Room-temperature formaldehyde removal catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of indoor environment catalytic purification, and discloses a room-temperature formaldehyde removal catalyst as well as a preparation method and application thereof. The room-temperature formaldehyde removal catalyst comprises a carbon-series material and a perylene derivative loaded on the carbon-series material; the mass ratio of the perylene derivative to the carbon-series material is (5: 1)-(1: 50). The catalyst disclosed by the invention has an excellent catalytic oxidation effect on formaldehyde, can effectively oxidize and remove formaldehyde at room temperature, does not have the problems of limited adsorption capacity, adsorption saturation and the like compared with a traditional formaldehyde removal material depending on an adsorption effect, is high in removal efficiency and long in service life, and can realize long-time formaldehyde removal.

Description

Technical Field

[0001] The invention relates to the technical field of indoor environment catalytic purification, and in particular to a room temperature formaldehyde removal catalyst and a preparation method and application thereof. Background Art

[0002] Formaldehyde (HCHO), as the most common indoor air pollutant, is a recognized source of allergic reactions and a potential carcinogen and mutagen. Based on the characteristics of indoor formaldehyde pollution sources, formaldehyde removal technologies can be divided into two categories: source control and end-of-pipe treatment. The source control method generally refers to the development and use of new building and decoration materials with no formaldehyde or low formaldehyde content, which is the most effective way to reduce indoor formaldehyde concentration. The catalytic oxidation method can completely degrade formaldehyde into CO2 and H2O. This method has the advantages of high degradation efficiency, non-toxic products, and energy saving. It is the preferred solution for indoor formaldehyde removal. The catalyst is the core of this technology. The supported precious metal catalyst shows high catalytic activity and can completely convert formaldehyde into CO2 and H2O at room temperature. However, due to the limited reserves of precious metals and high costs, its commercial application is severely restricted; although transition metal catalysts have the advantage of low price, it often requires a high temperature of more than 100°C to achieve complete removal of formaldehyde. When it is actually used in indoor formaldehyde removal, it is necessary to add additional heating catalytic devices, which increases energy consumption. Therefore, it is of great practical significance to develop a catalyst that can efficiently remove formaldehyde at room temperature.

[0003] CN202310685298 discloses a formaldehyde-removing graphene oxide hydrogel-loaded material, which can efficiently and quickly capture and absorb formaldehyde in the air and react with it to form a stable compound that is harmless to humans.

[0004] CN201910533514 discloses a polymer containing an aminooxy structure and a formaldehyde adsorbent. The formaldehyde adsorbent realizes reversible chemical adsorption of formaldehyde gas in the absence of a catalyst at room temperature and pressure. Combined with the high specific surface area of ​​the carrier and the three-dimensional porous structure of the foam, it can be used to specifically and efficiently adsorb gaseous formaldehyde. Moreover, formaldehyde can be desorbed under the action of dilute hydrochloric acid, making the formaldehyde adsorbent reusable.

[0005] Both of the above patents adopt the adsorption method, and graphene oxide hydrogel and aminooxy structure polymer are used as adsorbents, which have the problems of limited adsorption capacity and adsorption saturation. Summary of the invention

[0006] The present invention aims to overcome the above-mentioned problems existing in the room temperature formaldehyde removal catalyst in the prior art, and provides a room temperature formaldehyde removal catalyst and its preparation method and application. The perylene derivative is loaded on a carbon-based material, which can have an excellent catalytic oxidation effect on formaldehyde and can achieve long-term formaldehyde removal without significantly reducing the efficiency.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions: In a first aspect, the present invention provides a room temperature formaldehyde removal catalyst, comprising a carbon-based material and a perylene derivative supported on the carbon-based material; the mass ratio of the perylene derivative to the carbon-based material is 5:1 to 1:50.

[0008] The present invention loads a perylene derivative containing a perylene ring structure on a carbon-based material. The obtained catalyst has an excellent catalytic oxidation effect on formaldehyde and can effectively oxidize and remove formaldehyde at room temperature. Compared with traditional formaldehyde removal materials that rely on the adsorption effect of carbon-based materials, the catalyst in the present invention does not have the problems of limited adsorption capacity and adsorption saturation, has high removal efficiency, and has a long service life. It can achieve long-term formaldehyde removal without significantly reducing the efficiency.

[0009] Preferably, the perylene derivative is a substance containing a 3,4,9,10-perylenetetracarboxylic acid diimide structure.

[0010] Preferably, the carbon-based material is selected from one or more of graphite derivatives, activated carbon, carbon nanotubes, and carbon black.

