CN114471635B - Catalytic oxidation catalyst and preparation method and application thereof - Google Patents

Catalytic oxidation catalyst and preparation method and application thereof Download PDF

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CN114471635B
CN114471635B CN202011165953.5A CN202011165953A CN114471635B CN 114471635 B CN114471635 B CN 114471635B CN 202011165953 A CN202011165953 A CN 202011165953A CN 114471635 B CN114471635 B CN 114471635B
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oxidation catalyst
catalytic oxidation
phosphate
catalyst according
iron
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CN114471635A (en
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赵越
曹杰
张金河
蒋广安
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract

The invention discloses a catalytic oxidation catalyst and a preparation method and application thereof, wherein the catalyst comprises a carrier, an active component and an auxiliary component, wherein the active component is ferric phosphate, and the auxiliary component is calcium phosphate and/or magnesium phosphate; the carrier is one or more of active carbon, inorganic refractory oxide and molecular sieve. The preparation method comprises the steps of firstly preparing a catalytic precursor material, then carrying out contact reaction on the obtained catalytic precursor material and a solution containing phosphate radical, and further carrying out separation, washing, drying and roasting after the reaction to obtain the catalyst. Also provides a method for treating organic wastewater by adopting the catalyst. The catalyst disclosed by the invention has the advantages of high dispersity of active components, stable structure and high catalytic degradation capability of organic pollutants.

Description

Catalytic oxidation catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a catalytic oxidation catalyst and a preparation method thereof.
Background
In recent years, advanced oxidation technologies (AOPs) have been rapidly developed in the field of organic pollutant wastewater treatment. The advanced oxidation technology can utilize strong oxidative free radical species generated by the oxidant to rapidly oxidize and degrade the organic pollutants, and has the advantages of high reaction rate, strong oxidation capability, almost no selectivity to the organic matters, high mineralization rate and the like.
The conventional advanced oxidation catalyst usually uses transition metal as an active component, but metals such as Cu, co, ni, mn and the like are strictly limited in sewage discharge standard, and the metals are easy to dissolve out in application to cause secondary pollution. Therefore, iron and its compounds as the active components of the catalyst have obvious advantages in the application field.
Iron phosphate is commonly used as a raw material for lithium iron phosphate batteries, and there is little research for catalytic reactions. There are studies in the literature on bulk iron phosphate catalysts or iron phosphate supported noble metal catalysts as gas phase catalytic oxidation catalysts (iron phosphate catalyzed p-cresol gas phase selective oxidation in the presence of acetic acid, catalysis journal 2005; mesoporous iron hydroxyphosphate preparation, characterization and catalytic performance studies on supported noble metals, university of Nanjing, 2017). CN201511006268.7 discloses a process for preparing iron phosphate, which comprises the following steps: placing iron in phosphoric acid solution, heating to perform iron-dissolving reaction to obtain Fe (H) 2 PO 4 ) 2 Is a reaction solution of (a); adding hydrogen peroxide into the filtrate of the reaction liquid, carrying out oxidation reaction under stirring, adding polyethylene glycol, and continuously stirring to obtain Fe (H) 2 PO 4 ) 2 Reacting to generate ferric phosphate to obtain oxidized liquid; distilled water is added into the oxidized solution to carry out hydrolysis and crystallization reaction; carrying out solid-liquid separation on the hydrolyzed and crystallized feed liquid, washing the separated solid phase discharge until the pH value of the washed liquid reaches near neutral, and spin-drying to obtain solid ferric phosphate; sequentially drying and dehydrating the dried solid ferric phosphate to form a de-watering deviceIron phosphate in water.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention mainly aims to provide a catalytic oxidation catalyst and a preparation method thereof, in particular to a supported catalyst taking ferric phosphate as an active component and a preparation method thereof, wherein the catalyst has high dispersity of the active component, stable structure and high catalytic degradation capability of organic pollutants.
