Catalyst and application thereof in aspect of removing carbon-containing pollutants
By using a method of secondary addition of potassium permanganate and ferrous salt aqueous solution for quenching treatment, the prepared catalyst maintains high catalytic performance in a high humidity environment, solving the problem of insufficient structural strength of manganese-copper cluster catalysts and achieving a longer service life and stable catalytic effect.
Patent Information
- Application Number
- CN202511288080.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-10
- Publication Date
- 2025-11-07
AI Technical Summary
Manganese-copper cluster catalysts have low structural strength in high humidity environments, making them prone to pore collapse or blockage, which leads to reduced catalytic activity and shortened service life.
The catalyst was prepared by a two-stage addition of potassium permanganate and ferrous salt aqueous solution for quenching treatment. The catalyst activity was improved through a Fenton-like reaction, and the structural strength was enhanced to avoid stress defects.
Maintaining high catalytic performance in high humidity environments, extending catalyst lifespan, and improving catalyst structural strength and durability.
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of air purification materials, and particularly relates to a catalyst and application thereof in removal of carbon-containing pollutants. BACKGROUND
[0002] Compared with traditional catalysts, the manganese-copper cluster catalyst as a core material of a new generation of formaldehyde removal technology can produce superoxide anions in the catalytic process, and can realize efficient catalytic reaction at low temperature or normal temperature environment according to the action principle of singlet oxygen and hydroxyl radicals, so as to improve the decomposition efficiency of short carbon chains by using free radicals and quickly remove TVOC including short carbon chain alkenes and acetylenic carbon chains, which greatly broadens the use scenarios, and is particularly suitable for air purification in some cold regions or low-temperature working environments.
[0003] As an extremely effective technical innovation for indoor air treatment, the manganese-copper cluster catalyst overturns the limitations of traditional adsorption or oxidative decomposition technology, and realizes a leap in catalytic performance in terms of efficiency and environmental protection, however, when the manganese-copper cluster catalyst is used in a high-humidity environment, stress defects are prone to occur due to the low strength of the pore structure, resulting in pore collapse or blockage, reduction of active sites, reduction of catalytic activity, and poor stability, which affects the catalytic effect and service life of the catalyst. SUMMARY
[0004] To solve the problems in the background art, the application provides a catalyst and application thereof in removal of carbon-containing pollutants, which can effectively improve the structural strength of the catalyst while ensuring catalytic activity, and ensure efficient purification and long-term use of the catalyst for carbon-containing pollutants.
[0005] To achieve the above-mentioned purposes, the application provides the following technical solutions: a catalyst is prepared by the following steps:
[0006] S1. 2-3 mol of potassium permanganate, 1.5-2.5 mol of equivalent zinc source, 2-4 mol of equivalent iron source and 0.8-1.2 mol of equivalent copper source are added to a ferrous chloride aqueous solution, and stirred until completely dissolved to obtain a mixed solution;
[0007] S2. The reaction temperature of the mixed solution in step S1 is adjusted, and the reaction is carried out under ultrasonic stirring to obtain a reaction solution;
[0008] S3. Potassium permanganate solution is added to the reaction solution in step S2, and ultrasonic stirring is continued, then solid-liquid separation is performed, and the solid material is washed and dried to obtain a precursor;
[0009] S4. The precursor in step S3 is sintered at 280-320 DEG C for 4-6 h, and then quenched by using a ferrous salt aqueous solution, and filtered, crushed and dried until the water content is less than 5%, to obtain the catalyst.
[0010] Further, the molar concentration of potassium permanganate in the mixed solution in step S1 is 0.4-0.6 mol / L.
[0011] Further, the zinc source in step S1 is one or more than two kinds of mixture of zinc chloride, zinc sulfate and zinc nitrate.
[0012] Further, the iron source in step S1 is one or more than two kinds of mixture of ferric chloride, ferric sulfate and ferric nitrate.
[0013] Further, the copper source in step S1 is one or more than two kinds of mixture of cupric chloride, cupric sulfate and cupric nitrate.
[0014] Further, the molar concentration of ferrous chloride solution in step S1 is 0.04-0.06 mol / L.
[0015] Further, the reaction temperature of the mixed solution in step S2 is 55-65℃, and the reaction time is 25-35 min.
