CN107017443B

CN107017443B - A method for comprehensive recovery of valuable metals from waste lithium-ion batteries

Info

Publication number: CN107017443B
Application number: CN201710191599.5A
Authority: CN
Inventors: 王成彦; 张家靓; 胡军涛; 陈永强
Original assignee: University of Science and Technology Beijing USTB
Current assignee: GUANGDONG GUANGHUA SCI-TECH CO LTD
Priority date: 2017-03-28
Filing date: 2017-03-28
Publication date: 2019-04-09
Anticipated expiration: 2037-03-28
Also published as: CN107017443A

Abstract

The method of the invention discloses a kind of from waste and old lithium ion battery comprehensively recovering valuable metal.The following steps are included: being crushed after old and useless battery is carried out discharge treatment, after carrying out preroast at 300~400 DEG C, reducing agent is added and carries out reduction roasting at 450~700 DEG C.Fines after roasting obtains high purity lithium product through water logging, evaporative crystallization, block after leached mud and roasting leaches copper, nickel, cobalt 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 reduction 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 is by obtaining high-purity sulphuric acid cobalt liquor after vulcanizing heavy cobalt, oxidation acid leaching, extracting and purifying.This method is without sorting, and recovery rate of valuable metals is high, suitable for the processing of a variety of waste and old lithium ion battery raw materials and the efficient utilization of multielement.

Description

A 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 Recycle the smelting process of the valuable elements such as lithium, nickel, cobalt, manganese, copper, aluminium.Belong to recycling of WEEE processing, recycling field.

Background technique

In recent years, under environmentally protective historical background, there is rapid growth in China's new-energy automobile.Not with production capacity Disconnected to improve, waste and old lithium ion battery is increasing, and the shortage of resources and environmental problem thus caused is increasingly serious.

Processing to waste and old lithium ion battery mainly has chemical method and Mechanical Method (physical method), but both sides at present Method is both needed to that collector, positive pole powder, graphite powder, the diaphragm etc. in battery are classified by assorting room, and then to difference Component performs corresponding processing to obtain product.However since the structure of lithium ion battery is more special, such as CGR18650H type, outside Shell is nickel plated steel shell, and inside is rolled structure, has plastic film, main valuable material-positive electrode and aluminium foil between positive and negative anodes Collector bonding is close, is not only not easy to disintegrate and be crushed, but also in sorting, and the mechanical entrapment loss of positive electrode is serious, returns Yield is lower, this is the main reason for causing the valuable elements comprehensive recoveries such as entire technique cobalt, nickel, lithium low.

Domestic relevant manufacturers handle at present it is more be still worth higher positive electrode, for the whole battery scrapped, still Lack more mature treatment process and equipment.Individual producers are using sulfuric acid medium reducing leaching processing waste and old lithium ion battery Technique.Technical process are as follows: (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 to sort, although leaching the leaching of process Ni, Co, Mn Extracting rate is very high, but assorting room product mutually contains seriously, causes entire technique recovery rate of valuable metals lower.In addition, lithium metal exists As cobalt, nickel, manganese etc. enter in solution together in acid dissolution, after cobalt, nickel, manganese are extracted in extraction, most lithiums is stayed in In raffinate.The concentration of contained lithium is extremely low in raffinate at this time, while sodium ion in liquor content is high, therefrom recycles 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 break up It is broken, vibrosieve is carried out later, and the positive and negative anodes powder obtained after screening is roasted under protective atmosphere, maturing temperature 800 ~900 DEG C, simple substance cobalt, lithium carbonate powder, powdered graphite mixture are obtained after roasting, and 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 disadvantages of this method is screening process The mechanical entrapment loss of middle positive electrode is serious, not can guarantee the higher rate of recovery；In addition, being dissolved in the electricity in positive and negative pole material Solution liquid, which can be reacted in roasting process with lithium, generates LiF, Li₃PO₄Equal insoluble matters, reduce the rate of recovery of lithium.

Chinese patent CN 104577248A is passed through hydrogen treat cobalt acid lithium powder under the conditions of 580~780 DEG C, later will Calcining is dissolved with water, and slag dries to obtain cobalt oxide, and filtrate is then added sodium carbonate after circulation collection and obtains lithium carbonate；Chinese patent CN 106129511A then uses coal to carry out reduction roasting to applying waste lithium ionic positive electrode as reducing agent, and product of roasting uses Carbonating water logging, evaporative crystallization obtain lithium carbonate, and water logging slag then uses acidleach or ammonia to soak 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 Side reaction and volatilization caused by environmental problem.