The first aspect of the invention provides a catalytic oxidation catalyst, which comprises a carrier, an active component and an auxiliary component, wherein the active component is ferric phosphate, and the auxiliary component is calcium phosphate and/or magnesium phosphate; the content of the carrier is 30-60%, preferably 40-50% based on the weight of the catalyst; the content of the ferric phosphate is 5-30%, preferably 15-25%; the content of the auxiliary agent component is 20% -40%, preferably 25% -35%.
In the catalytic oxidation catalyst, the carrier is one or more of active carbon, inorganic refractory oxide and molecular sieve; preferably activated carbon; wherein the inorganic refractory oxide can be one or more of alumina, silica, titania, cerium oxide, magnesia and zirconia, and the molecular sieve is one or more of A-type, Y-type, beta-type, ZSM-series and MCM-series molecular sieves.
In the catalyst, active components of ferric phosphate and auxiliary agents are loaded on the outer surface of a carrier and inside a pore canal, and are baked and solidified.
In the catalyst of the invention, the properties of the catalyst are as follows: the specific surface area is 120-1200 m 2 Per gram, the pore volume is 0.1-1.5 cm 3 /g, abrasion rate<2.5wt% and side pressure strength of 80-200N/cm.
In the catalyst of the invention, the properties of the catalyst are as follows: in the pH range of 3-10, the Fe ion elution concentration is less than 300mg/L, preferably 0-200 mg/L.
The second aspect of the present invention provides a method for preparing a catalytic oxidation catalyst, the method comprising the following steps:
(1) Mixing an iron source, an auxiliary metal salt solution and a carrier material uniformly to obtain a catalytic precursor material;
(2) And (3) carrying out contact reaction on the catalytic precursor material obtained in the step (1) and a solution containing phosphate radical, and further separating, washing, drying and roasting after the reaction to obtain the catalyst.
In the preparation method of the catalytic oxidation catalyst, in the step (1), the iron source is a soluble ferric salt solution, and may be an inorganic ferric salt solution and/or an organic ferric salt solution, preferably an organic ferric salt solution, and more preferably a trivalent organic ferric salt solution; the iron oxide can be one or more of ferric sulfate, ferric nitrate, ferric chloride, ferric acrylate, ferric acetate, ferric citrate and dextran; preferably one or more of iron acrylate, iron acetate, iron citrate and iron dextran.
In the preparation method of the catalytic oxidation catalyst, the auxiliary metal in the step (1) is magnesium and/or calcium, and the auxiliary metal salt solution can be one or more of magnesium chloride, calcium chloride, magnesium nitrate and calcium nitrate.
In the preparation method of the catalytic oxidation catalyst, the carrier in the step (1) is one or more of active carbon, inorganic refractory oxide and molecular sieve; preferably activated carbon; wherein the inorganic refractory oxide can be one or more of alumina, silica, titania, cerium oxide, magnesia and zirconia, and the molecular sieve is one or more of A-type, Y-type, beta-type, ZSM-series and MCM-series molecular sieves. The activated carbon can be 200-600 mesh powder or 0.5-3mm activated carbon particles, and the specific surface area is 500-3000 m 2 Per gram, pore volume of 0.5-1.8 cm 3 And/g, wherein the average pore diameter is 0.5-4.0 nm, and the pore volume of pores with the pore diameter smaller than 2nm accounts for more than 90% of the total pore volume.
In the preparation method of the catalytic oxidation catalyst, the mass ratio of the iron source, the auxiliary metal salt solution and the carrier material in the step (1) is 1.8-11.1: 7.8 to 15.5 (5.5 to 11.1): 30 to 60 percent.
In the preparation method of the catalytic oxidation catalyst, the solution containing phosphate in the step (2) is one or more of phosphoric acid, phosphate and urea phosphate, preferably phosphate, and more preferably ammonium phosphate; the phosphoric acid is orthophosphoric acid, and the phosphoric acid can be one or more of sodium phosphate, potassium phosphate, ammonium phosphate, monoammonium phosphate and sodium hydrogen phosphate. In the solution containing phosphate radical, the concentration of the phosphate radical is 0.6-2.0 mol/L.
