CN111744492A

CN111744492A - Catalytic ozonation catalyst, preparation method thereof and sewage treatment method

Info

Publication number: CN111744492A
Application number: CN201910234699.0A
Authority: CN
Inventors: 刘祺; 李本高; 陈妍
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-03-26
Filing date: 2019-03-26
Publication date: 2020-10-09

Abstract

The invention relates to the field of waste treatment and sewage treatment, and discloses a catalytic ozonation catalyst, a preparation method thereof and a sewage treatment method. The catalytic ozonation catalyst comprises a carrier and a metal active component loaded on the carrier, wherein the carrier is an FCC spent catalyst, and the metal active component is at least one metal selected from IIA group, IB group, VIIB group, VIII group and rare earth elements. The recycling method of the FCC waste catalyst provided by the invention prepares a novel supported catalytic ozonation catalyst by taking the FCC waste catalyst as a carrier, provides a novel method for treating the FCC waste catalyst, and realizes 'treatment of waste by waste'. The invention takes FCC waste catalyst as carrier to prepare the load type catalytic ozonation catalyst which is applied to sewage, in particular to the catalytic oxidation treatment of phenol-containing sewage, and the effect is obvious.

Description

Catalytic ozonation catalyst, preparation method thereof and sewage treatment method

Technical Field

The invention relates to the field of waste treatment and sewage treatment, in particular to a catalytic ozonation catalyst, a preparation method thereof and a sewage treatment method, especially a phenol-containing sewage treatment method.

Background

The catalytic cracking (FCC) process is an important process flow in the petroleum refining process, and is one of the main processing processes for the conversion of heavy oil into light oil. Because the catalytic cracking process is generally adopted in China, the FCC catalyst is the catalyst with the largest use amount, the consumption of the FCC catalyst is about 350kt per year, the discharged waste catalyst contains rare earth oxide, vanadium iron and other metals, and belongs to solid waste. In recent years, the recycling of FCC spent catalyst has become a popular research, and there are two main treatment methods: demetallization regeneration or magnetic separation technology, which is limited in development due to problems of high cost, incomplete treatment and the like; and (II) applying the FCC waste catalyst to the aspects of producing ceramics, minerals, asphalt mixture and the like. However, with the upgrading and degradation of the raw oil, the service life of the FCC catalyst is obviously shortened, the amount of the generated FCC waste catalyst is increased, and the pollution problem is increasingly prominent. Therefore, based on the current situation, how to conduct harmless treatment and recycling of the FCC spent catalyst becomes a focus problem and also a problem to be solved.

Advanced oxidation technology is a key research direction in the field of sewage treatment in recent years, wherein catalytic ozone oxidation technology has attracted extensive attention due to the advantages of high reaction speed, good treatment effect, high ozone utilization rate, mild reaction conditions and the like. The catalyst plays an important role in the catalytic ozonation process, and the catalyst used in the catalytic ozonation technology comprises a homogeneous catalyst and a heterogeneous catalyst. Homogeneous catalysts are easily dissolved in solution in an ionic form, are difficult to separate from the solution, and easily cause catalyst waste, so that the homogeneous catalysts have been gradually replaced by heterogeneous solid catalysts. Heterogeneous catalysts have a long service life and are easy to separate and recover, wherein supported catalysts with noble metals as active components show high activity and stability, however, due to the high cost of noble metals, such catalysts tend to be expensive. Therefore, the development of a high-activity and high-stability catalyst is the key point for widely applying the catalytic ozone oxidation technology.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provides a method for recycling an FCC waste catalyst, in particular to a catalytic ozone oxidation catalyst and a preparation method thereof and a sewage treatment method, wherein the method is used for preparing the FCC waste catalyst into a supported catalyst and applying the supported catalyst to the sewage catalytic oxidation technology, so that the recycling of the FCC waste catalyst can be realized, and the sewage treatment effect is obvious.

In order to achieve the above object, according to one aspect of the present invention, there is provided a catalytic ozonation catalyst, wherein the catalytic ozonation catalyst comprises a carrier and a metal active component supported on the carrier, the carrier is an FCC spent catalyst, and the metal active component is at least one metal selected from group iia, group ib, group viib, group viii, and rare earth elements.

The second aspect of the present invention provides a method for preparing a catalytic ozonation catalyst, wherein the method comprises: impregnating the FCC spent catalyst support with a solution containing a soluble compound of at least one metal selected from the group consisting of group IIA, group IB, group VIIB, group VIII and rare earth elements, drying and calcining the impregnated FCC spent catalyst support.

In a third aspect, the invention provides a catalytic ozonation catalyst obtained according to the preparation method of the invention.

The fourth aspect of the invention provides a sewage treatment method, which comprises the step of mixing sewage to be treated with a catalytic ozonation catalyst and ozone, wherein the catalytic ozonation catalyst is the catalytic ozonation catalyst provided by the invention.

Compared with the prior art, the invention at least has the following advantages:

the recycling method of the FCC waste catalyst provided by the invention prepares a novel supported catalytic ozonation catalyst by taking the FCC waste catalyst as a carrier, provides a novel method for treating the FCC waste catalyst, and realizes 'treatment of waste by waste'. Moreover, the preparation method of the supported catalytic ozonation catalyst is simple, low in cost and easy to industrialize.

The invention takes FCC waste catalyst as carrier to prepare the load type catalytic ozonation catalyst which is applied to sewage, in particular to the catalytic oxidation treatment of phenol-containing sewage, and the effect is obvious.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, the catalytic ozonation catalyst comprises a carrier which is an FCC spent catalyst, and a metal active component supported on the carrier, the metal active component being at least one metal selected from group iia, group ib, group viib, group viii, and rare earth elements.

The inventor of the invention skillfully utilizes the FCC waste catalyst as a carrier, not only utilizes the metal active component loaded on the carrier to prepare the catalytic ozonation catalyst which has catalytic action on pollutants in sewage and has low cost when being used as the carrier, but also has certain adsorption action and catalytic activity under certain conditions, can oxidize and decompose part of pollutants adsorbed on the FCC waste catalyst to a certain extent, and ensures that the sewage, especially the phenol-containing sewage is treated more completely and thoroughly.

