CN101519726A - Method for directly roasting and treating waste lithium ion battery and recycling valuable metal - Google Patents
Method for directly roasting and treating waste lithium ion battery and recycling valuable metal Download PDFInfo
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- CN101519726A CN101519726A CN200910130828A CN200910130828A CN101519726A CN 101519726 A CN101519726 A CN 101519726A CN 200910130828 A CN200910130828 A CN 200910130828A CN 200910130828 A CN200910130828 A CN 200910130828A CN 101519726 A CN101519726 A CN 101519726A
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Abstract
A method for directly roasting and treating waste lithium ion batteries and recovering valuable metals, in particular to the recovery and treatment of the waste lithium ion batteries taking lithium cobaltate as a positive electrode material. Firstly, roasting at 500-850 ℃ to remove organic binders on organic diaphragm materials and electrode materials in batteries, crushing the roasted battery materials, mixing with sodium sulfate (or potassium sulfate) and concentrated sulfuric acid, mixing for size mixing, carrying out secondary heat treatment at 350-600 ℃ in an electric furnace to convert metals such as cobalt, copper and lithium in the waste lithium ion batteries into sulfates which are easily dissolved in water, leaching with water or dilute sulfuric acid solution, and then extracting cobalt and copper from leachate by using an organic extractant to obtain copper and cobalt products. After precipitating metallic lithium from the leaching solution from which cobalt and copper have been removed with sodium carbonate, the leaching solution is returned to the treatment of the hot secondary heat treatment material. The metal leaching rate is more than 99.5 percent, and the metal recovery rate is more than 99 percent.
Description
Technical field
The present invention relates to the processing of waste and old lithium ion battery and the method for recovery valuable metal, belong to environment protection and non-ferrous metal recycle utilization field.Be particularly related to processing that contains the cobalt waste and old lithium ion battery and the method that reclaims valuable metal.
Technical background
Lithium ion battery has been widely used in electronic products such as mobile phone, notebook computer, digital camera and pick up camera as a kind of portable rechargeable type power supply.Wherein be generally the work-ing life of mobile phone lithium ion battery 2～3 years, the annual waste and old lithium ion battery of eliminating is hundreds of millions of.
Waste and old lithium ion battery mainly contains materials such as cobalt acid lithium, lithium hexafluoro phosphate, organic carbonate, carbon materials, copper, aluminium, nickel, manganese.Kalamein aluminum hull, the also plastic again material shell of some surperficial outermost layer are formed by major portions such as positive pole, electrolytic solution, negative poles in the inside of general lithium ion battery.The positive pole of battery is by positive active material LiXMA
2Behind (cobalt acid lithium, lithium nickelate, lithium manganate, or mix the cobalt acid lithium of nickel, manganese, but mainly in the majority), acetylene black conductive agent, the organic binder bond uniform mixing, coat on the aluminum foil current collector of thick about 20 μ m with cobalt acid lithium.The negative pole of battery is made up of negative electrode active goods and materials carbon material, acetylene black conductive agent, adhesive material, coats behind the uniform mixing on the Copper Foil collector of thick about 20 μ m.Poly(vinylidene fluoride) (PVDF), vinylidene fluoride (VF
2) homopolymer and VF
2Multipolymer R 1216 (VF
2/ HFP) for binding agent commonly used, when the modulator electrode slurry, binding agent is dissolved with NMP, with positive active material or negative electrode active material mixing furnishing slurry, be coated in again and make membrane electrode on the metal collector.The thickness of positive and negative electrode is about 0.18～0.2mm, and middle polypropylene (PP) or polyethylene (PE) with the about 10 μ m of thickness separates, and fills to contain lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4) the organic carbonate electrolytic solution that waits.The diaphragm material of lithium ion cell electrode mainly contains polypropylene (PP), polyethylene (PE) individual layer microporous membrane, and by PP and PE compound multilayer microporous film, electrode materials and collector (as aluminium foil or Copper Foil) on anodal and the negative pole is separated respectively.Polymer Li-ion battery then adopts the electrolyte gel polymer dielectric, has barrier film and electrolytical effect.Waste and old lithium ion battery is as dealing with improperly, and the some of them material will pollute environment.