In " the electric powered motor Battery recycling benefit that National Development and Reform Committee, Ministry of Industry and Information, Deng Ji ministries and commissions, Chinese Ministry of Environmental Protection organize to set up With technical policy (version in 2015) " in require, the processing of old and useless battery should select advanced, environmentally friendly smelting process, hydrometallurgy For the comprehensive recovery of nickel, cobalt, manganese not less than 98%, the comprehensive recovery of pyrometallurgical smelting should be not less than 97% in the process.Therefore, exist Under conditions of current automatic high-efficiency sorting technology, equipment are still immature, assortment step is studied and developed and can high efficiente callback The method of valuable element, has important practical significance in waste and old lithium ion battery.

Summary 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 solution is as follows with related description:

Step (1): it is placed in alkaline earth oxide slurries after waste and old lithium ion battery punching and carries out discharge treatment, simultaneously Phosphate radical most in battery electrolyte and fluorine ion are changed into insoluble solids, and lithium is changed into soluble LiOH.The step Suddenly phosphate radical and fluorine ion can be converted to precipitating solidification under cryogenic, it is avoided to wave in subsequent roasting process Hair, while also can avoid generating LiF, Li in roasting process₃PO₄, reduce the leaching rate of lithium.

The battery of discharge off, which is pulled out, later is crushed, and suspended hood is arranged above crusher, collects the electrolyte of volatilization Exhaust gas CaO slurries make F, P deposition removal, and lithium is then stayed in the form of lithium bicarbonate in the solution, after filtering, filtrate with it is subsequent Carbonating water immersion liquid merges, and filter residue is then stored up.

Step (2): broken material 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 further decreasing the amount of electrolyte, avoid generating in reducing roasting process LiF, Li₃PO₄, reduce the leaching rate of lithium；Reducing agent is added after the completion of preroast at 450~700 DEG C and carries out reduction roasting, when 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 processing.

Step (3): screening process is carried out through reduction roasting treated material, send leaching tanks to handle less than 1mm fines, such as Carbonaceous reducing agent or CO are used when roasting, then are passed through CO when leaching₂Gas goes out lithium with water logging, and leachate send evaporative crystallization raw Produce lithium carbonate product；H is used when such as roasting₂Or NH₃, then directly gone out with water logging, leachate is passed through CO₂And evaporative crystallization produces carbon Sour lithium product or direct evaporative crystallization produce lithium hydroxide product.

Step (4): the leached mud after mentioning lithium is passed through compressed air and carries out oxidation ammonia leaching.It is packed into greater than the material of 1mm stainless In steel mesh frame, oxidation ammonia leaching is carried out in leaching tanks.During ammonia leaching, by Selectively leaching, iron, aluminium are not leached for nickel, cobalt, copper, 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, and again after screening, on-the-sieve material is aluminium enriched substance, undersize material and particulate to tailing Material ammonia leaching residue send manganese reducing leaching process to recycle manganese together.

Step (5): the separation of copper, nickel and cobalt, then the back extraction of chosen property are realized in the ammonia leaching solution use extraction of cupric, nickel, cobalt, Output high-purity sulphuric acid nickel and copper-bath respectively.Raffinate is precipitated cobalt by vulcanizing, and liquid returns to ammonia leaching after heavy cobalt.Cobalt sulfide Using oxidation acid leaching, leachate is purified, obtains high-purity sulphuric acid cobalt liquor after extraction.

Step (6): using reduction sulfuric acid leaching, leachate adding sodium hydroxide adjusts pH value of solution 3.5 or so for rich manganese material, Most copper, nickel, cobalt in solution are removed using vulcanization, then add appropriate hydrogen peroxide, and adding sodium hydroxide adjustment is molten Liquid pH is 5 or so, and depth hydrolysis remove iron, aluminium, while remaining trace copper, nickel, cobalt in adsorbing and removing solution, to obtain height Pure manganese sulfate solution.

In above-mentioned technical proposal, alkaline earth oxide described in step (1) is CaO or MgO.

