WO2022105463A1 - 一种废旧磷酸铁锂电池的综合回收利用方法 - Google Patents

一种废旧磷酸铁锂电池的综合回收利用方法 Download PDF

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WO2022105463A1
WO2022105463A1 PCT/CN2021/122292 CN2021122292W WO2022105463A1 WO 2022105463 A1 WO2022105463 A1 WO 2022105463A1 CN 2021122292 W CN2021122292 W CN 2021122292W WO 2022105463 A1 WO2022105463 A1 WO 2022105463A1
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lithium
iron phosphate
washing
filter cake
iron
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PCT/CN2021/122292
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English (en)
French (fr)
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刘训兵
欧阳剑君
张超文
王子
周群成
陈赞
吴山木
董雄武
刘畅
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湖南金源新材料股份有限公司
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Priority to JP2022563336A priority Critical patent/JP7393608B2/ja
Priority to EP21893613.6A priority patent/EP4122881A4/en
Priority to KR1020237004009A priority patent/KR20230038507A/ko
Publication of WO2022105463A1 publication Critical patent/WO2022105463A1/zh
Priority to US17/970,431 priority patent/US20230050044A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • 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
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/02—Preparation by double decomposition
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

Definitions

  • the invention relates to a recycling technology of waste and used lithium ion batteries, in particular to a comprehensive utilization method of waste and used lithium iron phosphate batteries.
  • lithium iron phosphate battery As a battery with excellent performance, lithium iron phosphate battery has become the first choice for new energy electric vehicles. With the rapid development of the new energy vehicle industry, the demand for lithium iron phosphate batteries will increase rapidly, and the recycling of waste lithium iron phosphate batteries has also become an important issue. Because the content of high-value lithium elements in waste lithium iron phosphate batteries is extremely low, while the low-value iron and phosphorus elements are very high, and the existing recycling technology is still in the immature stage, the recycling cost is very high, most companies can only recycle With high-value elements, few companies can comprehensively recycle waste lithium iron phosphate batteries. Even if some companies can comprehensively recycle them, it is difficult to achieve industrialized application due to complex processes and high production costs.
  • the patent application discloses a method for recovering iron phosphate from iron phosphorus slag after lithium iron phosphate battery extraction, comprising the following steps: S1) lithium iron phosphate The iron-phosphorus slag after lithium extraction from the battery is mixed and sized with water to obtain sizing liquid; S2) after the sizing liquid is mixed and reacted with an acid solution, solid-liquid separation is performed to obtain a separation liquid A; S3) the separation liquid A is mixed with an acid solution.
  • the solid-liquid separation is carried out to obtain a separation liquid B; S4) After the separation liquid B is ion-exchanged to remove aluminum by using an ion exchange resin, FeSO4 ⁇ 7H2O or H3PO4 is added to adjust the phosphorus-iron molar ratio in the system to (1 ⁇ 2): 1 to obtain a raw material solution; S5) mixing and reacting the raw material solution with hydrogen peroxide and ammonia water to form iron phosphate.
  • the deficiency lies in: dissolving the iron-phosphorus slag with strong acid and then neutralizing the excess acid with iron powder, adjusting the iron-phosphorus ratio with phosphoric acid, and finally synthesizing the ferric phosphate when the pH value is controlled, a large amount of alkali is consumed, and the production cost is high;
  • the ion exchange method is used to remove aluminum, the wastewater treatment volume is large, and there are also problems such as limited removal of impurities and low purity of iron phosphate.
  • the patent application discloses a method for treating waste and old lithium iron phosphate batteries, which includes the following steps: pre-processing the waste and old lithium iron phosphate batteries, such as discharging, disassembling, and separating, and then separating the waste and old lithium iron phosphate batteries.
  • the resulting lithium iron phosphate powder is put into water, stirred, and enhanced with ultrasonic waves; after a certain period of reaction, solid-liquid separation is performed to obtain a filtered lithium ion solution and iron phosphate precipitation; carbonate is added to the lithium ion solution to obtain lithium carbonate , the lithium carbonate and iron phosphate are mixed and roasted to obtain a regenerated lithium iron phosphate material.
  • ultrasonic strengthening treatment is a physical treatment method, which is not enough to separate lithium ion solution and iron phosphate precipitate, and it is impossible to regenerate battery-grade lithium iron phosphate without removing impurities from the separated iron phosphate precipitate.
  • the patent application discloses a method for recovering lithium from waste and old lithium iron phosphate batteries, and a method for recovering lithium and iron phosphate: comprising the following steps: a) mixing positive and negative electrode powder with Mixing and sizing with water to obtain sizing solution 1; b) after mixing and reacting the sizing solution 1 with concentrated sulfuric acid and hydrogen peroxide, solid-liquid separation is performed to obtain a primary leachate and a primary carbon-containing iron phosphorus slag; c) the positive and negative electrode powders are mixed with The primary leachate is mixed and slurried to obtain a slurried solution 2; d) after the slurried solution 2 is mixed and reacted with concentrated sulfuric acid and hydrogen peroxide, solid-liquid separation is performed to obtain a secondary leachate and a secondary carbon-containing iron-phosphorus slag; e) using alkaline The substance adjusts the pH of the secondary leaching solution
  • a method for reclaiming lithium and iron phosphate from waste and old lithium iron phosphate batteries is characterized in that, comprises the following steps: K1) recycling positive and negative electrode powder to obtain lithium carbonate, primary carbon-containing iron-phosphorus slag and secondary-containing iron-phosphorus slag Carbon-iron-phosphorus slag; the recycling process adopts the method described in any one of claims 1 to 6; K2) mixing the primary carbon-containing iron-phosphorus slag and the secondary carbon-containing iron-phosphorus slag with water to make a slurry to obtain adjusting slurry; K3) after mixing and reacting the sizing liquid and acid solution, separate solid-liquid to obtain a first separation liquid; K4) after mixing and reacting the first separation liquid with iron powder, separate solid-liquid to obtain a second separation liquid Separation liquid; K5) After ion exchange resin is used to remove aluminum from the second separation liquid, FeSO4 ⁇ 7H2O or H3PO4 is added to adjust the molar ratio of phosphorus to iron in the system to (1 ⁇ 2)
  • the shortcomings are: the decomposition of strong acid is to dissolve lithium and iron phosphate together, the follow-up treatment cost is high, and the waste of iron ions and phosphate ions is large; the ion exchange method is used in the manufacture of iron phosphate to remove aluminum, and the amount of waste water treatment is large. The types of impurities removed are limited, and battery-grade iron phosphate cannot be regenerated.
  • the purpose of the present invention is to overcome the defects of the prior art, and disclose a kind of comprehensive recycling and utilization of waste and old lithium iron phosphate batteries that can be used industrially, with simple process flow, low material consumption, high recovery rate, low waste water amount and low production cost. method.
  • the technical solution of the invention is: a comprehensive recycling method for waste lithium iron phosphate batteries, the special feature of which is that lithium is selectively extracted first, and then the lithium extraction residue is used to prepare iron phosphate.
  • lithium-containing solution For the selective extraction of lithium, first add water or lithium-containing solution to the waste lithium iron phosphate positive and negative powder to make a slurry, and then adjust the pH of the slurry to 1.5-2.0 with hydrochloric acid; then add solid sodium chlorate to the slurry, select The lithium is dissolved in the solution, the iron phosphate is left in the residue, and then the lithium-containing solution and the iron-phosphate-containing lithium extraction residue are obtained by solid-liquid separation.
  • the preparation of iron phosphate by using the lithium extraction residue take the following steps: S1).
  • the lithium extraction residue is added with water in a mass ratio of 1/3-5 to prepare a slurry.
  • the slurry obtained in the step S 2) is subjected to pressure filtration and washing, and the filter cake is a decomposed residue, which is harmlessly treated; the filtrate and the washing liquid enter the next process.
  • step S 4 The liquid obtained in step S 3) is press-filtered, and according to the content of iron and phosphorus, trisodium phosphate or ferric chloride is added, and the pH is controlled at 0.5-1.0, and the reaction is performed for at least 0.5 hours, and then the sodium hydroxide solution is used. Adjust pH to 1.5-2.0 to precipitate iron phosphate.
  • the waste lithium iron phosphate positive and negative electrode powders are mixed with water or a lithium-containing solution in a mass ratio of 1/3-5 to prepare a slurry.
  • solid sodium chlorate is added in an amount of 0.35-0.4 times the mass ratio of ferrous iron in the slurry.
  • the selective dissolving of lithium in the solution is performed after all the divalent iron ions in the slurry reacted by adding solid sodium chlorate are converted into trivalent iron ions.
  • Solid-liquid separation the filtrate is a lithium-containing solution, when the lithium content in the lithium-containing solution is less than 15g/L, return to the process of preparing slurry for slurrying to increase the lithium content of the lithium-containing solution.
  • the lithium-containing solution can be precipitated lithium carbonate: the lithium-containing solution is pumped into the lithium-precipitating tank, a saturated sodium carbonate solution is added to form a lithium carbonate precipitation, and the filtrate is processed after the pressure filtration. Return to the process of making slurry, and the filter cake is a lithium carbonate product.
  • the stirring reaction is to maintain the pH value with hydrochloric acid, and stir for 1-3 hours, preferably 2 hours.
  • the addition of trisodium phosphate or ferric chloride is performed by detecting the content of iron and phosphorus in the liquid, and adding trisodium phosphate or ferric chloride at a ratio of iron/phosphorus molar ratio of 1/0.97-1.02.
  • crude iron phosphate filter cake is configured with pure water and hydrochloric acid into a lotion with a pH value of 1.5, reverse washing three times, to wash away crude iron phosphate
  • Other metal salts in the mixture can be obtained to obtain a pure iron phosphate filter cake, which is dried and pulverized into a battery iron phosphate product.
  • washing solution configuration add high-grade pure hydrochloric acid to pure water to prepare a hydrochloric acid washing solution with a pH of 1.5-2.0 for use.
  • the first washing the crude iron phosphate filter cake is added to the second washing water at a mass ratio of 1/3-5, stirred for 30-60 minutes, filtered by pressure and washed with the second washing water, the filtrate and washing The liquid enters the wastewater treatment station, and the filter cake enters the second washing.
  • the second washing add the crude iron phosphate filter cake obtained from the first washing to the third washing water at a mass ratio of 1/3-5, stir for 30-60 minutes, filter under pressure and use the third washing Water washes, filtrate and washes are used for the first wash; the filter cake goes to the third wash.
  • the third washing add the prepared PH1.5-2.0 hydrochloric acid washing solution to the crude iron phosphate filter cake obtained from the second washing at a mass ratio of 1/3-5, stir for 30-60 minutes, and press Filter and wash with the prepared PH1.5-2.0 hydrochloric acid washing liquid, and the filtrate and washing liquid are used for the second washing; the filter cake is used as pure iron phosphate, after passing the test, it is dried and pulverized to obtain battery-grade iron phosphate products .
  • the drying and pulverizing the pure iron phosphate filter cake is dried in a microwave drying oven at a temperature of at most 90° C., dried to a water content of at most 0.1%, and pulverized by a jet mill to a maximum of 5 ⁇ m, and the packaging is a battery-grade iron phosphate product. .
