Ozone catalytic oxidation catalyst carrier, catalyst and preparation method and application thereof

Abstract

The present invention relates to the field of waste recycling and treatment, and discloses an ozone catalytic oxidation catalyst carrier, a catalyst, and a preparation method and application thereof. The ozone catalytic oxidation catalyst carrier of the present invention has a core-shell structure, the core of the ozone catalytic oxidation catalyst carrier is formed by a core composition, and the shell of the ozone catalytic oxidation catalyst carrier includes aluminum oxide, wherein the core composition contains waste FCC catalyst, active metal oxide and binder. The ozone catalytic oxidation catalyst carrier of the present invention can realize the resource utilization of waste FCC catalyst, and the obtained composite core-shell ozone catalytic oxidation catalyst has high catalytic activity and excellent catalytic oxidation effect on organic wastewater.

Description

Technical Field

[0001] The invention relates to the field of waste recycling and treatment, and in particular to an ozone catalytic oxidation catalyst carrier, a catalyst, and a preparation method and application thereof. Background Art

[0002] Catalytic cracking (FCC) is the most important heavy oil lightening process in the oil refining industry. The annual consumption of FCC catalyst ranks first among the catalysts used in my country's oil processing. The main active components of FCC catalyst (mainly molecular sieves), matrix (generally kaolin and alumina) and binder (mainly silica sol) are prepared by spray drying. It has a porous structure and a certain specific surface area and has strong adsorption properties.

[0003] Metal pollutants, sulfur compounds, colloids and other substances in crude oil pollute FCC catalysts in long-term operation, causing catalyst poisoning, making the catalyst reaction selectivity worse and the activity decreased, thus generating waste FCC catalysts. Waste FCC catalysts not only cause serious harm to the social environment, but also cause waste of resources due to simple landfill treatment. About 160,000 tons of waste catalysts are generated each year, which are basically disposed of by landfill and making cement and other building materials, with extremely low utilization rate.

[0004] Waste FCC catalysts are mainly composed of silicon-aluminum base. After de-hazardous treatment, they still have a certain specific surface area. They contain a large amount of lanthanum and cerium elements, as well as some residual transition metal elements such as nickel and vanadium, so they have a certain catalytic activity.

[0005] Ozone heterogeneous catalytic oxidation method is considered to be the preferred technology for treating refractory organic pollutants and is widely used in the field of water treatment. Ozone catalytic oxidation technology alone can only treat specific organic pollutants, and the amount of ozone used is large and the energy consumption is high. Under the action of the catalyst, the utilization efficiency of ozone can be greatly improved and the amount of ozone used can be reduced, providing an opportunity for the treatment of refractory organic wastewater in chemical comprehensive sewage treatment plants.

[0006] The method of treating organic wastewater with ozone heterogeneous catalytic oxidation has become an effective method for removing difficult-to-degrade organic wastewater due to its advantages of low energy consumption, high degradation efficiency and no secondary pollution. At present, ozone catalytic catalysts are mainly supported catalysts with porous silicon-aluminum materials as carriers and loaded active metals to provide active centers for catalytic reactions. At present, most ozone catalysts use Mn and Fe as active metals. In particular, the Mn element loss of Mn catalysts is relatively serious after long-term operation, which affects the life of the catalyst.

[0007] If the waste FCC catalyst can be used for the preparation of ozone catalyst, it will not only solve the problem of waste FCC resource disposal, but also bring certain economic value. In addition, by designing a certain structure to solve the loss of active metals, the service life of the catalyst will be extended, which also has certain practical significance. Summary of the invention

[0008] The object of the present invention is to provide an ozone catalytic oxidation catalyst carrier, a catalyst using the carrier, and a preparation method and application thereof. The ozone catalytic oxidation catalyst carrier can realize the resource utilization of waste FCC catalysts, and the obtained composite core-shell ozone catalytic oxidation catalyst has high catalytic activity and has excellent catalytic oxidation effect on organic wastewater.

