CN112500795A

CN112500795A - Preparation process of wall covering with formaldehyde removing function

Info

Publication number: CN112500795A
Application number: CN202011142020.4A
Authority: CN
Inventors: 冯国春; 刘华明
Original assignee: Fujian Bimiter Environmental Protection Group Co ltd
Current assignee: Fujian Bimiter Environmental Protection Group Co ltd
Priority date: 2020-10-23
Filing date: 2020-10-23
Publication date: 2021-03-16
Anticipated expiration: 2040-10-23
Also published as: CN112500795B

Abstract

The invention discloses a wall coating preparation process with a formaldehyde removing function in the technical field of wall coatings, wherein a ZnO/N-rGO compound with a ZnO nanorod array is added, the ZnO/N-rGO compound has a unique three-dimensional porous frame structure and a larger specific surface area, can bring higher light utilization rate, better formaldehyde adsorption capacity and superior separation efficiency of photo-generated charges, a 3D N-rGO porous material can be used as an excellent supporting material to promote the separation of electron-hole pairs and can be used as an active site for capturing and oxidizing formaldehyde, so that the efficiency of a photocatalytic reaction is improved, the ZnO/N-rGO can decompose the formaldehyde into carbon dioxide and water under the irradiation of visible light, the formaldehyde can be eliminated, and the graphene has a unique three-dimensional hollow structure, so that the coating prepared by modifying the graphene has a better physical isolation and waterproof effect, in addition, the graphene has excellent mechanical properties and chemical stability, has better scratch-resistant and wear-resistant mechanical properties, and prolongs the service life of the coating.

Description

Preparation process of wall covering with formaldehyde removing function

Technical Field

The invention relates to the technical field of wall coatings, in particular to a preparation process of a wall coating with a formaldehyde removing function.

Background

Along with the improvement of people's standard of living, more and more people focus on the quality of house decoration, and during the house decoration usually, these materials of artificial boards such as plywood, laminated wood board need be used, interior wall coating etc. furniture, cloth art furniture, kitchen furniture are also indispensable in addition, and these all can produce formaldehyde, still can produce harmful substance such as benzene, heavy metal, VOC simultaneously.

Formaldehyde is a colorless gas with strong pungent odor, is easily soluble in water, alcohol and ether, is a well-known allergic reaction source and is one of potential strong mutagens, chronic respiratory diseases can be caused by long-term exposure to low-dose formaldehyde, nasopharyngeal carcinoma, colon cancer, brain tumor, menstrual disorder and gene mutation of cell nucleus are caused, children and pregnant women are particularly sensitive to formaldehyde among all exposure persons, and the harm is larger. However, although the method can eliminate formaldehyde, the method still has the disadvantages of slow effect, unobvious effect, incomplete elimination and the like, so how to simply and rapidly eliminate indoor formaldehyde and purify indoor air becomes a problem to be solved at present.

The catalyst has no effective effect on the wall coating for removing formaldehyde in the prior art, and is caused by the reasons of low electron-hole mobility, small specific surface area and the like of the catalyst provided by the prior art.

Disclosure of Invention

The invention aims to provide a wall coating with a formaldehyde removing function, which has the arrangement of related structures such as hollow 3-dimensional structure nitrogen element (N) doped redox graphene (3N-rGO), nano zinc oxide array (NZO), diatomite and the like, can effectively remove effective substances such as indoor formaldehyde, benzene and the like, and has higher purification efficiency, in addition, the 3-dimensional structure N doped redox graphene (3N-rGO) has excellent mechanical property and chemical stability, so that the coating has better scratch-resistant and wear-resistant mechanical property, thereby prolonging the service life of the coating, the coating manufacturing process flow comprises formula feeding, dispersing, grinding, paint mixing and filtering packaging, the production and manufacturing are simple and convenient, the cost is lower, the coating has the advantage of better application prospect, and the problems of the existing plant absorption method, purifying agent spraying, activated carbon adsorption and the like in the formaldehyde removing process are solved, has the problems of slow effect, unobvious effect and incomplete removal.

In order to realize the purpose, the invention provides a preparation process of a wall coating with a formaldehyde removal function, which comprises the following steps:

preparing a graphene oxide solution in a first step: the graphene oxide is prepared by using natural graphite powder as a raw material through an improved Hummers method, and the solubility of the obtained GO suspension is 2.3gL^-1。

Second step 3D N-rGO synthesis: the melamine sponge was washed six times with ethanol and water alternately under ultrasonic conditions and then dried at 80 degrees for 12 hours. Then, the clean melamine sponge is immersed in the graphene oxide ethanol solution (the solution comprises 20 vol% GO suspension and 80 vol% ethanol), so that the melamine sponge can fully absorb the graphene oxide ethanol solution and reach a saturated state. Subsequently, the melamine sponge with adsorbed GO suspension was calcined in a furnace at a temperature of about 550 degrees for 3 minutes, which enabled sufficient removal of the melamine template to obtain 3D N-rGO.

