Wet catalytic oxidation catalyst and preparation method thereof

Abstract

The invention relates to a wet catalytic oxidation catalyst and a preparation method thereof. The preparation method comprises the following steps: mixing a composite activator solution containing alkali metal hydroxide and a hydrated sodium silicate solution with a dry mixture containing water-quenched blast furnace slag and metallurgical copper slag to form precursor slurry, wherein the weight ratio of the dry mixture to the composite activator solution is 3: 2-2: 1; dispersing a solid copper-based active component in the precursor slurry to form catalyst slurry, wherein the weight ratio of the copper-based active component to the precursor slurry is 2: 100 to 25: 100; the catalyst slurry is subjected to curing forming, acid pickling and drying, and the wet catalytic oxidation catalyst is obtained. The catalyst prepared by the invention not only effectively improves the catalytic degradation efficiency of a wet catalytic oxidation system on organic matters, but also can be conveniently recycled and reused, and the cost of wastewater treatment is remarkably reduced.

Description

Technical Field

[0001] The present application relates to the field of catalyst technology, and in particular to a wet catalytic oxidation catalyst and a preparation method thereof. Background Art

[0002] Wet catalytic oxidation is a highly effective wastewater treatment technology that uses oxygen or oxygen-enriched air as an oxidant under high temperature (100-280°C) and high pressure (1-8 MPa) conditions to efficiently remove organic matter from wastewater. Wet catalytic oxidation is suitable for treating high-concentration organic wastewater from the electroplating, coking, chemical, petroleum, and pharmaceutical manufacturing industries, and is particularly well-suited for the removal of highly toxic organic matter.

[0003] Catalyst materials are one of the core elements of wet catalytic oxidation technology. Because the operating environment of this technology system is characterized by high temperature, high pressure, and high concentration, the performance of the catalyst in this environment directly determines the technology's pollutant removal performance and application cost. Due to the high temperature and high pressure environment during the wet catalytic oxidation process, problems such as carbon deposition, loss of active components, and catalyst breakage often occur, resulting in a decrease in the system's catalytic effect and reactor blockage, limiting its pollutant removal effectiveness. At the same time, the raw materials for wet catalytic oxidation catalyst materials are often selected from relatively expensive precious metals (platinum, ruthenium, cerium, cobalt, copper, etc.) and their compounds. Due to the characteristics of the catalyst being easily deactivated during the wet catalytic oxidation process, the manufacturing costs of the catalyst products and the operation of the technology remain high.

[0004] In view of the above technologies and problems, there is an urgent need for an improved wet catalytic oxidation catalyst and a preparation method thereof. Summary of the Invention

[0005] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0006] In one aspect, the present application provides a method for preparing a wet catalytic oxidation catalyst, comprising the following steps: Mixing a composite activator solution comprising an alkali metal hydroxide and a hydrated sodium silicate solution with a dry mixture comprising water-quenched blast furnace slag and metallurgical copper slag to form a precursor slurry, wherein the weight ratio of the dry mixture to the composite activator solution is 3:2 to 2:1; Dispersing a solid copper-based active component in the precursor slurry to form a catalyst slurry, wherein the weight ratio of the copper-based active component to the precursor slurry is 2:100 to 25:100; The catalyst slurry is cured, shaped, acid-washed and dried to obtain the wet catalytic oxidation catalyst.

[0007] In this application, the term "water-quenched blast furnace slag" refers to the slag formed by the melt formed by iron ore and limestone flux under high temperature conditions during the blast furnace ironmaking process, which is discharged from the blast furnace and rapidly cooled by water quenching. Its main components are CaO (30wt%-50wt%), SiO2 (30wt%-40wt%), Al2O3 (10wt%-20wt%), and FeO (5wt%-10wt%). The four components together account for more than 85% of the mass of the water-quenched blast furnace slag.

[0008] In this application, the term "metallurgical copper slag" refers to the slag formed by other residual substances after the copper concentrate is reduced to copper at high temperature during the copper ore smelting process. Its main components are Fe2O3 and FeO (30wt%-40wt%), SiO2 (30wt%-40wt%), Al2O3 (about 10wt%), CaO (about 10wt%), and a small amount of Cu (0.5wt%-2.0wt%).

[0009] In one embodiment, the composite activator is prepared by the following method: adding 15 to 25 parts by weight of alkali metal hydroxide powder to 100 parts by weight of hydrated sodium silicate solution to form a mixed solution, ultrasonically vibrating the mixed solution until the mixed solution is clear and transparent, and then keeping the mixture warm.

