CN107017443A - A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery - Google Patents

A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery Download PDF

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CN107017443A
CN107017443A CN201710191599.5A CN201710191599A CN107017443A CN 107017443 A CN107017443 A CN 107017443A CN 201710191599 A CN201710191599 A CN 201710191599A CN 107017443 A CN107017443 A CN 107017443A
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cobalt
leaching
nickel
lithium
waste
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CN107017443B (en
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王成彦
张家靓
胡军涛
陈永强
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GUANGDONG GUANGHUA SCI-TECH CO LTD
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University of Science and Technology Beijing USTB
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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
    • 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
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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

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  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Metallurgy (AREA)
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Abstract

The invention discloses a kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery.Comprise the following steps：Old and useless battery is carried out to crush after discharge process, is carried out at 300~400 DEG C after preroast, is added reducing agent and reduction roasting is carried out at 450~700 DEG C.Fines after roasting obtains high purity lithium product through water logging, evaporative crystallization, leached mud leaches copper, nickel, cobalt with the block after roasting using oxidation ammonia leaching, ammonia leaching residue obtains iron, aluminium enriched substance through magnetic separation, screening, and screenings obtains high-purity sulphuric acid manganese solution after reducing acidleach, purification and impurity removal.Ammonia leaching solution is then using extraction, selectivity back extraction output high-purity sulphuric acid nickel and copper-bath, and raffinate after vulcanization heavy cobalt, oxidation acid leaching, extracting and purifying by obtaining high-purity sulphuric acid cobalt liquor.This method is without sorting, and recovery rate of valuable metals is high, it is adaptable to the processing of a variety of waste and old lithium ion battery raw materials and the efficient utilization of multielement.

Description

A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery
Technical field
The present invention relates to the processing method of waste and old lithium ion battery, more particularly to one kind are comprehensive from waste and old lithium ion battery Reclaim the smelting process of the valuable elements such as lithium, nickel, cobalt, manganese, copper, aluminium.Belong to recycling of WEEE processing, recycling field.
Background technology
In recent years, under the historical background of environmental protection, there is rapid growth in China's new-energy automobile.With production capacity not Disconnected to improve, waste and old lithium ion battery is increasing, and the shortage of resources and environmental problem thus triggered is increasingly serious.
Processing to waste and old lithium ion battery, mainly there is chemical method and Mechanical Method (physical method), but both sides at present Method is both needed to that the collector in battery, positive pole powder, graphite powder, barrier film etc. are classified by assorting room, and then to difference Component carries out corresponding processing and obtains product.Structure yet with lithium ion battery is more special, such as CGR18650H types, outside Shell is nickel plating box hat, and inside is to have plastic sheeting, main valuable material-positive electrode and aluminium foil between rolled structure, both positive and negative polarity Collector bonding is close, is not only difficult to disintegrate and crush, and in sorting, the mechanical entrapment loss of positive electrode is serious, returns Yield is relatively low, and this is to cause the low main cause of the valuable element comprehensive recovery such as whole technique cobalt, nickel, lithium.
Domestic relevant manufacturers handle more or are worth higher positive electrode at present, for the whole battery scrapped, still Lack the handling process and equipment of more maturation.Indivedual producers handle waste and old lithium ion battery using sulfuric acid medium reducing leaching Technique.Technical process is：(H is leached in broken disintegration-sorting-alkali leaching aluminium-alkali phase analysis sulfate reduction2O2Or Na2SO3 Make reducing agent)-purification-extraction-nickel, cobalt, manganese salt production.But due to needing sorting, although leach process Ni, Co, Mn leaching Extracting rate is very high, but assorting room product causes whole technique recovery rate of valuable metals relatively low mutually containing serious.In addition, lithium metal exists As cobalt, nickel, manganese etc. enter in solution together in acid dissolution, after extracting cobalt, nickel, manganese through extraction, most lithiums are stayed in In raffinate.Now the concentration of contained lithium is extremely low in raffinate, while sodium ion in liquor content is high, therefrom reclaims the difficulty of lithium It is very big.