[0009] In order to achieve the above-mentioned object, the present invention provides an ozone catalytic oxidation catalyst carrier on one hand, wherein the ozone catalytic oxidation catalyst carrier has a core-shell structure, the inner core of the ozone catalytic oxidation catalyst carrier is formed by an inner core composition, and the outer shell of the ozone catalytic oxidation catalyst carrier includes alumina, wherein the inner core composition contains a waste FCC catalyst, an active metal oxide and a binder.

[0010] Preferably, the core composition contains 80-99 mass % of spent FCC catalyst, 1-10 mass % of active metal oxide, and 1-10 mass % of binder.

[0011] Preferably, the spent FCC catalyst composition comprises: 40-60 mass % Al 2 O 3 , 35-55% by mass SiO 2 , 1.0-2.0 mass% La 2 O 3 , 2.0-3.0 mass% CeO 2 .

[0012] Preferably, the spent FCC catalyst is a spent catalyst that has been treated by a wet or dry de-hazard process.

[0013] Preferably, the active metal oxide comprises one or more of Mn, Fe, Cu, Ni, Co, and Ce oxides.

[0014] Preferably, the active metal oxide comprises manganese oxide.

[0015] Preferably, the adhesive comprises one or more of silica sol, alumina sol, carboxymethyl cellulose, polyvinyl alcohol and sesbania powder.

[0016] Preferably, the alumina is γ-alumina.

[0017] Preferably, the housing is formed from alumina.

[0018] Preferably, the inner core has a diameter of 1-10 mm.

[0019] Preferably, the thickness of the shell is 0.1-5 mm.

[0020] Preferably, the content of aluminum oxide in the shell is 1-15 mass % of the weight of the ozone catalytic oxidation catalyst carrier.

[0021] According to a second aspect of the present invention, a method for preparing the ozone catalytic oxidation catalyst carrier of the present invention is provided, wherein the method comprises the following steps:

[0022] 1) mixing and molding the spent FCC catalyst, the active metal oxide and its precursor and the binder, and then drying and first calcining to obtain a carrier core;

[0023] 2) After the aluminum sol solution is sprayed onto the outer surface of the carrier core, it is dried and calcined for the second time to obtain an alumina shell covering the carrier core.

[0024] Preferably, the precursor of the active metal oxide is a nitrate of an active metal.

[0025] Preferably, the first calcination conditions include: temperature of 250-900° C. and time of 1-30 h.

[0026] Preferably, the conditions for the second calcination include: a temperature of 250-900° C. and a time of 0.5-30 h.

[0027] According to a third aspect of the present invention, an ozone catalytic oxidation catalyst is provided, wherein the ozone catalytic oxidation catalyst comprises a carrier and a transition metal oxide on the carrier, and the carrier is the ozone catalytic oxidation catalyst carrier described in the present invention.

[0028] Preferably, the transition metal oxide comprises one or more of Cu, Ni, Co, Fe, Ce, and Mg oxides.

[0029] Preferably, the active metal oxide accounts for 0.5-15% by weight of the ozone catalytic oxidation catalyst.

[0030] According to a fourth aspect of the present invention, a method for preparing an ozone catalytic oxidation catalyst is provided, wherein the method comprises the steps of loading a transition metal oxide precursor on the ozone catalytic oxidation catalyst carrier of the present invention and performing drying and a third calcination.

[0031] According to a fifth aspect of the present invention, there is provided a method for degrading organic wastewater, the method comprising: a step of contacting an ozone catalytic oxidation catalyst with wastewater in the presence of ozone, wherein the ozone catalytic oxidation catalyst is the ozone catalytic oxidation catalyst of the present invention.

[0032] According to a sixth aspect of the present invention, there is provided an application of the ozone catalytic oxidation catalyst carrier of the present invention or the ozone catalytic oxidation catalyst of the present invention in sewage treatment.

[0033] The ozone catalytic oxidation catalyst carrier of the present invention can realize resource utilization of waste FCC catalysts, and the obtained ozone catalytic oxidation catalyst has high catalytic activity, has excellent catalytic oxidation effect on biologically refractory organic wastewater, and significantly improves biodegradability. DETAILED DESCRIPTION

[0034] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0035] According to a first aspect of the present invention, there is provided an ozone catalytic oxidation catalyst carrier, wherein the ozone catalytic oxidation catalyst carrier has a core-shell structure, the inner core of the ozone catalytic oxidation catalyst carrier is formed by an inner core composition, the outer shell of the ozone catalytic oxidation catalyst carrier comprises alumina, wherein the inner core composition contains a waste FCC catalyst, an active metal oxide and a binder.

