CN112500795B

CN112500795B - Preparation process of wall clothing with formaldehyde removal function

Info

Publication number: CN112500795B
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: 2023-10-03
Anticipated expiration: 2040-10-23
Also published as: CN112500795A

Abstract

The invention discloses a wall coating preparation process with formaldehyde removal function, which comprises the steps of adding ZnO/N-rGO compound with ZnO nano rod array, wherein the ZnO/N-rGO compound has a unique three-dimensional porous frame structure and a larger specific surface area, so that higher light utilization rate can be brought, better formaldehyde adsorption capacity and superior photo-generated charge separation efficiency are achieved, 3D N-rGO porous material can be used as a good support material, separation of electron-hole pairs and active sites for formaldehyde capture and oxidation are promoted, thus improving the efficiency of photocatalytic reaction, enabling ZnO/N-rGO to decompose formaldehyde into carbon dioxide and water under irradiation of visible light, further eliminating formaldehyde, and graphene has a unique three-dimensional hollow structure, so that the coating prepared after graphene modification has better physical isolation and waterproof effect, and the graphene has excellent mechanical property and chemical stability, better scratch resistance and wear resistance, and the service life of the coating is prolonged.

Description

Preparation process of wall clothing with formaldehyde removal function

Technical Field

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

Background

With the improvement of the living standard of people, more and more people pay attention to the quality of house decoration, in general house decoration, materials such as plywood, joinery board and the like, interior wall paint and the like are needed, and furniture, cloth furniture and kitchen furniture are also indispensable, and formaldehyde is generated, and harmful substances such as benzene, heavy metal, VOC and the like are also generated.

Formaldehyde is a colorless, strongly irritating gas, readily soluble in water, alcohols and ethers, is a well-known source of allergy and one of the potential strong mutagens, and long-term exposure to low doses of formaldehyde can cause chronic respiratory disease, cause nasopharyngeal carcinoma, colon cancer, brain tumor, menstrual disorder, and nuclear gene mutation, and in all contactors, children and pregnant women are particularly sensitive to formaldehyde and more harmful, and various methods have been proposed, such as plant absorption, detergent spraying, activated carbon adsorption, and the like. However, the method can eliminate formaldehyde, but has the defects of slow effect, unobvious effect, incomplete removal and the like, so that how to simply and rapidly eliminate indoor formaldehyde and purify indoor air becomes a problem to be solved urgently at present.

The wall coating for removing formaldehyde in the prior art cannot have an effective effect, and is caused by 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 formaldehyde removal 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) and diatomite, can effectively remove effective substances such as formaldehyde, benzene and the like in a room, has higher purification efficiency, and the 3-dimensional structure N-doped redox graphene (3N-rGO) has excellent mechanical property and chemical stability, so that the coating has better scratch resistance and wear resistance mechanical property, thereby prolonging the service life of the coating.

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

preparing graphene oxide solution in the first step: graphene oxide uses natural graphite powder asThe starting material was prepared by a modified Hummers method, the resulting GO suspension had a solubility of 2.3gL ^-1 。

Second step 3D N-rGO synthesis: the melamine sponge was alternately washed six times with ethanol and water under ultrasonic conditions and then dried at 80 degrees for 12 hours. The clean melamine sponge was then immersed in a graphene oxide ethanol solution (the solution comprising 20vol% go suspension and 80vol% ethanol) to ensure that the melamine sponge was able to adequately absorb the graphene oxide ethanol solution and reached saturation. The GO-suspension adsorbed melamine sponge is then calcined in a furnace at a temperature of about 550 degrees for 3 minutes, which allows 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 N-rGO prepared above was immersed in the zinc acetate solution for half an hour. And calcining the soaked N-rGO for 20 minutes in a furnace at 200 ℃ atmosphere to form a uniform seed layer of ZnO nano particles. Subsequently, in forming the N-rGO with seed layer, this mixed solution containing 0.75KG of zinc nitrate hexahydrate, 0.31KG of urea and 0.35KG of Hexamethylenetetramine (HMTA) was immersed in 50L of the mixed solution for a period of 1h. The solution containing N-rGO was then transferred to a stainless steel high pressure reactor and heated to 100 degrees for 12 hours. Finally, the product is washed by high-purity water for three times and then calcined for 1h at 450 ℃ in a furnace with nitrogen atmosphere, so as to remove the residual organic impurities in the product, and the ZnO/N-rGO compound with the ZnO nano rod array is obtained.

