Oil smoke purification catalytic coating as well as preparation method and application thereof
The catalytic coating composed of Pt, K-CeO2, La(1-xy)AgxCeyCo(1-z)CuzO3 and mesoporous molecular sieve SBA-15 solves the problem of low oil fume purification efficiency at low temperatures, and achieves the effects of high-efficiency purification and extended service life.
Patent Information
- Application Number
- CN202410016288.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-01-05
- Publication Date
- 2025-07-08
AI Technical Summary
Existing technologies make it difficult to efficiently purify the oil smoke and odor in the oven at low temperatures. Filtration technology cannot remove gaseous components, and traditional catalysts have poor purification effects at low temperatures.
The catalytic coating composed of Pt, K-CeO2, La(1-xy)AgxCeyCo(1-z)CuzO3 and mesoporous molecular sieve SBA-15 can efficiently decompose oil smoke at low temperature through synergistic catalysis. The high specific surface area and oxygen vacancies of SBA-15 are used to improve the activity, and Pt and the active layer synergistically catalyze.
It achieves efficient purification of oil fume odor at low temperature. The coating significantly improves the oil fume purification efficiency and extends its service life under the synergistic effect of mesoporous molecular sieve and active components.
Abstract
Description
Technical Field
[0001] The present invention relates to a coating for oil fume purification, which is applied to electrical appliances such as ovens, refrigerators, air purifiers, etc. The present invention also discloses a preparation method and specific applications of the coating. Background Art
[0002] In real family life, the generation of oil fume in the oven is a headache problem. A large amount of oil fume odor will be emitted during the cooking process and when opening the door. Therefore, the purification of oil fume generated by the oven has increasingly become the focus of attention of families and product manufacturers. At present, oil fume purification mainly solves the problem through technical means such as adsorption filtration and oxidation decomposition.
[0003] The filtration technology mainly intercepts oil fume particles with a HEPA net (also called a high-efficiency particulate air filter), etc. This method can effectively filter a part of the oil fume, but it cannot remove the oil fume odor of gaseous components, and the purification is not thorough; in addition, the service life of the filter screen of this method is short and needs to be replaced regularly, resulting in a low customer experience.
[0004] The decomposition technology mainly uses means such as catalytic oxidation to directly decompose oil fume molecules into carbon dioxide and water, so as to achieve the purpose of removing oil fume. In addition, compared with the filtration interception method, the service life of this technology is longer. However, it should be noted that in the actual oven use environment, the temperature is mostly below 250°C, while general catalysts require a higher catalytic temperature to have high purification ability. Therefore, this technology needs to develop high-performance catalysts at lower temperatures. Summary of the Invention
[0005] The first technical problem to be solved by the present invention is to provide an oil fume purification catalytic coating that can efficiently purify oil fume odor at a lower temperature in view of the above technical status.
[0006] The second technical problem to be solved by the present invention is to provide a preparation method of an oil fume purification catalytic coating that can efficiently purify oil fume odor at a lower temperature in view of the above technical status.
[0007] The third technical problem to be solved by the present invention is to provide an application of an oil fume purification catalytic coating that can efficiently purify oil fume odor at a lower temperature in view of the above technical status.
[0008] The technical solution adopted by the present invention to solve the above first technical problem is: an oil fume purification catalytic coating, characterized in that the oil fume purification catalytic coating includes Pt, K-CeO2, La (1-x-y) Ag x CeyCo (1-z) Cu zO3 and mesoporous molecular sieve SBA-15; the total loading amount of Pt relative to the coating is 0.1% to 3%, K-CeO2 is K-doped CeO2, the loading amount of K-CeO2 relative to SBA-15 is 0.1 to 10%, and the K / Ce atomic ratio is 0.001 to 0.1; La (1-x-y) Ag x Ce y Co (1-z) Cu z O is a LaCoO3 type perovskite modified by Ag, Ce and Cu elements, and its loading amount relative to the mesoporous molecular sieve SBA-15 is 0.1-15%, x is 0.01-0.5, y is 0.01-0.5, and z is 0.01-0.5.
[0009] Preferably, the La (1-x-y) Ag x Ce y Co (1-z) Cu z The loading amount of O relative to the mesoporous molecular sieve SBA-15 is 0.1-10%, the loading amount of K-CeO2 relative to SBA-15 is 0.5-5%, and the atomic ratio of K / Ce is 0.01-0.1.