[0036] According to the present invention, the ozone catalytic oxidation catalyst carrier is a core-shell structure, the core is formed by a core composition, and the shell of the ozone catalytic oxidation catalyst carrier includes alumina, wherein the core composition contains waste FCC catalyst, active metal oxide and binder.

[0037] Preferably, the kernel composition contains 80-99 mass % of spent FCC catalyst, 1-10 mass % of active metal oxide, 1-10 mass % of binder. More preferably, the kernel composition contains 80-90 mass % of spent FCC catalyst, 5-10 mass % of active metal oxide, 5-10 mass % of binder.

[0038] In a particularly preferred embodiment of the present invention, the core composition contains 80% by mass of spent FCC catalyst, 10% by mass of active metal oxide, and 10% by mass of binder.

[0039] Preferably, the spent FCC catalyst composition comprises: 40-60 mass % Al 2 O 3 , 35-55% by mass SiO 2 , 1.0-2.0 mass% La 2 O 3 , 2.0-3.0 mass% CeO 2 .

[0040] Preferably, the spent FCC catalyst is a spent catalyst that has been treated by a wet or dry de-hazard process.

[0041] Preferably, the active metal oxide comprises one or more of Mn, Fe, Cu, Ni, Co, and Ce oxides; more preferably, the active metal oxide is one or two of Mn and Ce oxides; further preferably, the active metal oxide is Mn oxide.

[0042] Examples of the active metal oxide include Mn oxide, Fe oxide, Cu oxide, Ni oxide, Co oxide, and Ce oxide.

[0043] In a preferred embodiment of the present invention, the active metal oxide is manganese dioxide.

[0044] When the active metal oxide is added to the ozone catalytic oxidation catalyst carrier, the active component is not easily lost during a long-term multi-phase ozone catalytic oxidation reaction, thereby ensuring the life of the catalyst.

[0045] According to the present invention, the binder is not particularly limited and can be a binder commonly used in the catalyst field. Preferably, the binder is one or more of silica sol, alumina sol, carboxymethyl cellulose, polyvinyl alcohol and sesbania powder; more preferably, the binder is one or more of silica sol, alumina sol and polyvinyl alcohol; further preferably, the binder is alumina sol. By using the above binder, the mechanical strength of the obtained ozone catalytic oxidation catalyst can be enhanced.

[0046] According to the present invention, preferably, the core of the ozone catalytic oxidation catalyst carrier is obtained by mixing and molding the waste FCC catalyst, the active metal oxide and its precursor and the binder, and then drying and first calcining.

[0047] The precursor of the active metal oxide may be a nitrate of an active metal. In addition, when the precursor of the active metal oxide is used, the amount of the active metal oxide is calculated based on the active metal oxide.

[0048] There is no particular limitation on the mixing method, and it can be carried out by a common method in the art. For example, the waste FCC catalyst, the active metal oxide and / or its precursor and the binder can be kneaded, and water can be added during the kneading process as needed.

[0049] There is no particular limitation on the above-mentioned molding method, and it can be carried out by the common methods in the art. Preferably, the molding is one or more of extrusion molding, granulation, ball rolling and spraying; more preferably, the molding is extrusion molding and / or granulation.

[0050] There is no particular limitation on the drying method, and it can be carried out using conventional methods in the art. Preferably, the drying conditions include: a temperature of 45-250°C and a time of 2-60 hours; more preferably, the drying conditions include: a temperature of 45-180°C and a time of 3-48 hours.

[0051] There is no particular limitation on the first calcination method, and it can be carried out by conventional methods in the art. Preferably, the calcination conditions include: temperature of 250-900°C and time of 1-30h; more preferably, the first calcination conditions include: temperature of 300-800°C and time of 1-24h.