Present various types of waste and old lithium ion battery mainly contains 5～23% cobalts, 0～10% nickel, 2～7% lithiums, 5～11% bronze medals, 3～10% aluminium, 3～15% organism, 1～7% plastics etc., also contains manganese and a small amount of tin etc.Produce lithium ion battery and consumed a large amount of non-ferrous metals, wherein the cobalt consumption accounts for 50% of domestic cobalt aggregate consumption.China's cobalt metals resources amount is about 1,400,000 t, and the overwhelming majority is an associated resources, and independent cobalt deposits is few.China's cobalt ore grade is lower, all reclaims as copper, nickel minerals mountain byproduct, because low, the complex manufacturing of grade, so metal recovery rate is low, production cost is high in the production process.Cobalt in waste lithium ion batteries content is higher 500～2000 times than cobalt ore, has become a kind of important cobalt raw material of carrying.
Many treatment processs have been proposed for the processing of waste and old lithium ion battery and the recovery of valuable metal both at home and abroad.The method of physics commonly used or chemistry is carried out pre-treatment, and the method with pyrometallurgy or hydrometallurgy reclaims valuable metal then.Separate or enriching method more, as with waste and old lithium ion battery its after discharge process, pass through operations such as roasting, fragmentation, magnetic separation, classification again, obtain the enriched substance of valuable metal, as the raw material of further processing.Adopt specific chemical reagent (organic solvent or mineral acid, alkali) substep to leach different components in the waste and old lithium ion battery, the starting acid of leach liquor (alkali) height, when reclaiming valuable metal wherein more respectively from different solution, need to add a large amount of acid (or alkali) neutralization again, the secondary waste liquid of generation, refuse are many, operational condition is poor, also often need to add special leaching agent, extraction time is long, its complex process, long flow path is operated loaded down with trivial details.And when adopting the direct high melt waste and old lithium ion battery of pyrometallurgy, its equipment requirements height, the rate of recovery of metal is lower, and product composition complexity, of low quality needs further to handle, to general enterprise incompatibility.Particularly some treatment processs need be separated heterogeneity material in the waste and old lithium ion battery in advance, and its employed treatment facility is many, and processing cost increases substantially, and have also produced many further intermediates of processing that are unfavorable for.
Waste and old lithium ion battery treatment process disclosed by the invention, waste and old lithium ion battery is not done sorting or substep leaching processing, directly with the waste and old lithium ion battery roasting, remove behind the organism broken earlier, again the waste and old lithium ion battery particle is mixed with sodium sulfate (or vitriolate of tartar), the vitriol oil and size mixing, carry out re-baking at low temperatures, leach, at last with method of extraction recovery valuable metals such as cobalt, copper and lithium wherein with hot water.This method has reduced the treatment process link and the chemical feedstocks consumption of waste and old lithium ion battery significantly, and intermediate product is few, has reduced production cost, and treatment capacity is big, the metal recovery rate height.Wherein key is the mixture by thermal treatment waste and old lithium ion battery and the sodium sulfate (or vitriolate of tartar) and the vitriol oil, make cobalt, copper and lithium etc. in the waste and old lithium ion battery generate vitriol soluble in water, thereby can adopt gentle leaching method, and simplify the removal process of valuable metal.
Summary of the invention
The objective of the invention is: a kind of processing of waste and old lithium ion battery is provided and reclaims the method for valuable metal, particularly at being the recycling of the waste and old lithium ion battery of positive electrode material with cobalt acid lithium.Remove the organic binder bond on the organic diaphragm material and electrode materials in the battery by the method for roasting, make part metals oxidations such as copper wherein simultaneously, the waste and old lithium ion battery material becomes fragile, and is easy to fragmentation.After the battery material fragmentation of roasting, mix and size mixing with sodium sulfate (or vitriolate of tartar), the vitriol oil, carry out second heat treatment, making the metallic transitions such as cobalt, copper and lithium in the waste and old lithium ion battery is vitriol soluble in water, after water or dilution heat of sulfuric acid leach, from leach liquor, extract cobalt, copper respectively with organic extractant again, copper, from the leach liquor that has removed cobalt and copper, precipitate metallic lithium with yellow soda ash after, leach liquor returns use.Metal leaching rate is greater than 99.5%, and metal recovery rate is greater than 99%.
