A catalyst for advanced oxidation reaction and its preparation method and application

Abstract

The present invention discloses a catalyst for advanced oxidation reactions, its preparation method, and its application, belonging to the technical field of environmentally friendly catalysts. Using S1 molecular sieve as a carrier, the present invention hydrothermally encapsulates the active components Fe, Co, Ni, and a metal additive in situ in the presence of a stabilizer to produce a one-step synthesis catalyst. This catalyst exhibits excellent catalytic activity for the degradation of various organic pollutants in industrial tailwater, reduces the dosage of reagents required in the advanced oxidation process, and improves the removal efficiency of refractory organic matter, facilitating the application of advanced oxidation technology in industrial tailwater treatment.

Description

Technical Field

[0001] The present invention belongs to the technical field of environmentally friendly catalysts, and more specifically, relates to a catalyst for advanced oxidation reactions, a preparation method thereof, and an application thereof. Background Art

[0002] Industries such as papermaking, printing and dyeing, pesticides, and electroplating discharge large amounts of wastewater during production. This wastewater contains a variety of organic pollutants, including organic acids, phenols, organic dyes, and pesticide intermediates. Due to the high concentrations of pollutants, resistance to degradation, and low biodegradability of these organic wastewaters, uncontrolled discharge not only pollutes the aquatic environment but also poses a threat to human health.

[0003] Currently, the main processes for removing pollutants from organic wastewater include coagulation, membrane separation, biochemical treatment, and advanced oxidation. Advanced oxidation, represented by the Fenton reaction, can oxidize organic matter into carbon dioxide and water under the action of strong oxidants, and has the advantages of strong degradation capacity and non-selectivity. However, because the Fenton reaction requires ferrous sulfate and hydrogen peroxide, as well as acid and alkali adjustments, it consumes a lot of reagents and produces hazardous waste such as ferric hydroxide sludge, increasing operating costs.

[0004] Heterogeneous advanced oxidation reactions use iron-based materials or other solid catalysts instead of ferrous sulfate to catalyze hydrogen peroxide to produce free radicals for oxidative degradation of pollutants, without producing iron sludge. Furthermore, heterogeneous advanced oxidation reactions using persulfate as an oxidant can operate under neutral and alkaline conditions, eliminating the need for acid or base adjustments or sludge disposal, significantly reducing reagent usage and operating costs, thus offering broad application prospects.

[0005] A search revealed that Chinese invention patent application number 201610638681.3, filed on August 5, 2016, discloses a method for preparing a sulfur-modified iron-based composite solid acid ceramic membrane layer as a high-efficiency Fenton-like catalyst and its application. This sulfur-modified iron-based composite solid acid ceramic membrane was applied to heterogeneous advanced oxidation reactions, achieving excellent catalytic performance. Separately, Chinese invention patent application number 201410109593.5, filed on March 21, 2014, discloses an activated carbon catalyst for Fenton-like technology, its preparation, and application. Using the activated carbon-supported composite catalyst, excellent advanced oxidation reaction results were achieved under low-temperature and neutral conditions.

[0006] For example, Chinese invention patent application No. 201611075189.6, filed on November 28, 2016, discloses an iron-doped FAU molecular sieve used in advanced oxidation reactions, achieving good degradation results. Chinese invention patent application No. 201510915258.9, filed on December 11, 2015, discloses the use of an iron-cobalt loaded molecular sieve for advanced oxidation degradation of phenolic dyes at room temperature and neutral conditions. The wastewater after the reaction contains only trace amounts of iron ions, significantly reducing subsequent treatment costs.

[0007] Since most current advanced oxidation catalysts are still primarily composed of iron oxide as their active component, high levels of iron ions can leach out even under slightly acidic conditions, leading to loss of active components and affecting stability. Therefore, it is necessary to develop a catalyst that can efficiently perform advanced oxidation reactions over a wide pH range and under neutral conditions, while also preventing loss of active components and maintaining high stability. Summary of the Invention

[0008] 1. Problem to be solved

[0009] To address the problems of existing advanced oxidation catalysts, such as the easy loss of active components, poor stability, and low oxidation efficiency, the present invention provides a catalyst for advanced oxidation reactions, its preparation method, and its application. The present invention utilizes a solution containing a support precursor, a structure-directing agent, the active components, an additive, and a complexing stabilizer as a raw material, followed by mixing and stirring, and then subjecting the solution to a hydrothermal reaction to produce a one-step synthesis of a solid catalyst. This catalyst is then used in industrial tailwater treatment, where it can stably and effectively catalyze advanced oxidation to remove organic matter from the tailwater, achieving a removal rate exceeding 99%.