[0016] Further, the molar concentration of potassium permanganate solution in step S3 is 0.2-0.3 mol / L, and the mass ratio of potassium permanganate solution to reaction solution is 0.8-1.2:5.
[0017] Further, the molar concentration of ferrous ions in the ferrous salt aqueous solution in step S4 is 0.01-0.03 mol / L, and the ferrous salt is one or more than two kinds of mixture of ferrous chloride, ferrous sulfate and ferrous nitrate.
[0018] The application of a catalyst, using the catalyst described in the above scheme for removing carbon-containing pollutants.
[0019] The present application has the following beneficial effects:
[0020] 1. The catalyst provided by the present application utilizes manganese oxygen vacancies to produce active oxygen (superoxide anion, singlet oxygen and hydroxyl radical, etc.), introduces iron source and zinc source, and a Fenton-like reaction occurs under superoxide anion conditions, which improves the decomposition efficiency of the catalyst for carbon-containing pollutants. Through secondary addition of potassium permanganate and ferrous salt quenching treatment, the catalyst product is single and safe, has no pollution hidden danger, can efficiently remove and decompose carbon-containing pollutants, and at the same time, the catalyst maintains high structural strength in a high humidity environment, ensures stable catalytic performance, and realizes longer service life.
[0021] 2. Through secondary addition of potassium permanganate, the reaction of reactants can be realized, the single nature and structural integrity of the reaction product are ensured, the catalytic activity and durability of the catalyst are improved, and through quenching treatment of ferrous salt, the sintered product can be quickly cooled, and the structure of the sintered product can be controlled. The proportion of the ferrous salt can optimize the surface electronic state of the catalyst, enhance the catalytic activity, and effectively reinforce the internal structure of the material under thermal stress, react with impurities introduced by the excessive addition of potassium permanganate, purify the reaction product, avoid stress defects caused by quenching, and improve the structural strength and durability of the material. DETAILED DESCRIPTION
[0022] The application will be further described in detail below in combination with examples.
[0023] The raw materials of the examples and comparative examples of the application are commercially available unless otherwise specified.
[0024] Example 1
[0025] A catalyst is prepared by the following steps:
[0026] S1. 2.5 mol of potassium permanganate, 2 mol equivalents of zinc source zinc chloride, 3 mol equivalents of iron source ferric chloride, and 1 mol equivalent of copper source copper chloride are added to a ferrous chloride aqueous solution with a molar concentration of 0.05 mol / L, and stirred until completely dissolved to obtain a mixed solution, wherein the molar concentration of potassium permanganate in the mixed solution is 0.5 mol / L.
[0027] S2. The mixed solution in step S1 is heated to 60℃, and the reaction is carried out under ultrasonic stirring conditions for 30 min to obtain a reaction solution;
[0028] S3. Potassium permanganate solution is added to the reaction solution in step S2, and the mass ratio of potassium permanganate solution to reaction solution is 0.8-1.2:5, the molar concentration of potassium permanganate solution is 0.25 mol / L, and after continuing ultrasonic stirring for 10 min, solid-liquid separation is carried out, the solid material is washed 4 times, and then dried at 100℃ to obtain a precursor;
[0029] S4. The precursor in step S3 is sintered at 300℃ for 5h, and quenched by using a ferrous salt aqueous solution with a molar concentration of 0.02 mol / L, filtered, crushed, and dried to a water content of less than 5% to obtain the catalyst, wherein the ferrous salt is ferrous chloride.
[0030] Example 2
[0031] A catalyst is prepared by the following steps:
[0032] S1. 2 mol of potassium permanganate, 1.5 mol equivalents of zinc source zinc sulfate, 2 mol equivalents of iron source iron sulfate and 0.8 equivalents of copper source copper sulfate were added to a ferrous chloride aqueous solution with a molar concentration of 0.04 mol / L, stirred until completely dissolved to obtain a mixed solution, wherein the molar concentration of potassium permanganate in the mixed solution was 0.4 mol / L.
[0033] S2. The reaction temperature of the mixed solution in step S1 was adjusted to 55°C, and the reaction was carried out under ultrasonic stirring for 35 min to obtain a reaction liquid.