In the preparation method of the catalytic oxidation catalyst, the molar ratio of the phosphate radical in the phosphate radical-containing solution in the step (2) to the iron ions and the auxiliary metal ions in the catalytic precursor material is not less than 1:1, preferably 1-1.1: 1.
in the above-mentioned method for producing a catalytic oxidation catalyst, the reaction temperature in the step (2) is 40 to 90 ℃, preferably 50 to 80 ℃.
In the above-mentioned method for preparing a catalytic oxidation catalyst, the reaction in step (2) is preferably carried out under ultrasonic oscillation at a frequency of 30 to 100 KHz.
In the preparation method of the catalytic oxidation catalyst, the separation in the step (2) may be any one of the methods capable of realizing liquid-solid two-phase separation in the prior art, such as filtration, centrifugal separation, spin drying and the like.
In the preparation method of the catalytic oxidation catalyst, the washing in the step (2) is carried out for 1 to 6 times, preferably 2 to 4 times by using water; the drying temperature is 80-150 ℃, preferably 90-120 ℃, and the drying treatment time is 3-24 h, preferably 6-12 h.
In the above-mentioned method for preparing a catalytic oxidation catalyst, the calcination in step (2) is performed under anaerobic conditions, preferably in the presence of an inert atmosphere, and the calcination temperature is 500 to 800 ℃, preferably 550 to 700 ℃; the roasting treatment time is 2-6 hours, preferably 3-5 hours. The inert atmosphere can be one or more of nitrogen, helium, neon, argon, krypton and xenon, and is preferably nitrogen.
In a third aspect, the present invention provides a method for treating organic wastewater, wherein the organic wastewater and an oxidant enter a reactor for treatment, and the catalytic oxidation catalyst is filled in the reactor.
In the organic wastewater treatment method, the organic wastewater is one or more of pharmaceutical wastewater, printing and dyeing wastewater, biochemical effluent, municipal wastewater, acrylic wastewater, coking wastewater and oily wastewater, and the COD range is 50-600 mg/L.
In the organic wastewater treatment method, the oxidant is one or more of ozone and hydrogen peroxide.
In the organic wastewater treatment method, the reaction conditions are normal pressure and volume space velocity of 0.25-2 h -1 The consumption of the oxidant is 0.5-3.0 times of the consumption of the oxidant required by the COD theory of the raw material organic wastewater.
Compared with the prior art, the catalytic oxidation catalyst and the preparation method and application thereof have the following advantages:
1. the invention provides a supported catalytic oxidation catalyst taking ferric phosphate as an active component for the first time, wherein the ferric phosphate is uniformly dispersed on the surface of a carrier and inside a pore canal, more active sites capable of participating in adsorption and catalytic reaction are exposed, the catalytic reaction efficiency is obviously enhanced compared with bulk catalysis, and the dosage of the ferric phosphate can be effectively reduced. Meanwhile, porous materials such as active carbon, oxide, molecular sieve and the like are used as carriers, so that the catalyst has strong adsorption capacity on organic pollutant components, and pollutant molecules can be adsorbed on the surface of the catalyst, so that the contact probability of the active components and the pollutant molecules is increased, the local concentration is improved, the initial reaction rate is improved, and the catalyst is beneficial to the catalytic reaction.
2. According to the preparation method of the catalytic oxidation catalyst, the iron phosphate is loaded on the catalyst carrier in an in-situ reaction mode, and the auxiliary agent component is simultaneously combined and introduced, so that under the combined action of the two means, on one hand, the active component can be ensured to be uniformly distributed on the carrier, on the other hand, the acting force between the active component and the carrier can be increased, the problem that the active component is easy to run off is solved, meanwhile, the wear resistance of the catalyst is improved, and on the other hand, the auxiliary agent component can play a role of supporting active carbon and solidifying the iron phosphate, so that the active carbon is not easy to run off on the surface of the active carbon.
