CN110066925A - The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium battery - Google Patents

The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium battery Download PDF

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Publication number
CN110066925A
CN110066925A CN201910348755.3A CN201910348755A CN110066925A CN 110066925 A CN110066925 A CN 110066925A CN 201910348755 A CN201910348755 A CN 201910348755A CN 110066925 A CN110066925 A CN 110066925A
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China
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cobalt
nickel
raffinate
sulfuric acid
added
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Inventor
詹稳
甄爱钢
余心亮
张景伟
李斌
陈健
赵海敏
陈红娟
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Zhejiang Tianneng New Materials Co Ltd
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Zhejiang Tianneng New Materials Co Ltd
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Priority to CN201910348755.3A priority Critical patent/CN110066925A/en
Publication of CN110066925A publication Critical patent/CN110066925A/en
Priority to PCT/CN2019/105497 priority patent/WO2020220559A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/10—Sulfates
    • 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
    • C22B1/005—Preliminary treatment of scrap
    • 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
    • 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
    • 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
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • 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
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B47/00—Obtaining manganese
    • 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
    • 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
    • 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
    • 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

Abstract

The invention discloses a kind of recovery methods of valuable metal in waste and old nickel-cobalt-manganese ternary lithium battery.Recovery method of the present invention by carrying out Fe before extraction2+、Al3+、Ca2+And Mg2+Impurity elimination processing, so that each valuable metal product purity of subsequent recovery is higher.When extracting cobalt, controlling oil-water ratio is 0.8~0.9: 1, controlling saponification rate is 55%~60%, saponification rate and appropriate reduction oil-water ratio are reduced in compared with the existing technology, cobalt in control water phase does not extract entirely, a small amount of cobalt continues to stay in water phase, and guarantee magnesium in this way will not be got on by extraction, to guarantee that magnesium addition is up to standard in cobaltous sulfate product.Increase step extraction magnesium operation before extracting nickel after extracting cobalt, remaining magnesium is eliminated as much as, the purity of nickel sulfate product obtained by extraction nickel is increased.Extract magnesium C272 extractant, the characteristic relatively opened is separated to cobalt magnesium, nickel extraction isothermal curve using it, only extraction magnesium cobalt does not extract nickel for control, to accomplish the separation of magnesium nickel.

Description

The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium battery
Technical field
The present invention relates to waste and old lithium ion battery recovery technology fields, more particularly to a kind of waste and old nickel-cobalt-manganese ternary lithium electricity The recovery method of valuable metal in pond.
Background technique
In recent years, as China's energy crisis is deepened, the stimulation such as the enhancing of common people's environmental consciousness and government policy subsidy Under, new-energy automobile industry is grown rapidly.Gradually mature in Development of HEV Technology, power battery cost gradually reduces big back Under scape, each large enterprises are flocked together one after another into new-energy automobile industry.The fast development of new-energy automobile, but also power battery produces Amount constantly increases.By 2017, the accumulative new-energy automobile total amount of promoting in China was more than 1,800,000, the monomer energy of power battery Metric density improved twice than 2012, and the price of every kilowatt hour has dropped 70% or more.Data show that the year two thousand twenty is estimated Chinese Domestic automobile power battery yield is up to 25.7 ten thousand tons, this data is up to 42.2 ten thousand tons within 2022.With new energy The fast development of automobile industry, China have become the first in the world big new-energy automobile production and marketing state, power accumulator volume of production and marketing also by Year is soaring, and power accumulator recycles extremely urgent.China is global maximum ternary battery production big country, ternary cell row One of the new high-tech industry that state key is supported was become already, with expiring for battery, old and useless battery is recycled again Using just as environmentally friendly urgent need to solve the problem.
In the prior art, often the design of entire removal process is not fine enough, and the rate of recovery is lower, and the purity of recovery product compared with Difference.
For example, the Chinese invention patent of Publication No. CN105591171A discloses a kind of waste and old nickel-cobalt-manganese ternary lithium ion Positive electrode is added alkali soluble solution by the recovery method of the positive electrode of battery, this method, and separation obtains lysate I and insoluble matter；It will Insoluble matter acidolysis obtains lysate II, adjusts pH value to alkalinity, forms precipitating, obtain filtrate I and sediment I；By sediment I Acidolysis obtains lysate III, and ammonium hydroxide is added thereto and is complexed, after adjusting pH value to alkalinity, adds soluble carbonic acid Salt, filtering obtain filtrate II and sediment II；Soluble carbonate salt is added into filtrate II, heats, obtains sediment III；Again After acidolysis, adjust pH value to 3.0~3.5, add hypochlorite and adjust pH value to 2.0~3.0, filtering, obtain filtrate II I and Sediment IV.
