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

Abstract

According to the method for recovering active metals of lithium secondary batteries according to an embodiment of the present invention, a waste positive electrode active material mixture is prepared from a waste positive electrode of a lithium secondary battery. The waste positive electrode active material mixture reacts with a reaction gas in a fluidized bed reactor to form a primary precursor mixture. The primary precursor mixture is cooled by injecting a first refrigerant and a second refrigerant different from each other into the primary precursor mixture. A lithium precursor is selectively recovered from the cooled primary precursor mixture.

Description

Technical Field

[0001] The present invention relates to a fluidized bed reactor and a method for recovering active metals of a lithium secondary battery using the same. More specifically, the present invention relates to a fluidized bed reactor including a dispersion plate and a method for recovering active metals of a lithium secondary battery using the same. Background Art

[0002] Recently, secondary batteries have been widely used as power sources for mobile electronic devices such as camcorders, mobile phones, notebook computers, etc., and vehicles such as electric vehicles, hybrid vehicles, etc. Lithium secondary batteries have attracted much attention among secondary batteries due to their advantages such as high operating voltage and high energy density per unit weight, high charging rate, and compact size.

[0003] Lithium metal oxide can be used as an active material for a positive electrode of a lithium secondary battery. Lithium metal oxide may further contain a transition metal such as nickel, cobalt, manganese, and the like.

[0004] Since the above-mentioned high-cost valuable metals are used for the positive electrode active material, the production cost of manufacturing the positive electrode material is more than 20%. In addition, due to the recent attention paid to environmental protection issues, research is being conducted on the recycling method of the positive electrode active material.

[0005] Conventionally, a method of sequentially recovering valuable metals by leaching spent positive electrode active materials in a strong acid such as sulfuric acid has been used, but the wet process may be disadvantageous in terms of regeneration selectivity and regeneration time, and may cause environmental pollution. Therefore, a method of recovering valuable metals using a dry reaction by contact with a reaction gas is being studied.

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

[0007] For example, Korean Registered Patent Publication No. 10-0709268 discloses an apparatus and method for recycling waste manganese batteries and alkaline batteries, but does not provide a dry method for regenerating valuable metals with high selectivity and high yield. Summary of the invention

[0008] [Technical goals]

[0009] According to one aspect of the present invention, a fluidized bed reactor with improved recovery efficiency is provided.

[0010] According to one aspect of the present invention, a method for recovering active metals of a lithium secondary battery with improved recovery efficiency is provided.

[0011] [Technical means]

[0012] In a method for recovering active metals of a lithium secondary battery according to an embodiment of the present invention, a waste positive electrode active material mixture is prepared from a waste positive electrode of a lithium secondary battery. A primary precursor mixture is formed by reacting the waste positive electrode active material mixture with a reaction gas in a fluidized bed reactor. The primary precursor mixture is cooled by spraying different first and second refrigerants to the primary precursor mixture. A lithium precursor is selectively recovered from the cooled primary precursor mixture.

[0013] In some embodiments, the first refrigerant may be a gas and the second refrigerant may be a liquid.

[0014] In some embodiments, the first refrigerant may include nitrogen or argon.

[0015] In some embodiments, the second refrigerant may include water.

[0016] In some embodiments, the injection rate ratio of the first refrigerant to the second refrigerant may be 0.1 to 10.

[0017] In some embodiments, cooling the primary precursor mixture may reduce the temperature of the primary precursor mixture to below 100°C.

[0018] In some embodiments, the fluidized bed reactor may include: a reactor body and a dispersion plate coupled to the bottom of the reactor body. The dispersion plate may include a bottom plate and an injection column and an auxiliary column protruding from the upper surface of the bottom plate. In cooling the primary precursor mixture, the first refrigerant may be injected through the injection column, and the second refrigerant may be injected through the auxiliary column.

[0019] In some embodiments, the first refrigerant and the second refrigerant may be injected together through an auxiliary column.

[0020] In some embodiments, a reactive gas including a reducing gas may be supplied through an injection column.

[0021] In some embodiments, the fluidized bed reactor may further include a first flow path for supplying the first refrigerant and a second flow path for supplying the second refrigerant, respectively, from a lower portion of the fluidized bed reactor.