[0052] In a preferred embodiment of the present invention, the inner core is obtained by the following method: after mixing a binder and a waste FCC catalyst, an aqueous solution of an active metal oxide and / or its precursor is added to the mixture for kneading and extrusion, drying at 45-180° C. to a moisture content of 5-40% by mass, cutting into pellets and breaking into strips of 1-2 mm, forming into spherical particles in a spherical pelletizer or a sugar coating pan, and then roasting in an air atmosphere at 300-800° C. for 1-24 hours.

[0053] According to the present invention, preferably the diameter of the inner core is 1-10 mm, more preferably 1-3 mm.

[0054] According to the present invention, the outer shell of the ozone catalytic oxidation catalyst carrier comprises aluminum oxide. Preferably, the outer shell of the ozone catalytic oxidation catalyst carrier is formed of aluminum oxide.

[0055] According to the present invention, preferably, the aluminum oxide is γ-aluminum oxide.

[0056] According to the present invention, the shell can be formed by the following method: spraying an aluminum sol solution onto the outer surface of the carrier core, followed by drying and a second calcination to obtain an alumina shell covering the carrier core.

[0057] The drying method is not particularly limited and can be carried out using conventional methods in the art. Preferably, the drying conditions include: a temperature of 45-250°C and a time of 2-60 hours; more preferably, the drying conditions include: a temperature of 45-180°C and a time of 3-48 hours.

[0058] There is no particular limitation on the second calcination method, and it can be carried out by conventional methods in the art. Preferably, the second calcination conditions include: temperature of 250-900°C, time of 0.5-30h; more preferably, the calcination conditions include: temperature of 400-800°C, time of 0.5-24h.

[0059] In a preferred embodiment of the present invention, the aluminum sol solution is sprayed onto the outer surface of the inner core by splashing, dried at 45-180° C., and calcined at 400-800° C. for 0.5-24 hours to obtain an ozone catalytic oxidation catalyst carrier.

[0060] According to the present invention, preferably, the thickness of the shell is 0.1-5 mm, more preferably 0.1-2 mm.

[0061] According to the present invention, preferably, the content of aluminum oxide in the shell is 1-15% by mass, preferably 5-10% by mass, based on the weight of the ozone catalytic oxidation catalyst carrier.

[0062] According to a second aspect of the present invention, a method for preparing an ozone catalytic oxidation catalyst carrier of the present invention is provided, wherein the method comprises the following steps:

[0063] 1) mixing and molding the spent FCC catalyst, the active metal oxide and its precursor and the binder, and then drying and first calcining to obtain a carrier core;

[0064] 2) After the aluminum sol solution is sprayed onto the outer surface of the carrier core, it is dried and calcined for the second time to obtain an alumina shell covering the carrier core.

[0065] The preparation methods and conditions of the core and shell are as described above and will not be repeated here.

[0066] According to a third aspect of the present invention, an ozone catalytic oxidation catalyst is provided, wherein the ozone catalytic oxidation catalyst comprises a carrier and a transition metal oxide on the carrier, and the carrier is the ozone catalytic oxidation catalyst carrier described in the present invention.

[0067] According to the present invention, the transition metal oxide comprises one or more of Cu, Ni, Co, Fe, Ce and Mg oxides.

[0068] Examples of the transition metal oxide include Cu oxide, Ni oxide, Co oxide, Fe oxide, Ce oxide, and Mg oxide.

[0069] Preferably, the active metal oxide accounts for 0.5-15% by weight of the ozone catalytic oxidation catalyst.

[0070] According to a fourth aspect of the present invention, a method for preparing an ozone catalytic oxidation catalyst is provided, wherein the method comprises the steps of loading a transition metal oxide precursor on the ozone catalytic oxidation catalyst carrier of the present invention and performing drying and a third calcination.

[0071] According to the present invention, preferably, the transition metal oxide precursor is a nitrate of a transition metal. In addition, when a transition metal oxide precursor is used, its feed amount is calculated as transition metal oxide.

[0072] Preferably, the transition metal oxide precursor comprises one or more nitrates of Cu, Ni, Co, Fe, Ce, and Mg.

