Efficient catalyst, preparation method and application

Abstract

The embodiment of the invention provides a high-efficiency catalyst, a preparation method and application, the catalyst comprises gamma-Al2O3 as a carrier and an iron element loaded on the carrier, and the preparation method comprises the following steps: placing gamma-Al2O3 in a ferric nitrate solution for dipping, and drying and roasting the dipped gamma-Al2O3 to obtain the high-efficiency catalyst. The catalyst disclosed by the invention is an ozone catalytic oxidation catalyst, is low in production cost, simple and convenient in preparation process, good in catalytic performance and high in stability, and can meet the high-efficiency and low-consumption application requirements of ozone catalytic oxidation in advanced treatment of wine brewing wastewater.

Description

Technical Field

[0001] The present application relates to the field of water treatment technology, and in particular to a high-efficiency catalyst, a preparation method and an application thereof. Background Art

[0002] Compound-slag sauce-flavor liquor wastewater is the result of secondary fermentation of primary distiller's grains. Many difficult-to-degrade substances are dissolved, including a large number of complex pollutants such as lignin decomposition products, tannins, and humic acid. It also contains high levels of COD, total nitrogen, and suspended solids, making it a difficult-to-degrade, high-concentration organic wastewater. Brewing wastewater originates from all stages of liquor production. From raw material processing to fermentation, distillation, and cleaning of finished liquor, various wastewaters are generated in each process, and their pollutant composition varies with the brewing stage. Among them, pot bottom water and cellar bottom water are high-concentration wastewaters. With relatively small volumes but extremely high COD concentrations, they are the primary source of high-concentration pollutants. Therefore, scientific and efficient treatment technologies are necessary to deeply treat brewing wastewater to ensure that it meets discharge standards and, in turn, ensure the sustainable development of the natural environment.

[0003] Traditional methods for treating brewery wastewater primarily rely on biological methods, namely anaerobic and aerobic treatment. Biological treatment offers advantages such as low cost, simple operation, and high throughput, and can remove most pollutants from wastewater. However, traditional biological treatment suffers from incomplete treatment and fails to achieve the desired degradation results. Therefore, a targeted, effective, and efficient deep-drain treatment technology for brewery wastewater is needed. Currently, major technologies for treating brewery wastewater include Fenton oxidation, catalytic ozone oxidation, membrane treatment, and electrochemical oxidation. Catalytic ozone oxidation has attracted considerable attention due to its strong oxidizing properties and low pollution levels. Catalytic ozone oxidation can be categorized by catalyst form into homogeneous catalytic ozone oxidation (catalyst in the form of metal ions) and heterogeneous catalytic ozone oxidation (catalyst in the form of metal oxides / metal oxide-supported carriers). Homogeneous catalysts are difficult to recycle during use, and the dissolution of metal ions during the reaction can easily lead to secondary pollution. Furthermore, high water treatment costs limit homogeneous catalytic ozone oxidation. The catalysts in heterogeneous ozone oxidation are different from those in homogeneous reactions. The catalysts are easy to recycle, low in cost, and basically have no secondary pollution. They can avoid the loss of catalysts in homogeneous catalysis, and therefore are receiving more and more attention.

[0004] In heterogeneous catalytic ozonation systems, catalysts are crucial for ozone catalytic oxidation. Currently, heterogeneous catalysts primarily fall into the following categories: ① Metal oxides, with commonly used metal oxide catalysts including CuO, MnO2, and Al2O3; ② Supported catalysts, which are made by loading catalytically active substances onto a support. Common supports include activated carbon, zeolites, and alumina, and catalytically active metals primarily include transition metals such as iron, titanium, manganese, and copper, as well as metal oxides. ③ Activated carbon is widely used in ozone treatment due to its adsorption capacity and ability to promote ozone catalytic oxidation. Supported catalyst preparation methods include precipitation, impregnation, sol-gel, and ion exchange. Impregnation is the most commonly used method, offering simplicity and ease of operation, and promising prospects for large-scale industrial use. Choosing the right catalyst support, loading the active components onto the support, and preparing a clogging-resistant, recyclable catalyst, while significantly reducing the amount of catalytic materials and ozone dosage, are key areas for overcoming existing technological bottlenecks and achieving low-energy, high-efficiency applications in ozone catalytic oxidation. Summary of the Invention

[0005] The present application aims to solve, at least to a certain extent, one of the technical problems in the related art. The purpose of the present application is to propose a high-efficiency catalyst, a preparation method and an application thereof, wherein the catalyst in the present application is a single metal atom catalytic ozone oxidation catalyst with high loading, high catalytic activity and high stability, which is applied in the deep treatment of brewing wastewater by ozone catalytic oxidation, and can degrade COD in the wastewater with high efficiency and low energy consumption, thereby achieving the purpose of deep treatment of brewing wastewater.

