CN112516787A - Indoor formaldehyde purification material and preparation method thereof - Google Patents
Indoor formaldehyde purification material and preparation method thereof Download PDFInfo
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- CN112516787A CN112516787A CN202011123118.5A CN202011123118A CN112516787A CN 112516787 A CN112516787 A CN 112516787A CN 202011123118 A CN202011123118 A CN 202011123118A CN 112516787 A CN112516787 A CN 112516787A
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Abstract
The invention provides an indoor formaldehyde purification material and a preparation method thereof. The environment-friendly purification material prepared by the invention has rich pores, large and small pore diameters, good adsorption effect on formaldehyde, high formaldehyde decomposition rate and wide application prospect, and can promote the decomposition of formaldehyde through oxidation and catalytic oxidation.
Description
Technical Field
The invention relates to the technical field of formaldehyde purification, in particular to an indoor formaldehyde environment-friendly purification material and a preparation method thereof.
Background
Formaldehyde is a common pollutant in indoor air, and is released from indoor building decorative materials such as artificial boards, products, coatings, carpets and the like. Formaldehyde is a colorless gas with a strong pungent odor at normal temperature and pressure, and is easily soluble in water, alcohols, ethers, and the like. Research has shown that formaldehyde can be released continuously for decades. The World Health Organization (WHO) research shows that the long-term exposure to the high-risk VOC containing formaldehyde and benzene series can cause cancers and leukemia, so that the requirements of purifying the air environment and improving the air quality are urgent in the life of people. According to the civil building indoor environmental pollution control standard and the indoor air quality standard, the content of the formaldehyde is less than or equal to 0.08mg/m3Or less than or equal to 0.1 mg/m3I.e.. ltoreq.80 mg/L or 100mg/L, formaldehyde in fact exceeds the above-mentioned standards severely in many indoor environments.
The existing purification method of formaldehyde in indoor air mainly comprises three methods, wherein the first method is physical adsorption, and formaldehyde adsorption is carried out through an adsorption material; secondly, chemical conversion, namely degrading formaldehyde into non-toxic products such as water, carbon dioxide and the like by using a chemical reagent to perform oxidation, addition, complexation and the like with the formaldehyde so as to achieve the purpose of eliminating indoor formaldehyde pollution; the third is a catalytic oxidation method of formaldehyde, which is divided into a photocatalytic method and a noble metal catalyst catalytic oxidation method. The existing purification method usually adopts one of the methods to be used independently, and the purification effect is poor.
Patent CN109647153A discloses a formaldehyde purification material, which uses nano live ore, coconut carbon, nickel-palladium alloy, alumina, titanium dioxide, bentonite and water-retaining agent as raw materials for preparing formaldehyde purification material, on one hand, nickel-palladium alloy is used, which is high in cost and not beneficial to popularization, and on the other hand, formaldehyde decomposition rate is below 95%, which still has great improvement space.
Disclosure of Invention
The invention aims to provide an indoor formaldehyde purification material and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of an indoor formaldehyde purification material comprises the following steps of:
(1) firstly, mixing 1 part of modified hydroxyapatite, 5-8 parts of modified silicon carbide and 0.5-0.7 part of acrylic acid premix for reaction to obtain a mixed solution;
(2) then adding 0.6-0.9 part of manganese sulfate monohydrate into the mixed solution, uniformly oscillating by ultrasonic waves, adding 10-12 parts of potassium permanganate solution with the mass concentration of 10-15% while stirring, reacting by stirring, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material;
wherein, the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on 3- (N-rare propyl amino) propyl trimethoxy silane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
Preferably, in the step (1), the process conditions of the stirring reaction are as follows: stirring and reacting for 4-6 hours at 70-75 ℃.
Preferably, in the step (2), the process conditions of the stirring reaction are as follows: stirring and reacting for 6-8 hours at 40-45 ℃.
Preferably, in the step (2), the drying process conditions are as follows: drying for 12-15 hours at 70-90 ℃.