  • the present invention overcomes the defects of the prior art because of the adoption of the above technical solutions, because the oxidant is used to selectively extract lithium and the pH value is controlled, so that most of the iron phosphate is retained in the lithium extraction slag; and the pH value is adjusted with hydrochloric acid to dissolve the slag.
  • the ferric phosphate in the slag is separated from other impurities in the slag. After the liquid-solid separation, the liquid is a crude ferric phosphate solution, and then trisodium phosphate or ferric chloride is added to adjust the ratio of iron to phosphate, and then the pH value is adjusted. Synthesize iron phosphate; obtain battery-grade iron phosphate products through reverse three-stage washing and impurity removal.
  • the technological process is simple, the material consumption is small, the direct yield of iron phosphate is more than 93%, and the amount of waste water is reduced by more than 75%, which not only solves the environmental protection problem, but also recovers all valuable elements, and greatly reduces the relative production cost by about 25%. use.
  • Fig. 1 is the process flow diagram of the present invention.
  • a comprehensive recycling method for waste lithium iron phosphate batteries the materials used in the implementation are: (disassembled positive and negative electrode material powder).
  • the steps are: S1), pulping: 5 tons of waste lithium iron phosphate positive and negative powders are prepared in a 20m 3 reaction kettle by adding water or a lithium-containing solution in a mass ratio of 1/4.
  • filter press filter press, wash, and thicken twice: filter press and wash with a plate and frame filter press, the filter cake is the lithium extraction residue, and the filtrate is a lithium-containing solution, return to the pulping link of step 1, perform pulping, and repeat Selectively extract lithium twice to increase the lithium content of the lithium-containing solution.
  • the filtrate is pumped into the lithium precipitation tank, and saturated sodium carbonate solution is added to form lithium carbonate precipitation, and the filtrate is returned to the pulping process of step 1 after pressure filtration; the filter cake is a lithium carbonate product.
  • step S7 dissolving iron phosphate: use a 20m 3 reaction kettle to undertake the lithium extraction residue of step S4), add water to make a slurry with a mass ratio of about 1/4, add concentrated hydrochloric acid and adjust to pH 0.5, while maintaining the pH value with hydrochloric acid , stir for 3 hours.
  • ferric phosphate synthesis in step 8, the filtrate and washing liquid after pressure filtration, detect the content of iron and phosphorus, add trisodium phosphate or ferric chloride to ensure that the iron/phosphorus molar ratio is 1/0.97-1.02 in the Within the ratio, and control the pH at 0.5, react for 1.5 hours, and then adjust the pH to 1.5 with sodium hydroxide solution to precipitate iron phosphate.
  • filter press and washing filter press and wash with a plate and frame filter press, and the filtrate and washing solution are combined into the wastewater treatment station; the filter cake is crude iron phosphate and enters the next process.
  • the first washing the crude iron phosphate filter cake is added with the second washing water at a mass ratio of 1/5, stirred for 30 minutes, filtered by pressure and washed with the second washing water, and the filtrate and the washing liquid enter the wastewater treatment station; The filter cake goes to the second wash.
  • washing for the second time the crude iron phosphate filter cake is added with washing water for the third time at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with washing water for the third time, and the filtrate and washing liquid are used for the first time. Wash; filter cake goes to third wash.
  • the third washing the crude iron phosphate filter cake is added with new washing water at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with new washing water, and the filtrate and the washing liquid are used for the second washing; filter cake As pure iron phosphate, it enters the drying process after passing the test.
  • the pure iron phosphate filter cake is dried in a microwave drying oven at a temperature of 90°C to a moisture content of 0.1%, and pulverized to within 5 ⁇ m with a jet mill, and the packaging is a battery-grade iron phosphate product.
  • Embodiment A comprehensive recycling method for waste lithium iron phosphate batteries, the special feature of which is that lithium is selectively extracted first, and then the lithium extraction residue is used to prepare iron phosphate.
  • lithium-containing solution For the selective extraction of lithium, first add water or lithium-containing solution to the waste lithium iron phosphate positive and negative powder to make a slurry, and then adjust the pH of the slurry to 1.5-2.0 with hydrochloric acid; then add solid sodium chlorate to the slurry, select The lithium is dissolved in the solution, the iron phosphate is left in the residue, and the lithium-containing solution and the lithium-extracting residue containing iron phosphate are obtained by filtration.
  • the preparation of iron phosphate by using the lithium extraction residue take the following steps: S1).
  • the lithium extraction residue is added with water in a mass ratio of 1/3-5 to prepare a slurry.
  • the slurry obtained in the step S 2) is subjected to pressure filtration and washing, and the filter cake is a decomposed residue, which is harmlessly treated; the filtrate and the washing liquid enter the next process.
  • step S 4 The liquid obtained in step S 3) is press-filtered, and according to the content of iron and phosphorus, trisodium phosphate or ferric chloride is added, and the pH is controlled at 0.5-1.0, and the reaction is performed for at least 0.5 hours, and then the sodium hydroxide solution is used. Adjust pH to 1.5-2.0 to precipitate iron phosphate.
  • hydrochloric acid and solid sodium chlorate are selected in the selective extraction of lithium because the sulfate radical in the product can be ignored during the subsequent regeneration of iron phosphate, and the chloride radical can be cleaned up with the washing solution.
  • the purpose of using solid sodium chlorate is to reduce the solid-liquid ratio to ensure that the addition of the oxidant does not increase the volume of the lithium-containing liquid and to ensure its lithium-containing concentration.
  • the pH value is determined to be between 1.5 and 2.0 because according to the reaction mechanism, iron phosphate has been formed while the lithium is selectively extracted.
  • the pH value is lower than 1.5, although the lithium recovery is slightly increased, the iron phosphate in the residue will have A large part is dissolved in the lithium-containing liquid, which not only brings difficulties to the subsequent impurity removal of the lithium-containing liquid, but also loses a large amount of iron and phosphorus sources, which greatly reduces the yield of the subsequent residue recovery of iron phosphate; if the pH value is higher than 2.0 , the dissolution rate of lithium is greatly reduced, so that the practical significance of the lithium extraction process is lost.
  • the material in the preparation of ferric phosphate using the lithium extraction residue, the material can only be framed by using hydrochloric acid and sodium chlorate, and the residue after selective lithium extraction at pH 1.5-2.0, other residues are not suitable for this process: because when lithium is extracted For residues whose pH value is lower than 1.5, almost all of the iron and phosphorus are lost, and the meaning of regenerating iron phosphate is lost; for residues whose pH value is higher than 2.0, there are too many impurities after dissolution, and the impurity removal process is complicated and the cost is high. Residue dissolution was determined to be hydrochloric acid because the solubility of iron phosphate in hydrochloric acid is much greater than that of other acids.
  • the reason why the pH value of the dissolved residue is set at 0.5-1.0 is because within this pH range, the dissolution rate of iron phosphate meets the recovery requirements. When precipitating iron phosphate after iron phosphate, it takes a lot of alkali to adjust the pH to 1.5, which makes the cost too high; if the pH value of the dissolved residue is higher than 1.0, the dissolution rate of iron phosphate will gradually decrease, and when it reaches 1.5, the dissolution rate of iron phosphate almost zero.
  • waste lithium iron phosphate positive and negative electrode powders are added with water or a lithium-containing solution according to a mass ratio of 1/3-5 to prepare a slurry.
  • water or a lithium-containing solution is added in a mass ratio of 1:4. Because the slurry is operated and transported under stirring, if the solid-liquid ratio is too small, it will be difficult to operate and transport, which may easily cause the phenomenon of clogging the pipeline; if the solid-liquid ratio is too large, the concentration of the target element in the dissolved liquid will be low. In general, the solid-liquid ratio is 1/ 3-5.
  • solid sodium chlorate is added in an amount of 0.35-0.4 times the mass ratio of ferrous iron in the slurry.
  • the mass ratio of sodium chlorate to iron is 0.35-0.4.
  • the selective extraction of lithium is that after solid sodium chlorate is added to the slurry for reaction, all divalent iron ions of lithium iron phosphate in the slurry are oxidized to trivalent iron ions , lithium iron phosphate is converted into iron phosphate, lithium ions are freed, and after solid-liquid separation, the filtrate is a lithium-containing solution.
  • the lithium content in the lithium-containing solution is less than 15g/L, it is returned to the slurry preparation process for pulping to increase
  • the lithium content of the concentrated lithium-containing solution when the lithium content in the lithium-containing solution is greater than 15g/L, add sodium hydroxide solution to adjust the pH value to 8.5-9.5, so that metal ions such as copper and aluminum in the solution form hydroxide precipitation,
  • the filter cake is copper and aluminum slag, which is reprocessed according to conventional methods or sold to relevant manufacturers; the filtrate is a pure lithium-containing solution.
  • the complete pH value of metal ion hydrolysis is 9.0, and the amphoteric aluminum oxide will dissolve when it exceeds 9.5, so the pH value controlled is between 8.5-9.5.
  • the lithium-containing solution is precipitated lithium carbonate: the lithium-containing solution is pumped into the lithium precipitation tank, the saturated sodium carbonate solution is added to form the lithium carbonate precipitation, and the filtrate after the pressure filtration is processed and returned to the selective extraction process.
  • the filter cake is a lithium carbonate product.
  • the lithium-containing solution is used to prepare lithium hydroxide, lithium phosphate, etc., according to conventional preparation methods well known to those skilled in the art.
  • step S2 the stirring reaction is to maintain the pH value with hydrochloric acid, and stir for 1-3 hours. Stir in some embodiments of the invention for 2 hours.
  • the described addition of trisodium phosphate or ferric chloride is by detecting the content of iron and phosphorus in the liquid, and adding trisodium phosphate or chlorine at a ratio of iron/phosphorus molar ratio of 1/0.97-1.02.
  • Iron Ferric chloride is added to supplement iron ions, and trisodium phosphate is added to supplement phosphorus to adjust the molar ratio of iron/phosphorus. If iron ions are less, add ferric chloride, and if phosphorus is less, add trisodium phosphate , depending on the detection situation.
  • Trisodium phosphate is alkaline and can save a certain amount of alkali when precipitating iron phosphate, which is more suitable than adding phosphoric acid or sodium dihydrogen phosphate.
  • the reaction is performed for at least 0.5 hours, and may be 0.5-2 hours, in some embodiments, 0.5 hours, 1 hour, 1.5 hours or 2 hours.
  • the 0.5 hour reaction is basically in place, and the 1-1.5 hour reaction is completely in place.
  • the present invention carries out reverse three-stage washing to remove impurities after preparing the crude iron phosphate: the crude iron phosphate filter cake is configured with pure water and hydrochloric acid into a washing solution with a pH value of 1.5, and reverse washing is performed three times to wash out the crude iron phosphate. From other metal salts, a pure iron phosphate filter cake is obtained, which is dried and pulverized into a battery iron phosphate product.
  • the purpose of reverse three-stage washing of the present invention is to save water, and the total water consumption of three-stage washing is equal to 1/3 of the three-time total water consumption of stand-alone washing, reducing the burden of waste water treatment;
  • Industrialized production results show that iron phosphate The product needs to meet the battery-level requirements, no more and no less, and three washings is the best result.
