Fluidized bed reactor and method for recovering active metal of lithium secondary battery using same

Abstract

A fluidized bed reactor according to an exemplary embodiment of the present invention may comprise: a reactor body; the dispersing plate comprises a base plate and a first spraying column protruding from the upper surface of the base plate; and a second injection column that injects a gas to form a gas flow that rotates along the 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 of lithium secondary batteries using the fluidized bed reactor. More specifically, the present invention relates to a fluidized bed reactor including a dispersion plate and a method for recovering active metals of lithium secondary batteries using the fluidized bed reactor. Background Art

[0002] In recent years, secondary batteries are being widely used and developed as power sources for portable electronic communication devices such as camcorders, mobile phones, and laptop computers, and vehicles such as hybrid cars and electric cars. Lithium secondary batteries, which are secondary batteries, have high operating voltage and energy density per unit weight and are advantageous in terms of charging speed and lightness, and are therefore being actively developed and used.

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

[0004] Since the above-mentioned high-cost valuable metals are used in the positive electrode active material, the production of the positive electrode material requires more than 20% of the production cost of the lithium secondary battery. In addition, as environmental protection issues have become increasingly prominent in recent years, methods for recycling positive electrode active materials are being studied.

[0005] In the past, a wet method was used to sequentially recover valuable metals by leaching spent positive electrode active materials with strong acids such as sulfuric acid, but the wet method is disadvantageous in terms of regeneration selectivity, regeneration time, etc., and may cause environmental pollution. Therefore, a method of recovering valuable metals by dry reaction through contact with a reaction gas is being studied.

[0006] However, as the size of the positive electrode active material particles supplied for the dry reaction becomes finer, the reaction may become non-uniform due to aggregation. In addition, the recovery rate of the active material may be reduced due to the local non-uniform supply of the reaction gas in the reactor.

[0007] For example, Korean Patent No. 10-0843601 discloses a fluidized bed reactor including a tuyere-type dispersion plate, but the fluidized bed reactor forms a dead zone in an area far from the tuyere (e.g., the outer periphery of the dispersion plate) where the gas ejected from the tuyere cannot reach. Summary of the invention

[0008] 1. Technical issues to be resolved

[0009] A technical problem of the present invention is to provide a fluidized bed reactor with improved reaction efficiency and reliability.

[0010] A technical problem of the present invention is to provide a method for recovering active metals from lithium secondary batteries using the fluidized bed reactor.

[0011] (II) Technical solution

[0012] A fluidized bed reactor according to an exemplary embodiment of the present invention may include: a reactor body; a dispersion plate, which is combined with the bottom of the reactor body and includes a base plate and a first injection column protruding from the top of the base plate; and a second injection column, which is adjacent to the periphery of the dispersion plate and injects gas to form a gas flow rotating along the inner surface of the reactor body.

[0013] In one embodiment, the gas flow formed by the second spray column may rotate in one direction (unidirection).

[0014] In one embodiment, a plurality of the second spray columns may be spaced apart along the circumference of the dispersion plate.

[0015] In one embodiment, when the perimeter of the dispersion plate is defined as L and the number of the second dispersion columns is defined as n, the second spray columns may be spaced apart at intervals of L / (n+1) to L / (n-1).

[0016] In one embodiment, a gas channel for supplying the gas to the second spray column may be further included.

[0017] In one embodiment, the second injection column may include: a gas receiving part receiving the gas from the gas channel; and a second injection port injecting the gas in a planar direction to circulate the gas inside the reactor body.

[0018] In one embodiment, the gas receiving part may be in contact with the upper surface of the substrate.

[0019] In one embodiment, the gas receiving part may be in contact with the inner surface of the reactor body.

[0020] In one embodiment, the second injection port may be parallel to a tangential direction of the dispersion plate.

[0021] In one embodiment, the second injection port may be inclined toward the inner surface of the reactor body.

[0022] In one embodiment, the first spray column may include: a column extending from the upper surface of the substrate, a cover covering an upper portion of the column, and a first spray port penetrating the column.

[0023] In one embodiment, the first ejection port may be inclined toward the upper surface of the substrate.

[0024] In one embodiment, the first spray columns may be arranged at a constant interval or in a constant grid shape.

[0025] In one embodiment, a reaction gas channel for supplying a reaction gas from a lower portion of the substrate in the reactor body may be further included.