[0011] Preferably, the graphite derivative is selected from one or more of flake graphite, expanded graphite, graphene, graphene oxide, and reduced graphene oxide.

[0012] In a second aspect, the present invention provides a method for preparing the above-mentioned room temperature formaldehyde removal catalyst, comprising the steps of: mixing and grinding or ultrasonically stirring a perylene derivative and a carbon-based material to obtain the room temperature formaldehyde removal catalyst.

[0013] Preferably, the mixing and grinding time is 2 to 200 hours, and the ultrasonic stirring time is 2 to 100 hours.

[0014] Preferably, the mixed grinding is wet grinding or dry grinding; a solvent is added during wet grinding, and a grinding aid is added during dry grinding.

[0015] Preferably, the mass ratio of the solvent added during wet grinding to the carbon-based material is 1:20 to 20:1; the solvent is selected from one or more of water, hydrochloric acid, ethanol, N-methylpyrrolidone, acetone, and propylene glycol methyl ether.

[0016] More preferably, the mass ratio of the solvent added during wet grinding to the carbon-based material is 1:1 to 10:1.

[0017] Preferably, the mass ratio of the grinding aid added during dry grinding to the carbon-based material is 1:10 to 10:1; the grinding aid is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, calcium carbonate, sodium sulfite, titanium dioxide, aluminum silicate, and ceramic powder.

[0018] More preferably, the mass ratio of the grinding aid added during dry grinding to the carbon-based material is 1:2 to 5:1.

[0019] In a third aspect, the present invention provides an application of the above-mentioned room temperature formaldehyde removal catalyst in a room temperature formaldehyde removal reaction.

[0020] Therefore, the present invention has the following beneficial effects: the catalyst of the present invention has excellent catalytic oxidation effect on formaldehyde, can effectively oxidize and remove formaldehyde at room temperature, and compared with traditional formaldehyde removal materials relying on adsorption, there is no problem of limited adsorption capacity and adsorption saturation, etc., the removal efficiency is high, the service life is long, and long-term formaldehyde removal can be achieved. DETAILED DESCRIPTION

[0021] The present invention is further described below in conjunction with specific implementation methods.

[0022] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments, unless otherwise specified, are conventional methods in the art.

[0023] Overall embodiment: A room temperature formaldehyde removal catalyst comprises a carbon material and a perylene derivative loaded on the carbon material; the mass ratio of the perylene derivative to the carbon material is 5:1-1:50.

[0024] As a specific embodiment, the perylene derivative is a substance containing a perylene ring structure, preferably a substance containing a 3,4,9,10-perylenetetracarboxylic acid diimide structure; the preparation method of the substance containing a 3,4,9,10-perylenetetracarboxylic acid diimide structure adopts the method in patent CN108862264B.

[0025] As a specific implementation, the carbon-based material is selected from one or more of graphite derivatives, activated carbon, carbon nanotubes, and carbon black.

[0026] As a specific embodiment, the graphite derivative is selected from one or more of flake graphite, expanded graphite, graphene, graphene oxide, and reduced graphene oxide.

[0027] The method for preparing the room temperature formaldehyde removal catalyst comprises the following steps: mixing and grinding the perylene derivative and the carbon material or subjecting them to ultrasonic stirring to obtain the room temperature formaldehyde removal catalyst.

[0028] As a specific implementation manner, the mixing and grinding time is 2 to 200 hours, and the ultrasonic stirring time is 2 to 100 hours.

[0029] As a specific implementation, the mixed grinding is wet grinding or dry grinding; a solvent is added during wet grinding, and a grinding aid is added during dry grinding.

[0030] As a specific implementation manner, the mass ratio of the solvent added during wet grinding to the carbon-based material is 1:20 to 20:1, preferably 1:1 to 10:1.

[0031] As a specific implementation, the solvent used in wet grinding is selected from one or more of water, hydrochloric acid, ethanol, N-methylpyrrolidone, acetone, and propylene glycol methyl ether.

[0032] As a specific implementation, the mass ratio of the grinding aid added during dry grinding to the carbon-based material is 1:10 to 10:1; preferably 1:2 to 5:1.

[0033] As a specific implementation, the grinding aid during dry grinding is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, calcium carbonate, sodium sulfite, titanium dioxide, aluminum silicate, and ceramic powder.

[0034] The catalyst of the present invention has excellent catalytic oxidation effect on formaldehyde, and can effectively oxidize and remove formaldehyde at room temperature. Compared with traditional formaldehyde removal materials relying on adsorption, it does not have the problems of limited adsorption capacity and adsorption saturation, etc. It has high removal efficiency and long service life, and can achieve long-term formaldehyde removal.

