Fluidized bed reactor and method for recovering active metals from lithium secondary batteries using the same

Abstract

A fluidized bed reactor according to an exemplary embodiment of the present invention may include a reactor body, a base plate, a distribution plate including first injection columns protruding from an upper surface of the base plate, and second injection columns that inject gas to form a gas flow that rotates along an inner surface of the reactor body.

Description

[Technical Field]

[0001] The present invention relates to a fluidized bed reactor and a method for recovering active metals from a lithium secondary battery using the same, and more particularly to a fluidized bed reactor including a dispersion plate and a method for recovering active metals from a lithium secondary battery using the same. [Background technology]

[0002] In recent years, secondary batteries have been widely developed and applied as power sources for portable electronic communication devices such as camcorders, mobile phones, and laptop computers, as well as for vehicles such as hybrid cars and electric cars. As secondary batteries, lithium secondary batteries have been actively developed and applied because of their high operating voltage and energy density per unit weight, as well as their advantages in terms of charging speed and light weight.

[0003] The positive electrode active material of the lithium secondary battery can be a lithium metal oxide, which can contain a transition metal such as nickel, cobalt, or manganese.

[0004] Since the cathode active material uses the aforementioned expensive valuable metals, the production of the cathode material accounts for more than 20% of the production cost of lithium secondary batteries. In addition, with the recent increase in interest in environmental protection, research into methods for recycling cathode active materials is progressing.

[0005] Conventionally, a wet process has been used in which waste cathode active material is leached in a strong acid such as sulfuric acid to recover valuable metals. However, this wet process has disadvantages in terms of regeneration selectivity and regeneration time, and may cause environmental pollution. Therefore, research has been conducted into methods for recovering valuable metals through dry-based reactions in which the waste cathode active material is contacted with a reactive gas.

[0006] However, as the size of the positive electrode active material particles supplied to the dry reaction becomes smaller, the reaction may become non-uniform due to aggregation, and the supply of the reaction gas within the reactor may become locally non-uniform, which may result in a decrease in the recovery rate of the active material.

[0007] For example, Korean Patent No. 10-0843601 discloses a fluidized bed reactor equipped with a tuyere-type distribution plate, but in this fluidized bed reactor, a dead zone is formed in an area away from the tuyere (e.g., the outer periphery of the distribution plate) where gas injected from the tuyere does not reach. Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a fluidized bed reactor with improved reaction efficiency and reliability.

[0009] Another object of the present invention is to provide a method for recovering active metals of a lithium secondary battery using the fluidized bed reactor. [Means for solving the problem]

[0010] A fluidized bed reactor according to an exemplary embodiment of the present invention may include a reactor body, a base plate coupled to a bottom of the reactor body, and a distribution plate including first injection columns protruding from an upper surface of the base plate, and second injection columns adjacent to the periphery of the distribution plate and configured to inject gas to form a gas flow rotating along an inner surface of the reactor body.

[0011] In one embodiment, the gas flow formed by the second injection column may rotate in one direction.

[0012] In one embodiment, a plurality of the second injection columns may be spaced around the circumference of the distribution plate.

[0013] In one embodiment, when the perimeter of the dispersion plate is defined as L and the number of the second injection columns is defined as n, the second injection columns may be spaced apart at intervals of L / (n+1) to L / (n-1).

[0014] In one embodiment, the gas supply system may further include a gas flow path for supplying the gas to the second injection column.

[0015] In one embodiment, the second injection column may include a gas receiving portion that receives the gas from the gas flow path, and a second injection port that injects the gas so as to circulate inside the reactor body in a planar direction.

[0016] In one embodiment, the gas receiving portion may contact the top surface of the base plate.

[0017] In one embodiment, the gas receiving portion can contact the inner surface of the reactor body.

[0018] In one embodiment, the second jet orifices may be parallel to the tangent direction of the distribution plate.

[0019] In one embodiment, the second jet orifices may be angled toward the inner surface of the reactor body.

[0020] In one embodiment, the first injection column may include a column body extending from the upper surface of the base plate, a cap portion covering an upper portion of the column body, and a first injection port penetrating the column body.

[0021] In one embodiment, the first jet may be angled towards the top surface of the base plate.

[0022] In one embodiment, the first injection columns may be arranged at a regular pitch or in a regular grid.