Preferably, the preparation method of the modified hydroxyapatite comprises the following steps: firstly, 0.08-0.1 part of hydroquinone is added into 100 parts of ethanol water solution with volume concentration of 85-95%, then glacial acetic acid is dripped until the pH is = 3.5-4, then 4-6 parts of 3- (N-diluted propylamino) propyl trimethoxy silane is added, stirring is carried out for 30-40 minutes, finally 1-2 parts of hydroxyapatite is added, ultrasonic oscillation is carried out for 10-20 minutes, heating is carried out to 60-70 ℃, heat preservation stirring is carried out for 2-3 hours, a solvent is removed, washing and drying are carried out, and the modified hydroxyapatite is obtained.
Further preferably, the washing is carried out for 3-4 times by using absolute ethyl alcohol and deionized water alternately, and the drying is carried out for 20-25 hours at the temperature of 70-80 ℃.
Preferably, the preparation method of the modified silicon carbide comprises the following steps: mixing 1 part of absolute ethyl alcohol and 2-3 parts of water, adding 0.01-0.02 part of 3-aminopropyltriethoxysilane and 0.008-0.01 part of silicon carbide, stirring for reaction in a nitrogen atmosphere, and centrifuging to obtain a solid; and adding the solid into 1-2 parts of dimethylformamide, carrying out ultrasonic treatment, finally adding 0.12-0.2 part of glutaric anhydride, stirring at 100-120 ℃ for reacting for 50-70 minutes, centrifuging, washing and drying to obtain the modified silicon carbide.
Further preferably, the process conditions of the stirring reaction are as follows: stirring and reacting for 8-12 hours at 75-85 ℃.
Further preferably, the process conditions of the ultrasonic treatment are as follows: ultrasonic oscillation at 500-800W for 40-60 minutes.
More preferably, the mixture is washed by deionized water for 2-3 times and dried for 18-22 hours at 70-80 ℃.
Preferably, the preparation method of the acrylic acid premix comprises the following steps: stirring and dripping 1 part of acrylic acid into 2-3 parts of 25-30% sodium hydroxide solution under the condition of ice-water bath, then adding 0.008-0.01 part of cross-linking agent, stirring in water bath at 60 ℃ until the acrylic acid is dissolved, and finally adding 0.001-0.002 part of initiator to obtain the acrylic acid premix; the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate.
In addition, the invention also claims an indoor formaldehyde environment-friendly purification material obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method comprises the steps of mixing and reacting modified hydroxyapatite, modified silicon carbide and acrylic acid premixed liquid to obtain mixed liquid, adding manganese sulfate monohydrate into the mixed liquid, adding a potassium permanganate solution after ultrasonic oscillation is uniform, and stirring and reacting to obtain the indoor formaldehyde environment-friendly purification material. The environment-friendly purification material has rich pores, large and small pore diameters, good adsorption effect on formaldehyde, high formaldehyde decomposition rate and extremely high popularization value, and can promote the decomposition of formaldehyde through oxidation and catalytic oxidation.
(2) The modified hydroxyapatite is prepared by using hydroxyapatite as a raw material and modifying the hydroxyapatite by 3- (N-rare propyl amino) propyl trimethoxy silane, so that the modified hydroxyapatite contains hydroxyl, carbon-carbon double bonds, amino and the like; the modified silicon carbide is prepared by using silicon carbide as a raw material and modifying the silicon carbide by using 3-aminopropyltriethoxysilane and glutaric anhydride, so that the modified silicon carbide contains carboxylic acid; the acrylic acid premix is obtained by mixing acrylic acid, a crosslinking agent and an initiator.