  • Reverse three-stage washing and impurity removal take the following steps: a). Washing solution configuration: add high-grade pure hydrochloric acid in pure water to prepare a hydrochloric acid washing solution with a pH of 1.5-2.0 for subsequent use;
  • the first washing the crude iron phosphate filter cake is added to the second washing water at a mass ratio of 1/3-5, stirred for 30-60 minutes, filtered by pressure and washed with the second washing water, the filtrate and washing The liquid enters the wastewater treatment station, and the filter cake enters the second washing.
  • the second washing add the crude iron phosphate filter cake obtained from the first washing to the third washing water at a mass ratio of 1/3-5, stir for 30-60 minutes, filter under pressure and use the third washing Water washing, filtrate and washing liquid are used for the first washing; the filter cake enters the third washing;
  • the third washing the crude iron phosphate filter cake obtained from the second washing is added to the configured PH1.5-2.0 hydrochloric acid lotion at a mass ratio of 1/3-5, stirred for 30-60 minutes, and pressed. Filter and wash with the prepared PH1.5-2.0 hydrochloric acid washing liquid, and the filtrate and washing liquid are used for the second washing; the filter cake is used as pure iron phosphate, after passing the test, it is dried and pulverized to obtain battery-grade iron phosphate products .
  • the drying and pulverizing of the present invention the pure iron phosphate filter cake is dried in a microwave drying furnace at a temperature of up to 90° C., dried to a water content of up to 0.1%, and pulverized by a jet mill to a maximum of 5 ⁇ m, and the packaging is a battery-grade iron phosphate product.
  • pure water and high-grade pure hydrochloric acid are used for the washing liquid of the crude iron phosphate filter cake, because we use the pickling washing liquid to wash off impurities without adding additional impurity removal procedures, so the impurities in the washing liquid are very high.
  • the pH value of the lotion is set at 1.5-2.0 because the loss of iron phosphate is the smallest in this pH range, and impurities can also be washed cleanly. If the pH value of the lotion is less than 1.5, some iron phosphate will be lost with the lotion. The iron recovery rate is reduced; if the PH value of the washing liquid is higher than 2.0, some impurities are insoluble in the washing liquid and remain in the iron phosphate, so that the product cannot meet the battery-grade requirements.
  • the method overcomes the defects of the prior art, because the oxidant is used to selectively extract lithium and the pH value is controlled, so that most of the iron phosphate remains in the lithium extraction slag; the pH value is adjusted with hydrochloric acid to dissolve the iron phosphate in the slag, and the slag is mixed with the slag. The other impurities are separated. After liquid-solid separation, the liquid is crude ferric phosphate solution, and then trisodium phosphate or ferric chloride is added to adjust the ratio of iron and phosphate, and then the pH value is adjusted to synthesize ferric phosphate; Grade washing and impurity removal to obtain battery grade iron phosphate products.
  • This yield refers to the one-time direct yield of iron phosphate in the residue, because in order to ensure the quality of iron phosphate and to reduce the amount of alkali used in precipitating iron phosphate, the acidity of the dissolved residue is reduced, so that a trace amount of iron phosphate is not dissolved. , and part of the iron phosphate is lost with the washing water during the cleaning and cleaning. This part of the lost iron phosphate is collected in the waste water station, and can be returned to the system after the precipitation is separated.
  • the dissolution rate of lithium is more than 98%, the sodium hydroxide is reduced by about 270kg per ton of lithium iron phosphate waste processed, and the amount of waste water is reduced by more than 75%, which not only solves the environmental protection problem, but also recovers all valuable elements, reducing the relative production cost by 25% left and right, and put it into industrial application.
  • the strong acid (4N) is decomposed, and the acidity at the end of the reaction is calculated as 2N.
  • the amount of alkali required for 18m 3 : 1.9x40x18 1.368 tons (NaOH) 273.6kg of alkali is consumed per ton of lithium iron phosphate waste.
  • the technical solution of the present invention selects to extract 273.6kg of sodium hydroxide per ton of lithium iron phosphate waste.
  • Embodiment 1 A comprehensive recycling method for waste and old lithium iron phosphate batteries, and the materials used in the implementation : (disassembled positive and negative electrode material powder).
  • the filtrate is pumped into the lithium precipitation tank, and saturated sodium carbonate solution is added to form lithium carbonate precipitation, and the filtrate is returned to the pulping process of step 1 after pressure filtration; the filter cake is a lithium carbonate product.
  • step S7 dissolving iron phosphate: use a 20m 3 reaction kettle to undertake the lithium extraction residue of step S6), add water to make a slurry with a mass ratio of about 1/4, add concentrated hydrochloric acid and adjust to pH 1.0, while maintaining the pH value with hydrochloric acid , stir for 3 hours.
  • step S8 ferric phosphate synthesis: step S8) in the filtrate and washing liquid after pressure filtration, detect the content of iron and phosphorus therein, and add trisodium phosphate or ferric chloride to ensure that the iron/phosphorus molar ratio is 1/0.97-1.02 Within the ratio, and control the pH at 0.5, react for 1.0 hour, then adjust the pH to 1.5 with sodium hydroxide solution to precipitate iron phosphate.
  • filter press and washing filter press and wash with a plate and frame filter press, and the filtrate and washing solution are combined into the wastewater treatment station; the filter cake is crude iron phosphate and enters the next process.
  • the first washing the crude iron phosphate filter cake is added with the second washing water at a mass ratio of 1/5, stirred for 30 minutes, filtered by pressure and washed with the second washing water, and the filtrate and the washing liquid enter the wastewater treatment station; The filter cake goes to the second wash.
  • washing for the second time the crude iron phosphate filter cake is added with washing water for the third time at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with washing water for the third time, and the filtrate and washing liquid are used for the first time. Wash; filter cake goes to third wash.
  • the third washing the crude iron phosphate filter cake is added with new washing water at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with new washing water, and the filtrate and the washing liquid are used for the second washing; filter cake As pure iron phosphate, it enters the drying process after passing the test.
  • the pure iron phosphate filter cake is dried in a microwave drying oven at a temperature of 60°C to a moisture content of 0.1%, and pulverized to within 5 ⁇ m with a jet mill, and the packaging is a battery-grade iron phosphate product.
  • the detection data is as follows.
  • the effect of this example 1 is as follows: the dissolution rate of lithium is 99.9%, the dissolution rate of ferrophosphorus is 97.45%, the dissolution rate of phosphorus: 96.54%, the dissolution rate of aluminum: 92.17%, the dissolution rate of copper: 91.82%,
  • the iron phosphate impurity content (dry basis %) is: Al: 0.0005, Cu: 0.0005, Co: 0.0025, Ni: 0.0005, Mn: 0.0013, Ca: 0.0014, Cd: 0.0005, the iron phosphate product meets the battery-grade quality requirements, and the yield is 93.93%.
  • the technological process is simple, the sodium hydroxide is reduced by 273.8kg per ton of lithium iron phosphate waste, the waste water volume is reduced by 75%, and the relative production cost is reduced by 25.8%.
  • Embodiment 2 a comprehensive recycling method of waste and old lithium iron phosphate battery, the material used is the same as that of embodiment 1.
  • the steps are: S1), pulping: 5 tons of waste lithium iron phosphate positive and negative powders are prepared in a 20m 3 reaction kettle by adding water or a lithium-containing solution in a mass ratio of 1/4.
  • filter press filter press, wash, and thicken twice: filter press and wash with a plate and frame filter press, the filter cake is the lithium extraction residue, and the filtrate is a lithium-containing solution, return to the pulping link of step 1, perform pulping, and repeat Selectively extract lithium twice to increase the lithium content of the lithium-containing solution.
  • the filtrate is pumped into the lithium precipitation tank, and saturated sodium carbonate solution is added to form lithium carbonate precipitation, and the filtrate is returned to the pulping process of step 1 after pressure filtration; the filter cake is a lithium carbonate product.
  • step S7 dissolving iron phosphate: use a 20m 3 reaction kettle to undertake the lithium extraction residue of step S4), add water to make a slurry with a mass ratio of about 1/4, add concentrated hydrochloric acid and adjust to pH 0.5, while maintaining the pH value with hydrochloric acid , stir for 3 hours.
  • ferric phosphate synthesis in step 8, the filtrate and washing liquid after pressure filtration, detect the content of iron and phosphorus, add trisodium phosphate or ferric chloride to ensure that the iron/phosphorus molar ratio is 1/0.97-1.02 in the Within the ratio, and control the pH at 0.5, react for 1.5 hours, and then adjust the pH to 1.5 with sodium hydroxide solution to precipitate iron phosphate.
  • filter press and washing filter press and wash with a plate and frame filter press, and the filtrate and washing solution are combined into the wastewater treatment station; the filter cake is crude iron phosphate and enters the next process.
  • the first washing the crude iron phosphate filter cake is added with the second washing water at a mass ratio of 1/5, stirred for 30 minutes, filtered by pressure and washed with the second washing water, and the filtrate and the washing liquid enter the wastewater treatment station; The filter cake goes to the second wash.
  • washing for the second time the crude iron phosphate filter cake is added with washing water for the third time at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with washing water for the third time, and the filtrate and washing liquid are used for the first time. Wash; filter cake goes to third wash.
  • the third washing the crude iron phosphate filter cake is added with new washing water at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with new washing water, and the filtrate and the washing liquid are used for the second washing; filter cake As pure iron phosphate, it enters the drying process after passing the test.
  • the pure iron phosphate filter cake is dried in a microwave drying oven at a temperature of 90°C to a moisture content of 0.1%, and pulverized to within 5 ⁇ m with a jet mill, and the packaging is a battery-grade iron phosphate product.
  • the detection data is as follows.
  • the effect of this example 2 is as follows: the dissolution rate of lithium is 99.9%, the dissolution rate of iron: 98.50%, the dissolution rate of phosphorus: 96.62%, the dissolution rate of aluminum: 99.10%, the dissolution rate of copper: 98.72%, the dissolution rate of phosphoric acid
  • the iron impurity content (dry basis%) is: Al: 0.0005, Cu: 0.0005, Co: 0.0025, Ni: 0.0005, Mn: 0.0008, Ca: 0.0009, Cd: 0.0005, the iron phosphate product meets the battery-grade quality requirements, and the yield is 93.98%.
  • the technological process is simple, the sodium hydroxide is reduced by 275.1kg for each ton of lithium iron phosphate waste processed, the waste water volume is reduced by 78%, and the relative production cost is reduced by 25%.
  • Comparative example 1 The materials used in the implementation are the same as those in Example 1, and the steps are: 1. pulping: 5 tons of waste lithium iron phosphate positive and negative electrode powders are added to 1/4 of the mass ratio by using a 20m reactor. The lithium solution was made into a slurry.
  • Pressure filtration and washing use a plate and frame filter press to filter and wash, the filter cake is the lithium extraction residue, and the filtrate is a lithium-containing solution.
  • Impurity removal add sodium hydroxide solution to adjust the pH value to 9.0, stir for 30 minutes, press filter, wash, filter cake is copper-aluminum slag, harmless treatment; filtrate and washing solution are controlled at 18m 3 , and enter the next process.
  • Precipitating lithium carbonate pump the filtrate into the lithium precipitation tank, add saturated sodium carbonate solution to form lithium carbonate precipitation, and return the filtrate to the pulping process of step 1 after pressure filtration; the filter cake is a lithium carbonate product.