[0006] To achieve the above-mentioned object, a method for preparing a high-efficiency catalyst according to the first aspect of the present application comprises the following steps: Wash the pickled γ-Al2O3 to neutrality and dry it; The dried γ-Al2O3 is immersed in a 0.05-1 mol / L ferric nitrate solution for 2-24 hours and dried; and then calcined at 200-700°C for 2-6 hours to obtain Fe@γ-Al2O3.

[0007] In some embodiments, the γ-Al 2 O 3 is in the form of pellets with a diameter of 3-5 mm.

[0008] In some embodiments, γ-Al2O3 is ultrasonically pickled using a 1 mol / L hydrochloric acid solution for 12 hours.

[0009] In some embodiments, the drying temperature is 105° C. and the drying time is 10-12 hours.

[0010] In some embodiments, the concentration of the ferric nitrate solution is 0.2 mol / L, and the immersion time is 10 h.

[0011] In some embodiments, the calcination temperature is 500° C. and the calcination time is 3 h.

[0012] According to a second aspect of the present application, a high-efficiency catalyst is proposed, which is prepared using the method described in any of the above embodiments.

[0013] According to the third aspect of the present application, the above-mentioned high-efficiency catalyst is used in the treatment of brewing wastewater, and the catalyst is used in the ozone catalytic oxidation of brewing wastewater.

[0014] In some embodiments, the catalyst is added to a reaction device for treating brewery wastewater; wherein the reaction device comprises: An ozone reactor, wherein the ozone reactor is provided with a supporting layer for placing a catalyst; An ozone generator is used to provide ozone of a set concentration and flow rate to the ozone reactor; the ozone is introduced into the ozone reactor through an aeration disk; the bubble diameter of the aeration disk is 0.5-1 mm; A liquid storage tank is connected to the ozone reactor and is used for introducing brewing wastewater thereinto.

[0015] In some embodiments, the addition amount of the catalyst and brewing wastewater is 5-30 g / L; the ozone flow rate is 0.4 L / min, and the addition amount is 3.6-25.2 mg / min.

[0016] Compared with the existing technology, this application has the following beneficial technical effects: 1. Using iron as the metal active component; this application takes into account that iron compounds are cheap and easily available and contain strong alkaline sites, and can be used as a green and efficient metal active component with a high loading capacity, ozone catalytic activity and a large specific surface area.

[0017] 2. The preparation method designed in this application has a simple process, the raw materials and reagents are common and easily available and have low cost, it is simple and easy to implement and has good stability, and is suitable for large-scale production.

[0018] Third, the carrier is γ-Al2O3, which has excellent performance and is granular, has good water absorption properties, and has a large pore volume and specific surface area. On the one hand, it is conducive to the deposition and loading of active metals during the impregnation process; on the other hand, during the ozone catalytic oxidation process, the organic matter in the wastewater is enriched on the catalyst surface, which is conducive to its degradation. Compared with powdered catalysts, it is easier to collect and reduces subsequent processing work. Fourth, in the deep treatment of brewing wastewater by ozone catalytic oxidation, the catalyst can improve the efficiency of catalytic ozone decomposition to produce active free radicals, improve ozone utilization efficiency, significantly reduce ozone dosage, and has strong green and low-carbon technical performance and market value.