[0023] In one embodiment, the reactor body may further include a reactant gas passage for supplying a reactant gas from a lower portion of the base plate.

[0024] In a method for recovering active metals for lithium secondary batteries according to an exemplary embodiment of the present invention, a mixture of used cathode active materials obtained from used cathodes of lithium secondary batteries may be prepared. The mixture of used cathode active materials may be reacted in the fluidized bed reactor to form a pre-precursor mixture. A lithium precursor may be selectively recovered from the pre-precursor mixture. [Effects of the Invention]

[0025] The fluidized bed reactor according to the exemplary embodiment of the present invention can prevent the occurrence of a dead zone where the reaction gas does not reach the distribution plate, thereby forming a uniform reaction region and fluidized bed.

[0026] The fluidized bed reactor according to the exemplary embodiment can be used in a recycling process of a positive electrode active material of a lithium secondary battery by hydrogen reduction. The fluidized bed reactor can form a uniform reaction region and a fluidized bed, thereby increasing the recovery efficiency of the positive electrode active material. [Brief explanation of the drawings]

[0027] [Figure 1] FIG. 1 is a schematic diagram illustrating the internal structure of a fluidized bed reactor according to an exemplary embodiment of the present invention. [Figure 2] FIG. 2 is a schematic plan view illustrating a dispersion plate according to an exemplary embodiment. [Figure 3] FIG. 3 is a schematic cross-sectional view of the dispersion plate of FIG. 2 taken along line "II-II'." [Figure 4] FIG. 4 is a schematic perspective view of a second injection column according to an exemplary embodiment. [Figure 5] FIG. 5 is a plan view showing the internal structure of the fluidized bed reactor of FIG. 1, taken along "II'." [Figure 6] FIG. 6 is a schematic diagram illustrating the arrangement of a second injection column according to some example embodiments. [Figure 7]FIG. 7 is a schematic diagram illustrating the arrangement of a second injection column according to some example embodiments. [Figure 8] FIG. 8 is a schematic diagram illustrating the direction in which the second injection ports are formed according to some example embodiments. [Figure 9] FIG. 9 is a schematic diagram illustrating the direction in which the second injection ports are formed according to some example embodiments. [Figure 10] FIG. 10 is a schematic diagram illustrating a method for recovering active metals of a lithium secondary battery using a fluidized bed reactor according to an exemplary embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0028] According to an exemplary embodiment of the present invention, a fluidized bed reactor can be provided that can form a uniform reaction zone and a fluidized bed.

[0029] Furthermore, according to an exemplary embodiment of the present invention, a dry-based recovery method for recovering active metals from lithium secondary batteries with high purity and high yield using the fluidized bed reactor can be provided.

[0030] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which are, however, merely illustrative and not limiting of the present invention.

[0031] As used herein, the term "precursor" is used to refer collectively to a compound containing a specific metal to provide the specific metal contained in the electrode active material.

[0032] FIG. 1 is a schematic diagram illustrating the internal structure of a fluidized bed reactor according to an exemplary embodiment of the present invention.

[0033] Referring to FIG. 1, a fluidized bed reactor 100 can include a reactor body 110 and a distribution plate 40 .

[0034] The reactor body 110 extends from the lower end to the upper end of the fluidized bed reactor 100, and a hollow portion may be formed inside the reactor body 110. The hollow portion may be defined by a dispersion plate 40.

[0035] Fig. 2 is a schematic plan view showing a dispersion plate according to an exemplary embodiment, and Fig. 3 is a schematic cross-sectional view of the dispersion plate of Fig. 2 taken along line "II-II'".

[0036] 2 and 3, the distribution plate 40 may include a base plate 50 and a plurality of first injection columns 60 protruding from the base plate 50.

[0037] For example, the base plate 50 may be a circular or polygonal plate made of a metal or ceramic material.

[0038] The first injection columns 60 may have a shape that protrudes from the upper surface of the base plate 50. The first injection columns 60 may be regularly arranged on the upper surface of the base plate 50 with a certain arrangement pattern (e.g., a certain grid arrangement) and arrangement pitch in order to uniformly diffuse and distribute the reaction gas.

[0039] For example, the injection columns 60, 70 may have an arrangement or lattice configuration in which they are arranged at the vertices of a polygon such as a triangle, square, hexagon, etc. For example, as shown in Figure 2, the first injection columns 60 may be arranged according to the pitch of an equilateral triangle.