[0010] 2. Technical solution

[0011] In order to solve the above problems, the technical solutions adopted by the present invention are as follows:

[0012] The present invention discloses a catalyst for advanced oxidation reaction. The catalyst is prepared from a carrier, an active component, an auxiliary agent and a stabilizer by a one-step hydrothermal synthesis method. 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 and Nd, and the stabilizer is tetrasodium ethylenediaminetetraacetic acid.

[0013] Preferably, the active component is loaded in an amount of 0.05% to 5% by mass based on the carrier.

[0014] Preferably, the loading amount of the auxiliary agent based on the carrier is 0.05% to 5% by mass.

[0015] A method for preparing a catalyst for advanced oxidation reaction of the present invention comprises the following steps:

[0016] S10, adding the carrier precursor and the structure directing agent into water and mixing them uniformly to obtain a first precursor solution;

[0017] S20, adding the active component precursor, the auxiliary agent precursor and the stabilizer into water and mixing them uniformly to obtain a second precursor solution;

[0018] S30, mixing the first precursor solution and the second precursor solution and stirring them to perform a hydrothermal synthesis reaction to obtain a catalyst solid in one step, and washing, drying, and calcining the catalyst to obtain a catalyst for an advanced oxidation reaction.

[0019] 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).

[0020] Preferably, in step S20, the ratio of the stabilizer to the sum of the mass of the active component precursor and the auxiliary agent precursor is 1.0 to 1.1.

[0021] Preferably, in step S20, the active component precursor is one or more of ferric nitrate, cobalt nitrate, and copper nitrate, the auxiliary agent precursor is one or more of lanthanum nitrate, cerium nitrate, praseodymium nitrate, and neodymium nitrate, and the stabilizer is tetrasodium ethylenediaminetetraacetic acid.

[0022] Preferably, the specific process of step S30 is: mixing and stirring the first precursor solution and the second precursor solution for 4 to 8 hours, and conducting a hydrothermal synthesis reaction at 140°C to 180°C, and then washing, drying, and calcining at 400°C to 600°C in an air atmosphere for 3 to 6 hours 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.

[0023] The above-mentioned catalyst for advanced oxidation reaction or the catalyst prepared according to the above-mentioned preparation method is used in advanced oxidation to remove organic matter from industrial tail water, wherein the catalyst and oxidant are added under the condition of pH 4.0 to 10.0, and the organic matter in the industrial tail water is degraded into inorganic matter under the action of the catalyst and the oxidant to remove the organic matter in the industrial tail water.

[0024] Preferably, the amount of the added catalyst is 0.1-1 g / L, and the mass ratio of the added oxidant to the COD in the tail water is 3-20.

[0025] Preferably, the oxidant is hydrogen peroxide or potassium persulfate.

[0026] 3. Beneficial effects

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) A catalyst for advanced oxidation reaction of the present invention uses S-1 all-silicon molecular sieve as a carrier, one or more of Fe, Co, and Cu as active components, and one or more of La, Ce, Pr, and Nd as additives. The catalyst is synthesized and loaded with the active components simultaneously by a one-step hydrothermal method in the presence of a stabilizer, so that the active components are uniformly dispersed in the molecular sieve carrier, and the active components are smaller in size and more fully exposed.

[0029] (2) The catalyst for advanced oxidation reaction of the present invention has an electron transfer effect provided by the auxiliary metal, thereby promoting the improvement of the catalyst reaction activity, and has a good catalytic effect on the advanced oxidation removal of organic matter in various industrial tail waters within a wide pH range, with a removal rate of more than 99%;

[0030] (3) The catalyst for advanced oxidation reaction of the present invention has higher stability with all-silicon molecular sieve as the carrier, and the element leaching amount after the reaction is less than or equal to 0.1 mg / L. In addition, the preparation method is simple and easy to operate, which is of great significance for promoting the advanced oxidation removal of organic matter in industrial wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The present invention is a schematic diagram of a process flow for preparing a catalyst for advanced oxidation reaction. DETAILED DESCRIPTION

[0032] The present invention will be further described below with reference to specific embodiments.