[0073] Examples of the transition metal oxide precursor include copper nitrate, nickel nitrate, cobalt nitrate, iron nitrate, cerium nitrate, and magnesium nitrate.

[0074] Preferably, the transition metal oxide precursor is used in an amount such that the transition metal oxide accounts for 0.5-15% by weight of the catalyst.

[0075] Preferably, the active metal loading method is spraying or immersion.

[0076] In the present invention, there is no particular limitation on the drying method, and it can be carried out by the common method in the art. Preferably, the drying conditions include: temperature of 45-180°C, time of 0.5-24h; more preferably, the drying conditions include: temperature of 60-150°C, time of 3-24h.

[0077] In the present invention, there is no particular limitation on the third calcination method, and it can be carried out by the common method in the art. Preferably, the third calcination conditions include: temperature of 400-800°C, time of 0.5-24h; more preferably, the calcination conditions include: temperature of 400-800°C, time of 1-12h.

[0078] According to a fifth aspect of the present invention, a method for degrading organic wastewater is provided, the method comprising: a step of contacting an ozone catalytic oxidation catalyst with wastewater in the presence of ozone, wherein the ozone catalytic oxidation catalyst is the ozone catalytic oxidation catalyst described in the present invention.

[0079] According to the present invention, preferably, the amount of the catalyst is 0.01-50 g relative to 1 mg COD of the wastewater; more preferably, the amount of the catalyst is 0.03-10 g relative to 1 mg COD of the wastewater; further preferably, the amount of the catalyst is 0.04-5 g relative to 1 mg COD of the wastewater; further preferably, the amount of the catalyst is 0.04-1 g relative to 1 mg COD of the wastewater.

[0080] According to the present invention, preferably, the ozone dosage is 0.01-2 mg relative to 1 mg COD of the wastewater; more preferably, the ozone dosage is 0.05-1 mg relative to 1 mg COD of the wastewater.

[0081] According to the present invention, preferably, the contact conditions include: the contact temperature is 5-50°C, and the contact time is 1-300 min; more preferably, the contact conditions include: the contact temperature is 15-40°C, and the contact time is 30-180 min.

[0082] Examples of the wastewater include papermaking organic wastewater, pharmaceutical non-degradable organic wastewater, and industrial organic amine wastewater.

[0083] According to a sixth aspect of the present invention, there is provided an application of the ozone catalytic oxidation catalyst carrier of the present invention or the ozone catalytic oxidation catalyst of the present invention in sewage treatment.

[0084] The ozone catalytic oxidation catalyst carrier of the present invention can realize resource utilization of waste FCC catalysts, has high catalytic activity, has excellent catalytic oxidation effect on organic wastewater, and significantly enhances biodegradability.

[0085] The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

[0086] Example 1

[0087] This embodiment is used to illustrate a method for preparing an ozone catalytic oxidation catalyst from a waste FCC catalyst, wherein the waste FCC catalyst, the active component calculated as active metal oxide, and the binder are respectively in the following mass ratios: 80% by mass of the waste FCC catalyst, and 10% by mass of MnO 2 10% by mass, binder (aluminum sol) 10% by mass.

[0088] The specific preparation method is as follows: 100g of waste FCC catalyst, aluminum sol (solid content 20% by mass) and manganese nitrate aqueous solution (manganese nitrate content 50% by mass) are mixed, then 50mL of deionized water is added, kneaded, extruded, dried at 50°C to 5% water content by mass, granulated and cut into strips to 1mm, shaped into spherical particles in a spherical granulator or sugar coating pan, and then roasted in an air atmosphere at 400°C for 1 hour to obtain a spherical waste FCC catalyst carrier core (diameter 1mm). Aluminum sol (solid content 20% by mass) is sprayed onto the outer surface of the waste FCC catalyst carrier core by a sputtering method, dried at 50°C, and roasted at a high temperature of 400°C for 1 hour to obtain a core-shell composite ozone catalytic oxidant carrier with a shell of γ-alumina (shell thickness 0.1mm, shell γ-alumina content 5% by mass).