For another example, it is comprehensive to disclose a kind of waste and old lithium ion battery for the Chinese invention patent of Publication No. CN109449523A Recovery method, comprising: leach ternary waste lithium cell battery core powder for the first time with sulfuric acid and potassium permanganate, obtain the first leachate and First leached mud；With sodium carbonate to the first leachate sinker, lithium carbonate is obtained；First is leached with hydrogen peroxide and sulfuric acid selective reduction Leached mud obtains the second leachate and the second leached mud；The pH to 4.2-4.5 for adjusting the second leachate is leached with P204 to second Liquid extraction, obtains P204 raffinate and P204 load organic phases；P204 load organic phases are stripped with sulfuric acid, sulphur is made in evaporative crystallization Sour manganese；The pH value of P204 raffinate is adjusted to 4.5-5, P204 raffinate is extracted with C272, C272 extract liquor is obtained and C272 is negative Carry organic phase；Cobalt sulfate solution is obtained to C727 load organic oppositing back-extraction with sulfuric acid, battery grade cobalt sulfate is made in evaporative crystallization；It adjusts The pH value of whole C272 raffinate is 5-5.5, extracts to obtain P507 load organic phases with P507 to C272 extract liquor, P507 load is organic It is mutually stripped to obtain nickel sulfate solution through sulfuric acid, evaporative crystallization obtains nickel sulfate.
Summary of the invention
The present invention is not fine enough for removal process existing in the prior art design, and the rate of recovery is lower, and recovery product Purity it is poor the problems such as, provide a kind of recovery method of valuable metal in waste and old nickel-cobalt-manganese ternary lithium battery
The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium battery, comprising the following steps:
(1) selection by winnowing separation powder and metallic particles after waste and old nickel-cobalt-manganese ternary lithium battery being crushed, carbonized；
(2) powder by step (1) separation uses sulfuric acid leaching, obtains leachate；
(3) Fe in leachate is removed2+、Al3+、Ca2+And Mg2+As liquid before extracting；
(4) liquid uses P204 abstraction impurity removal before extracting, and back extraction obtains the strip liquor containing manganese sulfate, and contains Co2+、 Ni2+、Li+Raffinate；It will be concentrated by evaporation after strip liquor copper removal, crystallize acquisition manganese sulfate；
(5) raffinate obtained by step (4) is extracted into cobalt using P507, when P507 extracts cobalt, control oil-water ratio is 0.8~0.9: 1, it is saponified using lye, control saponification rate is 55%~60%；Back extraction obtains the strip liquor containing cobaltous sulfate, and contains Ni2+And Li+Raffinate；Strip liquor is concentrated by evaporation, crystallization obtains cobaltous sulfate；
(6) raffinate obtained by step (5) is cleaned using C272 extraction magnesium, obtains and removes Mg2+C272 raffinate afterwards；
(7) C272 raffinate is extracted into nickel using P507, back extraction obtains the strip liquor containing nickel sulfate, and contains Li+Extraction Extraction raffinate；Strip liquor is concentrated by evaporation, crystallization obtains nickel sulfate；
(8) raffinate obtained by step (7) is collected into lithium carbonate using sodium carbonate reaction.
It needs first to carry out discharge treatment before general lithium battery is broken, remaining capacity is released, in order to avoid occur in shattering process Explosion or burning.Electric discharge can be used salting liquid and impregnate electric discharge.After broken, then particle is subjected to high temperature cabonization, organic matter is disappeared It consumes, so that remaining is mainly some metallic elements.Carbonization carries out generally in retort, and natural gas can be used and added Heat.It after carbonization, can be crushed again if necessary, so that electrode material becomes powdered, naturally it is also possible to after selection by winnowing, Remaining biggish particle is crushed again.The powder that selection by winnowing goes out is mainly electrode material, and for handling in next step, and lithium is electric The steel shell in pond etc. becomes graininess, after separating with powder, can directly recycle.
When step (2) uses sulfuric acid leaching, generally the concentrated sulfuric acid is used, it is preferable to use the concentrated sulfuric acid that concentration is 98%.
Preferably, in step (2) powder using sulfuric acid leaching when be divided into two steps leaching:
(a) powder adds water slurry, and sulfuric acid reaction is added, and adds reducing agent reduction, control pH in reaction process be 1.0~ 1.5, leachate I and filter residue I is obtained by filtration；
(b) sulfuric acid reaction is added in filter residue I plus water slurry, adds hydrogen peroxide hydrotropy, and control pH is 1.0~1.5, filtering Leachate II and filter residue II are obtained,
Leachate I and leachate II are mixed to get the leachate.
It is furthermore preferred that the quality of reducing agent is 0.2~0.5 times of powder；The quality of hydrogen peroxide is the 0.1~0.4 of filter residue I Times.
It needs first to handle powder or the water slurryization of filter residue I before adding sulfuric acid leaching, is convenient for subsequent leaching, wherein powder or filter The liquid-solid ratio of slag I and water can be 4~5: 1.When being leached using sulfuric acid, the parameter that the sulfuric acid of addition mainly controls is reaction PH, to have no particular/special requirement using the concentration of sulfuric acid.Leach by two-step method and can ensure leaching rate.Two steps leach The reaction time of reaction can be 1 hour, and certainly, the reaction time is longer, and leaching rate is higher, can detect down after the completion of reaction The concentration of respective metal element in leachate or filter residue, such as the concentration of Ni, Co, Mn, Li et al., to calculate leaching rate.
Preferably, the Fe in step (3) removal leachate2+、Al3+、Ca2+And Mg2+The step of include:
(a) Fe in leachate is detected2+Oxidant is added by Fe in concentration2+It is oxidized to Fe3+, neutralizer tune pH, which is added, makes Fe3+ And Al3+Precipitation simultaneously filters removal；
(b) sample detection Ca2+And Mg2+Content, fluoride, which is added, makes Ca2+And Mg2+Precipitation simultaneously filters removal.