The objective of the invention is to realize by following scheme:
1, waste and old lithium ion battery is put into 5～10% sodium chloride aqueous solution and soaked, put, take out 70～80 ℃ of oven dry except that the remaining capacity in the battery, put into electric furnace internal heating to 200～230 ℃, insulation 1.5～2h continues to be warming up to 500～850 ℃, is incubated 4～8 hours in air.Take out the cooling back, and it is crushed to area less than 5mm
2Particle.
2, the battery particle is mixed with solid sodium sulfate (or vitriolate of tartar), pour in the alumina crucible, adding 98% vitriol oil again sizes mixing, wherein battery particle and solid sodium sulfate (or vitriolate of tartar) weight of material is than being 1:0.4～1.3, battery particle and vitriol oil weight ratio are 1:0.6～1.5, are incubated 4～8h under 350～600 ℃ of temperature in electric furnace.
3, the mixture of the battery particle after the roasting and the sodium sulfate (or vitriolate of tartar) and the vitriol oil is poured in 60～90 ℃ the hot water or 1～5g/L dilute sulfuric acid aqueous solution into agitation leach 0.5～1h.
4, leach liquor is filtered, the pH value to 0.5 of regulating the dilute sulphuric acid leach liquor with the aqueous sodium hydroxide solution of 20～40g/L, or with the pH value to 0.5 of 50～80g/L dilute sulphuric acid adjusting hot water, with containing the removal of impurities of 10～30%P204 organic extractant.Re-adjustment pH of leaching solution to 4～5.0, with containing 10～30%LIX984 (or LIX984N) organic extractant extracting copper, by aqueous sulfuric acid back extraction copper from collection copper organic phase of 170～200g/L, the strip liquor of sulfur acid copper send electro deposited copper, or the evaporation concentration strip liquor obtains cupric sulfate crystals.Leach liquor is behind collection copper, regulate pH of leaching solution to 5.0～6.0, with containing 10～30%Cyanex272 organic extractant extraction cobalt, by aqueous hydrochloric acid back extraction cobalt from collection cobalt organic phase of 90～110g/L, cobalt with in the ammonium oxalate precipitate cobalt strip liquor obtains the cobalt oxalate product.With precipitating lithium ion the leach liquor of yellow soda ash after taking off cobalt, obtain lithium carbonate product, leach liquor returns handles the roasting material.
Embodiment
Embodiment of the present invention provides a kind of processing of waste and old lithium ion battery and reclaims the method for valuable metal, particularly at being the recycling of the waste and old lithium ion battery of positive electrode material with cobalt acid lithium.By 500～850 ℃ of roasting temperatures at first with organism in the battery, to remove organic waste and old lithium ion battery particle and sodium sulfate (or vitriolate of tartar) again, vitriol oil mixture carries out second heat treatment under 350～600 ℃ of temperature, make the cobalt in the waste and old lithium ion battery, metallic element such as copper and lithium changes vitriol soluble in water into, vitriol is dissolved in hot water or the 1～5g/L dilute sulphuric acid water, from the leach liquor of sulfur-bearing hydrochlorate, extract cobalt respectively with organic extractant then, copper, yellow soda ash precipitation metallic lithium, the leach liquor behind the extraction metal returns the vitriol that is used for stripping thermal treatment material.Below in conjunction with specific embodiment embodiment of the present invention is described further.