Various FCC spent catalysts known to those skilled in the art can be used in the present invention as supports for catalytic ozonation catalysts in accordance with the present invention. Preferably, in one embodiment of the present invention, the FCC dead catalyst has a composition of: based on the total weight of the FCC spent catalyst, the content of silicon dioxide is 30-70 wt%, the content of aluminum oxide is 20-60 wt%, the content of iron is 0.01-2 wt%, the content of vanadium is 0.01-2 wt%, the content of nickel is 0.01-2 wt%, the content of sodium is 0.01-1 wt%, the content of antimony is 0.01-1 wt%, the content of calcium is 0.01-1 wt%, the content of carbon is 0.1-1 wt%, and the content of rare earth metal is 0-10 wt%.

According to the present invention, from the viewpoint of further improving the catalytic oxidation effect of the catalytic ozonation catalyst, it is preferable that the specific surface area of the FCC spent catalyst is 100-300m²Pore volume of 0.1-0.4 ml/g.

In the invention, the aim of the invention can be achieved as long as the FCC spent catalyst is used as a carrier in the catalytic ozonation catalyst, and the metal active component loaded on the carrier is at least one metal active component selected from IIA group, IB group, VIIB group, VIII group and rare earth elements. Wherein, the content of the FCC spent catalyst carrier and the metal active component in the catalytic ozonation catalyst can be selected from a wide range, the content of the metal active component in the catalytic ozonation catalyst can be the content range of the existing metal active component capable of being used for catalyzing the catalytic ozonation catalyst, preferably, the content of the carrier is 70-99.9 wt% based on the total weight of the catalytic ozonation catalyst, and the content of the metal active component is 0.1-30 wt% based on oxides; further preferably, the carrier is present in an amount of 85 to 98 wt%, and the metal active component is present in an amount of 2 to 15 wt%, calculated as an oxide, based on the total weight of the catalytic ozonation catalyst.

According to the present invention, in the catalytic ozonation catalyst, the kinds of the respective groups of metal elements in the metal active component are wide in optional range, and most preferably, the metal active component is selected from one or more of copper, cobalt, palladium, ruthenium, rhodium, platinum, manganese, iron, nickel, cerium, lanthanum, magnesium, and silver.

According to the present invention, in order to further improve the catalytic oxidation effect of the catalytic ozonation catalyst of the present invention, preferably, the metal active component is selected from one or more of manganese, cerium, magnesium, and nickel, and in various combinations, preferably, a combination of manganese and cerium or a combination of magnesium and copper. Further preferably, the mass ratio of manganese to cerium, calculated as oxide, is from 0.1 to 3:1, more preferably from 1 to 3: 1; the mass ratio of magnesium to copper, calculated as oxide, is 0.1-5:1, more preferably 1-5: 1.

According to a second aspect of the present invention, the method for preparing the catalytic ozonation catalyst comprises: impregnating the FCC spent catalyst support with a solution containing a soluble compound of at least one metal selected from the group consisting of group IIA, group IB, group VIIB, group VIII and rare earth elements, drying and calcining the impregnated FCC spent catalyst support.

In the method of the present invention, only the preparation method of the catalytic ozonation catalyst is described, and the technical features same as those in the catalytic ozonation catalyst product will not be described repeatedly.

According to the present invention, preferably, the preparation method further comprises: before impregnation, the FCC spent catalyst carrier is calcined, and the calcined FCC spent catalyst carrier is subjected to an acid treatment step. The FCC spent catalyst is calcined to remove part of the carbon deposit attached to the active center, improve the catalytic activity and make the particles firmer. In order to better achieve the purpose, the temperature for calcining the FCC spent catalyst carrier can be 400-1000 ℃, preferably 600-900 ℃, and the calcining time can be 0.5-6h, preferably 1-4 h.

According to the present invention, the acid treatment of the calcined spent FCC catalyst support is performed for the purpose of removing part of the deposited heavy metals. Wherein the specific method of the acid treatment step comprises: the calcined FCC spent catalyst support is contacted with an acid solution, wherein the kind of acid used may be various inorganic acids or organic acids known to those skilled in the art, for example, one or more selected from hydrochloric acid, sulfuric acid, oxalic acid, acetic acid and nitric acid, and the mass concentration of the acid solution is preferably 1 to 15 wt% in order to more effectively remove heavy metals while avoiding the destruction of the molecular sieve framework structure due to the removal of aluminum and thereby reducing the crystallinity. The mass ratio of the calcined FCC spent catalyst carrier to the acid solution may be selected according to the concentration of the acid solution, and for example, the mass ratio of the calcined FCC spent catalyst carrier to the acid solution is preferably 1:2 to 10, provided that the mass concentration of the acid solution is selected as described above. The contacting of the calcined FCC spent catalyst carrier with the acid solution may be performed by mixing, spraying, dipping, etc. as long as the purpose of the acid treatment can be achieved, and preferably, for the purpose of the acid treatment, the contacting temperature is 0 to 100 ℃, preferably 30 to 80 ℃, and the contacting time may be appropriately selected according to the contacting temperature and the mass ratio of the calcined FCC spent catalyst carrier to the acid solution, and preferably, the contacting time is 2 to 8 hours.

According to the present invention, the method further comprises the steps of washing the FCC spent catalyst support after the acid treatment to remove residual acid solution and drying, and the specific methods and conditions are well known to those skilled in the art and will not be described herein.

