Air purification material and preparation method and application thereof
By loading permanganate and trifluoromethane sulfonate or nitrate onto a porous carrier, the problem of high-temperature treatment of alkane pollutants in existing technologies has been solved, achieving efficient decomposition and removal at room temperature, thus reducing energy consumption and safety risks.
Patent Information
- Application Number
- CN202410313231.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-19
- Publication Date
- 2025-12-30
- Estimated Expiration
- 2044-03-19
AI Technical Summary
Existing technologies require high-temperature heating to treat alkane pollutants, resulting in low treatment efficiency, high costs, and potential hazards. Furthermore, traditional adsorption materials are flammable and explosive, making it difficult to efficiently decompose alkane pollutants at room temperature.
Air purification materials are prepared by using porous carriers loaded with permanganate and trifluoromethane sulfonate or nitrate as oxidants and activators. The materials decompose alkanes at room temperature to generate C-OH intermediates, which are then further oxidized to ketones or carbon dioxide.
It achieves efficient decomposition of alkane pollutants at room temperature with a removal rate of over 90%, avoiding the energy consumption and safety risks associated with high-temperature heating. It also has a good removal effect on other pollutants such as formaldehyde.
Smart Images
Figure CN118001840B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of air purification materials, and relates to an air purification material and a preparation method and application thereof. BACKGROUND
[0002] Alkanes are widely used in the industries of industrial coating, petrochemical industry, automobile industry, etc. due to their simple structure and stable performance. Since alkanes only contain C-C single bond and C-H single bond, the strengths of the two bonds are very large, and the electronegativity difference between carbon and hydrogen is very small, so the C-H bond has very small polarity and belongs to a weak polar bond. Therefore, compared with other organic matters, the ionic reagent of alkanes has considerable chemical stability. In general, alkanes do not react with most reagents such as strong acid, strong base and strong oxidant.
[0003] Air pollution is mainly caused by the volatilization of alkanes with 5-8 carbons as solvents during use, and the alkanes in the polluted air are mainly alkanes with 5-8 carbons. Traditional solutions to alkanes VOC pollutants mostly adopt activated carbon adsorption. Although the activated carbon adsorption material can adsorb and remove alkanes at room temperature, it has problems such as small adsorption capacity, poor selectivity, easy desorption, etc. Moreover, the activated carbon material adsorbed with alkanes is flammable and explosive, and has high risk. When large petrochemical enterprises use RTO and RCO to treat alkanes pollutants, heating needs to be performed to 350 DEG C or even above 700 DEG C, so as to realize the oxidation and decomposition of alkanes pollutants in the air. Some use noble metal catalysts for catalytic oxidation technology, but heating also needs to be performed to above 100 DEG C to effectively decompose alkanes pollutants. The existing air purification technology has problems such as low treatment efficiency and high treatment cost, and therefore, it is urgent to invent an air purification material which can decompose alkanes at room temperature without high-temperature heating. SUMMARY
[0004] The application aims to provide an air purification material and a preparation method and application thereof.
[0005] The application achieves the above-mentioned purpose by the following technical scheme.
[0006] The purification material is accidentally discovered in an experiment. At that time, activated alumina is used as a porous carrier, potassium permanganate is used as an oxidant, and scandium trifluoromethane sulfonate is used as an activator in the formula. Subsequent screening experiments are performed on the basis, and thus the application is formed.
[0007] The air purification material comprises a porous carrier, an oxidant and an activator loaded on the porous carrier, and the water content of the air purification material is 5-20 wt%.
[0008] The oxidant is a permanganate.
[0009] The activator is one or more of trifluoromethanesulfonate and nitrate;
[0010] The porous carrier is activated alumina.
[0011] Preferably, the oxidant is potassium permanganate or sodium permanganate.
[0012] Preferably, the trifluoromethane sulfonate is one or more of scandium trifluoromethane sulfonate, potassium trifluoromethane sulfonate, zinc trifluoromethane sulfonate, lithium trifluoromethane sulfonate, and copper trifluoromethane sulfonate.
[0013] Preferably, the nitrate is one or more of scandium nitrate, aluminum nitrate, and copper nitrate.
[0014] Preferably, the specific surface area of the porous carrier is ≥250m². 2 / g, pore volume ≥0.4cc / g, average pore size 5-15nm, particle size 0.1-6mm.
