CN108011149B - A method of the Call Provision nickel lithium from discarded power battery - Google Patents
A method of the Call Provision nickel lithium from discarded power battery Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
- 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
- C22B7/007—Wet processes by acid leaching
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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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- 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
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
A method of the Call Provision nickel lithium from discarded power battery, steps are as follows: discarded power battery is discharged；Dismantling, is impregnated and is carried out using N-Methyl pyrrolidone ultrasonication, by screening, washing, drying, ball milling, obtain valuable metal recovery material；It is leached using gluconic acid and hydrochloric acid, and hydrogen peroxide is added as reducing agent；Sodium sulfide solution is added in leachate and is passed through hydrogen sulfide gas and carries out copper removal；Solution extraction and recovery Co after decopper(ing)；Raffinate recycles Ni；Li is recycled after distillation.It is at low cost, method is simple, recovery rate of valuable metals is high using this method.
Description
Technical field
The present invention relates to a kind of recovery methods of discarded metal, and in particular to one kind Call Provision nickel from discarded power battery
The method of lithium.
Background technique
With popularizing for automobile, people significantly promote the demand of petroleum, while making facing to motor vehicle exhaust emission
At problem of environmental pollution, environmental pollution have become currently has in face of and urgent problem.Lithium ion battery is ratio
Comparatively ideal power source, therefore electric car and mixed electric car have obtained the attention of more and more national, have now
A plurality of electric cars using lithium ion battery as the energy come out.The demand of power battery sharply increases, wherein to power is scrapped
The recovery processing of battery seems more more and more urgent.Contain Ni, Co, a variety of valuable metals of Li et al. in discarded power battery, contains
Heavy metal, electrolyte can all cause natural environment greatly to destroy.Its a variety of valuable metal contained, which has, greatly to return
Receive value and space.In face of the recycling of huge discarded power battery, China achieves in power battery recovery technology
Achievement, the recovery technology for studying discarded power battery make the valuable metal in waste battery be utilized effectively, both avoid providing
Source waste protects environment again.
Summary of the invention
The object of the present invention is to provide it is a kind of it is at low cost, method is simple, recovery rate of valuable metals is high from discarded power electric
The method of Call Provision nickel lithium in pond, steps are as follows:
(1) discarded power battery is discharged to 1.5-2V under constant current conditions, places 20-50min, is continued constant
It is discharged to 0.8-1.2V under current condition, places 20-50min, the discarded power battery for being discharged to 0.8-1.2V is put into concentration
It to impregnate 1-5h in the NaCl solution of 3-10mol/L, takes out and in 20-80 DEG C of drying 1-5h, that is discharged completely discarded moves
Power battery；
(2) the discarded power battery of discharging completely of obtaining of step (1) is disassembled, positive plate obtained in it is cut into
Sheet impregnates according to the per kilogram positive plate N-Methyl pyrrolidone of 10-30L at 30-100 DEG C, and carries out ultrasonication
0.5-3h, by filtering, sieving removal aluminium foil, be washed with deionized, dry again, drying temperature is 100-300 DEG C, when dry
Between be 1-5h, then at 60-80 DEG C, vacuum degree carries out ball milling 1-5h under the conditions of being 0.05-0.1MPa, obtains valuable metal recovery
Material；
(3) the valuable metal recovery material for obtaining step (2) uses the gluconic acid and 0.2-3mol/L of 0.2-3mol/L
Hydrochloric acid leached, solid-to-liquid ratio 15-35g/L, and hydrogen peroxide is added as reducing agent, extraction temperature is 50-100 DEG C, leaching
The time is 1-6h, stirring rate 100-900r/min out, is separated by solid-liquid separation, obtains leachate and leached mud；
(4) leached mud for obtaining step (3) is leached using the sulfuric acid solution of 0.5-3mol/L, the leaching that sulfuric acid leaching obtains
It is after 4-6 removes impurity A l, Fe, to precipitate to obtain manganese carbonate using carbonic acid or sodium carbonate that liquid, which adjusts pH value with alkali, out；