Embodiment one
The processing of mobile phone waste and old lithium ion battery.Every heavy 18.6g of certain brand mobile phone waste and old lithium ion battery, its major metal composition is Li 2.74%, Co 22.31%, Cu 7.47%, Ni 0.40%, Mn 0.08%, Al 9.78%.Get 20 of this waste and old lithium ion batteries, put into that 500ml concentration is housed is that 5% sodium chloride aqueous solution soaks 6h, take out to be placed in the porcelain dish 70 ℃ of oven dry 4h in electric drying oven with forced convection.After peelling off the aluminium shell of waste and old lithium ion battery, in the alumina crucible of packing into, be placed on and be heated to 200 ℃ in the electric furnace earlier, insulation 1.5h then is warming up to 700 ℃, feeds an amount of air, be incubated 6 hours, the gas that overflows in the heat-processed absorbs with the water slurry that contains 1% Wingdale.Take out cooling back, with its with mortar hand-crushed to area less than 5mm
2Particle, in the alumina crucible of packing into, add sodium sulfate 180g (or vitriolate of tartar 200g), be that 98% the vitriol oil is sized mixing with 100ml concentration, at electric furnace internal heating to 450 ℃, heat preservation hot processing 6h.Material after the thermal treatment is changed in the beaker of 3L, adding concentration is the dilute sulfuric acid aqueous solution 2L of 1g/L, is heated to 70 ℃, agitation leach 45 minutes.Leach liquor is filtered, and is the pH value to 0.5 of the aqueous sodium hydroxide solution adjusting dilute sulphuric acid leach liquor of 25g/L with concentration.With the 10%P204 organic extractant removal of impurities of kerosene dilution, organic phase is 1:2 with the ratio of water.After separating the P204 organic extractant, regulate pH of leaching solution to 5.0, with 15%LIX984 (or LIX984N) the organic extractant extracting copper of kerosene dilution, organic phase is 1 with the ratio of water; 1, behind separation LIX984 (or LIX984N) the collection copper organic extractant,, obtain the strip liquor of sulfur acid copper by aqueous sulfuric acid back extraction copper from collection copper organic phase of 180g/L, send electro deposited copper, the fine copper of output cupric 99.95%.Leach liquor is behind collection copper, regulate pH of leaching solution to 5.5,20%Cyanex272 organic extractant extraction cobalt with the kerosene dilution, aqueous hydrochloric acid back extraction cobalt from collection cobalt organic phase by 100g/L, be the cobalt in the ammonium oxalate aqueous solution precipitate cobalt strip liquor of 80g/L with concentration, obtain the cobalt oxalate product.After carrying copper, cobalt, be that the yellow soda ash of 60g/L precipitates lithium ion from leach liquor with concentration, obtain the Quilonum Retard material.After leach liquor is added sulfuric acid and water, return and leach the roasting material.Metal leaching rate is greater than 99.5% in the whole process, and metal recovery rate is greater than 99%.
Embodiment two
The waste and old lithium ion battery enriched substance is handled.Certain waste and old lithium ion battery is after mechanical powder is pulverized, sorted separation, and output contains cobalt, copper and lithium material, and its major metal composition is Li 4.15%, Co 3.26%, Cu 3.65%, Al 6.33%.Get this refuse battery enriched substance particle 230g, in the alumina crucible of packing into, be placed on electric furnace internal heating to 700 ℃, feed an amount of air, be incubated 6 hours, the gas that overflows in the heat-processed absorbs with the water slurry that contains 1% Wingdale.Take out cooling back, with its with mortar hand-crushed to area less than 5mm
2Particle, in the alumina crucible of packing into, add sodium sulfate 160g (or vitriolate of tartar 180g), be that 98% the vitriol oil is sized mixing with 120ml concentration, at electric furnace internal heating to 450 ℃, heat preservation hot processing 5h.Material after the thermal treatment is changed in the beaker of 3L, add water 2L, be heated to 80 ℃, agitation leach 40 minutes.Leach liquor is filtered, and is the pH value to 0.5 of the dilute sulphuric acid adjusting hot water of 60g/L with concentration.Remove small amount of impurities in the leach liquor with the 10%P204 organic extractant of kerosene dilution, organic phase is 1:2 with the ratio of water.After separating the P204 organic extractant, regulate pH of leaching solution to 5.0,15%LIX984 (or LIX984N) organic extractant extracting copper with the kerosene dilution, organic phase is 1:1 with the ratio of water, after separating LIX984 (or LIX984N) collection copper organic extractant, by aqueous sulfuric acid back extraction copper from collection copper organic phase of 170g/L, obtain the strip liquor of sulfur acid copper; The heating strip liquor, evaporation concentration is separated out copper sulfate after the cooling, filter to obtain the cupric sulphate crystal product.Leach liquor is behind collection copper, regulate pH of leaching solution to 6.0,10% Cyanex, 272 organic extractants extraction cobalt with the kerosene dilution, aqueous hydrochloric acid back extraction cobalt from collection cobalt organic phase by 90g/L, be the cobalt in the ammonium oxalate aqueous solution precipitate cobalt strip liquor of 80g/L with concentration, obtain the cobalt oxalate product.After carrying copper, cobalt, be that the yellow soda ash of 60g/L precipitates lithium ion from leach liquor with concentration, obtain the Quilonum Retard material.After leach liquor is added sulfuric acid and water, return and leach the roasting material.Metal leaching rate is greater than 99.5% in the whole process, and metal recovery rate is greater than 99%.