[0033] like Figure 1 As shown, a method for preparing a catalyst for advanced oxidation reaction of the present invention comprises the following steps:

[0034] S10, adding a carrier precursor and a structure-directing agent into water and mixing them uniformly 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 water is 13:(20-40);

[0035] S20, adding an active component precursor, an auxiliary agent precursor, and a stabilizer into water and mixing them uniformly to obtain a second precursor solution, wherein the active component precursor is one or more of ferric nitrate, cobalt nitrate, and copper nitrate, the auxiliary agent precursor is one or more of lanthanum nitrate, cerium nitrate, praseodymium nitrate, and neodymium nitrate, and the stabilizer is tetrasodium ethylenediaminetetraacetic acid, and the ratio of the stabilizer to the sum of the mass of the active component precursor and the auxiliary agent precursor is 1.0 to 1.1;

[0036] S30, mixing and stirring the first precursor solution and the second precursor solution for 4 to 8 hours, and conducting a hydrothermal synthesis reaction at 140°C to 180°C for 72 hours, and then washing, drying, and calcining at 400°C to 600°C in an air atmosphere for 3 to 6 hours to obtain a catalyst for an advanced oxidation reaction; wherein, 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.

[0037] The catalyst for advanced oxidation reaction of the present invention is prepared by a one-step hydrothermal synthesis method from a support, an active component, an auxiliary agent, and a stabilizer. The support is 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, and Nd, and the stabilizer is tetrasodium ethylenediaminetetraacetate. The active component is loaded on the support in an amount of 0.05% to 5% by mass, and the auxiliary agent is loaded on the support in an amount of 0.05% to 5% by mass. The catalyst is applied to remove organic matter from industrial tail water by advanced oxidation. The specific application method comprises: adding the catalyst and an oxidant (e.g., hydrogen peroxide or potassium persulfate) at a pH of 4.0 to 10.0, stirring and reacting for 1 hour, wherein the organic matter in the industrial tail water is degraded into inorganic matter under the action of the catalyst and oxidant to remove the organic matter from the industrial tail water, and filtering and removing the catalyst after the reaction. The mass of the added catalyst is 0.1 g / L to 1 g / L, and the mass ratio of the added oxidant to the COD in the tail water is 3 to 20.

[0038] Example 1

[0039] The method for preparing a catalyst for an advanced oxidation reaction of this embodiment comprises the following steps:

[0040] S10, adding 13 g of tetraethyl orthosilicate and 15.2 g of tetrapropylammonium hydroxide to 20 g of water and stirring to mix uniformly to obtain a first precursor solution, i.e., a molecular sieve precursor;

[0041] S20, adding 0.185 g of cobalt nitrate, 0.047 g of cerium nitrate, and 0.431 g of tetrasodium ethylenediaminetetraacetate to 4 g of water and stirring to mix uniformly to obtain a second precursor solution;

[0042] S30: The first precursor solution and the second precursor solution are mixed and stirred for 8 hours, and a hydrothermal synthesis reaction is carried out at 180° C. for 72 hours to obtain a solid. The solid is washed and dried, and then calcined at 500° C. in an air atmosphere for 3 hours to obtain a catalyst for an advanced oxidation reaction. The active component of the catalyst is Co 1 wt.%, and the additive is Ce 0.5 wt.% (denoted as 1Co0.5Ce-S1).

[0043] The catalyst was used in an advanced oxidation reaction to test its catalytic performance. The specific steps are as follows:

[0044] First, prepare 150 mL of a solution containing 20 mg / L of organic pollutants in a glass beaker. Adjust the pH by adding commercially available concentrated ammonia or 0.5 mol / L dilute sulfuric acid. Add 0.05 g of catalyst and stir for 30 minutes to mix thoroughly. Then, add a predetermined amount of oxidant to the mixture to initiate the reaction and time the reaction. After 30 minutes, measure the pollutant removal rate and total metal ion concentration. A higher removal rate indicates better Fenton-like reaction activity, while a lower total metal ion concentration indicates greater catalyst stability.