[0026] In the method for recovering active metals of a lithium secondary battery according to an exemplary embodiment of the present invention, a waste positive electrode active material mixture obtained from a waste positive electrode of a lithium secondary battery can be prepared. The waste positive electrode active material mixture can be reacted in the above-mentioned fluidized bed reactor to form a preliminary precursor mixture. A lithium precursor can be selectively recovered from the preliminary precursor mixture.

[0027] (III) Beneficial effects

[0028] The fluidized bed reactor according to the exemplary embodiment of the present invention can prevent the generation of a dead zone on the dispersion plate where the reaction gas does not reach, and thus, a uniform reaction area and a fluidized bed can be formed.

[0029] The fluidized bed reactor according to the exemplary embodiment can be applied to the recovery process of the positive active material of the lithium secondary battery by hydrogen reduction. The fluidized bed reactor can form a uniform reaction area and a fluidized bed, thus increasing the recovery efficiency of the positive active material. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a schematic diagram for explaining the internal structure of a fluidized bed reactor according to an exemplary embodiment of the present invention.

[0031] Figure 2 is a schematic plan view showing a dispersion plate according to an exemplary embodiment.

[0032] Figure 3 Yes Figure 2 Schematic cross-sectional view of the dispersion plate taken along the II-II' direction.

[0033] Figure 4 is a schematic perspective view illustrating a second spray column according to an exemplary embodiment.

[0034] Figure 5 It shows that Figure 1 A plan view of the internal structure of the fluidized bed reactor taken along the II' direction and observed.

[0035] Figure 6 and Figure 7 is a schematic diagram for explaining a disposition structure of a second spray column according to some exemplary embodiments.

[0036] Figure 8 and Fig. 9 is a schematic diagram for explaining a formation direction of a second ejection port according to some exemplary embodiments.

[0037] Fig.10 is a schematic diagram for explaining a method of recovering active metals of a lithium secondary battery using a fluidized bed reactor according to an exemplary embodiment. DETAILED DESCRIPTION

[0038] According to an exemplary embodiment of the present invention, a fluidized bed reactor that can form a uniform reaction zone and a fluidized bed can be provided.

[0039] Furthermore, according to an exemplary embodiment of the present invention, a method for recovering active metals from a lithium secondary battery with high purity and high yield, which is a dry-based method using the fluidized bed reactor, may be provided.

[0040] Hereinafter, the exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, but this is merely exemplary, and the present invention is not limited to the specific embodiments described exemplarily.

[0041] The term "precursor" used in this specification refers to a compound containing a specific metal in order to provide the specific metal contained in the electrode active material.

[0042] Figure 1 is a schematic diagram for explaining the internal structure of a fluidized bed reactor according to an exemplary embodiment of the present invention.

[0043] Reference Figure 1 The fluidized bed reactor 100 may include a reactor body 110 and a dispersion plate 40 .

[0044] The reactor body 110 may extend from the bottom to the top of the fluidized bed reactor 100 and may include a hollow portion formed inside the reactor body 110. The hollow portion may be partitioned by a dispersion plate 40.

[0045] Figure 2 is a schematic plan view showing a dispersion plate according to an exemplary embodiment. Figure 3 Yes Figure 2 Schematic cross-sectional view of the dispersion plate taken along the II-II' direction.

[0046] Reference Figure 2 and Figure 3The dispersion plate 40 may include a base plate 50 and a plurality of first spray pillars 60 protruding from the base plate 50 .

[0047] For example, the substrate 50 may be a circular or polygonal plate made of metal or ceramic.

[0048] The first injection pillars 60 may have a shape protruding from the upper surface of the substrate 50. The first injection pillars 60 may be regularly arranged on the upper surface of the substrate 50 with a constant arrangement shape (eg, a constant grid arrangement) and an arrangement interval to uniformly diffuse and distribute the reaction gas.

[0049] For example, the spray columns (60, 70) may have an arrangement shape or a grid shape arranged at the vertices of a polygon such as a triangle, a quadrilateral, or a hexagon. Figure 2 As shown, the first spray columns 60 may be arranged at a regular triangle pitch.

[0050] Reference Figure 3 The first spray column 60 may include a column body 62, a cover 64, and a first spray port 66 penetrating the first column body 62. For example, the first spray column 60 may have a bubble cap or tuyere structure.