Thirdly, synthesizing ZnO/N-rGO: the ZnO/N-rGO compound is prepared by a hydrothermal reaction method. First, 220KG of zinc acetate dihydrate was dissolved in 100L of ethanol solution, and then the N-rGO prepared above was immersed in the zinc acetate solution for half an hour. And calcining the soaked N-rGO in a furnace at 200 ℃ for 20 minutes to form a uniform ZnO nanoparticle seed layer. Subsequently, the N-rGO formed with the seed layer was immersed in 50L of a mixed solution containing 0.75KG of zinc nitrate hexahydrate, 0.31KG of urea and 0.35KG of Hexamethylenetetramine (HMTA) for 1 h. Then, the solution containing N-rGO was transferred to a stainless steel high pressure reactor and hydrothermal at 100 ℃ for 12 hours. And finally, washing the product with high-purity water for three times, and calcining the product for 1h at 450 ℃ in a furnace filled with nitrogen atmosphere to remove residual organic impurities in the product, thereby obtaining the ZnO/N-rGO compound with the ZnO nanorod array.

70-100 parts of the synthesized ZnO/N-rGO compound with the ZnO nanorod array, 80-200 parts of titanium dioxide, 40-550 parts of triple superphosphate, 60-350 parts of diatomite, 0.8-10 parts of a flatting agent, 0.5-120 parts of a defoaming agent, 0.6-140 parts of a wetting agent and 14-300 parts of natural resin.

Preferably, the wall coating with the formaldehyde removing function comprises the following raw materials in parts by weight: 80 parts of ZnO/N-rGO compound, 130 parts of titanium dioxide, 410 parts of triple superphosphate, 250 parts of diatomite, 1.5 parts of flatting agent, 19 parts of defoaming agent, 17 parts of wetting agent and 260 parts of natural resin.

Preferably, the leveling agent is polydimethylsiloxane.

Preferably, the defoamer is a dimethicone defoamer and the wetting agent is glycerol.

Compared with the prior art, the invention has the beneficial effects that:

firstly, the invention adds the ZnO/N-rGO compound with the ZnO nano-rod array, the ZnO/N-rGO compound has a unique three-dimensional porous frame structure and a larger specific surface area, can bring higher light utilization rate, better formaldehyde adsorption capacity and superior separation efficiency of photo-generated charges, the 3D N-rGO porous material can be used as an excellent supporting material to promote the separation of electron-hole pairs and be used as an active site for formaldehyde capture and oxidation, thereby improving the efficiency of photocatalytic reaction, leading the ZnO/N-rGO to decompose formaldehyde into carbon dioxide and water under the irradiation of visible light, further eliminating formaldehyde, leading the graphene to have a unique three-dimensional hollow structure, leading the coating prepared after graphene modification to have better physical isolation and waterproof effects, and leading the graphene to have excellent mechanical property and chemical stability, the coating has good mechanical properties of scratch resistance and wear resistance, thereby prolonging the service life of the coating.

The diatomite is mainly composed of opals, is rich in various beneficial mineral substances and has light and soft texture, an electron microscope shows that countless tiny holes are formed in the surface of diatomite ions, the porosity is over 90 percent, the specific surface area is as high as 65m2/g, and the diatomite has strong physical adsorption performance and ion exchange performance, so that the contact rate of the titanium dioxide and the graphene with the formaldehyde and other pollutants is increased under the action of the diatomite, free formaldehyde, benzene and other harmful substances in the air can be effectively eliminated, negative oxygen ions are released, the air is purified, and the purification effect and the purification efficiency are improved.

In conclusion, through the organic matching use of the three-dimensional N-doped graphene, the nano zinc oxide array, the diatomite and other related structures, the effective substances such as formaldehyde, benzene and the like in a room can be effectively eliminated, meanwhile, the purification efficiency is high, in addition, the graphene has excellent mechanical properties and chemical stability, so that the coating has good scratch-resistant and wear-resistant mechanical properties, the service life of the coating is prolonged, and the coating manufacturing process flow comprises the steps of formula feeding, dispersing, grinding, paint mixing, filtering and packaging, the production and the manufacture are simple and convenient, the cost is low, and the coating has good application prospects.

Drawings

Fig. 1 is a microscopic structure view of a three-dimensional nitrogen element hollow redox graphene of the present invention;

FIG. 2 is a microstructure diagram of a ZnO/N-rGO composite sample of the present invention;

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

According to the embodiment with the optimal proportion, the wall coating with the formaldehyde removing function comprises the following raw materials in parts by weight: 80 parts of ZnO/N-rGO compound, 130 parts of titanium dioxide, 410 parts of triple superphosphate, 250 parts of diatomite, 1.5 parts of flatting agent, 19 parts of defoaming agent, 17 parts of wetting agent and 260 parts of natural resin.