[0040] 3, each of the first injection columns 60 may include a column body 62, a cap portion 64, and a first injection port 66 penetrating the column body 62. For example, the first injection column 60 may have a bubble cap or tuyere structure.

[0041] 3, the first injection port 66 may be formed to be inclined from the top of the first injection column 60 toward the base plate 50. For example, the first injection port 66 may have a shape that expands from the top of the first injection column 60 toward the base plate 50.

[0042] In one embodiment, the angle of inclination between the first injection port 66 and the vertical direction from the upper surface of the base plate 50 may be approximately 30 to 60 degrees.

[0043] Since the first injection port 66 is formed to be inclined with respect to the upper surface of the base plate 50, the reactant gas can be injected so as to be diffused in the direction of the base plate 50. This can promote the formation of a fluidized layer while the reactants (e.g., precursor particles or active material particles) that settle on the upper surface of the base plate 50 rise.

[0044] As described above, when the first injection columns 60 are arranged on the base plate 50 at a predetermined pitch (e.g., a triangular arrangement), regions where the first injection columns 60 are not arranged at a predetermined interval may occur at the periphery or outer periphery of the base plate 50. This may result in a dead zone (D) where the reactant gas does not reach, as shown by the dashed oval in FIG.

[0045] In this case, the reaction gas may not reach the inner surface of the reactor body 110, and the fluidized bed may not be generated uniformly. Also, agglomerated reactant particles may adhere to the inner surface of the reactor body 110, and the reaction yield may decrease.

[0046] In contrast, as shown in FIG. 1, the fluidized bed reactor 110 according to the exemplary embodiment of the present invention includes a second injection column 70 arranged adjacent to the dispersion plate 40, thereby suppressing the formation of the dead zone (D).

[0047] FIG. 4 is a schematic perspective view of a second injection column according to an exemplary embodiment.

[0048] Referring to FIG. 4, the second injection column 70 may include, for example, a gas receiving section 73 that receives gas supplied from a gas flow path 104 described below, and a second injection port 75 that injects the gas so that it circulates inside the reactor body 110.

[0049] In one embodiment, the gas may include a carrier gas and / or a reactant gas, as described below.

[0050] Figure 5 is a plan view showing the internal structure of a fluidized bed reactor taken along "II'" in Figure 1. Figures 6 and 7 are schematic diagrams illustrating the arrangement of second injection columns according to some embodiments.

[0051] 5, the gas injected from the second injection column 70 may form a gas flow that rotates along the inner surface of the reactor body 110. This may prevent the formation of a dead zone D.

[0052] In one embodiment, the gas injected from the second injection column 70 may form a unidirectional rotating gas flow, which induces a unidirectional vortex and allows the reactants (e.g., precursor particles or active material particles) to be more uniformly dispersed.

[0053] 6 and 7, the fluidized bed reactor 100 can include a plurality of second injection columns 70. The plurality of second injection columns can be spaced apart along the circumference of the distribution plate 40.

[0054] For example, if the peripheral length of the dispersion plate 40 is defined as L and the number of the second injection columns is defined as n, the second injection columns may be spaced apart at intervals of L / (n+1) to L / (n-1).

[0055] For example, as shown in Figure 6, two second dispersion columns can be arranged at intervals of L / 2 around the periphery of the dispersion plate 40. Alternatively, as shown in Figure 7, four second dispersion columns can be arranged at intervals of L / 4 around the periphery of the dispersion plate 40. In this case, the vortex can be formed more effectively.

[0056] In one embodiment, the gas receiving portion 73 can contact the upper surface of the base plate 50. A gas flow path 104 can pass through the base plate 50 and connect to the gas receiving portion 73 to supply the gas.

[0057] In one embodiment, the gas receiving portion 73 can contact the inner surface of the reactor body 110. The gas flow passage 104 can pass through the reactor body 110 and connect to the gas receiving portion 73 to supply the gas.

[0058] 8 and 9 are schematic diagrams illustrating the formation direction ED of the second injection ports according to some embodiments.

[0059] In one embodiment, as shown in FIG. 8, the second injection ports 75 may be formed parallel to the tangential direction TD of the distribution plate 40 .