It is furthermore preferred that the additional amount of oxidant is Fe2+0.2~0.5 times of quality；The neutralizer is sodium carbonate, adjusts pH To 4.5~5.0.
It is furthermore preferred that the fluoride is sodium fluoride, additional amount Ca2+And Mg2+4~7 times of gross mass.
The impurity of non-primary components some in leachate is first removed operation, can be prepared when being conducive to subsequent extraction pure Higher product is spent, impurity therein is reduced.
Also it can choose washery slag operation containing ingredients such as a small amount of Ni, Co in the filter residue that step (2) and (3) generate to mention The high totality rate of recovery.Water can be used when washery slag by filter residue pulp, add water, at a higher temperature, for example soak at 90 DEG C Out, sulfuric acid can also be added, control reaction pH is 1.5~2.0 to accelerate to leach, and after the reaction was completed, filtering obtains filtrate, remainder Under filter residue detection Ni, Co concentration, washery slag operation can be terminated after requirement by reaching, and gained filtrate is used as step (2) leaching The water or mixed as leachate with leachate obtained by step (2) that pulp powder and filter residue I are used in the process, into lower one of work Sequence.
Preferably, the sulfuric acid solution that step (4) back extraction is 100~120g/L using concentration, step (5) back extraction use concentration For the sulfuric acid solution of 150~220g/L, the sulfuric acid solution that step (7) back extraction is 100~150g/L using concentration.Different extractions Agent is different to the isothermal curve of different metal ion extractions, successively extracts each metal ion species using different extractants, Then reuse various concentration sulfuric acid solution (dosage close in the case where, different pH may be implemented) be stripped, will It is extracted the metal ion that agent extracts to be stripped out, obtains corresponding sulfate, acquisition sulfate can be further processed Product, and the extractant after being stripped can repeat to recycle.And successive two step is extracted using P507, according to P507 extractant not The isothermal curve of metal ion extraction is determined under same pH and extracts nickel after first extracting cobalt, is just able to achieve the separation of cobalt nickel in this way.
Preferably, step (8) collects lithium carbonate before first by raffinate tune pH9 obtained by step (7) using sodium carbonate reaction ~10 clean, and concentration is except sodium salt acquisition mother liquor containing lithium after filter residue.Step (7) raffinate contains Li+Concentration is generally 1~3g/L, makes After sodium hydroxide solution tune pH9~10 removal of impurities, then filter residue is concentrated, and sodium salt is precipitated after reaching saturation in concentration process, sodium salt Main component is sodium sulphate, is packed in storage and sell after the sodium salt separation drying of precipitation.
It is furthermore preferred that Li in the mother liquor containing lithium+Concentration be 12~15g/L.In concentration process, periodic detection wherein Li+ Concentration, it is up to standard after stop concentration.
It is divided into two steps it is furthermore preferred that reacting using sodium carbonate and collecting lithium carbonate:
(a) sodium carbonate reaction is added in mother liquor containing lithium and obtains lithium carbonate precipitating；
(b) the lithium carbonate precipitating that step (a) obtains is added sulfuric acid and redissolves, and pH to 10~13 is adjusted to clean, and after filter residue, carbon is added Sour sodium reaction, reaction temperature are 95 DEG C~98 DEG C, and reaction acquisition lithium carbonate precipitating is washed, drying obtains lithium carbonate.
After sodium carbonate reaction is added, lithium carbonate Precipitation is used as lithium carbonate semifinished product, is answered after being collected by filtration It is molten and sodium carbonate reaction is added again, lithium carbonate precipitating is obtained, reaction temperature selection 95 DEG C~98 when second of prepared calcium carbonate lithium DEG C, it can guarantee to react products therefrom crystal form preferable at this temperature, it is not easy in being coated on sodium salt, and be adhered to the sodium on surface Salt can be through washing away, to keep products therefrom lithium carbonate purity preferable.
The recovery method of valuable metal in the waste and old nickel-cobalt-manganese ternary lithium battery of the present invention, by carrying out Fe before extraction2+、 Al3+、Ca2+And Mg2+Impurity elimination processing, so that each valuable metal product purity of subsequent recovery is higher.
When extracting cobalt, control oil-water ratio is 0.8~0.9: 1, and control saponification rate is 55%~60%, relative to existing skill Saponification rate and appropriate reduction oil-water ratio are reduced in art, the cobalt controlled in water phase does not extract entirely, and a small amount of cobalt continues to stay in water phase, Guarantee that magnesium will not be got on by extraction in this way, to guarantee that magnesium addition is up to standard in cobaltous sulfate product.
Increase step extraction magnesium operation before extracting nickel after extracting cobalt, remaining magnesium is eliminated as much as, sulfuric acid obtained by extraction nickel is increased The purity of nickel product.Extract magnesium C272 extractant, the characteristic relatively opened, control are separated to cobalt magnesium, nickel extraction isothermal curve using it Only extraction magnesium cobalt does not extract nickel, to accomplish the separation of magnesium nickel.
Specific embodiment
Embodiment 1
The waste and old nickel-cobalt-manganese ternary lithium battery of recycling is first subjected to discharge treatment, remaining capacity is released, in order to avoid be crushed Explosion or burning occur in journey.After broken, then particle is subjected to high temperature cabonization in retort, organic matter is consumed, thus Residue is mainly some metallic elements.After carbonization, it is crushed again, so that electrode material becomes powdered, using selection by winnowing, The powder that selection by winnowing goes out is mainly electrode material (the hereinafter referred to as black powder of ternary), for handling in next step, and the steel shell of lithium battery Deng become graininess, after being separated with powder, can directly recycle.
