CN111534697A - Selection-smelting combined comprehensive recovery method and device for waste lithium ion batteries - Google Patents

Abstract

The invention provides a method and a device for the combined comprehensive recovery of waste lithium ion batteries by beneficiation and metallurgy. The method includes: S1, pretreatment of the battery by fire method; S2, washing and classifying the pretreated product to obtain coarse-grained particles, medium-fine-sized particles, fine-sized particles and a first part of the lithium-containing solution; S3, magnetic separation of each particle , the obtained magnetic separation concentrate is nickel, cobalt and manganese intermediate products, the magnetic separation tailings of coarse and medium and fine particles are copper and aluminum products, and the magnetic separation tails of fine particles are graphite and black powder products; The powder product is subjected to slurry mixing and graphite flotation to obtain graphite product and black powder; S4, nickel-cobalt-manganese intermediate product and black powder are subjected to reduction roasting to obtain roasting slag; the roasting slag extracts lithium to obtain the second part of lithium-containing solution and water leaching slag; S5, combine the first and second parts of the lithium-containing solution to prepare a lithium product; S6, pickle and remove impurities from the water leaching slag. The invention can effectively recover the lithium element, other metals and graphite in the waste lithium ion battery.

Description

Method and device for combined comprehensive recovery of waste lithium-ion batteries

technical field

The invention relates to resource recovery of waste and used lithium ion batteries, in particular, to a method and device for combined comprehensive recovery of waste and used lithium ion batteries by beneficiation and smelting.

Background technique

With the advent of the scrapping tide of lithium-ion batteries, a large number of recycling processes have been developed and applied for a while. At present, the main problems in the recycling process of waste lithium-ion batteries are: 1. Most of the processes focus on the recovery of nickel-cobalt with high content and high market price in waste lithium-ion batteries, and less attention is paid to the recycling of low-content lithium elements , therefore, the recovery rate of nickel, cobalt, and manganese in most recovery processes is high, and the recovery rate of lithium is low. 2. At present, the definition of solid waste generated in the field of battery recycling is not perfect, and the treatment process for a large number of fluorine-containing and phosphorus-containing diaphragm plastic parts is not perfect. However, with the maturity of the recycling industry, a large amount of solid waste is facing Harmless treatment.

CN 109935922A discloses a method for recovering valuable metals from waste lithium ion battery positive electrode materials, using low-price sulfate mixtures such as sulfur and sulfide as reducing agents to reduce high-value compounds in positive electrode materials, and then using water or weak acid leaching reduction roasting slag, the leaching solution recovers lithium, and the leaching residue recovers nickel and cobalt after acid leaching. The core of this method is to use low-valent sulfide as a reducing agent for reduction roasting. After reduction, the lithium recovery can be improved by preferentially extracting lithium. However, it is difficult to control the degree of reduction whether it is sulfur or sulfide reduction roasting, and it is prone to excessive sulfidation. In this case, nickel-cobalt is calcined into low-price sulfate, which increases the difficulty of separating lithium and nickel-cobalt.

CN 108264068A discloses a method for electrochemically treating waste lithium ion power battery positive electrode materials, using sulfate and/or hydrogen sulfate as solution electrolyte to carry out the reaction, the essence of the reaction is to utilize the acid solution decomposed by electrolytic water to leach the positive electrode Lithium in the material, this method is novel, and the lithium in the positive electrode material is preferentially recovered, which can improve the recovery rate of lithium, but the reaction process is limited by the electrolysis efficiency of water, and the liquid-solid ratio of the electrolysis process is large and the efficiency is low.

CN 108767354A discloses a method for treating waste and old lithium ion battery positive electrode materials by using ammonium salt roasting process. After ammonium salt roasting, water immersion is adopted, and valuable metals Ni, Co, Mn and Li are all transferred into solution, and then recovered from the solution This process recycles ammonium salt, which can reduce production costs, but still has the shortcomings of long recovery process, dispersed lithium and low recovery rate.

CN 106505270A also discloses a process for treating waste and old ternary lithium ion battery positive electrode material by ammonium salt roasting method. After the aluminum foil is removed from the roasting slag after ammonium salt roasting, the cobalt and lithium are solutionized by acid leaching, and then the precipitation method is used to dissolve the cobalt and lithium into solution. Cobalt is precipitated as cobalt hydroxide, and lithium is finally recovered. This method avoids the extraction process and can effectively reduce the loss of lithium, but the method has limited applicability to waste lithium-ion batteries with complex compositions and scattered models.

It can be seen that in the prior art, the overall recovery rate is low when recovering the lithium element in the waste lithium-ion battery. In addition, there is currently a lack of comprehensive recovery methods for metals such as lithium, nickel, cobalt, manganese, copper, aluminum, and graphite in waste lithium-ion batteries, and the treatment of phosphorus-containing and fluorine-containing separators and plastic parts in batteries is not effective enough.

SUMMARY OF THE INVENTION

The main purpose of the present invention is to provide a method and device for the combined comprehensive recovery of waste and used lithium ion batteries, so as to improve the recovery rate of lithium elements in waste and used lithium ion batteries. Various metals such as manganese, copper, aluminum, and graphite are comprehensively recycled, and the phosphorus-containing and fluorine-containing separators and plastic parts in the battery are effectively treated.

In order to achieve the above object, according to one aspect of the present invention, a method for combined and comprehensive recovery of waste and used lithium ion batteries is provided, which comprises the following steps: S1, performing pyroprocessing on waste and used lithium ion batteries to obtain a pretreatment product ; S2, the pretreatment product is washed and classified to obtain coarse-grained particles, medium- and fine-grained particles, fine-grained particles and the first part of the lithium-containing solution, and the particle size of the coarse-grained particles is larger than that of the medium and fine-grained particles. The particle size of medium and fine-grained particles is larger than that of fine-grained particles; S3, magnetic separation of coarse-grained particles, medium- and fine-grained particles and fine-grained particles is carried out, respectively, and the magnetic separation concentrate is obtained. As nickel-cobalt-manganese intermediate products, the magnetic separation tailings of coarse-grained particles and medium-fine particles are used as copper-aluminum products, and the magnetic separation tailings of fine-grained particles are graphite and black powder products; Sizing and graphite flotation are carried out in sequence to obtain graphite products and black powder; S4, the nickel-cobalt-manganese intermediate product and black powder are subjected to reduction roasting to obtain roasting slag; the roasting residue is subjected to water leaching to extract lithium to obtain the second part containing lithium solution and water leaching residue; S5, combining the first part of the lithium-containing solution and the second part of the lithium-containing solution to obtain a combined solution; using the combined solution to prepare a lithium product; S6, performing acid leaching and impurity removal on the water leaching residue to obtain a nickel-containing solution Solution product of cobalt and manganese.

Further, in step S1, the fire pretreatment process includes: dismantling and crushing waste lithium-ion batteries to obtain crushed materials; preferably, the particle size of the crushed materials is below 50 mm; Low-temperature pyrolysis is carried out at a temperature of 700°C to obtain a pretreated product; preferably, the temperature of low-temperature pyrolysis is 600-650°C, more preferably 610-640°C; preferably, the time of low-temperature pyrolysis is 0.5-6h; Preferably, before the step of dismantling and crushing the waste lithium ion battery, step S1 further includes the step of discharging the waste lithium ion battery.

Further, in step S2, the particle diameter of the coarse-grained particle is greater than 2 mm, the particle diameter of the fine-grained particle is less than 0.2 mm, and the particle diameter of the medium and fine-grained particle is between the particle diameter of the coarse-grained particle and the fine-grained particle. Preferably, in step S3, the magnetic separation magnetic field strengths for the coarse-grained particles, the medium-fine-sized particles and the fine-grained particles are respectively 40-280 kA/m.

Further, the steps of sequentially performing slurry mixing and graphite flotation on the graphite and black powder products include: preparing the graphite and black powder products with water to form a flotation slurry with a concentration of 5-35wt%; adding a regulator, graphite to the flotation slurry Collector and foaming agent for graphite flotation to obtain graphite product and black powder.

Further, in step S4, the reducing agent used in the reduction roasting process is the graphite product obtained in step S3, or the reduction roasting process is carried out under a reducing atmosphere; preferably, the reducing atmosphere is composed of a reducing gas and an optional inert gas. Gas composition, the reducing gas is one or more of hydrogen, ammonia, methane and sulfur dioxide, and the inert gas is nitrogen and/or argon; 0.5～6h.

Further, in step S5, the lithium in the combined solution is evaporated and crystallized in the form of lithium hydroxide, or carbon dioxide is passed into the combined solution or soluble carbonate is added to precipitate lithium in the form of lithium carbonate to obtain a lithium product; Preferably, before the step of using the combined solution to prepare the lithium product, step S5 further includes the step of removing impurity ions in the combined solution by chemical precipitation or ion exchange resin.

Further, in step S6, acid leaching is performed on the water leaching residue to obtain an acid leaching solution; the impurity removal step includes: adjusting the pH value of the acid leaching solution to above 4.2, removing iron impurities and aluminum impurities, and obtaining an iron-removing aluminum solution; Adding fluoride to the iron-removing aluminum solution to remove magnesium impurities to obtain a magnesium-removing solution; preferably, the fluoride is sodium fluoride; adding sulfide salt and/or hydrogen sulfide to the magnesium-removing solution to remove copper impurities and zinc impurities, A solution product containing nickel, cobalt and manganese is obtained; preferably, the sulfide salt is sodium sulfide; or, the step of removing impurities includes: using an extractant to extract the acid leaching solution to obtain a solution product containing nickel, cobalt and manganese; preferably, the extractant is P204 extraction agent.

Further, before the step of acid leaching the water leaching slag, step S6 further includes the step of reducing and smelting the water leaching slag; nickel-cobalt-manganese alloy, and then performing acid leaching and impurity removal on the nickel-cobalt-manganese alloy in turn to obtain a solution product containing nickel, cobalt and manganese.

Further, the first flue gas is obtained in the fire pretreatment step, the second flue gas is obtained in the reduction smelting step, and the recovery method further includes sequentially performing secondary combustion, surface cooling, The steps of dust removal and exhaust gas purification.