(3) The hydroxyapatite and the silicon carbide have pore structures, and the modified hydroxyapatite, the modified silicon carbide and the acrylic acid premixed solution are subjected to mixing reaction, wherein carbon-carbon double bond polymerization and reaction between carboxyl and hydroxyl are involved, hydrogen bond action is formed between unreacted amino, carboxyl and the like, a net system is formed through covalent bonds, hydrogen bonds and the like, pores with different sizes are formed, and the single-molecule formaldehyde in the air and the aggregated formaldehyde molecules can be adsorbed, so that the high-efficiency adsorption of the formaldehyde is realized.
(4) According to the invention, manganese sulfate monohydrate is added into the mixed solution, the manganese sulfate is uniformly dissolved by ultrasonic oscillation so as to be uniformly distributed in the mixed solution, then potassium permanganate is added, and the generated manganese dioxide is uniformly dispersed in the system and deposited along with the reaction of the potassium permanganate and the manganese sulfate under the stirring condition, so that the environment-friendly purification material with the surface loaded with the nano-scale manganese dioxide is finally obtained. The formaldehyde is decomposed by the catalytic oxidation of manganese dioxide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
A preparation method of an indoor formaldehyde purification material comprises the following steps:
(1) firstly, mixing 1kg of modified hydroxyapatite, 5kg of modified silicon carbide and 0.7kg of acrylic acid premix for reaction to obtain a mixed solution;
(2) then adding 0.6kg of manganese sulfate monohydrate into the mixed solution, uniformly oscillating by ultrasonic waves, adding 12kg of potassium permanganate solution with the mass concentration of 10% while stirring, stirring for reaction, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material;
wherein, the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on 3- (N-rare propyl amino) propyl trimethoxy silane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
In the step (1), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 75 ℃ for 4 hours.
In the step (2), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 45 ℃ for 6 hours.
In the step (2), the drying process conditions are as follows: drying at 90 deg.C for 12 hr.
The preparation method of the modified hydroxyapatite comprises the following steps: firstly, adding 0.1kg of hydroquinone into 100kg of ethanol water solution with volume concentration of 85%, then dropwise adding glacial acetic acid until the pH is =4, then adding 4kg of 3- (N-diluted propylamino) propyl trimethoxy silane, stirring for 40 minutes, finally adding 1kg of hydroxyapatite, carrying out ultrasonic oscillation for 20 minutes, heating to 60 ℃, carrying out heat preservation and stirring for 3 hours, removing the solvent, washing and drying to obtain the modified hydroxyapatite. Alternately washing with anhydrous ethanol and deionized water for 3 times, and drying at 80 deg.C for 20 hr.
The preparation method of the modified silicon carbide comprises the following steps: mixing 1kg of absolute ethyl alcohol with 3kg of water, adding 0.01kg of 3-aminopropyltriethoxysilane and 0.01kg of silicon carbide, stirring for reaction in a nitrogen atmosphere, and centrifuging to obtain a solid; and adding the solid into 1kg of dimethylformamide, carrying out ultrasonic treatment, finally adding 0.2kg of glutaric anhydride, stirring at 100 ℃ for reacting for 70 minutes, centrifuging, washing and drying to obtain the modified silicon carbide. The technological conditions of the stirring reaction are as follows: the reaction was stirred at 75 ℃ for 12 hours. The process conditions of ultrasonic treatment are as follows: 500W ultrasonic oscillation is carried out for 60 minutes. Washed with deionized water 2 times and dried at 80 ℃ for 18 hours.
The preparation method of the acrylic acid premix comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then adding 0.01kg of cross-linking agent, stirring in water bath at 60 ℃ until the cross-linking agent is dissolved, and finally adding 0.001kg of initiator to obtain the acrylic acid premix; the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate.
Example 2
A preparation method of an indoor formaldehyde purification material comprises the following steps:
(1) firstly, mixing 1kg of modified hydroxyapatite, 8kg of modified silicon carbide and 0.5kg of acrylic acid premix for reaction to obtain a mixed solution;
(2) then adding 0.9kg of manganese sulfate monohydrate into the mixed solution, uniformly oscillating by ultrasonic waves, adding 10kg of potassium permanganate solution with the mass concentration of 15% while stirring, stirring for reaction, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material;
wherein, the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on 3- (N-rare propyl amino) propyl trimethoxy silane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
In the step (1), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 70 ℃ for 6 hours.
