A catalyst for catalytic wet oxidation of tetrabromobisphenol a wastewater, a preparation method and application thereof

Abstract

The application provides a catalyst for catalytic wet oxidation of tetrabromobisphenol A wastewater, a preparation method and application thereof, and belongs to the technical field of wastewater treatment. The catalyst comprises a main metal oxide and a crystal lattice adjusting metal oxide; the main metal oxide comprises one or more of MnO2, Co3O4, NiO or MoO3, and the crystal lattice adjusting metal oxide comprises an oxide of Ce and / or an oxide of La. The preparation method comprises the following steps: adding main metal salt, crystal lattice adjusting metal salt and citric acid into water, evaporating and concentrating, drying, first calcining, adding sodium hydroxide into water to perform a closed pressurized reaction, washing and drying, second calcining, placing into a nitric acid solution, heat treatment, washing and drying, placing into water with hydrogen peroxide and acetic acid to perform a heat reaction, filtering and drying, and obtaining the catalyst. The catalyst introduces a large number of oxygen defects through a mode of "lattice doping - partial metal removal - lattice distortion", so that the catalyst has a large oxygen storage capacity, can activate the C-Br bond, and can efficiently catalyze the oxidation of tetrabromobisphenol A wastewater.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of wastewater treatment, and particularly relates to a catalyst for catalytic wet oxidation of tetrabromobisphenol A wastewater as well as a preparation method and application thereof. BACKGROUND

[0002] Tetrabromobisphenol A is the most important bromine-based flame retardant, accounting for about 60% of the global bromine-based flame retardant market. Due to its special performance, it is widely used in the manufacture of electronic, electrical, plastic, textile, building material and other fireproof materials to prevent or reduce the flammability of polymers. Due to the lipophilicity of bromine-based flame retardants, it can be enriched in the body, thereby having toxic effects on the human body. In the production process of tetrabromobisphenol A, a large amount of high-COD organic wastewater is discharged, and the wastewater contains tetrabromobisphenol A and bromophenol and other bromine-containing aromatic hydrocarbons. These organic matters have relatively stable structures, and their B / C ratio is extremely low, so they are difficult to biodegrade. The concentration of tetrabromobisphenol A and the concentration of COD in tetrabromobisphenol A wastewater are as high as 20,000-30,000 mg / L, and the wastewater contains a high content of bromine ions, so it is difficult to treat. Patent CN112499753A uses a three-dimensional electrochemical combined biological treatment device to treat tetrabromobisphenol A wastewater, but the concentration of tetrabromobisphenol A in the wastewater is only 10-20 mg / L, so it is suitable for treating low-concentration tetrabromobisphenol A wastewater. Patent CN114634896B uses a biological degradation method to treat tetrabromobisphenol A wastewater, and the tolerance concentration of tetrabromobisphenol A to bacteria is 1,000 mg / L. Patent CN113816520A uses a combination of flocculants, activated carbon, resin adsorption and other methods to treat tetrabromobisphenol A wastewater, and this treatment method will produce secondary pollution such as flocculation and waste activated carbon.

[0003] The catalytic wet oxidation of organic wastewater technology is one of the most effective methods for treating high-concentration and refractory wastewater, and the key technology is a high-efficiency catalytic oxidation catalyst. Tetrabromobisphenol A, bromophenol and other bromine-containing aromatic hydrocarbons in tetrabromobisphenol A wastewater have stable structures and are difficult to oxidize. In order to catalyze such organic matters, the catalytic oxidation catalyst needs to have very strong oxidation capacity.

[0004] In view of this, the present application is proposed. SUMMARY

[0005] The present application aims to provide a catalyst for catalytic wet oxidation of tetrabromobisphenol A wastewater as well as a preparation method and application thereof, so as to solve the above problems.

[0006] To achieve the above-mentioned purposes, the present application adopts the following technical solutions:

[0007] A catalyst for catalytic wet oxidation of tetrabromobisphenol A wastewater comprises a main metal oxide and a lattice regulating metal oxide; the main metal oxide comprises one or more of MnO2, Co3O4, NiO or MoO3, and the lattice regulating metal oxide comprises Ce oxide and / or La oxide.

