Ozone catalyst and preparation method thereof

Abstract

The invention relates to an ozone catalyst. The ozone catalyst comprises a carrier raw material, an adhesive and a pore-forming agent, the raw materials comprise any one of pseudo-boehmite powder, aluminum chloride, aluminum hydroxide and aluminum nitrate and at least one of silicon carbide and silicon nitride; the binder comprises water and at least one of silica sol, alumina sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin and phenolic resin; the pore-forming agent comprises at least one of polyethylene glycol, ethanol, diethanol amine and urea; the prepared ozone catalyst has the advantages that the pollutant removal rate is obviously improved, the service life of the catalyst is effectively prolonged, and the catalytic effect is stable.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, in particular to an ozone catalyst and a preparation method thereof. Background Art

[0002] Silicon carbide (SiC) and silicon nitride (Si3N4) as ceramic materials have remarkable properties such as corrosion resistance, wear resistance, high strength, and high hardness. They also have excellent oxidation resistance and high thermal conductivity. Among them, silicon carbide, as a third-generation semiconductor, has the characteristics of wide band gap and high specific surface area, and is also widely used in the field of catalytic water purification.

[0003] Currently, high-difficulty wastewater and organic wastewater from industrial wastewater are often treated using advanced oxidation and biochemical methods. The catalysts used in ozone advanced oxidation technology are mostly aluminum-, silicon-aluminum-, or carbon-based catalysts loaded with active metals. However, pollutant removal efficiency is significantly affected by water quality, such as salinity, resulting in low removal efficiency. Existing catalysts modified with elements such as carbon, nitrogen, silicon, and phosphorus do not significantly improve catalytic effects, and all experience varying degrees of performance degradation and poor stability. Therefore, further research and improvement is needed in catalyst modification, active material screening, and loaded activation methods. Summary of the Invention

[0004] In view of this, the present application provides an ozone catalyst and a preparation method thereof. The ozone catalyst of the present application can improve the removal rate of pollutants and effectively extend the life of the ozone catalyst, making the effect of the ozone catalyst more stable.

[0005] An ozone catalyst comprises a carrier raw material, a binder and a pore-forming agent; wherein the raw material comprises any one of boehmite powder, aluminum chloride, aluminum hydroxide, and aluminum nitrate, and at least one of silicon carbide and silicon nitride; the binder comprises at least one of silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, and phenolic resin, and water; and the pore-forming agent comprises at least one of polyethylene glycol, ethanol, diethanolamine, and urea.

[0006] According to one aspect of the present application, the silicon carbide or the silicon nitride accounts for 10%-50% of the mass of the carrier raw material.

[0007] According to one aspect of the present application, the mass ratio of the carrier raw material, the adhesive, and the pore-forming agent is 70%-90%: 1%-20%: 5%-10%.

[0008] A method for preparing an ozone catalyst, using the above-mentioned materials, specifically comprising the following steps: Step 1: Grinding any one of the pseudo-boehmite powder, the aluminum chloride, the aluminum hydroxide, and the aluminum nitrate into a fine powder, and also grinding at least one of the silicon carbide and the silicon nitride into a fine powder, and then thoroughly mixing them to form a mixed powder; Step 2: Adding water to the silica sol, the aluminum sol, the nitric acid, the polyvinyl alcohol, the cellulose acetate butyrate, the polyethylene, the epoxy resin, and the phenolic resin, and at least one of the polyethylene glycol, the ethanol, the diethanolamine, and the urea to prepare a solution I; Step 3: Adding the prepared solution I to the mixed powder, thoroughly mixing, and molding the mixed powder to obtain a molded sphere; Step 4: Placing the molded sphere in a calcining furnace for drying and high-temperature calcining to obtain a catalyst carrier; Step 5: Impregnating and loading the catalyst carrier with an active component; Step 6: Drying and high-temperature calcining the impregnated and loaded catalyst carrier to obtain the product.

[0009] According to one aspect of the present application, the impregnation loading of the catalyst support with the active component includes the following steps: completely dissolving the active component in prepared water to form solution II, and completely immersing the catalyst support in solution II, and the volume ratio of the prepared water to the catalyst support is 0.8-1.5:1, the molar concentration of the solution II is 0.1-2 mol / L, and the catalyst support is immersed for 3-8 hours.

