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

Abstract

In a method for recovering active metals from lithium secondary batteries according to an embodiment of the present invention, a waste cathode active material mixture is prepared from waste cathodes of lithium secondary batteries. The waste cathode active material mixture is reacted with a reactant gas in a fluidized bed reactor to form a pre-precursor mixture. Different first and second refrigerants are injected into the pre-precursor mixture to cool the pre-precursor mixture. A lithium precursor is selectively recovered from the pre-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, and more particularly 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 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. Lithium secondary batteries have been actively developed and applied as secondary batteries 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 further contain a transition metal such as nickel, cobalt, or manganese.

[0004] Because the positive electrode active material uses the aforementioned expensive valuable metals, the production of the positive electrode 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 positive electrode active materials is progressing.

[0005] Conventionally, valuable metals have been recovered by leaching waste cathode active material in a strong acid such as sulfuric acid, but this wet process has disadvantages in terms of regeneration selectivity and regeneration time, and can cause environmental pollution. Therefore, research is being conducted into methods for recovering valuable metals using dry-based reactions by contact with reactive gases.

[0006] However, the size of the active material particles supplied for the dry reaction becomes smaller, which can lead to non-uniform reaction due to aggregation, and the recovery rate of the active material can be reduced due to localized non-uniform supply of the reaction gas within the reactor.

[0007] For example, Korean Patent No. 10-0709268 discloses an apparatus and method for recycling waste manganese batteries and alkaline batteries, but does not provide a dry-based method for recovering valuable metals with high selectivity and high yield. 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 having excellent recovery efficiency.

[0009] An object of the present invention is to provide a method for recovering active metals from a lithium secondary battery with excellent recovery efficiency. [Means for solving the problem]

[0010] In a method for recovering active metals from lithium secondary batteries according to an embodiment of the present invention, a mixture of waste cathode active materials is prepared from waste cathodes of lithium secondary batteries, the mixture of waste cathode active materials is reacted in a fluidized bed reactor to form a pre-precursor mixture, first and second coolants, which are different from each other, are injected into the pre-precursor mixture to cool the pre-precursor mixture, and a lithium precursor is selectively recovered from the cooled pre-precursor mixture.

[0011] In some embodiments, the first refrigerant may be a gas and the second refrigerant may be a liquid.

[0012] In some embodiments, the first refrigerant may include nitrogen or argon.

[0013] In some embodiments, the second refrigerant may include water.

[0014] In some embodiments, the ratio of the injection rate of the first refrigerant to the second refrigerant can be adjusted to 0.1-10.

[0015] In some embodiments, cooling the pre-precursor mixture may reduce the temperature of the pre-precursor mixture to 100° C. or less.

[0016] In some embodiments, the fluidized bed reactor includes a reactor body and a distribution plate connected to the bottom of the reactor body, and the distribution plate includes a base plate and a spray column and an auxiliary column protruding from an upper surface of the base plate. The first refrigerant can be sprayed from the spray column, and the second refrigerant can be sprayed from the auxiliary column.

[0017] In some embodiments, the auxiliary column can inject both the first refrigerant and the second refrigerant.

[0018] In some embodiments, the injection column may provide the reactant gas including a reducing gas.

[0019] In some embodiments, the fluidized bed reactor may further include a first flow path and a second flow path that supply the first and second refrigerants, respectively, from a lower portion of the fluidized bed reactor.

[0020] In some embodiments, the first flow path can connect to the injection column and the second flow path can connect to the auxiliary column.

[0021] A fluidized bed reactor according to an exemplary embodiment may include a reactor body, a base plate coupled to the bottom of the reactor body, and a distribution plate including a spray column and an auxiliary column protruding from an upper surface of the base plate, a first flow path for supplying a first refrigerant in a gaseous state from a lower portion of the reactor to the spray column, and a second flow path for supplying a second refrigerant in a liquid state from the lower portion of the reactor to the auxiliary column.

[0022] In some embodiments, the second flow path can include a first inlet through which the first refrigerant is supplied and a second inlet through which the second refrigerant is supplied.

[0023] In some embodiments, the injection columns and auxiliary columns may be arranged at a regular pitch or in a regular grid.

