KR101885917B1 - Method for Rematerializing Waste De-NOx Catalyst Using Organic Acid - Google Patents

Abstract

The present invention relates to a method for remanufacturing a waste denitration catalyst, which enables the reuse of waste catalyst by removing organic pollutants in a waste denitration catalyst to be discarded after being used in a power plant or the like.
Since the method of remanufacturing the waste denitration catalyst according to the present invention is a method of removing poisonous substances in the spent catalyst, the amount of effective catalyst components contained in the spent catalyst is minimized, and especially titanium dioxide and tungsten trioxide, which occupy most of the denitration catalyst, It is possible to reduce the cost of production of the catalyst by recovering and recycling the catalyst. Further, instead of separating and extracting tungsten and vanadium, which are expensive to recover from spent catalyst, poisoning of sodium, potassium, calcium, Since titanium dioxide and tungsten trioxide are recovered by removing the material, the cost required for the materialization process is small, and the recovered titanium dioxide and tungsten trioxide can be reused as a catalyst raw material without a separate processing step. The process can be reduced and vanadium pentoxide, which is a basic component of the denitration catalyst, can not be removed Since it is advantageous to reduce the amount of doped vanadium pentoxide.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for remineralizing a waste denitration catalyst using an organic acid,

The present invention relates to a method for remanufacturing a waste denitration catalyst, which enables the reuse of waste catalyst by removing organic pollutants in a waste denitration catalyst to be discarded after being used in a power plant or the like.

With rapid economic development, industrialization requires enormous amount of energy. As a result, the amount of fossil fuels has increased and the emission of a large amount of environmental pollutants has been made indiscreetly. As a result, serious environmental destruction has been caused, and in recent years, It is an opportunity to re-recognize the importance of

As the problem of air pollution among environmental pollution sources becomes more serious and the risk of nitrogen oxides in air pollution becomes important, regulation of emission of nitrogen oxides is strengthened. Most of domestic power generation facilities are equipped with deNOx system have.

The domestic market for NOx catalysts is gradually increasing from 40,000 ㎥ in 2011 to 45,000 ㎥ in 2015, and the cost of catalysts is gradually increasing from 150 billion won annually.

The denitration catalyst is contaminated by various routes such as dust, sulfur, alkali metal, arsenic, and phosphorus compounds contained in the exhaust gas and thereby the catalytic activity is gradually lowered. In general, the replacement cycle of the catalyst used in the exhaust- It has been replaced every three to five years.

The waste catalyst, which is replaced with depletion, is separated into waste and disposed of at the designated site. However, the recycled value of the waste catalyst is high because the waste catalyst contains valuable metals and various kinds of valuable metals. It is necessary to acquire the technology of recycling the spent catalyst because it can increase the competitiveness due to the reduction and increase the competitiveness with foreign companies.

The composition of the denitration catalyst varies depending on the manufacturer and the application, but most of the initial raw materials are composed of 80 to 90% of titanium dioxide, 5 to 10% of tungsten trioxide, and 1 to 2% of vanadium pentoxide. There is known a valuable metal recovering technique in which tungsten and vanadium metal classified as rare metals in the denitrification catalyst components (titanium dioxide, tungsten trioxide, vanadium pentoxide, etc.) are individually extracted by an alkaline wet leaching method.

The alkaline wet leaching method is a technique of extracting and reusing high value added tungsten and vanadium. Such a valuable metal recovery technology has a low recovery rate of tungsten and vanadium and a very difficult extraction process, and recovery of titanium dioxide Therefore, it is costly to apply to the field of catalyst materialization, and thus the efficiency of resource recycling is not satisfied.

In order to solve such a problem, Korean Patent Registration No. 1360292 discloses a method for recovering valuable metals from a spent catalyst by using a thermophilic strain, wherein the oil component of the waste catalyst generated in the petroleum refining step is removed first Fermenting a fermenting strain which oxidizes iron and sulfur in a non-ferrous 9K medium and inoculating the spent catalyst to recover biologically leached ferrous metal.

The present invention can be economically achieved by using a biological method and can raise the leaching rate of nickel (Ni) and vanadium (V) in a short time, and can recover iron (Fe), molybdenum (Mo) and aluminum However, titanium (Ti) and tungsten (W), which are the most abundant components in the catalyst, are difficult to be recovered and thus are not effective in terms of recycling the spent catalyst.