  • Dissolving iron phosphate use a 20m 3 reaction kettle to undertake the lithium extraction residue of step 4, add water to make a slurry with a mass ratio of about 1/4, add concentrated hydrochloric acid to adjust to pH 0.5, maintain the pH value with hydrochloric acid, stir 3 hours.
  • Ferric phosphate synthesis the filtrate and washing liquid after pressure filtration in step 8, detect the content of iron and phosphorus in it, and add trisodium phosphate or ferric chloride to ensure that the iron/phosphorus molar ratio is 1/0.97-1.02 in the ratio and control the pH at 0.5, react for 0.5 hours, and then adjust the pH to 1.5 with sodium hydroxide solution to precipitate iron phosphate.
  • Reverse three-stage impurity removal and washing the crude ferric phosphate filter cake is washed with a pH value of 1.0 for three times, and the other metal salts in the crude ferric phosphate are washed away to obtain a pure ferric phosphate filter cake.
  • the steps are as follows: (1) Lotion configuration: add 18m 3 of pure water into the acid-adjusting barrel of 20m 3 of pure water, and add excellent grade pure hydrochloric acid to make PH 1.0 for use.
  • the first washing the crude iron phosphate filter cake is added with the second washing water at a mass ratio of 1/5, stirred for 30 minutes, filtered by pressure and washed with the second washing water, and the filtrate and the washing liquid enter the wastewater treatment station; The filter cake goes to the second wash.
  • washing for the second time the crude iron phosphate filter cake is added with washing water for the third time at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with washing water for the third time, and the filtrate and washing liquid are used for the first time. Wash; filter cake goes to third wash.
  • the third washing the crude iron phosphate filter cake is added with new washing water at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with new washing water, and the filtrate and the washing liquid are used for the second washing; filter cake As pure iron phosphate, it enters the drying process after passing the test.
  • the pure iron phosphate filter cake is dried in a microwave drying oven at a temperature of 90°C to a moisture content of 0.1%, and powdered to within 5 ⁇ m by an air mill to obtain an iron phosphate product.
  • the detection data is as follows.
  • the PH value of selective lithium extraction was 1.0, the iron content in the lithium-containing solution was 24.4g/L, and the phosphorus content was 15.36g/L, and the loss of phosphorus and iron was very large; when the crude iron phosphate was washed, the pH of the washing solution is 1.0, the iron content in the washing solution is 15.96g/L, and the phosphorus content is 4.93g/L. The loss of phosphorus and iron is large, and the yield of iron phosphate is only 68.0%.
  • Comparative Example 2 The materials used in the implementation are the same as those in Example 1, and the steps are: 1. Pulp preparation: 5 tons of waste lithium iron phosphate positive and negative powders are added to 1/4 of the mass ratio by using a 20m reactor. The lithium solution was made into a slurry.
  • Filter press, wash, and thicken twice filter press and wash with a plate and frame filter press, the filter cake is the lithium extraction residue, and the filtrate is a lithium-containing solution, return to the pulping process of step 1, and perform pulping, and repeat the selection Lithium was extracted twice to increase the lithium content of the lithium-containing solution.
  • Impurity removal Add sodium hydroxide solution to the concentrated lithium solution to adjust the pH value to 9.0, stir for 30 minutes, filter by pressure, wash, filter cake is copper-aluminum slag, harmless treatment; filtrate and washing solution are controlled at 18m 3 , go to the next process.
  • Precipitating lithium carbonate pump the filtrate into the lithium precipitation tank, add saturated sodium carbonate solution to form lithium carbonate precipitation, and return the filtrate to the pulping process of step 1 after pressure filtration; the filter cake is a lithium carbonate product.
  • Dissolving iron phosphate use a 20m3 reaction kettle to carry out the lithium extraction residue of step 4, add water to make a slurry with a mass ratio of about 1/4, add concentrated hydrochloric acid and adjust to pH 0.1, while maintaining the pH value with hydrochloric acid, stirring 3 hours.
  • Ferric phosphate synthesis the filtrate and washing liquid after pressure filtration in step 8, detect the content of iron and phosphorus in it, and add trisodium phosphate or ferric chloride to ensure that the iron/phosphorus molar ratio is 1/0.97-1.02 in the ratio and control the pH at 0.5, react for 2.0 hours, and then adjust the pH to 1.5 with sodium hydroxide solution to precipitate iron phosphate.
  • Reverse three-stage impurity removal and washing the crude iron phosphate filter cake is washed with a pH value of 2.0 for three times, and the other metal salts in the crude iron phosphate are washed away to obtain a pure iron phosphate filter cake.
  • the steps are as follows: 1. Lotion configuration: add 18m 3 of pure water into the acid-adjusting barrel of 20m 3 of pure water, and add excellent grade pure hydrochloric acid to prepare a pH of 2.0 for use.
  • the first washing the crude iron phosphate filter cake is added with the second washing water at a mass ratio of 1/5, stirred for 30 minutes, filtered by pressure and washed with the second washing water, and the filtrate and the washing liquid enter the wastewater treatment station; The filter cake goes to the second wash.
  • washing for the second time the crude iron phosphate filter cake is added with washing water for the third time at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with washing water for the third time, and the filtrate and washing liquid are used for the first time. Wash; filter cake goes to third wash.
  • the third washing the crude iron phosphate filter cake is added with new washing water at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with new washing water, and the filtrate and the washing liquid are used for the second washing; filter cake As pure iron phosphate.
  • Drying and pulverization The pure iron phosphate filter cake is dried in a microwave oven at a temperature of 90°C to a moisture content of 0.1%, and then pulverized to within 5 ⁇ m with an air flow pulverizer to obtain the iron phosphate product.
  • the detection data is as follows.
  • Comparative example 3 The materials used in the implementation are the same as those in Example 1, and the steps are: 1. pulping: 5 tons of waste lithium iron phosphate positive and negative powders are added to 1/4 of the mass ratio by using a 20m reactor. The lithium solution was made into a slurry.
  • Impurity removal Add sodium hydroxide solution to the concentrated lithium solution to adjust the pH value to 9.0, stir for 30 minutes, filter by pressure, wash, filter cake is copper-aluminum slag, harmless treatment; filtrate and washing solution are controlled at 18m 3 , go to the next process.
  • Precipitating lithium carbonate pump the filtrate into the lithium precipitation tank, add saturated sodium carbonate solution to form lithium carbonate precipitation, and return the filtrate to the pulping process of step 1 after pressure filtration; the filter cake is a lithium carbonate product.
  • Dissolving iron phosphate use a 20m 3 reaction kettle to undertake the lithium extraction residue of step 4, add water to make a slurry with a mass ratio of about 1/4, add concentrated hydrochloric acid to adjust to pH 0.5, maintain the pH value with hydrochloric acid, and stir 3 hours.
  • Ferric phosphate synthesis the filtrate and washing liquid after pressure filtration in step 8, detect the content of iron and phosphorus in it, and add trisodium phosphate or ferric chloride to ensure that the iron/phosphorus molar ratio is 1/0.97-1.02 in the ratio and control the pH at 0.5, react for 1.5 hours, and then adjust the pH to 1.5 with sodium hydroxide solution to precipitate iron phosphate.
  • Reverse three-stage impurity removal and washing the crude ferric phosphate filter cake is washed with a washing solution with a pH value of 2.5, stirred and reversely washed three times, and other metal salts in the crude ferric phosphate are washed away to obtain a pure ferric phosphate filter cake.
  • the steps are as follows: 1. Washing solution configuration: add 18m 3 of pure water into the acid-adjusting barrel of 20m 3 of pure water, and add excellent grade pure hydrochloric acid to prepare a pH of 2.5 for use.
  • the first washing the crude iron phosphate filter cake is added with the second washing water at a mass ratio of 1/5, stirred for 30 minutes, filtered by pressure and washed with the second washing water, and the filtrate and the washing liquid enter the wastewater treatment station; The filter cake goes to the second wash.
  • washing for the second time the crude iron phosphate filter cake is added with washing water for the third time at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with washing water for the third time, and the filtrate and washing liquid are used for the first time. Wash; filter cake goes to third wash.
  • the third washing the crude iron phosphate filter cake is added with new washing water at a ratio of 1/5 by mass, stirred for 30 minutes, filtered by pressure and washed with new washing water, and the filtrate and the washing liquid are used for the second washing; filter cake As pure iron phosphate, it enters the drying process after passing the test.
  • the pure iron phosphate filter cake is dried in a microwave oven at a temperature of 90°C to a moisture content of 0.1%, and pulverized to 5 ⁇ m with an air-jet pulverizer to obtain the iron phosphate product.
  • the detection data is as follows.
  • the PH value of selective extraction of lithium is 2.5
  • the lithium-containing solution contains 18.96 g/L of lithium
  • the dissolution rate of lithium is only 74.2%
  • the loss of lithium is very large
  • the iron phosphate product contains 0.014% aluminum and 0.041% copper. The product does not meet the battery grade requirements.
  • the technology of the invention has been put into industrial production and application, the dissolution rate of lithium is 99.9%, the dissolution rate of ferrophosphorus is ⁇ 96.62%, the dissolution rate of phosphorus is ⁇ 96.54%, the dissolution rate of aluminum is ⁇ 92.17%, and the dissolution rate of copper is ⁇ 91.82%.
  • the iron phosphate products meet the battery-grade quality requirements, and the yield is ⁇ 93.93%.
  • the technological process is simple, the sodium hydroxide is reduced by more than 273.8kg per ton of lithium iron phosphate waste, the waste water volume is reduced by more than 75%, and the relative production cost is reduced by at least 25%.