Further, waste lithium-ion batteries are waste lithium cobalt oxide batteries, lithium manganate batteries, nickel-manganese binary composite lithium-ion batteries, nickel-cobalt binary composite lithium-ion batteries, cobalt-manganese binary composite lithium-ion batteries, nickel-cobalt-manganese binary composite lithium-ion batteries One or more of ternary composite lithium-ion batteries and nickel-cobalt-aluminum ternary composite lithium-ion batteries.

According to another aspect of the present invention, there is also provided a combined comprehensive recovery device for waste lithium ion batteries, which includes: a pyroprocessing unit, which has an inlet for spent lithium ion batteries and an outlet for pretreatment products, and a pyroprocessing unit. The unit is used for pyroprocessing waste lithium-ion batteries to obtain pretreated products; the ore washing and grading unit has a pretreatment product inlet and a first water inlet, the pretreatment product inlet is connected to the pretreatment product inlet, and the ore washing and grading unit is It is used for washing and classifying the pretreated product to obtain coarse-grained particles, medium and fine-grained particles, fine-grained particles and the first part of the lithium-containing solution, and the particle size of the coarse-grained particles is larger than that of the medium and fine-grained particles. Particle size, the particle size of the medium and fine particles is larger than the particle size of the fine particles; the magnetic separation unit is connected to the outlet of the washing and grading unit, and the magnetic separation unit is used to separate the coarse particles and the medium and fine particles respectively. Magnetic separation with fine-grained particles to obtain nickel-cobalt-manganese intermediates, coarse-grained magnetic separation tailings, medium and fine-grained magnetic separation tailings, fine-grained magnetic separation of tailings, and coarse-grained magnetic separation of tailings Tailings and tailings of medium and fine particle magnetic separation are used as copper and aluminum products, and tailings of fine particle magnetic separation are graphite and black powder products; the graphite recovery unit is connected to the outlet of the magnetic separation unit, and the graphite recovery unit includes the Sub-connected pulping unit and flotation unit, pulping unit is used for pulping graphite and black powder products, and flotation unit is used for graphite flotation to obtain graphite products and black powder; reduction roasting unit, respectively with magnetic The outlet of the selection unit is connected to the outlet of the flotation unit, and the reduction roasting unit is used for reducing and roasting the nickel cobalt manganese intermediate product and black powder to obtain roasting slag; the water leaching unit has a roasting slag inlet and a second water inlet, and the roasting The inlet is connected to the outlet of the reduction roasting unit, and the water leaching unit is used to extract lithium from the roasting slag to obtain the second part of the lithium-containing solution and the water leaching residue; The outlet of the ore classification unit is connected, and the lithium recovery unit is used to prepare lithium products by using the combined solution of the first part of the lithium-containing solution and the second part of the lithium-containing solution; the acid leaching unit has a water leaching slag inlet, an acid inlet and an acid leaching liquid outlet, The inlet of the water leaching slag is connected with the outlet of the water leaching unit, and the acid leaching unit is used for acid leaching the water leaching slag to obtain the acid leaching solution; Impurity removal is carried out to obtain a nickel-cobalt-manganese-containing solution product.

Further, the pyrolysis pretreatment unit includes: a dismantling and crushing unit, which has an inlet for waste lithium-ion batteries and an outlet for crushed materials; a low-temperature pyrolysis unit, which has an inlet for crushed materials, an inlet for inert gas, and an outlet for pretreatment products, and an inlet for crushed materials and an outlet for crushing materials. The material outlet is connected.

Further, the pyroprocessing unit further includes a discharge unit, the discharge unit is located upstream of the dismantling and crushing unit and connected to the inlet of the waste lithium ion battery, and the discharge unit is used for discharging the waste lithium ion battery.

Further, the graphite recovery unit further includes: a regulator supply unit, connected to the flotation unit, for supplying the regulator; a graphite collector supply unit, connected to the flotation unit, for supplying the graphite collector to it ; a frother supply unit, connected to the flotation unit, for supplying frother to it.

Further, the reduction roasting unit also has a first reducing agent inlet, and the first reducing agent inlet is connected to the outlet of the flotation unit, and is used to use the graphite product obtained in the graphite flotation process as the reducing agent in the reduction roasting process; Or, The reduction roasting unit also has a reducing gas inlet, the recovery device further includes a reducing gas supply unit, and the reducing gas supply unit is connected to the reducing gas inlet.

Further, the recovery device further includes an inert gas supply unit, and the inert gas supply unit is respectively connected to the reducing gas inlet and the inert gas inlet of the low temperature pyrolysis unit.

Further, the lithium recovery unit includes: an impurity removal agent supply unit for supplying an impurity remover; an impurity removal purification unit, the inlet of which is respectively connected with the outlet of the water leaching unit, the outlet of the washing and grading unit, and the impurity removal agent supply unit, The impurity removal and purification unit is used for performing the impurity removal reaction on the combined solution of the first part of the lithium-containing solution and the second part of the lithium-containing solution to obtain the impurity removal lithium solution; the lithium product preparation unit is connected to the outlet of the impurity removal and purification unit, and the lithium product is prepared The unit is used for evaporative crystallization or precipitation of lithium carbonate on the impurity-removing lithium solution to obtain lithium products.

Further, the impurity removal unit includes: a pH adjustment unit, which is connected to the outlet of the acid leaching solution, and the pH adjustment unit is used to adjust the pH value of the acid leaching solution to above 4.2 to obtain an iron and aluminum removal solution; the magnesium removal unit has a fluoride inlet. And the inlet of iron and aluminum solution, the inlet of iron and aluminum solution is connected with the outlet of pH adjustment unit, and the magnesium removal unit is used to remove magnesium impurities in iron and aluminum solution to obtain magnesium removal solution; copper and zinc removal unit, with magnesium removal solution inlet and the sulfide inlet, the magnesium removal solution inlet is connected to the outlet of the magnesium removal unit, the sulfide inlet is used to introduce sulfide salt and/or hydrogen sulfide, and the copper and zinc removal unit is used to remove copper impurities and zinc impurities in the magnesium solution, A solution product containing nickel, cobalt and manganese is obtained; or, the impurity removal unit is an extraction impurity removal unit.

Further, the recovery device also includes a reduction smelting unit, the reduction smelting unit is arranged on the flow path connecting the water leaching slag inlet and the water leaching unit, and the reduction smelting unit also has a flux inlet, and the reduction smelting unit is used for reducing the water leaching smelting smelting. to obtain a nickel-cobalt-manganese alloy, and the acid leaching unit is used for acid-leaching the nickel-cobalt-manganese alloy to obtain an acid leaching solution.

Further, the pyroprocessing unit also has a first flue gas outlet, the reduction smelting unit also has a second flue gas outlet, and the recovery device further includes a flue gas processing unit, which is respectively connected with the first flue gas outlet and the second flue gas outlet. The flue gas outlet is connected.

The present invention provides a method for combined comprehensive recovery of waste and used lithium ion batteries, which can more effectively recover lithium elements in waste and used lithium ion batteries in a shorter process, and can comprehensively recover lithium, nickel, cobalt, manganese, Copper, aluminum and other metals, as well as graphite, and the phosphorus-containing and fluorine-containing diaphragms and plastic parts in the battery are effectively removed by fire.

Description of drawings

The accompanying drawings forming a part of the present application are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the attached image:

FIG. 1 shows a flow chart of a method for combined and comprehensive recovery of waste lithium-ion batteries according to an embodiment of the present invention; and

FIG. 2 shows a structural block diagram of a combined beneficiation and metallurgical comprehensive recovery device for waste lithium-ion batteries according to an embodiment of the present invention.

Wherein, the above-mentioned drawings include the following reference signs:

10. Fire pretreatment unit; 11. Dismantling and crushing unit; 12. Low temperature pyrolysis unit; 13. Discharging unit; 20. Ore washing and classification unit; 30. Magnetic separation unit; 40. Graphite recovery unit; 41. Sizing unit; 42, flotation unit; 43, regulator supply unit; 44, graphite collector supply unit; 45, frother supply unit; 50, reduction roasting unit; 60, water immersion unit; 70, lithium recovery unit; 71, impurity removal agent supply unit; 72, impurity removal purification unit; 73, lithium product preparation unit; 80, acid leaching unit; 90, impurity removal unit; 91, pH adjustment unit; 92, magnesium removal unit; 93, copper removal Zinc unit; 100, inert gas supply unit; 110, reduction smelting unit; 120, flue gas treatment unit.

Detailed ways

It should be noted that the embodiments in the present application and the features of the embodiments may be combined with each other in the case of no conflict. The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

As described in the background art section, in the prior art, there is a problem of low recovery rate as a whole when recovering lithium elements in spent lithium-ion batteries. In addition, there is currently a lack of comprehensive recovery methods for metals such as lithium, nickel, cobalt, manganese, copper, aluminum, and graphite in waste lithium-ion batteries, and the treatment of phosphorus-containing and fluorine-containing separators and plastic parts in batteries is not effective enough.

In order to solve the above problems, the present invention provides a combined comprehensive recovery method for waste lithium ion batteries. As shown in FIG. 1 , the recovery method includes the following steps: S1, performing pyroprocessing on waste lithium ion batteries to obtain Pretreatment product; S2, washing and classifying the pretreated product to obtain coarse-grained particles, medium-fine-grained particles, fine-grained particles and the first part of the lithium-containing solution, and the particle size of the coarse-grained particles is larger than that of the medium-fine particles The particle size of the particle size, the particle size of the medium and fine particles is larger than the particle size of the fine particle; S3, the magnetic separation of the coarse particle, the medium and fine particles and the fine particle are carried out respectively, and the obtained magnetic The concentrate is used as the intermediate product of nickel, cobalt and manganese, the magnetic separation tailings of coarse particles and medium and fine particles are used as copper and aluminum products, and the magnetic separation tailings of fine particles are graphite and black powder products; The black powder product is subjected to slurry mixing and graphite flotation in sequence to obtain graphite product and black powder; S4, the nickel-cobalt-manganese intermediate product and black powder are subjected to reduction roasting to obtain roasting slag; Part of the lithium-containing solution and the water leaching residue; S5, combining the first part of the lithium-containing solution and the second part of the lithium-containing solution to obtain a combined solution; using the combined solution to prepare a lithium product; S6, performing acid leaching and impurity removal on the water leaching residue, A solution product containing nickel, cobalt and manganese is obtained.