In addition, Korean Patent Publication No. 1543243 discloses a method for separating and recovering molybdenum and vanadium, which are valuable metals, from a desulfurization spent catalyst, and an organic acid (oxalic acid) is added to a hydrodesulfurized waste catalyst containing molybdenum and vanadium (Amine, 2-hydroxy-5-nonylacetophenone oxime, tri-butyl phosphate) and a diluent (kerosene) are added to recover the molybdenum, and the molybdenum is recovered from the extraction filtrate , And the vanadium is recovered by stripping with a stripping agent (sodium carbonate or sulfuric acid).

The present invention can separate and recover molybdenum and vanadium at a high ratio from the remanufacturing solution of the hydrodesulfurized spent catalyst, and the vanadium recovered through the additional process can be used as the impregnation solution used in the preparation of the catalyst for the selective catalytic reduction reaction , The catalyst component contained in the spent catalyst can not be recovered from the organic acid but can not be recovered from titanium and tungsten, which are the major components of the catalyst. Thus, it is not economical to actually apply it to the industrial field.

DISCLOSURE Technical Problem Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a waste denitration catalyst which efficiently removes poisonous substances contained in a waste denitration catalyst, instead of a conventional method of separating and recovering valuable metals in a waste denitration catalyst, And to provide a method of materialization.

In order to solve the above problems, the present invention provides a method for removing NOx from a waste denitration catalyst module, A pretreatment step of pulverizing the collected spent catalyst component to a particle size of 100 to 2,000 mu m and then removing a metallic foreign substance in the waste catalyst component with a magnet having a strength of 7000 to 12000 Gauss; The pretreated spent catalyst is mixed with an aqueous solution of EDTA at a concentration of 0.1 to 1.0 M in an amount of 1: 5 to 10 by volume (spent catalyst: EDTA aqueous solution), stirred at 300 to 500 rpm at a temperature of 120 to 120 ° C for 30 to 120 minutes Thereby removing the poisonous substance in the spent catalyst. The spent catalyst in which the poisoning substance is primarily removed is treated with 0.1 to 2.0 M sulfuric acid aqueous solution or 0.1 to 2.0 M hydrochloric acid aqueous solution with 0.1 to 1.0 M hydrogen peroxide solution and 4 to 6: 4 to 6 volume ratio sulfuric acid aqueous solution or hydrochloric acid aqueous solution : Hydrogen peroxide solution) and reacting the reaction mixture with the reaction solution in a volume ratio of 1: 5 to 10: 10 (waste catalyst: reaction solution) to remove the poisoning material in the spent catalyst; Filtering the waste catalyst from which the poisoning material has been secondarily removed by filtration; Heating the washed spent catalyst at 140 to 160 ° C for 40 to 80 minutes, and then calcining at 300 to 450 ° C for 10 to 150 minutes; And finely pulverizing the calcined waste catalyst. The present invention also provides a method of remineralizing a waste denitration catalyst using an organic acid.

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Since the method of remanufacturing the waste denitration catalyst according to the present invention is a method of removing poisonous substances in the spent catalyst, the amount of effective catalyst component contained in the waste catalyst is minimized, and titanium dioxide and tungsten trioxide, which occupy most of the denitration catalyst, Most of the catalyst can be recovered and recycled to reduce the manufacturing cost of the catalyst.

In addition, instead of separating and extracting tungsten and vanadium, which are costly to recover from waste catalysts, removing poisoning substances such as sodium, potassium, calcium, and sulfur trioxide, which inhibit catalytic activity, to recover titanium dioxide and tungsten trioxide Since titanium dioxide and tungsten trioxide recovered at a low cost for the materialization process can be reused as a catalyst raw material without having to undergo a separate processing step, the manufacturing process of the materialization can be reduced and vanadium pentoxide, which is a basic component of the denitration catalyst, It is advantageous in that the amount of vanadium pentoxide can be reduced.