[0022] In some embodiments, the first flow path may be connected to the injection column, and the second flow path may be connected to the auxiliary column.

[0023] A fluidized bed reactor according to an exemplary embodiment includes a reactor body; a dispersion plate coupled to the bottom of the reactor body and including a bottom plate and an injection column and an auxiliary column protruding from the upper surface of the bottom plate; a first flow path for supplying a gaseous first refrigerant from a lower portion of the reactor to the injection column; and a second flow path for supplying a liquid second refrigerant from a lower portion of the reactor to the auxiliary column.

[0024] In some embodiments, the second flow path may include a first inlet supplying the first refrigerant and a second inlet supplying the second refrigerant.

[0025] In some embodiments, the injection pillars and the auxiliary pillars may be arranged at a constant pitch or in a constant grid shape.

[0026] In some embodiments, the ratio of the number of injection columns to the number of auxiliary columns may be 1 to 1,000.

[0027] [Effects of the Invention]

[0028] According to the above exemplary embodiment, the gaseous first refrigerant and the liquid second refrigerant may be sprayed to the primary precursor mixture formed in the fluidized bed reactor, so that the primary precursor mixture may be quickly cooled, thereby improving the recovery efficiency of the lithium precursor.

[0029] In the method for recovering active metals of a lithium secondary battery according to an exemplary embodiment, the injection rate ratio of the first refrigerant and the second refrigerant can be adjusted. Therefore, the damage to the fluidized bed reactor caused by the rapid cooling of the primary precursor mixture can be minimized. In addition, the amount of the second refrigerant accumulated in the lower part of the fluidized bed reactor can be minimized, so that the subsequent process can be performed faster. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a schematic diagram for describing a fluidized bed reactor and a method of recovering active metals of a lithium secondary battery using the same according to an exemplary embodiment.

[0031] Figure 2 is a schematic top view showing a dispersion plate of a fluidized bed reactor according to an exemplary embodiment.

[0032] Figure 3 is a schematic cross-sectional view illustrating the configuration of an injection column and an auxiliary column of a dispersion plate according to an exemplary embodiment. DETAILED DESCRIPTION

[0033] Embodiments of the present invention provide a method with high purity and high yield for recovering active metals from a lithium secondary battery using a gaseous first refrigerant and a liquid second refrigerant. In addition, a fluidized bed reactor capable of being used in a method for recovering active metals of a lithium secondary battery is also provided.

[0034] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, these embodiments are provided as examples, and the present invention is not limited to the specific embodiments described herein.

[0035] As used herein, the term "precursor" is used generically to refer to a compound containing a specific metal to provide the specific metal contained in the electrode active material.

[0036] Referring to Figure 1 , a waste cathode active material mixture can be prepared from a waste cathode of a lithium secondary battery (for example, in the S10 process).

[0037] A lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator layer interposed between the positive electrode and the negative electrode. The positive electrode and the negative electrode may include a positive electrode active material layer coated on a positive electrode current collector and a negative electrode active material layer coated on a negative electrode current collector, respectively.

[0038] For example, the positive electrode active material contained in the positive electrode active material layer may include an oxide containing lithium and a transition metal.

[0039] In some embodiments, the positive electrode active material may include a compound represented by the following Chemical Formula 1.

[0040] [Chemical Formula 1]

[0041] Li x M1 a M2 b M3 c O y

[0042] In Chemical Formula 1, M1, M2, and M3 may each be a transition metal 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, and 0 < a + b + c ≤ 1.

[0043] In some embodiments, the positive electrode active material may be an NCM-based lithium oxide including nickel, cobalt, and manganese.

[0044] The waste positive electrode can be recycled by separating the positive electrode from the waste lithium secondary battery. The waste positive electrode may include a positive electrode current collector (eg, aluminum (Al)) and a positive electrode active material layer as described above, and the positive electrode active material layer may include a conductive material and a binder as well as the positive electrode active material as described above.

[0045] The conductive material may include, for example, carbon-based materials such as graphite, carbon black, graphene, and carbon nanotubes. The binder may include a resin material such as polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, and the like.