Using the above process to treat waste lithium-ion batteries, through fire pretreatment, the plastic casing and phosphorus-containing and fluorine-containing separators in waste lithium-ion batteries can be effectively decomposed, and at the same time, nickel, cobalt, and manganese can be converted from non-magnetic to magnetic. The lithium-ion battery materials after fire pretreatment mainly include nickel, cobalt, manganese, copper, aluminum, iron, and black powder (black powder includes graphite, the original negative electrode material of the battery, carbon generated during the fire pretreatment process, and a part of lithium) . The pretreated product is divided into coarse-grained particles, medium-fine-sized particles, and fine-sized particles through ore washing and classification, and a part of the soluble lithium salts can enter the water to form the first part of the lithium-containing solution. Due to the small particle size of black powder, it is mainly concentrated in fine-grained particles, and the other components have larger particle sizes and are enriched in coarse-grained particles and medium-fine-sized particles. Magnetic separation can separate the magnetic nickel-cobalt-manganese in the particles of each particle size, and a part of lithium element will be entrained in it to obtain intermediate products of nickel-cobalt-manganese. The magnetic separation tailings of coarse particles and medium and fine particles are mainly The components are copper and aluminum, which can be used as copper-aluminum products, and the magnetic separation tailings of fine-grained particles are graphite and black powder products. After the graphite and black powder products are subjected to slurry mixing and graphite flotation in sequence, graphite can be enriched to obtain graphite products, and the flotation tailings are black powder. Secondly, in the present invention, the nickel-cobalt-manganese intermediate product and the black powder are reduced and roasted, and then lithium is extracted by water. An enrichment is obtained to form a second portion of the lithium-containing solution. After combining the first part of the lithium-containing solution and the second part of the lithium-containing solution, the lithium can be extracted by methods such as chemical precipitation, evaporative crystallization and the like to form a lithium product. After the water leaching, the remaining water leaching slag is subjected to acid leaching and impurity removal to obtain a solution product containing nickel, cobalt, and manganese.

From the perspective of lithium recovery process, the traditional waste lithium-ion battery is to recover nickel, cobalt and manganese first and then recover lithium. The lithium loss is serious (lithium recovery rate is less than 90% or even lower), the extraction and separation process is long, and the material flux is large. According to the different reducibility of lithium, nickel, cobalt and manganese, the invention adopts reduction roasting-leaching to preferentially extract lithium, which can effectively improve the recovery rate of lithium in waste batteries (>98%), reduce the extraction flux, and has obvious technological advantages. On the whole, the present invention comprehensively recovers various metals such as lithium, nickel, cobalt, manganese, copper, aluminum and graphite in the battery in the waste lithium ion battery by adopting the combined process of beneficiation and metallurgy. Due to the characteristics of the beneficiation process itself, the use of the beneficiation process to separate the valuable components in the waste battery has low comprehensive cost and remarkable separation effect. In addition, for the plastic casing and the phosphorus-containing and fluorine-containing separator in the battery, the present invention can also decompose them by fire pretreatment, and the obtained flue gas can be subjected to post-treatment.

In a preferred embodiment, in step S1, the fire pretreatment process includes: dismantling and crushing waste lithium-ion batteries to obtain crushed materials; preferably, the particle size of the crushed materials is below 50 mm; In a protective atmosphere and a temperature of 400-700°C, low-temperature pyrolysis is performed to obtain a pretreated product; preferably, the temperature of low-temperature pyrolysis is 600-650°C, more preferably 610-640°C; The time is 0.5～6h. Using the above process, on the one hand, the pyrolysis effect of the plastic casing and the phosphorus-containing and fluorine-containing diaphragm can be improved, and on the other hand, the nickel-cobalt-manganese can be more fully converted into magnetism, so that it can be more effectively obtained in the subsequent magnetic separation process. separation. The specific method of the above-mentioned dismantling and crushing can be carried out by a common method in the field. Preferably, nitrogen gas is introduced into the above-mentioned dismantling and crushing process as a protective gas to prevent the electric core from catching fire during the crushing process; the tail gas generated in the crushing process can be It is processed through the exhaust gas purification system, and the exhaust gas is discharged after reaching the standard.

Preferably, before the step of dismantling and crushing the waste lithium ion battery, step S1 further includes the step of discharging the waste lithium ion battery. When the battery is scrapped, the residual power will have an explosion hazard during storage and crushing. The discharge step can reduce the explosion risk, and at the same time avoid problems such as fire caused by the residual power during the dismantling and crushing process.

In a preferred embodiment, in step S2, the particle size of the coarse-grade particles is greater than 2 mm, the particle size of the fine-grade particles is less than 0.2 mm, and the particle size of the medium-fine-grade particles is between the coarse-grade particles and the fine-grade particles. between the particle sizes of the grade particles. Controlling the size of each grade of particles within the above range is more conducive to the separation of black powder and metal components (copper, aluminum, nickel-cobalt-manganese, etc.) Enriched in coarse and fine-grained particles.

In order to more fully remove magnetic impurities such as nickel, cobalt, manganese, etc., in a preferred embodiment, in step S3, the magnetic separation magnetic field intensity for coarse-grained particles, medium-fine-grained particles and fine-grained particles is respectively 40～ 280kA/m.

In order to further improve the recovery effect of graphite, in a preferred embodiment, the steps of sequentially performing slurry mixing and graphite flotation on graphite and black powder products include: preparing the graphite and black powder products with water to a concentration of 5-35wt% Flotation pulp; adding regulator, graphite collector and foaming agent to the flotation pulp in turn to conduct graphite flotation to obtain graphite products and black powder. Preferably, the graphite collector is a hydrocarbon oil collector, and the hydrocarbon oil collector is kerosene and/or diesel; preferably, the foaming agent is terpineol and/or methyl isobutyl methanol; preferably , and the adjusting agent is one or more of sodium hydrosulfide, sodium sulfide and ammonium sulfide. Using the above reagents, the recovery effect of graphite is better.

Preferably, in step S4, the reducing agent used in the reduction roasting process is the graphite product obtained in step S3, which is conducive to the full utilization of resources. Alternatively, the reduction calcination process is carried out in a reducing atmosphere. Preferably, the reducing atmosphere is composed of reducing gas and optional inert gas, the reducing gas is one or more of hydrogen, ammonia, methane and sulfur dioxide, and the inert gas is nitrogen and/or argon; preferably , the temperature of the reduction roasting process is 400～700℃, and the reaction time is 0.5～6h.

In a preferred embodiment, in step S5, the lithium in the combined solution is recovered in the form of lithium hydroxide or lithium carbonate to obtain a lithium product; in the specific operation process, carbon dioxide or soluble carbon can be introduced into the combined solution acid salts (such as sodium carbonate, etc.), the lithium element is precipitated in the form of lithium carbonate. Alternatively, the lithium hydroxide product can also be prepared by evaporative crystallization, the recovery rate of lithium is higher, and the treatment efficiency is higher.

In addition, in order to obtain a relatively pure lithium product, the impurity (Al, Cu, F, P, etc.) content in the combined solution can be analyzed first. If the impurity content is qualified, lithium hydroxide or lithium carbonate products are prepared from the leaching solution. The impurity content is not If qualified, lithium hydroxide or lithium carbonate products are prepared after the purification process. The purification process can be chemical precipitation method or ion exchange resin method to remove impurities.

In a preferred embodiment, in step S6, the water leaching residue is subjected to acid leaching to obtain an acid leaching solution; the impurity removal step includes: adjusting the pH value of the acid leaching solution to above 4.2, removing iron impurities and aluminum impurities, Obtain the iron-removing aluminum solution; add fluoride to the iron-removing aluminum solution to remove magnesium impurities to obtain a magnesium-removing solution; preferably, the fluoride is sodium fluoride; add sulfide and/or hydrogen sulfide to the magnesium-removing solution, remove Copper impurities and zinc impurities to obtain a solution product containing nickel, cobalt, and manganese; preferably, the sulfide salt is sodium sulfide; or, the step of removing impurities includes: using an extractant to extract an acid leaching solution to obtain a solution product containing nickel, cobalt, and manganese; preferably , the extractant is P204 extractant.

In a preferred embodiment, before the step of acid leaching the water leaching slag, step S6 further includes the step of reducing and smelting the water leaching slag. In this way, the reduction smelting process can more fully reduce and enrich the nickel, cobalt, and manganese in the water leaching slag, and the reduction smelting process also solves the problems of fluorine dispersion and difficulty in opening the circuit during the recovery process of power batteries, and can obtain F-containing smelting. slag, to achieve partial open circuit of F element, while recycling resources, it also takes into account the disposal of harmful substances. Preferably, the first flue gas generated in the above fire pretreatment process can be post-processed to obtain fluorine-containing gypsum slag, which can also be sent to the reduction smelting process for synergistic treatment, which is more conducive to improving the environmental protection of the process. Preferably, the water leaching slag is reduced and smelted at a temperature of 1200-1600° C. for 0.5-5 hours to obtain a nickel-cobalt-manganese alloy, and then the nickel-cobalt-manganese alloy is subjected to acid leaching and impurity removal to obtain a solution product containing nickel, cobalt, and manganese.

In the actual reduction smelting process, after mixing water leaching slag, flux and reducing agent, reduction smelting is carried out in a smelting furnace. The specific flux is preferably quartz sand, limestone, dolomite, calcite, etc. The specific reducing agent is preferably selected from Coal, coke, petroleum coke, activated carbon, etc. The specific dosage of each reagent can be adjusted according to the actual situation such as the amount of water leaching slag, which will not be repeated here.