[0089] The obtained carrier was loaded with active metal Fe oxide using an impregnation technique, that is, 100 g of the carrier was impregnated with a 0.5 mol / L ferric nitrate solution at room temperature for 1 hour, then dried at 50°C, and calcined at 400°C for 1 hour to obtain a core-shell composite ozone catalyst F1.

[0090] Example 2

[0091] This embodiment is used to illustrate a method for preparing an ozone catalytic oxidation catalyst from a waste FCC catalyst, wherein the waste FCC catalyst, the active component calculated as active metal oxide, and the binder are respectively in the following mass ratios: 85 mass% of the waste FCC catalyst, and 10 mass% of MnO. 2 7% by mass, adhesive (aluminum sol) 8% by mass.

[0092] The specific preparation method is as follows: 100g of waste FCC catalyst, aluminum sol (solid content 20% by mass) and manganese nitrate aqueous solution (manganese nitrate content 50% by mass) are mixed, then 50mL of deionized water is added, kneaded, extruded, dried at 80°C to 15% water content, granulated and cut into strips of 2mm, shaped into spherical particles in a spherical granulator or sugar coating pan, and then roasted in an air atmosphere at 550°C for 4 hours to obtain a spherical waste FCC catalyst carrier core (diameter 2mm). Spray aluminum sol (solid content 20% by mass) onto the outer surface of the waste FCC catalyst carrier core by a spraying method, dry at 80°C, and roast at a high temperature of 550°C for 4 hours to obtain a core-shell composite ozone catalytic oxidant carrier with a shell of γ-alumina (shell thickness 1mm, shell γ-alumina content 8% by mass).

[0093] The obtained carrier was loaded with active metal Cu oxide using impregnation technology, that is, 100g of the carrier was impregnated with 1 mol / L copper nitrate solution at room temperature for 2 hours, then dried at 80°C, and calcined at 550°C for 4 hours to obtain a core-shell composite ozone catalyst F2.

[0094] Example 3

[0095] This embodiment is used to illustrate a method for preparing an ozone catalytic oxidation catalyst from a waste FCC catalyst, wherein the waste FCC catalyst, the active component I calculated as active metal oxide, and the binder are respectively in the following mass ratios: 90 mass% of the waste FCC catalyst, and MnO 2 5% by mass, adhesive (aluminum sol) 5% by mass.

[0096] The specific preparation method is as follows: 100g of waste FCC catalyst, aluminum sol (solid content 20% by mass) and manganese nitrate aqueous solution (manganese nitrate content 50% by mass) are mixed, then 50mL of deionized water is added, kneaded, extruded, dried at 120°C to 30% by mass water content, granulated and cut into strips of 1mm, shaped into spherical particles in a spherical granulator or sugar coating pan, and then roasted in an air atmosphere at 650°C for 8 hours to obtain a spherical waste FCC catalyst carrier core (diameter 3mm). Spray aluminum sol (solid content 20% by mass) onto the outer surface of the waste FCC catalyst carrier core by a spraying method, dry at 120°C, and roast at a high temperature of 650°C for 8 hours to obtain a core-shell composite ozone catalytic oxidant carrier with a shell of γ-alumina (shell thickness 2mm, shell γ-alumina content 10% by mass).

[0097] The obtained carrier was loaded with active metal Ce oxide using impregnation technology, that is, 100g of the carrier was impregnated with 1.5mol / L cerium nitrate solution at room temperature for 4h, then dried at 120°C, and calcined at 650°C for 8h to obtain a core-shell composite ozone catalyst F3.

[0098] Comparative Example

[0099] A commercially available ozone catalytic oxidation catalyst (purchased from Shandong Ruihai Environmental Technology Co., Ltd., with a brand name of RHCY-1) was used as a comparison.

[0100] Test Example 1

[0101] The ozone catalytic oxidation catalyst obtained in the example and the commercially available ozone catalytic oxidation catalyst in the comparative example were used to treat wastewater (coking wastewater, COD is 3000 mg / L), with a catalyst dosage of 0.04 g per mg of wastewater COD, an ozone addition dosage of 0.04 mg, a residence time of 180 min, and wastewater COD was sampled and tested every half an hour. The COD removal rate was calculated as follows:

[0102] COD removal rate = (COD before treatment - COD during test) / COD before treatment × 100%

[0103] The results are shown in Table 1.