[0046] In an exemplary embodiment, the recycled waste positive electrode can be pulverized to produce a waste positive electrode active material mixture. Therefore, the waste positive electrode active material mixture can be prepared in a powder form. As described above, the waste positive electrode active material mixture can include a powder of a lithium-transition metal oxide, such as a powder of an NCM-based lithium oxide (e.g., Li(NCM)O2).

[0047] The term “waste positive electrode active material mixture” used in the present application may refer to a raw material that is input into a fluidized bed reaction process to be described below after the positive electrode current collector is substantially removed from the waste positive electrode.

[0048] In one embodiment, the spent positive active material mixture may include positive active material particles, such as NCM-based lithium oxide. In one embodiment, the spent positive active material mixture may include a component portion derived from a binder or a conductive material. In one embodiment, the spent positive active material mixture may be substantially composed of positive active material particles.

[0049] In some embodiments, the average particle size (D50) of the spent positive electrode active material mixture (e.g., the particle size at 50% of the volume fraction in the cumulative particle size distribution) may be 5 μm to 100 μm. Within the above range, the lithium-transition metal oxide to be recycled, such as Li(NCM)O2, can be easily separated from the positive electrode current collector, the conductive material contained in the spent positive electrode active material mixture, and the binder.

[0050] In some embodiments, the spent positive electrode active material mixture may be heat treated before being put into the fluidized bed reactor described below. Impurities such as conductive materials and binders contained in the spent positive electrode active material mixture may be substantially removed or reduced by heat treatment, so that the lithium-transition metal oxide may be introduced into the fluidized bed reactor with high purity.

[0051] The heat treatment temperature may be, for example, about 100° C. to 500° C., preferably about 350° C. to 450° C. Within the above range, impurities may be substantially removed while preventing the lithium-transition metal oxide from being decomposed and damaged.

[0052] For example, in the process of S20 , the spent positive electrode active material mixture may react in the fluidized bed reactor 100 to form a primary precursor mixture 80 .

[0053] like Figure 1 As shown, the fluidized bed reactor 100 may be divided into a reactor body 110 and a lower reactor part 120. The reactor body 110 may include a heating means such as a heater or may be integrated with a heating means such as a heater.

[0054] The above-mentioned dispersion plate may be coupled to the bottom of the reactor body 110. Therefore, a portion below the dispersion plate of the reactor body 110 may be defined as a lower reactor part 120.

[0055] The spent positive active material mixture may be supplied to the reactor body 110 through the supply flow path 108a. The spent positive active material mixture may be dropped through the supply flow path 108a connected to the upper portion of the reactor body 110. The spent positive active material mixture may be introduced into the bottom of the reactor body 110 through the supply flow path (not shown).

[0056] The reaction gas for converting the spent positive active material mixture into the primary precursor may be supplied to the reactor body 110 through the first flow path 104 connected to the lower reactor part 120. In an exemplary embodiment, the reaction gas may include a reducing gas, and may include, for example, hydrogen (H2).

[0057] The reaction gas may be released into the reactor body 110 through the injection column 60 included in the dispersion plate. The reaction gas may be supplied from the bottom of the fluidized bed reactor 100 to contact the spent positive active material mixture, so that the spent positive active material mixture may react with the reaction gas while moving to the upper portion of the reactor to be converted into a primary precursor.

[0058] In some embodiments, the lithium-transition metal oxide can be reduced by a reducing gas to produce a primary lithium precursor, which includes, for example, lithium hydroxide (LiOH), lithium oxide (e.g., Li2O) and a transition metal or transition metal oxide. For example, Ni, Co, NiO, CoO and MnO can be produced together with the primary lithium precursor by a reduction reaction.

[0059] The reduction reaction in the reactor body 110 may be performed at a temperature of about 400 to 700° C., preferably 450 to 550° C. Within the reaction temperature range, the reduction reaction may be promoted without causing reaggregation and recombination of the primary lithium precursor and the transition metal / transition metal oxide.

[0060] In some embodiments, a carrier gas may be supplied together with the reaction gas from the lower reactor portion 120. For example, the carrier gas may be supplied through the first flow path 104 together with the reaction gas.

[0061] For example, the carrier gas may include an inert gas such as nitrogen (N2) or argon (Ar). The carrier gas may also be released and supplied through the injection column 60 of the dispersion plate to promote the formation of the fluidized bed. For example, the formation of a cyclone by the carrier gas may be promoted.

