Aluminum-based ozone catalyst for deep treatment of petrochemical wastewater, preparation method and application thereof

Abstract

The present invention belongs to the technical field of deep treatment of petrochemical wastewater, and specifically discloses an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater, and its preparation method and application. The present invention first mixes an iron source, a cerium source, a cobalt source and a pore regulator with water to obtain an impregnation solution; then the alumina carrier is placed in the 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. The active components of the aluminum-based ozone catalyst prepared by the present invention are evenly distributed, which can promote the synergistic effect between the active components, catalyze ozone oxidation, and greatly increase the removal rate of COD in petrochemical wastewater, so that the effluent COD reaches below 40 mg / L. In addition, the preparation method of the catalyst of the present invention is simple, and the appropriate metal dosage can be selected according to specific industrial needs to control the production cost, and it can be produced in large quantities in industry.

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 the large amount of chemical wastewater, domestic sewage, cooling water, and other wastewater generated during the manufacturing process. This wastewater has complex composition, high salinity, and large fluctuations in water quality, making it difficult to degrade. In addition, as people's awareness of environmental protection deepens, petrochemical wastewater discharge standards are becoming increasingly stringent, and the limit on 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. Biochemical treatment alone is no longer enough to meet discharge standards. To alleviate discharge pressure, it is necessary to add advanced treatment processes after biochemical treatment.

[0003] Advanced treatment processes for petrochemical wastewater include 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, ozone oxidation alone results in low COD removal rates and incomplete mineralization of organic matter. Heterogeneous catalysts are often required to improve ozone utilization efficiency and fully mineralize organic matter. Heterogeneous catalysts are crucial in heterogeneous catalytic ozone oxidation systems for treating petrochemical wastewater.

[0004] Currently, the most commonly used heterogeneous ozone catalysts are those that incorporate metal oxides onto supports. This method avoids the problem of insufficient active sites in individual metals or oxides, reduces preparation costs, and ensures the catalyst's applicability in engineering projects. However, the overall catalytic ozone oxidation efficiency of heterogeneous ozone catalysts currently used in petrochemical wastewater advanced treatment processes is relatively low. The catalyst selection process fails to prioritize the active components of the catalyst and the underlying wastewater quality. Heterogeneous catalysts are selected based solely on empirical evidence, resulting in poor advanced treatment results for petrochemical wastewater and substandard effluent quality. Furthermore, it is not possible to achieve stable advanced treatment of petrochemical wastewater (maintaining a low COD level in the effluent).

[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, as well as its preparation method and application, to solve the problem that the ozone oxidation efficiency of heterogeneous ozone 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 solutions:

[0008] A method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater comprises the following steps:

[0009] 1) mixing an iron source, a cerium source, a cobalt source, and a pore regulator with water to obtain an impregnation solution;

[0010] 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.

[0011] 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.

[0012] Preferably, the iron source in step 1) comprises one or more of ferric nitrate, ferric acetate and ferric chloride;

[0013] The cerium source includes one or more of cerium nitrate, cerium acetate and cerium chloride;

[0014] The cobalt source includes one or more of cobalt nitrate, cobalt acetate and cobalt chloride;

[0015] The pore regulating agent includes one or more of glucose, polyethylene glycol and urea.

[0016] Preferably, the alumina support is γ-alumina;

[0017] The particle size of the alumina carrier is 3-5 mm.

[0018] Preferably, the immersion time in step 2) is 12 to 24 hours.

[0019] 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.

[0020] Preferably, the alumina support in step 2) further includes an activation step before being impregnated;

[0021] The activation steps are: acid leaching and alkali leaching are performed on the alumina carrier in sequence to complete the activation of the alumina carrier.

[0022] 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.

[0023] 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.

[0024] It can be seen from the above technical solutions that compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. The iron-cobalt-cerium trimetallic 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 efficient catalytic activity of Co, ensuring the stability of the catalyst's catalytic ozone oxidation efficiency. Furthermore, the Ce element can reduce the poisoning effect of chloride ions in wastewater on the active sites of the catalyst. Compared with other trimetallic loaded catalysts with engineering applications, the present invention can achieve efficient metal loading through impregnation, and does not experience the metal dissolution of the Mn element or the ozone side reaction triggered by the Ni element that consumes ozone. Compared with other catalysts, it has a higher organic pollutant degradation efficiency.

[0026] 2. The pore modifier can decompose under the calcination conditions disclosed in the present invention, leaving mesopores and macropores on the surface of the support, providing more active sites for the loading of active components;

[0027] 3. The preparation method disclosed in the present invention can evenly distribute the three metal active components on the surface of the carrier, promote the synergistic effect between the active components, catalyze ozone oxidation, and significantly increase the COD removal rate in petrochemical wastewater;

[0028] 4. The catalyst preparation method of the present invention is simple, the preparation process is simple, and it can be produced in large quantities in industry;

[0029] 5. The raw materials for catalyst production are low-priced, 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;

[0030] 6. The three metal active components are evenly distributed within the catalyst, which can reduce the problem of active component loss or shedding on the surface of heterogeneous catalysts. The impregnation preparation process can evenly load the active components into the carrier's pores, 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 high specific surface area carrier can provide more attachment sites for the loading of active components, preventing the active components from aggregating. The more uniform 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 is easily detached under the influence of the shear force of water.