[0045] In this example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex, and the pH was 7.0. The test results are shown in Table 1. As can be seen from Table 1, the catalyst of Example 1 removed over 99% of the organic pollutants in the wastewater under the given reaction conditions and time. Furthermore, the ion concentration leached into the solution after the reaction was only 0.01 mg / L, demonstrating excellent catalytic activity and stability.

[0046] Comparative Example 1

[0047] The basic content of this comparative example is the same as that of Example 1, except that only active components are added during the catalyst preparation process, and no promoter metal is added. The active component of the catalyst is Co1 wt.% (denoted as 1Co-S1).

[0048] The catalyst performance test method in Example 1 was used. In this comparative example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex salt, and the pH was 7.0. The test results are shown in Table 1.

[0049] Compared with the test results of Example 1, under the same reaction conditions, although the organic pollutant removal rate can reach 98.1% in the absence of auxiliary metal stabilizing active components, the ion leaching concentration after the reaction is 0.11 mg / L, which is significantly greater than that of the catalyst in Example 1, indicating that its catalytic stability is not as good as that of Example 1.

[0050] Comparative Example 2

[0051] The basic contents of this comparative example are the same as those of Example 1, except that only the promoter metal is added during the catalyst preparation process, and no active component is added. The promoter of the catalyst is 1 wt.% Ce (denoted as 1Ce-S1).

[0052] The catalyst performance test method in Example 1 was used. In this comparative example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex salt, and the pH was 7.0. The test results are shown in Table 1.

[0053] Compared with the test results of Example 1, under the same reaction conditions, although the leached ion concentration of the catalyst of this comparative example is 0.01 mg / L after the reaction, the organic pollutant removal rate is only 61.2% due to the lack of active components.

[0054] Comparative Example 3

[0055] This comparative example is essentially the same as Example 1, except that the stabilizer, tetrasodium ethylenediaminetetraacetate, is not added during the catalyst preparation process. The active component of the catalyst is 1 wt.% Co, and the additive is 0.5 wt.% Ce (denoted as 1Co0.5Ce-S1).

[0056] The catalyst performance test method in Example 1 was used. In this comparative example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex salt, and the pH was 7.0. The test results are shown in Table 1.

[0057] Compared with the test results of Example 1, in the catalyst preparation process of this comparative example, since no stabilizer was added, the active components and auxiliary agent precursors formed precipitation under alkaline synthesis conditions and could not completely enter the catalyst. Therefore, the removal rate was only 49.5% under the same reaction conditions.

[0058] Comparative Example 4

[0059] The basic content of this comparative example is the same as that of Example 1, except that the catalyst is prepared by an impregnation method. The preparation method of a catalyst for an advanced oxidation reaction in this comparative example comprises the following steps:

[0060] S10, adding S1 molecular sieve raw powder into water and stirring to mix evenly to obtain a first precursor solution;

[0061] S20, adding cobalt nitrate and cerium nitrate into water and stirring and mixing them uniformly to obtain a second precursor solution;

[0062] S30: The first precursor solution and the second precursor solution were mixed and stirred for 8 hours, and rotary evaporated at 90°C to obtain a solid. The solid was calcined at 500°C in air for 3 hours to obtain a catalyst. The active component of the catalyst was Co 1 wt.%, and the additive was Ce 0.5 wt.% (denoted as 1Co0.5Ce-S1).

[0063] The catalyst performance test method in Example 1 was used. In this comparative example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex salt, and the pH was 7.0. The test results are shown in Table 1.

[0064] Compared with the test results of Example 1, since the particle size of the active components and additives loaded by the impregnation method is significantly larger than that of the catalyst prepared by in-situ encapsulation of the complex stabilizer, the active components are not fully exposed. Under the same reaction conditions, the organic pollutant removal rate of the catalyst in this comparative example only reaches 85.2%.