[0034] S3. Potassium permanganate solution was added to the reaction liquid of step S2, the mass ratio of potassium permanganate solution to reaction liquid was 0.8:5, the molar concentration of potassium permanganate solution was 0.2 mol / L, and after continuing ultrasonic stirring for 5 min, solid-liquid separation was carried out, the solid phase material was washed for 3 times, and then dried at 80°C to obtain a precursor.
[0035] S4. The precursor of step S3 was sintered at 280°C for 6 h, quenched with a ferrous salt aqueous solution with a molar concentration of 0.01 mol / L, filtered, crushed and dried to a water content of less than 5% to obtain the catalyst, wherein the ferrous salt is ferrous sulfate.
[0036] Example 3
[0037] A catalyst was prepared by the following steps:
[0038] S1. 3 mol of potassium permanganate, 2.5 mol equivalents of zinc source zinc nitrate, 4 mol equivalents of iron source iron nitrate and 1.2 mol equivalents of copper source copper nitrate were added to a ferrous chloride aqueous solution with a molar concentration of 0.06 mol / L, stirred until completely dissolved to obtain a mixed solution, wherein the molar concentration of potassium permanganate in the mixed solution was 0.6 mol / L.
[0039] S2. The reaction temperature of the mixed solution in step S1 was adjusted to 65°C, and the reaction was carried out under ultrasonic stirring for 25 min to obtain a reaction liquid.
[0040] S3. Potassium permanganate solution was added to the reaction liquid of step S2, the mass ratio of potassium permanganate solution to reaction liquid was 1.2:5, the molar concentration of potassium permanganate solution was 0.3 mol / L, and after continuing ultrasonic stirring for 15 min, solid-liquid separation was carried out, the solid phase material was washed for 5 times, and then dried at 120°C to obtain a precursor.
[0041] S4. The precursor of step S3 was sintered at 320°C for 4 h, quenched with a ferrous salt aqueous solution with a molar concentration of 0.03 mol / L, filtered, crushed and dried to a water content of less than 5% to obtain the catalyst, wherein the ferrous salt is ferrous sulfate.
[0042] Comparative Example 1
[0043] The difference between this comparative example and Example 1 is only that in step S3, the secondary addition of potassium permanganate solution is not performed, i.e. the potassium permanganate solution is replaced by water, and the details are as follows:
[0044] S3. Water is added to the reaction solution of step S2, and after 10 minutes of continued ultrasonic stirring, solid-liquid separation is performed, the solid phase material is washed 4 times, and then drying is performed at 100°C to obtain a precursor.
[0045] Comparative Example 2
[0046] The difference between this comparative example and Example 1 is only that in step S4, the quenching treatment with an aqueous ferrous salt solution is not performed, i.e. the aqueous ferrous salt solution is replaced by water, and the details are as follows:
[0047] S4. The precursor of step S3 is sintered at 300°C for 5h, and quenching treatment is performed using water, and then filtration, crushing and drying to a water content of less than 5% are performed to obtain the catalyst, wherein the ferrous salt is ferrous chloride.
[0048] Comparative Example 3
[0049] The difference between this comparative example and Example 1 is only that in step S3, the secondary addition of potassium permanganate solution is not performed, and in step S4, the quenching treatment with an aqueous ferrous salt solution is not performed, and the details are as follows:
[0050] S3. Water is added to the reaction solution of step S2, and after 10 minutes of continued ultrasonic stirring, solid-liquid separation is performed, the solid phase material is washed 4 times, and then drying is performed at 100°C to obtain a precursor;
[0051] S4. The precursor of step S3 is sintered at 300°C for 5h, and quenching treatment is performed using water, and then filtration, crushing and drying to a water content of less than 5% are performed to obtain the catalyst, wherein the ferrous salt is ferrous chloride.
[0052] Effectiveness demonstration
[0053] The catalysts prepared in Examples 1-5 and Comparative Examples 1-3 are subjected to formaldehyde adsorption rate and durability testing, and the specific test results are shown in Table 1:
[0054] 1. Formaldehyde adsorption rate: the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 are loaded into a catalytic evaluation device for formaldehyde adsorption and catalytic degradation reaction, and the test conditions are as follows: formaldehyde is 500ppm, the test temperature is 23±2°C, the reaction space velocity is 6000h -1 , and the formaldehyde adsorption rate of the catalyst is determined;
[0055] 2. Durability: The catalysts prepared in Examples 1-3 and Comparative Examples 1-3 were placed in an experimental environment with a temperature of 23±2℃ and a humidity of 90±5% RH, treated for 3 days, and then the retention rate of the formaldehyde adsorption rate of the catalysts was tested, the retention rate of the formaldehyde adsorption rate = formaldehyde adsorption rate after treatment / formaldehyde adsorption rate before treatment x 100%.