[0024] In some embodiments, the ratio of the number of injection columns to the number of auxiliary columns may be between 1 and 1000. [Effects of the Invention]

[0025] According to the above exemplary embodiment, the pre-precursor mixture formed in the fluidized bed reactor can be rapidly cooled by injecting the first refrigerant in a gaseous state and the second refrigerant in a liquid state into the pre-precursor mixture, thereby improving the recovery efficiency of the lithium precursor.

[0026] In the method for recovering active metals for a lithium secondary battery according to an exemplary embodiment, the ratio of the injection rates of the first and second refrigerants can be adjusted, thereby minimizing damage to the fluidized bed reactor due to rapid cooling of the pre-precursor mixture. Furthermore, the amount of the second refrigerant accumulating in the lower part of the fluidized bed reactor can be minimized, allowing subsequent processes to proceed more quickly. [Brief explanation of the drawings]

[0027] [Figure 1] FIG. 1 is a schematic diagram illustrating a fluidized bed reactor according to an exemplary embodiment and a method for recovering active metals of a lithium secondary battery using the fluidized bed reactor. [Figure 2] FIG. 2 is a schematic plan view illustrating a distribution plate of a fluidized bed reactor according to an exemplary embodiment. [Figure 3] FIG. 3 is a schematic cross-sectional view showing the structure of the injection columns and auxiliary columns of the distribution plate according to an exemplary embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0028] An embodiment of the present invention provides a method for recovering active metals from lithium secondary batteries with high purity and high yield by using a first refrigerant in a gaseous state and a second refrigerant in a liquid state, and also provides a fluidized bed reactor that can be used for recovering active metals from lithium secondary batteries.

[0029] Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings. However, these embodiments are merely illustrative of the present invention and are not intended to limit the present invention.

[0030] 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.

[0031] Referring to FIG. 1, a waste positive electrode active material mixture can be prepared from waste positive electrodes of lithium secondary batteries (for example, step S10).

[0032] 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.

[0033] 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.

[0034] In some embodiments, the positive electrode active material may include a compound represented by Formula 1:

[0035] [Chemical formula 1] Li x M1 a M2 b M3 c O y

[0036] In Chemical Formula 1, M1, M2, and M3 are selected from Ni, Co, Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, or B. element 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。

[0037] In some embodiments, the active cathode material may be an NCM-based lithium oxide containing nickel, cobalt, and manganese.

[0038] 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.

[0039] The conductive material may include, for example, a carbon-based material such as graphite, carbon black, graphene, carbon nanotubes, etc. The binder may include, for example, a resin material such as vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, etc.

[0040] 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 powder form. The waste cathode active material mixture may include a lithium-transition metal oxide powder, such as an NCM-based lithium oxide powder (e.g., Li(NCM)O), as described above.

[0041] The term "waste positive electrode active material mixture" used in this application may refer to raw materials that are input into a fluidized bed reaction process described below after the positive electrode current collector has been substantially removed from the waste positive electrode.

[0042] In one embodiment, the waste cathode active material mixture may include particles of a cathode active material 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.

[0043] In some embodiments, the average particle size (D50) of the waste cathode active material mixture (e.g., the particle size at a volume fraction of 50% in the cumulative particle size distribution) may be about 5 to 100 μm. Within this range, the lithium-transition metal oxide to be recovered, such as Li(NCM)O, can be easily separated from the cathode current collector, conductive material, and binder contained in the waste cathode active material mixture.

[0044] 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, and the lithium-transition metal oxide may be introduced into the fluidized bed reactor with high purity.

[0045] The temperature of the heat treatment may 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.

[0046] 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 80.

[0047] 1, the fluidized bed reactor 100 can be divided into a reactor main body 110 and a reactor lower portion 120. The reactor main body 110 can include a heating means such as a heater or can be integrated with a heating means.

[0048] The dispersion plate may be attached to the bottom of the reactor body 110. Thus, the lower part of the dispersion plate in the reactor body 110 may be defined as the reactor lower part 120.

