Aluminum-based ozone catalyst for advanced treatment of petrochemical wastewater as well as preparation method and application of aluminum-based ozone catalyst

Abstract

The invention belongs to the technical field of advanced treatment of petrochemical wastewater, and particularly discloses an aluminum-based ozone catalyst for advanced treatment of petrochemical wastewater as well as a preparation method and application of the aluminum-based ozone catalyst. The preparation method comprises the following steps: mixing an iron source, a cerium source, a cobalt source and a pore regulator with water to obtain an impregnation liquid; then placing the alumina carrier in the impregnation liquid for impregnation, and after impregnation is completed, sequentially drying and calcining to obtain the aluminum-based ozone catalyst for advanced treatment of petrochemical wastewater. The active components of the aluminum-based ozone catalyst prepared by the invention are uniformly distributed, so that the synergistic effect among the active components can be promoted, ozone oxidation is catalyzed, the removal rate of COD (Chemical Oxygen Demand) in petrochemical wastewater is greatly increased, and the COD of effluent reaches 40 mg / L or below. In addition, the preparation method of the catalyst is simple, the production cost can be controlled by selecting a proper metal addition amount according to specific industrial requirements, and large-batch industrial production can be realized.

Description

Technical Field

[0001] The present invention relates to the technical field of deep treatment of petrochemical wastewater, and in particular to an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater and a preparation method and application thereof. Background Art

[0002] The petrochemical industry has become an indispensable part of the development of modern industrialization. Petrochemical wastewater refers to a large amount of chemical sewage, domestic sewage, cooling water and other wastewater generated in the process of manufacturing products. This wastewater has the characteristics of complex composition, high salinity and large fluctuations in water quality. It is a difficult-to-degrade wastewater. In addition, as people's awareness of environmental protection deepens, petrochemical wastewater discharge standards are becoming more and more stringent, and the limit of chemical oxygen demand (COD) has been reduced to less than 50 mg / L. However, the phenolic compounds, aldehyde compounds and heavy metals contained in petrochemical wastewater are difficult to biodegrade. Relying solely on biochemical treatment, the effluent water quality can no longer meet the discharge standards. In order to alleviate the discharge pressure, it is necessary to add a deep treatment process after biochemical treatment.

[0003] The deep treatment process of petrochemical wastewater includes adsorption, membrane separation and catalytic ozone oxidation. Ozone itself has a relatively high redox potential and can react with most organic matter in water. However, when ozone oxidation is used alone, the COD removal rate is low and the mineralization of organic matter is incomplete. It is often necessary to add heterogeneous catalysts to improve the utilization efficiency of ozone and completely mineralize organic matter. In the heterogeneous catalytic ozone oxidation system for treating petrochemical wastewater, heterogeneous catalysts are very critical.

[0004] At present, the most commonly used ozone heterogeneous catalyst is to load metal oxides onto a carrier. The heterogeneous catalyst prepared by this method can not only avoid the problem of insufficient active sites of a single metal or oxide, but also reduce the preparation cost to ensure that the catalyst can be used in engineering projects. However, at present, the overall catalytic ozone oxidation efficiency of the ozone heterogeneous catalyst used in the deep treatment process of petrochemical wastewater is relatively low. In the catalyst selection process, the active components of the catalyst are not combined with the basic water quality of the wastewater. The heterogeneous catalyst is selected only based on basic experience, resulting in poor deep treatment of petrochemical wastewater and substandard effluent water quality. And it is impossible to stably achieve deep treatment of petrochemical wastewater (to stabilize the effluent COD in a lower range).

[0005] Therefore, how to provide an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater and its preparation method and application, improve the catalytic ozone oxidation capacity, and achieve deep treatment of petrochemical wastewater is a difficult problem that needs to be solved urgently in this field. Summary of the invention

[0006] In view of this, the present invention provides an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater and a preparation method and application thereof, in order to solve the problem that the catalytic ozone oxidation efficiency of ozone heterogeneous catalysts on the current market is low and the effluent cannot meet the increasingly stringent petrochemical wastewater discharge standards.