[0010] In one embodiment, the alkali metal hydroxide is selected from potassium hydroxide and / or sodium hydroxide. In the present application, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are used to provide alkalinity. When both potassium hydroxide and sodium hydroxide are selected, potassium hydroxide and sodium hydroxide can be mixed in any proportion.

[0011] In one embodiment, the alkali metal hydroxide is potassium hydroxide and sodium hydroxide in a weight ratio of 1:1.

[0012] In one embodiment, the power of the ultrasound is 300-400W, the frequency of the ultrasound is 35-40KHz, and the ultrasound time is 3-5 minutes.

[0013] In one embodiment, the heat preservation comprises placing the clear and transparent mixed solution in a water bath and maintaining the temperature at 50±2°C.

[0014] In one embodiment, the mixed solution can be sealed, turned over and stirred, and then placed in an ultrasonic vibration environment for ultrasonic vibration.

[0015] In one embodiment, the dry mixture is prepared by the following method: mixing the water-quenched blast furnace slag and the metallurgical copper slag in a weight ratio of 1:1 to 4:1, crushing and grinding to form a dry mixture, wherein the particle size of the dry mixture is ≤150 μm.

[0016] In one embodiment, forming the precursor slurry includes mixing the composite activator solution and the dry mixture by stirring and removing bubbles by vibration.

[0017] In one embodiment, the composite activator solution and the dry blend may be stirred and mixed in a polyethylene reaction container.

[0018] In one embodiment, the composite activator solution and the dry mixture may be stirred and mixed, and then placed on a vibration table, and then the bubbles may be removed by vibration.

[0019] In one embodiment, the copper-based active component is selected from one or more of copper oxide, cuprous oxide, copper chloride and copper sulfate.

[0020] In one embodiment, dispersing the solid copper-based active component in the precursor slurry includes uniformly dispersing the copper-based active component in the precursor slurry by ultrasonic dispersion and removing bubbles by vibration.

[0021] In one embodiment, the copper-based active component can be evenly dispersed in the precursor slurry by an ultrasonic dispersing stirrer, and then placed on a vibration table to expel bubbles by vibration.

[0022] In one embodiment, the power of the ultrasonic wave used for ultrasonic dispersion is 2000W, and the frequency of the ultrasonic wave is 20KHz.

[0023] In one embodiment, the curing and molding comprises: pouring the precursor slurry into a mold at a temperature of 0±1° C. for molding, and then sealing and curing the molded catalyst in a curing box to obtain a molded catalyst.

[0024] In one embodiment, pouring the precursor slurry into a mold at a temperature of 0±1°C may include placing the mold in an ice-water mixture to reduce the temperature of the mold to 0±1°C; then quickly pouring the precursor slurry into the mold, and after the slurry in the mold is initially dried, completely sealing the mold with a polyethylene film.

[0025] In one embodiment, the mold is spherical or in other conventional shapes.

[0026] In one embodiment, the temperature and humidity in the curing box are controlled during the curing process; optionally, the temperature in the curing box is controlled at 25±2°C and the humidity is controlled at 100%.

[0027] In one embodiment, the acid washing comprises mixing and stirring the formed catalyst with a hydrochloric acid solution in a weight ratio of 1:10-1:20.

[0028] In one embodiment, the mixing and stirring may include using a high-speed stirrer to quickly stir the catalyst to complete the acid washing process.

[0029] In one embodiment, the pickling may be performed using a hydrochloric acid solution with a pH of 1.0.

[0030] In the present application, the shaped catalyst is activated by acid washing to reduce the effect of excess alkali on the catalytic degradation performance of the wet catalytic oxidation system during the catalyst preparation process.

[0031] In one embodiment, the drying comprises drying in a nitrogen environment at a drying temperature of 60±2° C. for a drying time of 12-24 hours.

[0032] The wet catalytic oxidation catalyst obtained after drying can be sealed and stored to be used in a wet catalytic oxidation system.

[0033] On the other hand, the present application also provides a wet catalytic oxidation catalyst, which is prepared by the above method.

[0034] The present application provides a method for preparing a catalyst suitable for wet catalytic oxidation technology by using bulk metallurgical solid waste as raw material, based on the self-transformation and self-supporting properties of the solid waste raw material after composite alkali excitation, thereby solving the problems of poor stability and high cost of catalyst materials in the application process of wet catalytic oxidation technology at this stage.

[0035] The catalyst prepared in this application has good catalytic effect, low preparation cost, small precious metal loading, and can simultaneously achieve full utilization of various elements in solid waste resources, thereby improving resource utilization and reducing solid waste environmental risks. In addition, the energy consumption and electricity consumption of the preparation process are low, and it has broad application prospects.