The leveling agent is polydimethylsiloxane, the polydimethylsiloxane is 1.5 parts by weight, the defoaming agent is a dimethyl silicone oil defoaming agent, the dimethyl silicone oil defoaming agent is 19 parts by weight, the wetting agent is glycerol, and the glycerol is 17 parts by weight.

The wall coating with the proportion is prepared into a sample for formaldehyde oxidation experiments, and the surface of the sample has an excellent formaldehyde removal function.

The working principle is as follows: when the formaldehyde-removing wall coating added with the ZnO/N-rGO compound with the ZnO nanorod array is used, through the arrangement of ZnO/N-rGO, firstly, the N-rGO has a special three-dimensional porous skeleton structure so that the N-rGO can be used as an ideal catalyst carrier, and the growth of the ZnO nanowire array on the surface of the ZnO nanowire array is facilitated. These ZnO nanowire arrays grown uniformly and compactly on the N-rGO surface provide more interfacial contact, speeding up the transport of carriers between these two components. It is well known that due to the two-dimensional sp2 hybridized pi-conjugated structure and low work function, N-rGO can act as an electron acceptor and transport carrier, and therefore, photo-generated electrons generated on the ZnO conduction band tend to be transferred to N-rGO more, and holes remain on the valence band of ZnO, resulting in efficient electron-hole separation. More importantly, in the prior art, the doping energy of the N element greatly affects the spin density and charge distribution of C atoms, which can induce the formation of an "active region" on the graphene surface. Graphite N in the N-rGO can form an activation region for electron migration, so that electrons can rapidly and effectively move from ZnO to the N-rGO and then are transferred to pyrrole type N and pyridine type N. This highly efficient electron transfer channel can be considered as a highway for electron transport, and can greatly improve the charge separation efficiency. On the other hand, pyrrole N and pyridine N are located at the edge of N-rGO or at the position of defects and can serve as active sites for the capture and activation of formaldehyde molecules, since they can form strong interactions with formaldehyde molecules through lewis acid-base or hydrogen bonds. Thus, both pyrrole N and pyridine N can act as active sites for formaldehyde oxidation reactions. These electrons transferred to the active site are capable of efficiently oxidizing formaldehyde. In addition, the three-dimensional hierarchical porous framework structure has higher specific surface area and pore volume, and can provide more transfer channels to improve the molecular diffusion dynamics and the effective utilization rate of light. The wall coating can decompose formaldehyde into carbon dioxide and water under the irradiation of visible light, and further can eliminate formaldehyde, and through the arrangement of the diatomite, the contact rate of a compound and pollutants such as formaldehyde and the like can be effectively increased, the main component of the diatomite is opal which is rich in various beneficial mineral substances and has light and soft texture, an electron microscope shows that the ion surface of the diatomite has countless tiny holes, high porosity and specific surface area, and stronger physical adsorption performance and ion exchange performance, so that the contact rate of the compound and the pollutants such as formaldehyde and the like is increased under the action of the diatomite, free harmful substances such as formaldehyde, benzene and the like in the air can be effectively eliminated, negative oxygen ions are released, the air is purified, the purification effect and the purification efficiency are improved, and the graphene has a unique structure, so that the coating prepared after the graphene is modified has a better physical isolation waterproof effect, in addition, the graphene has excellent mechanical properties and chemical stability, so that the coating has good scratch-resistant and wear-resistant mechanical properties, and the service life of the coating is prolonged.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. A preparation process of a wall coating with a formaldehyde removing function is characterized by comprising the following steps: the ZnO nano-rod array and the three-dimensional nitrogen-doped hollow redox graphene composite are prepared from, by weight, 70-100 parts of a ZnO nano-rod array and 70-100 parts of a three-dimensional nitrogen-doped hollow redox graphene composite, 80-200 parts of titanium dioxide, 40-550 parts of coarse whiting, 60-350 parts of diatomite, 0.8-10 parts of a flatting agent, 0.5-120 parts of a defoaming agent, 0.6-140 parts of a wetting agent and 14-300 parts of natural resin.

2. The preparation process of the wall coating with the formaldehyde removing function according to claim 1, which is characterized in that: the preferable proportion is that 80 parts of ZnO nanorod array and three-dimensional nitrogen-doped hollow redox graphene compound, 130 parts of titanium dioxide, 410 parts of triple superphosphate, 250 parts of diatomite, 1.5 parts of flatting agent, 19 parts of defoaming agent, 17 parts of wetting agent and 260 parts of natural resin are taken.

3. The preparation process of the wall coating with the formaldehyde removing function according to claim 2, which is characterized in that: the leveling agent is polydimethylsiloxane, and the weight part of the polydimethylsiloxane is 1.5 parts.

4. The preparation process of the wall coating with the formaldehyde removing function according to claim 3, which is characterized in that: the defoaming agent is a dimethyl silicone oil defoaming agent, and the weight part of the dimethyl silicone oil defoaming agent is 19 parts.

5. The preparation process of the wall coating with the formaldehyde removing function according to claim 4, which is characterized in that: the humectant is glycerin, and the weight part of the glycerin is 17 parts.