[0060] In one embodiment, as shown in FIG. 9, the second injection port 75 may be formed so as to be inclined toward the inner surface of the reactor body 110.

[0061] In some embodiments, the inclination angle between the tangential direction TD and the second injection port 75 may be 0 to 30°, preferably 0 to 20°, and more preferably 0 to 10°.

[0062] FIG. 10 is a schematic diagram illustrating a method for recovering active metals from a lithium secondary battery using a fluidized bed reactor 100 according to an exemplary embodiment.

[0063] Hereinafter, a method for recovering active metals from a lithium secondary battery and the configuration / structure of the fluidized bed reactor 100 will be described with reference to FIG.

[0064] Referring to FIG. 10, a waste positive electrode active material mixture can be prepared from waste positive electrodes of lithium secondary batteries (for example, step S10).

[0065] The lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and the positive electrode and the negative electrode may include a positive electrode active material layer and a negative electrode active material layer coated on a positive electrode current collector and a negative electrode current collector, respectively.

[0066] For example, the positive electrode active material contained in the positive electrode active material layer may include a lithium metal oxide containing lithium and a transition metal.

[0067] In some embodiments, the lithium metal oxide can be represented by Formula 1:

[0068] [Chemical formula 1] Li x M1 a M2 b M3 c O y

[0069] In Chemical Formula 1, M1, M2, and M3 can be selected from Ni, Co, Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, or B. In Chemical Formula 1, 0 <x≦1.1、2≦y≦2.02、0<a<1、0<b<1、0<c<1、0<a+b+c≦1であってもよい。

[0070] In some embodiments, the active cathode material may be an NCM-based lithium oxide containing nickel, cobalt, and manganese.

[0071] The positive electrode can be separated from the used lithium secondary battery to recover the used positive electrode. The used positive electrode includes a positive electrode current collector (e.g., aluminum (Al)) and a positive electrode active material layer as described above. The positive electrode active material layer may include a conductive material and a binder in addition to the positive electrode active material.

[0072] The conductive material may include, for example, a carbon-based material such as graphite, carbon black, graphene, or carbon nanotubes. The binder may include, for example, a resin material such as vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, or polymethylmethacrylate.

[0073] According to an exemplary embodiment, the recovered waste cathodes may be pulverized to produce a waste cathode active material mixture. The waste cathode active material mixture may be prepared in a powder form. The waste cathode active material mixture may include a lithium-transition metal oxide powder, such as an NCM-based lithium metal oxide powder, as described above.

[0074] The term "waste cathode active material mixture" as used herein may refer to raw materials input into a fluidized bed reaction process described below after the cathode current collector has been substantially removed from the waste cathode. In one embodiment, the waste cathode active material mixture may include cathode active material particles such as the NCM-based lithium oxide. In one embodiment, the waste cathode active material mixture may also include a component derived from the binder or the conductive material. In one embodiment, the waste cathode active material mixture may be substantially composed of the cathode active material particles.

[0075] In some embodiments, the average particle size (D50) of the waste cathode active material mixture may be 5 to 100 μm, which allows for easy separation of the lithium-transition metal oxide, such as Li(NCM)O, to be recovered from the cathode current collector, conductive material, and binder contained in the waste cathode active material mixture.

[0076] In some embodiments, the waste cathode active material mixture may be heat-treated before being introduced into a fluidized bed reactor, which will be described later. The heat treatment may remove or reduce impurities, such as the conductive material and binder, contained in the waste cathode active material mixture, allowing the lithium-transition metal oxide to be introduced into the fluidized bed reactor with high purity.

[0077] The heat treatment temperature can be, for example, about 100 to 500° C., preferably about 350 to 450° C. Within this range, the impurities are substantially removed, and decomposition and damage to the lithium-transition metal oxide can be prevented.

[0078] For example, in step S20, the waste cathode active material mixture may be reacted in a fluidized bed reactor 100 to form a pre-precursor mixture 90.

[0079] As shown in FIG. 10, the fluidized bed reactor 100 can be divided into a reactor body 110, a reactor lower portion 120, and a reactor upper portion .

[0080] The reactor body 110 may include a heating means such as a heater or may be integrated with a heating means.

[0081] The distribution plate 40 may be attached to the bottom of the reactor body 110. The lower part of the distribution plate 40 in the reactor body 110 may be defined as the reactor lower part 120.