The black powder test of ternary.
One, it leaches:
1,200 grams of the black powder of ternary is taken, ingredient analysis is as shown in table 1.
Table 1
Ni Co Mn Li
19.5% 11.23% 12.34% 5.25%
It is added in 1L water and opens stirring pulp 30 minutes.
2, it is slowly added into 98% sulfuric acid, adjusts pH 1.0, reducing agent sodium sulfite 65g is added, the reaction was continued 2 hours, process In continue plus 98% sulfuric acid, it is ensured that pH value of solution 1.0-1.5 is turned to only until pH is constant.
3, it filters, obtains filtrate 920ml, wet slag 52g, part main metal element content is detected, testing result is such as Shown in table 2.
Table 2
Project Ni Co Mn Li
Leachate 33.91g/L 19.53g/L 23.09g/L 10.0g/L
Leached mud 15% 8.63% 6.6% 1.92%
4, leached mud is added into water 200mL, pulp heats 80 DEG C, adds 98% sulfuric acid tune pH 1.0, be slowly added into hydrogen peroxide 10g (speed is slow, prevents from emitting slot), the reaction was continued 2 hours, guarantees pH 1.0-1.5 in the process, and after pH stablizes, filtering is obtained Bis- leachates of 180mL and 35g wet slag, detect part main metal element content, testing result is as shown in table 3.
Table 3
5, secondary leached mud adds 98% sulfuric acid tune pH 3.0 or so to be cleaned with clear water again, before wash water leaches after filtering Liquid uses.Leachate twice mixes to obtain 1100mL leachate, detects to part main metal element content, testing result As shown in table 4.
Table 4
Ni(g/L) Co(g/L) Mn(g/L) Li(g/L) Fe(g/L)
35.27 20.26 22.39 9.5 0.85
6, leachate is added in 2L beaker, stirring is warmed to 80 DEG C, after adding sodium carbonate tune pH to 5.0 to stablize, filters Filtrate 985mL, filter residue 45g, filter residue go to clean, detect to filtrate, and the results are shown in Table 5.
Table 5
Ni(g/L) Co(g/L) Mn(g/L) Li(g/L) Ca+Mg(g/L)
35.15 19.85 21.56 10.23 1.86
7,1L beaker is added in filtrate, stirring is warmed to 85 DEG C, is slowly added into sodium fluoride 11g, the reaction was continued 1 hour, mistake Filter, obtains filtrate 952mL, and filter residue carries out washery slag processing, detects to filtrate, the results are shown in Table 6.
Table 6
Ni(g/L) Co(g/L) Mn(g/L) Li(g/L) Ca(g/L) Mg(g/L) Fe(g/L)
34.21 18.53 21.05 9.95 0.043 0.035 0.0056
Two, it extracts
1, P204 cleans: matching 25%P204 organic phase 2L, adds the liquid alkaline (sodium hydroxide solution) that concentration is 32% to be saponified, soap Organic phase is added separatory funnel in the ratio for comparing 2: 1 with liquid before extraction, is extracted, shake 5 minutes and clarify 10 again by rate 70% Minute, it adds 100mL 15g/L sulfuric acid solution and carries out cleaning organic phase, shake and clarify again within 5 minutes 10 minutes, release the extraction of lower part Extraction raffinate, then 200mL100g/L sulfuric acid solution is added into separatory funnel and is stripped, it shakes and clarifies again within 5 minutes 10 minutes, under releasing Portion's strip liquor, raffinate and strip liquor testing result are as shown in table 7.
Table 7
Project Ni(g/L) Co(g/L) Mn(g/L) Ca(g/L) Cu(g/L)
Raffinate 30.85 16.81 0.0053 0.0011 0.0005
Strip liquor -- -- 100.2 0.21 0.52
After manganese sulphate solution adds akali sulphide to clean, then after removing Ca with P204 extractant, evaporative crystallization is at manganese sulfate crystal (sulfuric acid Manganese crystal is MnSO4·H2O, per molecule contain 1 crystallization water), obtain manganese sulfate crystal amount 76g, purity 99.6%, the rate of recovery 98.54%.
2, P507 extracts cobalt: matching 25%P507 organic phase 2L, adds 32% liquid alkaline to be saponified, saponification rate 60%, by organic phase and extraction Preceding liquid is added in the ratio compared to 0.9: 1 with separatory funnel, is extracted, shakes and clarify again within 5 minutes 10 minutes, add 300mL 15g/L sulfuric acid solution carries out cleaning organic phase, shakes and clarifies again within 5 minutes 10 minutes, releases the raffinate of lower part, then to separatory funnel Middle addition 100mL 200g/L sulfuric acid solution is stripped, and is shaken and is clarified again within 5 minutes 10 minutes, and lower counter liquid, raffinate are released 1400mL and strip liquor 300mL, raffinate and strip liquor testing result are as shown in table 8.