1 is a flowchart showing a method of removing a poisonous substance from a waste denitration catalyst according to the present invention and a method for recovering a waste catalyst.
FIG. 2 is a process diagram showing a pretreatment process during the materialization process of the waste denitration catalyst according to the present invention. FIG.
FIG. 3 is a process diagram showing a process of removing a poisonous substance from a pretreated waste denitration catalyst to make it a material.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for remanufacturing a waste denitration catalyst based on tungsten trioxide (WO ₃ -TiO ₂ ) used in domestic and overseas power plants and the like. The waste catalyst module is disassembled and air- Separating and pulverizing the waste catalyst component, collecting the waste catalyst component, pretreating the waste catalyst component with a magnet to remove metallic foreign substances, and removing the poisoning substance in the spent catalyst by reacting the pretreated waste catalyst with organic acid , Filtering and washing the waste catalyst and the reaction solution using pressure or vacuum, firing the washed spent catalyst, and finely dividing the fired waste catalyst to a fine size. Provides a method of materialization.

The present invention is the main component of the catalyst material by removing the causative factors of sodium that instead of extracting a specific component of the waste removal catalyst decreases the NOx removal efficiency (Na), potassium (K), calcium (Ca), sulfur trioxide (SO _3), etc. By recovering titanium dioxide, tungsten trioxide, and vanadium pentoxide, it is possible to minimize the loss of these waste catalysts during the reconditioning of spent catalysts.

Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

It is to be understood, however, that the invention is not to be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Will be apparent to those skilled in the art to which the present invention pertains.

FIG. 1 is a flowchart showing a method for remineralizing a waste denitration catalyst using an organic acid according to the present invention.

The method for remineralizing a waste denitration catalyst according to the present invention includes a pretreatment step (S10) for collecting waste catalysts from a waste denitration catalyst module to remove metallic foreign substances. The waste denitration catalyst module is disassembled and air- And the spent catalyst is collected, and the metallic foreign substance in the spent catalyst is removed using a magnet.

FIG. 2 is a flow chart of the preprocessing step S10 included in the flow chart.

In the pretreatment step S10, the wastewater denitration catalyst module 11 based on tungsten trioxide-WO ₃ -TiO ₂ , which is supplied to domestic and overseas power plants, is separated, and then an air compressor 15 Air brushing at a flow rate of ~ 400 L / min, metal mesh separation and crushing, and metallic or foreign materials are removed using magnets or electromagnets.

The waste denitration catalyst module may be applied to heavy fuel oil power generation, coal-fired power generation waste denitration catalyst and combined-cycle power generation waste denitration catalyst, and may be applied to all of the waste denitration catalysts based on tungsten trioxide-titanium dioxide.

The module type of the waste denitration catalyst can be divided into a plate type 13 and a honeycomb type 14. In the case of a plate type, a canister 12 is separated from a waste denitration catalyst module 11 The plate catalyst 13 is separated from the canister 12, and then the catalyst is separated from the metal net of the plate catalyst 13 and pulverized. In the case of the honeycomb type, the entire catalyst is crushed.

The pulverized spent catalyst 16 preferably has a particle size of 100 to 2,000 mu m and is preferably made of a metallic foreign substance in the spent catalyst 16 or a metallic contaminant 19 in the spent catalyst 16 by using a magnet or electromagnet 18 having a strength of 7000 to 12000 Gauss, To obtain a pretreated spent catalyst (17).

Next, the organic acid solution is reacted with the pretreated spent catalyst 17 to remove poisonous substances in the spent catalyst (S20).

The pretreated spent catalyst 17 is reacted with an appropriate organic acid solution because the type and content of the poisonous substance are different depending on the catalyst type of the power plant, the fuel, the control conditions of the selective catalytic reduction (SCR) Remove poisonous substances and react by adjusting temperature (room temperature ~ 120 ℃), stirring speed (300 ~ 500 rpm) and time (30 ~ 120min).

Citric acid (C ₆ H ₈ O ₇ ) and / or ethylenediaminetetraacetic acid (EDTA) are preferably used as the organic acid, citric acid is preferably an aqueous solution having a concentration of 0.1 to 1.5 M and EDTA is preferably 0.1 to 1.0 M When citric acid and EDTA are used together, it is preferable to mix citric acid: EDTA = 4 to 6: 4 to 6 by volume. It is more preferable that citric acid and EDTA are mixed in the same amount based on volume.

Most substances that degrade the denitrification performance of spent catalysts are alkaline (earth) metal oxides and metal oxides of phosphorus and arsenic.

