregnant solution and extractant using sulfuric acid, extractant is back to extraction process；It is added into extraction extraction raffinate
Oxalic acid obtains oxalic rare earth precipitates, and consumption of oxalic acid is 1.32 times that sulfuric acid rare earth chemically reacts stoichiometric number, reacts 41min, passes through
Filter obtains rare earth oxalate and filtrate, and rare earth yield is up to 99% or more；Filtrate recycle is in water dissolution process.
Claims (5)
1. a kind of method for scrapping the recycling of nickel-metal hydride battery valuable metal element, which is characterized in that the described method includes:
Scrap nickel-metal hydride battery pretreatment: will scrap more than nickel-metal hydride battery after discharge of electricity, disassembled, it is broken after obtain waste nickel-hydrogen battery powder
And steel shell；
Sulfating roasting: after the waste nickel-hydrogen battery powder and sulfuric acid are proportionally mixed, sulfating roasting is carried out；
Water dissolution: water dissolution, filtering are carried out to the product after sulfating roasting, obtain leached mud and leachate；
Extraction and back extraction: the leachate is extracted using extractant, nickel element and cobalt element is made to be enriched in organic phase
In, rare earth element is enriched in extraction extraction raffinate；Then the pregnant solution of nickeliferous cobalt element, extraction are obtained with acid solution back extraction organic phase
Agent is back to nickel cobalt extraction；
Rare earth element precipitating: oxalic rare earth precipitates and filtrate are obtained after oxalic acid precipitation, filtering is added into the extraction extraction raffinate；Filter
Liquid is back to water dissolution.
2. a kind of method for scrapping the recycling of nickel-metal hydride battery valuable metal element according to claim 1, which is characterized in that described
Sulfating roasting are as follows: the concentrated sulfuric acid that dry waste nickel-hydrogen battery powder and concentration are 98wt% is roasted 10 at 150 DEG C~800 DEG C
~120min, concentrated sulfuric acid additional amount are 1.0-1.1 times for chemically reacting stoichiometric number.
3. a kind of method for scrapping the recycling of nickel-metal hydride battery valuable metal element according to claim 1, which is characterized in that described
The condition control of water dissolution are as follows: using water dissolution sulfating roasting product, the liquid-solid ratio of water and the sulfating roasting product is 5
~20 (L/kg), water-soluble 15~180min at 20~100 DEG C.
4. a kind of method for scrapping the recycling of nickel-metal hydride battery valuable metal element according to claim 1, which is characterized in that in institute
In the step of stating rare earth element precipitating, oxalic acid precipitation rare earth is added into extraction extraction raffinate, oxalic acid additional amount is chemical reaction metering
Several 1.1-1.5 times, reaction time are 5~90min, and oxalic rare earth precipitates are obtained after filtering, and the rare earth element rate of recovery is 99%
More than.
5. a kind of method for scrapping the recycling of nickel-metal hydride battery valuable metal element according to claim 1, which is characterized in that described
The pretreated step of nickel-metal hydride battery is scrapped, specifically: nickel-metal hydride battery dismantling removal steel shell will be scrapped after electric discharge, is placed in crusher
It crushes, smashed material is subjected to wet screening, obtaining includes nickel, the particulate battery powder of cobalt and rare earth valuable metal element, so
Nickel-metal hydride battery powder is scrapped described in dry acquisition afterwards.
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