Detailed Description
The preparation method of the present invention will be further described with reference to specific examples, but the scope of the present invention is not limited to the examples.
The specific surface area and pore volume referred to in the examples and comparative examples of the present invention were measured by the GB/T19587-2017 method, pore volume was measured by the ASTM D6761-2007 method, abrasion rate was measured by the HG/T2976-2011 method, and side pressure strength was measured by the HG/T2783-1996 method.
Example 1
0.13mol of ferric nitrate and 0.32mol of calcium chloride are added with 300mL of distilled water to prepare a solution, and the solution is stirred uniformly. 45g of coconut shell activated carbon powder (95% on a dry basis) was added, and after stirring, a monoammonium phosphate solution was added in an amount such that the "sum" molar ratio of phosphate to iron and calcium ions was 1.05. The mixed solution is heated to 65 ℃ in a water bath, reacts for 6 hours under the ultrasonic oscillation of 50KHz, and is subjected to rotary evaporation, washing, filtering, drying at 110 ℃ for 6 hours and roasting at 600 ℃ for 4 hours under the nitrogen condition to obtain the catalyst A1. 10g of catalyst A1 is used for intermittently treating acid scarlet dye wastewater with COD of 100mg/L under the action of ozone with the concentration of 30mg/L, and the COD removal rate can reach 78.3 percent.
Example 2
0.10mol of ferric formate and 0.25mol of calcium chloride are taken and added with 300mL of distilled water to prepare a solution, and the solution is uniformly mixed. 55g of a bar-shaped ZSM-5 molecular sieve (80% on a dry basis) was added, and after stirring, a urea phosphate solution was added in an amount such that the "sum" molar ratio of phosphate to iron and calcium ions was 1.02. The mixed solution is heated to 75 ℃ in a water bath, reacts for 6 hours under the ultrasonic oscillation of 80KHz, and is subjected to rotary evaporation, washing, filtering, drying at 110 ℃ for 8 hours and roasting at 550 ℃ for 4 hours under the anaerobic condition to obtain the catalyst A2. 100g of catalyst A2 were packed in a tubular reactor for 1h -1 Airspeed, ozone addition of 60mg/L, H 2 O 2 The adding amount is 20mg/L, the garbage leachate with COD of 300mg/L is cooperatively treated, and the COD removal rate can reach 70.7%.
Example 3
0.12mol of ferric acetate and 0.34mol of magnesium chloride are added with 350mL of distilled water to prepare a solution, and the solution is uniformly mixed. 60g of spherical alumina (82% on dry basis) were added, and after stirring, a phosphoric acid solution was addedThe addition amount of the medium phosphoric acid satisfies the sum mole ratio of phosphate radical to iron ion and magnesium ion to be 1.1. The mixed solution was heated to 55℃in a water bath, stirred slowly and reacted for 8 hours. Ammonia water is added dropwise to adjust the pH to 4.6, and a solid sample is obtained through rotary evaporation. Washing, filtering, drying at 100 ℃ for 8h and roasting at 650 ℃ for 3h under the anaerobic condition to obtain the catalyst A3. 50g of catalyst A3 were packed in a tubular reactor for 0.5h -1 The airspeed and the ozone concentration are 30mg/L, the COD removal rate of the medical wastewater with the COD of 120mg/L can reach 66.7 percent.
Example 4
0.15mol of ferric citrate and 0.39mol of magnesium nitrate are added with 500mL of distilled water to prepare a solution, and the solution is uniformly mixed. 55g of granular activated carbon (90% on dry basis) were added, and after stirring, a phosphoric acid solution was added, wherein the amount of phosphoric acid added was such that the "sum" molar ratio of phosphate to iron and magnesium ions was 1:1. Heating the mixed solution to 70 ℃ in a water bath, stirring slowly, reacting for 7h, filtering, washing, drying at 120 ℃ for 6h, and roasting at 700 ℃ for 4h under anaerobic condition to obtain the catalyst A4. 50g of catalyst A4 were packed in a tubular reactor for 1.0h -1 The airspeed and the ozone concentration of 50mg/L treat biochemical effluent with COD of 80mg/L, and the COD removal rate can reach 63.6 percent.
