Graphene oxide cation anti-haze agent

Abstract

The invention discloses a graphene oxide cationic anti-haze agent, and relates to the technical field of air pollution abatement, and the graphene oxide cationic anti-haze agent comprises the following raw materials by mass: 6-60% of highly substituted cationic starch; 0.01 to 1 percent of graphene oxide; 1 to 10% of N, N-dimethyl formamide; 0.5 to 10 percent of cationic polyvinylpyrrolidone; 0.1%-1% of an antioxidant; 0.1 to 3 percent of halogenated ammonium salt; 0.1 to 3 percent of a cosolvent; 1.0 to 20 percent of low carbon polyol; 0.1 to 10 percent of methylal; 5.0%-50% of absolute ethyl alcohol; 5.0 to 60 percent of deionized water; when being sprayed (atomized) in the atmosphere with serious haze, the haze-removing agent can destroy negatively charged aerosol, generate demulsification and accelerate coagulation and sedimentation of positively charged particles, so that the air quality is improved, the haze is eliminated, and transparent and fresh air is restored.

Description

Technical Field

[0001] The present invention relates to the technical field of air pollution control, and in particular to a graphene oxide cationic anti-haze agent. Background Art

[0002] The United States proposed the PM2.5 standard in 1997, mainly to monitor PM2.5 particles that are harmful to the human body. The PM2.5 index has become an important index for measuring and controlling the degree of air pollution.

[0003] Haze is primarily composed of sulfur dioxide, nitrogen oxides, and inhalable particulate matter. Inhalable particulate matter, particularly PM2.5 (particles with an aerodynamic equivalent diameter of 2.5 microns or less), is considered the primary culprit. These particles are both pollutants themselves and carriers of toxic substances such as heavy metals and polycyclic aromatic hydrocarbons.

[0004] The deadly "killer" of haze is the production of aerosol ultrafine particles, which come from two sources: natural sources and human activities. Natural sources include smoke from volcanic eruptions, soil particles blown by the wind, and tiny particles and cosmic dust produced by meteor burning. The main source is man-made, including industrial waste gas produced by the combustion of coal, oil and other minerals, and exhaust emissions from motor vehicles, including dust, sulfuric acid, nitric acid, organic hydrocarbons, heavy metals and other particles dispersed into the air, which form secondary pollutants through a series of photochemical reactions.

[0005] my country's current main measures to prevent smog include: accelerating the adjustment of energy structure; solving the problem of coal combustion pollution; strengthening emission management of steel, oil refining, etc.; increasing pollution control of motor vehicles and upgrading of oil products; and strengthening environmental pollution supervision.

[0006] Refer to patent 1, application number: CN201922446691.9, inventor He Jun, "A haze elimination and purification device in the field of environmental protection", discloses a haze elimination and purification device in the field of environmental protection, a first filter component and a second filter component are respectively arranged at the air inlet and the air outlet of the purification box body, when the air enters the purifier, the air is filtered once, and when the air leaves the purification device, the air is purified again, thereby enhancing the ability of the haze purification device to purify the air, and a driving component is arranged in the purification device to increase the air circulation speed of the purification device, thereby improving the air purification efficiency of the purification device; the first filter component is supported by a support component, and when the first filter component is loose, the support component can support the filter component, so that the first filter component maintains a relatively fixed position with the purification box body, that is, when the first filter component is loose, it will not affect the purification ability of the haze elimination and purification device provided by the embodiment of the utility model.

[0007] Refer to Patent 2, Publication (Announcement) No.: CN211677109U, inventor Wang Quanling, "A City Street Air Pollutant Removal Vehicle" discloses a city street air pollutant removal vehicle, in which the motor vehicle is equipped with an air pollutant absorption and treatment device, and the air pollutant absorption and treatment device is equipped with an atmospheric particulate pollutant elimination device and / or an atmospheric harmful gas pollutant elimination device. Due to the strong mobility of the city street air pollutant removal vehicle, the city street air pollutant removal vehicle can quickly and centrally treat air pollutants in urban streets and even urban industrial areas, reduce the content of dust, floating dust, PM2.5 and toxic and harmful gases in the urban atmosphere, and reduce the probability of large-scale smog weather. By improving the overall quality of the urban atmosphere, the health rate of the entire population has been improved and the corresponding medical expenses have been reduced, which has great environmental significance.