According to the present invention, the soluble compound of at least one metal selected from the group consisting of group IIA, group IB, group VIIB, group VIII and the rare earth elements is selected from a wide range, and specifically, group IIA may be one or more of a soluble compound of magnesium, a soluble compound of calcium, a soluble compound of barium and the like; the IB group can be one or more of soluble compounds of copper, silver and gold; VIIB may be a soluble compound of manganese; the VIII group can be one or more of soluble compounds of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum; the rare earth element may be one or more of a soluble compound of lanthanum, a soluble compound of cerium, a soluble compound of praseodymium, a soluble compound of neodymium, and the like. Preferably, the soluble compound of the metal is selected from at least one of a copper compound, a cobalt compound, a palladium compound, a ruthenium compound, a rhodium compound, a platinum compound, a manganese compound, an iron compound, a nickel compound, a cerium compound, a lanthanum compound, a magnesium compound, and a silver compound, more preferably, the soluble compound of the metal is selected from one or more of a manganese compound, a cerium compound, a magnesium compound, and a nickel compound, and preferably, in various combinations, a combination of a manganese compound and a cerium compound or a combination of a magnesium compound and a copper compound. Preferably, the manganese compound and the cerium compound are used in such amounts that the mass ratio of manganese to cerium in the catalyst, calculated as oxide, is from 0.1 to 3: 1. Preferably, the magnesium compound and the copper compound are used in such amounts that the mass ratio of magnesium to copper, calculated as oxide, in the catalyst is from 0.1 to 5:1, more preferably from 1 to 5: 1. More specifically, the copper compound is copper nitrate and/or copper chloride; the cobalt compound is cobalt acetate and/or cobalt nitrate; the palladium compound is in palladium nitrate and/or palladium chloride; the ruthenium compound is ruthenium chloride; the rhodium compound is rhodium chloride; the platinum compound is platinum chloride; the manganese compound is selected from at least one of manganese nitrate, manganese chloride and manganese sulfate; the iron compound is selected from at least one of ferric nitrate, ferric chloride and ferric sulfate; the nickel compound is at least one of nickel nitrate, nickel sulfate and nickel chloride; the cerium compound is cerium nitrate and/or cerium chloride; the lanthanum compound is lanthanum nitrate and/or lanthanum chloride, and the magnesium compound is magnesium nitrate and/or magnesium acetate; the silver compound is silver nitrate.

The invention has no special requirement on the type of the solution of the metal compound, generally the solution is aqueous solution, and in special cases, in order to enable various metal compounds in the solution to be dissolved and well dispersed in the solution so as to enable the contact effect to be better, additional solvent can be added when needed to promote the dissolution and dispersion of the metal compounds in the solution. Those skilled in the art will appreciate that they will not be described in detail herein.

According to the present invention, when a plurality of metal active components need to be loaded, the FCC spent catalyst carriers preferably calcined and then acid-treated can be respectively impregnated with the solutions of the metal compounds, or the FCC spent catalyst carriers preferably calcined and then acid-treated can be co-impregnated with the mixed solution of the metal compounds. Further, the solution of the metal compound may be prepared according to conventional knowledge in the art, and an aqueous solution of an appropriate concentration may be prepared according to the amount of the metal active component supported.

The impregnation of the FCC spent catalyst support, preferably the FCC spent catalyst support which has been calcined and then acid-treated, with a solution containing a soluble compound of at least one metal selected from group iia, group ib, group viib, group viii and rare earth elements according to the present invention can be carried out by the impregnation methods which are conventional in the art, for example, by dry impregnation (i.e. by isovolumetric impregnation) or by incipient wetness impregnation.

According to the present invention, the impregnation conditions generally include an impregnation temperature and an impregnation time, the impregnation temperature may be 0 to 100 ℃, preferably 20 to 80 ℃, and the impregnation time may be appropriately selected according to the degree of dispersion of the metal active component, and preferably, the impregnation time may be 4 to 24 hours, preferably 6 to 12 hours. Furthermore, the amount of solvent in the solution containing the soluble compound of the metal active component is such that, on the one hand, the soluble compound containing the metal active component is sufficiently soluble in the solvent and, on the other hand, sufficient dispersion of the FCC spent catalyst support is ensured. Preferably, the amount of the solvent used in the solution containing the soluble compound of the metal active component is 5 to 50ml, preferably 6 to 20ml, based on 1g of the weight of the fcc spent catalyst support. The solvent is preferably at least one of water, ethanol, and propanol (including n-propanol and its isomer, isopropanol).

According to the invention, the dosage of the soluble compound of the FCC waste catalyst carrier and the metal active component can be selected from a wide range, and preferably, in order to further improve the catalytic oxidation performance of the catalytic ozonation catalyst, the dosage of the soluble compound of the FCC waste catalyst carrier and the metal active component is 70-99.9 wt% of the carrier based on the total weight of the catalytic ozonation catalyst, and the content of the metal active component is 0.1-30 wt% calculated by oxide; preferably, the carrier is present in an amount of 85 to 98 wt%, and the metal active component is present in an amount of 2 to 15 wt%, calculated as an oxide, based on the total weight of the catalytic ozonation catalyst.

The conditions for drying the impregnated FCC spent catalyst support according to the present invention may be conventional drying conditions for removing the solvent, for example, the drying temperature may be 90 to 125 ℃, the duration of the drying may be selected according to the drying temperature, and the drying temperature may be generally 1 to 12 hours.

According to the present invention, the conditions for calcining the impregnated FCC spent catalyst support may be conventional calcining conditions, for example, the calcining temperature may be 300-700 ℃, the duration of the calcining may be selected according to the calcining temperature, and the calcining time may be generally 2-6 h. The calcination is generally carried out in an air atmosphere, which includes both a flowing atmosphere and a static atmosphere.

According to a third aspect of the present invention, there is also provided a catalytic ozonation catalyst obtained by the preparation method according to the present invention.

According to a fourth aspect of the invention, the invention also provides a sewage treatment method, which comprises the step of mixing the sewage to be treated with the catalytic ozone oxidation catalyst and ozone, wherein the catalytic ozone oxidation catalyst is the catalytic ozone oxidation catalyst provided by the invention.