(5) sodium sulfide solution that 0.5-3mol/L is added in leachate that step (3) obtains is cleaned, removal of impurities it is same
When according to the amount that every liter of leachate is passed through 0.1-1L be per minute passed through hydrogen sulfide gas, obtain copper sulfide precipitation, be obtained by filtration de-
Solution after copper；
(6) pH value of the solution after the decopper(ing) for obtaining step (5) is adjusted to 3-5, and P507 is used to be extracted as extractant
It takes, is 1-3 ︰ 1-3 compared to O/A, extraction temperature is 30-50 DEG C, extraction time 10-120min, stands 5-20min, then uses
The sulfuric acid solution of 150-210g/L is stripped, and is 1-3 ︰ 1-3 compared to O/A, back extraction temperature is 30-50 DEG C, and back-extraction time is
10-120min stands 5-20min, and saturated oxalic acid solution is added into strip liquor, at 40-70 DEG C, stirs 20-50min, stirring
Rate is 100-300r/min, will be separated by solid-liquid separation obtained sediment and is washed with deionized 1-5 times, in 70-90 DEG C of dry 1-
Then 10h obtains cobalt oxide in 300-700 DEG C of calcining；
(7) pH value of the raffinate of step (6) is adjusted to 2-5, the sulfuric acid solution of 1-3mol/L is added, is warming up to 60-
90 DEG C, nickel sulfate crystal seed is added, cools to 30-45 DEG C in the case where vacuum degree is 0.05-0.08MPa, vacuum filtration, in 80-120
Nickel sulfate is dried to obtain at DEG C；
(8) filtrate that step (7) vacuum filtration obtains is subjected to distillation removal of impurities, carbonic acid or carbonic acid is then added into solution
Sodium obtains lithium carbonate.
Further, in step (1), the concentration of NaCl solution is 5-6mol/L；
Further, in step (1), the concentration of NaCl solution is 6mol/L.
Further, it in step (3), is leached using the gluconic acid of 1mol/L.
Further, it in step (6), is stripped with the sulfuric acid solution of 160-180g/L.
Further, in step (7), the pH value of raffinate is adjusted to 4.
Charging method of the invention makes the electric discharge of discarded power battery thorough.It is impregnated by N-Methyl pyrrolidone, is super
Sonicated, vacuum ball milling, so that valuable metal recovery material increased activity, is conducive to subsequent leaching recycling, improves leaching rate.
Gluconic acid and hydrochloric acid, which leach, substantially increases leaching rate.Extraction of the invention also improves the rate of recovery of cobalt nickel.Using
Vulcanized sodium and hydrogen sulfide mixing copper removal, improve dust removal rate.Using method of the invention, the rate of recovery of Co, Ni, Li exist respectively
92%, 95%, 97% or more.
Specific embodiment
The present invention will be further described below with reference to examples, it should be noted that embodiment is not constituted to the present invention
The limitation of claimed range.
Embodiment 1
A method of the Call Provision nickel lithium from from discarded power battery, steps are as follows:
(1) discarded power battery is discharged to 1.5V under constant current conditions, places 20min, is continued in constant current
Under the conditions of be discharged to 0.8V, place 20min, it is molten that the discarded power battery for being discharged to 0.8V is put into the NaCl that concentration is 3mol/L
1h is impregnated in liquid, is taken out and in 20 DEG C of drying 1h, the discarded power battery to be discharged completely；
(2) the discarded power battery of discharging completely of obtaining of step (1) is disassembled, positive plate obtained in it is cut into
Sheet impregnates according to the per kilogram positive plate N-Methyl pyrrolidone of 10L at 30 DEG C, and carries out ultrasonication 0.5h, passes through
Filtering, is washed with deionized again, dries screening removal aluminium foil, and drying temperature is 100 DEG C, then drying time 1h exists
60 DEG C, vacuum degree carries out ball milling 1h under the conditions of being 0.05MPa, obtains valuable metal recovery material；
(3) the valuable metal recovery material for obtaining step (2) is using the gluconic acid of 0.2mol/L and the salt of 0.2mol/L
Acid is leached, solid-to-liquid ratio 15g/L, and hydrogen peroxide is added as reducing agent, and extraction temperature is 50 DEG C, extraction time 1h,
Stirring rate is 100r/min, is separated by solid-liquid separation, obtains leachate and leached mud；
(4) leached mud for obtaining step (3) is leached using the sulfuric acid solution of 0.5mol/L, the leaching that sulfuric acid leaching obtains
After liquid alkali adjusts pH value as 4 removing impurity A l, Fe, precipitate to obtain manganese carbonate using carbonic acid or sodium carbonate；
(5) sodium sulfide solution that 0.5mol/L is added in leachate that step (3) obtains is cleaned, while removal of impurities