[0015] Preferably, the porous carrier content is 65-90 wt%, the oxidant content is 0.1-12 wt%, the activator content is 0.01-12 wt%, and the water content is 8-20 wt%. More preferably, the activator / porous carrier ratio is 0.1-10 wt%; the oxidant / porous carrier ratio is 0.5-10 wt%.
[0016] The preparation method of the above-mentioned air purification material includes the following steps:
[0017] (1) Dissolve the oxidant and activator in water to prepare an aqueous solution;
[0018] (2) Mix the aqueous solution with the porous support so that the oxidant and activator are loaded onto the porous support;
[0019] (3) After drying, it is made into an air purification material.
[0020] Preferably, the mass ratio of the aqueous solution to the porous carrier in step (2) is 0.1-0.7.
[0021] Preferably, the dissolution temperature in step (1) is 20-80℃; the drying in step (3) is heating drying at a temperature of 60-150℃.
[0022] Preferably, the material is used to decompose alkanes at room temperature, especially alkanes with 5-8 carbon atoms in polluted air.
[0023] A multifunctional composite filter material includes a support layer, a functional layer, and a filter layer stacked sequentially, with an adhesive between the three layers; the support layer is a skeleton nonwoven fabric; the functional layer is the aforementioned air purification material; the filter layer is meltblown fabric; and the adhesive is hot melt adhesive.
[0024] The preparation method of the multifunctional composite filter material includes the following steps:
[0025] (1) Spray the adhesive onto the support layer, and then evenly sprinkle the air purification material onto the support layer;
[0026] (2) The adhesive is sprayed onto the filter layer and then bonded to the support layer with adhesive and air purification material prepared in step (1) to form a multifunctional composite filter material with a sandwich structure.
[0027] The purification mechanism of this invention is hypothesized to be as follows: the added activator, such as scandium ions, directly connects with the MO (M representing a metal element) in the oxidant, greatly increasing the oxidation potential of M=O. This activates the CH in alkanes, oxidizing CH to generate the C-OH (alcohol) intermediate, which is then further oxidized to ketones, and even carbon dioxide. The increase in the oxidation potential of the oxidant is related to the activator's ability to remove negative ions.
[0028] Compared with the prior art, the present invention has the following beneficial effects:
[0029] (1) The air purification material of the present invention can purify alkane pollutants in the air at room temperature without heating the air, and the purification process has low energy consumption.
[0030] (2) The air purification material of the present invention not only adsorbs alkanes, but also decomposes and transforms alkanes, and will not cause secondary pollution due to desorption.
[0031] (3) The air purification material of the present invention has a better purification effect at room temperature, and the alkane removal rate can reach more than 90%, or even as high as 98%; at the same time, it also has a good removal effect on formaldehyde and other pollutants. Attached Figure Description
[0032] Figure 1 Color change diagrams of the air purification materials (scandium trifluoromethanesulfonate / activated alumina balls = 1% and 0.1%) prepared in Examples 1 and 1a when decomposing n-hexane.
[0033] Figure 2 This is a process diagram for the preparation of multifunctional composite filter media. Detailed Implementation
[0034] The present invention will be further described in detail below with reference to specific embodiments, but the implementation of the present invention is not limited thereto. For process parameters not specifically noted, conventional techniques can be referred to.
[0035] Example 1
[0036] Add 40g potassium permanganate, 10g scandium trifluoromethanesulfonate, and 400g water to a 1000ml round-bottom flask, and heat at 60℃ with stirring for 1 hour to dissolve and prepare an aqueous solution. Separately, take a 2500ml round-bottom flask, add 1000g activated alumina balls, and then pour the prepared aqueous solution into the flask. Shake the flask rapidly to ensure full contact between the aqueous solution and the activated alumina balls. After impregnation, there should be no obvious water on the surface of the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying device and dry at 60℃ for 1 hour to prepare an air purification material with a water content of 12wt%.
[0037] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized n-hexane was injected through the test chamber inlet to achieve a n-hexane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in the concentration of n-hexane in the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the concentration of n-hexane in the test chamber decreased to 0.02 mg / m³. 3 The hexane removal rate reached 98%.
[0038] Example 1a
[0039] The difference between this embodiment and Embodiment 1 is that the amount of scandium trifluoromethanesulfonate added is 1g.
