CN116532149A

CN116532149A - Catalyst for advanced oxidation reaction and preparation method and application thereof

Info

Publication number: CN116532149A
Application number: CN202310705695.2A
Authority: CN
Inventors: 黄金灿; 黄纯凯; 张璐; 喻学敏; 刘广兵; 刘伟京
Original assignee: Jiangsu Provincial Academy of Environmental Science
Current assignee: Jiangsu Provincial Academy of Environmental Science
Priority date: 2023-06-14
Filing date: 2023-06-14
Publication date: 2023-08-04

Abstract

The invention discloses a catalyst for advanced oxidation reaction, a preparation method and application thereof, and belongs to the technical field of environment-friendly catalysts. According to the invention, the S1 molecular sieve is used as a carrier, active components Fe, co, ni and auxiliary metal are loaded in situ through a hydrothermal method in the presence of a stabilizer, and the catalyst is obtained through one-step synthesis, has good catalytic activity on degradation of various organic pollutants in industrial tail water, ensures that the dosage of the agent in the advanced oxidation process is less, can improve the removal efficiency of refractory organic matters, and is beneficial to the application of the advanced oxidation technology in the industrial tail water treatment.

Description

Catalyst for advanced oxidation reaction and preparation method and application thereof

Technical Field

The invention belongs to the technical field of environment-friendly catalysts, and particularly relates to a catalyst for advanced oxidation reaction, and a preparation method and application thereof.

Background

The industries of papermaking, printing and dyeing, pesticides, electroplating and the like discharge a large amount of wastewater in the production process, wherein the wastewater contains various organic pollutants including organic acids, phenols, organic dyes and various pesticide intermediates. Because the organic wastewater has the characteristics of high pollutant concentration, difficult degradation and low biodegradability, once the organic wastewater is discharged without control, the organic wastewater not only can pollute the water environment, but also can harm the human health.

At present, the pollutant removal process in the organic wastewater mainly comprises coagulation, membrane separation, biochemical treatment, advanced oxidation and the like. Advanced oxidation represented by Fenton reaction can oxidize organic matters into carbon dioxide and water under the action of strong oxidant, and has the advantages of strong degradation capability and no selectivity. However, as the Fenton reaction requires ferrous sulfate and hydrogen peroxide and requires acid and alkali adjustment, the consumption of the medicament is high, and dangerous waste of ferric hydroxide sludge can be generated, so that the operation cost is increased.

The heterogeneous advanced oxidation reaction replaces ferrous sulfate with iron-based materials or other solid catalysts, catalyzes hydrogen peroxide to produce free radical oxidation degradation pollutants, and does not produce iron sludge. In addition, the heterogeneous advanced oxidation reaction using persulfate as an oxidant can be performed under neutral and alkaline conditions, and acid and alkali regulation and sludge treatment are not needed, so that the dosage of the medicament and the operation cost are greatly reduced, and the method has a wide application prospect.

According to the search, the Chinese patent application filed by the application number 201610638681.3 and the application date 2016, 8 and 5 discloses a method for preparing the high-efficiency Fenton-like catalyst of the sulfur-modified iron-based composite material solid acid ceramic membrane layer and application thereof, and the sulfur-modified iron-based composite material solid acid ceramic membrane is applied to heterogeneous advanced oxidation reaction, so that better catalytic performance is obtained. In addition, the Chinese patent application filed on 3 and 21 days of application No. 201410109593.5 and 2014 discloses an active carbon catalyst for Fenton-like technology, and preparation and application thereof, and a better advanced oxidation reaction result is obtained under the low-temperature and neutral conditions by using the active carbon supported composite catalyst.

For example, the Chinese patent application filed by the application No. 201611075189.6, the application of the year 2016, the year 11 and the month 28 discloses an iron-doped FAU molecular sieve which is used for advanced oxidation reaction, and a better degradation effect is obtained. The Chinese patent application filed on 12 months and 11 days of application No. 201510915258.9 and 2015 discloses that the iron-cobalt loaded molecular sieve is used for degrading phenolic dye through advanced oxidation reaction at room temperature and under neutral conditions, and the wastewater after the reaction only contains trace iron ions, so that the subsequent treatment cost is greatly reduced.