[0010] The technical solution adopted by the present invention to solve the above second technical problem is: a method for preparing a fume purification catalytic coating, characterized by comprising the following steps:
[0011] ① First, lanthanum nitrate, silver nitrate, cerium nitrate, cobalt nitrate and copper nitrate are dissolved in water and fully stirred, and then the mesoporous molecular sieve SBA-15 is added at the same time and fully stirred and dispersed; finally, aluminum sol is added and fully stirred to form a uniformly mixed slurry; the slurry is applied to a porous honeycomb ceramic substrate or foam ceramic by vacuum coating, and dried and calcined to obtain a ceramic substrate coated with a composite carrier;
[0012] ② Dispersing the Ce source and potassium citrate in water to form a uniform dispersion, and then dispersing them on the ceramic coating by an impregnation method, drying, and calcining to obtain a porous honeycomb catalytic coating module;
[0013] ③ Disperse the Pt source in water to form a uniform dispersion, then disperse the Pt source on the ceramic coating by an impregnation method, dry, and calcine under nitrogen conditions to obtain a fume purification catalytic coating module.
[0014] Preferably, the calcination temperature in step ① is 600-900°C; the calcination temperature in step ② is 400-700°C; and the calcination temperature in step ③ is 300-700°C.
[0015] Preferably, the drying temperature in step ① is 60 - 180 °C, the drying temperature in step ② is 60 - 180 °C, and the drying temperature in step ③ is 60 - 180 °C.
[0016] Preferably, the Pt source is at least one of chloroplatinic acid, platinum nitrate, and diethanolamine hexahydroxyplatinate.
[0017] The technical solution adopted by the present invention to solve the above - mentioned third technical problem is that the oil fume purification catalytic coating is applied to ovens, odor purifiers, air purifiers, and refrigerators.
[0018] Compared with the prior art, the advantages of the present invention are as follows:
[0019] The coating of the present invention is an SBA - 15 support, which is used to efficiently disperse La (1-x-y) Ag x CeyCo (1-z) Cu z O3, CeO2 active layers, and finally, the Pt active component is efficiently dispersed on the active layer; mainly through the synergistic catalytic effect of Pt with the active layer and the support, the efficient catalytic decomposition of oil fume is realized.
[0020] The SBA - 15 support is a mesoporous molecular sieve with a pore diameter of dozens of nanometers and a huge specific surface area. On the one hand, it can efficiently disperse the active layer, and on the other hand, it can effectively adsorb oil fume mixed components such as VOCs and oil fume particles, and has high hydrophobicity, which can effectively reduce the competitive adsorption interference of water molecules; due to the high specific surface area of the SBA - 15 support, La (1-x-y) Ag x CeyCo (1-z) Cu z O3 perovskite components and CeO2 components can be highly dispersed.
[0021] For the La (1-x-y) Ag x CeyCo (1-z) Cu z O3 perovskite component, through the doping modification of the A site by Ag and Ce, and the doping modification of the B site by Cu, a large number of oxygen vacancies and active sites are generated in the form of triple - element double - site co - doping, significantly enhancing the catalytic oxidation activity of LaCoO3.
[0022] The introduction of CeO2 will effectively improve the oxygen storage performance, which is beneficial to the transfer of active oxygen to the perovskite site. Secondly, the specially prepared K - CeO2 component has an extremely high oxygen vacancy content and a strong ability to activate oxygen.
[0023] Due to the existence of a large number of oxygen vacancies, the Pt component can be effectively dispersed, and at the same time, the synergistic catalytic effect of Pt with the active layer is significantly enhanced, realizing the effect of efficient catalytic decomposition of oil fume.
[0024] When preparing the coating, since the perovskite calcination temperature is high at 600-800 °C, by first dispersing La (1-x-y) Ag x CeyCo (1-z) Cu z O3 perovskite, and then dispersing K-CeO2 to prevent excessive agglomeration of CeO2 at ultra-high temperatures;
[0025] Potassium citrate is mainly used to modify CeO2. On the one hand, K can be doped to activate the lattice oxygen of CeO2. On the other hand, the appropriate amount of reducing carbon components provided by potassium citrate under high-temperature calcination can effectively reduce CeO2 and generate more oxygen vacancies.
[0026] The SBA-15 support can efficiently adsorb complex pollutants with different particle sizes generated by cooking fumes. The loaded K-CeO2La (1-x-y) Ag x CeyCo (1-z) Cu z O3 active layer will generate a large number of oxygen vacancies, which can efficiently disperse the Pt component; finally, the Pt component, oxygen vacancies, Ce sites and La (1-x-y) Ag x CeyCo (1-z) Cu z O3 sites act synergistically on the catalytic oxidation and decomposition of cooking fumes, and extremely high cooking fume purification efficiency can be achieved at a lower temperature. Detailed implementation methods
[0027] The present invention will be further described in detail below in conjunction with embodiments.