Abstract

一种废旧磷酸铁锂电池的综合回收利用方法，涉及废旧锂离子电池回收利用技术，其特殊之处在于：先选择性提锂，然后利用提锂残渣制备磷酸铁；所述利用提锂残渣制备磷酸铁：将提锂残渣加水调成料浆，加盐酸搅拌反应，使铁完全溶解，固液分离，根据所得液体的铁和磷的含量，加入磷酸三钠或氯化铁，再加氢氧化钠溶液沉淀粗制磷酸铁，再逆向三级洗涤除杂得电池磷酸铁产品。本发明工艺流程简单，物耗小，磷酸铁收率93%以上，废水量少75%以上，既解决了环保问题，又回收了全部有价元素，相对成本大幅降低25%左右，并投入到产业化运用。

Description

一种废旧磷酸铁锂电池的综合回收利用方法 技术领域
本发明涉及废旧锂离子电池回收利用技术，特别是废旧磷酸铁锂的电池综合利用方法。
 背景技术
磷酸铁锂电池作为一种性能优异的能力电池，已成为新能源电动汽车的首选。随着新能源汽车产业的快速发展，磷酸铁锂电池的需求将高速增长，而废旧磷酸铁锂电池的回收利用也成为一个重要问题。由于废旧磷酸铁锂电池中价值高的锂元素含量极低，而价值很低的铁、磷元素很高，加之现有的回收技术还处于非成熟阶段，回收成本很高，大多企业只能回收价值高元素，很少有企业能将废旧磷酸铁锂电池进行综合回收利用，既使有个别企业能够综合回收，也因为工艺复杂，生产成本高，也难以实现产业化运用。
专利申请（公开号为CN 111646447 A、公开日为2020.09.11）公开了一种从磷酸铁锂电池提锂后的铁磷渣中回收磷酸铁的方法，包括以下 步骤： S1)将磷酸铁锂电池提锂后的铁磷渣与水混合调浆，得到调浆液； S2)将所述调浆液与酸液混合反应后，固液分离，得到分离液A； S3)将所述分离液A与铁粉混合反应后，固液分离，得到分离液B； S4)采用离子交换树脂对所述分离液B进行离子交换除铝后，加入FeSO4·7H2O或H3PO4调节体系中磷铁摩尔比至(1～2)∶1，得到原料液； S5)将所述原料液与双氧水、氨水混合反应，形成磷酸铁。所存在不足在于：用强酸溶解铁磷渣再用铁粉中和多余的酸，用磷酸调节铁磷比，最后合成磷酸铁在控制PH值时，消耗大量的碱，生产成本高；磷酸铁制造中用离子交换法除铝，废水处理量大，还存在杂质去除种类有限，磷酸铁的纯度不高等问题。
专利申请（公开号为 CN111653846A、公开日为20200911）公开了一种废旧磷酸铁锂电池的处理方法，包括以下步骤：将废旧磷酸铁锂电池进行放电、拆解、分离等预处理，再将分离后的磷酸铁锂粉末放入水中，搅拌，利用超声波进行强化处理；反应一定时间后固液分离，得到过滤后的锂离子溶液以及磷酸铁沉淀；在锂离子溶液中加入碳酸盐得到碳酸锂，将碳酸锂和磷酸铁混合焙烧得到再生磷酸铁锂材料。所存在不足在于：超声波强化处理属物理处理手段，不足以分离锂离子溶液以及磷酸铁沉淀，且分离后的磷酸铁沉淀不除杂不可能再生电池级磷酸铁锂。
专利申请（公开号为 CN111675203A、公开日为20200918）公开了一种从废旧磷酸铁锂电池中回收锂的方法、以及回收锂和磷酸铁的方法：包括以下步骤：a)将正负极粉与水混合调浆，得到调浆液1；b)将所述调浆液1与浓硫酸、双氧水混合反应后，固液分离，得到一次浸出液和一次含碳铁磷渣；c)将正负极粉与一次浸出液混合调浆，得到调浆液2；d)将所述调浆液2与浓硫酸、双氧水混合反应后，固液分离，得到二次浸出液和二次含碳铁磷渣；e)利用碱性物质将所述二次浸出液的pH调至11～12.5反应后，固液分离，得到除杂液；f)将所述除杂液与碳酸钠反应，形成碳酸锂；所述正负极粉通过以下方式获得：将废旧磷酸铁锂电池中拆解的正负极片进行焙烧和粉碎筛分，得到铜铝混合粉和正负极粉。一种从废旧磷酸铁锂电池中回收锂和磷酸铁的方法，其特征在于，包括以下步骤：K1)将正负极粉进行回收处理，得到碳酸锂、一次含碳铁磷渣和二次含碳铁磷渣；所述回收处理采用权利要求1～6中任一项所述的方法；K2)将所述一次含碳铁磷渣及二次含碳铁磷渣与水混合调浆，得到调浆液；K3)将所述调浆液与酸液混合反应后，固液分离，得到第一分离液；K4)将所述第一分离液与铁粉混合反应后，固液分离，得到第二分离液；K5)采用离子交换树脂对所述第二分离液进行离子交换除铝后，加入FeSO4·7H2O或H3PO4调节体系中磷铁摩尔比至(1～2)∶1，得到原料液；K6)将所述原料液与双氧水、氨水混合反应，形成磷酸铁。所存在不足在于：用强酸分解是将锂和磷酸铁溶在一起，后续处理成本高，铁离子，磷酸根离子浪费大；磷酸铁制造中用离子交换法除铝，废水处理量大，还存在杂质去除种类有限，不能再生电池级磷酸铁等问题。
 技术问题
在上述现有技术中，综合回收锂和磷酸铁的工艺流程复杂，不能选择性提取锂，锂液浓度低，沉锂物耗大，磷酸根离子损失多，回收率低，生产成本高，产品纯度低，给后续加工增加除杂难度，加之废水量多，环保压力大，难以实现产业化应用。
本发明的目的在于克服现有技术的缺陷，公开一种工艺流程简单，物耗小，回收率高，废水量少，生产成本低的，能够产业化运用的一种废旧磷酸铁锂电池综合回收利用方法。
 技术解决方案
本发明的技术解决方案是：一种废旧磷酸铁锂电池的综合回收利用方法，其特殊之处在于：先选择性提锂，然后利用提锂残渣制备磷酸铁。
 所述选择性提锂，先将废磷酸铁锂正负极粉末加水或含锂溶液调成料浆后用盐酸调节料浆PH到1.5-2.0；然后在料浆中加入固态氯酸钠，选择性将锂溶解在溶液中，磷酸铁留在残渣中，再经固液分离得含锂溶液和含磷酸铁的提锂残渣。
所述利用提锂残渣制备磷酸铁：采取如下步骤：S1).将提锂残渣按质量比1/3-5的量加水调成料浆。
S 2).将料浆用盐酸调PH0.5-1.0，搅拌反应，使料浆固相的含铁量溶解至≤1.0%。
S 3).将S 2)步骤所得料浆经压滤、洗涤，滤饼为分解渣，无害处理；滤液和洗液进入下一工序。
S 4).将S 3).步骤压滤所得液体，根据其铁和磷的含量，加入磷酸三钠或氯化铁，控制PH在0.5-1.0，反应至少0.5小时，再用氢氧化钠溶液调节PH到1.5-2.0，沉淀磷酸铁。
S 5).在S 4)步骤后进行压滤、洗涤：滤液和洗液合并进入废水处理站，滤饼为粗制磷酸铁。
    优选地，在所述选择性提取锂工序中，废磷酸铁锂正负极粉末按质量比1/3-5的比例加水或含锂溶液调成料浆。
优选地，在所述选择性提锂工序中，按照料浆中二价铁质量比0.35-0.4倍的量加入固态氯酸钠。
优选地，在所述选择性提取锂工序中，所述选择性将锂溶解在溶液中是将加入固态氯酸钠反应后的料浆中的二价铁离子全部转化为三价铁离子后进行固液分离，滤液为含锂溶液，当含锂溶液中锂含量小于15g/L时，返回调成料浆环节进行制浆，以增浓含锂溶液的锂含量，当含锂溶液中锂含量大于15g/L时，加入氢氧化钠溶液调节PH值到8.5-9.5，使溶液中的铜和铝等金属离子形成氢氧化物沉淀，压滤、洗涤，滤饼为铜铝渣，滤液为纯净的含锂溶液。
进一步地，在所述选择性提锂工序后，可以将含锂溶液沉淀碳酸锂：将含锂溶液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液经处理后返回调成料浆环节，滤饼为碳酸锂产品。
    优选地，在S2)步骤中，所述搅拌反应是用盐酸维持PH值，搅拌1-3小时，优选2小时。
优选地，所述加入磷酸三钠或氯化铁，是通过检测液体中的铁和磷的含量，以铁/磷摩尔比1/0.97-1.02的比例，加入磷酸三钠或氯化铁。
进一步地，在制备粗制磷酸铁之后进行逆向三级洗涤除杂：粗制磷酸铁滤饼用纯水与盐酸配置成PH值为1.5的洗液，逆向洗涤三次，以洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，经烘干、粉碎为电池磷酸铁产品。
更进一步地，所述逆向三级洗涤除杂：采取如下步骤：b1).洗液配置：在纯水中加入优级纯盐酸配成PH1.5-2.0的盐酸洗液备用。
b2).第一次洗涤：粗制磷酸铁滤饼以质量比1/3-5的比率加入第二次洗涤水，搅拌30-60分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站，滤饼进入第二次洗涤。
b3).第二次洗涤：将第一次洗涤所得粗制磷酸铁滤饼以质量比1/3-5的比率加入第三次洗涤水，搅拌30-60分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤。
b4).第三次洗涤：将第二次洗涤所得粗制磷酸铁滤饼以质量比1/3-5的比率加入配置好的PH1.5-2.0盐酸洗液，搅拌30-60分钟，压滤并用配置好的PH1.5-2.0盐酸洗液进行洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁，经检测合格后进入烘干、粉碎制得电池级磷酸铁产品。
进一步地，所述烘干、粉碎：是将纯净磷酸铁滤饼用微波干燥炉，温度至多90℃，干燥至含水至多0.1%，用气流粉碎机粉碎至多5μm，包装即为电池级磷酸铁产品。
 有益效果
本发明由于采用了以上技术方案，克服了现有技术缺陷，由于利用氧化剂选择性提取锂，控制PH值，使得绝大部分磷酸铁保留在提锂渣中；再用盐酸调节PH值，溶解渣中的磷酸铁，与渣中的其他杂质分离，液固分离后，液体为粗制磷酸铁溶液，再补加磷酸三钠、或氯化铁调节铁与磷酸根的比率，再调节PH值，合成磷酸铁；经逆向三级洗涤除杂得到电池级磷酸铁产品。工艺流程简单，物耗小，磷酸铁直接收率93%以上，废水量减少75%以上，既解决了环保问题，又回收了全部有价元素，相对生产成本大幅降低25%左右，并投入到产业化运用。
 附图说明
图1为本发明工艺流程图。
 本发明的最佳实施方式
一种废旧磷酸铁锂电池的综合回收利用方法，实 施所用物料：（拆解后的正负极材料粉）。
Figure 481314dest_path_image001
。
其步骤为： S1）、制浆：用20m 3反应釜将废磷酸铁锂正负极粉5吨，按质量比1/4的量加水或含锂溶液调成浆状。
S2）、用盐酸调节物料浆PH到2.0。
S3）、选择性提锂：按照物料浆中二价铁质量比0.35倍的量加入固态氯酸钠532公斤，80℃下反应60分钟。
S4）、压滤、洗涤、增浓2次：用板框压滤机压滤、洗涤，滤饼为提锂残渣，滤液为含锂溶液，返回步骤1的制浆环节，进行制浆，重复选择性提锂2次，以增浓含锂溶液的锂含量。
S5）、除杂：增浓的含锂溶液，加入氢氧化钠溶液调节PH值到8.5，搅拌30分钟，压滤、洗涤，滤饼为铜铝渣，无害处理；滤液和洗液控制在18m 3，进入下一工序。
S6）、沉淀碳酸锂：将滤液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液返回步骤1的制浆工序；滤饼为碳酸锂产品。
S7）、溶解磷酸铁：用20m 3反应釜承接步骤S4）的提锂残渣，加水调成质量比约1/4的浆状物，加入浓盐酸调成PH0.5，同时用盐酸维持PH值，搅拌3小时。
S8）、压滤、洗涤：滤饼为分解渣，无害处理；滤液和洗液进入合并。
S9）、磷酸铁合成：步骤8中压滤后的滤液和洗液，检测其中的铁和磷的含量，加入磷酸三钠或氯化铁，以保证铁/磷摩尔比1/0.97-1.02在比例之内，并控制PH在0.5，反应1.5小时，再用氢氧化钠溶液调节PH到1.5，沉淀磷酸铁。
S10）、压滤、洗涤：用板框压滤机压滤和洗涤，滤液和洗液合并进入废水处理站；滤饼为粗制磷酸铁进入下一工序。
S11）、逆向三级除杂洗涤：粗制磷酸铁滤饼用PH值为1.5的洗液，搅拌、逆向洗涤三次，洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，其步骤如下：①  洗液配置：纯水20m 3的调酸桶内加入纯水18m 3,加入优级纯盐酸配成PH1.5备用。