At present, most of the active components of the advanced oxidation catalyst still take ferric oxide as a main component, and the active components of the catalyst are lost due to higher iron ion leaching under the slightly acidic condition, so that the stability is influenced. Therefore, there is a need to develop a catalyst which can efficiently perform advanced oxidation reaction under a wide pH range and neutral conditions, is less likely to lose active components, and has high stability.

Disclosure of Invention

1. Problems to be solved

Aiming at the problems of easy loss of active components, poor stability and low oxidation efficiency of the advanced oxidation catalyst in the prior art, the invention provides a catalyst for advanced oxidation reaction, and a preparation method and application thereof. The invention takes the solution containing the carrier precursor, the structure directing agent, the active component, the auxiliary agent and the complexing stabilizer as raw material liquid, mixes and stirs the raw material liquid to carry out hydrothermal reaction to synthesize the catalyst solid by one-step method, and the catalyst solid is used in industrial tail water treatment, can stably and effectively catalyze advanced oxidation to remove organic matters in industrial tail water, and the removal rate can reach more than 99 percent.

2. Technical proposal

In order to solve the problems, the technical scheme adopted by the invention is as follows:

the catalyst for the advanced oxidation reaction is prepared from a carrier, an active component, an auxiliary agent and a stabilizer by a one-step hydrothermal synthesis method, wherein the carrier is an S-1 all-silicon molecular sieve, the active component is one or more of Fe, co and Cu, the auxiliary agent is one or more of La, ce, pr, nd, and the stabilizer is tetrasodium ethylenediamine tetraacetate.

Preferably, the active ingredient is supported in an amount of 0.05% to 5% by mass based on the carrier.

Preferably, the loading amount of the auxiliary agent is 0.05 to 5% by mass based on the carrier.

The preparation method of the catalyst for the advanced oxidation reaction comprises the following steps:

s10, adding a carrier precursor and a structure directing agent into water, and uniformly mixing to obtain a first precursor solution;

s20, adding an active component precursor, an auxiliary agent precursor and a stabilizer into water, and uniformly mixing to obtain a second precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution to carry out hydrothermal synthesis reaction, obtaining catalyst solid by a one-step method, washing, drying and roasting to obtain the catalyst for advanced oxidation reaction.

Preferably, in step S10, the carrier precursor is tetraethyl orthosilicate, the structure directing agent is tetrapropylammonium hydroxide, the mass ratio of the carrier precursor to the structure directing agent is 13 (10-20), and the mass ratio of the carrier precursor to water is 13 (20-40).

Preferably, in step S20, the ratio of the stabilizer to the sum of the mass of the active component precursor and the additive precursor is 1.0 to 1.1.

Preferably, in step S20, the active component precursor is one or more of ferric nitrate, cobalt nitrate and cupric nitrate, the auxiliary precursor is one or more of lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate, and the stabilizer is tetrasodium ethylenediamine tetraacetate.

Preferably, the specific process of step S30 is: mixing and stirring the first precursor solution and the second precursor solution for 4-8 hours, performing hydrothermal synthesis reaction at 140-180 ℃, washing, drying, and roasting at 400-600 ℃ for 3-6 hours in an air atmosphere to obtain a catalyst for advanced oxidation reaction; wherein the mass ratio between the water in the first precursor solution and the water in the second precursor solution is 5:1.

The catalyst for advanced oxidation reaction or the application of the catalyst prepared by the preparation method in advanced oxidation removal of industrial tail water organic matters is disclosed, wherein the catalyst and the oxidant are added under the condition that the pH value is 4.0-10.0, and organic matters in the industrial tail water are degraded into inorganic matters under the action of the catalyst and the oxidant so as to remove the organic matters in the industrial tail water.

Preferably, the amount of the catalyst added is 0.1-1 g/L, and the mass ratio of the added oxidant to COD in the tail water is 3-20.