[0007] In order to achieve the above object, the present invention adopts the following technical solution: A method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater comprises the following steps: 1) mixing an iron source, a cerium source, a cobalt source and a pore regulator with water to obtain an impregnation solution; 2) The alumina carrier is placed in an impregnation solution for impregnation. After the impregnation is completed, it is dried and calcined in sequence to obtain an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater.

[0008] Preferably, in step 1), the molar concentration of iron ions in the impregnation solution is 0.3 mmol / L, the molar concentration of cerium ions is 0.5 mmol / L, the molar concentration of cobalt ions is 0.5 mmol / L, and the molar concentration of the pore regulator in the impregnation solution is 50-200 mmol / L.

[0009] Preferably, the iron source in step 1) includes one or more of ferric nitrate, ferric acetate and ferric chloride; The cerium source includes one or more of cerium nitrate, cerium acetate and cerium chloride; The cobalt source includes one or more of cobalt nitrate, cobalt acetate and cobalt chloride; The pore regulator includes one or more of glucose, polyethylene glycol and urea.

[0010] Preferably, the alumina carrier is γ-alumina; The particle size of the alumina carrier is 3-5 mm.

[0011] Preferably, the immersion time in step 2) is 12 to 24 hours.

[0012] Preferably, the calcination temperature in step 2) is 450-600° C., the calcination time is 4-6 hours, and the calcination atmosphere is an oxidizing atmosphere.

[0013] Preferably, the alumina carrier in step 2) further includes an activation step before impregnation; The activation step is: acid leaching and alkali leaching of the alumina carrier in sequence to complete the activation of the alumina carrier.

[0014] Another object of the present invention is to provide an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater prepared by a method for preparing the aluminum-based ozone catalyst for deep treatment of petrochemical wastewater.

[0015] Another object of the present invention is to provide an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater and its application in treating petrochemical wastewater.

[0016] It can be seen from the above technical solutions that, compared with the prior art, the present invention has the following beneficial effects: 1. The tri-metal-loaded aluminum-based ozone catalyst prepared by the present invention combines the redox ability of Fe, the oxygen storage capacity and stability of Ce, and the high-efficiency catalyst activity of Co, ensuring the stability of the catalytic ozone oxidation efficiency of the catalyst in the present invention, and the Ce element can reduce the poisoning effect of chloride ions in wastewater on the active sites of the catalyst. Compared with other tri-metal-loaded catalysts that can be applied in engineering, the present invention can achieve efficient metal loading through impregnation, and there will be no metal dissolution of Mn elements and the situation where Ni elements induce ozone side reactions and consume ozone. Compared with other catalysts, it has a higher organic pollutant degradation efficiency; 2. The pore regulator can decompose under the calcination conditions disclosed in the present invention and leave mesopores and macropores on the surface of the carrier, providing more active sites for the loading of active components; 3. The preparation method disclosed in the present invention can make the three metal active components evenly distributed on the surface of the carrier, promote the synergistic effect between the active components, catalyze ozone oxidation, and greatly increase the removal rate of COD in petrochemical wastewater; 4. The catalyst preparation method of the present invention is simple, the preparation process is simple, and can be produced in large quantities in industry; 5. The raw materials for catalyst production are cheap, the carrier can provide stable physical and chemical properties, and the abundant hydroxyl groups on the catalyst surface can efficiently catalyze ozone, making it suitable for engineering applications; 6. The three metal active components are evenly distributed in the catalyst, which can reduce the problem of loss or shedding of active components on the surface of heterogeneous catalysts. The impregnation preparation process can evenly load the active components into the carrier gap, and after high-temperature calcination, the bonding effect between the metal and the carrier can be strengthened; the addition of rare earth metals can increase the oxygen vacancies on the carrier surface and enhance the anchoring ability of the active components on the carrier surface; the carrier with a high specific surface area can provide more attachment sites for the loading of active components and prevent the aggregation of active components. The more even distribution of active components on the catalyst surface can prevent the active components from shedding. If the active components are aggregated together, the cluster structure itself is relatively loose, and it is easy to fall off under the influence of the shear force of water.