[0040] The air purification materials (scandium trifluoromethanesulfonate / activated alumina balls = 1% and 0.1%) prepared in Examples 1 and 1a were respectively added in 30ml capped glass bottles with 7g of the air purification material. Filter paper was placed at the mouth of the bottle, and 100ul of n-hexane was dropped onto the filter paper. The bottles were sealed and left to stand for 24 hours. The color change of the air purification material was recorded by taking pictures during the process. See details. Figure 1 .
[0041] Example 2
[0042] Add 10g of potassium permanganate, 10g of potassium trifluoromethanesulfonate, and 300g of water to a 1000ml round-bottom flask. Heat at 60℃ and stir for 0.5h to dissolve, preparing an aqueous solution. Separately, take a 2500ml round-bottom flask, add 1000g of activated alumina balls, and then pour the prepared aqueous solution into the flask. Shake the flask rapidly to ensure thorough contact between the aqueous solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 80℃ for 40min to obtain an air purification material with a water content of 14wt%.
[0043] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized n-hexane was injected through the test chamber inlet to achieve a n-hexane concentration of 1 mg / m³. 3Gas chromatography was used to detect changes in the concentration of n-hexane in the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the concentration of n-hexane in the test chamber decreased to 0.05 mg / m³. 3 The hexane removal rate reached 95%.
[0044] Example 3
[0045] Add 5g of potassium permanganate, 5g of zinc trifluoromethanesulfonate, and 300g of water to a 1000ml round-bottom flask. Heat at 60℃ and stir for 0.5h to dissolve, preparing an aqueous solution. Separately, take a 2500ml round-bottom flask and add 1000g of activated alumina balls. Pour the prepared aqueous solution into the flask and shake rapidly to ensure full contact between the solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 80℃ for 40min to prepare an air purification material with a water content of 10wt%.
[0046] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized isooctane was injected through the test chamber inlet to achieve an isooctane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in isooctane concentration within the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the isooctane concentration within the test chamber decreased to 0.09 mg / m³. 3 The isooctane removal rate reached 91%.
[0047] Example 4
[0048] Add 300g of 40% sodium permanganate aqueous solution, 50g of copper trifluoromethanesulfonate, and 300g of water to a 1000ml round-bottom flask. Heat at 60℃ and stir for 1.5 hours to dissolve, thus preparing an aqueous solution. Separately, take a 2500ml round-bottom flask, add 1000g of activated alumina balls, and then pour the prepared aqueous solution into the flask. Shake the flask rapidly to ensure full contact between the aqueous solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 100℃ for 1 hour to prepare an air purification material with a water content of 8wt%.
[0049] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized n-pentane was injected through the sample inlet to achieve a n-pentane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in the concentration of n-pentane in the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the concentration of n-pentane in the test chamber decreased to 0.05 mg / m³. 3 The n-butane removal rate reached 95%.
[0050] Example 5
[0051] In a 1000ml round-bottom flask, add 250g of 40% sodium permanganate aqueous solution, 30g of lithium trifluoromethanesulfonate, and 300g of water. Heat at 60℃ and stir for 1 hour to dissolve, preparing an aqueous solution. Separately, in a 2500ml round-bottom flask, add 1000g of activated alumina balls. Pour the prepared aqueous solution into the flask and shake rapidly to ensure thorough contact between the solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 140℃ for 30 minutes to prepare an air purification material with a moisture content of 20wt%.
[0052] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized n-heptane was injected through the test chamber inlet to achieve a n-heptane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in the concentration of n-heptane in the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the concentration of n-heptane in the test chamber decreased to 0.07 mg / m³. 3 The removal rate of n-heptane reached 93%.
[0053] Example 6
[0054] Add 15g of potassium permanganate, 1g of scandium nitrate, and 350g of water to a 1000ml round-bottom flask, and heat at 60℃ with stirring for 1 hour to dissolve and prepare an aqueous solution. Separately, take a 2500ml round-bottom flask, add 1000g of activated alumina balls, and then pour the prepared aqueous solution into the flask. Shake the flask rapidly to ensure thorough contact between the aqueous solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 60℃ for 1 hour to prepare an air purification material with a water content of 16wt%.
[0055] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized cyclohexane was injected through the test chamber inlet to achieve a cyclohexane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in cyclohexane concentration within the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the cyclohexane concentration within the test chamber decreased to 0.10 mg / m³. 3 The cyclohexane removal rate reached 90%.