Preferably, the oxidant is hydrogen peroxide or potassium hydrogen persulfate.

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that:

(1) The catalyst for advanced oxidation reaction takes the S-1 all-silicon molecular sieve as a carrier, one or more of Fe, co and Cu as an active component, one or more of La, ce, pr, nd as an auxiliary agent, and the molecular sieve synthesis and the active component loading are simultaneously completed by a one-step hydrothermal method in the presence of a stabilizer, so that the active component is uniformly dispersed in the molecular sieve carrier, the size of the active component is smaller, and the exposure is more sufficient;

(2) The catalyst for advanced oxidation reaction provided by the invention has the advantages that the auxiliary metal provides an electron transfer effect, the reaction activity of the catalyst is promoted to be improved, the catalyst has a good catalytic effect on removing organic matters in various industrial tail waters by advanced oxidation in a wider pH range, and the removal rate can reach more than 99%;

(3) The catalyst for advanced oxidation reaction has higher stability by taking the all-silicon molecular sieve as a carrier, has the leaching amount of elements less than or equal to 0.1mg/L after the reaction, has simple preparation method and easy operation, and has important significance for promoting advanced oxidation to remove organic matters in industrial wastewater.

Drawings

FIG. 1 is a schematic illustration of a process flow for preparing a catalyst for advanced oxidation reactions according to the present invention.

Detailed Description

The invention is further described below in connection with specific embodiments.

As shown in fig. 1, a method for preparing a catalyst for advanced oxidation reaction according to the present invention comprises the steps of:

s10, adding a carrier precursor and a structure directing agent into water, and uniformly mixing to obtain a first precursor solution, wherein the carrier precursor is tetraethyl orthosilicate, the structure directing agent is tetrapropylammonium hydroxide, the mass ratio of the carrier precursor to the structure directing agent is 13 (10-20), and the mass ratio of the carrier precursor to the water is 13 (20-40);

s20, adding an active component precursor, an auxiliary agent precursor and a stabilizer into water, and uniformly mixing to obtain a second precursor solution, wherein the active component precursor is one or more of ferric nitrate salt, cobalt nitrate salt and cupric nitrate salt, the auxiliary agent precursor is one or more of lanthanum nitrate salt, cerium nitrate salt, praseodymium nitrate salt and neodymium nitrate salt, the stabilizer is tetrasodium ethylenediamine tetraacetate, and the ratio of the sum of the mass of the stabilizer and the mass of the active component precursor to the mass of the auxiliary agent precursor is 1.0-1.1;

s30, mixing and stirring the first precursor solution and the second precursor solution for 4-8 hours, performing hydrothermal synthesis reaction at 140-180 ℃ for 72 hours, washing, drying, and roasting at 400-600 ℃ for 3-6 hours in an air atmosphere to obtain a catalyst for advanced oxidation reaction; in step S10 and step S20, the mass ratio between the water in the first precursor solution and the water in the second precursor solution is 5:1.

The catalyst for the advanced oxidation reaction is prepared from a carrier, an active component, an auxiliary agent and a stabilizer by a one-step hydrothermal synthesis method, wherein the carrier is an S-1 all-silicon molecular sieve, the active component is one or more of Fe, co and Cu, the auxiliary agent is one or more of La, ce, pr, nd, and the stabilizer is tetrasodium ethylenediamine tetraacetate; wherein, the active component is 0.05-5% of the loading amount based on the carrier by mass, and the auxiliary agent is 0.05-5% of the loading amount based on the carrier by mass. The catalyst is applied to advanced oxidation for removing industrial tail water organic matters, and the specific application method comprises the following steps: and (3) adding the catalyst and an oxidant (for example, hydrogen peroxide or potassium hydrogen persulfate) under the condition of pH of 4.0-10.0, stirring and reacting for 1 hour, degrading organic matters in the industrial tail water into inorganic matters under the action of the catalyst and the oxidant so as to remove the organic matters in the industrial tail water, and filtering to remove the catalyst after the reaction. The mass ratio of the added catalyst to COD in the tail water is 3-20, and the mass ratio of the added oxidant to the mass ratio of the added catalyst is 0.1-1 g/L.