The above; only be specific embodiments of the invention; succession between each embodiment does not cause any restriction to the present invention; protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (5)
1, a kind of direct roasting is handled waste and old lithium ion battery and is reclaimed the method for valuable metal, it is characterized in that: at first remove the organic binder bond on the organic diaphragm material and electrode materials in the battery by roasting, will through after the battery material fragmentation of roasting with sodium sulfate (or vitriolate of tartar), the vitriol oil mixes sizes mixing, carry out second heat treatment, make the cobalt in the waste and old lithium ion battery, metallic transition such as copper and lithium is a vitriol soluble in water, after water or dilution heat of sulfuric acid leach, from leach liquor, extract cobalt respectively with organic extractant again, copper, after precipitating metallic lithium with yellow soda ash from the leach liquor that has removed cobalt and copper, leach liquor returns use.Specifically may further comprise the steps successively:
(1), waste and old lithium ion battery put into 5～10% sodium chloride aqueous solution soak, put except that the remaining capacity in the battery, take out 70～80 ℃ of oven dry, put into electric furnace internal heating to 200～230 ℃, insulation 1.5～2h continues to be warming up to 500～850 ℃, is incubated 4～8 hours in air.Take out the cooling back, and it is crushed to area less than 5mm
2Particle.
(2), the battery particle is mixed with solid sodium sulfate (or vitriolate of tartar), pour in the alumina crucible, adding 98% vitriol oil again sizes mixing, wherein battery particle and solid sodium sulfate (or vitriolate of tartar) weight of material is than being 1:0.4～1.3, battery particle and vitriol oil weight ratio are 1:0.6～1.5, are incubated 4～8h under 350～600 ℃ of temperature in electric furnace.
(3), the mixture of the battery particle after the roasting and the sodium sulfate (or vitriolate of tartar) and the vitriol oil poured in 60～90 ℃ the hot water or 1～5g/L dilute sulfuric acid aqueous solution into agitation leach 0.5～1h.
(4), leach liquor is filtered, the pH value to 0.5 of regulating the dilute sulphuric acid leach liquor with the aqueous sodium hydroxide solution of 20～40g/L, or with the pH value to 0.5 of 50～80g/L dilute sulphuric acid adjusting hot water, with containing the removal of impurities of 10～30%P204 organic extractant.Re-adjustment pH of leaching solution to 4～5.0, with containing 10～30%LIX984 (or LIX984N) organic extractant extracting copper, by aqueous sulfuric acid back extraction copper from collection copper organic phase of 170～200g/L, the strip liquor of sulfur acid copper send electro deposited copper, or the evaporation concentration strip liquor obtains cupric sulfate crystals.Leach liquor is behind collection copper, regulate pH of leaching solution to 5.0～6.0, with containing 10～30%Cyanex272 organic extractant extraction cobalt, by aqueous hydrochloric acid back extraction cobalt from collection cobalt organic phase of 90～110g/L, cobalt with in the ammonium oxalate precipitate cobalt strip liquor obtains the cobalt oxalate product.With precipitating lithium ion the leach liquor of yellow soda ash after taking off cobalt, obtain lithium carbonate product, leach liquor returns handles the roasting material.
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