EDTA has four carboxyl groups and a negative charge can be generated in the oxygen due to the drop of H ⁺ ion. As a result, EDTA is adsorbed on the waste catalyst when EDTA is added to a ligand-binding metal and most heavy metals, As the metal ions are combined with the metal ions to form complex ions, the metal component acting as a poisoning substance can no longer coordinate with the waste catalyst component. Therefore, the waste catalyst reacted with EDTA is filtered to remove the poisonous substance from the waste catalyst can do.

In addition, hydrogen peroxide can be added to the organic acid to remove poisonous substances. For example, citric acid or EDTA may be mixed with hydrogen peroxide to remove poisonous substances from the spent catalyst 17, and citric acid (or EDTA) = 4 to 6: 4 to 6 by volume, and it is more preferable that citric acid (or EDTA) and hydrogen peroxide are mixed in the same amount in terms of volume.

The poisoning material removing step (S20) may be further decrypted as an organic acid reaction solution after decrypting the organic acid reaction solution as described above. If necessary, the inorganic acid added to the organic acid or the inorganic acid used for further decryption may be 0.1 to 2.0 M Aqueous solution of sulfuric acid (H ₂ SO ₄ ) and 0.1 to 2.0 M of hydrochloric acid (HCl) solution may be used. In addition, 0.1 to 1.0 M of hydrogen peroxide (H ₂ O ₂ ) may be added .

In addition, the inorganic acid reaction solution used for the further decryption is preferably a combination of sulfuric acid, hydrogen peroxide, hydrochloric acid and hydrogen peroxide, and more preferably the mixing ratio of the combined substances is 4: 6: 4 to 6: It is most preferable that the standards are mixed with the same amount.

The mixture amount of the waste catalyst and the reaction solution during the removal of the poisonous material and / or the additional detoxification is such that the poisonous substances contained in the waste catalyst are sufficiently removed, and the waste catalyst and the reaction solution are mixed at a volume ratio of 1: 5 to 10 desirable.

Next, the filtration and washing step (S30) for removing the organic acid as the reaction solution in the waste catalyst from which the poisoning substances have been removed is performed. First, the waste catalyst in the waste catalyst is removed by filtering the waste catalyst, Water is removed with the reaction solution.

It is preferable that the pore size of the filter is selected according to the particle size of the spent catalyst and the filter having a pore size of 1 to 50 탆 is used in consideration of the size of the normal spent catalyst particle. It is preferable to perform filtration using pressure or vacuum.

Also, it is preferable to use distilled water of 2 to 10 times the volume of the spent catalyst so that the reaction solution is sufficiently removed.

Next, the waste catalyst from which the reaction solution is removed is calcined and finely pulverized (S40). The calcination is preferably performed at 140 to 160 ° C. for 40 to 80 minutes and then at 300 to 450 ° C. for 10 to 150 minutes. The temperature and time can be controlled depending on the use of the catalyst.

The method of remanufacturing a waste denitration catalyst according to the present invention can reduce the cost of importing tungsten trioxide and titanium dioxide, the cost of manufacturing the catalyst, and the waste treatment cost of the spent catalyst, It also helps.

<Example 1> Reconstitution of waste denitration catalyst using citric acid

FIG. 3 is a process diagram according to an embodiment of the present invention showing a process of removing a poisoning substance of a waste catalyst and recovering a material for recovery of tungsten trioxide and titanium dioxide catalyst materials in a waste denitration catalyst.

2, the waste denitration catalyst pretreated in FIG. 2 is stored in a storage silo 21 and 50 kg of the spent catalyst in the storage silo 21 and 500 l of distilled water in the distilled water tank 23 are introduced into the primary washing tank 22, The waste catalysts were firstly washed with distilled water and then filtered through a primary filter 24 having a pore size of 23 탆. The generated wastewater was transferred to a wastewater treatment tank 25 and treated.

The distilled water in the distilled water tank 23 and the citric acid solution in the chemical solution storage tank 27 were transferred to the primary filtered catalyst and mixed with 500 L of a citric acid aqueous solution having a concentration of 0.8 mole in the chemical solution tank 26, And the mixture was stirred at 450 rpm for 1 hour.

After the reaction was completed, the reaction solution was removed from the secondary filter 31 having a pore size of 23 μm, and 500 L of the distilled water in the distilled water tank 23 was transferred from the secondary washing tank 33 to the second wash water. The generated wastewater was transferred to the chemical treatment tank 32 for treatment.