[0008] Through reviewing the above patents, various prevention and treatment methods for haze are mainly concentrated in the fields of protective hygiene products (masks), coatings, material adsorption, air purification devices, etc., which are local preventive measures. There are no specific methods for the atmosphere polluted by haze, and the R&D capabilities are relatively insufficient. In particular, there are few patents for the research on haze elimination agents in the air, and they remain in the scientific research stage.

[0009] The market is in urgent need of a product and method that can effectively remove air that has already formed serious haze pollution, and the present invention is developed for this purpose. Purpose of the Invention

[0010] The present invention mainly addresses the shortcomings of existing technologies and the urgent need for haze control. It can be sprayed in the atmosphere with severe haze to break up the negatively charged aerosol and accelerate the coagulation and sedimentation of positively charged particles, thereby improving air quality and effectively controlling haze to meet people's needs for environmental protection and health. Technical Solution

[0011] The present invention mainly aims at the deficiencies of the existing technology and provides a graphene oxide cationic anti-haze agent.

[0012] In order to achieve the above object, the present invention adopts the following technical solutions: A graphene oxide cationic anti-haze agent, composed of the following raw materials in percentage by mass:

[0013] The highly substituted cationic starch is a type of modified starch with a high degree of substitution, in which cationic groups are introduced into starch molecules. It is obtained by reacting the primary hydroxyl groups in the glucose residues of starch with an etherifying agent (tertiary amino compounds, quaternary amino compounds and imine compounds) under the catalytic action of an alkali.

[0014] Specifically, the high-substitution cationic starch uses 3-chloro-2-hydroxypropyltrimethylammonium chloride as a cationic etherifying agent to react with starch to prepare a high-substitution quaternary ammonium cationic starch ether, and the cationic high-substitution starch with a substitution degree between 0.1 and 0.7 is selected.

[0015] The graphene oxide: Graphene oxide has an extremely large specific surface area and a rich pore structure, which provides it with excellent adsorption performance. Its oxygen-containing functional groups (such as hydroxyl, epoxy, carboxyl, etc.) disperse it and form a stable colloidal solution, thereby effectively adsorbing various pollutants. At the same time, graphene oxide can complex with heavy metal ions through the oxygen-containing functional groups on its surface, thereby adsorbing heavy metal ions in the air, such as copper, zinc, cobalt, nickel, lead, etc. Graphene oxide can also adsorb toxic gas molecules such as formaldehyde and PM2.5 through electrostatic adsorption, dispersion interaction, van der Waals force, and charge transfer.

[0016] Specifically, the chemical methods for preparing graphene oxide mainly include Brodie method, Staudenmaier method and Hummers method for preparing graphite oxide, and specifically the graphene oxide prepared by Hummers is used.

[0017] The N,N-dimethylformamide: N,N-dimethylformamide (DMF) is a polar organic solvent with good solubility and dispersibility, and can effectively disperse graphene oxide to form a stable system.

[0018] The cationic polyvinyl pyrrolidone is prepared by introducing cationic groups into the PVP molecular chain. It is a variant of polyvinyl pyrrolidone (PVP) and a cationic polymer compound. PVP itself is non-ionic, but through chemical modification, cationic groups can be introduced into its molecular chain to obtain cationic PVP. Cationic PVP can also be used as an aerogel formed by haze to demulsify, flocculate or precipitate, thereby promoting the precipitation of haze particles. The cationic property enables it to effectively combine with negatively charged pollutants, thereby achieving efficient gas-solid separation. Cationic PVP can be used as a flocculant to promote the aggregation and sedimentation of suspended particles in the air through charge neutralization and bridging effects.

[0019] Specifically, the cationic polyvinyl pyrrolidone has a molecular weight between 4400 and 8500, and the alkyl halide ammonium salt is selected from one of hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, and dodecyltrimethylammonium bromide.