[0035] Embodiment 1: A room temperature formaldehyde removal catalyst, the preparation method of which is as follows: 1g of N,N-bis(diethylaminopropane)-3,4,9,10-perylenetetracarboxylic acid diimide, 6g of graphene (5-10 layers), 80g of N-methylpyrrolidone and 300g of zirconium beads are put into a grinding jar, planetary ball milled for 120h, filtered, washed and dried to obtain a room temperature formaldehyde removal catalyst A.

[0036] Embodiment 2: A room temperature formaldehyde removal catalyst, the preparation method of which is as follows: 2g of N,N-bis(diethylaminopropane)-3,4,9,10-perylenetetracarboxylic acid diimide, 6g of graphene (5-10 layers), 20g of sodium carbonate and 300g of zirconium beads are put into a grinding jar, and the mixture is ground by planetary ball milling for 120h, and then filtered, washed and dried to obtain a room temperature formaldehyde removal catalyst B.

[0037] Embodiment 3: A room temperature formaldehyde removal catalyst, the preparation method of which is as follows: 1g of N,N-bis(diethylaminopropane)-3,4,9,10-perylenetetracarboxylic acid diimide, 6g of activated carbon (100 mesh), 200g of water, and 0.5g of hydrochloric acid are added into a beaker, ultrasonically treated for 12h, filtered, washed, and dried to obtain a room temperature formaldehyde removal catalyst C.

[0038] Embodiment 4: A room temperature formaldehyde removal catalyst, the preparation method of which is as follows: 1 g of 3,4,9,10-perylenetetracarboxylic dianhydride, 6 g of graphene (5-10 layers), 80 g of N-methylpyrrolidone and 300 g of zirconium beads are put into a grinding jar, and the mixture is ground by planetary ball milling for 120 hours, and then filtered, washed and dried to obtain a room temperature formaldehyde removal catalyst D.

[0039] Embodiment 5: A room temperature formaldehyde removal catalyst, the preparation method of which is as follows: 1g of N,N-bis(dimethylaminoethane)-3,4,9,10-perylenetetracarboxylic acid diimide, 6g of expanded graphite (1000 mesh), 64g of water, 16g of ethanol and 300g of zirconium beads are put into a grinding jar, the mixture is subjected to planetary ball milling for 120h, and the room temperature formaldehyde removal catalyst E is obtained by filtering, washing and drying.

[0040] Application Example 1: 0.1 g of the room temperature formaldehyde removal catalyst A prepared in Example 1 was added to a VOCs catalyst evaluation microreactor (reaction temperature 25°C, gas flow rate 100 mL / min, formaldehyde concentration 1 ppm). After running for 48 hours, the formaldehyde removal rate was 94.2%; after running for 50 days, the formaldehyde removal rate was 93.5%.

[0041] Application Example 2: 0.1 g of the room temperature formaldehyde removal catalyst B prepared in Example 2 was added to a VOCs catalyst evaluation microreactor (reaction temperature 25°C, gas flow rate 100 mL / min, formaldehyde concentration 1 ppm). After running for 48 hours, the formaldehyde removal rate was 68.4%; after running for 50 days, the formaldehyde removal rate was 60.3%.

[0042] Application Example 3: 0.1 g of the room temperature formaldehyde removal catalyst C prepared in Example 3 was added to a VOCs catalyst evaluation microreactor (reaction temperature 25°C, gas flow rate 100 mL / min, formaldehyde concentration 1 ppm). After running for 48 hours, the formaldehyde removal rate was 65.7%; after running for 50 days, the formaldehyde removal rate was 51.5%.

[0043] Application example 4: 0.1 g of the room temperature formaldehyde removal catalyst D prepared in Example 4 was added to a VOCs catalyst evaluation microreactor (reaction temperature 25°C, gas flow rate 100 mL / min, formaldehyde concentration 1 ppm). After running for 48 hours, the formaldehyde removal rate was 24.6%; after running for 50 days, the formaldehyde removal rate was 9.4%.

[0044] Application Example 5: 0.1 g of the room temperature formaldehyde removal catalyst E prepared in Example 5 was added to a VOCs catalyst evaluation microreactor (reaction temperature 25°C, gas flow rate 100 mL / min, formaldehyde concentration 1 ppm). After running for 48 hours, the formaldehyde removal rate was 51.2%; after running for 50 days, the formaldehyde removal rate was 44.8%.