[0010] According to one aspect of the present application, the active component includes at least one of nitrates or acetates of nickel, copper, cobalt, cerium, zinc, manganese, iron, etc.

[0011] According to one aspect of the present application, the formed spheres are placed in a roasting furnace for drying and high-temperature roasting, the drying temperature is 60-150°C, the drying time is 4-12 hours, the high-temperature roasting temperature is 400-1500°C, nitrogen is filled in the roasting furnace during the high-temperature roasting process, and the high-temperature roasting is divided into two stages, including the first stage roasting and the second stage roasting.

[0012] According to one aspect of the present application, the first stage of calcination: the calcination temperature is 400-600°C, and the calcination time is 2-6 hours; the second stage: the calcination temperature is 800-1500°C, and the calcination time is 1-4 hours.

[0013] According to one aspect of the present application, the catalyst carrier after impregnation and loading is dried and calcined at high temperature, and the drying temperature is 60-150°C and the drying time is 4-12 hours; the high temperature calcination temperature is 300-800°C and the calcination time is 2-6 hours.

[0014] According to one aspect of the present application, the prepared solution I is added to the mixed powder by spraying, and the mixed powder is driven to rotate by a sugar coating machine so that the mixed powder and the solution I are fully mixed. The mixed powder gradually forms particles and the particle size gradually increases, and finally a formed sphere is obtained.

[0015] The beneficial effects of the present invention are as follows: an ozone catalyst carrier is prepared by mixing silicon carbide, silicon nitride and aluminum-based materials, and is calcined at high temperature in a nitrogen atmosphere to nitride the SiC to obtain an ozone catalyst doped with nitrogen and carbon. By controlling the calcination time and temperature, ozone catalysts with different degrees of nitridation can be obtained. The pollutant removal rate of the ozone catalyst is significantly improved, and the SiC nitridation loading method effectively prolongs the catalyst life and stabilizes the catalytic effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The COD removal rates of Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 are shown. DETAILED DESCRIPTION

[0017] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0018] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0019] The present application provides an ozone catalyst, comprising a carrier raw material, a binder, and a pore-forming agent; wherein the raw material comprises any one of pseudo-boehmite powder, aluminum chloride, aluminum hydroxide, and aluminum nitrate, and at least one of silicon carbide and silicon nitride; the binder comprises at least one of silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, and phenolic resin, and water; and the pore-forming agent comprises at least one of polyethylene glycol, ethanol, diethanolamine, and urea.

[0020] Furthermore, silicon carbide or silicon nitride accounts for 10%-50% of the mass of the carrier raw material.

[0021] Preferably, the mass ratio of the carrier raw material, the adhesive, and the pore-forming agent is 70%-90%: 1%-20%: 5%-10%.

[0022] A method for preparing an ozone catalyst, using the above-mentioned materials, specifically comprising the following steps: Step 1: Grinding any one of boehmite powder, aluminum chloride, aluminum hydroxide, and aluminum nitrate into a fine powder, and also grinding at least one of silicon carbide and silicon nitride into a fine powder, and then thoroughly mixing them to form a mixed powder;

[0023] Step 2: adding water to silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, phenolic resin and at least one of polyethylene glycol, ethanol, diethanolamine and urea to prepare solution I;

[0024] Step 3: adding the prepared solution I to the mixed powder, mixing thoroughly, and then shaping the mixed powder to obtain a shaped sphere; preferably, the prepared solution I is added to the mixed powder by spraying, and the powder is rotated by a sugar coating machine to fully mix the powder and the solution I, and the powder is gradually formed into particles with gradually increasing particle size, and finally a shaped sphere is obtained;

[0025] Step 4: Place the formed spheres into a calcination furnace for drying and high-temperature calcination to obtain a catalyst carrier. The drying temperature is 60-150°C, the drying time is 4-12h, and the high-temperature calcination temperature is 400-1500°C. Nitrogen is filled into the calcination furnace during the high-temperature calcination process, and the high-temperature calcination is divided into two stages, including the first stage calcination and the second stage calcination. The first stage calcination: the calcination temperature is 400-600°C and the calcination time is 2-6h; the second stage: the calcination temperature is 800-1500°C, the calcination time is 1-4h, and the heating rate is 5-10°C / mi.