[0020] The antioxidants include 2,6-di-tert-butyl-p-cresol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy)benzene, 4-hydroxydodecanoic acid anilide, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-di-tert-octyldiphenylamine, etc. Specifically, one of them or a mixture of two or more in any proportion is used.

[0021] The halide ammonium salt is preferably one of benzalkonium chloride, cetylpyridinium chloride, and cetyl ammonium bromide, or a mixture of two or more of the two in any proportion.

[0022] The cosolvents include Tween-80, Tween-60, Tween-20, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, peregal, TX-10, AEO7, dodecylamine oxide, and hexadecylbenzylammonium chloride, and one or a mixture of two or more of them in any proportion can be used.

[0023] The low-carbon polyol is selected from one of ethylene glycol, propylene glycol, glycerol, butanediol, and tetrahydrofuran, or a mixture of two or more of them in any proportion.

[0024] Specifically, the low-carbon polyol is a mixture of any two of ethylene glycol, propylene glycol, glycerol, butylene glycol, and tetrahydrofuran in a ratio of 1:1; or, the low-carbon polyol is a mixture of any three of ethylene glycol, propylene glycol, glycerol, butylene glycol, and tetrahydrofuran in a ratio of 1:1:1.

[0025] The methylal has the function of enhancing the use effect in the product, reducing the amount of co-solvent and anhydrous ethanol in the formula, and the methylal content is ≥99.5%.

[0026] The anhydrous ethanol is food grade anhydrous ethanol with a content of ≥98%; the deionized water is ultrapure water with a resistivity of ≥18.2MQ·cm (25° C.).

[0027] A graphene oxide cationic anti-haze agent comprises the following processing steps: Step A: Add anhydrous ethanol, low-carbon polyol, cosolvent and antioxidant into a stainless steel stirring and homogenizing reactor and start stirring until they are completely dissolved. Step B, continue stirring, add deionized water, and then add methylal, N,N-dimethylformamide, halogenated ammonium salt, and cationic polyvinylpyrrolidone in sequence. After dissolution, slowly add graphene oxide while stirring rapidly. After adding, turn on the averaging system and adjust the homogenization rate to 2000 rpm. Stop homogenizing after 5 minutes and continue stirring until uniformly dispersed. Step C: slowly add the highly substituted cationic starch while stirring rapidly. After adding, turn on the homogenization system and adjust the homogenization speed to 2500 rpm. Stop homogenizing after 5 minutes and continue stirring until it is completely dissolved and dispersed to obtain the finished product.

[0028] The present invention has the following beneficial effects

[0029] The present invention is a graphene oxide cationic anti-haze agent. When sprayed (atomized) in an atmosphere with severe haze, the product can destroy negatively charged aerosols, produce demulsification, and accelerate the coagulation and sedimentation of positively charged particles, thereby improving air quality, eliminating haze, and restoring transparent and fresh air.

[0030] In addition, the present invention also has the following advantages: 1. The product has good stability and is miscible with water at any ratio. It is suitable for deployment under different PM2.5 index conditions and has strong operability. 2. Easy to use: It can be sprayed by manual water cannon spraying; drone aerial spraying or targeted artillery shell technology (similar to artificial rainfall technology) spraying; ultrasonic technology can be used to form mist droplets for better effect during spraying. 3. The product is non-toxic and non-irritating, has no effect on soil, plants, animals, water, and human body, will not cause secondary pollution, and is environmentally friendly. DETAILED DESCRIPTION

[0031] The present invention will be further described below with reference to the embodiments.

[0032] Example 1

[0033] A graphene oxide cationic anti-haze agent is composed of the following raw materials in percentage by mass: 40% of highly substituted cationic starch; 0.5% of graphene oxide; 1% of N,N-dimethylformamide; 1.5% of cationic polyvinyl pyrrolidone; 0.1% of 2,6-di-tert-butyl-p-cresol; 2% of cetylpyridinium chloride; 0.5% of Tween-20; 3% of ethylene glycol; 1% of methylal; 30% of anhydrous ethanol; and 20.4% of deionized water.