According to the present invention, the ozone oxidizing agent can oxidize impurities such as organic substances in the wastewater, and thus the oxidation by ozone can effectively reduce the COD of the wastewater, and can also effectively remove phenol-containing substances in the wastewater, thereby improving the biodegradability of the wastewater. Preferably, under the action of the catalytic ozonation catalyst provided by the invention, the oxidation of ozone can be more effectively promoted, the COD (chemical oxygen demand) of the sewage can be further reduced, the removal rate of volatile phenol can be further improved, and the biodegradability of the sewage can be improved.

According to the present invention, the conditions for the mixing treatment and the amounts of the ozone and the catalyst can be selected within a wide range, as long as the conditions are sufficient to oxidize and decompose the impurities such as organic substances in the sewage, so as to satisfy a lower COD value of the treated sewage, and to effectively remove volatile phenols from phenol-containing substances in the sewage. Preferably, the amount of ozone is 0.1-15g/L, and more preferably 1-8g/L for the purpose of wastewater treatment and cost. Preferably, the mass ratio of ozone to the catalytic ozonation catalyst is 1:0.01 to 2, and more preferably, the mass ratio of ozone to the catalytic ozonation catalyst is 1:0.1 to 1.

According to the invention, compared with single ozone oxidation, ozone can react with organic pollutants more rapidly under the action of the catalytic ozone oxidation catalyst provided by the invention, the COD removal rate is higher, the ozone utilization rate is higher, and small molecular organic matters with poor effect on single ozone oxidation, such as: aldehydes, esters, organic acids and the like can be completely mineralized by catalytic ozonation, so that the catalytic ozonation catalyst provided by the invention plays an important role in the catalytic ozonation process.

According to the present invention, the temperature of the mixing treatment may be 0 to 100 ℃, preferably 20 to 80 ℃, and the time of the mixing treatment may be appropriately selected according to the amount of the catalytic ozonation catalyst and ozone used and the temperature of the mixing treatment, so long as the lower COD value of the treated sewage can be satisfied and the phenol-containing substances, particularly volatile phenol, in the sewage can be effectively removed. In general, the mixing treatment time may be generally 0.1 to 300 minutes, preferably 20 to 180 minutes.

The method for treating the sewage is particularly suitable for treating all the sewage containing volatile phenol, such as the sewage containing phenol in petrochemical industry, coal chemical industry and pharmaceutical industry. The content of volatile phenol in the sewage is not less than 0.5mg/L, and usually 0.5-1000 mg/L. Examples of the volatile phenol contained in the phenol-containing wastewater include, but are not limited to: phenol, 2, 5-dimethylphenol, 2, 4-dimethylphenol, 3, 5-dimethylphenol, o-methylphenol, 2-ethylphenol, 4-ethylphenol, p-methylphenol, m-methylphenol, alpha-naphthol, and the like.

According to the invention, the phenol-containing sewage can be at least one of various phenol-containing sewage, preferably phenol-containing alkaline sewage generated by alkali washing catalytic cracking gasoline, diesel oil and liquefied gas in the crude oil refining process, effluent water of the sewage after wet oxidation and mixed sewage of the sewage.

The present invention will be described in detail below by way of examples.

In the following preparation examples, the content of the metal active component in terms of oxide in the catalytic ozonation catalyst was measured by the XRF method.

In the following examples, the method for measuring the phenol content in the sewage and the phenol content in the treated sewage is 4-aminoantipyrine spectrophotometry (GB 7490-87); the COD is determined by dichromate method (GB 11914-89).

The dephenolization rate is 100 x (the phenol content in the sewage before treatment-the phenol content in the sewage after treatment)/the phenol content in the sewage before treatment.

The COD removal rate is 100 x (COD content in the sewage before treatment-COD content in the sewage after treatment)/COD content in the sewage before treatment.

In the following preparations 1 to 7 and preparations 10 and 11, the FCC spent catalyst carrier was taken from a refinery in north of hu and the composition is shown in the following table.

In the following preparations 8 to 9, the FCC spent catalyst carrier was obtained from a refinery in shandong and had the composition shown in the following table.

Preparation examples 1 to 11 are provided to illustrate the preparation of the catalytic ozonation catalyst provided by the present invention.

Examples 1 to 11 are provided for explaining the method of treating wastewater according to the present invention.

Preparation example 1

Pretreatment of the catalyst carrier: the FCC spent catalyst was placed in a muffle furnace and calcined at 700 deg.C for 3 hours. Preparing 8% hydrochloric acid aqueous solution, adding the FCC spent catalyst and the hydrochloric acid aqueous solution in a mass ratio of 1:5 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring speed at 60 ℃ and 1000r/min, and carrying out acid treatment for 2.5 h. After the reaction is finished, washing the reaction product by deionized water until the pH value is unchanged, and drying the reaction product in a vacuum drying oven at 105 ℃ for 8 hours.

And (3) dipping: adding deionized water into magnesium nitrate to prepare a steeping liquor with the concentration of 0.6mol/L, adding the steeping liquor into the FCC spent catalyst, uniformly stirring, and steeping for 12 hours at room temperature. After the impregnation is completed, the mixture is placed into a drying oven and dried for 12 hours at 115 ℃.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 500 ℃ for 4h to obtain the catalytic ozonation catalyst C1. The content of the FCC waste catalyst carrier was 96.16 wt% based on the total weight of the catalytic ozonation catalyst C1, and the content of the metal active component, magnesium, was 3.84 wt% in terms of oxide.

Example 1

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C1 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L of sewage, the reaction temperature is 30 ℃, and the reaction time is 100 min.

The phenol sewage water sample is prepared 500mg/L simulated phenol sewage, the initial pH value is 6.34, the initial COD is 1187.04mg/L, and the initial phenol content is 457.36 mg/L. After the reaction is carried out for 100min, the phenol removal rate reaches 98.94 percent, and the COD removal rate reaches 80.45 percent.