[0017] The aluminum-based catalyst prepared by the present invention has an efficiency of 30-50% higher in catalytic ozone oxidation treatment of petrochemical wastewater than the same type of ozone catalysts on the market. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0019] Figure 1 FTIR graph of the aluminum-based ozone catalyst prepared in Example 1 of the present invention; Figure 2 The XRD pattern of the aluminum-based ozone catalyst prepared in Example 1 of the present invention; Figure 3 This is a comparison chart of the catalytic ozone efficiency of different heterogeneous catalysts; Figure 4 The pilot test results of the aluminum-based ozone catalyst prepared in Example 1 of the present invention for treating petrochemical wastewater are shown in FIG. Figure 4 (a) is the COD value diagram of the inlet and outlet water in the pilot test. Figure 4 (b) is a comparison chart of ozone utilization between pilot test ozone oxidation and heterogeneous catalytic ozone oxidation; Figure 5 The pilot test results of the aluminum-based ozone catalyst prepared in Example 1 of the present invention in a petrochemical wastewater plant in Jiangsu; Figure 6 The catalytic efficiency comparison chart of aluminum-based ozone catalysts prepared in different concentrations of impregnation solutions. DETAILED DESCRIPTION

[0020] The present invention provides a method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater, comprising the following steps: 1) mixing an iron source, a cerium source, a cobalt source and a pore regulator with water to obtain an impregnation solution; 2) The alumina carrier is placed in an impregnation solution for impregnation. After the impregnation is completed, it is dried and calcined in sequence to obtain an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater.

[0021] In the present invention, the molar concentration of iron ions in the impregnation solution in step 1) is 0.3 mmol / L, the molar concentration of cerium ions is 0.5 mmol / L, and the molar concentration of cobalt ions is 0.5 mmol / L. The molar concentration of the pore regulator in the impregnation solution is 50-200 mmol / L, specifically 60 mmol / L, 80 mmol / L, 100 mmol / L, 120 mmol / L, 150 mmol / L, and 180 mmol / L.

[0022] In the present invention, the iron source in step 1) includes one or more of ferric nitrate, ferric acetate and ferric chloride.

[0023] In the present invention, the cerium source includes one or more of cerium nitrate, cerium acetate and cerium chloride.

[0024] In the present invention, the cobalt source includes one or more of cobalt nitrate, cobalt acetate and cobalt chloride.

[0025] In the present invention, the pore regulator includes one or more of glucose, polyethylene glycol and urea.

[0026] In the present invention, the hydroxyl group contained in the pore regulator itself can form a complex with iron, cerium and cobalt ions, accelerate the deposition of metal ions on the surface of the carrier, and facilitate the uniform distribution of active components on the surface of the carrier.

[0027] The pore regulator can generate carbon monoxide in the initial stage of calcination (heating stage), which is beneficial to the reduction of high-valent metals and the electron transfer in the subsequent catalytic ozone oxidation process (the whole process is as follows: the pore regulator will generate some carbon monoxide, which can reduce the high-valent metals in the oxide to low-valent metals, and the electron transfer between the high-valent metals and the low-valent metals is beneficial to the catalyst-catalyzed ozone oxidation); the carbon layer formed by the pore regulator after carbonization (a small part of it is converted into a carbon layer) can protect the active components from aggregation under high-temperature calcination, thereby ensuring a high loading amount of active components in the catalyst.

[0028] In the present invention, the alumina carrier is γ-alumina.

[0029] In the present invention, the particle size of the alumina carrier is 3-5 mm, specifically 3.2 mm, 3.5 mm, 3.8 mm, 4 mm, 4.2 mm, 4.5 mm, and 4.8 mm.

[0030] In the present invention, the immersion time in step 2) is 12 to 24 hours, specifically 14 hours, 15 hours, 16 hours, 18 hours, 20 hours, or 22 hours.

[0031] In the present invention, the calcination temperature in step 2) is 450-600°C, specifically 460°C, 480°C, 500°C, 520°C, 540°C, 550°C, 560°C, 580°C; the calcination time is 2-5h, specifically 2.5h, 3h, 3.5h, 4h, 4.5h; the calcination atmosphere is an oxidizing atmosphere, preferably an air atmosphere.

[0032] In the present invention, the heating rate before calcination is 5-10°C / min, specifically 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min.

[0033] In the present invention, the alumina carrier in step 2) further includes an activation step before being impregnated.