[0036] The wet catalytic oxidation catalyst material prepared by the method of the present application can be used in the wastewater treatment process of organic pollutants, and is suitable for the treatment of high-concentration, highly toxic, and low-biodegradable organic wastewater, covering industrial fields such as medicine, dyes, coking, printing and dyeing, petrochemicals, and leather manufacturing.

[0037] The method of the present application utilizes the self-crosslinking and self-forming properties of the monomer structure after the solid waste is dissolved, and can be directly cast and formed under normal temperature and pressure conditions for use, without the need for high temperature, high pressure, calcination, roasting, sintering and other process steps. It has the advantages of less raw material quality loss, low energy loss, near-zero carbon emissions, pollution-free preparation process, and short processing route, which greatly enhances the potential for large-scale manufacturing of materials.

[0038] The wet catalytic oxidation catalyst prepared by the method of the present application adopts iron-containing water-quenched slag and metallurgical copper slag, utilizes iron oxides in solid waste to form a composite copper-based compound, combines silicon-aluminum compounds as the main structural matrix and metal components to form a multi-component composite reaction center, promotes electron migration in the system, reduces the loss of active metal components, enhances the material reuse effect, and effectively improves the catalytic degradation efficiency of the wet catalytic oxidation system for organic matter.

[0039] Other features and advantages of the present application will be described in the following description, and in part will become apparent from the description, or will be understood by practicing the present application. Other advantages of the present application can be realized and obtained by the solutions described in the description. DETAILED DESCRIPTION

[0040] To make the purpose, technical solutions and advantages of this application more clear, the embodiments of this application are described in detail below. It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of this application can be combined with each other in any way.

[0041] In the following examples and comparative examples, all operations without specified conditions were carried out under conventional conditions or those recommended by the manufacturer. All raw materials without specified manufacturers and specifications were commercially available.

[0042] Example 1 This embodiment provides a preparation process of a wet catalytic oxidation catalyst, comprising the following steps: (1) A composite activator solution comprising an alkali metal hydroxide and a hydrated sodium silicate solution is mixed with a dry mixture comprising water-quenched blast furnace slag and metallurgical copper slag to form a precursor slurry.

[0043] Specifically, the method includes fully mixing 10 parts by weight of potassium hydroxide and 10 parts by weight of sodium hydroxide, and then adding the mixture to 100 parts by weight of a hydrated sodium silicate solution (such as a nonahydrate sodium silicate solution); sealing the mixed solution, flipping and shaking it, and placing it in an ultrasonic vibration environment for rapid vibration, with an ultrasonic power of 400W, an ultrasonic frequency of 40KHz, and an ultrasonic time of 5 minutes. After the mixed solution becomes clear and transparent, it is placed in a water bath and maintained at 50°C to obtain a composite activator solution to be used; mixing 80 parts by weight of water-quenched blast furnace slag with 20 parts by weight of smelting copper slag, and then ball milling and sieving to obtain a dry mixture with a particle size of less than 150 μm. The dry mixture is mixed with 50 parts by weight of the obtained composite activator solution in a polyethylene reaction container, and the catalyst matrix precursor is obtained after sufficient stirring; then the catalyst matrix precursor is placed on a vibration table, and the bubbles in the slurry are expelled by vibration to obtain a precursor slurry.

[0044] (2) Dispersing the solid copper-based active component in the precursor slurry to form a catalyst slurry.

[0045] Specifically, the method includes adding 10 parts by weight of copper oxide to 100 parts by weight of a precursor slurry; uniformly dispersing the copper oxide in the slurry using an ultrasonic disperser with an ultrasonic power of 2000W and an ultrasonic frequency of 20KHz, while simultaneously using a vibrating table to vibrate and expel bubbles generated during the mixing process of the mixed slurry to obtain a catalyst slurry.

[0046] (3) The catalyst slurry is shaped, cured, pickled and dried.

[0047] Specifically, the method may include placing a spherical mold in an ice-water mixture and lowering the mold temperature to 0±1°C; quickly pouring the catalyst slurry into the spherical mold, and after the slurry in the mold is initially dried for 10 minutes, completely sealing the mold with a polyethylene film; placing the mold in a curing box, controlling the temperature in the curing box at 25±2°C and the humidity at 100%, and curing for 24 hours to form a shaped catalyst; using 5 parts by weight of a hydrochloric acid solution with a pH=1.0 to acid-wash and activate 20 parts by weight of the shaped catalyst, and using a high-speed stirrer to quickly stir to complete the acid washing process of the catalyst, with the stirrer speed being 400 rpm; after acid washing, the catalyst is dried at 60°C for 24 hours in a nitrogen environment to obtain the catalyst, and sealed and stored for use in a wet catalytic oxidation system.