[0026] Step 5: Impregnation and loading of active components on the catalyst support;

[0027] Step 6: drying and high-temperature calcining the impregnated and loaded catalyst support, with the drying temperature being 60-150° C. and the drying time being 4-12 h; the high-temperature calcination temperature being 300-800° C. and the calcination time being 2-6 h, to finally obtain the product.

[0028] Among them, the impregnation loading of the catalyst carrier with the active component includes the following steps: completely dissolving the active component in the prepared water to form solution II, and completely immersing the catalyst carrier in solution II, and the volume ratio of the prepared water to the catalyst carrier is 0.8-1.5:1, the molar concentration of solution II is 0.1-2 mol / L, and the catalyst carrier is immersed for 3-8 hours.

[0029] Preferably, the active component includes at least one of nitrates or acetates of nickel, copper, cobalt, cerium, zinc, manganese, iron, etc.

[0030] Example 1

[0031] The mass ratio of a carrier material, a binder and a pore-forming agent of an ozone catalyst is 85%:10%:5%, and the carrier material is aluminum hydroxide, silicon carbide and silicon nitride; the mass ratio of silicon carbide, silicon nitride and aluminum hydroxide is 10%:5%:85%.

[0032] A method for preparing an ozone catalyst, using the above-mentioned materials, specifically comprises the following steps: Step 1: grinding aluminum hydroxide, silicon carbide, and silicon nitride into fine powders, and then thoroughly mixing them to form a mixed powder;

[0033] Step 2: adding water to silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, phenolic resin and at least one of polyethylene glycol, ethanol, diethanolamine and urea to prepare solution I;

[0034] Step 3: adding the prepared solution I to the mixed powder, mixing thoroughly, and then shaping the mixed powder to obtain a shaped sphere; preferably, the prepared solution I is added to the mixed powder by spraying, and the mixed powder is rotated by a sugar coating machine to fully mix the mixed powder and the solution I, and the mixed powder is gradually formed into particles with gradually increasing particle size, and finally a shaped sphere is obtained;

[0035] Step 4: Place the formed spheres into a calcination furnace for drying and high-temperature calcination to obtain a catalyst carrier. The drying temperature is 60°C, the drying time is 12 hours, and the high-temperature calcination temperature is 400-1500°C. Nitrogen is filled into the calcination furnace during the high-temperature calcination process, and the high-temperature calcination is divided into two stages, including the first stage calcination and the second stage calcination. The first stage calcination: the calcination temperature is 450°C and the calcination time is 4 hours; the second stage: the calcination temperature is 1400°C, the calcination time is 1 hour, and the heating rate is 10°C / min.

[0036] Step 5: Impregnation loading of the active component on the catalyst support: completely dissolve the active component in the prepared water to form solution II, and completely immerse the catalyst support in solution II. The volume ratio of the prepared water to the catalyst support is 0.7, the molar concentration of solution II is 0.2 mol / L, and the catalyst support is immersed for 8 hours.

[0037] Step 6: Dry and high-temperature calcine the impregnated and loaded catalyst support at a drying temperature of 80° C. for 12 h; and a high-temperature calcination temperature of 500° C. for 5 h to obtain the product.

[0038] The ozone catalyst prepared by the above method was used for ozone catalytic oxidation. The experimental parameters were as follows: raw water COD 500 mg / L, chloride ion 100 mg / L, water volume 1 L, catalyst dosage 500 ml, reaction time 1 h, ozone dosage 500 mg / L; the COD of the produced water was 138 mg / L, and the COD removal rate was 72.4%.

[0039] Example 2

[0040] The invention discloses an ozone catalyst having a carrier material, a binder and a pore-forming agent in a mass ratio of 85%:10%:5%, wherein the carrier material comprises pseudo-boehmite powder, silicon carbide and silicon nitride; and the mass ratio of silicon carbide, silicon nitride and pseudo-boehmite powder is 5%:5%:90%.