[0104] Table 1

[0105] It can be seen from Table 1 that the catalytic activity of the ozone catalytic oxidation catalysts obtained in Examples 1-3 of the present invention is close to that of existing commercial catalysts and has excellent catalytic oxidation activity.

[0106] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An ozone catalytic oxidation catalyst, It is characterized in that The ozone catalytic oxidation catalyst comprises a carrier and a transition metal oxide supported on the carrier, wherein the carrier has a core-shell structure, the core of the carrier is formed by a core composition, and the shell of the carrier comprises alumina, wherein the core composition contains 80-99% by mass of a waste FCC catalyst, 1-10% by mass of an active metal oxide, and 1-10% by mass of a binder, and the active metal oxide comprises one or more of Mn, Fe, Cu, Ni, Co, and Ce oxides.

2. The ozone catalytic oxidation catalyst according to claim 1, in, The spent FCC catalyst composition contains: 40-60 mass% Al 2 O 3 , 35-55% by mass SiO 2 , 1.0-2.0 mass% La 2 O 3 , 2.0-3.0 mass% CeO 2 .

3. The ozone catalytic oxidation catalyst according to claim 1, in, The active metal oxide comprises manganese oxide.

4. The ozone catalytic oxidation catalyst according to claim 1, in, The adhesive comprises one or more of silica sol, aluminum sol, carboxymethyl cellulose, polyvinyl alcohol and sesbania powder.

5. The ozone catalytic oxidation catalyst according to claim 1, in, The alumina is γ-alumina.

6. The ozone catalytic oxidation catalyst according to claim 1, in, The housing is formed of aluminum oxide.

7. The ozone catalytic oxidation catalyst according to claim 1, in, The diameter of the inner core is 1-10 mm.

8. The ozone catalytic oxidation catalyst according to claim 1, in, The thickness of the shell is 0.1-5 mm.

9. The ozone catalytic oxidation catalyst according to any one of claims 1 to 8, in, The content of aluminum oxide in the shell is 1-15 mass % of the weight of the ozone catalytic oxidation catalyst carrier.

10. The ozone catalytic oxidation catalyst according to any one of claims 1 to 8, in, The preparation method of the carrier comprises the following steps: 1) mixing and molding the spent FCC catalyst, the active metal oxide and its precursor and the binder, and then drying and first calcining to obtain a carrier core; 2) After the aluminum sol solution is sprayed onto the outer surface of the carrier core, it is dried and calcined for the second time to obtain an alumina shell covering the carrier core.

11. The ozone catalytic oxidation catalyst according to claim 10, in, The precursor of the active metal oxide is a nitrate of an active metal.

12. The ozone catalytic oxidation catalyst according to claim 10, in, The first calcination conditions include: temperature of 250-900° C. and time of 1-30 h.

13. The ozone catalytic oxidation catalyst according to claim 10, in, The second calcination conditions include: temperature of 250-900° C. and time of 0.5-30 h.

14. The catalyst according to claim 1, in, The transition metal oxide includes one or more of Cu, Ni, Co, Fe, Ce, and Mg oxides.

15. The catalyst according to claim 1, in, The active metal oxide accounts for 0.5-15% by weight of the ozone catalytic oxidation catalyst.

16. A method for preparing an ozone catalytic oxidation catalyst, It is characterized in that The method comprises the steps of loading a transition metal oxide precursor on the ozone catalytic oxidation catalyst carrier according to any one of claims 1 to 15 and performing drying and a third calcination.

17. A method for degrading organic wastewater, the method include: The step of contacting the ozone catalytic oxidation catalyst with the wastewater in the presence of ozone is characterized in that the ozone catalytic oxidation catalyst is the ozone catalytic oxidation catalyst according to any one of claims 1-15.

18. Use of the ozone catalytic oxidation catalyst according to any one of claims 1 to 15 in sewage treatment.

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