[0051] For example, Figure 3 As shown, the first injection port 66 may be formed to be inclined from the upper portion of the injection column 60 toward the substrate 50. For example, the first injection port 66 may have a shape that expands from the upper portion of the injection column 60 toward the substrate 50.

[0052] In one embodiment, the tilt angle between the vertical direction of the upper surface of the substrate 50 and the first injection port 66 may be about 30-60 degrees. o .

[0053] Since the first injection port 66 is formed obliquely with respect to the upper surface of the substrate 50, the reaction gas can be injected to diffuse toward the substrate 50. Therefore, as the reaction material (e.g., precursor particles or active material particles) deposited on the upper surface of the substrate 50 rises, the formation of a fluidized bed can be promoted.

[0054] As described above, when the first spray columns 60 are arranged at a predetermined interval (for example, in a triangular arrangement) on the substrate 50, a region where the spray columns 60 are not arranged at a predetermined interval may be generated in the peripheral portion or outer portion of the substrate 50. Figure 2 As indicated by the dotted ellipse, a dead zone D may be generated where the reaction gas cannot reach.

[0055] In this case, the reaction gas cannot reach the inner surface of the reactor body 110, so the fluidized bed may not be uniformly generated. In addition, the reaction material particles are attached and aggregated on the inner surface of the reactor body 110, so the reaction yield may be reduced.

[0056] However, if Figure 1 As shown, the fluidized bed reactor 110 according to an exemplary embodiment of the present invention includes the second spray column 70 disposed adjacent to the periphery of the dispersion plate 40, so that the formation of the dead zone D can be suppressed.

[0057] Figure 4 is a schematic perspective view illustrating a second spray column according to an exemplary embodiment.

[0058] Reference Figure 4 The second injection column 70 may include, for example, a gas receiving portion 73 that receives a gas supplied from a gas passage 104 described below, and a second injection port 75 that injects the gas to circulate the gas inside the reactor body 110 .

[0059] In one embodiment, the gas may include a carrier gas and / or a reactive gas as described below.

[0060] Figure 5 It shows that Figure 1 A plan view of the internal structure of the fluidized bed reactor taken and observed along the II' direction. In addition, Figure 6 and Figure 7 is a schematic diagram for explaining the arrangement structure of the second spray column according to some embodiments.

[0061] like Figure 5 As shown, the gas injected from the second injection column 70 may form a gas flow rotating along the inner surface of the reactor body 110. Therefore, the formation of the dead zone D may be suppressed.

[0062] In one embodiment, the gas injected from the second injection column 70 may form a gas flow rotating in one direction (unidirectional). Therefore, a vortex in one direction may be induced, and thus the reaction materials (eg, precursor particles or active material particles) may be more uniformly dispersed.

[0063] like Figure 6 and Figure 7 As shown, the fluidized bed reactor 100 may include a plurality of second injection columns 70. The plurality of second injection columns may be spaced apart along the circumference of the dispersion plate 40.

[0064] For example, when the circumference of the dispersion plate 40 is defined as L and the number of the second dispersion columns is defined as n, the second spray columns may be spaced apart at intervals of L / (n+1) to L / (n-1).

[0065] For example, Figure 6 As shown in FIG. 2 , two second dispersion columns may be arranged at intervals of L / 2 along the periphery of the dispersion plate 40. Alternatively, as shown in FIG. Figure 7 As shown, four second dispersion columns may be arranged at intervals of L / 4 along the circumference of the dispersion plate 40. In this case, the vortex may be better formed.

[0066] In one embodiment, the gas receiving part 73 may be in contact with the upper surface of the substrate 50. The gas channel 104 penetrates the substrate 50 and is connected to the gas receiving part 73 to supply the gas.

[0067] In one embodiment, the gas receiving part 73 may be in contact with the inner surface of the reactor body 110. The gas channel 104 may penetrate the reactor body 110 and be connected to the gas receiving part 73 to supply the gas.

[0068] Figure 8 and Fig. 9 is a schematic diagram for explaining a formation direction (ED) of a second ejection port according to some embodiments.

[0069] In one embodiment, if Figure 8 As shown, the second injection port 75 may be formed in parallel with the tangential direction (TD) of the dispersion plate 40 .