[0008] The key to improving the oxidation capacity of catalytic wet oxidation catalysts is the construction of oxygen defect sites on the catalyst surface. The main metal oxide is doped with Ce and La lattice regulating metals to form a bimetallic doped composite metal oxide. The composite metal oxide then selectively removes part of the lattice regulating metal, thereby causing the composite metal oxide to undergo lattice distortion and generate a large number of oxygen defects on the surface, providing oxygen storage performance for the catalyst, thereby giving the catalyst catalytic oxidation ability.

[0009] Furthermore, according to the weight ratio, the main metal oxide accounts for 70.5-82.3wt%, and the lattice regulating metal oxide accounts for 17.7-29.5wt%; the oxygen storage capacity of the catalyst is 542-983μmol / g, and the specific surface area is 183.9-264.6m 2 / g.

[0010] The present invention also provides a method for preparing the catalyst, comprising the following steps:

[0011] S1: The main metal salt, the lattice regulating metal salt and citric acid are added to deionized water, evaporated and concentrated into a paste, dried, and subjected to a first calcination to obtain sample 1.

[0012] The purpose of adding citric acid is to allow the citric acid to complex the metal ions, thereby forming a stable crystal structure after the first calcination.

[0013] Furthermore, the main metal salt is one or more of nitrates of Mn, Co, Ni or Mo.

[0014] Furthermore, the salt of the lattice regulating metal is nitrate of Ce and / or nitrate of La.

[0015] Furthermore, the mass ratio of the primary metal salt, the lattice-adjusting metal salt, and citric acid is (79.2-86.5):(12.3-21.6):8.6. Only by meeting this ratio can the two metal oxides be fully doped and have a rich porous structure. Deviation from this ratio will result in insufficient metal doping and a low specific surface area.

[0016] Furthermore, the evaporation and concentration process is performed at 60-90°C, the drying process is performed at 100-120°C, and the first calcination process is performed at 600-700°C. By performing evaporation and concentration followed by drying, the materials can be evenly mixed, avoiding direct drying of the solution at temperatures above 100°C, which can cause large amounts of the solution to boil and affect process control. The first calcination process also allows the sample to form a stable crystal structure.

[0017] S2: Sample 1 and sodium hydroxide are added to deionized water to form a suspension, which is then subjected to a sealed, pressurized reaction. The suspension is cooled to room temperature, washed, dried, and then subjected to a second calcination to obtain Sample 2. The pressurized, sealed reaction after the addition of sodium hydroxide dissociates the original crystal structure of Sample 1, forming hydroxyl species with the sodium hydroxide, facilitating the subsequent selective removal of the lattice modifier metal.

[0018] Optionally, the mass ratio of the sample 1, sodium hydroxide and deionized water is (8-10):(9-12):100ml.

[0019] Optionally, the closed pressurized reaction is carried out at 250-300° C. and 1.0-2.0 MPa for 2-5 hours.

[0020] Optionally, the second calcination is performed at 300-500° C. for 3-6 hours.

[0021] S3: placing the sample 2 in a nitric acid solution, subjecting it to heat treatment, washing, and drying, to obtain a sample 3. The heat treatment after adding nitric acid can remove part of the Ce and / or La metal in the sample 2.

[0022] Optionally, the usage ratio of the sample 2 and the nitric acid solution is (11-15g):100ml.

[0023] Optionally, the concentration of the nitric acid solution is 0.5-2M.

[0024] Optionally, the heat treatment is performed at 200-250° C. for 30-60 min.

[0025] Once the sample is treated with sodium hydroxide in step S2 and nitric acid in step S3, 30.2-40.5% of Ce and / or La can be removed. After some Ce and / or La are removed from the original composite metal oxide, the metal ratio changes, causing lattice rearrangement and lattice distortion of the main metal and lattice-modifying metal.

[0026] S4: placing the sample 3, hydrogen peroxide and acetic acid in deionized water, heating for reaction, filtering and drying to obtain the catalyst.