Example 1

A method for preparing a catalyst for advanced oxidation reaction of the present embodiment includes the steps of:

s10, adding 13g of tetraethyl orthosilicate and 15.2g of tetrapropylammonium hydroxide into 20g of water, and stirring and mixing uniformly to obtain a first precursor solution, namely a molecular sieve precursor;

s20, adding 0.185g of cobalt nitrate, 0.047g of cerium nitrate and 0.431g of tetrasodium ethylenediamine tetraacetate into 4g of water, and stirring and mixing uniformly to obtain a second precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution for 8 hours, carrying out hydrothermal synthesis reaction at 180 ℃ for 72 hours to obtain a solid, washing and drying, and roasting at 500 ℃ for 3 hours in an air atmosphere to obtain the catalyst for advanced oxidation reaction. The active component of the catalyst was Co1 wt.%, and the promoter was Ce0.5 wt.% (noted as 1 Co0.5Ce-S1).

The catalyst was used for advanced oxidation reactions and the catalytic performance was tested. The method comprises the following specific steps:

firstly, 150mL of a solution with the concentration of the organic pollutants being 20mg/L is prepared in a glass beaker, commercial strong ammonia water or dilute sulfuric acid with the concentration of 0.5mol/L is added to adjust the pH, 0.05g of catalyst is added and stirred for 30 minutes to be uniformly mixed, then a certain amount of oxidant is added into the mixture to start the reaction and time, and the pollutant removal rate and the total concentration of metal ions are measured after 30 minutes of the reaction. Higher removal rates indicate better Fenton-like reactivity, and lower total metal ion concentrations indicate better catalyst stability.

In this example, the degradation target is activated red X-3B, the oxidant is potassium hydrogen persulfate compound salt 0.3g, and the pH is 7.0. The test results are shown in Table 1. As is clear from Table 1, the catalyst of example 1 removed more than 99% of the organic contaminants in the wastewater under the given reaction conditions and time, and the leached ion concentration in the solution after the reaction was only 0.01mg/L, and had excellent catalytic activity and stability.

Comparative example 1

The basic content of this comparative example is the same as in example 1, except that: only active components are added in the preparation process of the catalyst, and no auxiliary metal is added. The active component of the catalyst was Co1 wt.% (denoted 1 Co-S1).

The catalyst performance test method in example 1 was adopted, the degradation object in this comparative example was active red X-3B, the oxidant was potassium hydrogen persulfate composite salt 0.3g, and the pH was 7.0. The test results are shown in Table 1.

Compared with the test result of the example 1, under the same reaction condition, the removal rate of the auxiliary metal stable active component without the auxiliary metal stable active component can reach 98.1 percent, but the ion leaching concentration after the reaction is 0.11mg/L, which is obviously higher than that of the catalyst of the example 1, and the catalytic stability is not as good as that of the catalyst of the example 1.

Comparative example 2

The basic content of this comparative example is the same as in example 1, except that: during the preparation process of the catalyst, only auxiliary metal is added, and no active component is added, wherein the auxiliary of the catalyst is Ce1 wt% (recorded as 1 Ce-S1).

Compared with the test results of example 1, under the same reaction conditions, although the leached ion concentration after the catalyst of the present comparative example was reacted was 0.01mg/L, the organic contaminant removal rate was only 61.2% due to the lack of the active component.

Comparative example 3

The basic content of this comparative example is the same as in example 1, except that: the stabilizer ethylene diamine tetraacetic acid tetrasodium is not added in the preparation process of the catalyst. The active component of the catalyst was Co1 wt.%, and the promoter was Ce0.5 wt.% (noted as 1 Co0.5Ce-S1).

Compared with the test result of example 1, the catalyst preparation process of the comparative example does not add a stabilizer, and the active component and the auxiliary agent precursor generate precipitate under the alkaline synthesis condition and can not completely enter the catalyst, so that the removal rate is only 49.5% under the same reaction condition.