In a preferred embodiment, the first flue gas is obtained in the fire pretreatment step, the second flue gas is obtained in the reduction smelting step, and the recovery method further includes sequentially performing two steps on the first flue gas and the second flue gas. The steps of secondary combustion, surface cooling, dust removal and exhaust gas purification can be discharged after the exhaust gas purification reaches the standard. The dust removal process can use a high-temperature bag filter, and the specific exhaust gas purification steps can be one or more combinations of common waste gas treatment devices such as alkali absorption device, activated carbon device, UV photolysis device, and biological filtration purification device.

Preferably, after obtaining the nickel-cobalt-manganese-containing solution product, the nickel-cobalt-manganese elements can be further separated by wet processing.

The above-mentioned waste lithium-ion batteries refer to waste lithium-ion batteries obtained after safe discharge, and/or waste products generated in the production process of lithium-ion batteries. In a preferred embodiment, the waste lithium ion battery is a waste lithium cobalt oxide battery, a lithium manganate battery, a nickel-manganese binary composite lithium-ion battery, a nickel-cobalt binary composite lithium ion battery, a cobalt-manganese binary composite lithium ion battery One or more of ion batteries, nickel-cobalt-manganese ternary composite lithium-ion batteries, and nickel-cobalt-aluminum ternary composite lithium-ion batteries.

According to another aspect of the present invention, a combined comprehensive recovery device for beneficiation and smelting of waste lithium ion batteries is also provided. As shown in FIG. 2 , the recovery device includes a pyroprocessing unit 10 , a ore washing and grading unit 20 , and a magnetic separation unit 10 . Unit 30, graphite recovery unit 40, reduction roasting unit 50, water leaching unit 60, lithium recovery unit 70, acid leaching unit 80, impurity removal unit 90, fire pretreatment unit 10 with waste lithium ion battery inlet and pretreatment product outlet , the pyroprocessing unit 10 is used for pyroprocessing waste lithium-ion batteries to obtain a pretreated product; the ore washing and classification unit 20 has a preprocessing product inlet and a first water inlet, a preprocessing product inlet and a preprocessing product inlet In connection, the washing and classifying unit 20 is used for washing and classifying the pretreated product to obtain coarse-grained particles A, medium and fine-grained particles B, fine-grained particles C and the first part of the lithium-containing solution D, and the coarse-grained The particle size of particle A is larger than the particle size of medium and fine particle B, and the particle size of medium and fine particle B is larger than that of fine particle C; the magnetic separation unit 30 is connected to the outlet of the ore washing and classification unit 20, The separation unit 30 is used for magnetic separation of coarse-grained particles A, medium and fine-grained particles B, and fine-grained particles C to obtain nickel-cobalt-manganese intermediate products G, coarse-grained particles magnetic separation tailings, and medium- and fine-grained particles Granular magnetic separation tailings and fine-grained magnetic separation tailings, coarse-grained magnetic separation tailings and medium and fine-grained magnetic separation tailings are used as copper and aluminum products E, and fine-grained magnetic separation tailings are graphite and the black powder product F; the graphite recovery unit 40 is connected to the outlet of the magnetic separation unit 30, and the graphite recovery unit 40 includes a slurry conditioning unit 41 and a flotation unit 42 connected in sequence, and the slurry conditioning unit 41 is used for the graphite and black powder products. F is for slurry mixing, and the flotation unit 42 is used for graphite flotation to obtain graphite products H and black powder J; the reduction roasting unit 50 is respectively connected to the outlet of the magnetic separation unit 30 and the outlet of the flotation unit 42, and the reduction roasting unit 50 For reducing and roasting the nickel-cobalt-manganese intermediate product G and the black powder J to obtain roasting slag; 60 is used to carry out water leaching lithium to the roasting slag to obtain the second part of lithium-containing solution K and water leaching slag L; the inlet of lithium recovery unit 70 is respectively connected with the outlet of water leaching unit 60 and the outlet of ore washing and grading unit 20, The lithium recovery unit 70 is used to perform lithium recovery processing on the combined solution of the first part of the lithium-containing solution D and the second part of the lithium-containing solution K to obtain a lithium product M; the acid leaching unit 80 has a water leaching slag inlet, an acid inlet and an acid leaching solution The outlet, the water leaching slag inlet is connected with the outlet of the water leaching unit 60, and the acid leaching unit 80 is used for acid leaching the water leaching slag to obtain acid leaching liquid; the impurity removing unit 90 is connected with the acid leaching liquid outlet, and the impurity removing unit 90 is used for For removing impurities from the acid leaching solution to obtain a solution product N containing nickel, cobalt and manganese.

Using the above-mentioned device to treat waste lithium-ion batteries can effectively decompose the plastic casing and phosphorus-containing and fluorine-containing separators in the waste lithium-ion batteries through fire pretreatment, and at the same time, nickel, cobalt, and manganese can be converted from non-magnetic to magnetic. The lithium-ion battery materials after fire pretreatment mainly include nickel, cobalt, manganese, copper, aluminum, iron, and black powder (black powder includes graphite, the original negative electrode material of the battery, carbon generated during the fire pretreatment process, and a part of lithium) . The pretreated product is divided into coarse-grained particles, medium-fine-sized particles, and fine-sized particles through ore washing and classification, and a part of the soluble lithium salts can enter the water to form the first part of the lithium-containing solution. Due to the small particle size of black powder, it is mainly concentrated in fine-grained particles, and the other components have larger particle sizes and are enriched in coarse-grained particles and medium-fine-sized particles. Magnetic separation can separate the magnetic nickel-cobalt-manganese in the particles of each particle size, and a part of lithium element will be entrained in it to obtain intermediate products of nickel-cobalt-manganese. The magnetic separation tailings of coarse particles and medium and fine particles are mainly The components are copper and aluminum, which can be used as copper-aluminum products, and the magnetic separation tailings of fine-grained particles are graphite and black powder products. After the graphite and black powder products are subjected to slurry mixing and graphite flotation in sequence, graphite can be enriched to obtain graphite products, and the flotation tailings are black powder. Secondly, in the present invention, the nickel-cobalt-manganese intermediate product and the black powder are reduced and roasted, and then lithium is extracted by water. An enrichment is obtained to form a second portion of the lithium-containing solution. After combining the first part of the lithium-containing solution and the second part of the lithium-containing solution, the lithium can be extracted by chemical precipitation or evaporative crystallization to form a lithium product. After the water leaching, the remaining water leaching slag is subjected to acid leaching and impurity removal to obtain a solution product containing nickel, cobalt, and manganese.

From the perspective of lithium recovery process, the traditional waste lithium-ion battery is to recover nickel, cobalt and manganese first and then recover lithium. The lithium loss is serious (lithium recovery rate is less than 90% or even lower), the extraction and separation process is long, and the material flux is large. According to the different reducibility of lithium, nickel, cobalt and manganese, the invention adopts reduction roasting-leaching to preferentially extract lithium, which can effectively improve the recovery rate of lithium in waste batteries (>98%), reduce the extraction flux, and has obvious technological advantages. On the whole, the present invention comprehensively recovers various metals such as lithium, nickel, cobalt, manganese, copper, aluminum and graphite in the battery in the waste lithium ion battery by adopting the combined process of beneficiation and metallurgy. Due to the characteristics of the beneficiation process itself, the use of the beneficiation process to separate the valuable components in the waste battery has low comprehensive cost and remarkable separation effect. In addition, for the plastic casing and the phosphorus-containing and fluorine-containing separator in the battery, the present invention can also decompose them by fire pretreatment, and the obtained flue gas can be subjected to post-treatment.

In a preferred embodiment, the pyroprocessing unit 10 includes a dismantling and crushing unit 11 and a low-temperature pyrolysis unit 12. The dismantling and crushing unit 11 has an inlet for waste lithium-ion batteries and an outlet for crushed materials; the low-temperature pyrolysis unit 12, It has a crushed material inlet, an inert gas inlet and an outlet of pretreatment products, and the crushed material inlet is connected with the crushed material outlet. In this way, the waste lithium-ion battery is disassembled and broken and then pyrolyzed at a low temperature, so that the plastic casing and the phosphorus-containing and fluorine-containing separator in the battery can be pyrolyzed and removed. The discharged crushed material is subjected to low temperature pyrolysis at a temperature of 400-700°C to obtain a pretreated product.

In a preferred embodiment, the pyroprocessing unit 10 further includes a discharge unit 13, the discharge unit 13 is located upstream of the dismantling and crushing unit 11 and is connected to the inlet of the waste lithium ion battery, and the discharge unit 13 is used for the waste lithium ion battery. The battery is discharged. When the battery is scrapped, the residual power will have an explosion hazard during storage and crushing. The discharge step can reduce the explosion risk, and at the same time avoid problems such as fire caused by the residual power during the dismantling and crushing process.

In a preferred embodiment, as shown in FIG. 1 , the graphite recovery unit 40 further includes a conditioning agent supply unit 43, a graphite collector supply unit 44 and a foaming agent supply unit 45; the conditioning agent supply unit 43 and the flotation The unit 42 is connected to supply the graphite conditioner; the graphite collector supply unit 44 is connected to the flotation unit 42 and is used to supply the collector; the frother supply unit 45 is connected to the flotation unit 42 to use to supply it with a blowing agent. In this way, the graphite product and black powder after sizing can be subjected to graphite flotation under the action of graphite collector, foaming agent and regulator, so as to recover and separate graphite more fully.

In a preferred embodiment, the reduction and roasting unit 50 also has a first reducing agent inlet, and the first reducing agent inlet is connected to the outlet of the flotation unit 42 for using the graphite product obtained in the graphite flotation process as the reduction roasting or, the reduction roasting unit 50 further has a reducing gas inlet, and the recovery device further includes a reducing gas supply unit, and the reducing gas supply unit is connected to the reducing gas inlet. Preferably, the recovery device further includes an inert gas supply unit 100, and the inert gas supply unit 100 is connected to the reducing gas inlet and the inert gas inlet of the low temperature pyrolysis unit 12, respectively. In this way, the inert gas can be introduced into the reducing and roasting unit 50 to form a reducing atmosphere together with the first reducing gas, so that the black powder and the nickel-cobalt-manganese intermediate product can be reduced and roasted.