[0019] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which: Figure 1 This is the SEM image of Fe@γ-Al2O3 proposed in Example 1 of the present application; Figure 2 This is the XRD pattern of Fe@γ-Al2O3 proposed in Example 1 of the present application; Figure 3 This is the infrared spectrum FT-IR graph of Fe@γ-Al2O3 proposed in Example 1 of the present application; Figure 4 This is a schematic structural diagram of an ozone catalytic oxidation reaction device proposed in one embodiment of the present application; Figure 5 The pollutant removal effect before and after the catalyst reaction in Examples 1-4 and Comparative Examples 1-2 of the present application is shown; Figure 6 This is a diagram showing the COD removal effect before and after the reaction of Examples 5-12 of the present application; Figure 4 Among them, 1. Ozone reactor; 2. Ozone generator; 3. Liquid storage tank; 4. Ozone concentration analyzer; 5. Gas flow meter; 6. Aeration plate; 7. Support layer. DETAILED DESCRIPTION

[0021] The embodiments of the present application are described in detail below. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended only to explain the present application and are not to be construed as limiting the present application. On the contrary, the embodiments of the present application include all variations, modifications, and equivalents that fall within the spirit and scope of the appended claims.

[0022] The term "COD" (Chemical Oxygen Demand) used in this application is measured in milligrams per liter (mg / L), which is the amount of oxidant consumed to oxidize the reducing substances in 1 liter of water sample, and is converted into milligrams of oxygen required to completely oxidize each liter of water sample.

[0023] In this application, the term “UV 254 ” (UV absorbance at 254 nm), measured in cm －1The water sample was diluted to an appropriate multiple and filtered with a 0.45 μm filter membrane. A blank water sample was used as a reference. The absorbance was measured at a wavelength of 254 nm using a UV-visible spectrophotometer and the UV 254 .

[0024] The term "deep wastewater treatment" as used herein generally refers to the further treatment of residual organic matter in secondary effluent after biochemical or other treatment using advanced oxidation or other techniques. All raw materials are not particularly limited in their source and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art. Furthermore, all raw materials are not particularly limited in their purity; the embodiments of this application preferably use analytically pure or conventionally used purity in the field of metal oxide catalyst materials.

[0025] To achieve the above-mentioned object, a method for preparing a high-efficiency catalyst according to the first aspect of the present application comprises the following steps: Step 1: Wash the acid-washed γ-Al2O3 to neutrality and dry it; Step 2: The dried γ-Al2O3 is immersed in a 0.05-1 mol / L ferric nitrate solution for 2-24 hours and dried; and then calcined at 200-700°C for 2-6 hours to obtain Fe@γ-Al2O3.

[0026] Among them, in step 1, a small ball of γ-Al2O3 with a diameter of 3-5 mm is used as a carrier of the catalyst and is pickled for pretreatment, that is, the γ-Al2O3 is completely immersed in a 1 mol / L hydrochloric acid solution and ultrasonically pickled for 12 hours. The pickled γ-Al2O3 is then taken out and washed with distilled water until the pH of the washing solution is neutral, and then placed in an oven at 105°C for 10-12 hours for drying.

[0027] Wherein, in step 2, the pretreated γ-Al2O3 pellets obtained in step 1 are loaded with active ingredients. Specifically, the γ-Al2O3 carrier is placed in a ferric nitrate solution with a concentration of 0.05-1mol / L and impregnated for 2-24h to submerge the γ-Al2O3 in ferric nitrate. Preferably, the concentration of the ferric nitrate solution is 0.2mol / L, and the impregnation time is 10h. The γ-Al2O3 pellets impregnated with the ferric nitrate solution are then placed in a 105°C baking oven and dried for 10-12h. The pellets are then placed in a muffle furnace and calcined at 200-700°C for 2-6h. Preferably, the calcination temperature is 500°C and the calcination time is 3h. The pellets are taken out after natural cooling to obtain Fe@γ-Al2O3.

[0028] According to the second aspect of the present application, a high-efficiency catalyst is proposed, which is prepared using the method in any of the above embodiments.

[0029] According to the third aspect of the present application, the above-mentioned high-efficiency catalyst is used in the treatment of brewing wastewater, and the catalyst is used in the ozone catalytic oxidation of brewing wastewater.

[0030] In this application, the γ-Al2O3 in the ozone catalytic oxidation of wastewater includes three parts: adsorption, activation, and desorption. The surface of γ-Al2O3 has a certain adsorption capacity, and can adsorb organic molecules during the reaction. When the organic molecules come into contact with the surface of γ-Al2O3, the organic molecules will be adsorbed onto the surface of γ-Al2O3 to form new chemical adsorption species. Some of the organic matter adsorbed on the surface of γ-Al2O3 will be oxidized by direct reaction with ozone. At the same time, γ-Al2O3 has a high surface oxidation activity, which can promote the decomposition of ozone to form active species, such as ·OH. These active oxygen species also react with organic molecules adsorbed on the surface of γ-Al2O3, decomposing the organic matter into smaller organic and inorganic substances, which are desorbed from the surface of γ-Al2O3 and released into the solution.