It is passed through hydrogen sulfide gas according to the amount that every liter of leachate is passed through 0.1L per minute, copper sulfide precipitation is obtained, after decopper(ing) is obtained by filtration
Solution；
(6) pH value of the solution after the decopper(ing) for obtaining step (5) is adjusted to 3, and P507 is used to be extracted as extractant,
It is 1 ︰ 1 compared to O/A, extraction temperature is 30 DEG C, extraction time 10min, stands 5min, then anti-with the sulfuric acid solution of 150g/L
Extraction is 1 ︰ 1 compared to O/A, and back extraction temperature is 30 DEG C, back-extraction time 10min, stands 5min, is added into strip liquor
Saturated oxalic acid solution stirs 20min, stirring rate 100r/min at 40 DEG C, will be separated by solid-liquid separation obtained sediment spend from
Then sub- water washing 1 time obtains cobalt oxide in 300 DEG C of calcinings in 70 DEG C of dry 1h；
(7) pH value of the raffinate of step (6) is adjusted to 2, the sulfuric acid solution of 1mol/L is added, be warming up to 60 DEG C, then
Nickel sulfate crystal seed is added, cools to 30 DEG C in the case where vacuum degree is 0.05MPa, vacuum filtration is dried to obtain nickel sulfate at 80 DEG C；
(8) filtrate that step (7) vacuum filtration obtains is subjected to distillation removal of impurities, carbonic acid or carbonic acid is then added into solution
Sodium obtains lithium carbonate.
Embodiment 2
A method of the Call Provision nickel lithium from from discarded power battery, steps are as follows:
(1) discarded power battery is discharged to 2V under constant current conditions, places 50min, is continued in constant current item
It is discharged to 1.2V under part, places 50min, it is molten that the discarded power battery for being discharged to 1.2V is put into the NaCl that concentration is 10mol/L
5h is impregnated in liquid, is taken out and in 80 DEG C of drying 5h, the discarded power battery to be discharged completely；
(2) the discarded power battery of discharging completely of obtaining of step (1) is disassembled, positive plate obtained in it is cut into
Sheet impregnates according to the per kilogram positive plate N-Methyl pyrrolidone of 30L at 100 DEG C, and carries out ultrasonication 3h, passes through
Filtering, is washed with deionized again, dries screening removal aluminium foil, and drying temperature is 300 DEG C, drying time 5h, then 80
DEG C, vacuum degree carries out ball milling 5h under the conditions of being 0.1MPa, obtains valuable metal recovery material；
(3) the valuable metal recovery material for obtaining step (2) using 3mol/L gluconic acid and 3mol/L hydrochloric acid into
Row leaches, solid-to-liquid ratio 35g/L, and hydrogen peroxide is added as reducing agent, and extraction temperature is 100 DEG C, extraction time 6h, stirring
Rate is 900r/min, is separated by solid-liquid separation, obtains leachate and leached mud；
(4) leached mud for obtaining step (3) is leached using the sulfuric acid solution of 3mol/L, the leachate that sulfuric acid leaching obtains
After adjusting pH value with alkali as 6 removing impurity A l, Fe, precipitate to obtain manganese carbonate using carbonic acid or sodium carbonate；
(5) sodium sulfide solution that 3mol/L is added in leachate that step (3) obtains is cleaned, removal of impurities while presses
The amount for being passed through 1L per minute according to every liter of leachate is passed through hydrogen sulfide gas, obtains copper sulfide precipitation, molten after decopper(ing) is obtained by filtration
Liquid；
(6) pH value of the solution after the decopper(ing) for obtaining step (5) is adjusted to 5, and P507 is used to be extracted as extractant,
It is 1 ︰ 3 compared to O/A, extraction temperature is 50 DEG C, extraction time 120min, stands 20min, then uses the sulfuric acid solution of 210g/L
Back extraction is 1 ︰ 3 compared to O/A, and back extraction temperature is 50 DEG C, back-extraction time 120min, 20min is stood, into strip liquor
Saturated oxalic acid solution is added, at 70 DEG C, stirs 50min, stirring rate 300r/min, obtained sediment will be separated by solid-liquid separation and used
Deionized water is washed 5 times, in 90 DEG C of dry 10h, then obtains cobalt oxide in 700 DEG C of calcinings；
(7) pH value of the raffinate of step (6) is adjusted to 5, the sulfuric acid solution of 3mol/L is added, be warming up to 90 DEG C, then
Nickel sulfate crystal seed is added, cools to 45 DEG C in the case where vacuum degree is 0.08MPa, vacuum filtration is dried to obtain sulfuric acid at 120 DEG C
Nickel；
(8) filtrate that step (7) vacuum filtration obtains is subjected to distillation removal of impurities, carbonic acid or carbonic acid is then added into solution
Sodium obtains lithium carbonate.