It is ammonium hydroxide and ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, chlorination that ammonia described in step (4), which soaks leaching agent, 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, and extraction time is 2~12 hours, and temperature is 20~90 DEG C.

The waste and old lithium ion battery includes cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, iron manganese phosphate for lithium, nickel cobalt One of binary, nickel manganese binary, cobalt manganese binary, nickel-cobalt-manganese ternary, nickel cobalt aluminium ternary battery or mixture.

This method is different from the characteristics of passing method and is with advantage:

(1) old and useless battery only needs simple crushing, without sorting, fundamentally ensure that Co, Cu, Ni etc. are main valuable in this way The high-recovery of metal, and the pre- pre-treatment of battery is enormously simplified, reduce processing cost.

(2) it is discharged using CaO or MgO slurries old and useless battery, while can made under normal temperature conditions big in electrolyte Partial phosphate radical and fluorine ion is converted to precipitating solidification, avoids it from volatilizing in subsequent roasting process and pollutes；The step Suddenly it also can avoid generating the indissoluble object containing lithium in reducing roasting process together with subsequent low temperature preroast process, reduce the recycling of lithium Rate.

(3) lithium in battery can simply and efficiently be recycled using the dipped journey of reduction roasting-carbonating water；It is simultaneously and traditional Acid leaching process is compared, and the consumption of ammonia leaching process chemical and corresponding brine waste quantum of output are also greatly reduced, and can fit For the processing of a variety of waste and old lithium ion battery raw materials and the efficient utilization of multielement.

Detailed description of the invention

Fig. 1 is that waste and old lithium ion battery multielement composite utilizes principle process flow

Specific embodiment

To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment, But the protection scope of the present invention is not limited to the following specific embodiments.It should be pointed out that the ordinary skill people of this field 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 scope.

Embodiment 1

Step (1): CaO slurries will be put into after 1000g cobalt acid lithium, nickel-cobalt-manganese ternary, the punching of nickel cobalt aluminium ternary battery waste Battery for 24 hours, is pulled out be crushed later by middle immersion, and suspended hood is arranged above crusher, and the electrolyte exhaust gas for collecting volatilization is used CaO slurries absorption processing.After filtering, filtrate merges with subsequent carbonating water immersion liquid, and filter residue is then stored up.

Step (2): broken battery material is placed in Muffle furnace, carries out preroast, preroast under the conditions of 350 DEG C Time 1h.After material is mixed with 80g lignite (phosphorus content 60%) later, the reduction roasting 2h at 600 DEG C.Preroast and reduction The flue gas of roasting process output uses CaO slurries absorption to handle.

Step (3): reduction roasting treated material is sieved with the vibrating screen that mesh is 1mm, thin less than 1mm Material carries out room temperature and carbonates water logging, is passed through CO₂Flow be 3L/min, liquid-solid ratio 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 99.1%；Leached mud after mentioning lithium is passed through compressed air and carries out oxidation ammonia leaching, and leaching agent is ammonium sulfate 2mol/L, ammonium hydroxide 1.5mol/L, ammonia soak temperature 60 C, time 5h, liquid-solid ratio 20:1.In screening greater than the aluminium foil of 1mm, copper foil, Iron sheet etc. is fitted into stainless steel screen frame, carried out in leaching tanks oxidation ammonia leaching, leaching condition is consistent with fines, analyze ammonia is dipped Cheng Zhongtong, cobalt, nickel leaching rate be respectively 99.3%, 99.1% and 98.7%, the leaching content of other metals is few.Subsequent two Extraction process is sent in the ammonia leaching solution merging divided, and the ammonia leaching residue resided in stainless steel screen frame send magnetic separation to handle, and magnetic field strength 200T is obtained To the iron enriched substance of iron content 95%, for magnetic tailing again after the screening of 1mm vibrating screen, on-the-sieve material is the aluminium enrichment containing aluminium 90% Object, undersize material and fine ammonia leaching residue send manganese reducing leaching process to recycle manganese together.