Example 5
0.11mol of ferric sulfate and 0.23mol of calcium nitrate are taken and added with 350mL of distilled water to prepare a solution, and the solution is uniformly mixed. 50g of powdered activated carbon (95% on a dry basis) was added, and after stirring, a sodium hydrogen phosphate solution was added in an amount such that the "sum" molar ratio of phosphate to iron and calcium ions was 1.05. The mixed solution is heated to 65 ℃ in a water bath, reacted for 3 hours under the ultrasonic oscillation of 50KHz, and the solid sample is obtained by rotary evaporation. Washing, filtering, drying at 120 ℃ for 10 hours, and roasting at 700 ℃ for 4 hours under anaerobic condition to obtain the catalyst A5. 50g of catalyst A5 are packed in a tubular reactor for 1.5h -1 The space velocity is 0.5g/L, H2O2 is added, the fuel wastewater with COD of 460mg/L is treated, and the COD removal rate can reach 65.5%.
Comparative example 1
The reagent iron phosphate powder was used as catalyst DA1. Example 1 was repeated, with catalyst A1 replaced with DA1 and the COD removal was 55.7%.
Comparative example 2
Mixing active carbon powder and ferric phosphate powder according to the mass ratio of 3:1, adding a binder, extruding and molding to prepare a 2mm cylindrical catalyst, and drying and roasting to obtain the catalyst DA2. Example 3 was repeated, with catalyst A3 replaced with DA2 and the COD removal was 48.9%.
Comparative example 3
Mixing ZSM-5 molecular sieve, calcium phosphate and ferric phosphate powder according to the mass ratio of 6:3:1, preparing a spherical catalyst with the diameter of 2mm by adopting a conventional method, drying and roasting to obtain the catalyst DA3. Example 3 was repeated, with catalyst A3 replaced with DA3 and the COD removal was 42.5%.
Comparative example 4
Adding nitric acid into aluminum oxide powder to prepare an adhesive, mixing the adhesive with magnesium phosphate and ferric phosphate powder according to the mass ratio of 5.5:2.5:2.0, extruding and molding to prepare a 3mm cylindrical catalyst, and drying and roasting to obtain the catalyst DA4. Example 4 was repeated, with catalyst A4 replaced with DA4 and the COD removal was 56.3%.

Claims (39)

1. A catalytic oxidation catalyst, which comprises a carrier, an active component and an auxiliary component, wherein the active component is ferric phosphate, and the auxiliary component is calcium phosphate and/or magnesium phosphate; the carrier is one or more of active carbon, inorganic refractory oxide and molecular sieve; the content of the carrier is 40% -50% based on the weight of the catalyst; the content of ferric phosphate is 15% -25%; the content of the auxiliary agent component is 25% -35%;
the catalytic oxidation catalyst is used for treating organic wastewater, and when the organic wastewater is treated, the organic wastewater and an oxidant enter a reactor for treatment, and the catalytic oxidation catalyst is filled in the reactor;
the preparation method of the catalytic oxidation catalyst comprises the following steps:
(1) Mixing an iron source, an auxiliary metal salt solution and a carrier material uniformly to obtain a catalytic precursor material;
(2) And (3) carrying out contact reaction on the catalytic precursor material obtained in the step (1) and a solution containing phosphate radical, and further separating, washing, drying and roasting after the reaction to obtain the catalyst.
2. The catalytic oxidation catalyst according to claim 1, wherein the inorganic refractory oxide is one or more of alumina, silica, titania, ceria, magnesia, and zirconia, and the molecular sieve is one or more of a type a, Y type, beta type, ZSM series, and MCM series molecular sieves.