[0070] In one embodiment, if Fig. 9 As shown, the second injection port 75 may be formed to be inclined toward the inner surface of the reactor body 110 .

[0071] In some embodiments, the inclination angle between the tangent direction (TD) and the second injection port 75 may be 0-30°. o , preferably 0-20 o , more preferably 0-10 o .

[0072] Fig.10 1 is a schematic diagram for explaining a method of recovering active metals of a lithium secondary battery using a fluidized bed reactor 100 according to an exemplary embodiment.

[0073] Below, refer to Fig.10 , together with the method for recovering active metals of lithium secondary batteries and the composition / structure of the above-mentioned fluidized bed reactor 100.

[0074] Reference Fig.10, a waste positive electrode active material mixture can be prepared from a waste positive electrode of a lithium secondary battery (eg, S10 process).

[0075] The lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator between the positive electrode and the negative electrode. 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 collector and a negative electrode collector, respectively.

[0076] For example, the positive electrode active material included in the positive electrode active material layer may include a lithium metal oxide containing lithium and a transition metal.

[0077] In some embodiments, the lithium metal oxide may be represented by the following Chemical Formula 1.

[0078] [Chemical formula 1]

[0079] Li x M1 a M2 b M3 c O y

[0080] In Chemical Formula 1, M1, M2, and M3 may 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。

[0081] In some embodiments, the positive active material may be an NCM-based lithium oxide including nickel, cobalt, and manganese.

[0082] The positive electrode can be separated from the waste lithium secondary battery to recover the waste positive electrode. As described above, the waste positive electrode includes a positive electrode current collector (eg, aluminum (Al)) and a positive electrode active material layer, and the positive electrode active material layer may include the above-mentioned positive electrode active material as well as a conductive material and a binder.

[0083] The conductive material may include carbon-based materials such as graphite, carbon black, graphene, carbon nanotubes, etc. The adhesive may include resin materials such as vinylidene fluoride-co-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, etc.

[0084] According to an exemplary embodiment, the recycled waste positive electrode can be pulverized to generate a waste positive electrode active material mixture. Therefore, the waste positive electrode active material mixture can be made into a powder form. As described above, the waste positive electrode active material mixture contains a powder of a lithium transition metal oxide, for example, it can contain an NCM-based lithium metal oxide powder.

[0085] The term "waste positive electrode active material mixture" used in the present application may refer to a raw material added to the fluidized bed reaction treatment described later after substantially removing the positive electrode current collector from the waste positive electrode. In one embodiment, the waste positive electrode active material mixture may include positive electrode active material particles such as the NCM-based lithium oxide. In one embodiment, the waste positive electrode active material mixture may also include a portion of components derived from the binder or the conductive material. In one embodiment, the waste positive electrode active material mixture may be substantially composed of the positive electrode active material particles.

[0086] In some embodiments, the average particle size (D50) of the waste positive electrode active material mixture may be 5-100 μm. Within the above range, the lithium transition metal oxide such as Li(NCM)O2 as the recycling object can be easily separated from the positive electrode current collector, conductive material and binder contained in the waste positive electrode active material mixture.

[0087] In some embodiments, the spent positive electrode active material mixture may be heat treated before being added to the fluidized bed reactor described later. Impurities such as the conductive material and the binder contained in the spent positive electrode active material mixture are removed or reduced by the heat treatment, so that the lithium transition metal oxide can be added to the fluidized bed reactor with high purity.

[0088] The heat treatment temperature may be, for example, about 100-500° C., preferably about 350-450° C. Within the above range, the impurities may be substantially removed, and the decomposition and damage of the lithium transition metal oxide may be prevented.

[0089] For example, in the S20 process, the spent positive electrode active material mixture may be reacted in a fluidized bed reactor 100 to form a preliminary precursor mixture 90 .

[0090] like Fig.10 As shown, the fluidized bed reactor 100 can be divided into a reactor body 110 , a reactor lower part 120 and a reactor upper part 130 .

[0091] The reactor body 110 may include a heating device such as a heater, or may be integrated with the heating device.

[0092] The dispersion plate 40 may be combined with the bottom of the reactor body 110. A lower portion of the dispersion plate 40 in the reactor body 110 may be defined as a reactor lower portion 120.