Step (4): ammonia leaching solution uses 20%LIX984N extracting copper, nickel, and extraction phase ratio O/A=1.5:1 is real through 2 grades of extractions The separation of existing copper, nickel and cobalt.120g/L sulfuric acid solution is used when back extraction, is being compared O/A=10:1, is being stripped series 8, strip liquor pH It is selectively stripped nickel under conditions of=5, obtains high-purity sulphuric acid nickel solution, uses 180g/L sulfuric acid solution later, is comparing O/A= 10:1, back extraction copper obtains copper-bath under conditions of being stripped series 2.Raffinate containing cobalt is added ammonium sulfide and carries out heavy cobalt, crystal seed Additional amount 700%, reaction time 2h are filtered after precipitating, and obtained cobalt sulfide is using oxidation sulfuric acid leaching, liquid-solid ratio 4:1, 80 DEG C of reaction temperature, the additional amount of oxidant hydrogen peroxide is 150g/L, and leachate uses 10% P204 extracting copper, iron, manganese etc. Impurity, raffinate are high-purity sulphuric acid cobalt liquor.

Step (5): rich manganese material is passed through SO₂Carry out reduction sulfuric acid leaching, sulfuric acid concentration 50g/L, 60 DEG C of extraction temperature, when Between 6h, leachate adding sodium hydroxide adjusts pH value of solution 3.5, be added 10g/L ammonium sulfide remove most copper in solution, Nickel, cobalt, then add the hydrogen peroxide of 30g/L, and with sodium hydroxide adjustment pH value of solution 5 or so, depth hydrolysis remove iron, Aluminium, while remaining trace copper, nickel, cobalt in adsorbing and removing solution, to obtain high-purity sulphuric acid manganese solution.

The ingredient 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

NiSO₄

<5mg/L

85g/L

<5mg/L

CoSO₄

<5mg/L

0.1g/L

93g/L

<5mg/L

MnSO₄

<5mg/L

108g/L

<5mg/L

Embodiment 2

Step (1): MgO slurries will be put into after 1000g cobalt acid lithium, nickel-cobalt-manganese ternary, the punching of nickel cobalt aluminium ternary battery waste Battery for 24 hours, is pulled out be crushed later by middle immersion, and suspended hood is arranged above crusher, and the electrolyte exhaust gas for collecting volatilization is used CaO slurries absorption processing.After filtering, filtrate merges with subsequent carbonating water immersion liquid, and filter residue is then stored up.

Step (2): broken battery material is placed in Muffle furnace, carries out preroast, preroast under the conditions of 320 DEG C Time 2h.Material is passed through H at 450 DEG C later₂Reduction roasting 1.5h, H₂Flow is 1L/min, preroast and reduction roasting The flue gas of journey output uses CaO slurries absorption to handle.

Step (3): reduction roasting treated material is sieved with the vibrating screen that mesh is 1mm, thin less than 1mm Material carries out room temperature water logging, and liquid-solid ratio 4:1, extraction time 2h are filtered after the completion of leaching, analyze the leaching rate of Li is 91.2%.Leachate evaporative crystallization at 95 DEG C obtains lithium hydroxide under conditions of percent crystallization in massecuite is 90%, and purity is 99.0%；Leached mud after mentioning lithium is passed through compressed air and carries out oxidation ammonia leaching, and leaching agent is ammonium carbonate 2.5mol/L, ammonium hydroxide 1.0mol/L, ammonia soak 40 DEG C of temperature, time 8h, liquid-solid ratio 20:1.The loadings such as aluminium foil, copper foil, iron sheet in screening greater than 1mm are not Become rusty steel mesh frame in, carried out in leaching tanks oxidation ammonia leaching, 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 closes And extraction process is sent, the ammonia leaching residue resided in stainless steel screen frame send magnetic separation to handle, and magnetic field strength 200T obtains iron content 95% Iron enriched substance, magnetic tailing again through 1mm vibrating screen screening 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 recycle manganese together.