[0031] 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 similar ozone catalysts on the market. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0033] Figure 1 FTIR graph of the aluminum-based ozone catalyst prepared in Example 1 of the present invention;

[0034] Figure 2 This is the XRD pattern of the aluminum-based ozone catalyst prepared in Example 1 of the present invention;

[0035] Figure 3 This is a comparison chart of the catalytic ozone efficiency of different heterogeneous catalysts;

[0036] 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 below: Figure 4 (a) is the COD value diagram of the inlet and outlet water of the pilot test. Figure 4 (b) is a comparison chart of ozone utilization efficiency between pilot test ozone oxidation and heterogeneous catalytic ozone oxidation;

[0037] Figure 5 The results of a pilot test of the aluminum-based ozone catalyst prepared in Example 1 of the present invention in a petrochemical wastewater plant in Jiangsu Province are shown below:

[0038] Figure 6 A comparison chart of the catalytic efficiency of aluminum-based ozone catalysts prepared in impregnation solutions of different concentrations. DETAILED DESCRIPTION

[0039] The present invention provides a method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater, comprising the following steps:

[0040] 1) mixing an iron source, a cerium source, a cobalt source, and a pore regulator with water to obtain an impregnation solution;

[0041] 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.

[0042] 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, or 180 mmol / L.

[0043] In the present invention, the iron source in step 1) includes one or more of ferric nitrate, ferric acetate and ferric chloride.

[0044] In the present invention, the cerium source includes one or more of cerium nitrate, cerium acetate and cerium chloride.

[0045] In the present invention, the cobalt source includes one or more of cobalt nitrate, cobalt acetate and cobalt chloride.

[0046] In the present invention, the pore regulating agent includes one or more of glucose, polyethylene glycol and urea.

[0047] In the present invention, the hydroxyl groups contained in the pore regulator itself can form complexes with iron, cerium and cobalt ions, accelerate the deposition of metal ions on the carrier surface, and facilitate the uniform distribution of active components on the carrier surface.

[0048] 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, and carbon monoxide can reduce the high-valent metals in the oxide to low-valent metals. 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.

[0049] In the present invention, the alumina carrier is γ-alumina.

[0050] 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, or 4.8 mm.

[0051] 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.

[0052] 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, or 580°C; the calcination time is 2-5h, specifically 2.5h, 3h, 3.5h, 4h, or 4.5h; and the calcination atmosphere is an oxidizing atmosphere, preferably an air atmosphere.

[0053] 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, and 10°C / min.

[0054] In the present invention, the alumina support in step 2) further includes an activation step before being impregnated.

[0055] In the present invention, the activation step involves sequentially subjecting the alumina support to acid and alkali leaching to complete activation. During the activation process, acid and alkali leaching removes impurities from the alumina support surface, expands the pores on the alumina support surface, and introduces acidic and basic groups to increase the amount and success rate of active component loading on the support surface.

[0056] 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% and 10%.

[0057] In the present invention, the alkaline solution used in the alkaline 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%.

[0058] 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.

[0059] The present invention also provides a method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater, and the obtained aluminum-based ozone catalyst for deep treatment of petrochemical wastewater.

[0060] The present invention also provides an application of an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater in treating petrochemical wastewater.

[0061] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0062] Example 1

[0063] 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 in an oven at 105°C for 10 hours to obtain an activated alumina carrier.

[0064] Preparation of the impregnation solution: Ferric nitrate, cerium nitrate, and cobalt nitrate were dissolved in water to prepare a mixed solution, and a glucose aqueous solution was added to the mixed solution as a pore regulator to obtain an impregnation solution (iron ion concentration of 0.3 mmol / L, cerium ion concentration of 0.5 mmol / L, cobalt ion concentration of 0.5 mmol / L, glucose concentration of 50 mmol / L). The activated alumina support was placed in the prepared impregnation solution for impregnation for 12 hours and then dried. The catalyst precursor was then placed in a muffle furnace, heated to 500°C at a heating rate of 6°C / min, and calcined for 5 hours to obtain a heterogeneous catalyst. The prepared catalyst was washed in deionized water and dried to obtain an aluminum-based ozone catalyst loaded with three active components, recorded as Ce-Co-FeO x / Al2O3.

[0065] 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 surface of the aluminum-based ozone catalyst prepared by the present invention has abundant hydroxyl groups; the XRD pattern 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 support in the form of oxides.

[0066] Comparative Example 1

[0067] The only difference between this comparative example and Example 1 is that no glucose was added.