In a preferred embodiment, the lithium recovery unit 70 includes: an impurity removal agent supply unit 71 for supplying an impurity removal agent; an impurity removal and purification unit 72, the inlet of which is respectively connected with the outlet of the water leaching unit 60 and the ore washing and grading unit. The outlet of 20 is connected with the impurity-removing agent supply unit 71, and the impurity-removing purification unit 72 is used to make the combined solution of the first part of the lithium-containing solution and the second part of the lithium-containing solution carry out the impurity-removing purification reaction to obtain the impurity-removing lithium solution; lithium product preparation The unit 73 is connected to the outlet of the impurity removal and purification unit 72, and the lithium product preparation unit 73 is used for evaporating and crystallizing the impurity removal lithium solution or precipitating lithium carbonate to obtain a lithium product. Preferably, the magnesium removing agent is sodium hydroxide, calcium hydroxide, and sodium fluoride, and preferably the calcium removing agent is sodium carbonate and sodium fluoride.

In a preferred embodiment, the impurity removal unit 90 includes: a pH adjustment unit 91, which is connected to the outlet of the acid leaching solution, and the pH adjustment unit 91 is used to adjust the pH value of the acid leaching solution to above 4.2, so as to obtain an iron-removing aluminum solution ; Magnesium removal unit 92 has a fluoride inlet and an iron removal aluminum solution inlet, and the iron removal aluminum solution inlet is connected to the outlet of the pH adjustment unit 91, and the magnesium removal unit 92 is used to remove the magnesium impurities in the iron and aluminum solution to obtain the removal of magnesium. solution; copper and zinc removal unit 93, with magnesium removal solution inlet and sulfide inlet, the magnesium removal solution inlet is connected with the outlet of magnesium removal unit 92, the sulfide inlet is used to pass sulfide salt and/or hydrogen sulfide, copper and zinc removal unit 93 is used to remove copper impurities and zinc impurities in the magnesium solution to obtain a solution product containing nickel, cobalt, and manganese. Alternatively, the impurity removal unit 90 is an extraction impurity removal unit. When an extraction and impurity removal unit is used, the extractant is preferably a P204 extractant.

In a preferred embodiment, the recovery device further includes a reduction smelting unit 110, the reduction smelting unit 110 is arranged on the flow path connecting the water leaching slag inlet and the water leaching unit 60, and the reduction smelting unit 110 also has a flux inlet, and the reduction smelting unit 110 also has a flux inlet. The unit 110 is used for reducing and smelting the water leaching slag to obtain a nickel-cobalt-manganese alloy, and the acid leaching unit 80 is used for acid leaching the nickel-cobalt-manganese alloy to obtain an acid leaching solution. In this way, the reduction smelting process can more fully reduce and enrich the nickel, cobalt, and manganese in the water leaching slag, and the reduction smelting process also solves the problems of fluorine dispersion and difficulty in opening the circuit during the recovery process of power batteries, and can obtain F-containing smelting. slag, to achieve partial open circuit of F element, while recycling resources, it also takes into account the disposal of harmful substances. Preferably, the first flue gas generated in the above fire pretreatment process can be post-processed to obtain fluorine-containing gypsum slag, which can also be sent to the reduction smelting process for synergistic treatment, which is more conducive to improving the environmental protection of the process.

More preferably, the above reduction smelting unit 110 further has a second reducing agent inlet for introducing a reducing agent into the reduction smelting unit 110 to complete the reduction smelting of the water-leaching slag.

In order to further improve the degree of innocence of the process, in a preferred embodiment, the pyroprocessing unit 10 further has a first flue gas outlet, the reduction smelting unit 110 also has a second flue gas outlet, and the recovery device further includes a flue gas outlet. The gas processing unit 120, the flue gas processing unit 120 is respectively connected with the first flue gas outlet and the second flue gas outlet. Preferably, the above-mentioned flue gas treatment unit 120 includes a secondary combustion unit, a surface cooling unit, a dust removal unit, and an exhaust gas purification unit connected in sequence, and the secondary combustion unit is respectively connected to the first flue gas outlet and the second flue gas outlet.

The present application will be described in further detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed by the present application.

Example 1

The battery used in the embodiment is a square ternary lithium-ion battery from a factory in Hunan.

(1) The waste ternary lithium-ion battery is treated by chemical discharge, and the discharged battery is multi-stage crushed to less than 50mm in a nitrogen atmosphere. The crushed battery was subjected to pyrolysis pretreatment under a nitrogen atmosphere at 500°C for 2 hours to obtain pyrolysis products. The generated pyrolysis flue gas was discharged after secondary combustion, surface cooling, high temperature cloth bag dust collection, and exhaust gas purification.

(2) The pyrolysis product is washed and classified into three grades >2mm, 0.15~2mm, and below 0.15mm and lithium-rich solution. The three grades are respectively in the magnetic field strength of 240kA/m. product. The magnetic separation tailings with two particle sizes >2mm and 0.15-2mm were used as copper and aluminum products, and the recovery rates were 90.41% and 89.51%, respectively. The magnetic separation tailings with a particle size below 0.15mm are black powder and graphite products, which are slurried with water to form a flotation slurry with a concentration of 30wt%, and 500g/t of sodium sulfide and 200g/t of diesel oil are added to the flotation slurry. , 40g/t of pine alcohol oil is used for graphite flotation. After flotation, graphite with a C grade of 91.36% and a recovery rate of 88.59% is obtained, and the flotation tailings are black powder.

(3) The black powder and the nickel-cobalt-manganese intermediate product were reduced and roasted under a hydrogen reducing atmosphere at 500 °C for 1 h to obtain a reduced roasting slag. Water was used as a leaching agent, and the roasting slag was leached at a liquid-solid ratio of 3:1 at 80 °C for 1 h, and the water leaching slag and lithium-containing leaching solution were obtained by solid-liquid separation treatment. The lithium-containing solution obtained in the beneficiation process and the lithium-containing leaching solution obtained by water leaching are combined, and _CO2 is introduced to carry out evaporative crystallization to obtain a lithium carbonate product, and the comprehensive recovery rate of lithium is 98.6%.

(4) Reductive smelting of water leaching slag, flux quartz sand and limestone, and reducing agent coke at 1600°C for 2 hours to obtain nickel-cobalt-manganese alloy and smelting slag. Direct landfill disposal. The flue gas produced by reduction smelting is discharged after secondary combustion, waste heat boiler, surface cooling, high temperature bag dust collection and exhaust gas purification and absorption.

(5) The nickel-cobalt-manganese alloy was leached with 5.5mol/L sulfuric acid, liquid-solid ratio of 5:1, temperature of 90 °C, and 1 h. The acid leaching solution obtained by leaching was extracted with P204 to remove impurities, and the purified solution of nickel-cobalt-manganese obtained can be used as Raw materials for downstream lithium-ion battery material manufacturers.

(6) After the combined comprehensive recovery and treatment of beneficiation and smelting, the obtained product purity is as follows: the recovery rate of copper and aluminum in copper and aluminum products can reach 90.41% and 89.51%, and the recovery rate of graphite can reach 88.59%. The purity of lithium carbonate was 99.7%, and the recoveries of lithium, nickel, cobalt, and manganese were 98.6%, 99.1%, 99.3%, and 98.7%, respectively.

Example 2

The battery used in the embodiment is a cylindrical 18650 ternary lithium-ion battery from a factory in Jiangsu.

(1) The waste ternary lithium-ion battery is treated by chemical discharge, and the discharged battery is multi-stage crushed to less than 50mm in a nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment at 600°C for 3 hours to obtain pyrolysis products. The generated pyrolysis flue gas is discharged through secondary combustion, surface cooling, high temperature cloth bag dust collection, and exhaust gas purification.

(2) The pyrolysis product is washed and classified into three grades >3mm, 0.2~3mm, and below 0.2mm and a lithium-rich solution. The three grades are respectively in the magnetic field strength of 200kA/m. product. The magnetic separation tailings with two particle sizes >3mm and 0.2~3mm were used as copper and aluminum products, and the recovery rates were 89.29% and 90.88%, respectively. The magnetic separation tailings with a particle size below 0.2mm are black powder and graphite products. They are slurried with water to form a flotation slurry with a concentration of 15wt%, and 400g/t of sodium sulfide and 150g/t of diesel oil are added to the flotation slurry. , 45g/t of pine alcohol oil for graphite flotation, through flotation, graphite with carbon grade of 92.87% and recovery rate of 87.46% was obtained, and the flotation tailings were black powder.

(3) The black powder and the nickel-cobalt-manganese intermediate product were reduced and roasted under a hydrogen reducing atmosphere at 450°C for 1.5 h to obtain a reduced roasting slag. Water was used as a leaching agent, and the hydrogen reduction roasting slag was leached at a liquid-solid ratio of 5:1 at 60 °C for 1 h. The lithium-containing solution obtained in the beneficiation process and the lithium-containing leaching solution obtained by water leaching were combined, and CO ₂ was introduced to carry out evaporative crystallization to obtain a lithium carbonate product, and the comprehensive recovery rate of lithium was 99.6%.

(4) Reductive smelting of water leaching slag, flux quartz sand and limestone, and reducing agent coal at 1500 °C for 3 hours to obtain nickel-cobalt alloy and smelting slag. The smelting slag is harmless slag after high temperature solidification treatment, and can be landfill disposal. The flue gas produced by reduction smelting is discharged after secondary combustion, waste heat boiler, surface cooling, high temperature bag dust collection and exhaust gas purification and absorption.

(5) Using 5mol/L sulfuric acid, liquid-solid ratio 6:1, temperature 90℃, 1h to leaching nickel-cobalt alloy, the acid leaching solution obtained by leaching is extracted with P204 to remove impurities, and the purified solution of nickel-cobalt-manganese can be used as downstream lithium ion Raw materials for battery material manufacturers.