Embodiment 3
A method of the Call Provision nickel lithium from from discarded power battery, steps are as follows:
(1) discarded power battery is discharged to 1.6V under constant current conditions, places 30min, is continued in constant current
Under the conditions of be discharged to 0.9V, place 30min, it is molten that the discarded power battery for being discharged to 0.9V is put into the NaCl that concentration is 5mol/L
2h is impregnated in liquid, is taken out and in 40 DEG C of drying 2h, the discarded power battery to be discharged completely；
(2) the discarded power battery of discharging completely of obtaining of step (1) is disassembled, positive plate obtained in it is cut into
Sheet impregnates according to the per kilogram positive plate N-Methyl pyrrolidone of 15L at 40 DEG C, and carries out ultrasonication 1h, passes through
Filtering, is washed with deionized again, dries screening removal aluminium foil, and drying temperature is 150 DEG C, drying time 2h, then 65
DEG C, vacuum degree carries out ball milling 2h under the conditions of being 0.06MPa, obtains valuable metal recovery material；
(3) the valuable metal recovery material for obtaining step (2) is using the gluconic acid of 0.8mol/L and the salt of 0.8mol/L
Acid is leached, solid-to-liquid ratio 20g/L, and hydrogen peroxide is added as reducing agent, and extraction temperature is 60 DEG C, extraction time 2h,
Stirring rate is 300r/min, is separated by solid-liquid separation, obtains leachate and leached mud；
(4) leached mud for obtaining step (3) is leached using the sulfuric acid solution of 1mol/L, the leachate that sulfuric acid leaching obtains
After adjusting pH value with alkali as 5 removing impurity A l, Fe, precipitate to obtain manganese carbonate using carbonic acid or sodium carbonate；
(5) sodium sulfide solution that 1mol/L is added in leachate that step (3) obtains is cleaned, removal of impurities while presses
The amount for being passed through 0.5L per minute according to every liter of leachate is passed through hydrogen sulfide gas, obtains copper sulfide precipitation, after decopper(ing) is obtained by filtration
Solution；
(6) pH value of the solution after the decopper(ing) for obtaining step (5) is adjusted to 4, and P507 is used to be extracted as extractant,
It is 3 ︰ 1 compared to O/A, extraction temperature is 35 DEG C, extraction time 50min, stands 10min, then uses the sulfuric acid solution of 180g/L
Back extraction, comparing O/A is 3 ︰ 1, and back extraction temperature is 35 DEG C, back-extraction time 50min, stands 10min, adds into strip liquor
Enter saturated oxalic acid solution, at 50 DEG C, stir 30min, stirring rate 150r/min, obtained sediment will be separated by solid-liquid separation and spent
Ion water washing 2 times, in 75 DEG C of dry 3h, cobalt oxide then is obtained in 400 DEG C of calcinings；
(7) pH value of the raffinate of step (6) is adjusted to 4, the sulfuric acid solution of 2mol/L is added, be warming up to 70 DEG C, then
Nickel sulfate crystal seed is added, cools to 35 DEG C in the case where vacuum degree is 0.06MPa, vacuum filtration is dried to obtain nickel sulfate at 90 DEG C；
(8) filtrate that step (7) vacuum filtration obtains is subjected to distillation removal of impurities, carbonic acid or carbonic acid is then added into solution
Sodium obtains lithium carbonate.