[0027] Optionally, the ratio of sample 3, hydrogen peroxide, acetic acid, and deionized water is (10-13g):(3-6g):(2-5g):100ml. After treatment with hydrogen peroxide and acetic acid, sample 3 significantly increases the concentration of surface oxygen defects, demonstrating efficient catalytic oxidation capability. Treatment with hydrogen peroxide and acetic acid can cause etching and oxidation of the sample, forming a large number of oxygen defects on the surface and improving catalytic oxidation capability.

[0028] Optionally, the heating reaction is performed at 50-80° C. The heating temperature is the optimal temperature range for the formation of oxygen defects on the sample surface. Below this temperature, insufficient oxygen defects are introduced. Above this temperature, sample 3 is over-etched and oxidized, resulting in structural damage.

[0029] The catalyst prepared by the above method has an oxygen storage capacity of 542-983 μmol / g, has the ability to activate C-Br bonds, and can be used to efficiently catalyze the wet oxidation of tetrabromobisphenol A wastewater.

[0030] The present invention also provides an application of the catalyst in catalytic wet oxidation of tetrabromobisphenol A wastewater: placing the catalyst in a fixed bed reactor and heating the reactor at an air space velocity of 150-400h -1 , at a pressure of 3.0-7.0 MPa, the temperature is raised to 180-230°C at a rate of 0.5-2.0°C / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20000-22000 mg / L is heated at a liquid space velocity of 1.0-3.0 h -1 Feed the reaction.

[0031] Compared with the existing technology, the present invention creatively introduces a large number of oxygen defects on the catalyst surface through the method of "lattice doping - partial metal removal - lattice distortion", so that the catalyst has a large amount of oxygen storage capacity and the ability to activate and oxidize C-Br bonds, and can efficiently catalyze the oxidation of tetrabromobisphenol A wastewater.

[0032] The preparation method provided by the present invention is simple to operate, has controllable conditions, and has the potential for large-scale industrial application.

[0033] When the catalyst provided by the present invention is used to treat tetrabromobisphenol A wastewater, the COD removal rate is greater than 93%. DETAILED DESCRIPTION

[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0035] Example 1

[0036] A preparation method for catalytic wet oxidation of tetrabromobisphenol A wastewater:

[0037] 83.1g of nickel nitrate, 14.9g of cerium nitrate and 8.6g of citric acid are added to 500ml of deionized water, evaporated and concentrated to a paste at 80°C, dried at 100°C, and then calcined at 600°C to obtain sample one; 16g of sample one and 18g of NaOH are added to 200ml of deionized water to form a suspension, placed in a high-pressure reactor, reacted at 250°C and 1.2MPa for 3h, taken out and cooled to room temperature, washed and dried, and then calcined at 350°C for 4h to obtain sample two; 16.5g of sample two is placed in 150ml of 1M nitric acid solution, heat treated at 220°C for 30min, washed, and dried to obtain sample three; 10g of sample three, 3g of hydrogen peroxide and 3g of acetic acid are placed in 100ml of deionized water, reacted at 60°C for 2h, filtered, and dried to obtain the catalyst.

[0038] The obtained catalyst consists of 71.4 wt% of the main metal oxide NiO and 28.6 wt% of the lattice regulating metal oxide CeO2. The catalyst has an oxygen storage capacity of 542 μmol / g and a specific surface area of ​​223.2 m 2 / g.

[0039] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1 , under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20450mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0040] Example 2

[0041] A preparation method for catalytic wet oxidation of tetrabromobisphenol A wastewater:

[0042] Example 1

[0043] The obtained catalyst comprises 73.5wt% of main metal oxide Co304and 26.5wt% of lattice adjusting metal oxide Ce02, and the catalyst has an oxygen storage capacity of 835 μmol / g and a specific surface area of 244.4 m2 / g. 2

[0044] The above catalyst was placed in a fixed bed reactor, and tetrabromobisphenol A wastewater with a COD concentration of 21360 mg / L was reacted at a liquid space velocity of 2.0 h -1 -1under air space velocity of 200 h -1 -1, pressure of 4.0 MPa, and temperature of 200℃, which was raised at a rate of 1.0℃ / min. The reaction results are shown in Table 1.