[0065] Comparative Example 5

[0066] The basic content of this comparative example is the same as that of Example 1, except that the catalyst is prepared using an alumina carrier and an impregnation method. The preparation method of a catalyst for an advanced oxidation reaction in this comparative example comprises the following steps:

[0067] S10, adding alumina raw powder to water and stirring and mixing uniformly to obtain a first precursor solution;

[0068] S20, adding cobalt nitrate and cerium nitrate into water and stirring and mixing them uniformly to obtain a second precursor solution;

[0069] S30: The first precursor solution and the second precursor solution were mixed and stirred for 8 hours, and rotary evaporated at 90° C. to obtain a solid. The solid was calcined at 500° C. in an air atmosphere for 3 hours to obtain a catalyst. The active component of the catalyst was Co 1 wt.%, and the additive was Ce 0.5 wt.% (denoted as 1Co0.5Ce-Al).

[0070] The catalyst performance test method in Example 1 was used. In this comparative example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex salt, and the pH was 7.0. The test results are shown in Table 1.

[0071] Since the alumina carrier has a smaller specific surface area and porosity than the S1 molecular sieve, the organic pollutant removal rate of the catalyst of this comparative example is further reduced to 74.4% under the same reaction conditions, and the ion leaching concentration is also increased, and the stability is reduced.

[0072] Comparative Example 6

[0073] The basic contents of this comparative example are the same as those of Example 1, except that Mn was added as an active component during the catalyst preparation process. The active component of the catalyst was 1 wt.% Mn, and the additive was 0.5 wt.% Ce (denoted as 1Mn0.5Ce-S1).

[0074] The catalyst performance test method in Example 1 was used. In this comparative example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex salt, and the pH was 7.0. The test results are shown in Table 1.

[0075] Compared with the test results of Example 1, this comparative example uses less active Mn instead of Fe, Co, and Ni as the active component. Under the same reaction conditions, the organic pollutant removal rate is only 82.8%, which is lower than that of the catalyst in Example 1.

[0076] Comparative Example 7

[0077] The basic content of this comparative example is the same as that of Example 1, except that the loading amount of the active component and the auxiliary agent of the catalyst is lower than that of Example 1. A method for preparing a catalyst for advanced oxidation reaction in this comparative example comprises the following steps:

[0078] S10, adding tetraethyl orthosilicate and tetrapropylammonium hydroxide into water and stirring to mix uniformly to obtain a first precursor solution;

[0079] S20, adding 0.018 g of cobalt nitrate, 0.009 g of cerium nitrate, and 0.057 g of tetrasodium ethylenediaminetetraacetate into water and stirring and mixing to obtain a second precursor solution;

[0080] S30: The first precursor solution and the second precursor solution are mixed and stirred for 8 hours, and a hydrothermal synthesis reaction is carried out at 180° C. for 72 hours to obtain a solid. The solid is washed and dried, and then calcined at 500° C. in an air atmosphere for 3 hours to obtain a catalyst for an advanced oxidation reaction. The active component of the catalyst is Co 0.1 wt.%, and the additive is Ce 0.1 wt.% (denoted as 0.1Co0.1Ce-S1).

[0081] The catalyst performance test method in Example 1 was used. In this comparative example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex salt, and the pH was 7.0. The test results are shown in Table 1.

[0082] In this comparative example, due to the low loading amount of active components and auxiliary agents, the organic pollutant removal rate was only 59.5% under the same reaction conditions, which was much lower than that of the catalyst in Example 1.

[0083] Comparative Example 8

[0084] The basic content of this comparative example is the same as that of Example 1, except that the loading amount of the active component and the auxiliary agent of the catalyst is higher than that of Example 1. A method for preparing a catalyst for advanced oxidation reaction in this comparative example comprises the following steps:

[0085] S10, adding tetraethyl orthosilicate and tetrapropylammonium hydroxide into water and stirring to mix uniformly to obtain a first precursor solution;

[0086] S20, adding cobalt nitrate, cerium nitrate and tetrasodium ethylenediaminetetraacetate into water and stirring and mixing them uniformly to obtain a second precursor solution;

[0087] S30: The first precursor solution and the second precursor solution are mixed and stirred for 8 hours, and a hydrothermal synthesis reaction is carried out at 180° C. for 72 hours to obtain a solid. The solid is washed and dried, and then calcined at 500° C. in an air atmosphere for 3 hours to obtain a catalyst for an advanced oxidation reaction. The active component of the catalyst is Co 10 wt.%, and the additive is Ce 5 wt.% (denoted as 10Co5Ce-S1).