70-100 parts of ZnO/N-rGO compound synthesized into the ZnO nano rod array, 80-200 parts of titanium dioxide, 40-550 parts of heavy calcium carbonate, 60-350 parts of diatomite, 0.8-10 parts of flatting agent, 0.5-120 parts of defoamer, 0.6-140 parts of wetting agent and 14-300 parts of natural resin.

Preferably, the wall coating with 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 heavy calcium carbonate, 250 parts of diatomite, 1.5 parts of flatting agent, 19 parts of defoamer, 17 parts of wetting agent and 260 parts of natural resin.

Preferably, the leveling agent is polydimethylsiloxane.

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

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

1. according to the invention, by adding 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, higher light utilization rate can be brought, better formaldehyde adsorption capacity and superior photo-generated charge separation efficiency are achieved, the 3D N-rGO porous material can be used as a good supporting material, separation of electron-hole pairs and active sites for formaldehyde capture and oxidation are promoted, so that the efficiency of photocatalytic reaction is improved, the ZnO/N-rGO can decompose formaldehyde into carbon dioxide and water under the irradiation of visible light, formaldehyde can be eliminated, the graphene has a unique three-dimensional hollow structure, the prepared coating has better physical isolation and waterproof effect, and the graphene has excellent mechanical property and chemical stability, so that the coating has better scratch resistance and wear resistance, and the service life of the coating is prolonged.

2. According to the invention, through the arrangement of the diatomite, the contact rate of pollutants such as titanium dioxide, graphene and formaldehyde can be effectively increased, the diatomite is mainly composed of opal, and is rich in various beneficial minerals, the texture is light and soft, an electron microscope shows that the diatomite ion surface has countless tiny holes, the porosity is more than 90%, the specific surface area is as high as 65m < 2 >/g, and the diatomite has stronger physical adsorption performance and ion exchange performance, so that the contact rate of the pollutants such as titanium dioxide, graphene and formaldehyde is increased under the action of the diatomite, thereby effectively eliminating free formaldehyde, benzene and other harmful substances in the air, releasing negative oxygen ions, purifying the air, and improving the purification effect and purification efficiency.

3. In summary, through the organic cooperation of three-dimensional N-doped graphene, nano zinc oxide array and diatomite and other related structures, effective substances such as formaldehyde and benzene in a room can be effectively eliminated, meanwhile, the purification efficiency is higher, in addition, graphene has excellent mechanical properties and chemical stability, so that the paint has better scratch-resistant and wear-resistant mechanical properties, the service life of the paint is prolonged, and the paint manufacturing process flow comprises formula feeding, dispersing, milling, paint mixing and filtering packaging, so that the paint is simple and convenient to produce and manufacture, has lower cost and better application prospect.

Drawings

FIG. 1 is a microstructure of a three-dimensional nitrogen element hollow redox graphene of the present invention;

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

Detailed Description

The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

By taking the optimal proportion as an example, the wall coating with the formaldehyde removing function is added, and comprises the following raw materials in parts by weight: 80 parts of ZnO/N-rGO compound, 130 parts of titanium dioxide, 410 parts of heavy calcium carbonate, 250 parts of diatomite, 1.5 parts of flatting agent, 19 parts of defoamer, 17 parts of wetting agent and 260 parts of natural resin.

The leveling agent is polydimethylsiloxane, the weight part of the polydimethylsiloxane is 1.5 parts, the defoaming agent is simethicone defoaming agent, the weight part of the simethicone defoaming agent is 19 parts, the wetting agent is glycerin, and the weight part of the glycerin is 17 parts.