[0062] A primary precursor mixture 80 including a primary lithium precursor and a primary transition metal precursor (eg, a transition metal or a transition metal oxide) may be formed in the reactor body 110 .

[0063] The primary lithium precursor may include, for example, lithium hydroxide, lithium oxide, and / or lithium carbonate.

[0064] For example, in the process of S30 , the primary precursor mixture 80 may be cooled using the first refrigerant and the second refrigerant.

[0065] In an exemplary embodiment, the first refrigerant may be a gas and the second refrigerant may be a liquid. When the first refrigerant and the second refrigerant have different phases, the primary precursor mixture 80 can be cooled more effectively by adjusting the content ratio of the liquid having a fast cooling rate and the gas having a relatively slow cooling rate.

[0066] For example, the first refrigerant may include an inert gas. For example, the first refrigerant may include nitrogen or argon. For example, the first refrigerant may gradually cool the primary precursor mixture 80, thereby suppressing damage to the fluidized bed reactor 100 caused by rapid cooling of the primary precursor mixture 80.

[0067] For example, the second refrigerant may contain water. For example, the second refrigerant may be sprayed in the form of mist to the primary precursor mixture 80 to assist the cooling of the first refrigerant. Therefore, the cooling rate of the primary precursor mixture 80 may be further increased compared to the cooling rate when the first refrigerant is used alone. In addition, the second refrigerant may be used as an auxiliary refrigerant together with the gaseous first refrigerant, thereby suppressing damage to the fluidized bed reactor 100 due to rapid cooling.

[0068] For example, the first refrigerant may be injected into the primary precursor mixture 80 as a main refrigerant, and the second refrigerant may be injected into the primary precursor mixture 80 as an auxiliary refrigerant. Therefore, the cooling efficiency may be appropriately improved while preventing damage to the fluidized bed reactor 100.

[0069] For example, the injection rate ratio (e.g., flow rate ratio) of the first refrigerant to the second refrigerant may be in the range of about 0.1 to 10. Within the range of the injection rate ratio, the cooling rate of the primary precursor mixture 80 may be increased, and the liquid second refrigerant may be prevented from accumulating in the lower portion of the fluidized bed reactor 100.

[0070] In some exemplary embodiments, the first refrigerant and the second refrigerant may be sprayed so that the primary precursor mixture 80 may be cooled to below about 100° C. More preferably, the primary precursor mixture 80 may be cooled to about 50° C. to 100° C. When the primary precursor mixture 80 is cooled to the above temperature range, the recovery efficiency of the lithium precursor may be improved when the lithium precursor is recovered, which will be described below.

[0071] Figure 2 is a schematic top view showing a dispersion plate of a fluidized bed reactor according to an exemplary embodiment. Figure 3 Schematic cross-sectional view showing the configuration of the injection column of the dispersion plate according to an exemplary embodiment. For example, Figure 3 is along Figure 2 A cross-sectional view taken along line II'.

[0072] Reference Figure 2 and Figure 3 The dispersion plate may include a bottom plate 50 and a plurality of injection pillars 60 and auxiliary pillars 70 protruding from the bottom plate 50 .

[0073] For example, the injection column 60 may inject the first refrigerant, and the auxiliary column 70 may inject the second refrigerant. For example, the auxiliary column 70 may inject the first refrigerant and the second refrigerant together.

[0074] The bottom plate 50 may be, for example, a circular or polygonal plate formed of a metal material or a ceramic material.

[0075] The injection pillars 60 and the auxiliary pillars 70 may have a shape protruding from the upper surface of the base plate 50. The injection pillars 60 and the auxiliary pillars 70 may be arranged on the upper surface of the base plate 50 in a constant arrangement form (e.g., a constant grid arrangement) and arrangement pitch for uniform diffusion and distribution of the reaction gas.

[0076] For example, the injection pillars 60 and the auxiliary pillars 70 may have an array shape or a grid shape arranged at the vertices of a polygon such as a triangle, a quadrilateral, or a hexagon. For example, the injection pillars 60 and the auxiliary pillars 70 may be appropriately arranged to reduce an area (e.g., a dead zone D) where the injection pillars 60 are not formed around the bottom plate 50. Figure 2 As shown, the implant pillars 60 may be arranged according to, for example, an equilateral triangle pitch.