②第一次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第二次洗涤水，搅拌30分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站；滤饼进入第二次洗涤。
③第二次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第三次洗涤水，搅拌30分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤。
④第三次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入新洗涤水，搅拌30分钟，压滤并用新洗涤水洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁，经检测合格后进入烘干工序。
S12）、烘干、粉碎：纯净磷酸铁滤饼用微波干燥炉，温度90℃，干燥至含水0.1%，用气流粉碎机粉碎至5μm以内，包装即为电池级磷酸铁产品。
 本发明的实施方式
为了便于更清楚地理解本发明，下面结合图1用具体实施方式对本发明作进一步的说明。
实施方式：一种废旧磷酸铁锂电池的综合回收利用方法，其特殊之处在于：先选择性提锂，然后利用提锂残渣制备磷酸铁。
 所述选择性提锂，先将废磷酸铁锂正负极粉末加水或含锂溶液调成料浆后用盐酸调节料浆PH到1.5-2.0；然后在料浆中加入固态氯酸钠，选择性将锂溶解在溶液中，磷酸铁留在残渣中，再经过滤得含锂溶液和含磷酸铁的提锂残渣。
其反应机理为： 6LiFePO4 +NaClO3+6HCl= 6FePO4↓ +6LiCl +NaCl+3H2O。
所述利用提锂残渣制备磷酸铁：采取如下步骤：S1).将提锂残渣按质量比1/3-5的量加水调成料浆。
S 2).将料浆用盐酸调PH0.5-1.0，搅拌反应，使料浆固相中的铁离子含量溶解至≤1.0%。
S 3).将S 2)步骤所得料浆经压滤、洗涤，滤饼为分解渣，无害处理；滤液和洗液进入下一工序。
S 4).将S 3).步骤压滤所得液体，根据其铁和磷的含量，加入磷酸三钠或氯化铁，控制PH在0.5-1.0，反应至少0.5小时，再用氢氧化钠溶液调节PH到1.5-2.0，沉淀磷酸铁。
S 5).在S 4)步骤后进行压滤、洗涤：滤液和洗液合并进入废水处理站，滤饼为粗制磷酸铁。
本发明在选择性提锂中选择盐酸和固体氯酸钠是因为后续磷酸铁再生时产品中的硫酸根可以不予考虑，而氯根可以随洗液清理干净。采用固体氯酸钠的目的是降低固液比，以保证氧化剂的加入不增加含锂液体积，保证其含锂浓度。PH值确定在1.5-2.0之间是因为根据反应机理，在选择性提锂的同时，磷酸铁已经形成，如果PH值低于1.5，虽然锂回收稍有上升，但残渣中的磷酸铁会有很大一部分溶解到含锂液中，不仅给后续含锂液的除杂带来困难，还损失大量的铁和磷源，使后续残渣回收磷酸铁时收率大幅降低；如果PH值高于2.0时，则锂的溶出率大幅降低，以至于失去提锂工序的实际意义。
      本发明在利用提锂残渣制备磷酸铁中，物料的框定只能是用盐酸和氯酸钠，在PH1.5-2.0选择性提锂后的残渣，其他残渣不适合本流程：因为提锂时的PH值低于1.5的残渣，铁和磷几乎被全部损失掉了，失去再生磷酸铁意义；PH值高于2.0的残渣，溶解后杂质太多，除杂工序复杂，成本偏高。残渣溶解框定用盐酸是因为磷酸铁在盐酸中的溶解度远大于其他酸。
溶解残渣的PH值框定在0.5-1.0原因是：因为在此PH范围内，磷酸铁的溶解率达到了回收要求，如果溶解残渣的PH值低于0.5时，耗费的酸相对较多，在合成磷酸铁后沉淀磷酸铁时要耗费大量碱调节PH到1.5，使得成本过高；如果溶解残渣的PH值高于1.0时，磷酸铁的溶解率会逐步降低，达到1.5时，磷酸铁的溶解率几乎为零。
本发明在选择性提取锂工序中，废磷酸铁锂正负极粉末按质量比1/3-5的比例加水或含锂溶液调成料浆。在本发明的一些实施例中按质量比1：4的比例加水或含锂溶液。因为矿浆是在搅拌状态下运行、输送，固液比太小则运行和输送困难，容易造成堵塞管道现象；固液比太大则溶解液目的元素浓度低，一般状态下固液比取1/3-5。
本发明在选择性提锂工序中，按照料浆中二价铁质量比0.35-0.4倍的量加入固态氯酸钠。
其反应机理为：6LiFePO 4 +NaClO 3+6HCl= 6FePO 4 ↓+6LiCl +NaCl+3H 2O。
氯酸钠与铁的摩尔比为1/6，即质量比为106/6x56=0.3154 。
过量系数取1.1~1.25,则氯酸钠与铁的质量比为0.35-0.4。
本发明在所述选择性提取锂工序中，所述选择性提锂，是将物料浆中加入固态氯酸钠反应后，料浆中磷酸铁锂的二价铁离子全部氧化为三价铁离子，磷酸铁锂转化为磷酸铁，锂离子被游离，固液分离后，滤液为含锂溶液，当含锂溶液中锂含量小于15g/L时，返回调成料浆环节进行制浆，以增浓含锂溶液的锂含量，当含锂溶液中锂含量大于15g/L时，加入氢氧化钠溶液调节PH值到8.5-9.5，使溶液中的铜和铝等金属离子形成氢氧化物沉淀，压滤、洗涤，滤饼为铜铝渣，按常规方法进行再加工或出售给相关生产厂家；滤液为纯净的含锂溶液。金属离子水解完全的PH值在9.0，超过9.5两性氧化物铝又会溶解，所以控制的PH值在8.5-9.5之间。
本发明在选择性提锂工序后，将含锂溶液沉淀碳酸锂：将含锂溶液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液经处理后返回选择性提锂的制浆环节，滤饼为碳酸锂产品。在本发明的一些实施例中将含锂溶液用于制备氢氧化锂、磷酸锂等，按照本领域技术人员熟知的常规制备方法即可。
本发明在S2)步骤中，所述搅拌反应是用盐酸维持PH值，搅拌1-3小时。在本发明一些实施例中搅拌2小时。
本发明S4)步骤中，所述加入磷酸三钠或氯化铁，是通过检测液体中的铁和磷的含量，以铁/磷摩尔比1/0.97-1.02的比例，加入磷酸三钠或氯化铁。加入氯化铁是为了补充铁离子，加入磷酸三钠为了补充磷元素，用以调节铁/磷的摩尔比，如果铁离子少了就加用氯化铁，磷元素少了就加磷酸三钠，根据检测情况而定。磷酸三钠呈碱性，在沉淀磷酸铁时，可以节约一定量的碱，比加入磷酸或磷酸二氢钠要合适。
本发明S4)步骤中，所述反应至少0.5小时，可以为0.5-2小时，在一些实施例中为0.5小时，1小时，1.5小时或2小时。0.5小时反应基本到位，1-1.5小时反应已完全到位。
本发明在制备粗制磷酸铁之后进行逆向三级洗涤除杂：粗制磷酸铁滤饼用纯水与盐酸配置成PH值为1.5的洗液，逆向洗涤三次，以洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，经烘干、粉碎为电池磷酸铁产品。
本发明的逆向三级洗涤的目的:逆向洗涤的目的是节约用水，三级洗涤的总用水量等于单机洗涤三次总用水量的1/3，减轻废水处理的负担；工业化生产结果表明，磷酸铁产品要达到电池级要求，不多也不少，三次洗涤是最佳效果。
本发明所述逆向三级洗涤除杂：采取如下步骤：a).洗液配置：在纯水中加入优级纯盐酸配成PH1.5-2.0的盐酸洗液备用;。
b).第一次洗涤：粗制磷酸铁滤饼以质量比1/3-5的比率加入第二次洗涤水，搅拌30-60分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站，滤饼进入第二次洗涤。
c).第二次洗涤：将第一次洗涤所得粗制磷酸铁滤饼以质量比1/3-5的比率加入第三次洗涤水，搅拌30-60分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤;。
d).第三次洗涤：将第二次洗涤所得粗制磷酸铁滤饼以质量比1/3-5的比率加入配置好的PH1.5-2.0盐酸洗液，搅拌30-60分钟，压滤并用配置好的PH1.5-2.0盐酸洗液进行洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁，经检测合格后进入烘干、粉碎制得电池级磷酸铁产品。
本发明所述烘干、粉碎：是将纯净磷酸铁滤饼用微波干燥炉，温度至多90℃，干燥至含水至多0.1%，用气流粉碎机粉碎至多5μm，包装即为电池级磷酸铁产品。
本发明将粗磷酸铁滤饼洗涤的洗液框定用纯水和优级纯盐酸是因为我们使用酸洗洗液洗去杂质，无需增加额外的除杂程序，所以对洗液的杂质要求很高。洗液的PH值框定1.5-2.0是因为在此PH范围内磷酸铁损失最小，杂质也能洗得最干净，如果洗液的PH值小于1.5，有部分磷酸铁会随洗液流失，使磷酸铁回收率降低；如果洗液的PH值高于2.0，则有部分杂质不溶于洗液，留在磷酸铁中，使产品达不到电池级要求。
本发明克服了现有技术缺陷，由于利用氧化剂选择性提取锂，控制PH值，使得绝大部分磷酸铁保留在提锂渣中；再用盐酸调节PH值，溶解渣中的磷酸铁，与渣中的其他杂质分离，液固分离后，液体为粗制磷酸铁溶液，再补加磷酸三钠、或氯化铁调节铁与磷酸根的比率，再调节PH值，合成磷酸铁；经逆向三级洗涤除杂得到电池级磷酸铁产品。工艺流程简单，物耗减少，磷酸铁直接收率93%以上。这个收率是指残渣中磷酸铁的一次直接收率，因为为了保证磷酸铁的质量，以及为降低沉淀磷酸铁时的碱用量而降低了溶解残渣溶解的酸度，以至于微量的磷酸铁未溶解，并且有部分磷酸铁随除杂洗涤时的洗水流失，这部分流失的磷酸铁汇集到废水站后，沉淀分离出后，再可以返回系统。锂的溶解率98%以上，每处理1吨磷酸铁锂废料减少氢氧化钠约270kg，废水量少75%以上，既解决了环保问题，又回收了全部有价元素，相对生产成本降低25%左右，并投入到产业化运用。
   本发明有关效果数据计算依据如下。
1、物耗减少计算依据：提锂时：用强酸溶解和用低酸溶解，都必须用碱控制PH在1.5-2.0沉淀磷酸铁，多余的酸必须用碱中和：HCl+NaOH=NaCl+H2O   反应摩尔比为1/1。
强酸（4N）分解，反应终了酸度以2N计，如按5吨磷酸铁锂废料控制在18m 3溶液核定，最终PH1.5，约为0.10N计算，酸度减少量：2-0.1=1.9N ，中和需要碱量：1.9N，18m 3需要碱量：1.9x40x18=1.368吨（NaOH）  每吨磷酸铁锂废料需耗碱273.6kg。
低酸（PH1.5约为0.10N）时碱用量：如按5吨磷酸铁锂废料控制在18m 3溶液核定，最终PH1.5计算，酸度减少量：0.1-0.1=0 N，中和需要碱量：0 N，18m 3需要碱量：这种情况几乎无需中和。
因此，本发明技术方案选择提锂每吨磷酸铁锂废料减少氢氧化钠273.6kg。
2、废水量减少计算依据：①离子交换法除杂，采用3％～10％(质量分数)硫酸溶液以3BV/h流速进行洗脱，共用硫酸溶液量6BV，再用水洗涤至pH大于6，洗水量为6-8BV，仅树脂再生一项洗水就达15m 3/每吨磷酸铁锂废料。
②逆向三级洗涤洗水用量：5吨磷酸铁锂废料用洗水18m 3,每吨磷酸铁锂废料用水3.6m 3，减少用水量为：（15-3.6）/15ⅹ100=76%。
3、生产成本降低计算依据：①盐酸节约量为：273.6/40x36=336.24 kg，市售盐酸含量为32%，价500元/吨，   336.24/0.32/1000x500= 525.38元。
②氢氧化钠节约量：273.6/1000x3500= 957.6元。
③水处理费用：每吨水处理费用约为80元，（15-3.6）x80= 912元。
每处理1吨磷酸铁锂废料节约成本约为 525.38+ 957.6+912=2394.98元，约占总生产成本的25%。
实施例 1 ：一种废旧磷酸铁锂电池的综合回收利用方法，实 施所用物料：（拆解后的正负极材料粉）。
Figure 314186dest_path_image001
。 