The ingredient 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

NiSO₄

<5mg/L

83g/L

<5mg/L

CoSO₄

<5mg/L

0.2g/L

87g/L

<5mg/L

MnSO₄

<5mg/L

98g/L

<5mg/L

Claims

1. a method for comprehensive recovery of valuable metals from waste and old lithium ion batteries, is characterized in that the recovery step is as follows:

Step (1): After the waste lithium-ion battery is punched, it is placed in the alkaline earth metal oxide slurry for discharge treatment. At the same time, most of the phosphate and fluoride ions in the battery electrolyte are converted into insoluble solids, while lithium is converted into soluble solids. LiOH; then the discharged battery is taken out for crushing, and a suction hood is set above the crusher to collect the volatilized electrolyte waste gas, and absorb and treat it with CaO slurry to precipitate and remove F and P, while lithium remains in the form of lithium bicarbonate. In the solution, after filtration, the filtrate is combined with the subsequent carbonated water leaching solution, and the filter residue is deposited;

Step (2): The crushed material is first pre-baked at 300~400°C to thermally decompose the organic binder, film and residual electrolyte in the battery; then a reducing agent is added at 450~700°C for reduction Roasting, the roasting time is 1~3h; the reducing agent is carbonaceous reducing agent or CO or H ₂ or NH ₃ , and the tail gas produced in the pre-roasting and reducing roasting process is absorbed and treated with CaO slurry;

Step (3): The material after reduction and roasting treatment is screened, and the fine material smaller than 1mm is sent to the leaching tank for processing. If a carbonaceous reducing agent or CO is used in the roasting, CO ₂ gas is introduced during the leaching, and the lithium is leached with water. , the leaching solution is sent to evaporative crystallization to produce lithium carbonate products; if H ₂ or NH ₃ is used during roasting, it is directly leached with water, and the leaching solution is passed into CO ₂ and evaporated and crystallized to produce lithium carbonate products or directly evaporated and crystallized to produce lithium hydroxide products;

Step (4): the leaching residue after lithium extraction is passed into compressed air for ammonia oxidation leaching; materials larger than 1 mm are loaded into the stainless steel mesh frame, and ammonia oxidation leaching is carried out in the leaching tank; during the ammonia leaching process, nickel, cobalt, copper It is selectively leached, iron and aluminum are not leached, and manganese is converted into MnO ₂ and precipitated into the slag; then the ammonia leaching solution is sent to the extraction process, and the ammonia leaching slag retained in the stainless steel mesh frame is sent to magnetic separation to obtain iron enrichment and Magnetic separation of tailings, after the tailings are screened again, the material on the screen is aluminum enrichment, and the material under the screen and the fine-grained material ammonia leaching residue are sent to the manganese reduction leaching process to recover manganese;

Step (5): the ammonia leaching solution containing copper, nickel and cobalt is extracted to realize the separation of copper, nickel and cobalt, and then selectively stripped to produce high-purity nickel sulfate and copper sulfate solutions respectively; Cobalt is precipitated, and the liquid is returned to ammonia leaching after cobalt precipitation; cobalt sulfide is leached with oxidative acid, and the leaching solution is purified and extracted to obtain high-purity cobalt sulfate solution;

Step (6): the manganese-rich material is leached with reduced sulfuric acid, the leaching solution is added with sodium hydroxide to adjust the pH of the solution to 3.5, and most of the copper, nickel and cobalt in the solution are removed by the sulfidation method, then 30g/L hydrogen peroxide is added, and hydrogen Sodium oxide adjusts the pH of the solution to 5, deep hydrolysis removes iron and aluminum, and at the same time absorbs and removes traces of copper, nickel and cobalt remaining in the solution, thereby obtaining a high-purity manganese sulfate solution.

2 . The method for comprehensively recovering valuable metals from spent lithium-ion batteries according to claim 1 , wherein the alkaline earth metal oxide described in step (1) is CaO or MgO. 3 .

3. The method for comprehensively recovering valuable metals from waste lithium-ion batteries according to claim 1, wherein the leaching agent for ammonia leaching in step (4) is ammonia water and ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, The mixed solution of one or two ammonium salts in ammonium bicarbonate and ammonium chloride; wherein the ammonium salt concentration is 0.5～4mol/L, the ammonia concentration is 1～5mol/L, and the solid-liquid ratio is 1:4～1: 20. The leaching time is 2~12 hours, and the temperature is 20~90℃.

4. the method for comprehensively reclaiming valuable metals from waste and old lithium ion batteries according to any one of claims 1 to 3, is characterized in that, described waste and old lithium ion batteries comprises lithium cobaltate, lithium nickelate, lithium manganate , lithium iron phosphate, lithium iron manganese phosphate, nickel-cobalt binary, nickel-manganese binary, cobalt-manganese binary, nickel-cobalt-manganese ternary, nickel-cobalt-aluminum ternary battery or a mixture.