Chinese patent CN 104593606B, CN 104577249B carry out high-speed punching to waste and old cobalt acid lithium battery first and broken up Broken, the both positive and negative polarity powder for carrying out obtaining after vibrosieve, screening afterwards is calcined under protective atmosphere, and sintering temperature is 800 ~900 DEG C, simple substance cobalt, lithium carbonate powder, powdered graphite mixture are obtained after roasting, wet type magnetic then is carried out to the mixture Choosing, obtains thick cobalt powder and graphite powder, magnetic separation filtrate heating evaporation obtains lithium carbonate powder.The shortcoming of this method is screening process The mechanical entrapment loss of middle positive electrode is serious, it is impossible to ensure the higher rate of recovery；In addition, being dissolved in the electricity in positive and negative pole material Solving liquid can be in roasting process and lithium reaction generation LiF, Li3PO4Deng insoluble matter, the rate of recovery of lithium is reduced.
Chinese patent CN 104577248A are passed through hydrogen treat cobalt acid lithium powder under the conditions of 580~780 DEG C, afterwards will Calcining water dissolves, and slag drying obtains cobalt oxide, and filtrate then adds sodium carbonate after circulation collection and obtains lithium carbonate；Chinese patent CN 106129511A then carry out reduction roasting to applying waste lithium ionic positive electrode using coal as reducing agent, and product of roasting is used Carbonating water logging, evaporative crystallization obtain lithium carbonate, and water logging slag is then using acidleach or ammonia leaching Call Provision, nickel, manganese.However, above-mentioned The process object of method is the anode material for lithium-ion batteries obtained after crushing and screening, and does not consider electrolyte and lithium equally The environmental problem that causes of side reaction and volatilization.
Organized to set up in National Development and Reform Committee, Ministry of Industry and Information, Deng Ji ministries and commissions of Chinese Ministry of Environmental Protection《Electric powered motor Battery recycling profit With technical policy (version in 2015)》Middle to require, the processing of old and useless battery should select advanced, environmentally friendly smelting process, hydrometallurgy During nickel, cobalt, the comprehensive recovery of manganese be not less than 98%, the comprehensive recovery of pyrometallurgical smelting should be not less than 97%.Therefore, exist Current automatic high-efficiency sorting technology, equip it is still jejune under the conditions of, study and develop assortment step and can high efficiente callback The method of valuable element, has important practical significance in waste and old lithium ion battery.
The content of the invention
The invention aims to provide one kind synthetical recovery lithium, nickel, cobalt, manganese, copper, aluminium etc. from waste and old lithium ion battery The smelting process of valuable element.
The principle flow chart of this method is as shown in figure 1, technical scheme is as follows with related description：
Step (1)：Inserted after waste and old lithium ion battery punching and discharge process is carried out in alkaline earth oxide slurries, simultaneously Most phosphate radical in battery electrolyte and fluorine ion are changed into insoluble solids, and lithium is changed into solvable LiOH.The step Suddenly phosphate radical and fluorine ion can be changed into precipitation solidification under cryogenic, it is to avoid it is waved in follow-up roasting process Hair, while can also avoid generating LiF, Li in roasting process3PO4, reduce the leaching rate of lithium.
The battery of discharge off, which is pulled out, afterwards is crushed, and suspended hood is set above disintegrating machine, collects the electrolyte of volatilization Waste gas CaO slurries make F, P deposition removal, and lithium is then stayed in the solution with lithium bicarbonate form, after filtering, filtrate with it is follow-up Carbonating water immersion liquid merges, and filter residue is then stored up.
Step (2)：Material after broken carries out preroast under the conditions of 300~400 DEG C first, makes organic viscous in battery Knot agent, film etc. are thermally decomposed, while the further amount of reduction electrolyte, it is to avoid produced in reducing roasting process LiF, Li3PO4, reduce the leaching rate of lithium；Reducing agent is added at 450~700 DEG C after the completion of preroast and carry out reduction roasting, during roasting Between 1~3h.Reducing agent is carbonaceous reducing agent or CO or H2Or NH3.After reduction roasting, the lithium in battery is changed into Li2CO3Or LiOH, cobalt, nickel are changed into metal simple-substance, and manganese is changed into MnO.Preroast and the tail gas of reducing roasting process output are starched with CaO Liquid absorption is handled.
Step (3)：Material after being handled through reduction roasting carries out screening process, send leaching tanks to handle less than 1mm fineves, such as Carbonaceous reducing agent or CO are used during roasting, then is passed through CO when leaching2Gas, lithium is gone out with water logging, and leachate send evaporative crystallization to give birth to Produce lithium carbonate product；H is used when being such as calcined2Or NH3, then directly gone out with water logging, leachate is passed through CO2And evaporative crystallization production carbon Sour lithium product or direct evaporative crystallization produce lithium hydroxide product.