In the step (2), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 40 ℃ for 8 hours.
In the step (2), the drying process conditions are as follows: dried at 70 ℃ for 15 hours.
The preparation method of the modified hydroxyapatite comprises the following steps: firstly, adding 0.08kg of hydroquinone into 100kg of ethanol aqueous solution with volume concentration of 95%, then dropwise adding glacial acetic acid until the pH is =3.5, then adding 6kg of 3- (N-diluted propylamino) propyl trimethoxy silane, stirring for 30 minutes, finally adding 2kg of hydroxyapatite, carrying out ultrasonic oscillation for 10 minutes, heating to 70 ℃, carrying out heat preservation and stirring for 2 hours, removing the solvent, washing and drying to obtain the modified hydroxyapatite. Washing with anhydrous ethanol and deionized water alternately for 4 times, and drying at 70 deg.C for 25 hr.
The preparation method of the modified silicon carbide comprises the following steps: mixing 1kg of absolute ethyl alcohol with 2kg of water, then adding 0.02kg of 3-aminopropyltriethoxysilane and 0.008kg of silicon carbide, stirring for reaction under the nitrogen atmosphere, and centrifuging to obtain a solid; and adding the solid into 2kg of dimethylformamide, carrying out ultrasonic treatment, finally adding 0.12kg of glutaric anhydride, stirring at 120 ℃ for reacting for 50 minutes, centrifuging, washing and drying to obtain the modified silicon carbide. The technological conditions of the stirring reaction are as follows: the reaction was stirred at 85 ℃ for 8 hours. The process conditions of ultrasonic treatment are as follows: ultrasonic oscillation at 800W for 40 minutes. Washed 3 times with deionized water and dried at 70 ℃ for 22 hours.
The preparation method of the acrylic acid premix comprises the following steps: stirring and dripping 1kg of acrylic acid into 2kg of sodium hydroxide solution with the mass concentration of 30% under the condition of ice-water bath, then adding 0.008kg of cross-linking agent, stirring in water bath at 60 ℃ until the cross-linking agent is dissolved, and finally adding 0.002kg of initiator to obtain the acrylic acid premix; the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate.
Example 3
A preparation method of an indoor formaldehyde purification material comprises the following steps:
(1) firstly, mixing 1kg of modified hydroxyapatite, 6kg of modified silicon carbide and 0.6kg of acrylic acid premix for reaction to obtain a mixed solution;
(2) then adding 0.7kg of manganese sulfate monohydrate into the mixed solution, uniformly oscillating by ultrasonic waves, adding 11kg of potassium permanganate solution with the mass concentration of 12% while stirring, stirring for reaction, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material;
wherein, the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on 3- (N-rare propyl amino) propyl trimethoxy silane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
In the step (1), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 72 ℃ for 5 hours.
In the step (2), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 43 ℃ for 7 hours.
In the step (2), the drying process conditions are as follows: dried at 80 ℃ for 13 hours.
The preparation method of the modified hydroxyapatite comprises the following steps: firstly, adding 0.09kg of hydroquinone into 100kg of 90% ethanol aqueous solution with volume concentration, then dropwise adding glacial acetic acid until the pH is =4, then adding 5kg of 3- (N-diluted propylamino) propyl trimethoxy silane, stirring for 35 minutes, finally adding 1.5kg of hydroxyapatite, carrying out ultrasonic oscillation for 15 minutes, heating to 65 ℃, carrying out heat preservation and stirring for 2.5 hours, removing the solvent, washing and drying to obtain the modified hydroxyapatite. Alternately washing with anhydrous ethanol and deionized water for 3 times, and drying at 75 deg.C for 22 hr.