[0045] Example 3

[0046] A preparation method of a catalyst for catalytic wet oxidation of tetrabromobisphenol A wastewater:

[0047] 86.5g of manganese nitrate, 21.6g of cerium nitrate and 8.6g of citric acid were added to 500ml of deionized water, concentrated into paste at 90℃, dried at 120℃, and then calcined at 650℃ to obtain sample one. 20g of sample one and 24g of NaOH were added to 200ml of deionized water to form a suspension, which was placed in an autoclave and reacted at 280℃ and 1.0MPa for 4h. After cooling to room temperature, the product was washed, dried and calcined at 450℃ for 3h to obtain sample two. 22.5g of sample two was added to 150ml of 2M nitric acid solution, heated at 250℃ for 60min, washed, dried to obtain sample three. 13g of sample three, 6g of hydrogen peroxide and 5g of acetic acid were added to 100ml of deionized water, and reacted at 50℃ for 2h. After filtration and drying, the catalyst was obtained.

[0048] ​The obtained catalyst consists of 79.6 wt% of the main metal oxide MnO2 and 20.4 wt% of the lattice regulating metal oxide CeO2. The catalyst has an oxygen storage capacity of 605 μmol / g and a specific surface area of ​​183.9 m 2 / g.

[0049] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1 , under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with COD concentration of 21630mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0050] Example 4

[0051] A preparation method for catalytic wet oxidation of tetrabromobisphenol A wastewater:

[0052] 86.5g of manganese nitrate, 19.5g of lanthanum nitrate and 8.6g of citric acid are added to 500ml of deionized water, evaporated and concentrated to a paste at 60°C, dried at 110°C, and then calcined at 700°C to obtain sample one; 18g of sample one and 22g of NaOH are added to 200ml of deionized water to form a suspension, placed in a high-pressure reactor and reacted at 300°C and 1.0MPa for 5h, taken out and cooled to room temperature, washed and dried, and then calcined at 500°C for 6h to obtain sample two; 18g of sample two is placed in 150ml of 1.5M nitric acid solution, heat treated at 200°C for 60min, washed, and dried to obtain sample three; 11g of sample three, 5g of hydrogen peroxide and 3g of acetic acid are placed in 100ml of deionized water, reacted at 80°C for 2h, filtered, and dried to obtain the catalyst.

[0053] The obtained catalyst consists of 71.8 wt% of the main metal oxide MnO2 and 28.2 wt% of the lattice regulating metal oxide La2O3. The catalyst has an oxygen storage capacity of 716 μmol / g and a specific surface area of ​​198.1 m 2 / g.

[0054] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1 , under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20654mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0055] Example 5

[0056] A preparation method for catalytic wet oxidation of tetrabromobisphenol A wastewater:

[0057] 79.2g of molybdenum nitrate, 12.3g of cerium nitrate and 8.6g of citric acid are added to 500ml of deionized water, evaporated and concentrated to a paste at 75°C, dried at 110°C, and then calcined at 650°C to obtain sample one; 18g of sample one and 20g of NaOH are added to 200ml of deionized water to form a suspension, placed in a high-pressure reactor, reacted at 250°C and 1.2MPa for 3h, taken out and cooled to room temperature, washed and dried, and then calcined at 350°C for 4h to obtain sample two; 18g of sample two is placed in 150ml of 1.5M nitric acid solution, heat treated at 230°C for 50min, washed, and dried to obtain sample three; 12g of sample three, 4g of hydrogen peroxide and 3g of acetic acid are placed in 100ml of deionized water, reacted at 70°C for 2h, filtered, and dried to obtain the catalyst.

[0058] The obtained catalyst consists of 82.3 wt% of the main metal oxide MoO3 and 17.7 wt% of the lattice regulating metal oxide CeO2. The catalyst has an oxygen storage capacity of 808 μmol / g and a specific surface area of ​​232.5 m 2 / g.