[0031] Under ozone catalytic oxidation conditions, the participation of Fe2O3 in the reaction mainly follows the free radical theory and the oxygen vacancy theory. First of all, oxygen vacancies refer to the missing oxygen atoms in the crystal. In Fe2O3 catalysts, oxygen vacancies are a common defect that can serve as reactive sites, adsorbing water molecules and oxygen molecules, thereby catalyzing ozone oxidation reactions. Ozone (O3) will decompose into oxygen free radicals (O·) and oxygen molecules (O2) in water. O· will react with water molecules to generate ·OH and H + The cavities on the Fe2O3 catalyst surface can adsorb water molecules and cause them to dissociate, forming ·OH, which reacts with organic pollutants and degrades them. Considering the degradation mechanisms of γ-Al2O3 and Fe2O3, the catalyst in this application has a good pollutant removal effect by catalytically oxidizing organic wastewater with ozone.

[0032] In some embodiments, a catalyst is added to a reaction device for treating brewery wastewater; wherein the reaction device comprises: The ozone reactor 1 is provided with a supporting layer 7 for placing a catalyst; The ozone generator 2 is used to provide ozone of a set concentration and flow rate to the ozone reactor 1; the ozone is introduced into the ozone reactor 1 through the aeration disk 6; the bubble diameter of the aeration disk 6 is 0.5-1mm; The liquid storage tank 3 is connected to the ozone reactor 1 and is used for introducing brewing wastewater thereinto.

[0033] The reaction device in this application includes an ozone reactor 1, an ozone generator 2 and a liquid storage tank 3; wherein the ozone generator 2 is used to generate ozone of a set concentration and provide ozone of a set concentration and flow rate to the ozone reactor 1, and the liquid storage tank 3 is connected to the ozone reactor 1 and is used to inject brewing wastewater into the ozone reactor 1. Figure 4 As shown, the ozone generator 2 is connected to the ozone concentration analyzer 4 and the gas flow meter 5 through an air pipe. The ozone output by the gas flow enters the ozone reactor 1 through the aeration plate 6. The ozone generator 2 is connected to the ozone reactor 1 through the liquid storage tank 3, which is used to introduce brewing wastewater into the ozone reactor 1. The ozone that completes the reaction in the ozone reactor 1 is output through the top of the ozone reactor 1 and discharged into the atmosphere after passing through the ozone concentration analyzer 4.

[0034] For example, the ozone reactor 1 is made of cylindrical acrylic material, with a reactor size of 10 cm in diameter, 80 cm in height, and an effective reaction volume of 5 L. A supporting layer 7 is provided inside it for placing the catalyst; the air pipe material is all polytetrafluoroethylene; the ozone aeration disk 6 is a microporous aeration disk 6, and the bubble diameter generated is 0.5-1 mm.

[0035] In some embodiments, the amount of catalyst added to brewing wastewater is 5-30 g / L; the ozone concentration is 9-63 mg / min, and its flow rate is 0.4 L / min, that is, the ozone dosage is 3.6-25.2 mg / min.

[0036] In some embodiments, the ozone generator 2 is connected to the ozone concentration analyzer 4 and the gas flow meter 5 through an air pipe. The ozone concentration generated by the ozone generator 2 is 9-63 mg / L, and the ozone gas flow rate is 0.4 L / min; when the COD of the influent wastewater to be treated is 150-250 mg / L, the O / C is 1.7-2.0; the amount of catalyst and brewing wastewater added is 5-30 g / L; and the ozone dosage is 3.6-25.2 mg / min.

[0037] The wastewater to be treated is introduced into the above-mentioned wastewater ozone catalytic oxidation reactor for treatment. During the treatment, ozone is introduced into the reactor. Among them, the ozone concentration is 9-63 mg / L, the filling amount of the ozone catalyst is 20 g / L; the ozone inlet flow rate is 0.4 L / min, and the initial pH of the wastewater is 3-11. Furthermore, when the initial state of the wastewater to be treated, i.e., brewing wastewater, is COD 150-250 mg / L, O / C is 1.7-2.0. The ozone catalyst in this embodiment has good catalytic performance, and can effectively promote the efficient conduct of the ozone catalytic reaction at a smaller usage amount.