[0082] The waste cathode active material mixture may be supplied into the reactor body 110 through the supply passages 106a and 106b. The waste cathode active material mixture may be added dropwise through the first supply passage 106a connected to the upper part 130 of the reactor, or may be added through the second supply passage 106b connected to the bottom of the reactor body 110. In one embodiment, the waste cathode active material mixture may be supplied using both the first and second supply passages 106a and 106b.

[0083] A reactant gas for converting the waste cathode active material mixture into a pre-precursor may be supplied into the reactor body 110 through a reactant gas passage 102 connected to the reactor lower portion 120. According to an exemplary embodiment, the reactant gas may include a reducing gas, such as hydrogen (H).

[0084] The reactant gas may be injected into the reactor body 110 through a first injection column 60. The reactant gas is supplied from the lower part of the fluidized bed reactor 100 and contacts the waste cathode active material mixture, and the waste cathode active material mixture may react with the reactant gas while moving to the upper part 130 of the reactor and be converted into the pre-precursor.

[0085] Dead zones formed on the outer periphery or periphery of the base plate 50 can be removed by gas (e.g., reactant gas and / or carrier gas) injected through the second injection column 70. In addition, the gas forms a vortex, which can induce a uniform reaction between the waste cathode active material and the reactant gas.

[0086] In one embodiment, a reactant gas passage 102 that supplies the reactant gas and / or carrier gas to the first injection column 60 and a gas passage 104 that supplies the gas to the second injection column 70 may be separated from each other. This allows the gas flow through the second injection column 70 to be artificially and variably adjusted, thereby easily achieving optimization of the gas flow rate to eliminate dead zones.

[0087] In some embodiments, the lithium-transition metal oxide can be reduced by the hydrogen gas to produce, for example, lithium hydroxide (LiOH), a preliminary lithium precursor including a lithium oxide (e.g., LiO), and a transition metal or transition metal oxide. For example, the reductive reaction can produce Ni, Co, NiO, CoO, and MnO along with the preliminary lithium precursor.

[0088] The reduction reaction in the reactor main body 110 can be carried out at a temperature of about 400 to 700° C., preferably 450 to 550° C. Within this reaction temperature range, the reduction reaction can be promoted without causing re-aggregation or recombination of the preliminary lithium precursor and the transition metal / transition metal oxide.

[0089] In some embodiments, a carrier gas may be supplied together with the reaction gas from the reactor lower portion 120 via the reaction gas passage 102. For example, the carrier gas may include an inert gas such as nitrogen (N) or argon (Ar). The carrier gas may also be supplied by injection through the first injection column 60 of the dispersion plate to promote the formation of a fluidized bed. For example, the carrier gas may promote the formation of a vortex.

[0090] Within the reactor body 110, a pre-precursor mixture 90 can be formed that includes preliminary lithium precursor particles 94 and transition metal-containing particles 92 (e.g., the transition metal or transition metal oxide). The preliminary lithium precursor particles 94 can include, for example, lithium hydroxide, lithium oxide, and / or lithium carbonate.

[0091] In one embodiment, the transition metal-containing particles 92, including nickel, cobalt, or manganese, are relatively heavier than the reserve lithium precursor particles 94, so the reserve lithium precursor particles 94 may be collected first via the outlets 160a, 160b.

[0092] In one embodiment, the preliminary lithium precursor particles 94 can be discharged through a first outlet 160a connected to the reactor upper portion 130. In this case, selective recovery of the preliminary lithium precursor particles 94 can be facilitated by a weight gradient.

[0093] In one embodiment, the pre-precursor mixture 90 containing the preliminary lithium precursor particles 94 and the transition metal-containing particles 92 can be collected through the second outlet 160b connected to the reactor body 110. In this case, the pre-precursor mixture 90 can be directly recovered in the fluidized bed formation zone to increase the yield.

[0094] In one embodiment, the pre-precursor mixture 90 may be collected via both the first and second outlets 160a, 160b.

[0095] The preliminary lithium precursor particles 94 collected through the outlets 160a and 160b can be recovered as lithium precursor (for example, step S30).