[0077] like Figure 2As shown, the support unit of the dispersion plate may be connected to the central portion (C) of the dispersion plate. In one embodiment, for example, the injection column 60 may also be disposed in the central portion C, and the auxiliary column 70 may also be arranged together.

[0078] For example, the injection column 60 may include a column body and a cap portion. For example, the injection column 60 may have a bubble cap or tuyere structure. For example, the injection column 60 may include an injection hole 60a that penetrates the column body.

[0079] In one embodiment, an inclination angle between a vertical direction to the upper surface of the bottom plate 50 and the injection hole may be about 30° to 60°.

[0080] For example, the injection hole may be formed to be inclined with respect to the upper surface of the base plate 50 so that the reaction gas may be injected to diffuse in the direction of the base plate 50. Therefore, the reaction material (e.g., precursor particles or active material particles) deposited on the upper surface of the base plate 50 may rise, thereby promoting the formation of the fluidized bed.

[0081] For example, the auxiliary column 70 may include a spray. In this case, the first refrigerant or the second refrigerant may be sprayed in the form of mist, thereby improving the cooling efficiency of the primary precursor mixture 80.

[0082] In some exemplary embodiments, the ratio of the number of injection pillars 60 formed on the bottom plate 50 to the number of auxiliary pillars 70 may be 1 to 1000, for example, 10 to 100. For example, within the range of the number ratio, the ratio of the first refrigerant and the second refrigerant injected per unit time may be easily adjusted, so that the cooling speed of the primary precursor mixture 80 may be effectively controlled.

[0083] In some exemplary embodiments, the fluidized bed reactor 100 may further include a second flow path 106 for supplying the first refrigerant or the second refrigerant from the lower reactor portion 120 .

[0084] For example, the first flow path 104 may be connected to the injection column 60, and the second flow path 106 may be connected to the auxiliary column 70. For example, the first refrigerant may be supplied to the lower reactor portion 120 through the first flow path 104 to be injected into the reactor body 110 through the injection column 60. For example, the first refrigerant or the second refrigerant may be supplied through the second flow path 106 to be injected into the reactor body 110 through the auxiliary column 70.

[0085] For example, the second flow path 106 may include a first inlet 106 a through which the first refrigerant may be supplied and a second inlet 106 b through which the second refrigerant may be supplied.

[0086] For example, the first refrigerant and the second refrigerant may be simultaneously injected into the first refrigerant inlet 106a and the second refrigerant inlet 106b, respectively. In this case, the first refrigerant and the second refrigerant may be simultaneously injected into the primary precursor mixture 80 located inside the reactor body 110 through the auxiliary column 70.

[0087] In some exemplary embodiments, the second flow path 106 may further include an injection control unit for controlling the injection of the first refrigerant and the second refrigerant. For example, the supply of the first refrigerant may be blocked by the injection control unit. In this case, only the second refrigerant may be supplied to the auxiliary column 70. For example, the supply of the second refrigerant may be blocked by the injection control unit. In this case, only the first refrigerant may be supplied to the auxiliary column 70.

[0088] The lithium precursor may be selectively recovered from the cooled primary precursor mixture 80 (eg, in the process of S40 ).

[0089] In some embodiments, the cooled primary lithium precursor mixture 80 may be washed with water to recover the primary lithium precursor. Primary lithium precursor particles in the form of lithium hydroxide (LiOH) may be substantially dissolved in water by washing, separated from the transition metal precursor, and recovered in advance. A lithium precursor substantially consisting of lithium hydroxide may be obtained by subjecting lithium hydroxide dissolved in water to a crystallization process, etc.

[0090] In one embodiment, the primary lithium precursor in the form of lithium oxide and lithium carbonate may be substantially removed by the washing process. In one embodiment, the primary lithium precursor particles in the form of lithium oxide and lithium carbonate may be at least partially converted to lithium hydroxide by the washing process.

[0091] In some embodiments, the primary lithium precursor can be reacted with a carbon-containing gas such as carbon monoxide (CO), carbon dioxide (CO2), etc. to obtain lithium carbonate (e.g., Li2CO3) as a lithium precursor. A crystalline lithium precursor can be obtained by reacting with a carbon-containing gas. For example, lithium carbonate can be collected by injecting a carbon-containing gas together during a scrubbing process.