[0034] A graphene oxide cationic anti-haze agent comprises the following processing steps: Step A: In a 120L stainless steel stirring homogenizing reactor, add 30kg of anhydrous ethanol, 3kg of ethylene glycol, 0.5kg of Tween-20, and 0.1kg of 2,6-di-tert-butyl-p-cresol and stir until completely dissolved. Step B, continue stirring, add 20.4 kg of deionized water, then add 1 kg of methylal, 1 kg of N, N-dimethylformamide, 2 kg of cetylpyridinium chloride, and 1.5 kg of cationic polyvinyl pyrrolidone in sequence. After complete dissolution, slowly add 0.5 kg of graphene oxide while stirring rapidly. After adding, turn on the averaging system, adjust the homogenization rate to 2000 rpm, stop homogenizing after 5 minutes, and continue stirring until uniformly dispersed. Step C: slowly add 40 kg of highly substituted cationic starch while stirring rapidly. After the addition is complete, turn on the homogenization system and adjust the homogenization rate to 2500 rpm. Stop homogenizing after 5 minutes and continue stirring until it is completely dissolved and dispersed to obtain the finished product.

[0035] Example 2

[0036] A graphene oxide cationic anti-haze agent is composed of the following raw materials in percentage by mass: 30% of highly substituted cationic starch; 0.8% of graphene oxide; 5% of N,N-dimethylformamide; 5% of cationic polyvinylpyrrolidone; 0.2% of 4-hydroxydodecanoic acid anilide; 3% of cetyl ammonium bromide; 1.5% of Tween-60; 5% of propylene glycol; 3% of methylal; 20% of anhydrous ethanol; and 26.5% of deionized water.

[0037] The processing steps of this embodiment are the same as those of embodiment 1 and will not be repeated here.

[0038] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the invention.

Claims

1. A graphene oxide cationic anti-haze agent, characterized in that The product is composed of the following raw materials in percentage by mass: The method comprises the following processing steps: step A, adding anhydrous ethanol, a low-carbon polyol, a cosolvent, and an antioxidant into a reaction kettle with a stainless steel belt for stirring and homogenizing, and stirring until completely dissolved; step B, continuing stirring, adding deionized water, and then sequentially adding methylal, N,N-dimethylformamide, a halide ammonium salt, and cationic polyvinyl pyrrolidone; after dissolution, slowly adding graphene oxide while rapidly stirring; after adding, turning on a homogenizing system, adjusting the homogenizing rate to 2000 rpm, homogenizing for 5 minutes, stopping, and continuing to stir until uniformly dispersed; and step C, slowly adding high-substitution cationic starch while rapidly stirring; after adding, turning on a homogenizing system, adjusting the homogenizing rate to 2500 rpm, homogenizing for 5 minutes, stopping, and continuing to stir until completely dissolved and dispersed, thereby obtaining a finished product.

2. According to claim 1, it is characterized in that: The high-substitution cationic starch uses 3-chloro-2-hydroxypropyltrimethylammonium chloride as a cationic etherifying agent to react with starch to prepare a high-substitution quaternary ammonium cationic starch ether, and the cationic high-substitution starch with a substitution degree between 0.1 and 0.7 is selected.

3. According to claim 1, it is characterized in that: The chemical methods for preparing graphene oxide mainly include Brodie method, Staudenmaier method and Hummers method for preparing graphite oxide, and specifically the graphene oxide prepared by Hummers is used.

4. According to claim 1, it is characterized in that: The cationic polyvinyl pyrrolidone is selected from polyvinyl pyrrolidone with a molecular weight between 4400 and 8500, and the alkyl halide ammonium salt is selected from one of hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride and dodecyltrimethylammonium bromide.

5. According to claim 1, it is characterized in that: The halide ammonium salt is preferably one of benzalkonium chloride, cetylpyridinium chloride, and cetyl ammonium bromide, or a mixture of two or more of the two in any proportion.

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