[0049] The waste cathode active material mixture may be supplied into the reactor body 110 through the supply channel 108a. The waste cathode active material mixture may be dropped through the supply channel 108a connected to the top of the reactor body 110. The waste cathode active material mixture may also be introduced through a supply channel (not shown) connected to the bottom of the reactor body 110.

[0050] 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 first flow path 104 connected to the reactor lower portion 120. According to an exemplary embodiment, the reactant gas may include a reducing gas, such as hydrogen (H).

[0051] The reaction gas may be injected into the reactor body 110 through injection columns 60 included in the dispersion plate. As the reaction gas is supplied from the lower part of the fluidized bed reactor 100 and contacts the waste cathode active material mixture, the waste cathode active material mixture moves to the upper part of the reactor and reacts with the reaction gas to be converted into the pre-precursor.

[0052] In some embodiments, the lithium-transition metal oxide is reduced by the reducing gas, e.g., to lithium hydroxide (LiOH), lithium oxide (e.g., Li 2 O ), and a transition metal or transition metal oxide. For example, a reductive reaction can produce Ni, Co, NiO, CoO, and MnO along with the reserve lithium precursor.

[0053] The reduction reaction in the reactor main body 110 can be carried out at a temperature of about 400 to 700° C., preferably about 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.

[0054] In some embodiments, a carrier gas may be supplied together with the reactant gas from the reactor lower portion 120. For example, the carrier gas may be supplied together with the reactant gas via the first flow path 104.

[0055] For example, the carrier gas may include an inert gas such as nitrogen (N2) or argon (Ar). The carrier gas may also be injected through the dispersion 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 cyclone for the formation of a fluidized bed.

[0056] Within the reactor body 110, a pre-precursor mixture 80 can be formed that includes a pre-lithium precursor and a pre-transition metal precursor (eg, the transition metal or transition metal oxide).

[0057] The reserve lithium precursors can include, for example, lithium hydroxide, lithium oxide and / or lithium carbonate.

[0058] For example, in step S30, the pre-precursor mixture 80 can be cooled using a first refrigerant and a second refrigerant.

[0059] According to 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 pre-precursor mixture 80 can be cooled more effectively by adjusting the content ratio of the liquid, which has a fast cooling rate, and the gas, which has a relatively slow cooling rate.

[0060] For example, the first coolant may include an inert gas. For example, the first coolant may include nitrogen or argon. For example, the first coolant may gradually cool the pre-precursor mixture 80, thereby preventing damage to the fluidized bed reactor 100 due to rapid cooling of the pre-precursor mixture 80.

[0061] For example, the second refrigerant may include water. For example, the second refrigerant may be sprayed onto the preliminary precursor mixture 80 in the form of a mist to assist the cooling performed by the first refrigerant. This may increase the cooling rate of the preliminary precursor mixture 80 compared to when the first refrigerant is used alone. Furthermore, by using the second refrigerant as an auxiliary refrigerant in combination with the first refrigerant in a gaseous state, damage to the fluidized bed reactor 100 due to rapid cooling may be suppressed.

[0062] For example, the first refrigerant may be injected into the preliminary precursor mixture 80 as a main refrigerant, and the second refrigerant may be injected into the preliminary precursor mixture 80 as an auxiliary refrigerant, thereby appropriately improving cooling efficiency while suppressing damage to the fluidized bed reactor 100.

[0063] For example, the injection rate ratio (e.g., flow rate ratio) of the first refrigerant to the second refrigerant may be about 0.1 to 10. Within this range of injection rate ratio, the cooling rate of the pre-precursor mixture 80 is improved, and the accumulation of the second refrigerant in a liquid state at the bottom of the fluidized bed reactor 100 can be prevented.

[0064] In some exemplary embodiments, pre-precursor mixture 80 can be cooled to approximately 100° C. or less by injecting the first refrigerant and the second refrigerant. More preferably, pre-precursor mixture 80 can be cooled to approximately 50 to 100° C. Cooling pre-precursor mixture 80 to this temperature range can improve the recovery efficiency of the lithium precursor during the lithium precursor recovery process described below.

[0065] Fig. 2 is a schematic plan view showing a dispersion plate of a fluidized bed reactor according to an exemplary embodiment. Fig. 3 is a schematic cross-sectional view showing the structure of the injection column of the dispersion plate according to an exemplary embodiment. For example, Fig. 3 is a cross-sectional view taken along line II' in Fig. 2.