Comparative example 4

The basic content of this comparative example is the same as in example 1, except that: the catalyst is prepared by an impregnation method. A method for preparing a catalyst for advanced oxidation reaction of the present comparative example, comprising the steps of:

s10, adding the S1 molecular sieve raw powder into water, and stirring and mixing uniformly to obtain a first precursor solution;

s20, adding cobalt nitrate and cerium nitrate into water, and stirring and mixing uniformly to obtain a second precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution for 8 hours, performing rotary evaporation at 90 ℃ to obtain a solid, and roasting the obtained solid at 500 ℃ in an air atmosphere for 3 hours to obtain the catalyst. The active component of the catalyst was Co1 wt.%, and the promoter was Ce0.5 wt.% (noted as 1 Co0.5Ce-S1).

Compared with the test result of the example 1, the particle size of the active component and the auxiliary agent loaded by the impregnation method is obviously larger than that of the catalyst prepared by the in-situ encapsulation of the complex stabilizer, the exposure of the active component is insufficient, and the removal rate of organic pollutants of the catalyst of the comparative example only reaches 85.2% under the same reaction condition.

Comparative example 5

The basic content of this comparative example is the same as in example 1, except that: the catalyst is prepared by adopting an alumina carrier and an impregnation method. A method for preparing a catalyst for advanced oxidation reaction of the present comparative example, comprising the steps of:

s10, adding the alumina raw powder into water, and uniformly stirring and mixing to obtain a first precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution for 8 hours, performing rotary evaporation at 90 ℃ to obtain a solid, and roasting the obtained solid at 500 ℃ in an air atmosphere for 3 hours to obtain the catalyst. The active component of the catalyst was Co1 wt.%, and the promoter was Ce0.5 wt.% (noted as 1 Co0.5Ce-Al).

Because the alumina carrier has smaller specific surface area and porosity than the S1 molecular sieve, the organic pollutant removal rate of the catalyst of the comparative example is further reduced to 74.4% under the same reaction condition, the ion leaching concentration is also improved, and the stability is reduced.

Comparative example 6

The basic content of this comparative example is the same as in example 1, except that: mn is added as an active component in the preparation process of the catalyst. The active component of the catalyst is Mn1 wt.%, and the promoter is Ce0.5 wt.% (denoted as 1Mn0.5 Ce-S1).

In comparison with the test results of example 1, the comparative example uses Mn with lower activity instead of Fe, co and Ni as active components, and the organic pollutant removal rate is only 82.8% under the same reaction conditions, which is lower than that of the catalyst of example 1.

Comparative example 7

The basic content of this comparative example is the same as in example 1, except that: the loading of the active components and auxiliaries of the catalyst was lower than in example 1. A method for preparing a catalyst for advanced oxidation reaction of the present comparative example, comprising the steps of:

s10, adding tetraethyl orthosilicate and tetrapropylammonium hydroxide into water, and stirring and mixing uniformly to obtain a first precursor solution;

s20, adding 0.018g of cobalt nitrate, 0.009g of cerium nitrate and 0.057g of tetrasodium ethylenediamine tetraacetate into water, and stirring and mixing uniformly to obtain a second precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution for 8 hours, carrying out hydrothermal synthesis reaction at 180 ℃ for 72 hours to obtain a solid, washing and drying, and roasting at 500 ℃ for 3 hours in an air atmosphere to obtain the catalyst for advanced oxidation reaction. The active component of the catalyst was Co0.1 wt.%, and the promoter was Ce0.1 wt.% (noted as 0.1Co0.1Ce-S1).

The organic pollutant removal rate of the comparative example is only 59.5% under the same reaction conditions due to the smaller loading of the active components and the auxiliary agents, which is far lower than that of the catalyst of the example 1.