Table 8
Project Ni(g/L) Co(g/L) Mn(g/L) Ca(g/L) Mg(g/L)
Raffinate 24.29 1.25 -- 0.0048 0.10
Strip liquor -- 119.5 -- 0.0042 0.0045
At cobaltous sulfate crystal, (cobaltous sulfate crystal is CoSO to cobaltous sulfate liquid evaporative crystallization4·7H2O, per molecule is containing 7 crystallizations Water), obtain cobaltous sulfate crystal 108g, purity 99.3%, the rate of recovery 98.57%.
3, C272 extracts magnesium: matching 10%C272 organic phase 500mL, adds 32% liquid alkaline to be saponified, saponification rate 200%, by organic phase With extract before liquid add with separatory funnel in the ratio for comparing 0.3: 1, extracted, shake and clarify again within 5 minutes 10 minutes, add 100mL 15g/L sulfuric acid solution carries out cleaning organic phase, shakes and clarifies again within 5 minutes 10 minutes, releases the raffinate of lower part, then to point 50mL 200g/L sulfuric acid solution is added in liquid funnel to be stripped, shakes and clarifies again within 5 minutes 10 minutes, releases lower counter liquid, extraction Extraction raffinate 1500mL and strip liquor 300mL, raffinate and strip liquor testing result are as shown in table 9.
Table 9
Project Ni(g/L) Co(g/L) Ca(g/L) Mg(g/L)
Raffinate 22.08 -- 0.0001 0.0002
Strip liquor -- 4.5 0.0042 2.8
After strip liquor returns leaching plus sodium fluoride demagging, liquid before P204 extracts is entered back into.
4, P507 extracts nickel: matching 25%P507 organic phase 2L, adds 32% liquid alkaline to be saponified, saponification rate 70%, by organic phase and extraction Preceding liquid is added in the ratio compared to 1.5: 1 with separatory funnel, is extracted, shakes and clarify again within 5 minutes 10 minutes, add 300mL 15g/L sulfuric acid solution carries out cleaning organic phase, shakes and clarifies again within 5 minutes 10 minutes, releases the raffinate of lower part, then to separatory funnel Middle addition 300mL 200g/L sulfuric acid solution is stripped, and is shaken and is clarified again within 5 minutes 10 minutes, and lower counter liquid, raffinate are released 1800mL and strip liquor 300mL, raffinate and strip liquor testing result are as shown in table 10.
Table 10
Project Ni(g/L) Co(g/L) Na(g/L) Li(g/L) Mg(g/L)
Raffinate 0.012 0.008 -- 5.3 0.10
Strip liquor 103.2 --- 0.22 -- 0.0045
Nickel sulfate solution evaporative crystallization is at nickel sulfate hexahydrate crystal (nickel sulfate hexahydrate crystal NiSO4·6H2O, per molecule is containing 6 crystallizations Water), obtain nickel sulfate hexahydrate crystal 182g, purity 99.35%, the rate of recovery 98%.
Three, heavy lithium carbonate
1, P507 extraction nickel extraction raffinate heating is concentrated into 600mL, lithium concentration be enriched to 15g/L on, sodium sulphate is removed in filtering Salt, remaining lithium water are heated to 80 DEG C, and the saturated solution of sodium carbonate prepared is added, and adjust pH 11, filter to obtain crude lithium carbonate.
2, crude lithium carbonate is added in 500mL clear water, the stirring of 98% sulfuric acid is added to be completely dissolved, pH 3-4, filtering, filtrate Add 32% liquid adjusting PH with base 10-13, filtering gained 545mL filtrate is heated to 95 DEG C in new beaker again.
3, match saturated solution of sodium carbonate 200mL, 95 DEG C are heated to after filtering, stirring is opened, is slowly uniformly added into step The hot lithium water managed keeps 95 DEG C of temperature or more in the process, continues stirring insulation reaction 1 hour after adding material.
4, it filters, then is dried after washing 3 times with 95 DEG C or more of hot pure water after reaction, obtain battery-level lithium carbonate 50.8g, the rate of recovery 90.5%.Gained lithium carbonate purity and partial impurities are detected, testing result is as shown in table 11, gained Lithium carbonate purity is high, sodium salt content are few.
Table 11
Li2CO3 Fe Na Ca Mg Mn Cu Sulfate radical
99.59% 0.0024% 0.023% 0.0011% 0.0007% 0.0023% 0.0003% 0.003%
Embodiment 2
The waste and old nickel-cobalt-manganese ternary lithium battery of recycling is first subjected to discharge treatment, remaining capacity is released, in order to avoid be crushed Explosion or burning occur in journey.After broken, then particle is subjected to high temperature cabonization in retort, organic matter is consumed, thus Residue is mainly some metallic elements.After carbonization, it is crushed again, so that electrode material becomes powdered, using selection by winnowing, The powder that selection by winnowing goes out is mainly electrode material (the hereinafter referred to as black powder of ternary), for handling in next step, and the steel shell of lithium battery Deng become graininess, after being separated with powder, can directly recycle.
The black powder test of ternary.
One, it leaches:
1,200 grams of the black powder of ternary is taken, ingredient analysis is as shown in table 12.
Table 12
Ni Co Mn Li
15.03% 9.59% 11.22% 5.33%
It is added in 1L water and opens stirring pulp 30 minutes.
2, it is slowly added into 98% sulfuric acid, adjusts pH 1.0, reducing agent sodium sulfite 65g is added, the reaction was continued 2 hours, process In continue plus 98% sulfuric acid, it is ensured that pH value of solution 1.0-1.5 is turned to only until pH is constant.