[0041] A method for preparing an ozone catalyst, using the above-mentioned materials, specifically comprises the following steps: Step 1: Grinding pseudo-boehmite powder, silicon carbide, and silicon nitride into fine powder, and then thoroughly mixing them to form a mixed powder;

[0042] Step 2: adding water to silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, phenolic resin and at least one of polyethylene glycol, ethanol, diethanolamine and urea to prepare solution I;

[0043] Step 3: adding the prepared solution I to the mixed powder, mixing thoroughly, and then shaping the mixed powder to obtain a shaped sphere; preferably, the prepared solution I is added to the mixed powder by spraying, and the mixed powder is rotated by a sugar coating machine to fully mix the mixed powder and the solution I, and the mixed powder is gradually formed into particles with gradually increasing particle size, and finally a shaped sphere is obtained;

[0044] Step 4: Place the formed spheres into a calcination furnace for drying and high-temperature calcination to obtain a catalyst carrier. The drying temperature is 60°C, the drying time is 12 hours, and the high-temperature calcination temperature is 400-1500°C. Nitrogen is filled into the calcination furnace during the high-temperature calcination process, and the high-temperature calcination is divided into two stages, including the first stage calcination and the second stage calcination. The first stage calcination: the calcination temperature is 450°C and the calcination time is 4 hours; the second stage: the calcination temperature is 1400°C, the calcination time is 1 hour, and the heating rate is 10°C / min.

[0045] Step 5: Impregnation loading of the active component on the catalyst support: completely dissolve the active component in the prepared water to form solution II, and completely immerse the catalyst support in solution II. The volume ratio of the prepared water to the catalyst support is 0.7, the molar concentration of solution II is 0.2 mol / L, and the catalyst support is immersed for 8 hours.

[0046] Step 6: Dry and high-temperature calcine the impregnated and loaded catalyst support at a drying temperature of 80° C. for 12 h; and a high-temperature calcination temperature of 500° C. for 5 h to obtain the product.

[0047] The catalyst prepared in Example 1 was used for ozone catalytic oxidation, and the experimental parameters were as follows:

[0048] The raw water COD is 800 mg / L, chloride ion is 100 mg / L, water volume is 1 L, catalyst dosage is 500 ml, reaction time is 1 hour, ozone dosage is 500 mg / L; the produced water COD is 452 mg / L, and the COD removal rate is 43.5%.

[0049] Example 3

[0050] The mass ratio of a carrier material, a binder and a pore-forming agent of an ozone catalyst is 85%:10%:5%, and the carrier material is aluminum nitrate, silicon carbide and silicon nitride; the mass ratio of silicon carbide, silicon nitride and aluminum nitrate is 10%:10%:80%.

[0051] A method for preparing an ozone catalyst, using the above-mentioned materials, specifically comprises the following steps: Step 1: grinding aluminum nitrate, silicon carbide, and silicon nitride into fine powders, and then thoroughly mixing them to form a mixed powder;

[0052] Step 2: adding water to silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, phenolic resin and at least one of polyethylene glycol, ethanol, diethanolamine and urea to prepare solution I;

[0053] Step 3: adding the prepared solution I to the mixed powder, mixing thoroughly, and then shaping the mixed powder to obtain a shaped sphere; preferably, the prepared solution I is added to the mixed powder by spraying, and the mixed powder is rotated by a sugar coating machine to fully mix the mixed powder and the solution I, and the mixed powder is gradually formed into particles with gradually increasing particle size, and finally a shaped sphere is obtained;

[0054] Step 4: Place the formed spheres into a calcination furnace for drying and high-temperature calcination to obtain a catalyst carrier. The drying temperature is 60°C, the drying time is 12 hours, and the high-temperature calcination temperature is 400-1500°C. Nitrogen is filled into the calcination furnace during the high-temperature calcination process, and the high-temperature calcination is divided into two stages, including the first stage calcination and the second stage calcination. The first stage calcination: the calcination temperature is 450°C and the calcination time is 4 hours; the second stage: the calcination temperature is 1400°C, the calcination time is 1 hour, and the heating rate is 10°C / min.