[0045] It can be seen from the test results in the above application examples that the catalyst prepared by the method of the present invention has a good formaldehyde removal effect at room temperature, and after a long time (50 days) of operation, the efficiency of formaldehyde removal has not been significantly reduced. Compared with traditional formaldehyde removal materials that rely on adsorption, it has a long service life.

[0046] Moreover, in Example 1, when the perylene derivative uses N,N-bis(diethylaminopropane)-3,4,9,10-perylenetetracarboxylic acid diimide, the carbon-based material uses graphene, and the perylene derivative is loaded on the carbon-based material by wet grinding, the catalyst has the best formaldehyde removal effect at room temperature. In Example 2, the types of perylene derivatives and carbon-based materials remain unchanged, and when the perylene derivative is loaded on the carbon-based material by dry grinding, the formaldehyde removal effect of the catalyst is significantly reduced compared with the wet grinding method in Example 1. In Example 3, activated carbon is used instead of graphene as the carbon-based material, and the formaldehyde removal effect of the catalyst is reduced compared with that in Example 1, and the decrease in formaldehyde removal rate after long-term operation is also more obvious than that in Example 1. In Example 4, 3,4,9,10-perylenetetracarboxylic acid dianhydride was used instead of N,N-bis(diethylaminopropane)-3,4,9,10-perylenetetracarboxylic acid diimide as the perylene derivative, and the formaldehyde removal effect of the catalyst was significantly reduced compared with that in Example 1; the formaldehyde removal rate was also significantly reduced after 50 days of operation, and the service life was significantly reduced compared with that in Example 1. In Example 5, expanded graphite was used instead of graphene as the carbon material, and the formaldehyde removal effect of the catalyst was also reduced compared with that in Example 1. It can be seen that the type of perylene derivative, the type of carbon material, and the loading method of perylene derivative on carbon material all have an impact on the room temperature formaldehyde removal effect of the catalyst.

[0047] Although specific embodiments have been used to illustrate the invention, it is understood that the above embodiments are used to understand the methods and core matters of the present invention and cannot be understood as limitations on the present invention. A person of ordinary skill in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and purpose of the present invention. Any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention shall be deemed to be within the protection scope of the present invention.

Claims

1. A room temperature formaldehyde removal catalyst, characterized in that: It includes carbon-based materials and perylene derivatives loaded on the carbon-based materials; the mass ratio of the perylene derivatives to the carbon-based materials is 5:1-1:

50.

2. The room temperature formaldehyde removal catalyst according to claim 1, characterized in that: The perylene derivative is a substance containing a 3,4,9,10-perylenetetracarboxylic acid diimide structure.

3. The room temperature formaldehyde removal catalyst according to claim 1 or 2, characterized in that: The carbon-based material is selected from one or more of graphite derivatives, activated carbon, carbon nanotubes, and carbon black.

4. The room temperature formaldehyde removal catalyst according to claim 3, characterized in that: The graphite derivative is selected from one or more of flake graphite, expanded graphite, graphene, graphene oxide, and reduced graphene oxide.

5. A method for preparing a room temperature formaldehyde removal catalyst as claimed in any one of claims 1 to 4, characterized in that the steps are: mixing and grinding or ultrasonically stirring a perylene derivative and a carbon-based material to obtain the room temperature formaldehyde removal catalyst.

6. The method for preparing the room temperature formaldehyde removal catalyst according to claim 5, characterized in that: The mixing and grinding time is 2~200h, and the ultrasonic stirring time is 2~100h.

7. The method for preparing a room temperature formaldehyde removal catalyst according to claim 5 or 6, characterized in that: Mixed grinding can be wet grinding or dry grinding; solvents are added during wet grinding, and grinding aids are added during dry grinding.

8. The method for preparing the room temperature formaldehyde removal catalyst according to claim 7, characterized in that: The mass ratio of the solvent added during wet grinding to the carbon-based material is 1:20-20:1; the solvent is selected from one or more of water, hydrochloric acid, ethanol, N-methylpyrrolidone, acetone, and propylene glycol methyl ether.

9. The method for preparing a room temperature formaldehyde removal catalyst according to claim 7, characterized in that: The mass ratio of the grinding aid added during dry grinding to the carbon material is 1:10~10:1; the grinding aid is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, calcium carbonate, sodium sulfite, titanium dioxide, aluminum silicate, and ceramic powder.

10. Use of a room temperature formaldehyde removal catalyst as claimed in any one of claims 1 to 4, characterized in that: Applicable to formaldehyde removal reaction at room temperature.