[0088] The catalyst performance test method in Example 1 was used. In this comparative example, the degradation target was Reactive Red X-3B, the oxidant was 0.3 g of potassium persulfate complex salt, and the pH was 7.0. The test results are shown in Table 1.

[0089] In this comparative example, due to the excessive loading of active components and auxiliary agents, the active components are more likely to form large particles dispersed in the catalyst, and the active components are not fully exposed. Although the organic pollutant removal rate reaches 99.3% under the same reaction conditions, the ion leaching concentration after the reaction is 0.21 mg / L, which is much higher than the catalyst in Example 1, and the stability is greatly reduced.

[0090] Table 1 Catalyst performance test results of Example 1 and Comparative Examples 1-8

[0091]

[0092]

[0093] The above Example 1 and Comparative Examples 1-8 illustrate that the catalyst of the present invention has the advantages of high catalytic activity and high stability when applied to the advanced oxidation removal of organic pollutants.

[0094] Example 2

[0095] The basic content of this embodiment is the same as that of Example 1, except that the method for preparing a catalyst for an advanced oxidation reaction in this embodiment comprises the following steps:

[0096] S10, adding tetraethyl orthosilicate and tetrapropylammonium hydroxide into water and stirring to mix uniformly to obtain a first precursor solution, i.e., a molecular sieve precursor;

[0097] S20, adding ferric nitrate, praseodymium nitrate and tetrasodium ethylenediaminetetraacetate into water and stirring and mixing them uniformly to obtain a second precursor solution;

[0098] S30: The first precursor solution and the second precursor solution are mixed and stirred for 8 hours, and a hydrothermal synthesis reaction is carried out at 180° C. for 72 hours to obtain a solid. The solid is washed and dried, and then calcined at 500° C. in an air atmosphere for 3 hours to obtain a catalyst for an advanced oxidation reaction. The active component of the catalyst is Fe3 wt.%, and the additive is Pr2 wt.% (denoted as 3Fe2Pr-S1).

[0099] The catalyst performance test method in Example 1 was used, with sulfamethoxazole as the degradation target, 1.0 g of 30% hydrogen peroxide as the oxidant, and a pH of 4.0. The organic matter removal rate was 99.5%, and the ion concentration was 0.01 mg / L.

[0100] Example 3

[0101] The basic content of this embodiment is the same as that of Example 1, except that the method for preparing a catalyst for an advanced oxidation reaction in this embodiment comprises the following steps:

[0102] S10, adding tetraethyl orthosilicate and tetrapropylammonium hydroxide into water and stirring to mix uniformly to obtain a first precursor solution, i.e., a molecular sieve precursor;

[0103] S20, adding nickel nitrate, lanthanum nitrate, praseodymium nitrate and tetrasodium ethylenediaminetetraacetic acid into water and stirring and mixing to obtain a second precursor solution;

[0104] S30: The first precursor solution and the second precursor solution are mixed and stirred for 8 hours, and a hydrothermal synthesis reaction is carried out at 180° C. for 72 hours to obtain a solid. The solid is washed and dried, and then calcined at 500° C. in an air atmosphere for 3 hours to obtain a catalyst for an advanced oxidation reaction. The active component of the catalyst is Ni4 wt.%, and the additive is La2 wt.%, and Nd2 wt.% (denoted as 4Ni2La2Pr-S1).

[0105] The catalyst performance test method in Example 1 was used, with bisphenol A as the degradation target, 0.3 g of potassium persulfate complex salt as the oxidant, and a pH of 9.0. The organic matter removal rate was 99.6%, and the ion concentration was 0.02 mg / L.

[0106] Example 4

[0107] The basic content of this embodiment is the same as that of Example 1, except that the method for preparing a catalyst for an advanced oxidation reaction in this embodiment comprises the following steps:

[0108] S10, adding tetraethyl orthosilicate and tetrapropylammonium hydroxide into water and stirring to mix uniformly to obtain a first precursor solution, i.e., a molecular sieve precursor;

[0109] S20, adding cobalt nitrate, lanthanum nitrate, cerium nitrate and tetrasodium ethylenediaminetetraacetic acid into water and stirring and mixing to obtain a second precursor solution;

[0110] S30: The first precursor solution and the second precursor solution are mixed and stirred for 8 hours, and a hydrothermal synthesis reaction is carried out at 180° C. for 72 hours to obtain a solid. The solid is washed and dried, and then calcined at 500° C. in an air atmosphere for 3 hours to obtain a catalyst for an advanced oxidation reaction. The active component of the catalyst is Co 5 wt.%, and the additive is La 2 wt.%, and Ce 2 wt.% (denoted as 5Co2La2Ce-S1).