[0093] The spent positive electrode active material mixture can be supplied to the reactor body 110 through the supply channels (106a, 106b). The spent positive electrode active material mixture is added dropwise through the first supply channel 106a connected to the reactor upper part 130, or can be added through the second supply channel 106b connected to the bottom of the reactor body 110. In one embodiment, the spent positive electrode active material mixture can also be supplied using the first supply channel 106a and the second supply channel 106b together.

[0094] A reaction gas for converting the spent positive active material mixture into a preliminary precursor may be supplied to the reactor body 110 through a reaction gas channel 102 connected to the reactor lower portion 120. According to an exemplary embodiment, the reaction gas includes a reducing gas, for example, hydrogen (H2) may be supplied.

[0095] The reaction gas may be injected into the reactor body 110 through the first injection column 60. The reaction gas is supplied from the lower portion of the fluidized bed reactor 100 and contacts the spent positive electrode active material mixture, so the spent positive electrode active material mixture may move to the reactor upper portion 130 and react with the reaction gas to be converted into the preliminary precursor.

[0096] The gas (eg, reaction gas and / or carrier gas) injected by the second injection column 70 can remove a dead zone formed at the outer or peripheral portion of the substrate 50. In addition, the gas forms a vortex, thereby inducing a uniform reaction between the spent positive active material and the reaction gas.

[0097] In one embodiment, the reaction gas channel 102 for supplying the reaction gas and / or carrier gas to the first injection column 60 and the gas channel 104 for supplying the gas to the second injection column 70 may be distinguished from each other. Therefore, the gas flow according to the second injection column 70 may be artificially and variably adjusted, and thus the gas flow rate for eliminating the dead zone may be easily optimized.

[0098] In some embodiments, the lithium transition metal oxide can be reduced by the hydrogen gas to generate, for example, a preliminary lithium precursor including lithium hydroxide (LiOH), a lithium oxide (e.g., Li2O) and a transition metal or transition metal oxide. For example, Ni, Co, NiO, CoO and MnO can be generated while generating the preliminary lithium precursor through a reductive reaction.

[0099] The reduction reaction in the reactor body 110 may be performed at about 400-700° C., preferably 450-550° C. Within the above reaction temperature range, the preliminary lithium precursor and the transition metal / transition metal oxide will not be re-aggregated and re-combined, and the reduction reaction may be promoted.

[0100] In some embodiments, a carrier gas may be supplied from the reactor lower portion 120 together with the reaction gas through the carrier gas passage 104. For example, the carrier gas may include an inert gas such as nitrogen (N2), argon (Ar), etc. The carrier gas may also be sprayed and supplied through the first dispersion column 60 of the dispersion plate to promote the formation of a fluidized bed. For example, the formation of a vortex by the carrier gas may be promoted.

[0101] A preliminary precursor mixture 90 including preliminary lithium precursor particles 94 and particles 92 containing transition metals (eg, the transition metal or transition metal oxide) may be formed in the reactor body 110. The preliminary lithium precursor particles 94 may include, for example, lithium hydroxide, lithium oxide, and / or lithium carbonate (lithium carbonate).

[0102] In one embodiment, the transition metal-containing particles 92 including nickel, cobalt, or manganese are relatively heavy compared to the preliminary lithium precursor particles 94, and thus can be collected first through the discharge ports (160a, 160b).

[0103] In one embodiment, the preliminary lithium precursor particles 94 may be discharged through the first discharge port 160a connected to the reactor upper portion 130. In this case, selective recovery of the preliminary lithium precursor particles 94 according to a weight gradient may be facilitated.

[0104] In one embodiment, the preliminary precursor mixture 90 including the preliminary lithium precursor particles 94 and the transition metal-containing particles 92 may be collected through the second discharge port 160b connected to the reactor body 130. In this case, the preliminary precursor mixture 90 is directly recovered from the fluidized bed formation region, thereby increasing the yield.

[0105] In one embodiment, the preliminary precursor mixture 90 may be collected together through the first discharge port 160a and the second discharge port 160b.

[0106] The preliminary lithium precursor particles 94 collected through the discharge ports ( 160 a , 160 b ) may be recovered as a lithium precursor (eg, S30 process).