采取如下步骤：S1）、制浆：用20m 3反应釜将废磷酸铁锂正负极粉5吨，按质量比1/4的量加水或含锂溶液调成浆状。
S2）、用盐酸调节物料浆PH到1.5。
S3）、选择性提锂：按照物料浆中二价铁质量比0.35倍的量加入固态氯酸钠532公斤，80℃下反应60分钟。
S4）、压滤、洗涤，增浓1次：用板框压滤机压滤、洗涤，滤饼为提锂残渣，滤液为含锂溶液，返回步骤1重复提锂，进行锂液增浓1次。
S5）、除杂：增浓后的锂液，加入氢氧化钠溶液调节PH值到9.0，搅拌30分钟，压滤、洗涤，滤饼为铜铝渣，无害处理；滤液和洗液控制在18m 3，进入下一工序。
S6）、沉淀碳酸锂：将滤液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液返回步骤1的制浆工序；滤饼为碳酸锂产品。
S7）、溶解磷酸铁：用20m 3反应釜承接步骤S6）的提锂残渣，加水调成质量比约1/4的浆状物，加入浓盐酸调成PH1.0，同时用盐酸维持PH值，搅拌3小时。
S8）、压滤、洗涤：滤饼为分解渣，无害处理；滤液和洗液进入合并。
S9）、磷酸铁合成：步骤S8）中压滤后的滤液和洗液，检测其中的铁和磷的含量，加入磷酸三钠或氯化铁，以保证铁/磷摩尔比1/0.97-1.02在比例之内，并控制PH在0.5，反应1.0小时，再用氢氧化钠溶液调节PH到1.5，沉淀磷酸铁。
S10）、压滤、洗涤：用板框压滤机压滤和洗涤，滤液和洗液合并进入废水处理站；滤饼为粗制磷酸铁进入下一工序。
S11）、逆向三级除杂洗涤：粗制磷酸铁滤饼用PH值为1.5的洗液，搅拌、逆向洗涤三次，洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，其步骤如下：①洗液配置：纯水20m 3的调酸桶内加入纯水18m 3,加入优级纯盐酸配成PH1.5备用。
②第一次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第二次洗涤水，搅拌30分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站；滤饼进入第二次洗涤。
③第二次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第三次洗涤水，搅拌30分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤。
④第三次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入新洗涤水，搅拌30分钟，压滤并用新洗涤水洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁，经检测合格后进入烘干工序。
S12）、烘干、粉碎：纯净磷酸铁滤饼用微波干燥炉，温度60℃，干燥至含水0.1%，用气流粉碎机粉碎至5μm以内，包装即为电池级磷酸铁产品。
检测数据如下。
Figure 48924dest_path_image002
。
本实施例1的效果表现为：锂的溶出率为99.9%，磷铁的溶出率为97.45%，磷的溶出率：96.54%，铝的溶出率：92.17%，铜的溶出率：91.82%，磷酸铁杂质含量（干基%）为：Al：0.0005，Cu：0.0005，Co：0.0025，Ni：0.0005，Mn：0.0013，Ca：0.0014，Cd：0.0005，磷酸铁产品符合电池级质量要求，收率为93.93%。工艺流程简单，每吨磷酸铁锂废料减少氢氧化钠273.8kg，废水量减少75%，相对生产成本降低25.8%。
实施例 2 ：一种废旧磷酸铁锂电池的综合回收利用方法，实 施所用物料同实施例1。其步骤为： S1）、制浆：用20m 3反应釜将废磷酸铁锂正负极粉5吨，按质量比1/4的量加水或含锂溶液调成浆状。
S2）、用盐酸调节物料浆PH到2.0。
S3）、选择性提锂：按照物料浆中二价铁质量比0.35倍的量加入固态氯酸钠532公斤，80℃下反应60分钟。
S4）、压滤、洗涤、增浓2次：用板框压滤机压滤、洗涤，滤饼为提锂残渣，滤液为含锂溶液，返回步骤1的制浆环节，进行制浆，重复选择性提锂2次，以增浓含锂溶液的锂含量。
S5）、除杂：增浓的含锂溶液，加入氢氧化钠溶液调节PH值到8.5，搅拌30分钟，压滤、洗涤，滤饼为铜铝渣，无害处理；滤液和洗液控制在18m 3，进入下一工序。
S6）、沉淀碳酸锂：将滤液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液返回步骤1的制浆工序；滤饼为碳酸锂产品。
S7）、溶解磷酸铁：用20m 3反应釜承接步骤S4）的提锂残渣，加水调成质量比约1/4的浆状物，加入浓盐酸调成PH0.5，同时用盐酸维持PH值，搅拌3小时。
S8）、压滤、洗涤：滤饼为分解渣，无害处理；滤液和洗液进入合并。
S9）、磷酸铁合成：步骤8中压滤后的滤液和洗液，检测其中的铁和磷的含量，加入磷酸三钠或氯化铁，以保证铁/磷摩尔比1/0.97-1.02在比例之内，并控制PH在0.5，反应1.5小时，再用氢氧化钠溶液调节PH到1.5，沉淀磷酸铁。
S10）、压滤、洗涤：用板框压滤机压滤和洗涤，滤液和洗液合并进入废水处理站；滤饼为粗制磷酸铁进入下一工序。
S11）、逆向三级除杂洗涤：粗制磷酸铁滤饼用PH值为1.5的洗液，搅拌、逆向洗涤三次，洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，其步骤如下：①  洗液配置：纯水20m 3的调酸桶内加入纯水18m 3,加入优级纯盐酸配成PH1.5备用。
②第一次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第二次洗涤水，搅拌30分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站；滤饼进入第二次洗涤。
③第二次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第三次洗涤水，搅拌30分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤。
④第三次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入新洗涤水，搅拌30分钟，压滤并用新洗涤水洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁，经检测合格后进入烘干工序。
S12）、烘干、粉碎：纯净磷酸铁滤饼用微波干燥炉，温度90℃，干燥至含水0.1%，用气流粉碎机粉碎至5μm以内，包装即为电池级磷酸铁产品。
检测数据如下。
Figure 923339dest_path_image003
。
本实施例2的效果表现为：锂的溶出率为99.9%，铁的溶出率：98.50%，磷的溶出率：96.62%，铝的溶出率：99.10%，铜的溶出率：98.72%，磷酸铁杂质含量（干基%）为：Al：0.0005，Cu：0.0005，Co：0.0025，Ni：0.0005，Mn：0.0008，Ca：0.0009，Cd：0.0005，磷酸铁产品符合电池级质量要求，收率为93.98%。工艺流程简单，每处理1吨磷酸铁锂废料减少氢氧化钠275.1kg，废水量减少78%，相对生产成本降低25%。
对比例 1 ：实 施所用物料同实施例1，其步骤为：1、制浆：用20m 3反应釜将废磷酸铁锂正负极粉5吨，按质量比1/4的量加水或含锂溶液调成浆状。
2、用盐酸调节物料浆PH到1.0。
3、选择性提锂：按照物料浆中二价铁质量比0.35倍的量加入固态氯酸钠532公斤。80℃下反应60分钟。
4、压滤、洗涤：用板框压滤机压滤、洗涤，滤饼为提锂残渣，滤液为含锂溶液。
5、除杂：加入氢氧化钠溶液调节PH值到9.0，搅拌30分钟，压滤、洗涤，滤饼为铜铝渣，无害处理；滤液和洗液控制在18m 3，进入下一工序。
6、沉淀碳酸锂：将滤液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液返回步骤1的制浆工序；滤饼为碳酸锂产品。
7、溶解磷酸铁：用20m 3反应釜承接步骤4的提锂残渣，加水调成质量比约1/4的浆状物，加入浓盐酸调成PH0.5，同时用盐酸维持PH值，搅拌3小时。
8、压滤、洗涤：滤饼为分解渣，无害处理；滤液和洗液进入合并。
9、磷酸铁合成：步骤8中压滤后的滤液和洗液，检测其中的铁和磷的含量，加入磷酸三钠或氯化铁，以保证铁/磷摩尔比1/0.97-1.02在比例之内，并控制PH在0.5，反应0.5小时，再用氢氧化钠溶液调节PH到1.5，沉淀磷酸铁。
10、压滤、洗涤：用板框压滤机压滤和洗涤，滤液和洗液合并进入废水处理站；滤饼为粗制磷酸铁进入下一工序。
11、逆向三级除杂洗涤：粗制磷酸铁滤饼用PH值为1.0的洗液，搅拌、逆向洗涤三次，洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，其步骤如下：①洗液配置：纯水20m 3的调酸桶内加入纯水18m 3,加入优级纯盐酸配成PH1.0备用。
②第一次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第二次洗涤水，搅拌30分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站；滤饼进入第二次洗涤。
③第二次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第三次洗涤水，搅拌30分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤。
④第三次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入新洗涤水，搅拌30分钟，压滤并用新洗涤水洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁，经检测合格后进入烘干工序。
12、烘干、粉碎：纯净磷酸铁滤饼用微波干燥炉，温度90℃，干燥到含水率0.1%，用气流粉碎机粉至5μm以内，得到磷酸铁产品。
  检测数据如下。
Figure 283782dest_path_image004
 。
对比例1中选择性提锂PH值在1.0，含锂溶液中含铁24.4g/L,含磷15.36g/L，磷和铁的损失很大；粗磷酸铁洗杂时，洗涤液的PH为1.0，洗涤液中含铁15.96g/L,含磷4.93g/L，磷和铁损失大，磷酸铁收率仅为68.0%。
对比例 2 ：实 施所用物料同实施例1，其步骤为：1、制浆：用20m 3反应釜将废磷酸铁锂正负极粉5吨，按质量比1/4的量加水或含锂溶液调成浆状。
2、用盐酸调节物料浆PH到2.0。
3、选择性提锂：按照物料浆中二价铁质量比0.35倍的量加入固态氯酸钠532公斤。80℃下反应60分钟。
4、压滤、洗涤，增浓2次：用板框压滤机压滤、洗涤，滤饼为提锂残渣，滤液为含锂溶液，返回步骤1的制浆环节，进行制浆，重复选择性提锂2次，以增浓含锂溶液的锂含量。
5、除杂：增浓后的锂液，加入氢氧化钠溶液调节PH值到9.0，搅拌30分钟，压滤、洗涤，滤饼为铜铝渣，无害处理；滤液和洗液控制在18m 3，进入下一工序。
6、沉淀碳酸锂：将滤液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液返回步骤1的制浆工序；滤饼为碳酸锂产品。
7、溶解磷酸铁：用20m 3反应釜承接步骤4的提锂残渣，加水调成质量比约1/4的浆状物，加入浓盐酸调成PH0.1，同时用盐酸维持PH值，搅拌3小时。