Comparative example 8

The basic content of this comparative example is the same as in example 1, except that: the loading of the active components and auxiliaries of the catalyst was higher than in example 1. A method for preparing a catalyst for advanced oxidation reaction of the present comparative example, comprising the steps of:

s20, adding cobalt nitrate, cerium nitrate and tetrasodium ethylenediamine tetraacetate into water, and stirring and mixing uniformly to obtain a second precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution for 8 hours, carrying out hydrothermal synthesis reaction at 180 ℃ for 72 hours to obtain a solid, washing and drying, and roasting at 500 ℃ for 3 hours in an air atmosphere to obtain the catalyst for advanced oxidation reaction. The active component of the catalyst is Co10 wt.%, and the auxiliary agent is Ce5 wt.% (recorded as 10Co5 Ce-S1).

In the comparative example, because the loading of the active component and the auxiliary agent is too large, the active component is easier to generate large particles to be dispersed in the catalyst, the exposure of the active component is insufficient, and the removal rate of the organic pollutants reaches 99.3 percent under the same reaction condition, but the ion leaching concentration after the reaction is 0.21mg/L, which is far greater than that of the catalyst of the example 1, and the stability is greatly reduced.

TABLE 1 results of catalyst Performance test for example 1 and comparative examples 1-8

The above example 1 and comparative examples 1-8 illustrate the application of the catalyst of the present invention to advanced oxidative removal of organic contaminants with the advantage of high catalytic activity and high stability.

Example 2

The basic content of this embodiment is the same as embodiment 1, except that: a method for preparing a catalyst for advanced oxidation reaction of the present embodiment includes the steps of:

s10, adding tetraethyl orthosilicate and tetrapropylammonium hydroxide into water, and stirring and mixing uniformly to obtain a first precursor solution, namely a molecular sieve precursor;

s20, adding ferric nitrate, praseodymium nitrate and tetrasodium ethylenediamine tetraacetate into water, and stirring and mixing uniformly to obtain a second precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution for 8 hours, carrying out hydrothermal synthesis reaction at 180 ℃ for 72 hours to obtain a solid, washing and drying, and roasting at 500 ℃ for 3 hours in an air atmosphere to obtain the catalyst for advanced oxidation reaction. The active component of the catalyst is Fe3 wt.%, and the auxiliary agent is Pr2 wt.% (denoted as 3Fe2 Pr-S1).

By adopting the catalyst performance test method in the example 1, the degradation object is sulfamethoxazole, the oxidant is 30% hydrogen peroxide solution 1.0g, and the pH is 4.0. The organic removal rate was 99.5%, and the ion concentration was 0.01mg/L.

Example 3

s20, adding nickel nitrate, lanthanum nitrate, praseodymium nitrate and tetrasodium ethylenediamine tetraacetate into water, and stirring and mixing uniformly to obtain a second precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution for 8 hours, carrying out hydrothermal synthesis reaction at 180 ℃ for 72 hours to obtain a solid, washing and drying, and roasting at 500 ℃ for 3 hours in an air atmosphere to obtain the catalyst for advanced oxidation reaction. The active component of the catalyst is Ni4 wt%, the auxiliary agent is La2 wt%, and Nd2 wt% (recorded as 4Ni2La2 Pr-S1).

The catalyst performance test method in example 1 was used, the degradation target was bisphenol A, the oxidant was potassium hydrogen persulfate composite salt 0.3g, and the pH was 9.0. The organic removal rate was 99.6% and the ion concentration was 0.02mg/L.

Example 4

s20, adding cobalt nitrate, lanthanum nitrate, cerium nitrate and tetrasodium ethylenediamine tetraacetate into water, and stirring and mixing uniformly to obtain a second precursor solution;

s30, mixing and stirring the first precursor solution and the second precursor solution for 8 hours, carrying out hydrothermal synthesis reaction at 180 ℃ for 72 hours to obtain a solid, washing and drying, and roasting at 500 ℃ for 3 hours in an air atmosphere to obtain the catalyst for advanced oxidation reaction. The active component of the catalyst is Co5 wt%, the auxiliary agent is La2 wt%, and Ce2 wt% (marked as 5Co2La2 Ce-S1).