[0107] In some embodiments, the preliminary lithium precursor particles 94 may be subjected to a water washing process. Through the water washing process, the preliminary lithium precursor particles in the form of lithium hydroxide (LiOH) are substantially dissolved in water and separated from the transition metal precursor, so that they can be preferentially recovered. A lithium precursor substantially composed of lithium hydroxide can be obtained through a crystallization process of lithium hydroxide dissolved in water, etc.

[0108] In one embodiment, the preliminary lithium precursor particles in the form of lithium oxide and lithium carbonate can be substantially removed by the water washing treatment. In one embodiment, at least a portion of the preliminary lithium precursor particles in the form of lithium oxide and lithium carbonate can be converted into lithium hydroxide by the water washing treatment.

[0109] In some embodiments, lithium carbonate (e.g., Li2CO3) as a lithium precursor may be obtained by reacting the preliminary lithium precursor particles 94 with a carbon-containing gas such as carbon monoxide (CO), carbon dioxide (CO2), etc. A crystallized lithium precursor may be obtained by reacting with the carbon-containing gas. For example, a carbon-containing gas may be injected together during the water washing process to collect lithium carbonate.

[0110] In some embodiments, a transition metal precursor may be obtained from the collected transition metal-containing particles 92 (eg, S40 process).

[0111] For example, the preliminary lithium precursor particles 94 may be collected through the discharge ports (160a, 160b) to recover the transition metal-containing particles 92. Thereafter, the transition metal-containing particles 92 may be treated with an acid solution to form a precursor in the form of an acid salt of each transition metal.

[0112] In one embodiment, the acid solution may use sulfuric acid. In this case, NiSO4, MnSO4 and CoSO4 may be recovered as the transition metal precursors.

[0113] As described above, the lithium precursor is collected through a dry process and then the transition metal precursor is selectively extracted with an acid solution, thereby improving the purity and selectivity of each metal precursor and reducing the load of the wet process, thereby reducing the increase of wastewater and by-products.

Claims

1. A fluidized bed reactor, comprising: Reactor body; a dispersion plate, the dispersion plate being combined with the bottom of the reactor body, and the dispersion plate comprising a base plate and a first spray column protruding from an upper surface of the base plate; as well as The second injection column is adjacent to the periphery of the dispersion plate and injects gas to form a gas flow rotating along the inner surface of the reactor body.

2. The fluidized bed reactor according to claim 1, wherein: The airflow formed by the second spray column rotates in one direction, that is, unidirectionally.

3. The fluidized bed reactor according to claim 1, wherein A plurality of the second spray columns are spaced apart and arranged along the circumference of the dispersion plate.

4. The fluidized bed reactor according to claim 3, wherein: When the perimeter of the dispersion plate is defined as L and the number of the second dispersion columns is defined as n, the second spray columns are spaced apart at intervals of L / (n+1) to L / (n-1).

5. The fluidized bed reactor according to claim 1, wherein The fluidized bed reactor further includes a gas channel for supplying the gas to the second spray column.

6. The fluidized bed reactor according to claim 5, wherein: The second spray column comprises: a gas receiving portion that receives the gas from the gas passage; and The second injection port injects the gas in a planar direction so that the gas circulates inside the reactor body.

7. The fluidized bed reactor according to claim 6, wherein: The gas receiving portion is in contact with the upper surface of the substrate.

8. The fluidized bed reactor according to claim 6, wherein: The gas receiving part is in contact with the inner surface of the reactor body.

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

11. The fluidized bed reactor according to claim 1, wherein: The first injection column includes: a column extending from the upper surface of the substrate, a cover covering an upper portion of the column, and a first injection port penetrating the column.

12. The fluidized bed reactor according to claim 11, wherein: The first injection port is inclined toward the upper surface of the substrate.

13. The fluidized bed reactor according to claim 1, wherein: The first spray columns are arranged at a constant interval or in a constant grid shape.

14. The fluidized bed reactor according to claim 1, wherein: The fluidized bed reactor further includes a reaction gas channel in the reactor body to supply a reaction gas from a lower portion of the substrate.

15. A method for recovering active metals from a lithium secondary battery, comprising the following steps: preparing a waste positive electrode active material mixture obtained from waste positive electrodes of lithium secondary batteries; reacting the spent positive electrode active material mixture in the fluidized bed reactor of claim 1 to form a preliminary precursor mixture; and A lithium precursor is selectively recovered from the preliminary precursor mixture.

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