3. The catalytic oxidation catalyst according to claim 1, wherein the support is activated carbon.
4. The catalytic oxidation catalyst according to claim 1, wherein the active component iron phosphate and the auxiliary agent are supported on the outer surface of the carrier and inside the pore channels, and are cured by calcination.
5. The catalytic oxidation catalyst according to claim 1, wherein the catalyst has the following properties: the specific surface area is 120-1200 m 2 Per gram, the pore volume is 0.1-1.5 cm 3 /g, abrasion rate<2.5wt% and side pressure strength of 80-200N/cm.
6. The catalytic oxidation catalyst according to claim 1, wherein the catalyst has the following properties: in the pH range of 3-10, the Fe ion dissolution concentration is less than 300 mg/L.
7. The catalytic oxidation catalyst according to claim 1, which has the following properties: in the pH range of 3-10, the Fe ion dissolution concentration is 0-200 mg/L.
8. The method for preparing the catalytic oxidation catalyst according to any one of claims 1 to 7, comprising the following steps:
(1) Mixing an iron source, an auxiliary metal salt solution and a carrier material uniformly to obtain a catalytic precursor material;
(2) And (3) carrying out contact reaction on the catalytic precursor material obtained in the step (1) and a solution containing phosphate radical, and further separating, washing, drying and roasting after the reaction to obtain the catalyst.
9. The method for preparing a catalytic oxidation catalyst according to claim 8, wherein the iron source in step (1) is a soluble iron salt solution, and the soluble iron salt solution is an inorganic iron salt solution and/or an organic iron salt solution.
10. The method for preparing a catalytic oxidation catalyst according to claim 9, wherein the iron source in step (1) is an organic ferric salt solution.
11. The method for preparing a catalytic oxidation catalyst according to claim 9, wherein the iron source in step (1) is a trivalent organic iron salt.
12. The method for preparing a catalytic oxidation catalyst according to claim 8, wherein the iron source in step (1) is one or more of iron sulfate, iron nitrate, iron chloride, iron acrylate, iron acetate, iron citrate, and iron dextran.
13. The method for preparing a catalytic oxidation catalyst according to claim 12, wherein the iron source in step (1) is one or more of iron acrylate, iron acetate, iron citrate, and iron dextran.
14. The method for preparing a catalytic oxidation catalyst according to claim 8, wherein the auxiliary metal in the step (1) is magnesium and/or calcium, and the auxiliary metal salt solution is one or more of magnesium chloride, calcium chloride, magnesium nitrate and calcium nitrate.
15. The method for preparing a catalytic oxidation catalyst according to claim 8, wherein the carrier in the step (1) is one or more of activated carbon, inorganic refractory oxide and molecular sieve.
16. The method for producing a catalytic oxidation catalyst according to claim 15, wherein the carrier in step (1) is activated carbon.
17. The method for preparing a catalytic oxidation catalyst according to claim 15, wherein the inorganic refractory oxide in the step (1) is one or more of alumina, silica, titania, ceria, magnesia and zirconia, and the molecular sieve is one or more of a type a, a type Y, a type β, a ZSM series and an MCM series molecular sieve.
18. The method for preparing a catalytic oxidation catalyst according to claim 15, wherein the activated carbon is 200-600 mesh powder or 0.5-3mm activated carbon particles, and the specific surface area is 500-3000 m 2 Per gram, pore volume of 0.5-1.8 cm 3 And/g, wherein the average pore diameter is 0.5-4.0 nm, and the pore volume of pores with the pore diameter smaller than 2nm accounts for more than 90% of the total pore volume.
19. The method for preparing a catalytic oxidation catalyst according to claim 8, wherein the iron source, the additive metal salt solution and the carrier material in the step (1) are used in an amount of 1.8 to 11.1 in terms of mass ratio of iron atoms, calcium (magnesium) atoms and carrier: 7.8 to 15.5 (5.5 to 11.1): 30 to 60 percent.