Preparation example 2

Pretreatment of the FCC spent catalyst: the FCC spent catalyst was placed in a muffle furnace and calcined at 600 deg.C for 3 hours. Preparing an oxalic acid aqueous solution with the mass fraction of 4%, adding the FCC spent catalyst and the oxalic acid aqueous solution in a mass ratio of 1:2 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring speed at 50 ℃ and 1000r/min, and carrying out acid treatment for 2 h. After the reaction is finished, washing the reaction product by deionized water until the pH value is unchanged, and drying the reaction product in a vacuum drying oven at 105 ℃ for 8 hours.

And (3) dipping: adding manganese acetate and deionized water to prepare a steeping liquor with the concentration of 0.2mol/L, adding the steeping liquor into the FCC spent catalyst, uniformly stirring, and steeping for 8 hours at room temperature. After the impregnation was completed, the mixture was placed in a vacuum oven and dried at 105 ℃ for 8 hours.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 400 ℃ for 3h to obtain the catalytic ozonation catalyst C2. Based on the total weight of the catalytic ozonation catalyst C2, the content of the FCC spent catalyst carrier is 91.70 wt%, and the content of the metal active component manganese is 8.30 wt% calculated by oxide.

Example 2

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C2 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 3g/L of sewage, the reaction temperature is 20 ℃, and the reaction time is 100 min.

The phenol sewage water sample is prepared 500mg/L simulated phenol sewage, the initial pH value is 6.33, the initial COD is 1184.31mg/L, and the initial phenol content is 489.48 mg/L. After reacting for 2h, the phenol removal rate reaches 94.36%, and the COD removal rate reaches 78.62%.

Preparation example 3

Pretreatment of the catalyst carrier: the FCC spent catalyst was placed in a muffle furnace and calcined at 800 deg.C for 4 hours. Preparing 10% hydrochloric acid aqueous solution, adding the FCC spent catalyst and the hydrochloric acid aqueous solution in a mass ratio of 1:8 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring speed at 80 ℃ and 1000r/min, and carrying out acid treatment for 6 h. After the reaction is finished, washing the reaction product by deionized water until the pH value is unchanged, and drying the reaction product in a vacuum drying oven at 105 ℃ for 8 hours.

And (3) dipping: and adding cerium nitrate and deionized water to prepare a steeping liquor with the concentration of 0.3mol/L, adding the steeping liquor into the FCC spent catalyst, uniformly stirring, and steeping for 16 hours at room temperature. After the impregnation is completed, the mixture is placed into a drying oven and dried for 8 hours at 115 ℃.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 500 ℃ for 4h to obtain the catalytic ozonation catalyst C3. Based on the total weight of the catalytic ozonation catalyst C3, the content of the FCC spent catalyst carrier is 97.13 wt%, and the content of the metal active component cerium is 2.87 wt% calculated by oxide.

Example 3

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C3 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 5g/L of sewage, the reaction temperature is 40 ℃, and the reaction time is 100 min.

The phenol sewage water sample is prepared 500mg/L simulated phenol sewage, the initial pH value is 6.34, the initial COD is 1126.61mg/L, and the initial phenol content is 476.47 mg/L. After the reaction is carried out for 100min, the phenol removal rate reaches 99.15%, and the COD removal rate reaches 86.98%.

Preparation example 4

Pretreatment of the FCC spent catalyst: the FCC spent catalyst was placed in a muffle furnace and calcined at 900 deg.C for 6 hours. Preparing a sulfuric acid aqueous solution with the mass fraction of 12%, adding the FCC spent catalyst and the sulfuric acid aqueous solution in a mass ratio of 1:8 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring rotating speed at 80 ℃ and 1000r/min, and carrying out acid treatment for 3 h. After the reaction is finished, the mixture is washed by deionized water until the pH value is unchanged, and the mixture is placed into a vacuum drying oven and dried for 12 hours at 105 ℃.

And (3) dipping: taking ferric sulfate and deionized water to prepare a steeping liquor with the concentration of 0.5mol/L, adding the steeping liquor into the FCC spent catalyst, uniformly stirring, and steeping for 24 hours at room temperature. After the impregnation was completed, the mixture was placed in a vacuum oven and dried at 105 ℃ for 12 hours.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 600 ℃ for 4h to obtain the catalytic ozonation catalyst C4. The content of the FCC waste catalyst carrier was 88.34 wt% based on the total weight of the catalytic ozonation catalyst C4, and the content of the metal active component, iron, was 11.66 wt% in terms of oxide.

Example 4

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C4 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L, the reaction temperature is 10 ℃, and the reaction time is 100 min.

The phenol sewage water sample is prepared 500mg/L simulated phenol sewage, the initial pH value is 6.30, the initial COD is 1106.40mg/L, and the initial phenol content is 484.20 mg/L. After the reaction is carried out for 100min, the phenol removal rate reaches 82.36 percent, and the COD removal rate reaches 56.26 percent.

Preparation example 5

Pretreatment of the FCC spent catalyst: the FCC spent catalyst is put into a muffle furnace and calcined for 6 hours at 800 ℃. Preparing an acetic acid aqueous solution with the mass fraction of 8%, adding the FCC spent catalyst and the acetic acid aqueous solution in a mass ratio of 1:6 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring rotating speed at 60 ℃ and 1000r/min, and carrying out acid treatment for 2 h. After the reaction is finished, the mixture is washed by deionized water until the pH value is unchanged, and the mixture is placed into a vacuum drying oven and dried for 12 hours at 105 ℃.

And (3) dipping: adding silver nitrate and deionized water to prepare a steeping liquor with the concentration of 0.3mol/L, adding the steeping liquor into the FCC spent catalyst, uniformly stirring, and steeping for 24 hours at room temperature. After the impregnation was completed, the mixture was placed in a vacuum oven and dried at 105 ℃ for 12 hours.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 600 ℃ for 4h to obtain the catalytic ozonation catalyst C5. The content of the FCC waste catalyst carrier was 97.55 wt% based on the total weight of the catalytic ozonation catalyst C5, and the content of the metal active component, silver, was 2.45 wt% in terms of oxide.