[0092] In some embodiments, the transition metal precursor may be obtained from the collected primary transition metal precursor (eg, in the process of S50 ).

[0093] For example, the primary lithium precursor may be collected through the outlet 108b, and then the primary transition metal precursor may be recovered. Thereafter, the primary transition metal precursor may be treated with an acid solution to form a precursor in the form of an acid salt of each transition metal.

[0094] In one embodiment, sulfuric acid can be used as the acid solution. In this case, NiSO4, MnSO4 and CoSO4 can each be recovered as a transition metal precursor.

[0095] As described above, the primary precursor mixture 80 can be formed by a dry process, and then the lithium precursor and the transition metal precursor can be selectively extracted by washing and acid solution treatment, respectively. Therefore, the purity and selectivity of each metal precursor can be improved, the workload of the wet process can be reduced, and the amount of wastewater and by-products can also be reduced.

Claims

1. A method for recovering active metals from a lithium secondary battery, comprising: preparing a waste positive electrode active material mixture from waste positive electrodes of lithium secondary batteries; forming a primary precursor mixture by reacting the spent positive electrode active material mixture with a reaction gas in a fluidized bed reactor; cooling the primary precursor mixture by injecting different first and second refrigerants into the primary precursor mixture; and selectively recovering a lithium precursor from the cooled primary precursor mixture; The first refrigerant is a gas and contains an inert gas, and the second refrigerant is a liquid.

2. The method for recovering active metals from lithium secondary batteries according to claim 1, wherein: The first refrigerant includes nitrogen or argon.

3. The method for recovering active metals from lithium secondary batteries according to claim 1, wherein: The second refrigerant includes water.

4. The method for recovering active metals from lithium secondary batteries according to claim 1, wherein: The injection rate ratio of the first refrigerant to the second refrigerant is 0.1 to 10.

5. The method for recovering active metals from lithium secondary batteries according to claim 1, wherein: The cooling of the primary precursor mixture reduces the temperature of the primary precursor mixture to below 100°C.

6. The method for recovering active metals from lithium secondary batteries according to claim 1, wherein: The fluidized bed reactor comprises: a reactor body; and a dispersion plate coupled to the bottom of the reactor body, the dispersion plate comprising a bottom plate; and an injection column and an auxiliary column protruding from an upper surface of the bottom plate, Wherein, cooling the primary precursor mixture includes injecting the first refrigerant through the injection column and injecting the second refrigerant through the auxiliary column.

7. The method for recovering active metals from lithium secondary batteries according to claim 6, wherein: The first refrigerant and the second refrigerant are injected together through the auxiliary column.

8. The method for recovering active metals from lithium secondary batteries according to claim 6, wherein: Forming the primary precursor mixture includes supplying a reactive gas including a reducing gas through the injection column.

9. The method for recovering active metals from lithium secondary batteries according to claim 6, wherein: The fluidized bed reactor further includes a first flow path and a second flow path for supplying the first refrigerant and the second refrigerant, respectively, from a lower portion of the fluidized bed reactor.

10. The method for recovering active metals from lithium secondary batteries according to claim 9, wherein: The first flow path is connected to the injection column, and the second flow path is connected to the auxiliary column.

11. A fluidized bed reactor comprising: Reactor body; a dispersion plate coupled to the bottom of the reactor body, the dispersion plate comprising a bottom plate and an injection column and an auxiliary column protruding from an upper surface of the bottom plate; a first flow path for supplying a gaseous first refrigerant from a lower portion of the reactor to the injection column; and a second flow path for supplying a liquid second refrigerant from a lower portion of the reactor to the auxiliary column, wherein the first flow path is connected to the injection column through the lower reactor portion, The second flow path is connected to the auxiliary column, and The first flow path is independent of the second flow path.

12. The fluidized bed reactor according to claim 11, wherein: The injection pillars and the auxiliary pillars are arranged at a constant interval or in a constant grid shape.

13. The fluidized bed reactor according to claim 11, wherein: The ratio of the number of the injection columns to the number of the auxiliary columns is 1 to 1000.

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