3, it filters, obtains filtrate 945ml, wet slag 78g, part main metal element content is detected, testing result is such as Shown in table 13.
Table 13
Project Ni Co Mn Li
Leachate 27.86g/L 17.75g/L 20.79g/L 8.71g/L
Leached mud 4.78% 3.09% 3.58% 3.12%
4, leached mud is added into water 300mL, pulp heats 80 DEG C, adds 98% sulfuric acid tune pH 1.0, be slowly added into hydrogen peroxide 8g (speed is slow, prevents from emitting slot), the reaction was continued 2 hours, guarantees pH 1.0-1.5 in the process, and after pH stablizes, filtering is obtained Bis- leachates of 225mL and 65g wet slag, detect part main metal element content, testing result is as shown in table 14.
Table 14
Project Ni Co Mn Li
Secondary leachate 14.92g/L 9.64g/L 11.16g/L 9.72g/L
Secondary leached mud 0.57% 0.37% 0.43% 0.37%
5, secondary leached mud adds 98% sulfuric acid tune pH 3.0 or so to be cleaned with clear water again, before wash water leaches after filtering Liquid uses.Leachate twice mixes to obtain 1170mL leachate, detects to part main metal element content, testing result As shown in Table 15.
Table 15
Ni(g/L) Co(g/L) Mn(g/L) Li(g/L) Fe(g/L)
25.37 16.19 18.94 8.90 1.15
6, leachate is added in 2L beaker, stirring is warmed to 80 DEG C, after adding sodium carbonate tune pH to 5.0 to stablize, filters Filtrate is diluted with water 1468mL, filter residue 55g, and filter residue goes to clean, detect to filtrate, as a result as shown in table 16.
Table 16
7,1L beaker is added in filtrate, stirring is warmed to 85 DEG C, is slowly added into sodium fluoride 19g, the reaction was continued 1 hour, mistake Filter, obtains filtrate 1402mL, and filter residue carries out washery slag processing, detects to filtrate, as a result as shown in table 17.
Table 17
Ni(g/L) Co(g/L) Mn(g/L) Li(g/L) Ca(g/L) Mg(g/L) Fe(g/L)
19.1 12.3 14.5 6.8 0.033 0.027 0.0038
Two, it extracts
1, P204 cleans: matching 25%P204 organic phase 3L, 32% sodium hydroxide solution is added to be saponified, saponification rate 70% will have Separatory funnel is added in the ratio for comparing 2: 1 with liquid before extraction in machine phase, is extracted, shakes and clarify again within 5 minutes 10 minutes, add 200mL 15g/L sulfuric acid solution carries out cleaning organic phase, shakes and clarifies again within 5 minutes 10 minutes, releases the raffinate 1600mL of lower part, 200mL 100g/L sulfuric acid solution is added into separatory funnel again to be stripped, shakes and clarifies again within 5 minutes 10 minutes, it is anti-to release lower part Extract liquid, raffinate and strip liquor testing result are as shown in table 18.
Table 18
Project Ni(g/L) Co(g/L) Mn(g/L) Ca(g/L) Cu(g/L)
Raffinate 16.75 10.79 -- 0.0008 0.0003
Strip liquor -- -- 100.1 0.19 0.43
After manganese sulphate solution adds akali sulphide to clean, then after removing Ca with P204 extractant, evaporative crystallization is at manganese sulfate crystal (sulfuric acid Manganese crystal is MnSO4·H2O, per molecule contain 1 crystallization water), obtain manganese sulfate crystal 68.93g, purity 99.5%, the rate of recovery 98.76%.
2, P507 extracts cobalt: matching 25%P507 organic phase 2L, adds 32% liquid alkaline to be saponified, saponification rate 60%, by organic phase and extraction Preceding liquid is added in the ratio compared to 0.9: 1 with separatory funnel, is extracted, shakes and clarify again within 5 minutes 10 minutes, add 300mL 15g/L sulfuric acid solution carries out cleaning organic phase, shakes and clarifies again within 5 minutes 10 minutes, releases the raffinate of lower part, then to separatory funnel Middle addition 150mL 200g/L sulfuric acid solution is stripped, and is shaken and is clarified again within 5 minutes 10 minutes, and lower counter liquid, raffinate are released 1900mL and strip liquor 150mL, raffinate and strip liquor testing result are as shown in table 19.
Table 19
Project Ni(g/L) Co(g/L) Mn(g/L) Ca(g/L) Mg(g/L)
Raffinate 14.11 0.98 -- 0.0045 0.15
Strip liquor -- 125.73 -- 0.0022 0.0025
At cobaltous sulfate crystal, (cobaltous sulfate crystal is CoSO to cobaltous sulfate liquid evaporative crystallization4·7H2O, per molecule is containing 7 crystallizations Water), obtain cobaltous sulfate crystal 92g, purity 99.3%, the rate of recovery 98.74%.
3, C272 extracts magnesium: match 10%C272 organic phase 500mL, 32% liquid alkaline added to be saponified, saponification rate 20%, by organic phase and Liquid is added by the ratio for comparing 0.3: 1 with separatory funnel before extracting, and is extracted, shakes and clarify again within 5 minutes 10 minutes, add 100mL 15g/L sulfuric acid solution carries out cleaning organic phase, shakes and clarifies again within 5 minutes 10 minutes, releases the raffinate 1950mL of lower part, then to point 50mL 200g/L sulfuric acid solution is added in liquid funnel to be stripped, shakes and clarifies again within 5 minutes 10 minutes, releases lower counter liquid, extraction Extraction raffinate 1950mL and strip liquor 50mL, raffinate and strip liquor testing result are as shown in table 20.