[0059] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1 , under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with COD concentration of 21630mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0060] Example 6

[0061] A preparation method for catalytic wet oxidation of tetrabromobisphenol A wastewater:

[0062] 58.4g of nickel nitrate, 22.1g of molybdenum nitrate, 15.6g of cerium nitrate and 8.6g of citric acid were added to 500ml of deionized water, evaporated and concentrated to a paste at 70°C, dried at 110°C, and then calcined at 650°C to obtain sample one; 18g of sample one and 20g of NaOH were added to 200ml of deionized water to form a suspension, placed in a high-pressure reactor and reacted at 250°C and 1.2MPa for 3h, taken out and cooled to room temperature, washed and dried, and then calcined at 350°C for 4h to obtain sample two; 18g of sample two was placed in 150ml of 1M nitric acid solution, heat treated at 240°C for 50min, washed, and dried to obtain sample three; 12g of sample three, 4g of hydrogen peroxide and 3g of acetic acid were placed in 100ml of deionized water, reacted at 70°C for 2h, filtered, and dried to obtain the catalyst.

[0063] The obtained catalyst includes 75.2wt% of main metal oxides NiO and MoO3 and 24.8wt% of lattice regulating metal oxide CeO2. The catalyst has an oxygen storage capacity of 983μmol / g and a specific surface area of ​​264.6m 2 / g.

[0064] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1 , under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20984mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0065] Comparative Example 1

[0066] Compared with Example 1, the difference is that the lattice-adjusting metal nitrate cerium nitrate is not doped.

[0067] The obtained catalyst contains only NiO, with an oxygen storage capacity of 154 μmol / g and a specific surface area of ​​199.7 m 2 / g.

[0068] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1 , under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20450mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0069] Comparative Example 2

[0070] 83.1g of nickel nitrate, 14.9g of cerium nitrate and 8.6g of citric acid were added to 500ml of deionized water, evaporated and concentrated at 80°C to a paste, dried at 100°C, and then calcined at 650°C to obtain sample 1; 10g of sample 1, 3g of hydrogen peroxide and 3g of acetic acid were placed in 100ml of deionized water, reacted at 60°C for 2h, filtered, and dried to obtain a catalyst.

[0071] The obtained catalyst consists of 84.7 wt% of the main metal oxide NiO and 15.3 wt% of the lattice regulating metal oxide CeO2. The catalyst has an oxygen storage capacity of 171 μmol / g and a specific surface area of ​​158.4 m 2 / g.

[0072] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1, under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20450mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0073] Comparative Example 3

[0074] Compared with Example 1, the difference is that no acetic acid was added when treating Sample 3.

[0075] The obtained catalyst has an oxygen storage capacity of 343 μmol / g and a specific surface area of ​​217.2 m 2 / g.

[0076] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1 , under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20450mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0077] Comparative Example 4

[0078] Compared with Example 1, the difference is that after obtaining Sample 3, it is directly filtered and dried to obtain the catalyst.

[0079] The obtained catalyst has an oxygen storage capacity of 274 μmol / g and a specific surface area of ​​205.8 m 2 / g.

[0080] The above catalyst was placed in a fixed bed reactor and heated at an air space velocity of 200 h -1 , under the pressure of 4.0MPa, the temperature was raised to 200℃ at a rate of 1.0℃ / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20450mg / L was heated at a liquid space velocity of 2.0h -1 The reaction results are listed in Table 1.

[0081] Table 1 Catalyst performance test results of Examples 1-3 and Comparative Examples 1-4

[0082]

[0083]

[0084] The test results of Examples 1-6 in Table 1 show that the catalyst obtained according to the preparation method and preferred parameters provided by the present invention has a COD removal rate greater than 93% and a B / C ratio greater than 0.45 when treating tetrabromobisphenol A wastewater.

[0085] From the test results of Comparative Example 1 in Table 1, it can be seen that when the lattice-modulating metal nitrate is not doped, the oxygen storage capacity of the catalyst is significantly reduced, so that a large number of oxygen defects cannot be generated on the catalyst surface, and the catalytic oxidation ability is weak.

[0086] From the test results of Comparative Example 2 in Table 1, it can be seen that without the NaOH and nitric acid treatment, it is impossible to selectively remove part of the lattice-adjusting metal Ce, and it is also impossible to cause the lattice distortion of the metal oxide.