[0038] Example 1 A small ball of γ-Al2O3 with a diameter of 3mm was completely immersed in a 1mol / L hydrochloric acid solution and ultrasonically pickled for 12 hours. The pickled γ-Al2O3 was then taken out and washed with distilled water until the pH of the washing solution was neutral. It was then placed in an oven at 105°C for 10 hours for drying.

[0039] The γ-Al2O3 carrier dried after acid washing was placed in a 0.2 mol / L iron nitrate solution and immersed for 10 hours to allow the iron nitrate to submerge the γ-Al2O3. The γ-Al2O3 pellets immersed in the iron nitrate solution were then placed in an oven at 105°C for 10 hours for drying, and placed in a muffle furnace at 5°C / min to 500°C for 3 hours. After natural cooling, they were taken out to obtain Fe@γ-Al2O3. The obtained Fe@γ-Al2O3 was tested, as shown in the following figure. Figure 1-Figure 3 As shown, Figure 1 The SEM images of the catalyst before and after preparation are shown in Figure 2. Figure 1 It can be seen that the surface of Fe@γ-Al2O3 is uniformly and heavily loaded with granular materials, and the pore structure is reduced; Figure 2 is the XRD pattern of the catalyst before and after preparation. Figure 2 It can be seen that the Fe element in the catalyst after preparation mainly exists in the form of Fe2O3; Figure 3 The FT-IR images of the catalyst before and after preparation are shown in Figure 1. Figure 3 It can be seen that the surface of the catalyst contains hydroxyl groups after preparation.

[0040] Different embodiments were obtained by adjusting the parameters in the high-efficiency catalyst preparation method according to Table 1, and other technical features were the same as those in the embodiment.

[0041] Table 1 Preparation methods of high-efficiency catalysts in different examples Ferric nitrate solution concentration mol / L Ferric nitrate solution immersion time h Calcination temperature ℃ Roasting time h Example 2 0.1 8 400 2 Example 3 0.3 12 600 4 Example 4 0.1 10 500 3 Comparative Example 1 Comparative Example 1 is different from Example 1 in that 0.2 mol / L magnesium nitrate solution is used for impregnation in the metal salt solution, and the remaining method step parameters including impregnation time, roasting temperature and roasting time are the same as those in Example 1.

[0042] Comparative Example 2 Compared with Example 1, Comparative Example 2 differs in that a composite metal salt solution of ferric nitrate and magnesium nitrate is used for impregnation in the metal salt solution, and the concentration of ferric nitrate: magnesium nitrate = 0.2 mol / L: 0.2 mol / L. The remaining method step parameters including impregnation time, roasting temperature and roasting time are the same as those in Example 1.

[0043] like Figure 4, inject 5L of secondary effluent from brewing wastewater or water with a concentration of 100mg / L tannic acid into the ozone reactor. The initial COD concentration of the secondary effluent from brewing wastewater is 220mg / L. UV 254 The initial value is 2.800, and 20 g / L of the catalysts in Examples 1 to 4 and Comparative Examples 1 to 2 are added to the reactor, the ozone concentration is 54 mg / L, the ozone inlet flow rate is 0.4 L / min, and the initial pH of the water to be treated is 9. The effects of the catalyst on COD, UV 254 and tannic acid removal rates, such as Figure 5 As shown. Figure 5 It was found that when the ferric nitrate impregnation concentration was 0.2 mol / L, the impregnation time was 10 h, the calcination temperature was 500 ° C, and the calcination time was 3 h, the catalyst prepared by the above method had the highest ozone catalytic oxidation activity, among which, the COD, UV 254 The removal rates of ethanol, ethanol and tannic acid were 61.36%, 87.06% and 96.12% respectively.

[0044] Example 5 5L of secondary effluent from brewing wastewater was injected into the ozone reactor. The initial pH of the water to be treated was 9, the initial COD concentration was 220mg / L, and UV 254 The initial value is 2.400, and 20g / L of the high-efficiency catalyst obtained in Example 1 is added thereto. The ozone concentration is 54mg / L, the ozone inlet flow rate is 0.4L / min, and the ozone dosage is 21.6mg / min. According to Table 2, different catalyst dosages, ozone dosages and different initial pH values are adjusted to obtain the COD removal rates in actual wastewater in different embodiments. Figure 5 shown.