Table 20
Project Ni(g/L) Co(g/L) Ca(g/L) Mg(g/L)
Raffinate 13.75 -- 0.0001 0.0002
Strip liquor -- 4.2 0.0032 1.57
After strip liquor returns leaching plus sodium fluoride demagging, liquid before P204 extracts is entered back into.
4, P507 extracts nickel: matching 25%P507 organic phase 2L, adds 32% liquid alkaline to be saponified, saponification rate 70%, by organic phase and extraction Preceding liquid is added in the ratio compared to 1.5: 1 with separatory funnel, is extracted, shakes and clarify again within 5 minutes 10 minutes, add 300mL 15g/L sulfuric acid solution carries out cleaning organic phase, shakes and clarifies again within 5 minutes 10 minutes, releases the raffinate of lower part, then to separatory funnel Middle addition 250mL 200g/L sulfuric acid solution is stripped, and is shaken and is clarified again within 5 minutes 10 minutes, and lower counter liquid, raffinate are released 2250mL and strip liquor 300mL, raffinate and strip liquor testing result are as shown in table 21.
Table 21
Project Ni(g/L) Co(g/L) Na(g/L) Li(g/L) Mg(g/L)
Raffinate 0.010 0.005 -- 3.3 0.050
Strip liquor 107.25 -- 0.28 -- 0.0045
Nickel sulfate solution evaporative crystallization is at nickel sulfate hexahydrate crystal (nickel sulfate hexahydrate crystal NiSO4·6H2O, per molecule is containing 6 crystallizations Water), obtain nickel sulfate hexahydrate crystal 140g, purity 99.6%, the rate of recovery 98.2%.
Three, heavy lithium carbonate
1, P507 extraction nickel extraction raffinate heating is concentrated into 600mL, lithium concentration be enriched to 15g/L on, sodium sulphate is removed in filtering Salt, remaining lithium water are heated to 80 DEG C, and the saturated solution of sodium carbonate prepared is added, and adjust pH 11, filter to obtain crude lithium carbonate.
2, crude lithium carbonate is added in 500mL clear water, the stirring of 98% sulfuric acid is added to be completely dissolved, pH 3-4, filtering, filtrate Add 32% liquid adjusting PH with base 10-13, filtering gained 545mL filtrate is heated to 95 DEG C in new beaker again
3, match saturated solution of sodium carbonate 200mL, 95 DEG C are heated to after filtering, stirring is opened, is slowly uniformly added into step The hot lithium water managed keeps 95 DEG C of temperature or more in the process, continues stirring insulation reaction 1 hour after adding material.
4, it filters, then is dried after washing 3 times with 95 DEG C or more of hot pure water after reaction, obtain battery-level lithium carbonate 52g, the rate of recovery 91.23%.Gained lithium carbonate purity and partial impurities are detected, testing result is as shown in table 22, gained Lithium carbonate purity is high, sodium salt content are few.
Table 22
Li2CO3 Fe Na Ca Mg Mn Cu Sulfate radical
99.58% 0.0019% 0.019% 0.0022% 0.0005% 0.0015% 0.0001% 0.0028%
Comparative example 1
The same black powder of batch ternary is tested in Example 1, and leaching operation is also in the same manner as in Example 1, extraction Method difference, when step 2 P507 extracts cobalt, saponification rate control is 65%, and oil-water ratio (liquid additional proportion before organic phase and extraction) is 1 : 1, finally extracting cobalt acquisition cobaltous sulfate crystal, (cobaltous sulfate crystal is CoSO4·7H2O, per molecule contain 7 crystallizations water) 93.5g, purity 98.21%, it is 0.0078% that wherein Co content, which is 19.9%, Mg content,.
Then extract magnesium without C272 but directly carry out P507 extraction nickel after extracting cobalt, finally obtain nickel sulfate hexahydrate crystal (sulphur Sour nickel crystal is NiSO4·6H2O, per molecule contain 6 crystallizations water) 135g, purity 98.32%, wherein Ni content is 20.65%, Mg content is 0.0069%.
Comparative example 2
It will be leached by 2 same procedure of embodiment, P507 extracted extraction nickel extraction raffinate progress lithium carbonate precipitating, lithium carbonate is heavy Only temperature uses 80 DEG C when shallow lake, other steps are all the same, last gained lithium carbonate product purity detecting, purity 98.52%, Na Content 0.25%, for comparative example 2 compared in Examples 1 and 2, sodium salt impurity is more.Illustrate at a lower temperature, when lithium carbonate precipitates It is easy for sodium salt to be coated on interior.
In the present invention, when detecting each material purity and content, percentage is mass percent.