[0056] Table 1
[0057] Formaldehyde adsorption rate / % Durability / % Example 1 82.2 89.2 Example 2 81.4 88.9 Example 3 81.8 88.6 Comparative Example 1 77.3 80.4 Comparative Example 2 78.6 76.3 Comparative Example 3 74.2 63.2
[0058] Result analysis
[0059] From the analysis of Examples 1-3 and Comparative Examples 1-3 and the data in Table 1, it can be seen that the formaldehyde adsorption rate of the catalyst prepared in the present application is 81.4% or more, and the durability is 88.6% or more. It can be seen that the catalyst prepared in the present application can efficiently remove and decompose carbon-containing pollutants, and also has high durability.
[0060] From the comprehensive analysis of Comparative Examples 1-3 and Example 1, it can be seen that the secondary addition of potassium permanganate solution in step S3 and the quenching treatment with ferrous salt aqueous solution in step S4 can both improve the formaldehyde adsorption rate and durability of the catalyst. More importantly, the secondary addition of potassium permanganate solution and the quenching treatment with ferrous salt aqueous solution can produce synergistic effect when used together, greatly improving the durability of the catalyst.
[0061] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present application will not further describe various possible combinations.
[0062] In addition, various different embodiments of the present application can also be combined in any manner, as long as they do not deviate from the idea of the present application, and they should also be considered as disclosed by the present application.
Claims
1. A catalyst characterized in that, Prepared by the following steps: S1. 2-3 mol of potassium permanganate, 1.5-2.5 mol of zinc source, 2-4 mol of iron source and 0.8-1.2 mol of copper source are added to a ferrous chloride aqueous solution, stirred until completely dissolved to obtain a mixed solution; S2. The reaction temperature of the mixed solution in step S1 is adjusted, and the reaction is carried out under ultrasonic stirring to obtain a reaction solution; S3. Potassium permanganate solution is added to the reaction solution in step S2, and ultrasonic stirring is continued, then solid-liquid separation is carried out, the solid material is washed and dried to obtain a precursor; S4. The precursor in step S3 is sintered at 280-320℃ for 4-6h, and after sintering is completed, the sintered material is quenched with a ferrous salt aqueous solution, filtered, crushed and dried to obtain the catalyst.
2. The catalyst according to claim 1, characterized in that, The molar concentration of potassium permanganate in the mixed solution in step S1 is 0.4-0.6 mol / L.
3. The catalyst of claim 1, wherein The zinc source in step S1 is one or a mixture of two or more of zinc chloride, zinc sulfate and zinc nitrate.
4. The catalyst of claim 1, wherein The iron source in step S1 is one or a mixture of two or more of iron chloride, iron sulfate and iron nitrate.
5. The catalyst of claim 1, wherein The copper source in step S1 is one or a mixture of two or more of copper chloride, copper sulfate and copper nitrate.
6. The catalyst of claim 1, wherein The molar concentration of ferrous chloride solution in step S1 is 0.04-0.06 mol / L.
7. The catalyst of claim 1, wherein The reaction temperature of the mixed solution in step S2 is 55-65℃, and the reaction time is 25-35 min.
8. The catalyst of claim 1, wherein The molar concentration of potassium permanganate solution in step S3 is 0.2-0.3 mol / L, and the mass ratio of potassium permanganate solution to reaction solution is 0.8-1.2:
5.
9. The catalyst of claim 1, wherein The molar concentration of ferrous ions in the ferrous salt aqueous solution in step S4 is 0.01-0.03 mol / L, and the ferrous salt is one or a mixture of two or more of ferrous chloride, ferrous sulfate and ferrous nitrate.
10. Use of a catalyst, characterized in that The catalyst according to any one of claims 1-9 is used for removing carbon-containing pollutants.