Embodiment 4
A method of the Call Provision nickel lithium from from discarded power battery, steps are as follows:
(1) discarded power battery is discharged to 1.8V under constant current conditions, places 40min, is continued in constant current
Under the conditions of be discharged to 1.1V, place 40min, it is molten that the discarded power battery for being discharged to 1.1V is put into the NaCl that concentration is 8mol/L
4h is impregnated in liquid, is taken out and in 70 DEG C of drying 4h, the discarded power battery to be discharged completely；
(2) the discarded power battery of discharging completely of obtaining of step (1) is disassembled, positive plate obtained in it is cut into
Sheet impregnates according to the per kilogram positive plate N-Methyl pyrrolidone of 25L at 80 DEG C, and carries out ultrasonication 2h, passes through
Filtering, is washed with deionized again, dries screening removal aluminium foil, and drying temperature is 200 DEG C, drying time 4h, then 70
DEG C, vacuum degree carries out ball milling 4h under the conditions of being 0.09MPa, obtains valuable metal recovery material；
(3) the valuable metal recovery material for obtaining step (2) using 2mol/L gluconic acid and 2mol/L hydrochloric acid into
Row leaches, solid-to-liquid ratio 30g/L, and hydrogen peroxide is added as reducing agent, and extraction temperature is 90 DEG C, extraction time 5h, stirring
Rate is 700r/min, is separated by solid-liquid separation, obtains leachate and leached mud；
(4) leached mud for obtaining step (3) is leached using the sulfuric acid solution of 2mol/L, the leachate that sulfuric acid leaching obtains
After adjusting pH value with alkali as 5 removing impurity A l, Fe, precipitate to obtain manganese carbonate using carbonic acid or sodium carbonate；
(5) sodium sulfide solution that 2mol/L is added in leachate that step (3) obtains is cleaned, removal of impurities while presses
The amount for being passed through 0.8L per minute according to every liter of leachate is passed through hydrogen sulfide gas, obtains copper sulfide precipitation, after decopper(ing) is obtained by filtration
Solution；
(6) pH value of the solution after the decopper(ing) for obtaining step (5) is adjusted to 4, and P507 is used to be extracted as extractant,
It is 2 ︰ 1 compared to O/A, extraction temperature is 40 DEG C, extraction time 90min, stands 15min, then uses the sulfuric acid solution of 190g/L
Back extraction, comparing O/A is 2 ︰ 1, and back extraction temperature is 40 DEG C, back-extraction time 90min, stands 15min, adds into strip liquor
Enter saturated oxalic acid solution, at 60 DEG C, stir 40min, stirring rate 200r/min, obtained sediment will be separated by solid-liquid separation and spent
Ion water washing 4 times, in 85 DEG C of dry 8h, cobalt oxide then is obtained in 600 DEG C of calcinings；
(7) pH value of the raffinate of step (6) is adjusted to 4, the sulfuric acid solution of 2mol/L is added, be warming up to 80 DEG C, then
Nickel sulfate crystal seed is added, cools to 40 DEG C in the case where vacuum degree is 0.07MPa, vacuum filtration is dried to obtain nickel sulfate at 90 DEG C；
(8) filtrate that step (7) vacuum filtration obtains is subjected to distillation removal of impurities, carbonic acid or carbonic acid is then added into solution
Sodium obtains lithium carbonate.
Claims (6)
1. a kind of method of the Call Provision nickel lithium from discarded power battery, which is characterized in that steps are as follows:
(1) discarded power battery is discharged to 1.5-2V under constant current conditions, places 20-50min, is continued in constant current
Under the conditions of be discharged to 0.8-1.2V, place 20-50min, it is 3- that the discarded power battery for being discharged to 0.8-1.2V, which is put into concentration,
1-5h is impregnated in the NaCl solution of 10mol/L, is taken out and in 20-80 DEG C of drying 1-5h, the discarded power electric to be discharged completely
Pond；
(2) the discarded power battery of discharging completely of obtaining of step (1) is disassembled, by positive plate obtained in it, is cut into sheet,
It is impregnated at 30-100 DEG C according to the per kilogram positive plate N-Methyl pyrrolidone of 10-30L, and carries out ultrasonication 0.5-
3h, by filtering, sieving removal aluminium foil, be washed with deionized, dry again, drying temperature is 100-300 DEG C, and drying time is
1-5h, then at 60-80 DEG C, vacuum degree carries out ball milling 1-5h under the conditions of being 0.05-0.1MPa, obtains valuable metal recovery material；
(3) the valuable metal recovery material for obtaining step (2) is using the gluconic acid of 0.2-3mol/L and the salt of 0.2-3mol/L
Acid is leached, solid-to-liquid ratio 15-35g/L, and hydrogen peroxide is added as reducing agent, and extraction temperature is 50-100 DEG C, when leaching