[0111] The catalyst performance test method described in Example 1 was used to degrade polyvinyl alcohol 1788, using 0.3 g of potassium persulfate as the oxidant at a pH of 10.0. The organic matter removal rate was 99.7%, and the ion concentration was 0.03 mg / L. The catalyst was collected and retested four times, resulting in an organic matter removal rate of 99.6% and an ion concentration of 0.01 mg / L.

[0112] The test results of Examples 2-4 show that the catalyst of the present invention can achieve efficient removal of different types of organic pollutants represented by sulfamethoxazole, bisphenol A and polyvinyl alcohol 1788 when the pH is between 4.0 and 10.0 using hydrogen peroxide or potassium persulfate as an oxidant, with a pollutant removal rate greater than 99%. After five repeated tests, the ion concentration of the active component leaching is no more than 0.03 mg / L, indicating that the catalyst has good stability and reusability.

[0113] The above is a schematic description of the present invention and its embodiments, which is not restrictive. The data used is only one embodiment of the present invention, and the actual data combination is not limited thereto. Therefore, if a person skilled in the art is inspired by this and, without departing from the purpose of the present invention, designs similar embodiments and examples to the technical solution without creative design, they shall all fall within the scope of protection of the present invention.

Claims

1. Application of a catalyst in advanced oxidation removal of organic matter from industrial tail water, characterized in that: Under the condition of pH 7.0, a catalyst and an oxidant are added, and under the action of the catalyst and the oxidant, organic matter in the industrial tail water is degraded into inorganic matter to remove the organic matter in the industrial tail water; wherein the organic matter is Reactive Red X-3B, and the oxidant is potassium persulfate complex salt; the catalyst is prepared by a one-step hydrothermal synthesis method from a carrier, an active component, an auxiliary agent, a structure-directing agent and a stabilizer, wherein the carrier is S-1 all-silicon molecular sieve, the active component is Co, the auxiliary agent is Ce, the structure-directing agent is tetrapropylammonium hydroxide, and the stabilizer is tetrasodium ethylenediaminetetraacetic acid.

2. The use according to claim 1, characterized in that: The active component is loaded in an amount of 0.05% to 5% by mass based on the carrier.

3. The use according to claim 1, characterized in that: The loading amount of the auxiliary agent based on the carrier is 0.05% to 5% by mass.

4. The use according to claim 1, characterized in that: The preparation method of the catalyst comprises the following steps: S10, adding a carrier precursor and a structure-directing agent into water and mixing them uniformly to obtain a first precursor solution, wherein the carrier precursor is tetraethyl orthosilicate and the structure-directing agent is tetrapropylammonium hydroxide; S20, adding an active component precursor, an auxiliary agent precursor, and a stabilizer into water and mixing them uniformly to obtain a second precursor solution, wherein the active component precursor is cobalt nitrate, the auxiliary agent precursor is cerium nitrate, and the stabilizer is tetrasodium ethylenediaminetetraacetic acid; S30, mixing the first precursor solution and the second precursor solution and stirring them to perform a hydrothermal synthesis reaction to obtain a catalyst solid in one step, and washing, drying, and calcining the catalyst to obtain a catalyst for an advanced oxidation reaction.

5. The use according to claim 4, characterized in that: In step S10, 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 use according to claim 4, characterized in that: In step S20, the ratio of the stabilizer to the sum of the mass of the active component precursor and the auxiliary agent precursor is 1.0-1.

1.

7. The use according to claim 4, characterized in that: The specific process of step S30 is as follows: the first precursor solution and the second precursor solution are mixed and stirred for 4 to 8 hours, and a hydrothermal synthesis reaction is carried out at 140° C. to 180° C., followed by washing, drying, and calcination at 400° C. to 600° C. in an air atmosphere for 3 to 6 hours to obtain a catalyst for an advanced oxidation reaction; The mass ratio of water in the first precursor solution to water in the second precursor solution is 5:

1.

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

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