Step (4)：Carry the leached mud after lithium and be passed through compressed air progress oxidation ammonia leaching.Material more than 1mm loads stainless In steel mesh frame, oxidation ammonia leaching is carried out in leaching tanks.During ammonia leaching, nickel, cobalt, copper are selectively leached, and iron, aluminium are not leached, Manganese is then converted into MnO2It is precipitated into slag.Subsequent ammonia leaching solution send extraction process, and the ammonia leaching residue resided in stainless steel screen frame send magnetic separation Processing, obtains iron enriched substance and magnetic tailing, again after screening, on-the-sieve material is aluminium enriched substance, undersize material and particulate to mine tailing Material ammonia leaching residue send manganese reducing leaching process to reclaim manganese together.
Step (5)：Cupric, nickel, the ammonia leaching solution of cobalt realize the separation of copper, nickel and cobalt, then the back extraction of chosen property using extraction, Difference output high-purity sulphuric acid nickel and copper-bath.Raffinate is precipitated cobalt by vulcanizing, and liquid returns to ammonia leaching after heavy cobalt.Cobalt sulfide Using oxidation acid leaching, leachate is purified, obtain high-purity sulphuric acid cobalt liquor after extraction.
Step (6)：Rich manganese material adjusts pH value of solution 3.5 or so using reduction sulfuric acid leaching, leachate hydrogenation sodium oxide molybdena, Most copper, nickel, cobalt in solution are removed using vulcanization method, appropriate hydrogen peroxide is then added, and it is molten to be hydrogenated with sodium oxide molybdena adjustment Liquid pH is 5 or so, and depth hydrolysis remove iron, aluminium, while the trace copper remained in adsorbing and removing solution, nickel, cobalt, so as to obtain height Pure manganese sulfate solution.
In above-mentioned technical proposal, the alkaline earth oxide described in step (1) is CaO or MgO.
Ammonia leaching leaching agent described in step (4) is ammoniacal liquor and ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, chlorination The mixed solution of one or both of ammonium ammonium salt；Wherein ammonium salt concentration is 0.5~4mol/L, and ammonia concn is 1~5mol/L, Solid-to-liquid ratio is 1:4~1:20, extraction time is 2~12 hours, and temperature is 20~90 DEG C.
Described waste and old lithium ion battery includes cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, iron manganese phosphate for lithium, nickel cobalt Binary, nickel manganese binary, cobalt manganese binary, nickel-cobalt-manganese ternary, one kind in nickel cobalt aluminium ternary battery or mixture.
The characteristics of this method is different from passing method is with advantage：
(1) old and useless battery only needs simple crushing, without sorting, so fundamentally ensure that Co, Cu, Ni etc. are main valuable The high-recovery of metal, and the pre- pre-treatment of battery is enormously simplify, reduce processing cost.
(2) old and useless battery is discharged using CaO or MgO slurries, while can make under normal temperature condition big in electrolyte Partial phosphate radical changes into precipitation solidification with fluorine ion, it is to avoid it volatilizees in follow-up roasting process pollutes；The step Suddenly it can also avoid generating the indissoluble thing containing lithium in reducing roasting process together with follow-up low temperature preroast process, reduce the recovery of lithium Rate.
(3) lithium in battery can simply and efficiently be reclaimed using the dipped journey of reduction roasting-carbonating water；It is simultaneously and traditional Acid leaching process is compared, and the consumption and corresponding brine waste quantum of output of ammonia leaching process chemical are also greatly reduced, and can fit Processing and the efficient utilization of multielement for a variety of waste and old lithium ion battery raw materials.
Brief description of the drawings
Fig. 1 is that waste and old lithium ion battery multielement composite utilizes principle technological process
Embodiment
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment, But protection scope of the present invention is not limited to embodiment in detail below.It should be pointed out that to the ordinary skill people of this area For member, without departing from the inventive concept of the premise, various modifications and improvements can be made, but these belong to the present invention Protection domain.
Embodiment 1
Step (1)：CaO slurries will be put into after 1000g cobalt acid lithiums, nickel-cobalt-manganese ternary, the punching of nickel cobalt aluminium ternary battery waste Middle immersion 24h, battery is pulled out crushed afterwards, and suspended hood is set above disintegrating machine, and the electrolyte waste gas for collecting volatilization is used The absorption of CaO slurries is handled.After filtering, filtrate merges with follow-up carbonating water immersion liquid, and filter residue is then stored up.