Between be 1-6h, stirring rate 100-900r/min, be separated by solid-liquid separation, obtain leachate and leached mud；
(4) leached mud for obtaining step (3) is leached using the sulfuric acid solution of 0.5-3mol/L, the leachate that sulfuric acid leaching obtains
Adjusting pH value with alkali is after 4-6 removes impurity A l, Fe, to precipitate to obtain manganese carbonate using carbonic acid or sodium carbonate；
(5) sodium sulfide solution that 0.5-3mol/L is added in leachate that step (3) obtains is cleaned, removal of impurities while presses
The amount for being passed through 0.1-1L per minute according to every liter of leachate is passed through hydrogen sulfide gas, obtains copper sulfide precipitation, after decopper(ing) is obtained by filtration
Solution；
(6) pH value of the solution after the decopper(ing) for obtaining step (5) is adjusted to 3-5, uses P507 to be extracted as extractant, phase
It is that (1-3) ︰ (1-3), extraction temperature are 30-50 DEG C, extraction time 10-120min, stand 5-20min, then use than O/A
The sulfuric acid solution of 150-210g/L is stripped, and is that (1-3) ︰ (1-3), back extraction temperature are 30-50 DEG C, when back extraction compared to O/A
Between be 10-120min, stand 5-20min, into strip liquor be added saturated oxalic acid solution, at 40-70 DEG C, stir 20-50min,
Stirring rate is 100-300r/min, will be separated by solid-liquid separation obtained sediment and is washed with deionized 1-5 times, dry at 70-90 DEG C
Then dry 1-10h obtains cobalt oxide in 300-700 DEG C of calcining；
(7) pH value of the raffinate of step (6) is adjusted to 2-5, the sulfuric acid solution of 1-3mol/L is added, is warming up to 60-90 DEG C,
Nickel sulfate crystal seed is added, cools to 30-45 DEG C in the case where vacuum degree is 0.05-0.08MPa, vacuum filtration, at 80-120 DEG C
It is dried to obtain nickel sulfate；
(8) filtrate that step (7) vacuum filtration obtains is subjected to distillation removal of impurities, carbonic acid or sodium carbonate is then added into solution,
Obtain lithium carbonate.
2. as described in claim 1 from discarded power battery Call Provision nickel lithium method, which is characterized in that in step (1),
The concentration of NaCl solution is 5-6mol/L.
3. such as the method for the described in any item Call Provision nickel lithiums from discarded power battery of claim 1-2, which is characterized in that step
Suddenly in (1), the concentration of NaCl solution is 6mol/L.
4. as described in claim 1 from discarded power battery Call Provision nickel lithium method, which is characterized in that in step (3),
It is leached using the gluconic acid of 1mol/L.
5. as described in claim 1 from discarded power battery Call Provision nickel lithium method, which is characterized in that in step (6),
It is stripped with the sulfuric acid solution of 160-180g/L.
6. as described in claim 1 from discarded power battery Call Provision nickel lithium method, which is characterized in that in step (7),
The pH value of raffinate is adjusted to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711259460.6A CN108011149B (en) | 2017-12-04 | 2017-12-04 | A method of the Call Provision nickel lithium from discarded power battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711259460.6A CN108011149B (en) | 2017-12-04 | 2017-12-04 | A method of the Call Provision nickel lithium from discarded power battery |
Publications (2)
| Publication Number | Publication Date |
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| CN108011149A CN108011149A (en) | 2018-05-08 |
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| CN108728650A (en) * | 2018-05-30 | 2018-11-02 | 嘉兴星创科技有限公司 | A method of recycling lithium from old and useless battery |
| CN109244579B (en) * | 2018-09-18 | 2020-07-03 | 余姚市鑫和电池材料有限公司 | Preparation method of ternary precursor powder with high specific surface area |
| CN110649344A (en) * | 2019-09-12 | 2020-01-03 | 金川集团股份有限公司 | Method for separating and recycling electrolyte in waste power lithium battery by using ultrasonic enhanced extraction method |
| JP7156491B1 (en) * | 2021-04-22 | 2022-10-19 | 住友金属鉱山株式会社 | Method for producing cobalt sulfate |
| CN113621819B (en) * | 2021-07-21 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for extracting valuable metals from low-grade nickel matte converter slag |
| CN113846219B (en) * | 2021-09-06 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for extracting lithium from waste lithium batteries |
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| CN104157926A (en) * | 2014-08-07 | 2014-11-19 | 柳州市生产力促进中心 | Technology for recovering lithium batteries |
| CN105206889B (en) * | 2015-07-29 | 2018-10-26 | 浙江三晟化工有限公司 | A kind of processing method of waste and old nickle cobalt lithium manganate ternary cell positive material |
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