[0034] In the present invention, the activation step is: acid leaching and alkali leaching are performed on the alumina carrier in sequence to complete the activation of the alumina carrier. During the activation process, acid leaching and alkali leaching can remove impurities on the surface of the alumina carrier, expand the pores on the surface of the alumina carrier, and introduce acidic / alkaline groups to increase the number and success rate of active components loaded on the carrier surface.

[0035] In the present invention, the acid solution used for acid leaching includes one or more of hydrochloric acid, sulfuric acid solution and nitric acid solution; the mass concentration of the acid solution is preferably 4-10%, specifically 4%, 5%, 6%, 7%, 8%, 9%, 10%.

[0036] In the present invention, the alkaline solution used for alkali leaching includes one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water; the mass concentration of the alkaline solution is preferably 4-12%, specifically 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, and 12%.

[0037] In the present invention, the treatment time of the acid leaching and the alkali leaching is independently 2-3 hours, specifically 2.2 hours, 2.4 hours, 2.5 hours, 2.6 hours, and 2.8 hours.

[0038] The present invention also provides a method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater, and the prepared aluminum-based ozone catalyst for deep treatment of petrochemical wastewater.

[0039] The present invention also provides an application of an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater in treating petrochemical wastewater.

[0040] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] Example 1 100 g of the purchased γ-alumina carrier (particle size 3~5 mm) was rinsed in distilled water until neutral, soaked in 10% HCl solution for 2 hours, washed with deionized water until neutral, then immersed in 10% NaOH solution for 2 hours, washed with deionized water until neutral, and finally dried the carrier in an oven at 105°C for 10 hours to obtain an activated alumina carrier.

[0042] Preparation of impregnation solution: dissolve ferric nitrate, cerium nitrate and cobalt nitrate in water to prepare a mixed solution, add glucose aqueous solution to the mixed solution as a pore regulator to obtain an impregnation solution (iron ion concentration is 0.3 mmol / L, cerium ion concentration is 0.5 mmol / L, cobalt ion concentration is 0.5 mmol / L, glucose concentration is 50 mmol / L); put the activated alumina carrier into the prepared impregnation solution for impregnation, and dry it after impregnation for 12 hours; then put the catalyst precursor into a muffle furnace, heat it to 500°C at a heating rate of 6°C / min, and calcine it for 5 hours to obtain a heterogeneous catalyst; put the prepared catalyst into deionized water for washing and drying to obtain an aluminum-based ozone catalyst loaded with three active components, recorded as Ce-Co-FeO x / Al 2 O 3 .

[0043] The FTIR image of the aluminum-based ozone catalyst prepared by the present invention is as follows: Figure 1 As shown, through Figure 1 It can be seen that the aluminum-based ozone catalyst prepared by the present invention has abundant hydroxyl groups on its surface; the XRD diagram is as follows Figure 2 As shown, through Figure 2 It can be seen that the active components Fe, Co and Ce are successfully loaded on the alumina carrier in the form of oxides.

[0044] Comparative Example 1 The difference between this comparative example and Example 1 is only that no glucose is added.