Step (2)：Battery material after will be broken is inserted in Muffle furnace, and preroast, preroast are carried out under the conditions of 350 DEG C Time 1h.After material is mixed with 80g lignite (phosphorus content 60%) afterwards, the reduction roasting 2h at 600 DEG C.Preroast and reduction The flue gas of roasting process output is handled with the absorption of CaO slurries.
Step (3)：The vibratory sieve that material after reduction roasting is handled is 1mm with mesh is sieved, thin less than 1mm Material carries out normal temperature carbonating water logging, is passed through CO2Flow be 3L/min, liquid-solid ratio is 5:1, extraction time 2h, after the completion of leaching Filtering, analyze Li leaching rate be 89.7%.Leachate evaporative crystallization at 95 DEG C, under conditions of percent crystallization in massecuite is 80% To lithium carbonate, purity is 99.1%；Carry the leached mud after lithium and be passed through compressed air progress oxidation ammonia leaching, leaching agent is ammonium sulfate 2mol/L, ammoniacal liquor 1.5mol/L, ammonia leaching temperature 60 C, time 5h, liquid-solid ratio 20:1.In screening more than 1mm aluminium foil, copper foil, Iron sheet etc. is fitted into stainless steel screen frame, oxidation ammonia leaching is carried out in leaching tanks, leaching condition is consistent with fines, analyze ammonia is dipped Cheng Zhongtong, cobalt, the leaching rate of nickel are respectively 99.3%, 99.1% and 98.7%, and the leaching content of other metals is few.Subsequent two The ammonia leaching solution divided, which merges, send extraction process, and the ammonia leaching residue resided in stainless steel screen frame send magnetic separation to handle, magnetic field intensity 200T, obtains To the iron enriched substance of iron content 95%, after magnetic tailing is sieved through 1mm vibratory sieves again, on-the-sieve material is the aluminium enrichment containing aluminium 90% Thing, undersize material and fine ammonia leaching residue send manganese reducing leaching process to reclaim manganese together.
Step (4)：Ammonia leaching solution uses 20%LIX984N extracting coppers, nickel, and extraction phase compares O/A=1.5:1, it is real through 2 grades of extractions The separation of existing copper, nickel and cobalt.120g/L sulfuric acid solutions are used during back extraction, compared to O/A=10:1, it is stripped series 8, strip liquor pH Nickel is selectively stripped under conditions of=5, high-purity sulphuric acid nickel solution is obtained, afterwards using 180g/L sulfuric acid solutions, compared to O/A= 10:1, back extraction copper obtains copper-bath under conditions of being stripped series 2.Raffinate containing cobalt adds ammonium sulfide and carries out heavy cobalt, crystal seed Addition 700%, reaction time 2h, precipitation is filtered after terminating, and obtained cobalt sulfide is using oxidation sulfuric acid leaching, liquid-solid ratio 4:1, 80 DEG C of reaction temperature, the addition of oxidant hydrogen peroxide is 150g/L, and leachate uses 10% P204 extracting coppers, iron, manganese etc. Impurity, raffinate is high-purity sulphuric acid cobalt liquor.
Step (5)：Rich manganese material is passed through SO2Progress reduction sulfuric acid leaching, sulfuric acid concentration 50g/L, 60 DEG C of extraction temperature, when Between 6h, leachate hydrogenation sodium oxide molybdena adjustment pH value of solution 3.5, add 10g/L ammonium sulfide remove most copper in solution, Nickel, cobalt, then add 30g/L hydrogen peroxide, and adjust pH value of solution 5 or so with sodium hydroxide, depth hydrolysis' removing iron, Aluminium, while the trace copper remained in adsorbing and removing solution, nickel, cobalt, so as to obtain high-purity sulphuric acid manganese solution.
The composition of obtained all-fulfate solution is as shown in the table.
Cu Ni Co Mn Fe Al Ca Mg
CuSO4 52g/L <1.2g/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L
NiSO4 <5mg/L 85g/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L
CoSO4 <5mg/L 0.1g/L 93g/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L
MnSO4 <5mg/L <5mg/L <5mg/L 108g/L <5mg/L <5mg/L <5mg/L <5mg/L
Embodiment 2
Step (1)：MgO slurries will be put into after 1000g cobalt acid lithiums, nickel-cobalt-manganese ternary, the punching of nickel cobalt aluminium ternary battery waste Middle immersion 24h, battery is pulled out crushed afterwards, and suspended hood is set above disintegrating machine, and the electrolyte waste gas for collecting volatilization is used The absorption of CaO slurries is handled.After filtering, filtrate merges with follow-up carbonating water immersion liquid, and filter residue is then stored up.