[0028] The following will explain each specific implementation method in detail. It should be understood that the specific implementation methods described here are only used to illustrate and explain the present invention, and are not used to limit the present invention.
[0029] Example 1
[0030] The coating composition of this example is Pt / K-CeO2 / La (1-x-y) Ag x CeyCo (1-z) Cu z O3 / SBA-15; among them, La (1-x-y) Ag x CeyCo (1-z) Cu z The loading amount of O3 relative to SBA-15 is 7%, x is 0.1, y is 0.2, and z is 0.25; the loading amount of K-CeO2 relative to SBA-15 is 3%, and the K / Ce atomic ratio is 0.05; the total loading amount of Pt relative to the coating is 0.6%.
[0031] The steps for preparing the coating are as follows:
[0032] (1) First, dissolve a certain proportion of lanthanum nitrate, silver nitrate, cerium nitrate, cobalt nitrate, and copper nitrate in water and stir well. Then, add a certain amount of SBA-15 at the same time and stir well to disperse. Finally, add a certain amount of aluminum sol and stir well to form a uniformly mixed slurry. Coat it on a porous honeycomb ceramic substrate or a foam ceramic by vacuum coating, dry it, and calcine it at 750 °C to obtain a ceramic substrate coated with a composite support. The main function of the aluminum sol here is to bond the coating and the substrate through high-temperature calcination.
[0033] (2) Disperse a certain amount of Ce source and potassium citrate in water to form a uniform dispersion liquid, and then disperse it on the ceramic coating by the impregnation method, dry it at 120 °C, and calcine it at 500 °C to obtain the final porous honeycomb catalytic coating module.
[0034] (3) Disperse a certain amount of chloroplatinic acid in water to form a uniform dispersion liquid, and then impregnate and disperse the Pt source on the ceramic coating by the impregnation method, dry it at 120 °C, and calcine it under nitrogen at 500 °C to obtain the final porous honeycomb catalytic coating module.
[0035] Example 2
[0036] This example changes the doping ratio in La (1-x-y) Ag x CeyCo (1-z) Cu z O3, where x is 0.01, y is 0.2, and z is 0.25. The rest of the specific operations are as shown in Example 1.
[0037] Example 3
[0038] This example changes the doping ratio in La (1-x-y) Ag x CeyCo (1-z) Cu z O3, where x is 0.1, y is 0.01, and z is 0.25. The rest of the specific operations are as shown in Example 1.
[0039] Example 4
[0040] This example changes the doping ratio in La (1-x-y) Ag x CeyCo (1-z) Cu z O3, where x is 0.1, y is 0.2, and z is 0.01. The rest of the specific operations are as shown in Example 1.
[0041] Example 5
[0042] In this example, La (1-x-y) Agx CeyCo (1-z) Cu z The loading amount of O3 relative to SBA-15 is 0.1%, and the rest of the specific operations are as shown in Example 1.
[0043] Example 6
[0044] In this example, the loading amount of K-CeO2 relative to SBA-15 is changed to 0.1%, and the rest of the specific operations are as shown in Example 1.
[0045] Example 7
[0046] In this example, the K / Ce atomic ratio is changed to 0.001, and the rest of the specific operations are as shown in Example 1.
[0047] Example 8
[0048] In this example, the total loading amount of Pt relative to the coating is changed to 0.1%, and the rest of the specific operations are as shown in Example 1.
[0049] Example 9
[0050] In this example, La is changed (1-x-y) Ag x CeyCo (1-z) Cu z The loading amount of O3 relative to SBA-15 is 15%, x is 0.5, y is 0.01, z is 0.5; the loading amount of K-CeO2 relative to SBA-15 is 0.1%, and the K / Ce atomic ratio is 0.001 - 0.1; the total loading amount of Pt relative to the coating is 3%. In the preparation steps, the calcination temperature in step (1) is changed to 600 °C, the calcination temperature in step (2) is changed to 400 °C, and the calcination temperature in step (3) is changed to 300 °C; the rest of the specific operations are as shown in Example 1.
[0051] Example 10
[0052] In this example, La is changed (1-x-y) Ag x CeyCo (1-z) Cu z The loading amount of O3 relative to SBA-15 is 0.1%, x is 0.01, y is 0.5, z is 0.01; the loading amount of K-CeO2 relative to SBA-15 is 10%, and the K / Ce atomic ratio is 0.1; the total loading amount of Pt relative to the coating is 3%. In the preparation steps, the calcination temperature in step (1) is changed to 900 °C, the calcination temperature in step (2) is changed to 700 °C, and the calcination temperature in step (3) is changed to 700 °C; the rest of the specific operations are as shown in Example 1.