[0045] Experimental Example 1 Heterogeneous ozone catalysts from different companies sold on the market and the catalysts prepared in Example 1 and Comparative Example 1 were selected for catalytic ozone oxidation treatment of petrochemical wastewater. In the test, the petrochemical wastewater was taken from a petrochemical wastewater plant in Zhejiang, China. The influent of the wastewater plant includes organic chemical raw material manufacturing, petrochemical medicine, and methane dehydrogenation to ethylene. The test water quality parameters are shown in Table 1. The heterogeneous catalytic ozone oxidation process is a deep treatment process after biochemical treatment. The influent of the deep treatment process does not include biodegradable organic matter, but mainly includes difficult biodegradable organic matter or toxic organic matter. The organic matter and its proportion in the influent of this experimental example are shown in Table 2. The COD value of the overall influent is low. In order to ensure that the effluent water quality meets the standard and realize the reuse of water resources, the wastewater is further treated. The main measured indicator in the deep treatment stage is the effluent COD value, and the value of the COD removal rate is only used as a reference value. The commercially available catalysts were purchased from Jiangxi Pingxiang Huihua Technology Co., Ltd.'s petrochemical wastewater special catalyst (referred to as catalyst 1), Shandong Ruihai Environmental Protection Technology Co., Ltd.'s petrochemical wastewater catalyst (referred to as catalyst 2), Henan Jiufeng Water Treatment Co., Ltd.'s petrochemical wastewater catalyst (referred to as catalyst 3) and Henan Yiheng Environmental Protection Technology Co., Ltd.'s petrochemical wastewater catalyst (referred to as catalyst 4). Comparative Example 1 was recorded as catalyst 5, and Example 1 was recorded as the present invention. The efficiency of catalytic ozone oxidation by different catalysts and the aluminum-based ozone catalyst prepared in Example 1 of the present invention was compared on a small-scale test scale. The effluent from the high-efficiency sedimentation tank in the petrochemical wastewater plant was used as the treatment target, the inlet ozone concentration was 40 mg / L, the air intake was 0.2 L / min, the catalyst filling amount was 50 g / L, and the effective volume of the small-scale test reaction column was 3 L. The test results are as follows Figure 3 As shown, it can be seen from the test results that the ability of the heterogeneous catalyst prepared by the present invention to catalyze ozone is much higher than that of commercially available catalysts.

[0046] Table 1 Test water quality parameters

[0047] Table 2 Types and contents of organic matter in the influent of the deep treatment process of petrochemical wastewater plant (Zhejiang)

[0048] Experimental Example 2 The pilot test verified the efficiency of the aluminum-based ozone catalyst prepared in Example 1 of the present invention in catalyzing ozone oxidation to treat petrochemical wastewater. Figure 4 As shown ( Figure 4 (a) is the COD value diagram of the inlet and outlet water in the pilot test. Figure 4(b) is a comparison chart of ozone utilization between pilot test ozone oxidation and heterogeneous catalytic ozone oxidation). When the ozone dosage is 30 mg / L, the catalyst loading thickness is 20 cm, the residence time is 30 min, and the reflux ratio is 150%, the pilot test influent COD is higher than 80 mg / L, and the COD of the treated petrochemical wastewater effluent is lower than 40 mg / L. The COD removal rate is stable at 40.00~60.00%. The treatment effect is stable and can meet the emission standards of petrochemical wastewater plants.

[0049] Experimental Example 3 In order to verify the treatment efficiency and stability of the heterogeneous catalyst catalytic ozone oxidation treatment of petrochemical wastewater when the COD of the influent of the deep treatment process is high, the biochemical process effluent of a petrochemical wastewater plant in Jiangsu was selected. The front end of the sewage plant mainly undertakes the effluent treated by the crude oil desalting process manufacturer and the catalytic cracking organic matter preparation process manufacturer, and the COD of the wastewater is relatively high. The water quality parameters of the influent of the deep treatment process of the sewage plant are shown in Table 3. Considering the high COD of the influent, the ozone dosage in the pilot experiment is 80 mg / L, the catalyst filling thickness is 20 cm, the residence time is 1h, and the reflux ratio is 150%. It is continuously operated for 30 days. The experimental results are as follows Figure 5 As shown, during the entire pilot test, the COD removal rate was stable at 70%~90%, the ozone utilization rate was stable between 1.2-1.7; and the effluent COD was maintained below 30 mg / L.

[0050] Table 3 Test water quality parameters

[0051] Comparative Example 2 In order to verify the high efficiency of the active component combination in the present invention, the concentration of the active component in the impregnation solution was adjusted (as shown in Table 4), and the water sample in Example 1 was used for comparison with the small test conditions. The experimental results are as follows: Figure 6 As shown, from Figure 6 It can be seen that the efficiency of catalytic ozone oxidation treatment of petrochemical wastewater by heterogeneous catalysts with different active component ratios is not the same. When the concentration changes, the COD removal rate in the entire system and the effluent COD change greatly, proving that the impregnation solution concentration ratio determined in the present invention is the optimal ratio.