The preparation method of the modified silicon carbide comprises the following steps: mixing 1kg of absolute ethyl alcohol and 2.5kg of water, adding 0.015kg of 3-aminopropyltriethoxysilane and 0.009kg of silicon carbide, stirring for reaction in a nitrogen atmosphere, and centrifuging to obtain a solid; and adding the solid into 1.5kg of dimethylformamide, carrying out ultrasonic treatment, finally adding 0.18kg of glutaric anhydride, stirring and reacting for 60 minutes at 110 ℃, centrifuging, washing and drying to obtain the modified silicon carbide. The technological conditions of the stirring reaction are as follows: the reaction was stirred at 80 ℃ for 10 hours. The process conditions of ultrasonic treatment are as follows: ultrasonic oscillation at 700W for 50 minutes. Washed with deionized water 3 times and dried at 75 ℃ for 20 hours.
The preparation method of the acrylic acid premix comprises the following steps: stirring and dripping 1kg of acrylic acid into 2.5kg of sodium hydroxide solution with the mass concentration of 28% under the condition of ice-water bath, then adding 0.009kg of cross-linking agent, stirring in water bath at 60 ℃ until the acrylic acid is dissolved, and finally adding 0.0015kg of initiator to obtain the acrylic acid premix; the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate.
Comparative example 1
A preparation method of an indoor formaldehyde purification material comprises the following steps:
(1) firstly, 1kg of hydroxyapatite, 5kg of silicon carbide and 0.7kg of acrylic acid premix are mixed and reacted to obtain mixed liquor;
(2) then adding 0.6kg of manganese sulfate monohydrate into the mixed solution, uniformly oscillating by ultrasonic waves, adding 12kg of potassium permanganate solution with the mass concentration of 10% while stirring, stirring for reaction, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material;
wherein the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
In the step (1), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 75 ℃ for 4 hours.
In the step (2), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 45 ℃ for 6 hours.
In the step (2), the drying process conditions are as follows: drying at 90 deg.C for 12 hr.
The preparation method of the acrylic acid premix comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then adding 0.01kg of cross-linking agent, stirring in water bath at 60 ℃ until the cross-linking agent is dissolved, and finally adding 0.001kg of initiator to obtain the acrylic acid premix; the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate.
Comparative example 2
A preparation method of an indoor formaldehyde purification material comprises the steps of mixing 1kg of modified hydroxyapatite, 5kg of modified silicon carbide and 0.7kg of acrylic acid premix for reaction to obtain a mixed solution, centrifuging and drying to obtain the indoor formaldehyde environment-friendly purification material;
wherein, the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on 3- (N-rare propyl amino) propyl trimethoxy silane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
The technological conditions of the stirring reaction are as follows: the reaction was stirred at 75 ℃ for 4 hours.
The drying process conditions are as follows: drying at 90 deg.C for 12 hr.
The preparation method of the modified hydroxyapatite comprises the following steps: firstly, adding 0.1kg of hydroquinone into 100kg of ethanol water solution with volume concentration of 85%, then dropwise adding glacial acetic acid until the pH is =4, then adding 4kg of 3- (N-diluted propylamino) propyl trimethoxy silane, stirring for 40 minutes, finally adding 1kg of hydroxyapatite, carrying out ultrasonic oscillation for 20 minutes, heating to 60 ℃, carrying out heat preservation and stirring for 3 hours, removing the solvent, washing and drying to obtain the modified hydroxyapatite. Alternately washing with anhydrous ethanol and deionized water for 3 times, and drying at 80 deg.C for 20 hr.