(6) After the combined comprehensive recovery and treatment of beneficiation and smelting, the obtained product purity is as follows: the recovery rate of copper and aluminum in copper and aluminum products can reach 89.29% and 90.88%, and the recovery rate of graphite can reach 87.46%. The purity of lithium carbonate was 99.8%, and the recoveries of lithium, nickel, cobalt, and manganese were 99.6%, 99.3%, 99.4%, and 98.9%, respectively.

Example 3

The difference with embodiment 1 is: there is no reduction smelting step, and the concrete process is as follows,

(1) The waste ternary lithium-ion battery is treated by chemical discharge, and the discharged battery is multi-stage crushed to less than 50mm in a nitrogen atmosphere. The crushed battery was subjected to pyrolysis pretreatment under a nitrogen atmosphere at 500°C for 2 hours to obtain pyrolysis products. The generated pyrolysis flue gas was discharged after secondary combustion, surface cooling, high temperature cloth bag dust collection, and exhaust gas purification.

(2) The pyrolysis product is washed and classified into three grades >2mm, 0.15~2mm, and below 0.15mm and lithium-rich solution. The three grades are respectively in the magnetic field strength of 240kA/m. product. The magnetic separation tailings with two particle sizes >2mm and 0.15-2mm were used as copper and aluminum products, and the recovery rates were 90.37% and 89.15%, respectively. The magnetic separation tailings with a particle size below 0.15mm are black powder and graphite products. They are slurried with water to form a flotation slurry with a concentration of 30wt%, and 200g/t of sodium sulfide and 200g/t of diesel oil are added to the flotation slurry. , 40g/t of pine alcohol oil is used for graphite flotation. After flotation, graphite with a C grade of 91.42% and a recovery rate of 88.93% is obtained, and the flotation tailings are black powder.

(3) The black powder and the nickel-cobalt-manganese intermediate product were reduced and roasted under a hydrogen reducing atmosphere at 500 °C for 1 h to obtain a reduced roasting slag. Water was used as a leaching agent, and the roasting slag was leached at a liquid-solid ratio of 3:1 at 80 °C for 1 h, and the water leaching slag and lithium-containing leaching solution were obtained by solid-liquid separation treatment. The lithium-containing solution obtained in the beneficiation process and the lithium-containing leaching solution obtained by water leaching are combined, and _CO2 is introduced to carry out evaporative crystallization to obtain a lithium carbonate product, and the comprehensive recovery rate of lithium is 98.6%.

(4) The water leaching residue obtained in step (3) is leached with sulfuric acid having a concentration of 4.6 mol/L to obtain a leaching solution containing nickel, cobalt, and manganese. Iron and aluminum are removed by neutralization and precipitation (pH value is 4.4), copper and zinc are removed by sodium sulfide, and magnesium is removed by sodium fluoride to obtain a purified solution, which is a solution product containing nickel, cobalt, and manganese.

(5) After the combined comprehensive recovery and treatment of beneficiation and smelting, the obtained product purity is as follows: the recovery rate of copper and aluminum in copper and aluminum products can reach 90.37% and 89.15%, and the recovery rate of graphite can reach 88.93%. The purity of lithium carbonate was 99.7%, and the recoveries of lithium, nickel, cobalt, and manganese were 98.5%, 98.9%, 98.2%, and 98.1%, respectively.

Example 4

The battery used in the embodiment is a cylindrical 18650 ternary lithium-ion battery from a factory in Zhejiang.

(1) The waste ternary lithium-ion battery is treated by chemical discharge, and the discharged battery is subjected to multi-stage crushing in a nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment at 600°C for 3 hours to obtain pyrolysis products. The generated pyrolysis flue gas is discharged through secondary combustion, surface cooling, high temperature cloth bag dust collection, and exhaust gas purification.

(2) The pyrolysis product is washed and classified into three grades >5mm, 0.45~5mm, and below 0.45mm and lithium-rich solution. The three grades are respectively in the magnetic field strength of 220kA/m. The product, magnetic separation tailings with two particle sizes >5mm and 0.45-5mm were used as copper and aluminum products, and the recovery rates were 92.47% and 90.37%, respectively. The magnetic separation tailings with a particle size below 0.45mm are black powder and graphite products. They are slurried with water to form a flotation slurry with a concentration of 10wt%, and 1000g/t of sodium sulfide and 200g/t of diesel oil are added to the flotation slurry. , 40g/t of pine alcohol oil for graphite flotation. After flotation, graphite with carbon grade of 91.17% and recovery rate of 88.10% was obtained.

(3) The black powder nickel-cobalt-manganese intermediate product was reduced and roasted under a hydrogen reducing atmosphere at 450°C for 1.5 hours to obtain a reduced roasting slag. Water was used as a leaching agent, and the hydrogen reduction roasting slag was leached at a liquid-solid ratio of 4:1 at 80 °C for 1 h. The lithium-rich solution and the lithium-containing leaching solution are combined, and _CO2 is introduced for evaporation and crystallization to obtain a lithium carbonate product. The comprehensive recovery rate of lithium is 99.6%.

(4) leaching the water leaching residue obtained in step (3) with sulfuric acid having a concentration of 5 mol/L to obtain a leaching solution containing nickel, cobalt, and manganese. Iron and aluminum are removed by neutralization and precipitation (pH value is 4.6), copper and zinc are removed by sodium sulfide, and magnesium is removed by sodium fluoride to obtain a purified solution, which is a solution product containing nickel, cobalt, and manganese.

(5) After the combined comprehensive recovery and treatment of beneficiation and smelting, the obtained product purity is as follows: the recovery rate of copper and aluminum in copper and aluminum products can reach 92.47% and 90.37%, and the recovery rate of graphite can reach 88.10%. The purity of lithium carbonate was 99.8%, and the recoveries of lithium, nickel, cobalt, and manganese were 98.6%, 99.3%, 99.5%, and 99.2%, respectively.

Example 5

The battery used in the embodiment is a cylindrical 18650 ternary lithium-ion battery from a factory in Zhejiang.

(1) The waste ternary lithium-ion battery is treated by chemical discharge, and the discharged battery is subjected to multi-stage crushing in a nitrogen atmosphere. The broken battery is subjected to pyrolysis pretreatment under a nitrogen atmosphere at 400°C for 6 hours to obtain pyrolysis products. The generated pyrolysis flue gas is discharged through secondary combustion, surface cooling, high temperature cloth bag dust collection, and exhaust gas purification.

(2) The pyrolysis product is washed and classified into three grades >5mm, 0.2~5mm, and below 0.20mm and lithium-rich solution. The three grades are respectively in the magnetic field strength of 280kA/m. The product, magnetic separation tailings with two particle sizes >20mm and 0.2-5mm were used as copper and aluminum products, and the recovery rates were 93.19% and 91.42%, respectively. The magnetic separation tailings with a particle size below 0.20mm are black powder and graphite products. They are slurried with water to form a flotation slurry with a concentration of 5wt%, and 1000g/t of sodium sulfide and 200g/t of diesel oil are added to the flotation slurry. , 40g/t of pine alcohol oil for graphite flotation. After flotation, graphite with carbon grade of 92.82% and recovery rate of 87.36% was obtained.

(3) The black powder nickel-cobalt-manganese intermediate product was reduced and roasted under a hydrogen reducing atmosphere at 750°C for 1.5 h to obtain a reduced roasting slag. Water was used as a leaching agent, and the hydrogen reduction roasting slag was leached at a liquid-solid ratio of 4:1 at 80 °C for 1 h. The lithium-rich solution and the lithium-containing leaching solution were combined, and _CO2 was introduced for evaporation and crystallization to obtain a lithium carbonate product. The comprehensive recovery rate of lithium was 69.6%.

(4) leaching the water leaching residue obtained in step (3) with sulfuric acid having a concentration of 5 mol/L to obtain a leaching solution containing nickel, cobalt, and manganese. Iron and aluminum are removed by neutralization and precipitation (pH value is 4.6), copper and zinc are removed by sodium sulfide, and magnesium is removed by sodium fluoride to obtain a purified solution, which is a solution product containing nickel, cobalt, and manganese.

(5) After the combined comprehensive recovery and treatment of beneficiation and smelting, the obtained product purity is as follows: the recovery rate of copper and aluminum in copper and aluminum products can reach 92.47% and 90.37%, and the recovery rate of graphite can reach 88.10%. The purity of lithium carbonate was 99.8%, and the recoveries of lithium, nickel, cobalt, and manganese were 69.6%, 99.3%, 99.5%, and 99.2%, respectively.

Example 6

The battery used in the embodiment is a cylindrical 18650 ternary lithium-ion battery from a factory in Zhejiang.

(1) The waste ternary lithium-ion battery is treated by chemical discharge, and the discharged battery is subjected to multi-stage crushing in a nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment at 700℃ for 0.5h to obtain pyrolysis products. The generated pyrolysis flue gas is discharged after secondary combustion, surface cooling, high temperature cloth bag dust collection, and exhaust gas purification.

(2) The pyrolysis product is washed and classified into three grades >3mm, 0.20~3mm, and below 0.20mm and a lithium-rich solution. The three grades are respectively at a magnetic field strength of 40kA/m. The product, magnetic separation tailings with two particle sizes >3mm and 0.20-3mm were used as copper and aluminum products, and the recovery rates were 93.98% and 92.13%, respectively. The magnetic separation tailings with a particle size of less than 0.20mm are black powder and graphite products. They are slurried with water to form a flotation slurry with a concentration of 35wt%, and 1000g/t of sodium sulfide and 200g/t of diesel oil are added to the flotation slurry. , 40g/t of pine alcohol oil for graphite flotation. After flotation, graphite with carbon grade of 87.05% and recovery rate of 87.29% is obtained.

(3) The black powder nickel-cobalt-manganese intermediate product was reduced and roasted at 650°C in a hydrogen reducing atmosphere for 7 hours to obtain a reduced roasting slag. Water was used as a leaching agent, and the hydrogen reduction roasting slag was leached at a liquid-solid ratio of 4:1 at 80 °C for 1 h. The lithium-rich solution and the lithium-containing leaching solution were combined, and _CO2 was introduced for evaporation and crystallization to obtain a lithium carbonate product. The comprehensive recovery rate of lithium was 77.6%.