[0055] Step 5: Impregnation loading of the active component on the catalyst support: completely dissolve the active component in the prepared water to form solution II, and completely immerse the catalyst support in solution II. The volume ratio of the prepared water to the catalyst support is 0.7, the molar concentration of solution II is 0.2 mol / L, and the catalyst support is immersed for 8 hours.

[0056] Step 6: Dry and high-temperature calcine the impregnated and loaded catalyst support at a drying temperature of 80° C. for 12 h; and a high-temperature calcination temperature of 500° C. for 5 h to obtain the product.

[0057] The catalyst prepared in Example 1 was used for ozone catalytic oxidation, and the experimental parameters were as follows:

[0058] The raw water COD is 200 mg / L, chloride ion is 100 mg / L, water volume is 1 L, catalyst dosage is 500 ml, reaction time is 1 hour, ozone dosage is 200 mg / L; the produced water COD is 56 mg / L, and the COD removal rate is 72%.

[0059] Example 4

[0060] The mass ratio of a carrier material, a binder and a pore-forming agent of an ozone catalyst is 85%:10%:5%, and the carrier material is aluminum chloride, silicon carbide and silicon nitride; the mass ratio of silicon carbide, silicon nitride and aluminum chloride is 15%:15%:70%.

[0061] A method for preparing an ozone catalyst, using the above-mentioned materials, specifically comprises the following steps: Step 1: grinding aluminum chloride, silicon carbide, and silicon nitride into fine powders, and then thoroughly mixing them to form a mixed powder;

[0062] Step 2: adding water to silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, phenolic resin and at least one of polyethylene glycol, ethanol, diethanolamine and urea to prepare solution I;

[0063] Step 3: adding the prepared solution I to the mixed powder, mixing thoroughly, and then shaping the mixed powder to obtain a shaped sphere; preferably, the prepared solution I is added to the mixed powder by spraying, and the mixed powder is rotated by a sugar coating machine to fully mix the mixed powder and the solution I, and the mixed powder is gradually formed into particles with gradually increasing particle size, and finally a shaped sphere is obtained;

[0064] Step 4: Place the formed spheres into a calcination furnace for drying and high-temperature calcination to obtain a catalyst carrier. The drying temperature is 60°C, the drying time is 12 hours, and the high-temperature calcination temperature is 400-1500°C. Nitrogen is filled into the calcination furnace during the high-temperature calcination process, and the high-temperature calcination is divided into two stages, including the first stage calcination and the second stage calcination. The first stage calcination: the calcination temperature is 450°C and the calcination time is 4 hours; the second stage: the calcination temperature is 1400°C, the calcination time is 1 hour, and the heating rate is 10°C / min.

[0065] Step 5: Impregnation loading of the active component on the catalyst support: completely dissolve the active component in the prepared water to form solution II, and completely immerse the catalyst support in solution II. The volume ratio of the prepared water to the catalyst support is 0.7, the molar concentration of solution II is 0.2 mol / L, and the catalyst support is immersed for 8 hours.

[0066] Step 6: Dry and high-temperature calcine the impregnated and loaded catalyst support at a drying temperature of 80° C. for 12 h; and a high-temperature calcination temperature of 500° C. for 5 h to obtain the product.

[0067] The catalyst prepared in Example 1 was used for ozone catalytic oxidation, and the experimental parameters were as follows:

[0068] The raw water COD is 500 mg / L, chloride ion is 1000 mg / L, water volume is 1 L, catalyst dosage is 500 ml, reaction time is 1 hour, ozone dosage is 500 mg / L; the produced water COD is 174 mg / L, and the COD removal rate is 65.2%.

[0069] Example 5

[0070] The mass ratio of a carrier material, a binder and a pore-forming agent of an ozone catalyst is 85%:10%:5%, and the carrier material is aluminum hydroxide, silicon carbide and silicon nitride; the mass ratio of silicon carbide, silicon nitride and aluminum hydroxide is 10%:5%:85%.