[0048] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 100%, the COD removal rate was 84.92%, and the TOC removal rate was 80.59%.

[0049] Example 2 In this embodiment, except for adding cuprous oxide as the copper-based active component, the remaining steps are the same as those in Example 1.

[0050] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 100%, the COD removal rate was 86.49%, and the TOC removal rate was 83.32%.

[0051] Example 3 In this embodiment, except for adding copper chloride dihydrate as the copper-based active component, the remaining steps are the same as those in Example 1.

[0052] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 100%, the COD removal rate was 90.88%, and the TOC removal rate was 86.12%.

[0053] In addition, the catalyst prepared by using copper chloride dihydrate in this embodiment has a loose and porous structure and slightly poor stability, and needs to be stored carefully.

[0054] Example 4 In this embodiment, except for adding copper sulfate pentahydrate as the copper-based active component, the remaining steps are the same as those in Example 1.

[0055] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 100%, the COD removal rate was 90.13%, and the TOC removal rate was 85.98%.

[0056] Example 5 In this embodiment, except that the weight ratio of copper sulfate pentahydrate to precursor slurry is 5:100, the remaining steps are the same as those in Example 1.

[0057] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 100%, the COD removal rate was 88.89%, and the TOC removal rate was 84.22%.

[0058] Example 6 In this embodiment, except that the weight ratio of copper sulfate pentahydrate to precursor slurry is 2:100, the remaining steps are the same as those in Example 1.

[0059] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 100%, the COD removal rate was 84.33%, and the TOC removal rate was 85.62%.

[0060] Example 7 In this embodiment, except that the weight ratio of copper sulfate pentahydrate to precursor slurry is 25:100, the remaining steps are the same as those in Example 1.

[0061] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 100%, the COD removal rate was 91.24%, and the TOC removal rate was 87.92%.

[0062] Example 8 In this embodiment, except that the mixing ratio of water-quenched blast furnace slag and smelting copper slag is 1:1 (i.e., 40 parts by weight of water-quenched blast furnace slag and 40 parts by weight of smelting copper slag are mixed), the remaining steps are the same as those in Example 1.

[0063] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 100%, the COD removal rate was 89.37%, and the TOC removal rate was 85.76%.

[0064] The above test results show that the wet catalytic oxidation catalyst prepared by the method of the present application can achieve a degradation efficiency of 100% for phenol with a concentration of 10,000 mg / L in wastewater under the conditions of reaction temperature of 190°C, reaction pressure of 4 MPa, reaction time of 2 hours, and catalyst dosage of 10 g / L, and the removal rate of COD with a concentration of 23,830 mg / L exceeds 84% and the removal rate of TOC with a concentration of 7,660 mg / L exceeds 80%.

[0065] This shows that the wet catalytic oxidation catalyst prepared by the method of the present application has an excellent effect when applied to a wet catalytic oxidation system to remove organic matter in wastewater.

[0066] Comparative Example 1 In this comparative example, except that no copper-based active component was added, the remaining steps were similar to those of Example 1.

[0067] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 86.22%, the COD removal rate was 78.55%, and the TOC removal rate was 74.26%.

[0068] From the above results, it can be seen that the removal rate of organic matter is significantly reduced without adding copper-based active components.

[0069] Comparative Example 2 In this comparative example, except that the dry mixture only includes water-quenched blast furnace slag and does not include smelting copper slag, the remaining steps are similar to those of Example 4.

[0070] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 91.12%, the COD removal rate was 80.24%, and the TOC removal rate was 75.22%.

[0071] Comparative Example 3 In this comparative example, except that an ultrasonic disperser is no longer used to uniformly disperse copper sulfate pentahydrate in the slurry, the remaining steps are similar to those of Example 4.

[0072] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 98.88%, the COD removal rate was 81.21%, and the TOC removal rate was 80.78%.

[0073] Comparative Example 4 In this comparative example, the spherical mold was no longer placed in the ice-water mixture, but the mold temperature was controlled at room temperature (25±2° C.). The remaining steps were similar to those of Example 4.

[0074] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 93.66%, the COD removal rate was 80.26%, and the TOC removal rate was 78.23%.

[0075] Comparative Example 5 In this comparative example, the steps are similar to those in Example 4, except that the formed catalyst is not subjected to acid washing and activation treatment but is directly used in the wet catalytic oxidation system.

[0076] The prepared catalyst was used in a wet catalytic oxidation system to remove organic matter from wastewater. In the wastewater, the phenol concentration was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L. The reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L. After the reaction, the detection showed that the phenol removal rate was 94.65%, the COD removal rate was 79.64%, and the TOC removal rate was 74.26%.