(4) leaching the water leaching residue obtained in step (3) with sulfuric acid having a concentration of 5 mol/L to obtain a leaching solution containing nickel, cobalt, and manganese. Iron and aluminum are removed by neutralization and precipitation (pH value is 4.6), copper and zinc are removed by sodium sulfide, and magnesium is removed by sodium fluoride to obtain a purified solution, which is a solution product containing nickel, cobalt, and manganese.

(5) After the combined comprehensive recovery and treatment of beneficiation and smelting, the obtained product purity is as follows: the recovery rate of copper and aluminum in copper and aluminum products can reach 92.47% and 90.37%, and the recovery rate of graphite can reach 88.10%. The purity of lithium carbonate was 98.8%, and the recoveries of lithium, nickel, cobalt, and manganese were 77.6%, 99.3%, 99.5%, and 99.2%, respectively.

Example 7

The battery used in the embodiment is a cylindrical 18650 ternary lithium-ion battery from a factory in Zhejiang.

(1) The waste ternary lithium-ion battery is treated by chemical discharge, and the discharged battery is subjected to multi-stage crushing in a nitrogen atmosphere. The crushed battery was subjected to pyrolysis pretreatment at 640°C for 2 hours to obtain pyrolysis products. The generated pyrolysis flue gas was discharged through secondary combustion, surface cooling, high temperature bag dust collection, and exhaust gas purification.

(2) The pyrolysis product is washed and classified into three grades >2mm, 0.15-2mm, and below 0.15mm and lithium-rich solution. The three grades are respectively in the magnetic field strength of 180kA/m. The product, magnetic separation tailings with two particle sizes >2mm and 0.15-2mm were used as copper and aluminum products, and the recovery rates were 92.89% and 91.22%, respectively. The magnetic separation tailings with a particle size below 0.15mm are black powder and graphite products. They are slurried with water to form a flotation slurry with a concentration of 20wt%, and 1000g/t of sodium sulfide and 200g/t of diesel oil are added to the flotation slurry. , 40g/t of pine alcohol oil for graphite flotation. After flotation, graphite with carbon grade of 90.33% and recovery rate of 87.11% was obtained.

(3) The black powder nickel-cobalt-manganese intermediate product was reduced and roasted under a hydrogen reducing atmosphere at 350°C for 5 hours to obtain a reduced roasting slag. Water was used as a leaching agent, and the hydrogen reduction roasting slag was leached at a liquid-solid ratio of 4:1 at 80 °C for 1 h. The lithium-rich solution and the lithium-containing leaching solution are combined, and _CO2 is introduced for evaporation and crystallization to obtain a lithium carbonate product, and the comprehensive recovery rate of lithium is 23.5%.

(4) leaching the water leaching residue obtained in step (3) with sulfuric acid having a concentration of 5 mol/L to obtain a leaching solution containing nickel, cobalt, and manganese. Iron and aluminum are removed by neutralization and precipitation (pH value is 4.6), copper and zinc are removed by sodium sulfide, and magnesium is removed by sodium fluoride to obtain a purified solution, which is a solution product containing nickel, cobalt, and manganese.

(5) After the combined comprehensive recovery and treatment of beneficiation and smelting, the obtained product purity is as follows: the recovery rate of copper and aluminum in copper and aluminum products can reach 92.47% and 90.37%, and the recovery rate of graphite can reach 88.10%. The purity of lithium carbonate was 99.8%, and the recoveries of lithium, nickel, cobalt, and manganese were 23.5%, 99.3%, 99.5%, and 99.2%, respectively.

Example 8

The battery used in the embodiment is a cylindrical 18650 ternary lithium-ion battery from a factory in Zhejiang.

(1) The waste ternary lithium-ion battery is treated by chemical discharge, and the discharged battery is subjected to multi-stage crushing in a nitrogen atmosphere. The broken battery was subjected to pyrolysis pretreatment under a nitrogen atmosphere at 610°C for 3 hours to obtain a pyrolysis product. The generated pyrolysis flue gas was discharged after secondary combustion, surface cooling, high temperature cloth bag dust collection, and exhaust gas purification.

(2) The pyrolysis product is washed and classified into three grades >2mm, 0.15-2mm, and below 0.15mm and lithium-rich solution. The three grades are respectively in the magnetic field strength of 180kA/m. The product, magnetic separation tailings with two particle sizes >2mm and 0.15-2mm were used as copper and aluminum products, and the recovery rates were 89.04% and 89.12%, respectively. The magnetic separation tailings with a particle size below 0.15mm are black powder and graphite products. They are slurried with water to form a flotation slurry with a concentration of 15wt%, and 1000g/t of sodium sulfide and 200g/t of diesel oil are added to the flotation slurry. , 40g/t of pine alcohol oil is used for graphite flotation. After flotation, graphite with carbon grade of 89.59% and recovery rate of 88.40% is obtained.

(3) The black powder nickel-cobalt-manganese intermediate product was reduced and roasted under a hydrogen reducing atmosphere at 480°C for 2 hours to obtain a reduced roasting slag. Water was used as a leaching agent, and the hydrogen reduction roasting slag was leached at a liquid-solid ratio of 4.5:1 at 80 °C for 1 h. The lithium-rich solution and the lithium-containing leaching solution are combined, and _CO2 is introduced for evaporation and crystallization to obtain a lithium carbonate product. The comprehensive recovery rate of lithium is 99.1%.

(4) Reductive smelting of water leaching slag, flux quartz sand and limestone, and reducing agent coal at 1200 °C for 5 hours to obtain nickel-cobalt alloy and smelting slag. The smelting slag is harmless slag after high temperature solidification treatment landfill disposal. The flue gas produced by reduction smelting is discharged after secondary combustion, waste heat boiler, surface cooling, high temperature bag dust collection and exhaust gas purification and absorption.

(5) After the combined comprehensive recovery and treatment of beneficiation and smelting, the obtained product purity is as follows: the recovery rate of copper and aluminum in copper and aluminum products can reach 92.47% and 90.37%, and the recovery rate of graphite can reach 88.10%. The purity of lithium hydroxide was 99.8%, and the recoveries of lithium, nickel, cobalt, and manganese were 99.1%, 99.3%, 99.5%, and 99.2%, respectively.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (20)