[0096] In some embodiments, the preliminary lithium precursor particles 94 can be subjected to a water washing process. The water washing process allows the preliminary lithium precursor particles in the form of lithium hydroxide (LiOH) to be substantially dissolved in water and separated from the transition metal precursor, allowing them to be preferentially recovered. The lithium hydroxide dissolved in water can be subjected to a crystallization process or the like to obtain a lithium precursor substantially composed of lithium hydroxide.

[0097] In one embodiment, the reserve lithium precursor particles in the form of lithium oxide and lithium carbonate can be substantially removed by the water washing process, hi one embodiment, the reserve lithium precursor particles in the form of lithium oxide and lithium carbonate can be at least partially converted to lithium hydroxide by the water washing process.

[0098] In some embodiments, the preliminary lithium precursor particles 94 can be reacted with a carbon-containing gas, such as carbon monoxide (CO) or carbon dioxide (CO), to produce lithium carbonate (e.g., LiCO) as the lithium precursor. The reaction with the carbon-containing gas can produce a crystallized lithium precursor. For example, lithium carbonate can be collected by co-injecting a carbon-containing gas during the water washing process.

[0099] In some embodiments, a transition metal precursor can be obtained from the collected transition metal-containing particles 92 (eg, step S40).

[0100] For example, the preliminary lithium precursor particles 94 can be collected via outlets 160a and 160b, followed by recovery of the transition metal-containing particles 92. The transition metal-containing particles 92 can then be treated with an acid solution to form precursors of the acid salt forms of the respective transition metals.

[0101] In one embodiment, sulfuric acid can be used as the acid solution, and in this case, NiSO4, MnSO4, and CoSO4 can be recovered as the transition metal precursors, respectively.

[0102] As described above, by collecting the lithium precursor through a dry process and then selectively extracting the transition metal precursor using an acid solution, the purity and selectivity of each metal precursor are improved, and the load of the wet process is reduced, thereby suppressing the increase in wastewater and by-products.

Claims

1. A reactor body; a dispersion plate coupled to the bottom of the reactor body, the dispersion plate including a base plate and a first injection column protruding from an upper surface of the base plate; a second injection column adjacent to the periphery of the dispersion plate and injecting gas so as to form a gas flow rotating along the inner surface of the reactor body.

2. 2. The fluidized bed reactor of claim 1, wherein the gas flow formed by the second injection column rotates in one direction.

3. 2. The fluidized bed reactor of claim 1, wherein a plurality of said second injection columns are spaced around said distribution plate.

4. If the perimeter of the dispersion plate is defined as L and the number of second injection columns is defined as n, then:

4. The fluidized bed reactor of claim 3, wherein the second injection columns are spaced apart at intervals of L / (n+1) to L / (n-1).

5. 10. The fluidized bed reactor of claim 1, further comprising a gas flow path for supplying said gas to said second injection column.

6. The second injection column a gas receiving portion that receives the gas from the gas flow path; 6. The fluidized bed reactor according to claim 5, further comprising: a second injection port for injecting the gas in a planar direction so as to circulate inside the reactor body.

7. 7. The fluidized bed reactor of claim 6, wherein the gas receiving portion contacts the upper surface of the base plate.

8. 7. The fluidized bed reactor according to claim 6, wherein the gas receiving portion contacts the inner surface of the reactor body.

9. 9. The fluidized bed reactor according to claim 8, wherein the second injection port is parallel to a tangential direction of the dispersion plate.

10. 9. The fluidized bed reactor of claim 8, wherein the second injection port is inclined toward the inner surface of the reactor body.

11. 2. The fluidized bed reactor according to claim 1, wherein the first injection column includes a column body extending from the upper surface of the base plate, a cap portion covering an upper portion of the column body, and a first injection port penetrating the column body.

12. 12. The fluidized bed reactor of claim 11, wherein the first jet orifices are inclined toward the upper surface of the base plate.

13. 10. The fluidized bed reactor of claim 1, wherein the first injection columns are arranged at a fixed pitch or in a fixed grid pattern.

14. 2. The fluidized bed reactor according to claim 1, further comprising a reaction gas passage for supplying a reaction gas from a lower portion of the base plate in the reactor body.

15. preparing a waste positive electrode active material mixture obtained from waste positive electrodes of lithium secondary batteries; reacting the waste cathode active material mixture in a fluidized bed reactor according to claim 1 to form a pre-precursor mixture; and selectively recovering a lithium precursor from the preliminary precursor mixture.

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