Example 5

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C5 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L, the reaction temperature is 20 ℃, and the reaction time is 100 min.

The phenol sewage water sample is 500mg/L of prepared simulated phenol sewage, the initial pH value is 6.31, the initial COD is 1078.45mg/L, and the initial phenol content is 474.34 mg/L. After the reaction is carried out for 100min, the removal rate of phenol reaches 86.49%, and the removal rate of COD reaches 59.75%.

Preparation example 6

Pretreatment of the catalyst carrier: the FCC spent catalyst was placed in a muffle furnace and calcined at 700 deg.C for 3 hours. Preparing 8% hydrochloric acid aqueous solution, adding the FCC spent catalyst and the hydrochloric acid aqueous solution in a mass ratio of 1:5 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring speed at 60 ℃ and 1000r/min, and carrying out acid treatment for 4 hours. After the reaction is finished, washing the reaction product by deionized water until the pH value is unchanged, and drying the reaction product in a vacuum drying oven at 105 ℃ for 8 hours.

And (3) dipping: adding deionized water into manganese sulfate and cerium nitrate according to the mass ratio of 2:1 to prepare a 0.6mol/L impregnation solution, adding the impregnation solution into the FCC spent catalyst, uniformly stirring, and impregnating for 12 hours at room temperature. After the impregnation is completed, the mixture is placed into a drying oven and dried for 12 hours at 115 ℃.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 500 ℃ for 4h to obtain the catalytic ozonation catalyst C6. Based on the total weight of the catalytic ozonation catalyst C6, the content of the FCC spent catalyst carrier is 94.13 wt%, the total content of metal active components manganese and cerium is 5.87 wt% calculated by oxides, and the mass ratio of manganese to cerium is 1.87:1 calculated by oxides.

Example 6

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C6 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L, the reaction temperature is 30 ℃, and the reaction time is 100 min.

The phenol sewage water sample is 500mg/L of prepared simulated phenol sewage, the initial pH value is 6.35, the initial COD is 1147.47mg/L, and the initial phenol content is 464.32 mg/L. After the reaction is carried out for 100min, the phenol removal rate reaches 99.14 percent, and the COD removal rate reaches 83.62 percent.

Preparation example 7

Pretreatment of the catalyst carrier: the spent FCC catalyst was placed in a muffle furnace and calcined at 750 ℃ for 4 h. Preparing a hydrochloric acid aqueous solution with the mass fraction of 6%, adding the FCC spent catalyst and the hydrochloric acid aqueous solution in a mass ratio of 1:5 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring speed at 60 ℃ and 1000r/min, and carrying out acid treatment for 3 h. After the reaction is finished, washing the reaction product by deionized water until the pH value is unchanged, and drying the reaction product in a vacuum drying oven at 105 ℃ for 8 hours.

And (3) dipping: adding deionized water into copper nitrate and magnesium nitrate according to the mass ratio of 1:3 to prepare 0.4mol/L impregnation liquid, adding the impregnation liquid into FCC spent catalyst, uniformly stirring, and impregnating for 12 hours at room temperature. After the impregnation is completed, the mixture is placed into a drying oven and dried for 12 hours at 115 ℃.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 500 ℃ for 4h to obtain the catalytic ozonation catalyst C7. The content of the FCC waste catalyst carrier was 96.36 wt% based on the total weight of the catalytic ozonation catalyst C7, and the total content of the metal active components copper and magnesium was 3.64 wt% in terms of oxide, and the mass ratio of copper to magnesium was 1:2.96 in terms of oxide.

Example 7

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C7 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L, the reaction temperature is 30 ℃, and the reaction time is 100 min.

The phenol sewage water sample is prepared 500mg/L simulated phenol sewage, the initial pH value is 6.32, the initial COD is 1113.49mg/L, and the initial phenol content is 473.10 mg/L. After the reaction is carried out for 100min, the phenol removal rate reaches 98.17 percent, and the COD removal rate reaches 80.42 percent.

Preparation example 8

Taking Qingdao refined FCC spent catalyst, and the pretreatment step of the catalyst carrier comprises the following steps: the spent FCC catalyst was placed in a muffle furnace and calcined at 750 ℃ for 4 h. Preparing a hydrochloric acid aqueous solution with the mass fraction of 6%, adding the FCC spent catalyst and the hydrochloric acid aqueous solution in a mass ratio of 1:4 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring speed at 60 ℃ and 1000r/min, and carrying out acid treatment for 2.5 h. After the reaction is finished, the mixture is washed by deionized water until the pH value is unchanged, and the mixture is placed into a vacuum drying oven and dried for 12 hours at 105 ℃.

And (3) dipping: adding deionized water into magnesium nitrate to prepare a steeping liquor with the concentration of 0.5mol/L, adding the steeping liquor into the FCC spent catalyst, uniformly stirring, and steeping for 24 hours at room temperature. After the impregnation is completed, the mixture is placed into a drying oven and dried for 12 hours at 115 ℃.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 500 ℃ for 4h to obtain the catalytic ozonation catalyst C8. The content of the FCC waste catalyst carrier was 96.14 wt% based on the total weight of the catalytic ozonation catalyst C8, and the content of the metal active component, magnesium, was 3.86 wt% in terms of oxide.

Example 8

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C8 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L, the reaction temperature is 30 ℃, and the reaction time is 100 min.

The phenol sewage water sample is prepared 500mg/L simulated phenol sewage, the initial pH value is 6.30, the initial COD is 1202.04mg/L, and the initial phenol content is 493.20 mg/L. After the reaction is carried out for 100min, the phenol removal rate reaches 98.78 percent, and the COD removal rate reaches 83.97 percent.