1. a beneficiation combined comprehensive recovery method of waste and old lithium ion batteries, is characterized in that, described recovery method comprises the following steps: S1, the waste lithium ion battery is subjected to pyroprocessing to obtain a pretreated product; S2, washing and classifying the pretreated product to obtain coarse-grained particles, medium- and fine-grained particles, fine-grained particles and a first part of the lithium-containing solution, and the particle size of the coarse-grained particles is larger than that of the The particle diameter of the medium and fine-grained particles, the particle diameter of the medium and fine-grained particles being larger than the particle diameter of the fine-grained particles; S3, magnetic separation is performed on the coarse-grained particles, the medium-fine-grained particles, and the fine-grained particles, respectively, and the obtained magnetic separation concentrate is used as an intermediate product of nickel, cobalt, and manganese, and the coarse-grained particles and the The magnetic separation tailings of the medium and fine-grained particles are used as copper-aluminum products, and the magnetic separation tailings of the fine-grained particles are graphite and black powder products; Select to obtain graphite products and black powder; S4, reducing and roasting the nickel-cobalt-manganese intermediate product and the black powder to obtain a roasting slag; extracting lithium with water from the roasting slag to obtain a second part of a lithium-containing solution and a water-leaching slag; S5, combining the first part of the lithium-containing solution and the second part of the lithium-containing solution to obtain a combined solution; using the combined solution to prepare a lithium product; S6, the water leaching residue is subjected to acid leaching and impurity removal to obtain a solution product containing nickel, cobalt and manganese. 2. recovery method according to claim 1, is characterized in that, in described step S1, described fire method pretreatment process comprises: Dismantling and crushing the waste lithium-ion battery to obtain crushed material; preferably, the particle size of the crushed material is below 50 mm; The crushed material is subjected to low-temperature pyrolysis in a protective atmosphere at a temperature of 400-700° C. to obtain the pretreated product; preferably, the temperature of the low-temperature pyrolysis is 600-650° C., more preferably 610- 640°C; preferably, the low-temperature pyrolysis time is 0.5-6h; Preferably, before the step of dismantling and crushing the waste lithium ion battery, the step S1 further includes the step of discharging the waste lithium ion battery. 3. recovery method according to claim 1 and 2 is characterized in that, in described step S2, the particle diameter of described coarse-grained particle is greater than 2mm, and the particle diameter of described fine-grained particle is less than 0.2mm, so The particle diameter of the medium and fine-grained particles is between the particle diameters of the coarse-grained and fine-grained particles; Preferably, in the step S3, the magnetic separation magnetic field strengths for the coarse-grained particles, the medium-fine-grained particles and the fine-grained particles are respectively 40-280 kA/m. 4. recovery method according to claim 3 is characterized in that, the step of carrying out slurry mixing and graphite flotation successively by described graphite and black powder product comprises: The graphite and black powder products are prepared into flotation pulp with a concentration of 5-35wt% with water; A modifier, a graphite collector and a foaming agent are added to the flotation pulp to conduct graphite flotation to obtain the graphite product and the black powder. 5. the recovery method according to any one of claims 1 to 4, is characterized in that, in the described step S4, the reducing agent that adopts in the described reduction roasting process is the described graphite product obtained in the described step S3 , or the reduction roasting process is carried out under a reducing atmosphere; Preferably, the reducing atmosphere is composed of a reducing gas and an optional inert gas, the reducing gas is one or more of hydrogen, ammonia, methane and sulfur dioxide, and the inert gas is nitrogen and/or or argon; Preferably, the temperature of the reduction roasting process is 400-700° C., and the reaction time is 0.5-6 h. 6. according to the recovery method described in any one of claim 1 to 4, it is characterized in that, in described step S5, the lithium in described combined solution is evaporated and crystallized in the form of lithium hydroxide, or to described Carbon dioxide is introduced into the combined solution or soluble carbonate is added to precipitate lithium in the form of lithium carbonate to obtain the lithium product; Preferably, before the step of using the combined solution to prepare the lithium product, the step S5 further includes the step of removing impurity ions in the combined solution by chemical precipitation or ion exchange resin. 7. The recovery method according to any one of claims 1 to 4, wherein in the step S6, the water leaching residue is subjected to acid leaching to obtain an acid leaching solution; Described impurity removal step comprises: The pH value of the acid leaching solution is adjusted to more than 4.2, and iron impurities and aluminum impurities are removed to obtain an iron-removing aluminum solution; Adding fluoride to the iron-removing aluminum solution to remove magnesium impurities to obtain a magnesium-removing solution; preferably, the fluoride is sodium fluoride; Add sulfide salt and/or hydrogen sulfide to the magnesium removal solution to remove copper impurities and zinc impurities to obtain the solution product containing nickel, cobalt and manganese; preferably, the sulfide salt is sodium sulfide; Miscellaneous steps include: The acid leaching solution is extracted with an extractant to obtain the solution product containing nickel, cobalt and manganese; preferably, the extractant is a P204 extractant. 8. The recovery method according to any one of claims 1 to 5, wherein before the step of acid leaching the water leaching slag, the step S6 further comprises reducing smelting the water leaching slag Preferably, the water leaching slag is reduced and smelted at a temperature of 1200-1600 ℃ for 0.5-5 h to obtain a nickel-cobalt-manganese alloy, and then the nickel-cobalt-manganese alloy is sequentially subjected to the acid leaching, the removal to obtain the solution product containing nickel, cobalt and manganese. 9. The recovery method according to claim 8, characterized in that, the first flue gas is obtained in the pyroprocessing step, the second flue gas is obtained in the reduction smelting step, and the recovery method further comprises: The steps of secondary combustion, surface cooling, dust removal, and exhaust gas purification are sequentially performed on the first flue gas and the second flue gas. 10. The recovery method according to claim 1, wherein the waste lithium ion battery is a waste lithium cobalt oxide battery, a lithium manganate battery, a nickel-manganese binary composite lithium ion battery, and a nickel-cobalt binary composite lithium battery. One or more of ion batteries, cobalt-manganese binary composite lithium-ion batteries, nickel-cobalt-manganese ternary composite lithium-ion batteries, and nickel-cobalt-aluminum ternary composite lithium-ion batteries. 11. A beneficiation and smelting combined comprehensive recovery device for waste and used lithium ion batteries, characterized in that the recovery device comprises: A pyroprocessing unit (10), having an inlet for waste lithium ion batteries and an outlet for a pretreatment product, the pyroprocessing unit (10) is used for pyroprocessing the waste lithium ion battery to obtain a pretreatment product ; The ore washing and grading unit (20) is provided with a pretreatment product inlet and a first water inlet, the pretreatment product inlet is connected to the pretreatment product inlet, and the ore washing and grading unit (20) is used for the pretreatment product The product is subjected to ore washing and classification treatment to obtain coarse-grained particles, medium and fine-grained particles, fine-grained particles and a first part of the lithium-containing solution, and the particle size of the coarse-grained particles is larger than that of the medium and fine-grained particles. diameter, the particle diameter of the medium and fine-grained particles is greater than that of the fine-grained particles; A magnetic separation unit (30), connected to the outlet of the ore washing and classifying unit (20), the magnetic separation unit (30) is used to separate the coarse particles, the medium and fine particles and the The fine-grained particles are subjected to magnetic separation to obtain nickel-cobalt-manganese intermediate products, coarse-grained particle magnetic separation tailings, medium-fine particle magnetic separation tailings, and fine-grained magnetic separation tailings, the coarse-grained particle magnetic separation tailings. The tailings and the medium-fine particle magnetic separation tailings are used as copper and aluminum products, and the fine-grain magnetic separation tailings are graphite and black powder products; A graphite recovery unit (40) is connected to the outlet of the magnetic separation unit (30), the graphite recovery unit (40) includes a slurry conditioning unit (41) and a flotation unit (42) connected in sequence, and the conditioning The slurry unit (41) is used for slurrying the graphite and black powder products, and the flotation unit (42) is used for graphite flotation to obtain graphite products and black powder; A reduction roasting unit (50) is respectively connected with the outlet of the magnetic separation unit (30) and the outlet of the flotation unit (42), and the reduction roasting unit (50) is used to convert the nickel-cobalt-manganese intermediate product Carry out reduction roasting with the black powder to obtain roasting slag; A water immersion unit (60) is provided with a roasting slag inlet and a second water inlet, the roasting slag inlet is connected to the outlet of the reduction roasting unit (50), and the water immersion unit (60) is used for treating the roasting slag Carry out water leaching of lithium to obtain the second part of lithium-containing solution and water leaching residue; A lithium recovery unit (70), the inlet of which is respectively connected with the outlet of the water leaching unit (60) and the outlet of the ore washing and classification unit (20), the lithium recovery unit (70) is used for using the first part The lithium-containing solution and the combined solution of the second part of the lithium-containing solution prepare a lithium product; The acid leaching unit (80) has a water leaching slag inlet, an acid inlet and an acid leaching liquid outlet, the water leaching slag inlet is connected to the outlet of the water leaching unit (60), and the acid leaching unit (80) is used for Acid leaching is performed on the water leaching residue to obtain an acid leaching solution; The impurity removal unit (90) is connected to the outlet of the acid leaching solution, and the impurity removal unit (90) is used for removing impurities from the acid leaching solution to obtain a solution product containing nickel, cobalt, and manganese. 12. The recovery device according to claim 11, characterized in that, the pyroprocessing unit (10) comprises: Dismantling the crushing unit (11), which has the waste lithium-ion battery inlet and the crushing material outlet; The low-temperature pyrolysis unit (12) has a crushed material inlet, an inert gas inlet and an outlet of the pretreated product, and the crushed material inlet is connected to the crushed material outlet. 13. The recovery device according to claim 12, characterized in that, the pyroprocessing unit (10) further comprises a discharge unit (13), and the discharge unit (13) is located in the dismantling and crushing unit (11) ) and connected to the inlet of the waste lithium ion battery, the discharge unit (13) is used for discharging the waste lithium ion battery. 14. The recovery device according to any one of claims 11 to 13, wherein the graphite recovery unit (40) further comprises: a conditioning agent supply unit (43), connected to the flotation unit (42), for supplying conditioning agent thereto; a graphite collector supply unit (44), connected to the flotation unit (42), for supplying the graphite collector thereto; A frother supply unit (45) is connected to the flotation unit (42) for supplying frother to it. 15. The recovery device according to claim 12 or 13, characterized in that, The reduction and roasting unit (50) also has a first reducing agent inlet, and the first reducing agent inlet is connected to the outlet of the flotation unit (42), and is used for the The graphite product is used as the reducing agent in the reduction roasting process; or, The reduction roasting unit (50) further has a reducing gas inlet, and the recovery device further includes a reducing gas supply unit, and the reducing gas supply unit is connected to the reducing gas inlet. 16. The recovery device according to claim 15, characterized in that, the recovery device further comprises an inert gas supply unit (100), the inert gas supply unit (100) being respectively connected to the reducing gas inlet and the The inert gas inlet of the low temperature pyrolysis unit (12) is connected. 17. The recovery device according to any one of claims 11 to 13, wherein the lithium recovery unit (70) comprises: Impurity removing agent supply unit (71) for supplying impurity removing agent; The impurity removal and purification unit (72), the inlet of which is respectively connected with the outlet of the water leaching unit (60), the outlet of the ore washing and classification unit (20), and the impurity removal agent supply unit (71). The impurity purification unit (72) is configured to perform an impurity removal reaction on the combined solution of the first part of the lithium-containing solution and the second part of the lithium-containing solution to obtain an impurity-removed lithium solution; The lithium product preparation unit (73) is connected to the outlet of the impurity removal and purification unit (72), and the lithium product preparation unit (73) is used for evaporative crystallization or precipitation of lithium carbonate to obtain the impurity removal lithium solution. Lithium products. 18. The recovery device according to any one of claims 11 to 13, characterized in that, The impurity removal unit (90) includes: A pH adjusting unit (91) is connected to the outlet of the acid leaching solution, and the pH adjusting unit (91) is used to adjust the pH value of the acid leaching solution to be above 4.2 to obtain an iron-removing aluminum solution; The magnesium removal unit (92) has a fluoride inlet and an iron removal aluminum solution inlet, the iron removal aluminum solution inlet is connected to the outlet of the pH adjustment unit (91), and the magnesium removal unit (92) is used to remove all Describe the magnesium impurity in the iron-removing aluminum solution to obtain the magnesium-removing solution; The copper and zinc removal unit (93) has a magnesium removal solution inlet and a sulfide inlet, the magnesium removal solution inlet is connected to the outlet of the magnesium removal unit (92), and the sulfide inlet is used for introducing sulfide salt and/or sulfide. or hydrogen sulfide, the copper-removing zinc unit (93) is used to remove copper impurities and zinc impurities in the magnesium-removing solution to obtain the solution product containing nickel, cobalt, and manganese; Alternatively, the impurity removal unit (90) is an extraction impurity removal unit. 19. The recovery device according to claim 18, characterized in that, the recovery device further comprises a reduction smelting unit (110), The reduction smelting unit (110) is arranged on a flow path where the water leaching slag inlet is connected to the water leaching unit (60), and the reduction smelting unit (110) further has a flux inlet, and the reduction smelting unit ( 110) is used for reducing and smelting the water leaching slag to obtain a nickel-cobalt-manganese alloy, and the acid leaching unit (80) is used for acid-leaching the nickel-cobalt-manganese alloy to obtain the acid leaching solution. 20. The recovery device according to claim 19, characterized in that, the pyroprocessing unit (10) further has a first flue gas outlet, and the reduction smelting unit (110) further has a second flue gas outlet, The recovery device further includes a flue gas processing unit (120), and the flue gas processing unit (120) is respectively connected with the first flue gas outlet and the second flue gas outlet.

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