[0066] 2 and 3, the distribution plate may include a base plate 50 and a plurality of injection columns 60 and auxiliary columns 70 protruding from the base plate 50.

[0067] For example, the injection column 60 can inject the first refrigerant and the auxiliary column 70 can inject the second refrigerant. For example, the auxiliary column 70 can inject both the first refrigerant and the second refrigerant.

[0068] The base plate 50 may be, for example, a circular or polygonal plate made of metal or ceramic material.

[0069] The injection columns 60 and the auxiliary columns 70 may have a shape that protrudes from the upper surface of the base plate 50. The injection columns 60 and the auxiliary columns 70 may be regularly arranged on the upper surface of the base plate 50 with a certain arrangement pattern (e.g., a certain lattice arrangement) and arrangement pitch to uniformly diffuse and distribute the reaction gas.

[0070] For example, the injection columns 60 and auxiliary columns 70 may have an arrangement or lattice configuration in which they are arranged at the vertices of a polygon such as a triangle, square, or hexagon. For example, the injection columns 60 and auxiliary columns 70 may be appropriately arranged to reduce areas where the injection columns 60 are not formed (e.g., dead zones D) around the periphery of the base plate 50. As shown in Fig. 2, the injection columns 60 may be arranged, for example, at the pitch of an equilateral triangle.

[0071] A support portion of the dispersion plate can be connected to the center portion C of the dispersion plate shown in Figure 2. In one embodiment, the spray column 60 can also be arranged in the center portion C, and the auxiliary column 70 can also be arranged therewith.

[0072] 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 port 60a penetrating the column body.

[0073] In one embodiment, the angle of inclination between the vertical direction from the upper surface of the base plate 50 and the injection port may be about 30 to 60°.

[0074] For example, by forming the injection port at an angle with respect to the upper surface of the base plate 50, the reactive gas can be injected so as to diffuse toward the base plate 50. This causes the reactants (e.g., precursor particles or active material particles) that settle on the upper surface of the base plate 50 to rise, facilitating the formation of a fluidized layer.

[0075] For example, the auxiliary column 70 may include a mist spray, in which case the first or second refrigerant is sprayed in the form of mist, thereby improving the cooling efficiency of the preliminary precursor mixture 80.

[0076] In some exemplary embodiments, the ratio of the number of injection columns 60 to the number of auxiliary columns 70 formed on base plate 50 may be 1 to 1000, for example, 10 to 100. For example, when the ratio is satisfied, the ratio of the first refrigerant and the second refrigerant injected per unit time can be easily adjusted, and the cooling rate of pre-precursor mixture 80 can be efficiently adjusted.

[0077] In some exemplary embodiments, the fluidized bed reactor 100 can further include a second flow path 106 that supplies the first refrigerant or the second refrigerant from a lower reactor portion 120 .

[0078] 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 reactor lower portion 120 via the first flow path 104 and then injected into the reactor main body 110 via the injection column 60. For example, the first refrigerant or the second refrigerant may be supplied via the second flow path 106 and then injected into the reactor main body 110 via the auxiliary column 70.

[0079] For example, the second flow path 106 may include a first inlet 106a for supplying the first refrigerant and a second inlet 106b for supplying the second refrigerant.

[0080] For example, the first refrigerant and the second refrigerant can 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 can be simultaneously injected into the preliminary precursor mixture 80 located inside the reactor body 110 by the auxiliary column 70.

[0081] In some exemplary embodiments, second flow path 106 may further include an injection adjustment unit that adjusts the injection of the first refrigerant and the second refrigerant. For example, the injection adjustment unit may shut off the supply of the first refrigerant. In this case, only the second refrigerant may be supplied to auxiliary column 70. For example, the injection adjustment unit may shut off the supply of the second refrigerant. In this case, only the first refrigerant may be supplied to auxiliary column 70.

[0082] The lithium precursor can be selectively recovered from the cooled pre-precursor mixture 80 (for example, step S40).