8、压滤、洗涤：滤饼为分解渣，无害处理；滤液和洗液进入合并。
9、磷酸铁合成：步骤8中压滤后的滤液和洗液，检测其中的铁和磷的含量，加入磷酸三钠或氯化铁，以保证铁/磷摩尔比1/0.97-1.02在比例之内，并控制PH在0.5，反应2.0小时，再用氢氧化钠溶液调节PH到1.5，沉淀磷酸铁。
10、压滤、洗涤：用板框压滤机压滤和洗涤，滤液和洗液合并进入废水处理站；滤饼为粗制磷酸铁进入下一工序。
11、逆向三级除杂洗涤：粗制磷酸铁滤饼用PH值为2.0的洗液，搅拌、逆向洗涤三次，洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，其步骤如下：①洗液配置：纯水20m 3的调酸桶内加入纯水18m 3,加入优级纯盐酸配成PH2.0备用。
②第一次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第二次洗涤水，搅拌30分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站；滤饼进入第二次洗涤。
③第二次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第三次洗涤水，搅拌30分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤。
④第三次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入新洗涤水，搅拌30分钟，压滤并用新洗涤水洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁。
12、烘干、粉碎：纯净磷酸铁滤饼用微波干燥炉，温度90℃，干燥到含水0.1%，用气流粉碎机粉碎至5μm以内，得到磷酸铁产品。
检测数据如下。
Figure 497726dest_path_image005
。
对比例2中选择性提锂PH值在2.0，含锂溶液中含锂23.0g/L,锂的溶解率仅为90%；锂的损失很大；粗磷酸铁洗杂时，洗涤液的PH为2.0，磷酸铁产品中含铝0.017%,含铜0.051%，产品不符合电池级要求。
对比例 3 ：实 施所用物料同实施例1，其步骤为：1、制浆：用20m 3反应釜将废磷酸铁锂正负极粉5吨，按质量比1/4的量加水或含锂溶液调成浆状。
2、用盐酸调节物料浆PH到2.5。
3、选择性提锂：按照物料浆中二价铁质量比0.35倍的量加入固态氯酸钠532公斤。80℃下反应60分钟。
4、压滤、洗涤、增浓2次：用板框压滤机压滤、洗涤，滤饼为提锂残渣，滤液为含锂溶液，返回步骤1的制浆环节，进行制浆，重复选择性提锂2次，以增浓含锂溶液的锂含量。
5、除杂：增浓后的锂液，加入氢氧化钠溶液调节PH值到9.0，搅拌30分钟，压滤、洗涤，滤饼为铜铝渣，无害处理；滤液和洗液控制在18m 3，进入下一工序。
6、沉淀碳酸锂：将滤液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液返回步骤1的制浆工序；滤饼为碳酸锂产品。
7、溶解磷酸铁：用20m 3反应釜承接步骤4的提锂残渣，加水调成质量比约1/4的浆状物，加入浓盐酸调成PH0.5，同时用盐酸维持PH值，搅拌3小时。
8、压滤、洗涤：滤饼为分解渣，无害处理；滤液和洗液进入合并。
9、磷酸铁合成：步骤8中压滤后的滤液和洗液，检测其中的铁和磷的含量，加入磷酸三钠或氯化铁，以保证铁/磷摩尔比1/0.97-1.02在比例之内，并控制PH在0.5，反应1.5小时，再用氢氧化钠溶液调节PH到1.5，沉淀磷酸铁。
10、压滤、洗涤：用板框压滤机压滤和洗涤，滤液和洗液合并进入废水处理站；滤饼为粗制磷酸铁进入下一工序。
11、逆向三级除杂洗涤：粗制磷酸铁滤饼用PH值为2.5的洗液，搅拌、逆向洗涤三次，洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，其步骤如下：①洗液配置：纯水20m 3的调酸桶内加入纯水18m 3,加入优级纯盐酸配成PH2.5备用。
②第一次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第二次洗涤水，搅拌30分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站；滤饼进入第二次洗涤。
③第二次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入第三次洗涤水，搅拌30分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤。
④第三次洗涤：粗制磷酸铁滤饼以质量比1/5的比率加入新洗涤水，搅拌30分钟，压滤并用新洗涤水洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁，经检测合格后进入烘干工序。
12、烘干、粉碎：纯净磷酸铁滤饼用微波干燥炉，温度90℃，干燥到含水0.1%，用气流粉碎机粉碎至5μm，得到磷酸铁产品。
检测数据如下。
Figure 154097dest_path_image006
 。
对比例3中选择性提锂PH值在2.5，含锂溶液中含锂18.96g/L,锂的溶解率仅为74.2%；锂的损失很大；粗磷酸铁洗杂时，洗涤液的PH为2.5，磷酸铁产品中含铝0.014%,含铜0.041%，产品不符合电池级要求。
以上所述，仅为本发明的说明实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，做出的若干改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明精神和范围的情况下，利用以上所揭示的技术内容做出的些许更改、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所做的任何等同变化的更改、修饰与演变，均仍属于本发明的保护范围。
 工业实用性
本发明技术已投入工业化生产应用，锂的溶出率达99.9%，磷铁的溶出率≥96.62%，磷的溶出率≥96.54%，铝的溶出率≥92.17%，铜的溶出率≥91.82%，磷酸铁产品符合电池级质量要求，收率≥93.93%。工艺流程简单，每吨磷酸铁锂废料减少氢氧化钠273.8kg以上，减少废水量75%以上，相对生产成本至少降低25%。

Claims (8)

  1. 一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：先选择性提锂，然后利用提锂残渣制备磷酸铁；
     所述选择性提锂，先将废磷酸铁锂正负极粉末加水或含锂溶液调成料浆后用盐酸调节料浆PH至1.5-2.0；然后在料浆中加入固态氯酸钠，选择性将锂溶解在溶液中，磷酸铁留在残渣中，再经过滤得含锂溶液和含磷酸铁的提锂残渣；
    所述利用提锂残渣制备磷酸铁：采取如下步骤：
    S1).将提锂残渣按质量比1/3-5的量加水调成料浆；
    S 2).将料浆用盐酸调PH0.5-1.0，搅拌反应，使料浆尾渣中的铁溶解至含量≤1.0%；
    S 3).将S 2)步骤所得料浆经压滤、洗涤，滤饼为分解渣，无害处理；滤液和洗液进入下一工序；
    S 4).将S 3).步骤压滤所得液体，根据其铁和磷的含量，加入磷酸三钠或氯化铁，控制PH在0.5-1.0，反应至少0.5小时，再用氢氧化钠溶液调节PH到1.5-2.0，沉淀磷酸铁；
    S 5).在S 4)步骤后进行压滤、洗涤：滤液和洗液合并进入废水处理站，滤饼为粗制磷酸铁。
  2. 根据权利要求1所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：在所述选择性提取锂工序中，废磷酸铁锂正负极粉末按质量比1/3-5的比例加水或含锂溶液调成料浆。
  3. 根据权利要求1所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：在所述选择性提锂工序中，按照料浆中二价铁质量比0.35-0.4倍的量加入固态氯酸钠。
  4. 根据权利要求1所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：在所述选择性提取锂工序中，所述选择性将锂溶解在溶液中是将加入固态氯酸钠反应后的料浆中的二价铁离子全部转化为三价铁离子后进行渣液分离，滤液为含锂溶液，当含锂溶液中锂含量小于15g/L时，返回调成料浆环节进行制浆，以增浓含锂溶液的锂含量，当含锂溶液中锂含量大于15g/L时，加入氢氧化钠溶液调节PH值到8.5-9.5，使溶液中的铜和铝形成氢氧化物沉淀，压滤、洗涤，滤饼为铜铝渣，滤液为含锂溶液。
  5. 根据权利要求1所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：在所述选择性提锂工序后，将含锂溶液沉淀碳酸锂：将含锂溶液泵入沉锂桶内，加入饱和碳酸钠溶液形成碳酸锂沉淀，压滤后滤液经处理后返回调成料浆环节，滤饼为碳酸锂产品。
  6. 根据权利要求1所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：在S2)步骤中，所述搅拌反应是用盐酸维持PH值，搅拌1-3小时，优选2小时。
  7. 根据权利要求1所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：在S 4)步骤中，所述加入磷酸三钠或氯化铁，是通过检测液体中的铁和磷的含量，以铁/磷摩尔比1/0.97-1.02的比例，加入磷酸三钠或氯化铁。
  8. 根据权利要求1所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于在制备粗制磷酸铁之后进行逆向三级洗涤除杂：粗制磷酸铁滤饼用纯水与盐酸配置成PH值为1.5的洗液，逆向洗涤三次，以洗去粗制磷酸铁中其他金属盐，得到纯净的磷酸铁滤饼，经烘干、粉碎为电池磷酸铁产品。
    9.根据权利要求8所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：所述逆向三级洗涤除杂：采取如下步骤：
    b1).洗液配置：在纯水中加入优级纯盐酸配成PH1.5-2.0的盐酸洗液备用;
    b2).第一次洗涤：粗制磷酸铁滤饼以质量比1/3-5的比率加入第二次洗涤水，搅拌30-60分钟，压滤并用第二次洗涤水洗涤，滤液和洗液进入废水处理站，滤饼进入第二次洗涤；
    b3).第二次洗涤：将第一次洗涤所得粗制磷酸铁滤饼以质量比1/3-5的比率加入第三次洗涤水，搅拌30-60分钟，压滤并用第三次洗涤水洗涤，滤液和洗液用于第一次洗涤；滤饼进入第三次洗涤;
    b4).第三次洗涤：将第二次洗涤所得粗制磷酸铁滤饼以质量比1/3-5的比率加入配置好的PH1.5-2.0盐酸洗液，搅拌30-60分钟，压滤并用配置好的PH1.5-2.0盐酸洗液进行洗涤，滤液和洗液用于第二次洗涤；滤饼作为纯净磷酸铁，经检测合格后进入烘干、粉碎制得电池级磷酸铁产品。
    10.根据权利要求9所述的一种废旧磷酸铁锂电池的综合回收利用方法，其特征在于：所述烘干、粉碎：是将纯净磷酸铁滤饼用微波干燥炉，温度至多90℃，干燥至含水至多0.1%，用气流粉碎机粉碎至多5μm，包装即为电池级磷酸铁产品。
     
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