[0056] Example 7
[0057] Add 80g of potassium permanganate, 100g of aluminum nitrate, and 600g of water to a 1000ml round-bottom flask, and heat at 80℃ while stirring for 1 hour to dissolve, thus preparing an aqueous solution. Separately, take a 2500ml round-bottom flask, add 1000g of activated alumina balls, and then pour the prepared aqueous solution into the flask. Shake the flask rapidly to ensure thorough contact between the aqueous solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 140℃ for 1 hour to prepare an air purification material with a water content of 18wt%.
[0058] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized n-hexane was injected through the test chamber inlet to achieve a n-hexane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in the concentration of n-hexane in the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the concentration of n-hexane in the test chamber decreased to 0.04 mg / m³. 3 The cyclohexane removal rate reached 96%.
[0059] Example 8
[0060] Add 250g potassium permanganate, 70g copper nitrate, and 300g water to a 1000ml round-bottom flask, heat to 80℃ and stir for 1 hour to dissolve, thus preparing an aqueous solution. Separately, take a 2500ml round-bottom flask, add 1000g activated alumina balls, then pour the prepared aqueous solution into the flask and shake rapidly to ensure full contact between the aqueous solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 150℃ for 30 minutes to prepare an air purification material with a water content of 14wt%.
[0061] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized n-hexane was injected through the test chamber inlet to achieve a n-hexane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in the concentration of n-hexane in the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the concentration of n-hexane in the test chamber decreased to 0.06 mg / m³. 3 The cyclohexane removal rate reached 94%.
[0062] Example 9
[0063] Using a glue spraying machine, hot melt adhesive is sprayed onto the non-woven fabric skeleton at a rate of 10 g / m². Using a spreading machine, air purification material granules are evenly spread onto the non-woven fabric skeleton coated with hot melt adhesive at a rate of 200 g / m². Using another glue spraying machine, hot melt adhesive is sprayed onto the meltblown fabric at a rate of 10 g / m². Following the sequence of "non-woven fabric skeleton - hot melt adhesive - air purification material - hot melt adhesive - meltblown fabric", they are pressed together using a pressing machine to create a multifunctional composite filter material.
[0064] The multifunctional composite filter material prepared above is made into a flat-plate filter with an unfolded area of approximately 2.8 square meters, and is installed in a device with a design air volume of 500 m³ / h. 3 An air purifier with a clean air delivery rate (CADR) of 450 m³ / h was tested. The test was conducted according to the national standard GB / T18801-2022, and the measured particulate matter clean air delivery rate (CADR) was 450 m³ / h. 3 / h, formaldehyde clean air delivery rate is 230m³ / h 3 / h, the clean air delivery rate for n-hexane is 180m³ / h. 3 / h, TVOC clean air delivery rate is 165m³ / h 3 / h.
[0065] Comparative Example 1
[0066] Cyclohexane natural decay test. At 1m 3 Inside the test chamber, vaporized cyclohexane was injected through the test chamber inlet to achieve a cyclohexane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in cyclohexane concentration within the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the cyclohexane concentration within the test chamber decreased to 0.97 mg / m³. 3 The natural decay rate of cyclohexane is 3%.
[0067] Comparative Example 2
[0068] 1000g of unmodified activated alumina balls were placed in a 1m... 3 Inside the test chamber, vaporized n-hexane was injected through the test chamber inlet to achieve a n-hexane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in the concentration of n-hexane in the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the concentration of n-hexane in the test chamber decreased to 0.89 mg / m³. 3 The hexane removal rate reached 11%.
[0069] Comparative Example 3
[0070] Add 40g of potassium permanganate and 400g of water to a 1000ml round-bottom flask, heat at 60℃ and stir for 1 hour to dissolve, thus preparing an aqueous solution. Separately, take a 2500ml round-bottom flask, add 1000g of activated alumina balls, then pour the prepared aqueous solution into the flask and shake rapidly to ensure full contact between the aqueous solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 60℃ for 1 hour to prepare an air purification material with a water content of 12wt%.
[0071] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, vaporized cyclohexane was injected through the test chamber inlet to achieve a cyclohexane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in cyclohexane concentration within the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the cyclohexane concentration within the test chamber decreased to 0.81 mg / m³. 3 The cyclohexane removal rate was 19%.