Step (2)：Battery material after will be broken is inserted in Muffle furnace, and preroast, preroast are carried out under the conditions of 320 DEG C Time 2h.Material is passed through H at 450 DEG C afterwards2Reduction roasting 1.5h, H2Flow is 1L/min, preroast and reduction roasting The flue gas of journey output is handled with the absorption of CaO slurries.
Step (3)：The vibratory sieve that material after reduction roasting is handled is 1mm with mesh is sieved, thin less than 1mm Material carries out normal temperature water logging, and liquid-solid ratio is 4:1, extraction time 2h, are filtered after the completion of leaching, analyze Li leaching rate is 91.2%.Leachate evaporative crystallization at 95 DEG C, obtains lithium hydroxide, purity is under conditions of percent crystallization in massecuite is 90% 99.0%；Carry the leached mud after lithium and be passed through compressed air progress oxidation ammonia leaching, leaching agent is ammonium carbonate 2.5mol/L, ammoniacal liquor 1.0mol/L, ammonia 40 DEG C of temperature of leaching, time 8h, liquid-solid ratio 20:1.Aluminium foil, copper foil, iron sheet in screening more than 1mm etc. load not Become rusty in steel mesh frame, oxidation ammonia leaching carried out in leaching tanks, leaching condition is consistent with fines, analyze ammonia soak during copper, cobalt, nickel Leaching rate be respectively 99.2%, 99.3% and 98.6%, the leaching content of other metals is few.Then two-part ammonia leaching solution is closed And extraction process is sent, the ammonia leaching residue resided in stainless steel screen frame send magnetic separation to handle, magnetic field intensity 200T, obtains iron content 95% Iron enriched substance, magnetic tailing again through 1mm vibratory sieves sieve after, on-the-sieve material be the aluminium enriched substance containing aluminium 90%, undersize material and Fine ammonia leaching residue send manganese reducing leaching process to reclaim manganese together.
Step (4)：Ammonia leaching solution uses 20%LIX984N extracting coppers, nickel, and extraction phase compares O/A=1.5:1, it is real through 2 grades of extractions The separation of existing copper, nickel and cobalt.120g/L sulfuric acid solutions are used during back extraction, compared to O/A=10:1, it is stripped series 8, strip liquor pH Nickel is selectively stripped under conditions of=5, high-purity sulphuric acid nickel solution is obtained, afterwards using 180g/L sulfuric acid solutions, compared to O/A= 10:1, back extraction copper obtains copper-bath under conditions of being stripped series 2.Raffinate containing cobalt adds ammonium sulfide and carries out heavy cobalt, crystal seed Addition 700%, reaction time 2h, precipitation is filtered after terminating, and obtained cobalt sulfide is using oxidation sulfuric acid leaching, liquid-solid ratio 4:1, 80 DEG C of reaction temperature, the addition of oxidant hydrogen peroxide is 150g/L, and leachate uses 10% P204 extracting coppers, iron, manganese etc. Impurity, raffinate is high-purity sulphuric acid cobalt liquor.
Step (5)：Rich manganese material is passed through SO2Progress reduction sulfuric acid leaching, sulfuric acid concentration 50g/L, 60 DEG C of extraction temperature, when Between 6h, leachate hydrogenation sodium oxide molybdena adjustment pH value of solution 3.5, add 10g/L ammonium sulfide remove most copper in solution, Nickel, cobalt, then add 30g/L hydrogen peroxide, and adjust pH value of solution 5 or so with sodium hydroxide, depth hydrolysis' removing iron, Aluminium, while the trace copper remained in adsorbing and removing solution, nickel, cobalt, so as to obtain high-purity sulphuric acid manganese solution.
The composition of obtained all-fulfate solution is as shown in the table.