The catalyst performance test method in example 1 was used, the degradation target was polyvinyl alcohol 1788, the oxidant was potassium hydrogen persulfate composite salt 0.3g, and the pH was 10.0. The organic removal rate was 99.7%, and the ion concentration was 0.03mg/L. And the catalyst after the reaction was collected and subjected to the test again for 4 times, the removal rate of the organic matters was 99.6%, and the ion concentration was 0.01mg/L.

The test results of examples 2-4 show that the catalyst provided by the invention can realize high-efficiency removal of different organic pollutants represented by sulfamethoxazole, bisphenol A and polyvinyl alcohol 1788 by using hydrogen peroxide or potassium hydrogen persulfate as an oxidant at pH of 4.0-10.0, the pollutant removal rate is more than 99%, and the concentration of leached ions of the active component is not more than 0.03mg/L after 5 repeated tests, so that the catalyst has good stability and reusability.

The invention and its embodiments have been described above schematically, without limitation, and the data used is only one of the embodiments of the invention, and the actual data combination is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the invention should not be construed as being limited to the embodiments and examples similar to the technical solutions without departing from the spirit of the invention.

Claims

1. A catalyst for advanced oxidation reactions, characterized by: the catalyst is prepared from a carrier, an active component, an auxiliary agent and a stabilizer through a one-step hydrothermal synthesis method, wherein the carrier is an S-1 all-silicon molecular sieve, the active component is one or more of Fe, co and Cu, the auxiliary agent is one or more of La, ce, pr, nd, and the stabilizer is tetrasodium ethylenediamine tetraacetate.

2. A catalyst for advanced oxidation reactions, characterized by: the active component is 0.05-5% of the loading amount based on the carrier by mass.

3. A catalyst for advanced oxidation reactions, characterized by: the loading amount of the auxiliary agent based on the carrier is 0.05-5% by mass.

4. A method for preparing a catalyst for advanced oxidation reactions, characterized by: the method comprises the following steps:

5. The method for preparing a catalyst for advanced oxidation reactions according to claim 4, wherein: in the step S10, the carrier precursor is tetraethyl orthosilicate, the structure directing agent is tetrapropylammonium hydroxide, the mass ratio of the carrier precursor to the structure directing agent is 13 (10-20), and the mass ratio of the carrier precursor to water is 13 (20-40).

6. The method for preparing a catalyst for advanced oxidation reactions according to claim 4, wherein: in step S20, the ratio of the stabilizer to the sum of the mass of the active component precursor and the mass of the auxiliary precursor is 1.0-1.1.

7. The method for preparing a catalyst for advanced oxidation reactions according to claim 4, wherein: in step S20, the active component precursor is one or more of ferric nitrate, cobalt nitrate and cupric nitrate, the auxiliary precursor is one or more of lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate, and the stabilizer is tetrasodium ethylenediamine tetraacetate.

8. The method for preparing a catalyst for advanced oxidation reactions according to claim 4, wherein: the specific process of step S30 is: mixing and stirring the first precursor solution and the second precursor solution for 4-8 hours, performing hydrothermal synthesis reaction at 140-180 ℃, washing, drying, and roasting at 400-600 ℃ for 3-6 hours in an air atmosphere to obtain a catalyst for advanced oxidation reaction; wherein the mass ratio between the water in the first precursor solution and the water in the second precursor solution is 5:1.

9. Use of a catalyst for advanced oxidation reactions according to any one of claims 1-3 or a catalyst prepared according to the preparation method of any one of claims 4-8 for advanced oxidation removal of industrial tail water organics, characterized in that: under the condition that the pH value is 4.0-10.0, the catalyst and the oxidant are added, and organic matters in the industrial tail water are degraded into inorganic matters under the action of the catalyst and the oxidant, so that the organic matters in the industrial tail water are removed.

10. The use according to claim 9, characterized in that: the amount of the added catalyst is 0.1-1 g/L, and the mass ratio of the added oxidant to COD in the tail water is 3-20.