[0083] In some embodiments, the cooled pre-precursor mixture 80 can be washed with water to recover the pre-lithium precursor. The water washing process allows the pre-lithium precursor particles in the form of lithium hydroxide (LiOH) to be substantially dissolved in water and preferentially recovered separately from the transition metal precursor. A lithium precursor substantially composed of lithium hydroxide can be obtained, such as by a crystallization process of the lithium hydroxide dissolved in water.

[0084] 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. In 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.

[0085] In some embodiments, the preliminary lithium precursor 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, the carbon-containing gas can be co-injected during the water wash process, and lithium carbonate can be collected.

[0086] In some embodiments, the transition metal precursor can be obtained from the collected preliminary transition metal precursor (eg, step S50).

[0087] For example, the preliminary lithium precursor can be collected through outlet 108b, followed by recovery of the preliminary transition metal precursor, which can then be treated with an acid solution to form precursors in the form of acid salts of the respective transition metals.

[0088] 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.

[0089] As described above, after forming the preliminary precursor mixture 80 through the dry process, the lithium precursor is selectively extracted using a water washing process and the transition metal precursor is selectively extracted using an acid solution. This improves the purity and selectivity of each metal precursor, reduces the load of the wet process, and reduces the increase in wastewater and by-products.

Claims

1. preparing a waste positive electrode active material mixture from waste positive electrodes of lithium secondary batteries; reacting the waste cathode active material mixture with a reactant gas in a fluidized bed reactor to form a pre-precursor mixture; injecting different first and second refrigerants into the pre-precursor mixture to cool the pre-precursor mixture; and selectively recovering a lithium precursor from the cooled preliminary precursor mixture, The fluidized bed reactor comprises: A reactor body; a dispersion plate coupled to the bottom of the reactor body, The dispersion plate is A base plate and an injection column and an auxiliary column protruding from an upper surface of the base plate; The step of cooling the preliminary precursor mixture comprises injecting the first refrigerant through the injection column and injecting the second refrigerant through the auxiliary column.

2. 2. The method for recovering active metals from a lithium secondary battery according to claim 1, wherein the first refrigerant is a gas and the second refrigerant is a liquid.

3. The method for recovering active metals from a lithium secondary battery according to claim 1 , wherein the first refrigerant contains nitrogen or argon.

4. The method for recovering active metals from a lithium secondary battery according to claim 1 , wherein the second refrigerant contains water.

5. 2. The method for recovering active metals from a lithium secondary battery according to claim 1, wherein the ratio of the injection rate of the first refrigerant to the injection rate of the second refrigerant is 0.1 to 10.

6. 2. The method for recovering active metals of a lithium secondary battery according to claim 1, wherein the step of cooling the pre-precursor mixture reduces the temperature of the pre-precursor mixture to 100° C. or less.

7. The method for recovering active metals from a lithium secondary battery according to claim 1 , wherein the first refrigerant and the second refrigerant are both injected through the auxiliary column.

8. 2. The method for recovering active metals of a lithium secondary battery according to claim 1, wherein the step of forming the preliminary precursor mixture comprises supplying the reactant gas containing a reducing gas through the injection column.

9. 2. The method of claim 1, wherein the fluidized bed reactor further comprises 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 a lithium secondary battery 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. The fluidized bed reactor used in the method for recovering active metals from a lithium secondary battery according to claim 1, comprising: A reactor body; a dispersion plate coupled to the bottom of the reactor body, the dispersion plate including a base plate, and a spray column and an auxiliary column protruding from the upper surface of the base plate; a first flow path for supplying a first refrigerant in a gaseous state from a lower portion of the reactor to the injection column; a second flow path for supplying a second refrigerant in a liquid state from a lower portion of the reactor to the auxiliary column.

12. 12. The fluidized bed reactor according to claim 11, wherein the second flow path includes a first inlet through which the first refrigerant is supplied and a second inlet through which the second refrigerant is supplied.

13. 12. The fluidized bed reactor of claim 11, wherein the injection columns and the auxiliary columns are arranged in a regular pitch or regular grid pattern.

14. 12. The fluidized bed reactor of claim 11, wherein the ratio of the number of said injection columns to the number of said auxiliary columns is 1 to 1000.

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