Preparation example 9

Taking Qingdao refined FCC waste catalyst, and pretreating the FCC waste catalyst: the FCC spent catalyst was placed in a muffle furnace and calcined at 800 ℃ for 3 h. Preparing an oxalic acid aqueous solution with the mass fraction of 4%, adding the FCC spent catalyst and the sulfuric acid aqueous solution in a mass ratio of 1:8 into a reaction bottle with a reflux device, controlling the heating temperature of a water bath and the magnetic stirring rotating speed at 80 ℃ and 1000r/min, and carrying out acid treatment for 3 h. After the reaction is finished, the mixture is washed by deionized water until the pH value is unchanged, and the mixture is placed into a vacuum drying oven and dried for 12 hours at 105 ℃.

And (3) dipping: and adding the cerium nitrate and deionized water to prepare a steeping liquor with the concentration of 1.0mol/L, adding the steeping liquor into the FCC spent catalyst, uniformly stirring, and steeping for 24 hours at room temperature. After the impregnation was completed, the mixture was placed in a vacuum oven and dried at 105 ℃ for 12 hours.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 500 ℃ for 4h to obtain the catalytic ozonation catalyst C9. Based on the total weight of the catalytic ozonation catalyst C9, the content of the FCC spent catalyst carrier is 78.05% by weight, and the content of the metal active component cerium is 21.95% by weight calculated by oxides.

Example 9

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C9 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L, the reaction temperature is 30 ℃, and the reaction time is 100 min.

The phenol sewage water sample is prepared 500mg/L simulated phenol sewage, the initial pH value is 6.36, the initial COD is 1123.11mg/L, and the initial phenol content is 486.06 mg/L. After the reaction is carried out for 100min, the removal rate of phenol reaches 71.03%, and the removal rate of COD reaches 43.26%.

Preparation example 10

And (3) dipping: adding deionized water into manganese sulfate to prepare a maceration extract with the concentration of 0.6mol/L, adding into FCC spent catalyst, stirring uniformly, and macerating for 12h at room temperature. After the impregnation is completed, the mixture is placed into a drying oven and dried for 12 hours at 115 ℃.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 500 ℃ for 4h to obtain the catalytic ozonation catalyst C10. The content of the FCC waste catalyst carrier was 93.62 wt% based on the total weight of the catalytic ozonation catalyst C10, and the content of the metal active component, manganese, was 6.38 wt% calculated as an oxide.

Example 10

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C10 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L, the reaction temperature is 30 ℃, and the reaction time is 100 min.

The phenol sewage water sample is 500mg/L of prepared simulated phenol sewage, the initial pH value is 6.35, the initial COD is 1147.47mg/L, and the initial phenol content is 464.32 mg/L. After the reaction is carried out for 100min, the phenol removal rate reaches 98.06 percent, and the COD removal rate reaches 76.32 percent.

Preparation example 11

And (3) dipping: adding deionized water into copper nitrate to prepare a steeping liquor with the concentration of 0.6mol/L, adding the steeping liquor into the FCC waste catalyst, uniformly stirring, and steeping for 12 hours at room temperature. After the impregnation is completed, the mixture is placed into a drying oven and dried for 12 hours at 115 ℃.

And (3) roasting: and (3) putting the dried solid powder into a muffle furnace, and roasting at 500 ℃ for 4h to obtain the catalytic ozonation catalyst C11. Based on the total weight of the catalytic ozonation catalyst C11, the content of the FCC spent catalyst carrier is 95.96 wt%, and the content of the metal active component copper is 4.04 wt% calculated by oxide.

Example 11

1L of phenol sewage water sample is taken, 1g/L of catalytic ozonation catalyst C11 is taken, continuous aeration is carried out in the catalytic ozonation reaction, the adding amount of ozone is 2g/L of sewage, the reaction temperature is 30 ℃, and the reaction time is 100 min.

The phenol sewage water sample is 500mg/L of prepared simulated phenol sewage, the initial pH value is 6.35, the initial COD is 1161.13mg/L, and the initial phenol content is 461.05 mg/L. After the reaction is carried out for 100min, the removal rate of phenol reaches 78.30 percent, and the removal rate of COD reaches 59.15 percent.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. The catalytic ozonation catalyst is characterized by comprising a carrier and a metal active component loaded on the carrier, wherein the carrier is an FCC spent catalyst, and the metal active component is at least one metal selected from IIA group, IB group, VIIB group, VIII group and rare earth elements.

2. The catalytic ozonation catalyst of claim 1, wherein the support is present in an amount of 70 to 99.9 wt%, based on the total weight of the catalytic ozonation catalyst, and the metal active component is present in an amount of 0.1 to 30 wt%, calculated as an oxide;

preferably, the carrier is present in an amount of 85 to 98 wt%, and the metal active component is present in an amount of 2 to 15 wt%, calculated as an oxide, based on the total weight of the catalytic ozonation catalyst.

3. A catalytic ozonation catalyst according to claim 1 or 2, wherein the metal active component is selected from one or more of copper, cobalt, palladium, ruthenium, rhodium, platinum, manganese, iron, nickel, cerium, lanthanum, magnesium and silver.

4. A catalytic ozonation catalyst according to any one of claims 1 to 3, wherein the metal active component is selected from one or more of manganese, cerium, magnesium and nickel, preferably a combination of manganese and cerium or a combination of magnesium and copper in various combinations, preferably the mass ratio of manganese to cerium, calculated as oxides, is 0.1-3:1, more preferably 1-3: 1; the mass ratio of magnesium to copper, calculated as oxide, is 0.1-5:1, more preferably 1-5: 1.

5. A catalytic ozonation catalyst according to any one of claims 1 to 4, wherein the silica is present in an amount of 30 to 70 wt%, the alumina is present in an amount of 20 to 60 wt%, the iron is present in an amount of 0.01 to 2 wt%, the vanadium is present in an amount of 0.01 to 2 wt%, the nickel is present in an amount of 0.01 to 2 wt%, the sodium is present in an amount of 0.01 to 1 wt%, the antimony is present in an amount of 0.01 to 1 wt%, the calcium is present in an amount of 0.01 to 1 wt%, the carbon is present in an amount of 0.1 to 1 wt%, and the rare earth metal is present in an amount of 0 to 10 wt%, based on the total weight of the FCC spent catalyst.