[0077] Comparative Example 6 In this comparative example, copper oxide powder and cuprous oxide powder were directly used in a wet catalytic oxidation system to remove organic matter from wastewater, wherein the phenol concentration in the wastewater was 10,000 mg / L, the COD concentration was 23,830 mg / L, and the TOC concentration was 7,660 mg / L; the reaction temperature was 190°C, the reaction pressure was 2 MPa, the reaction time was 2.0 hours, and the catalyst dosage was 10 g / L; after the reaction, for copper oxide, the phenol removal rate was detected to be 100%, the COD removal rate was 91.02%, and the TOC removal rate was 85.55%; in contrast, for cuprous oxide, the phenol removal rate was detected to be 100%, the COD removal rate was 90.08%, and the TOC removal rate was 84.28%.

[0078] The applicant has discovered that when copper oxide or cuprous oxide powder is used directly in a wet catalytic oxidation system to remove organic matter from wastewater, it is difficult to separate the copper oxide or cuprous oxide powder catalyst and the copper ions in the solution from the carbon produced during the reaction, making it impossible to recover and reuse the catalyst and posing a risk of clogging the reactor pipeline. In contrast, the catalyst prepared in this application, when used in wastewater treatment, does not produce carbon during the reaction. Therefore, the catalyst can be separated using conventional solid-liquid separation methods, allowing for reuse of the catalyst and significantly reducing application costs.

[0079] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Those skilled in the art can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A method for preparing a wet catalytic oxidation catalyst, characterized in that: The steps include: Mixing a composite activator solution comprising an alkali metal hydroxide and a hydrated sodium silicate solution with a dry mixture comprising water-quenched blast furnace slag and metallurgical copper slag to form a precursor slurry, wherein the weight ratio of the dry mixture to the composite activator solution is 3:2 to 2:1; Dispersing a solid copper-based active component in the precursor slurry to form a catalyst slurry, wherein the weight ratio of the copper-based active component to the precursor slurry is 2:100 to 25:100; The catalyst slurry is cured, shaped, acid-washed and dried to obtain the wet catalytic oxidation catalyst.

2. The method according to claim 1, characterized in that The composite activator solution is prepared by the following method: 15 to 25 parts by weight of alkali metal hydroxide powder is added to 100 parts by weight of hydrated sodium silicate solution to form a mixed solution; the mixed solution is ultrasonically shaken until the mixed solution is clear and transparent, and then the mixed solution is kept warm to obtain the composite activator solution.

3. The method according to claim 2, characterized in that The alkali metal hydroxide is selected from potassium hydroxide and / or sodium hydroxide; Optionally, the power of the ultrasound is 300-400W, the frequency of the ultrasound is 35-40KHz, and the ultrasound time is 3-5min; Optionally, the heat preservation comprises placing the clear and transparent mixed solution in a water bath and maintaining the temperature at 50±2°C.

4. The method according to claim 1, wherein The dry mixture is prepared by the following method: mixing the water-quenched blast furnace slag and the metallurgical copper slag in a weight ratio of 1:1 to 4:1, crushing and grinding to form a dry mixture, wherein the particle size of the dry mixture is ≤150 μm.

5. The method according to claim 1, wherein Forming the precursor slurry includes mixing the composite activator solution with the dry mixture by stirring and removing bubbles by vibration.

6. The method according to claim 1, characterized in that Dispersing the solid copper-based active component in the precursor slurry includes uniformly dispersing the copper-based active component in the precursor slurry by ultrasonic dispersion and expelling bubbles by vibration; Optionally, the power of the ultrasonic wave is 2000W, and the frequency of the ultrasonic wave is 20KHz.

7. The method according to claim 1, characterized in that The curing molding comprises: pouring the precursor slurry into a mold at a temperature of 0±1° C. for molding, and then sealing and placing the mold in a curing box for curing to obtain a molded catalyst.

8. The method according to claim 1, characterized in that The pickling comprises mixing and stirring the formed catalyst with a hydrochloric acid solution at a weight ratio of 1:10 to 1:20; and / or, The drying includes drying in a nitrogen environment at a drying temperature of 60±2° C. and a drying time of 12-24 hours.

9. The method according to any one of claims 1 to 8, characterized in that The copper-based active component is selected from one or more of copper oxide, cuprous oxide, copper chloride dihydrate and copper sulfate pentahydrate.

10. A wet catalytic oxidation catalyst, characterized in that: The wet catalytic oxidation catalyst is prepared by the method according to any one of claims 1 to 9.