[0087] From the test results in Table 1, it can be seen that the catalyst performance of Comparative Example 4 is far inferior to that of Example 1 because it is not treated with hydrogen peroxide and acetic acid. The performance of Comparative Example 3 is almost the same as that of Comparative Example 4 because it is only treated with hydrogen peroxide without adding acetic acid.

[0088] Please note that the technical features of the above embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification. The above embodiments only express several implementation methods of the present application. The description is relatively specific and detailed, but it cannot be understood as a limitation on the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of this application, several variations and improvements can be made, which all fall within the scope of protection of this application. Therefore, the scope of protection of the patent in this application shall be based on the attached claims.

Claims

1. A method for preparing a catalyst for catalytic wet oxidation of tetrabromobisphenol A wastewater, characterized in that: The steps include: S1: adding the main metal salt, the lattice regulating metal salt and citric acid into deionized water, evaporating and concentrating to a paste, drying, and performing a first calcination to obtain sample 1; S2: adding the sample 1 and sodium hydroxide into deionized water to form a suspension, subjecting the suspension to a closed pressurized reaction, cooling to room temperature, washing, drying, and then performing a second calcination to obtain sample 2; S3: placing the sample 2 in a nitric acid solution, heat-treating, washing, and drying to obtain a sample 3; S4: placing the sample 3, hydrogen peroxide and acetic acid in deionized water, heating for reaction, filtering and drying to obtain the catalyst; The catalyst includes a main metal oxide and a lattice regulating metal oxide; the main metal oxide includes one or more of MnO2, Co3O4, NiO or MoO3, and the lattice regulating metal oxide includes Ce oxide and / or La oxide.

2. The preparation method according to claim 1, characterized in that In step S1, the main metal salt is one or more of the nitrates of Mn, Co, Ni or Mo; The salt of the lattice regulating metal is Ce nitrate and / or La nitrate.

3. The preparation method according to claim 1 or 2, characterized in that In step S1, the mass ratio of the main metal salt, the lattice regulating metal salt and citric acid is (79.2-86.5):(12.3-21.6):8.

6.

4. The preparation method according to claim 1, characterized in that In step S1, the evaporation concentration is carried out at 60-90°C; The drying is carried out at 100-120°C; The first calcination is performed at 600-700°C.

5. The preparation method according to claim 1, characterized in that Step S2 satisfies: The closed pressurized reaction is carried out at 250-300°C and 1.0-2.0 MPa for 2-5 hours; The second calcination is performed at 300-500° C. for 3-6 h.

6. The preparation method according to claim 1, characterized in that Step S3 satisfies: The usage ratio of the sample 2 and the nitric acid solution is (11-15 g):100 ml; The concentration of the nitric acid solution is 0.5-2 M; The heat treatment is carried out at 200-250° C. for 30-60 min.

7. The preparation method according to claim 1, characterized in that Step S4 satisfies: The usage ratio of sample 3, hydrogen peroxide, acetic acid and deionized water is (10-13 g): (3-6 g): (2-5 g): 100 ml; The heating reaction is carried out at 50-80°C.

8. A catalyst for catalytic wet oxidation of tetrabromobisphenol A wastewater, characterized in that: Prepared by the preparation method according to any one of claims 1 to 7.

9. The catalyst according to claim 8, characterized in that According to the weight ratio, the main metal oxide accounts for 70.5-82.3 wt% and the lattice regulating metal oxide accounts for 17.7-29.5 wt%; The catalyst has an oxygen storage capacity of 542-983 μmol / g and a specific surface area of ​​183.9-264.6 m 2 / g.

10. Use of the catalyst according to claim 8 or 9 in catalytic wet oxidation of tetrabromobisphenol A wastewater, characterized in that: The catalyst is placed in a fixed bed reactor and heated at an air space velocity of 150-400 h -1 , at a pressure of 3.0-7.0 MPa, the temperature was raised to 180-230 ° C at a rate of 0.5-2.0 ° C / min, and the tetrabromobisphenol A wastewater with a COD concentration of 20000-22000 mg / L was heated at a liquid space velocity of 1.0-3.0 h -1 Feed the reaction.

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