Cu Ni Co Mn Fe Al Ca Mg
CuSO4 56g/L <1.7g/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L
NiSO4 <5mg/L 83g/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L
CoSO4 <5mg/L 0.2g/L 87g/L <5mg/L <5mg/L <5mg/L <5mg/L <5mg/L
MnSO4 <5mg/L <5mg/L <5mg/L 98g/L <5mg/L <5mg/L <5mg/L <5mg/L

Claims (4)

1. a kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery, it is characterised in that recycling step is as follows：
Step (1)：Insert discharge process is carried out in alkaline earth oxide slurries after waste and old lithium ion battery punching, while by electricity Most phosphate radical is changed into insoluble solids with fluorine ion in the electrolyte of pond, and lithium is changed into solvable LiOH；Discharge afterwards The battery finished, which is pulled out, to be crushed, and suspended hood is set above disintegrating machine, collects the electrolyte waste gas of volatilization, and uses CaO slurries Absorption is handled, and makes F, P deposition removal, lithium is then stayed in the solution with lithium bicarbonate form, after filtering, filtrate and follow-up carbonic acid Change infusion to merge, filter residue is then stored up；
Step (2)：Material after broken carries out preroast under the conditions of 300~400 DEG C first, makes the organic adhesive in battery Agent, film and remaining electrolyte are thermally decomposed；Reducing agent is then added at 450~700 DEG C and carries out reduction roasting, roasting time 1~3h；Reducing agent is carbonaceous reducing agent or CO or H2Or NH3, the tail gas CaO slurries of preroast and reducing roasting process output Absorption is handled；
Step (3)：Material after being handled through reduction roasting carries out screening process, send leaching tanks to handle less than 1mm fineves, is such as calcined Shi Caiyong carbonaceous reducing agents or CO, then be passed through CO when leaching2Gas, lithium is gone out with water logging, and leachate send evaporative crystallization to produce carbon Sour lithium product；H is used when being such as calcined2Or NH3, then directly gone out with water logging, leachate is passed through CO2And evaporative crystallization production lithium carbonate Product or direct evaporative crystallization production lithium hydroxide product；
Step (4)：Carry the leached mud after lithium and be passed through compressed air progress oxidation ammonia leaching；Material more than 1mm loads stainless (steel) wire In frame, oxidation ammonia leaching is carried out in leaching tanks；During ammonia leaching, nickel, cobalt, copper are selectively leached, and iron, aluminium are not leached, and manganese is then It is converted into MnO2It is precipitated into slag；Subsequent ammonia leaching solution send extraction process, and the ammonia leaching residue resided in stainless steel screen frame send magnetic separation to handle, Iron enriched substance and magnetic tailing are obtained, again after screening, on-the-sieve material is aluminium enriched substance, undersize material and fine ammonia to mine tailing Phase analysis send manganese reducing leaching process to reclaim manganese together；
Step (5)：Cupric, nickel, the ammonia leaching solution of cobalt realize the separation of copper, nickel and cobalt, then the back extraction of chosen property using extraction, respectively Output high-purity sulphuric acid nickel and copper-bath；Raffinate is precipitated cobalt by vulcanizing, and liquid returns to ammonia leaching after heavy cobalt；Cobalt sulfide is used Oxidation acid leaching, leachate is purified, obtain high-purity sulphuric acid cobalt liquor after extraction；
Step (6)：Rich manganese material is using reduction sulfuric acid leaching, and leachate hydrogenation sodium oxide molybdena adjustment pH value of solution is 3.5, using vulcanization Method removes most copper, nickel, cobalt in solution, then adds appropriate hydrogen peroxide, and adjusts pH value of solution to 5 with sodium hydroxide, Depth hydrolysis' removing iron, aluminium, while the trace copper remained in adsorbing and removing solution, nickel, cobalt, so that it is molten to obtain high purity manganese sulfate Liquid.
2. the method for the comprehensively recovering valuable metal according to claim 1 from waste and old lithium ion battery, it is characterised in that Alkaline earth oxide described in step (1) is CaO or MgO.
3. the method for comprehensively recovering valuable metal, its feature in the material according to claim 1 from waste and old lithium ion battery It is, the leaching agent that ammonia soaks in step (4) is in ammoniacal liquor and ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride The mixed solution of one or two kinds of ammonium salts；Wherein ammonium salt concentration is 0.5~4mol/L, and ammonia concn is 1~5mol/L, solid-to-liquid ratio For 1:4~1:20, extraction time is 2~12 hours, and temperature is 20~90 DEG C.
4. the method for the comprehensively recovering valuable metal according to claims 1 to 3 from waste and old lithium ion battery, its feature exists In, described waste and old lithium ion battery include cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, iron manganese phosphate for lithium, nickel cobalt binary, Nickel manganese binary, cobalt manganese binary, nickel-cobalt-manganese ternary, one kind in nickel cobalt aluminium ternary battery or mixture.
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