20. The method for preparing a catalytic oxidation catalyst according to claim 8, wherein the phosphate-containing solution in step (2) is one or more of phosphoric acid, phosphate and urea phosphate.
21. The method for producing a catalytic oxidation catalyst according to claim 20, wherein the phosphate-containing solution in step (2) is a phosphate.
22. The method for producing a catalytic oxidation catalyst according to claim 20, wherein the phosphate-containing solution in step (2) is an ammonium phosphate salt.
23. The method for preparing a catalytic oxidation catalyst according to claim 20, wherein the phosphoric acid is orthophosphoric acid, and the phosphoric acid salt is one or more of sodium phosphate, potassium phosphate, ammonium phosphate, monoamine phosphate, monoammonium phosphate, and sodium hydrogen phosphate.
24. The method for producing a catalytic oxidation catalyst according to claim 8, wherein the concentration of phosphate in the phosphate-containing solution is 0.6 to 2.0mol/L.
25. The method for producing a catalytic oxidation catalyst according to claim 8, wherein the molar ratio of phosphate in the phosphate-containing solution in step (2) to iron ions and promoter metal ions in the catalytic precursor material is not less than 1:1.
26. The method for preparing a catalytic oxidation catalyst according to claim 25, wherein the molar ratio of phosphate in the phosphate-containing solution in step (2) to iron ions and promoter metal ions in the catalytic precursor material is 1 to 1.1:1.
27. the method for producing a catalytic oxidation catalyst according to claim 8, wherein the reaction temperature in step (2) is 40 to 90 ℃.
28. The method for producing a catalytic oxidation catalyst according to claim 8, wherein the reaction temperature in step (2) is 50 to 80 ℃.
29. The method for producing a catalytic oxidation catalyst according to claim 8, wherein the reaction in step (2) is carried out under ultrasonic oscillation at a frequency of 30 to 100 KHz.
30. The process for producing a catalytic oxidation catalyst according to claim 8, wherein the drying temperature in step (2) is 80 to 150℃and the drying treatment time is 3 to 24 hours.
31. The process for producing a catalytic oxidation catalyst according to claim 7, wherein the drying temperature in step (2) is 90 to 120℃and the drying treatment time is 6 to 12 hours.
32. The method for producing a catalytic oxidation catalyst according to claim 8, wherein the calcination in step (2) is performed under oxygen-free conditions, and the calcination temperature is 500 to 800 ℃; the roasting treatment time is 2-6 h.
33. The method for producing a catalytic oxidation catalyst according to claim 8, wherein the calcination in step (2) is performed in the presence of an inert atmosphere, and the calcination temperature is 550 to 700 ℃; the roasting treatment time is 3-5 h.
34. The method for preparing a catalytic oxidation catalyst according to claim 33, wherein the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton, and xenon.
35. The method for preparing a catalytic oxidation catalyst according to claim 34, wherein the inert atmosphere is nitrogen.
36. A method for treating organic wastewater, wherein the organic wastewater and an oxidant enter a reactor for treatment, and the catalytic oxidation catalyst as claimed in any one of claims 1 to 7 is arranged in the reactor.
37. The method for treating organic wastewater according to claim 36, wherein the organic wastewater is one or more of pharmaceutical wastewater, printing and dyeing wastewater, biochemical effluent, municipal wastewater, acrylic wastewater, coking wastewater and oily wastewater, and has a COD range of 50-600 mg/L.
38. The method for treating organic wastewater according to claim 36, wherein the oxidizing agent is one or more of ozone and hydrogen peroxide.
39. The method for treating organic wastewater according to claim 36, wherein the reaction conditions are normal pressure and a volume space velocity of 0.25 to 2 hours -1 The consumption of the oxidant is 0.5-3.0 times of the consumption of the oxidant required by the COD theory of the raw material organic wastewater.
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