The waste water that has been washed secondarily was again filtered by a tertiary filter 34 having a pore size of 23 μm and the generated wastewater was transferred to a wastewater treatment tank 35 for treatment. , And then heated at a temperature of 150 DEG C for one hour while supplying air to the firing furnace 41, and then calcined at a temperature of 400 DEG C for two hours.

The calcined spent catalyst was transferred to a pulverizing mill (42) to be finely divided into less than 45 탆 and made into a material.

<Example 2> Reconstitution of a waste denitration catalyst using mixed reaction solution of citric acid and hydrogen peroxide

60 kg of the waste denitration catalyst of the storage silo 21 pretreated in FIG. 2 and 600 L of distilled water of the distilled water tank 23 are transferred to the primary washing tank 22, and the waste catalyst is firstly rinsed with distilled water, And filtered through a primary filter 24 having a diameter of 23 mu m.

The distilled water from the distilled water tank 23 and the citric acid and hydrogen peroxide in the chemical solution storage tank 27 were transferred to the primary filtered catalyst and mixed with a reaction solution in which a solution of citric acid in a concentration of 0.4 mole and hydrogen peroxide And the mixture was reacted in a chemical solution tank 26 at a temperature of 100 DEG C for one hour at 450 rpm for reaction.

After the reaction was completed, the reaction solution was completely removed from the secondary filter 31 having a pore size of 23 μm, and then 600 L of the distilled water in the distilled water tank 23 was transferred to the secondary washing tank 33, The waste catalyst washed with water was filtered through a tertiary filter (34) having a pore size of 23 mu m.

The third filtered catalyst was heated at a temperature of 150 ° C. for one hour while being supplied with air from a calcining furnace 41 and then calcined at a temperature of 400 ° C. for two hours. The calcined spent catalyst was passed through a differentiator (42) By weight.

<Example 3> Reconstitution of waste denitration catalyst using mixed reaction solution of citric acid, hydrogen peroxide and EDTA

60 kg of the denitrification catalyst of the storage silo 21 pretreated in FIG. 2 and 600 L of the distilled water of the distilled water tank 23 are transferred to the primary washing tank 22 and stirred. The spent catalyst is firstly rinsed with distilled water, And filtered through a primary filter 24 having a diameter of 23 mu m.

The dehydrated water from the distilled water tank 23 and citric acid, hydrogen peroxide, and EDTA in the chemical solution storage tank 27 were transferred to the primary filtrate, and a 0.1 molar aqueous citric acid solution, hydrogen peroxide solution and EDTA were mixed The mixture was reacted with the reaction solution at a temperature of 100 ° C. for 1 hour at 450 rpm in a chemical solution tank 26 to react.

After the reaction was completed, the reaction solution was completely removed from the secondary filter 31 having a pore size of 23 μm, and then 600 L of the distilled water in the distilled water tank 23 was transferred to the secondary washing tank 33, The waste catalyst washed with water was filtered through a tertiary filter 34 having a pore size of 23 mu m.

The third filtered catalyst was heated at a temperature of 150 ° C. for one hour while being supplied with air from a calcining furnace 41 and then calcined at a temperature of 400 ° C. for two hours. The calcined spent catalyst was passed through a differentiator (42) By weight.

&Lt; Test Example > Analysis of poisoning substance removal efficiency and denitrification efficiency

3 shows the results of analyzing the components of the waste denitration catalyst before and after the poisoning material removal process. The results are shown in Table 1 below.

XRF (X-Ray Flourescence Spectrometry, ZSX Primus II, Rigaku, Japan) was used for the analysis of the components.