[0071] A method for preparing an ozone catalyst, using the above-mentioned materials, specifically comprises the following steps: Step 1: grinding aluminum hydroxide, silicon carbide, and silicon nitride into fine powders, and then thoroughly mixing them to form a mixed powder;

[0072] Step 2: adding water to silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, phenolic resin and at least one of polyethylene glycol, ethanol, diethanolamine and urea to prepare solution I;

[0073] Step 3: adding the prepared solution I to the mixed powder, mixing thoroughly, and then shaping the mixed powder to obtain a shaped sphere; preferably, the prepared solution I is added to the mixed powder by spraying, and the mixed powder is rotated by a sugar coating machine to fully mix the mixed powder and the solution I, and the mixed powder is gradually formed into particles with gradually increasing particle size, and finally a shaped sphere is obtained;

[0074] Step 4: Place the formed spheres into a calcination furnace for drying and high-temperature calcination to obtain a catalyst carrier. The drying temperature is 60°C, the drying time is 12 hours, and the high-temperature calcination temperature is 400-1500°C. Nitrogen is filled into the calcination furnace during the high-temperature calcination process, and the high-temperature calcination is divided into two stages, including the first stage calcination and the second stage calcination. The first stage calcination: the calcination temperature is 450°C and the calcination time is 4 hours; the second stage: the calcination temperature is 1400°C, the calcination time is 1 hour, and the heating rate is 10°C / min.

[0075] Step 5: Impregnation loading of the active component on the catalyst support: completely dissolve the active component in the prepared water to form solution II, and completely immerse the catalyst support in solution II. The volume ratio of the prepared water to the catalyst support is 0.7, the molar concentration of solution II is 0.2 mol / L, and the catalyst support is immersed for 8 hours.

[0076] Step 6: Dry and high-temperature calcine the impregnated and loaded catalyst support at a drying temperature of 80° C. for 12 h; and a high-temperature calcination temperature of 500° C. for 5 h to obtain the product.

[0077] The catalyst prepared in Example 1 was used for ozone catalytic oxidation, and the experimental parameters were as follows:

[0078] The raw water COD is 500 mg / L, chloride ion is 1500 mg / L, water volume is 1 L, catalyst dosage is 500 ml, reaction time is 1 hour, ozone dosage is 500 mg / L; the produced water COD is 207 mg / L and the COD removal rate is 58.6%.

[0079] Comparative Example 1

[0080] Compared with Example 1, in Comparative Example 2, silicon nitride and silicon carbide were not added to the carrier raw materials, and the remaining raw materials, auxiliary materials, preparation steps and parameters were the same.

[0081] The catalyst prepared in this comparative example was used for ozone catalytic oxidation under the same experimental conditions as in Example 1, and the COD removal rate was 43%.

[0082] Comparative Example 2

[0083] Compared with Example 1, in Comparative Example 3, silicon nitride and silicon carbide were not added to the carrier raw materials, and there was no nitrogen atmosphere during the high-temperature calcination process, but the atmosphere was air. The remaining raw materials, preparation steps, and parameters were the same.

[0084] The catalyst prepared in this comparative example was used for ozone catalytic oxidation under the same experimental conditions as in Example 1, and the COD removal rate was 43.5%.

[0085] Comparative Example 3

[0086] Compared with Example 1, in Comparative Example 3, there is no nitrogen atmosphere during the high-temperature roasting process, and the atmosphere is air. The other raw materials, preparation steps and parameters are the same.

[0087] The catalyst prepared in this comparative example was used for ozone catalytic oxidation under the same experimental conditions as in Example 1, and the COD removal rate was 51%.

[0088] By comparing Example 1 with Comparative Examples 1, 2, and 3, it can be seen that the COD removal rate of the catalyst prepared by this method is significantly improved to 72.4%. In Comparative Examples 1, 2, and 3, the silicon carbide and silicon nitride materials in the material carrier are omitted, the silicon carbide, silicon nitride materials and nitrogen atmosphere in the material carrier are omitted, and the atmosphere is omitted when the materials are the same; the COD removal rate of Comparative Example 3 is higher than that of Comparative Examples 1 and 2 because the addition of silicon carbide and silicon nitride related materials has a certain improvement on the ozone catalytic effect, but the COD removal rate is still lower than that of Example 1. This is also because the roasting atmosphere is air, and the N and C elements do not form effective doping, so the effect is not good.