[0053] Comparative Example 1
[0054] The coating composition of this comparative example is Pt / SBA-15; among them, the total loading amount of Pt relative to the coating is 0.6%. The remaining specific preparation operations are as shown in Example 1.
[0055] Comparative Example 2
[0056] The coating composition of this comparative example is Pt / LaCoO3 / SBA-15; among them, the loading amount of LaCoO3 relative to SBA-15 is 7%, and the total loading amount of Pt relative to the coating is 0.6%.
[0057] Comparative Example 3
[0058] The coating composition of this comparative example is Pt / CeO2 / SBA-15; among them, the loading amount of CeO2 relative to SBA-15 is 3%, and the total loading amount of Pt relative to the coating is 0.6%.
[0059] Place the catalytic modules prepared in the example components and comparative examples respectively in a purification device with the same parameters, and conduct tests in the same oven and operating program. Bake a certain amount of cooking oil in the oven, set the cooking temperature at 200 °C, set the time at 30 min, generate a certain concentration of oil fume, and then start the purification fixed time to conduct the oil fume purification effect test.
[0060] Serial number Example Oil fume removal rate 1 Example 1 95％ 2 Example 2 80％ 3 Example 3 83％ 4 Example 4 85％ 5 Example 5 70％ 6 Example 6 73％ 7 Example 7 85％ 8 Example 8 57％ 9 Example 9 75％ 10 Example 10 63％ 11 Comparative example 1 49％ 12 Comparative example 2 55％ 13 Comparative example 3 60％
[0061] First of all, it should be noted that although in the following description, the coating of the present invention can typically be applied to the oil fume purification environment of an oven, the present invention is not limited thereto. In occasions and devices that require odor removal and purification, such as odor eliminators, air purifiers, etc., this catalytic coating can be applied, and they all belong to the protection scope of the present invention.
Claims
1. A fume purification catalytic coating, characterized in that The oil fume purification catalytic coating includes Pt, K-CeO2, La (1-x-y) Ag x CeyCo (1-z) Cu z O3 and mesoporous molecular sieve SBA-15; the total loading of Pt relative to the coating is 0.1% to 3%, K-CeO2 is K-doped CeO2, the loading of K-CeO2 relative to SBA-15 is 0.1 to 10%, and the K / Ce atomic ratio is 0.001 to 0.1; La (1-x-y) Ag x Ce y Co (1-z) Cu z O is a LaCoO3-type perovskite mineral modified by Ag, Ce, and Cu elements, and the loading relative to the mesoporous molecular sieve SBA-15 is 0.1 to 15%, x is 0.01 to 0.5, y is 0.01 to 0.5, and z is 0.01 to 0.
5.
2. The oil fume purification catalytic coating according to claim 1, characterized in that The La (1-x-y) Ag x Ce y Co (1-z) Cu z The loading amount of O relative to the mesoporous molecular sieve SBA-15 is 0.1-10%, the loading amount of K-CeO2 relative to SBA-15 is 0.5-5%, and the K / Ce atomic ratio is 0.01-0.
1.
3. The preparation method of the fume purification catalytic coating according to claim 1 or 2, characterized in that The steps include: ① First, lanthanum nitrate, silver nitrate, cerium nitrate, cobalt nitrate and copper nitrate are dissolved in water and fully stirred, and then the mesoporous molecular sieve SBA-15 is added at the same time and fully stirred and dispersed; finally, aluminum sol is added and fully stirred to form a uniformly mixed slurry; the slurry is applied to a porous honeycomb ceramic substrate or foam ceramic by vacuum coating, and dried and calcined to obtain a ceramic substrate coated with a composite carrier; ② Dispersing the Ce source and potassium citrate in water to form a uniform dispersion, and then dispersing them on the ceramic coating by an impregnation method, drying, and calcining to obtain a porous honeycomb catalytic coating module; ③ Disperse the Pt source in water to form a uniform dispersion, then disperse the Pt source on the ceramic coating by an impregnation method, dry, and calcine under nitrogen conditions to obtain a fume purification catalytic coating module.
4. The preparation method according to claim 3, characterized in that The calcination temperature in step ① is 600-900° C.; the calcination temperature in step ② is 400-700° C.; the calcination temperature in step ③ is 300-700° C.
5. The preparation method according to claim 3, characterized in that The drying temperature in step ① is 60-180°C, the drying temperature in step ② is 60-180°C, and the drying temperature in step ③ is 60-180°C.
6. The preparation method according to claim 3, characterized in that The Pt source is at least one of chloroplatinic acid, platinum nitrate and hexahydroxyplatinic acid diethanolamine.
7. The oil fume purification catalytic coating according to claim 1 or 2 is used in ovens, deodorizers, air purifiers and refrigerators.