XRF analysis results (% by weight) before and after the poisoning material removal ingredient Waste Denitration Catalyst (Before Removing Poisonous Substance) Reformatization denitration catalyst (after removal of poisonous substance) Citric acid Citric acid + hydrogen peroxide Citric acid + hydrogen peroxide + EDTA Na ₂ O 0.2469 0 0 0 Al ₂ O ₃ 3.0082 2.5493 2.6330 2.5951 SiO ₂ 10.1863 10.2866 10.3641 10.3345 P ₂ O ₅ 0.1204 0.0927 0.0989 0.1040 SO ₃ 4.4093 0.3502 0.3013 0.2052 K ₂ O 0.1607 0.0272 0.0257 0.0181 CaO 0.0641 0.0120 0 0 TiO ₂ 68.3582 74.9728 74.8037 74.0061 V ₂ O ₅ 0.8955 0.6870 0 0.8620 Fe ₂ O ₃ 2.7842 1.1924 1.4459 1.5076 ZrO ₂ 0.0150 0.0196 0.0163 0.0156 As ₂ O ₃ 0.5414 0.4499 0.5119 0.5009 Nb ₂ O ₅ 0.1065 0.1321 0.1413 0.1413 MoO ₃ 0.0617 0.0447 0.0656 0.0732 WO ₃ 9.0416 9.1835 9.5923 9.6364 system 100 100 100 100

Poisonous substance removal rate (%) ingredient Citric acid Citric acid + hydrogen peroxide Citric acid + hydrogen peroxide + EDTA Na ₂ O 100.0 100.0 100.0 K ₂ O 83.0 84.0 88.7 CaO 81.2 100.0 100.0 SO ₃ 92.0 93.1 95.3

Table 1 and Table 2 show that the poisonous components of sodium and calcium are 100% removed, the sulfur trioxide component is more than 90%, the calcium component is more than 80%, and citric acid is more effective than citric acid It is more efficient to use hydrogen peroxide together, and it can be seen that the use of both citric acid, hydrogen peroxide and EDTA is most effective for removing poisonous substances.

The reformate denitration catalyst from which the poisoning substance was removed was placed in a fixed-bed reactor filled with nitrogen, and a flow rate of 600 cc, a space velocity of 60000 h ^-1 , an O ₂ content of 3 vol.%, An NO content of 800 ppm, NH ₃ / NO mole ratio of 1.0, and a reaction temperature of 350 ° C. The denitrification efficiency was 80% or more on average in all of Examples 1 to 3.

From the test results, it can be seen that the denitration catalyst that has been reformed by the method of the present invention economically recycles the waste catalyst and can exert a denitrification effect to a certain level or more, thereby enabling the waste denitration catalyst to be efficiently restored.

11: a waste denitration catalyst module, 12: a canister separated from the module, 13: a plate catalyst separated from the canister, 14: a honeycomb catalyst separated from the module, 15: an air compressor, 16: A pretreatment waste catalyst from which metallic foreign substances have been removed, 18: a magnet, 19: a metallic foreign matter, 21: a spent catalyst storage silo, 22: a primary washing tank, 23: a distilled water tank, 24: A chemical solution tank, a chemical solution tank, a chemical tank, a chemical tank, a chemical tank, a chemical tank, a chemical tank, Calcination furnace, 42: differentiator

Claims (9)

Collecting spent catalyst components from the waste denitration catalyst module;
A pretreatment step of pulverizing the collected spent catalyst component to a particle size of 100 to 2,000 mu m and then removing a metallic foreign substance in the waste catalyst component with a magnet having a strength of 7000 to 12000 Gauss;
The pretreated spent catalyst is mixed with an aqueous solution of EDTA at a concentration of 0.1 to 1.0 M in an amount of 1: 5 to 10 by volume (spent catalyst: EDTA aqueous solution), stirred at 300 to 500 rpm at a temperature of 120 to 120 ° C for 30 to 120 minutes Thereby removing the poisonous substance in the spent catalyst.
The spent catalyst in which the poisoning substance is primarily removed is treated with 0.1 to 2.0 M sulfuric acid aqueous solution or 0.1 to 2.0 M hydrochloric acid aqueous solution with 0.1 to 1.0 M hydrogen peroxide solution and 4 to 6: 4 to 6 volume ratio sulfuric acid aqueous solution or hydrochloric acid aqueous solution : Hydrogen peroxide solution) and reacting the reaction mixture with the reaction solution in a volume ratio of 1: 5 to 10: 10 (waste catalyst: reaction solution) to remove the poisoning material in the spent catalyst;
Filtering the waste catalyst from which the poisoning material has been secondarily removed by filtration;
Heating the washed spent catalyst at 140 to 160 ° C for 40 to 80 minutes, and then calcining at 300 to 450 ° C for 10 to 150 minutes; And
And finely pulverizing the calcined waste catalyst. The method of claim 1, delete delete delete delete delete delete delete delete

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