[0045] Different embodiments were obtained by adjusting the parameters in the high-efficiency catalyst application method according to Table 2. Other technical features were the same as those in Example 5.

[0046] Table 2 Process parameters of catalyst treatment of brewery wastewater in different embodiments Catalyst dosage g / L Ozone dosage mg / min Initial pH Example 6 15 25.2 9 Example 7 25 18 9 Example 8 25 25.2 9 Example 9 20 18 7 Example 10 20 25.2 7 Example 11 20 18 11 Example 12 15 21.6 7 like Figure 4 5L of secondary effluent from brewery wastewater was injected into the ozone reactor. The initial COD concentration of the secondary effluent from brewery wastewater was 220mg / L. Different amounts of the catalyst in Example 1 were added to the reactor. The catalyst in Example 1 was applied under the reaction conditions of Examples 5-12 to obtain the COD removal rate of the catalyst in brewery wastewater, as shown in FIG. Figure 6 As shown. Figure 6It can be seen that when the ozone dosage is 21.6 mg / L, the catalyst dosage is 20 g / L, and the initial pH is 9, that is, in Example 5, the COD removal efficiency in brewing wastewater is the highest, and the COD removal rate reaches 64.18%.

[0047] in conclusion It can be seen from Example 1 that the optimal preparation conditions of the ozone catalytic oxidation catalyst for brewing wastewater in the present application are: ferric nitrate impregnation concentration 0.2 mol / L, impregnation time 10 h, roasting temperature 500°C, and roasting time 3 h. The main component of the catalyst surface is Fe2O3 and contains hydroxyl radicals; according to Example 5, the catalyst is added to the reaction device for brewing wastewater treatment, the optimal catalyst dosage is 20 g / L, the optimal ozone dosage is 21.6 mg / min, and the initial wastewater pH is optimally 9. Compared with the prior art, the present application provides a catalyst preparation method and application for deep treatment of brewing wastewater by ozone catalytic oxidation, which has low production cost, mild treatment conditions, simple reaction operation, no secondary pollution, is suitable for industrial treatment requirements, and can be widely promoted and used.

[0048] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with that embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0049] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A method for preparing a high-efficiency catalyst, characterized in that: The steps include: Wash the pickled γ-Al2O3 to neutrality and dry it; The dried γ-Al2O3 is immersed in a 0.05-1 mol / L ferric nitrate solution for 2-24 hours and dried; and then calcined at 200-700°C for 2-6 hours to obtain Fe@γ-Al2O3.

2. The method according to claim 1, wherein γ-Al2O3 is a small ball with a diameter of 3-5 mm.

3. The method according to claim 1, wherein γ-Al2O3 was ultrasonically pickled using a 1 mol / L hydrochloric acid solution for 12 h.

4. The method according to claim 1, wherein The drying temperature is 105° C. and the drying time is 10-12 hours.

5. The method according to claim 1, wherein The concentration of the ferric nitrate solution is 0.2 mol / L, and the immersion time is 10 h.

6. The method according to claim 1, wherein The calcination temperature is 500°C and the calcination time is 3 hours.

7. A high efficiency catalyst, characterized in that Prepared by the method according to any one of claims 1 to 6.

8. The catalyst according to claim 7 is used in the treatment of brewery wastewater, characterized in that: The catalyst is used in ozone catalytic oxidation of brewing wastewater.

9. The use according to claim 8, characterized in that The catalyst is added to a reaction device to treat brewery wastewater; wherein the reaction device comprises: An ozone reactor, wherein the ozone reactor is provided with a supporting layer for placing a catalyst; An ozone generator is used to provide ozone of a set concentration and flow rate to the ozone reactor; the ozone is introduced into the ozone reactor through an aeration disk; the bubble diameter of the aeration disk is 0.5-1 mm; and A liquid storage tank is connected to the ozone reactor and is used to introduce brewing wastewater therein.

10. The use according to claim 8, characterized in that The addition amount of the catalyst and brewing wastewater is 5-30 g / L; the ozone flow rate is 0.4 L / min, and the addition amount is 3.6-25.2 mg / min.

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