[0052] Table 4 Concentration of active components in the impregnation solution

[0053] Example 2 100 g of the purchased γ-alumina carrier (particle size 3~5 mm) was rinsed in distilled water until neutral, soaked in 10% HCl solution for 2 hours, washed with deionized water until neutral, then immersed in 10% NaOH solution for 2 hours, washed with deionized water until neutral, and finally dried the carrier in an oven at 105°C for 10 hours to obtain an activated alumina carrier.

[0054] Preparation of impregnation solution: dissolve ferric nitrate, cerium nitrate and cobalt nitrate in water to prepare a mixed solution, add glucose solution to the mixed solution as a pore regulator to obtain an impregnation solution (iron ion concentration is 0.3 mmol / L, cerium ion concentration is 0.5 mmol / L, cobalt ion concentration is 0.5 mmol / L, glucose concentration is 100 mmol / L); put the activated alumina carrier into the prepared impregnation solution for impregnation, and dry it after impregnation for 18 hours; then put the catalyst precursor into a muffle furnace, heat it to 450°C at a heating rate of 5°C / min, and calcine it for 6 hours to obtain a heterogeneous catalyst; put the prepared catalyst into deionized water for cleaning and drying to obtain an aluminum-based ozone catalyst loaded with three active components.

[0055] Example 3

[0056] 100 g of the purchased γ-alumina carrier (particle size 3~5 mm) was rinsed in distilled water until neutral, soaked in 10% HCl solution for 2 hours, washed with deionized water until neutral, then immersed in 10% NaOH solution for 2 hours, washed with deionized water until neutral, and finally dried the carrier in an oven at 105°C for 10 hours to obtain an activated alumina carrier.

[0057] Preparation of impregnation solution: dissolve ferric nitrate, cerium nitrate and cobalt nitrate in water to prepare a mixed solution, add glucose solution to the mixed solution as a pore regulator to obtain an impregnation solution (iron ion concentration is 0.3 mmol / L, cerium ion concentration is 0.5 mmol / L, cobalt ion concentration is 0.5 mmol / L, glucose concentration is 200 mmol / L); put the activated alumina carrier into the prepared impregnation solution for impregnation, and dry it after impregnation for 24 hours; then put the catalyst precursor into a muffle furnace, heat it to 600°C at a heating rate of 10°C / min and calcine it for 4 hours to obtain a heterogeneous catalyst; put the prepared catalyst into deionized water for cleaning and drying to obtain an aluminum-based ozone catalyst loaded with three active components.

[0058] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0059] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater, characterized in that: The steps include: 1) mixing an iron source, a cerium source, a cobalt source and a pore regulator with water to obtain an impregnation solution; 2) The alumina carrier is placed in an impregnation solution for impregnation. After the impregnation is completed, it is dried and calcined in sequence to obtain an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater.

2. The method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 1, characterized in that: In step 1), the molar concentration of iron ions in the impregnation solution is 0.3 mmol / L, the molar concentration of cerium ions is 0.5 mmol / L, the molar concentration of cobalt ions is 0.5 mmol / L, and the molar concentration of the pore regulator in the impregnation solution is 50-200 mmol / L.

3. The method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 2, characterized in that: The iron source in step 1) includes one or more of ferric nitrate, ferric acetate and ferric chloride; The cerium source includes one or more of cerium nitrate, cerium acetate and cerium chloride; The cobalt source includes one or more of cobalt nitrate, cobalt acetate and cobalt chloride; The pore regulator includes one or more of glucose, polyethylene glycol and urea.

4. The method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to any one of claims 1 to 3, characterized in that: The alumina carrier is γ-alumina; The particle size of the alumina carrier is 3-5 mm.

5. The method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 4, characterized in that: The immersion time in step 2) is 12 to 24 hours.

6. The method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 5, characterized in that: The calcination temperature in step 2) is 450-600° C., the calcination time is 4-6 hours, and the calcination atmosphere is an oxidizing atmosphere.

7. The method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 5 or 6, characterized in that: The alumina carrier in step 2) further includes an activation step before being impregnated; The activation step is: acid leaching and alkali leaching of the alumina carrier in sequence to complete the activation of the alumina carrier.

8. The aluminum-based ozone catalyst for deep treatment of petrochemical wastewater prepared by the method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to any one of claims 1 to 7.

9. Use of the aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 8 in treating petrochemical wastewater.

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