[0072] Comparative Example 4
[0073] Add 10g of scandium trifluoromethanesulfonate and 400g of water to a 1000ml round-bottom flask, heat at 60℃ and stir for 1 hour to dissolve, thus preparing an aqueous solution. Separately, take a 2500ml round-bottom flask, add 1000g of activated alumina balls, then pour the prepared aqueous solution into the flask, and quickly shake the flask to ensure full contact between the aqueous solution and the activated alumina balls. Place the alumina balls loaded with oxidant and activator in a drying apparatus and dry at 60℃ for 1 hour to prepare an air purification material with a water content of 14wt%.
[0074] Place the above 1000g air purification material in a 1m... 3 Inside the test chamber, 1 mg of vaporized cyclohexane was injected through the sample inlet to achieve a cyclohexane concentration of 1 mg / m³. 3 Gas chromatography was used to detect changes in cyclohexane concentration within the test chamber, with concentration data recorded every hour for a 24-hour period. After 24 hours of decomposition, the cyclohexane concentration within the test chamber decreased to 0.88 mg / m³. 3 The cyclohexane removal rate was 12%.
[0075] Table 1. Differences in composition and alkane decomposition effects between the examples and comparative examples.
[0076]
[0077]
[0078] Comparative Examples 1-3 show that porous supports, oxidants, and activators must be present simultaneously to achieve good room-temperature decomposition of alkanes.
[0079] Examples 1-5 show that the amount of oxidant and activator added has little impact on the purification effect, and the overall purification effect is good, with the alkane removal rate reaching over 90%.
[0080] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.
Claims
1. An air purification material, characterized by, The air purification material comprises a porous carrier and an oxidant and an activator supported on the porous carrier, wherein the water content of the air purification material is 5-20 wt%; The oxidant is potassium permanganate or sodium permanganate; The activator is trifluoromethane sulfonate, or trifluoromethane sulfonate and nitrate; The porous carrier is activated alumina.
2. The air cleaning material according to claim 1, wherein The oxidant is potassium permanganate or sodium permanganate; The trifluoromethane sulfonate is one or two or more of scandium trifluoromethane sulfonate, potassium trifluoromethane sulfonate, zinc trifluoromethane sulfonate, lithium trifluoromethane sulfonate, and copper trifluoromethane sulfonate. The nitrate is one or two or more of scandium nitrate, aluminum nitrate, and copper nitrate.
3. The air cleaning material according to claim 1 or 2, characterized in that, The specific surface area of the porous carrier is > 250 m 2 / g, pore volume > 0.4 cc / g, average pore diameter 5-15 nm, particle size 0.1-6 mm.
4. The air cleaning material according to claim 1 or 2, characterized in that, The content of the porous carrier is 65-90 wt%, the content of the oxidant is 0.1-12 wt%, the content of the activator is 0.01-12 wt%, and the content of water is 8-20 wt%.
5. The method of producing the air cleaning material according to any one of claims 1 to 4, characterized by, The method comprises the following steps: (1) dissolving the oxidant and the activator in water to form an aqueous solution; (2) mixing the aqueous solution with the porous carrier to support the oxidant and the activator on the porous carrier; (3) drying to form the air purification material.
6. The preparation method according to claim 5, characterized in that, The mass ratio of the aqueous solution to the porous carrier in step (2) is 0.1-0.
7.
7. The production method according to claim 5 or 6, characterized by, The temperature for dissolving in step (1) is 20-80℃, and the drying in step (3) is heating drying at a temperature of 60-150℃.
8. Use of the air cleaning material according to any one of claims 1 to 4, characterized in that The material is used for decomposing alkanes at room temperature.
9. A multifunctional composite filter material, characterized by The multifunctional composite filter comprises a support layer, a functional layer, and a filter layer stacked in sequence, and a binder is further provided between the three layers; the support layer is a skeleton non-woven fabric; the functional layer is the air purification material according to any one of claims 1-4; the filter layer is a melt-blown fabric; and the binder is a hot melt adhesive.
10. The method of claim 9, wherein the multi-functional composite filter material is prepared by the steps of: The method comprises the following steps: (1) spraying the binder on the support layer, and then uniformly sprinkling the air purification material on the support layer; (2) spraying the binder on the filter layer, and then adhering the support layer with the binder and the air purification material prepared in step (1) to form a sandwich-structured multifunctional composite filter.
Citation Information
Patent Citations
Light hydrocarbon tail gas purification agent and preparation method thereof
CN105080280A