[0068] Experimental Example 1

[0069] Heterogeneous ozone catalysts from different companies sold on the market, as well as the catalysts prepared in Example 1 and Comparative Example 1, were selected for catalytic ozone oxidation treatment of petrochemical wastewater. The petrochemical wastewater in the experiment was taken from a petrochemical wastewater plant in Zhejiang, China. The influent of this wastewater plant includes industries such as organic chemical raw material manufacturing, petrochemical pharmaceuticals, and methane dehydrogenation to ethylene. The test water quality parameters are shown in Table 1. The heterogeneous catalytic ozone oxidation process is an advanced treatment process after biochemical treatment. The influent of the advanced treatment process does not contain biodegradable organic matter, but mainly includes difficultly biodegradable organic matter or toxic organic matter. The organic matter in the influent of this experimental example and its proportion are shown in Table 2. The overall COD value of the influent is low. In order to ensure that the effluent water quality meets the standards and realize the reuse of water resources, the wastewater is further treated. The main indicator measured in the advanced treatment stage is the effluent COD value, and 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 referred to as catalyst 5, and Example 1 was referred to 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.

[0070] Table 1 Test water quality parameters

[0071]

[0072] Table 2 Types and contents of organic matter in the influent of the advanced treatment process of the petrochemical wastewater plant (Zhejiang)

[0073]

[0074] Experimental Example 2

[0075] The pilot test verified the performance 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 of 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 filling thickness is 20 cm, the residence time is 30 min, and the reflux ratio is 150%, the process is continuously operated for 30 days. The COD of the pilot test influent 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 discharge standards of petrochemical wastewater plants.

[0076] Experimental Example 3

[0077] 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 deep treatment process influent 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 crude oil desalination process manufacturers and catalytic cracking organic matter production process manufacturers, and the COD of the wastewater is relatively high. The water quality parameters of the deep treatment process influent of the sewage plant are shown in Table 3. Considering the high COD of the influent, the ozone dosage in the pilot experiment was 80 mg / L, the catalyst filling thickness was 20 cm, the residence time was 1 hour, and the reflux ratio was 150%. It was operated continuously for 30 days. The experimental results are as follows: Figure 5 As shown, during the entire pilot test, the COD removal rate remained stable at 70%~90%, the ozone utilization rate remained stable between 1.2-1.7; and the effluent COD remained below 30mg / L.

[0078] Table 3 Test water quality parameters

[0079]

[0080] Comparative Example 2

[0081] 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, which proves that the impregnation solution concentration ratio determined in the present invention is the optimal ratio.

[0082] Table 4 Concentration of active components in the impregnation solution

[0083]

[0084] Example 2

[0085] 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 in an oven at 105°C for 10 hours to obtain an activated alumina carrier.

[0086] Preparation of the impregnation solution: Ferric nitrate, cerium nitrate, and cobalt nitrate were dissolved in water to prepare a mixed solution, and glucose solution was added to the mixed solution as a pore regulator to obtain an impregnation solution (iron ion concentration of 0.3 mmol / L, cerium ion concentration of 0.5 mmol / L, cobalt ion concentration of 0.5 mmol / L, glucose concentration of 100 mmol / L); the activated alumina support was placed in the prepared impregnation solution for impregnation for 18 hours and then dried; the catalyst precursor was then placed in a muffle furnace, heated to 450°C at a heating rate of 5°C / min, and calcined for 6 hours to obtain a heterogeneous catalyst; the prepared catalyst was washed and dried in deionized water to obtain an aluminum-based ozone catalyst loaded with three active components.

[0087] Example 3

[0088] 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 in an oven at 105°C for 10 hours to obtain an activated alumina carrier.

[0089] Preparation of the impregnation solution: Ferric nitrate, cerium nitrate and cobalt nitrate were dissolved in water to prepare a mixed solution, and glucose solution was added to the mixed solution as a pore regulator to obtain an impregnation solution (iron ion concentration of 0.3 mmol / L, cerium ion concentration of 0.5 mmol / L, cobalt ion concentration of 0.5 mmol / L, glucose concentration of 200 mmol / L); the activated alumina support was placed in the prepared impregnation solution for impregnation, and the mixture was dried after impregnation for 24 hours; the catalyst precursor was then placed in a muffle furnace, heated to 600°C at a heating rate of 10°C / min, and calcined for 4 hours to obtain a heterogeneous catalyst; the prepared catalyst was washed and dried in deionized water to obtain an aluminum-based ozone catalyst loaded with three active components.

[0090] 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.

[0091] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily 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 is not limited to the embodiments shown herein but is intended to conform 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; 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 regulating agent in the impregnation solution is 50-200 mmol / L; The alumina carrier is γ-alumina; The particle size of the alumina carrier is 3-5 mm; The pore regulating agent is glucose; 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; The alumina support in step 2) further includes an activation step before being impregnated; The activation steps are: acid leaching and alkali leaching are performed on the alumina carrier in sequence to complete the activation of the alumina carrier.

2. The method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 1, 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.

3. The method for preparing an aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 1, characterized in that: The soaking time in step 2) is 12 to 24 hours.

4. 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 3.

5. Use of the aluminum-based ozone catalyst for deep treatment of petrochemical wastewater according to claim 4 in treating petrochemical wastewater.

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