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

Working principle: when the formaldehyde-removing wall coating added with the ZnO/N-rGO compound with the ZnO nano rod array is used, through the arrangement of the ZnO/N-rGO, firstly, the N-rGO has a special three-dimensional porous skeleton structure, so that the ZnO/N-rGO compound can be used as an ideal catalyst carrier, and the growth of the ZnO nano rod array on the surface of the formaldehyde-removing wall coating is facilitated. These uniform and compact ZnO nanowire arrays grown on the N-rGO surface provide more interfacial contact, speeding up carrier migration 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, so that the photo-generated electrons generated on the ZnO conduction band are more prone to transfer to N-rGO, and holes remain on the valence band of ZnO, resulting in efficient electron-hole separation. More importantly, the doping energy of N element is disclosed in the prior art to greatly influence the spin density and charge distribution of C atoms, and the formation of an 'activation region' can be induced on the surface of graphene. Graphite N in N-rGO can form an activation region for electron migration, which is favorable for electrons to rapidly and effectively move from ZnO to N-rGO and then transfer to pyrrole N and pyridine N. This efficient electron transfer channel can be considered as an expressway of electron transport, and can greatly improve the charge separation efficiency. On the other hand, pyrrole N and pyridine N are at the edge or defect site of N-rGO and can act as active sites for formaldehyde molecule capture and activation, since they can form strong interactions with formaldehyde molecules through lewis acid bases 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 can effectively oxidize 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 molecular diffusion kinetics and enhance the effective utilization rate of light. The wall coating can decompose formaldehyde into carbon dioxide and water under the irradiation of visible light, formaldehyde can be eliminated, the contact rate of the compound and formaldehyde and other pollutants can be effectively increased through the arrangement of diatomite, the main component of the diatomite is opal, the diatomite is rich in various beneficial minerals, the texture is soft, an electron microscope shows that the diatomite ion surface has numerous tiny holes, the porosity is high, the specific surface area is high, the physical adsorption performance and the ion exchange performance are relatively strong, the contact rate of the compound and formaldehyde and other pollutants is increased under the action of the diatomite, thereby the free formaldehyde, benzene and other harmful substances 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, the graphene has the unique structure, the paint prepared after the graphene is modified has relatively good physical isolation and waterproof effect, and the graphene has excellent mechanical property and chemical stability, so that the paint has relatively good scratch resistance and wear resistance, and the service life is further prolonged.

Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein 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 formaldehyde removal function is characterized by comprising the following steps: the composite comprises the following components of 70-100 parts of ZnO nano rod array and three-dimensional nitrogen doped hollow redox graphene composite, 80-200 parts of titanium dioxide, 40-550 parts of heavy calcium carbonate, 60-350 parts of diatomite, 0.8-10 parts of flatting agent, 0.5-120 parts of defoaming agent, 0.6-140 parts of wetting agent and 14-300 parts of natural resin;

the preparation process of the redox graphene composite comprises the following steps:

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

Second step 3D N-rGO synthesis: alternately cleaning melamine sponge with ethanol and water for six times under ultrasonic conditions, drying at 80 ℃ for 12 hours, immersing clean melamine sponge into graphene oxide ethanol solution, wherein the solution comprises 20vol% of GO suspension and 80vol% of ethanol, ensuring that the melamine sponge can fully absorb the graphene oxide ethanol solution and reach a saturated state, and calcining the melamine sponge adsorbed with the GO suspension in a furnace at 550 ℃ for 3 minutes to obtain 3D N-rGO;

thirdly, synthesizing ZnO/N-rGO: firstly, 220kg zinc acetate dihydrate is dissolved in 100L ethanol solution, then the N-rGO prepared above is immersed in the zinc acetate solution for half an hour, the immersed N-rGO is calcined for 20 minutes in a furnace under 200 ℃ atmosphere to form a uniform seed layer of ZnO nano particles, then the N-rGO with the seed layer is immersed in 50L mixed solution, the mixed solution contains 0.75kg zinc nitrate hexahydrate, 0.31kg urea and 0.35kg Hexamethylenetetramine (HMTA), the immersion time is 1h, and then the solution containing the N-rGO is transferred into a stainless steel high-pressure reaction furnace, and 100 ℃ water is heated for 12 hours; finally, the product is washed three times by high-purity water and calcined at 450 ℃ in a furnace filled with nitrogen atmosphere for 1h, so as to remove residual organic impurities in the product, and a ZnO/N-rGO compound with a ZnO nano rod array is obtained.

2. The wall coating preparation process with formaldehyde removal function according to claim 1, wherein the process is characterized in that: the ratio is that the ZnO nano rod array and the three-dimensional nitrogen doped hollow redox graphene compound are 80 parts, 130 parts of titanium dioxide, 410 parts of heavy calcium, 250 parts of diatomite, 1.5 parts of flatting agent, 19 parts of defoamer, 17 parts of wetting agent and 260 parts of natural resin.

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

4. A process for preparing a wall covering with formaldehyde removal function according to claim 3, characterized in that: the defoamer is simethicone defoamer, and the weight part of the simethicone defoamer is 19 parts.

5. The process for preparing the wall coating with formaldehyde removing function according to claim 4, wherein the process comprises the following steps: the wetting agent is glycerin, and the weight part of glycerin is 17 parts.