[0089] Furthermore, it can be seen from Examples 1-5 and Comparative Examples 1-3 that preparation parameters such as silicon carbide, silicon nitride materials, and nitrogen atmosphere have a significant impact on catalyst performance, and the N / C doping formed by the nitridation of silicon carbide during the preparation process plays a key role in the ozone catalyst.

[0090] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solutions and concepts of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. An ozone catalyst, characterized in that Including carrier raw materials, adhesives and pore-forming agents; Wherein, the raw materials include any one of pseudo-boehmite powder, aluminum chloride, aluminum hydroxide, aluminum nitrate and at least one of silicon carbide and silicon nitride; The binder comprises at least one of silica sol, aluminum sol, nitric acid, polyvinyl alcohol, cellulose acetate butyrate, polyethylene, epoxy resin, phenolic resin and water; The pore-forming agent comprises at least one of polyethylene glycol, ethanol, diethanolamine, and urea.

2. The ozone catalyst according to claim 1, characterized in that The silicon carbide or the silicon nitride accounts for 10%-50% of the mass of the carrier raw material.

3. The ozone catalyst according to claim 2, characterized in that The mass ratio of the carrier raw material, the adhesive and the pore-forming agent is 70%-90%: 1%-20%: 5%-10%.

4. A method for preparing an ozone catalyst, characterized in that: Using the material according to any one of claims 1 to 3, the specific steps are: Step 1: Grinding any one of the boehmite powder, the aluminum chloride, the aluminum hydroxide, and the aluminum nitrate into a fine powder, and also grinding at least one of the silicon carbide and the silicon nitride into a fine powder, and then fully mixing them to form a mixed powder; Step 2: adding water to the silica sol, the aluminum sol, the nitric acid, the polyvinyl alcohol, the cellulose acetate butyrate, the polyethylene, the epoxy resin, and the phenolic resin, and at least one of the polyethylene glycol, the ethanol, the diethanolamine, and the urea to prepare solution I; Step 3: adding the prepared solution I to the mixed powder, mixing thoroughly, and then molding the mixed powder to obtain a molded sphere; Step 4: Place the formed spheres into a calcination furnace for drying and high-temperature calcination to obtain a catalyst carrier; Step 5: Impregnation and loading of active components on the catalyst support; Step 6: Drying and high-temperature calcining the impregnated and loaded catalyst carrier to obtain the product.

5. The method for preparing an ozone catalyst according to claim 4, wherein: The impregnation loading of the catalyst support with active components includes the following steps: completely dissolving the active components in prepared water to form solution II, and completely immersing the catalyst support in solution II, wherein the volume ratio of the prepared water to the catalyst support is 0.8-1.5:1, the molar concentration of solution II is 0.1-2 mol / L, and the catalyst support is immersed for 3-8 hours.

6. The method for preparing an ozone catalyst according to claim 5, wherein: The active component includes at least one of nitrates or acetates of nickel, copper, cobalt, cerium, zinc, manganese, iron, etc.

7. The method for preparing an ozone catalyst according to claim 4, wherein: The formed spheres are placed in a roasting furnace for drying and high-temperature roasting. The drying temperature is 60-150°C, the drying time is 4-12 hours, and the high-temperature roasting temperature is 400-1500°C. Nitrogen is filled in the roasting furnace during the high-temperature roasting process, and the high-temperature roasting is divided into two stages, including the first stage roasting and the second stage roasting.

8. The method for preparing an ozone catalyst according to claim 7, wherein: The first stage of calcination: the calcination temperature is 400-600℃ and the calcination time is 2-6h; The second stage: the roasting temperature is 800-1500° C. and the roasting time is 1-4 hours.

9. The method for preparing an ozone catalyst according to claim 4, wherein: The catalyst carrier after impregnation and loading is dried and calcined at high temperature, and the drying temperature is 60-150° C. and the drying time is 4-12 hours; the high-temperature calcination temperature is 300-800° C. and the calcination time is 2-6 hours.

10. The method for preparing an ozone catalyst according to claim 4, wherein: The prepared solution I is added to the mixed powder by spraying, and the mixed powder is rotated by a sugar coating machine to fully mix the mixed powder and the solution I. The mixed powder gradually forms particles and the particle size gradually increases, and finally a formed sphere is obtained.

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