6. A method of preparing a catalytic ozonation catalyst, the method comprising: impregnating the FCC spent catalyst support with a solution containing a soluble compound of at least one metal selected from the group consisting of group IIA, group IB, group VIIB, group VIII and rare earth elements, drying and calcining the impregnated FCC spent catalyst support.

7. The production method according to claim 6, wherein the production method further comprises: before impregnation, the FCC spent catalyst carrier is calcined, and the calcined FCC spent catalyst carrier is subjected to an acid treatment step.

8. The preparation method as claimed in claim 7, wherein the temperature for calcining the FCC spent catalyst carrier is 400-1000 ℃, preferably 600-900 ℃, and the calcining time is 0.5-6h, preferably 1-4 h.

9. The preparation method of claim 7, wherein the method of acid-treating the calcined FCC spent catalyst support comprises: contacting the roasted FCC spent catalyst carrier with an acid solution, wherein the acid is selected from one or more of hydrochloric acid, sulfuric acid, oxalic acid, acetic acid and nitric acid, the mass concentration of the acid solution is 1-15 wt%, the mass ratio of the roasted FCC spent catalyst carrier to the acid solution is 1:2-10, the contact temperature is 0-100 ℃, preferably 30-80 ℃, and the contact time is 2-8 h.

10. The production method according to claim 6 or 7, wherein the soluble compound of the metal is selected from at least one of a copper compound, a cobalt compound, a palladium compound, a ruthenium compound, a rhodium compound, a platinum compound, a manganese compound, an iron compound, a nickel compound, a cerium compound, a lanthanum compound, a magnesium compound, and a silver compound, preferably the soluble compound of the metal is selected from one or more of a manganese compound, a cerium compound, a magnesium compound, and a nickel compound, preferably a combination of a manganese compound and a cerium compound or a combination of a magnesium compound and a copper compound in various combinations; preferably, the manganese compound and the cerium compound are used in such amounts that the mass ratio of manganese to cerium, calculated as oxide, in the catalyst is from 0.1 to 3:1, more preferably from 1 to 3: 1; the magnesium compound and the copper compound are used in such amounts that the mass ratio of magnesium to copper, calculated as oxide, in the catalyst is from 0.1 to 5:1, more preferably from 1 to 5: 1;

wherein the copper compound is copper nitrate and/or copper chloride; the cobalt compound is cobalt acetate and/or cobalt nitrate; the palladium compound is palladium nitrate and/or palladium chloride; the ruthenium compound is ruthenium chloride; the rhodium compound is rhodium chloride; the platinum compound is platinum chloride; the manganese compound is selected from at least one of manganese nitrate, manganese chloride and manganese sulfate; the iron compound is selected from at least one of ferric nitrate, ferric chloride and ferric sulfate; the nickel compound is at least one of nickel nitrate, nickel sulfate and nickel chloride; the cerium compound is cerium nitrate and/or cerium chloride; the lanthanum compound is lanthanum nitrate and/or lanthanum chloride; the magnesium compound is magnesium nitrate and/or magnesium acetate; the silver compound is silver nitrate.

11. The preparation method according to claim 10, wherein the FCC spent catalyst support and the soluble compound of the metal are used in an amount such that the content of the support is 70 to 99.9% by weight and the content of the metal active component is 0.1 to 30% by weight in terms of oxide, based on the total weight of the catalytic ozonation catalyst;

preferably, the FCC spent catalyst support and the soluble compound of the metal are used in an amount such that the support is present in an amount of 85 to 98 wt%, and the metal active component is present in an amount of 2 to 15 wt%, calculated as the oxide, based on the total weight of the catalytic ozonation catalyst.

12. The production method according to claim 6 or 7, wherein the conditions for impregnation include: the dipping temperature is 0-100 ℃, preferably 20-80 ℃, and the dipping time is 4-24h, preferably 6-12 h; drying the impregnated FCC spent catalyst carrier at the temperature of 90-125 ℃ for 1-12 h; the temperature for roasting the impregnated FCC dead catalyst carrier is 300-700 ℃, and the roasting time is 2-6 h.

13. The preparation method of claim 6 or 7, wherein the silica is contained in an amount of 30 to 70 wt%, the alumina is contained in an amount of 20 to 60 wt%, the iron is contained in an amount of 0.01 to 2 wt%, the vanadium is contained in an amount of 0.01 to 2 wt%, the nickel is contained in an amount of 0.01 to 2 wt%, the sodium is contained in an amount of 0.01 to 1 wt%, the antimony is contained in an amount of 0.01 to 1 wt%, the calcium is contained in an amount of 0.01 to 1 wt%, the carbon is contained in an amount of 0.1 to 1 wt%, and the rare earth metal is contained in an amount of 0 to 10 wt%, based on the total weight of the FCC spent catalyst.

14. The catalytic ozonation catalyst obtained by the production method according to any one of claims 1 to 13.

15. A method for treating sewage, which comprises mixing sewage to be treated with a catalytic ozonation catalyst and ozone, wherein the catalytic ozonation catalyst is the catalytic ozonation catalyst obtained by the preparation method according to any one of claims 1 to 13, or the catalytic ozonation catalyst according to claim 14.

16. The treatment method according to claim 15, wherein the amount of ozone is 0.1-15g/L, preferably 1-8 g/L; the mass ratio of the ozone to the catalytic ozone oxidation catalyst is 1:0.01-2, preferably 1: 0.1-1.

17. The process according to claim 15 or 16, wherein the temperature of the mixing process is between 0 and 100 ℃, preferably between 20 and 80 ℃.

18. The treatment method according to claim 15 or 16, wherein the wastewater to be treated is phenol-containing wastewater, and the content of volatile phenol in the wastewater to be treated is 0.5-1000 mg/L.