Claims (10)

1. the recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium battery, which comprises the following steps:
(1) selection by winnowing separation powder and metallic particles after waste and old nickel-cobalt-manganese ternary lithium battery being crushed, carbonized；
(2) powder by step (1) separation uses sulfuric acid leaching, obtains leachate；
(3) Fe in leachate is removed2+、Al3+、Ca2+And Mg2+As liquid before extracting；
(4) liquid uses P204 abstraction impurity removal before extracting, and back extraction obtains the strip liquor containing manganese sulfate, and contains Co2+、Ni2+、Li+Raffinate；It will be concentrated by evaporation after strip liquor copper removal, crystallize acquisition manganese sulfate；
(5) raffinate obtained by step (4) is extracted into cobalt using P507, when P507 extracts cobalt, control oil-water ratio is 0.8~0.9: 1, is made It is saponified with lye, control saponification rate is 55%~60%；Back extraction obtains the strip liquor containing cobaltous sulfate, and contains Ni2+ And Li+Raffinate；Strip liquor is concentrated by evaporation, crystallization obtains cobaltous sulfate；
(6) raffinate obtained by step (5) is cleaned using C272 extraction magnesium, obtains and removes Mg2+C272 raffinate afterwards；
(7) C272 raffinate is extracted into nickel using P507, back extraction obtains the strip liquor containing nickel sulfate, and contains Li+Raffinate； Strip liquor is concentrated by evaporation, crystallization obtains nickel sulfate；
(8) raffinate obtained by step (7) is collected into lithium carbonate using sodium carbonate reaction.
2. recovery method as described in claim 1, which is characterized in that in step (2) powder using sulfuric acid leaching when be divided into two Step leaches:
(a) powder adds water slurry, and sulfuric acid reaction is added, and adds reducing agent reduction, and controlling pH in reaction process is 1.0~1.5, Leachate I and filter residue I is obtained by filtration；
(b) sulfuric acid reaction is added in filter residue I plus water slurry, adds hydrogen peroxide hydrotropy, and control pH is 1.0~1.5, is obtained by filtration Leachate II and filter residue II,
Leachate I and leachate II are mixed to get the leachate.
3. recovery method as claimed in claim 2, which is characterized in that the quality of reducing agent is 0.2~0.5 times of powder；It is double The quality of oxygen water is 0.1~0.4 times of filter residue I.
4. recovery method as described in claim 1, which is characterized in that step (3) removes the Fe in leachate2+、Al3+、Ca2+ And Mg2+The step of include:
(a) Fe in leachate is detected2+Oxidant is added by Fe in concentration2+It is oxidized to Fe3+, neutralizer tune pH, which is added, makes Fe3+And Al3+ Precipitation simultaneously filters removal；
(b) sample detection Ca2+And Mg2+Content, fluoride, which is added, makes Ca2+And Mg2+Precipitation simultaneously filters removal.
5. recovery method as claimed in claim 4, which is characterized in that the additional amount of oxidant is Fe2+The 0.2~0.5 of quality Times；The neutralizer is sodium carbonate, adjusts pH to 4.5~5.0.
6. recovery method as claimed in claim 4, which is characterized in that the fluoride is sodium fluoride, additional amount Ca2+With Mg2+4~7 times of gross mass.
7. recovery method as described in claim 1, which is characterized in that step (4) back extraction is 100~120g/L's using concentration Sulfuric acid solution, the sulfuric acid solution that step (5) back extraction is 150~220g/L using concentration, step (7) back extraction are 100 using concentration The sulfuric acid solution of~150g/L.
8. recovery method as described in claim 1, which is characterized in that step (8) using sodium carbonate reaction collect lithium carbonate it Preceding that first raffinate tune pH9~10 obtained by step (7) cleans, concentration is except sodium salt acquisition mother liquor containing lithium after filter residue.
9. recovery method as claimed in claim 8, which is characterized in that Li in the mother liquor containing lithium+Concentration be 12~15g/L.
10. recovery method as claimed in claim 8, which is characterized in that react collection lithium carbonate using sodium carbonate and be divided into two steps:
(a) sodium carbonate reaction is added in mother liquor containing lithium and obtains lithium carbonate precipitating；
(b) the lithium carbonate precipitating that step (a) obtains is added sulfuric acid and redissolves, and pH to 10~13 is adjusted to clean, and after filter residue, sodium carbonate is added Reaction, reaction temperature are 95 DEG C~98 DEG C, and reaction acquisition lithium carbonate precipitating is washed, drying obtains lithium carbonate.
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WO2022228233A1 (en) * 2021-04-25 2022-11-03 湖南金源新材料股份有限公司 Method for extracting and preparing battery-grade lithium carbonate from p507 raffinate, and extraction device
CN114349078A (en) * 2021-12-29 2022-04-15 广西中伟新能源科技有限公司 Method for removing chlorine and magnesium in nickel hydroxide and application
CN114349078B (en) * 2021-12-29 2024-04-26 广西中伟新能源科技有限公司 Method for removing chlorine and magnesium in nickel hydroxide and application thereof
CN114853093A (en) * 2022-05-27 2022-08-05 中国恩菲工程技术有限公司 Preparation method of battery-grade nickel sulfate
CN115057481A (en) * 2022-06-09 2022-09-16 云南金浔资源股份有限公司 Production method of cobalt sulfate for high-performance lithium ion power battery
CN115369251A (en) * 2022-10-27 2022-11-22 杭州天易成环保设备股份有限公司 Extraction recovery line, method and application of ternary lithium battery material
CN116902999A (en) * 2023-05-31 2023-10-20 广东盛祥新材料科技有限公司 Ternary powder/lithium iron powder/lithium carbonate processing method and waste battery recycling method

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Application publication date: 20190730