The preparation method of the modified silicon carbide comprises the following steps: mixing 1kg of absolute ethyl alcohol with 3kg of water, adding 0.01kg of 3-aminopropyltriethoxysilane and 0.01kg of silicon carbide, stirring for reaction in a nitrogen atmosphere, and centrifuging to obtain a solid; and adding the solid into 1kg of dimethylformamide, carrying out ultrasonic treatment, finally adding 0.2kg of glutaric anhydride, stirring at 100 ℃ for reacting for 70 minutes, centrifuging, washing and drying to obtain the modified silicon carbide. The technological conditions of the stirring reaction are as follows: the reaction was stirred at 75 ℃ for 12 hours. The process conditions of ultrasonic treatment are as follows: 500W ultrasonic oscillation is carried out for 60 minutes. Washed with deionized water 2 times and dried at 80 ℃ for 18 hours.
The preparation method of the acrylic acid premix comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then adding 0.01kg of cross-linking agent, stirring in water bath at 60 ℃ until the cross-linking agent is dissolved, and finally adding 0.001kg of initiator to obtain the acrylic acid premix; the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate.
Comparative example 3
A preparation method of an indoor formaldehyde purification material comprises the following steps:
(1) firstly, mixing 1kg of modified hydroxyapatite and 5kg of modified silicon carbide for reaction to obtain a mixed solution;
(2) then adding 0.6kg of manganese sulfate monohydrate into the mixed solution, uniformly oscillating by ultrasonic waves, adding 12kg of potassium permanganate solution with the mass concentration of 10% while stirring, stirring for reaction, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material;
the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on the hydroxyapatite by using 3-aminopropyltriethoxysilane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
In the step (1), the process conditions of the mixing reaction are as follows: the reaction was stirred at 75 ℃ for 4 hours.
In the step (2), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 45 ℃ for 6 hours.
In the step (2), the drying process conditions are as follows: drying at 90 deg.C for 12 hr.
The preparation method of the modified hydroxyapatite comprises the following steps: firstly, adding 0.1kg of hydroquinone into 100kg of 85% ethanol aqueous solution with volume concentration, then dropwise adding glacial acetic acid until the pH is =4, then adding 4kg of 3-aminopropyltriethoxysilane, stirring for 40 minutes, finally adding 1kg of hydroxyapatite, ultrasonically oscillating for 20 minutes, heating to 60 ℃, preserving heat and stirring for 3 hours, removing the solvent, washing and drying to obtain the modified hydroxyapatite. Alternately washing with anhydrous ethanol and deionized water for 3 times, and drying at 80 deg.C for 20 hr.
The preparation method of the modified silicon carbide comprises the following steps: mixing 1kg of absolute ethyl alcohol with 3kg of water, adding 0.01kg of 3-aminopropyltriethoxysilane and 0.01kg of silicon carbide, stirring for reaction in a nitrogen atmosphere, and centrifuging to obtain a solid; and adding the solid into 1kg of dimethylformamide, carrying out ultrasonic treatment, finally adding 0.2kg of glutaric anhydride, stirring at 100 ℃ for reacting for 70 minutes, centrifuging, washing and drying to obtain the modified silicon carbide. The technological conditions of the stirring reaction are as follows: the reaction was stirred at 75 ℃ for 12 hours. The process conditions of ultrasonic treatment are as follows: 500W ultrasonic oscillation is carried out for 60 minutes. Washed with deionized water 2 times and dried at 80 ℃ for 18 hours.
Comparative example 4
A preparation method of an indoor formaldehyde purification material comprises the following steps:
(1) firstly, mixing 1kg of modified hydroxyapatite, 5kg of modified silicon carbide and 0.7kg of acrylic acid premix for reaction to obtain a mixed solution, centrifuging and drying to obtain an intermediate product;
(2) adding the intermediate product into a 25 mass percent manganese sulfate aqueous solution (prepared by dissolving 0.6kg of manganese sulfate monohydrate in water), uniformly oscillating by ultrasonic waves, adding 12kg of a 10 mass percent potassium permanganate solution while stirring, reacting while stirring, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material;
wherein, the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on 3- (N-rare propyl amino) propyl trimethoxy silane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
In the step (1), the technological conditions of the stirring reaction are as follows: stirring and reacting for 4 hours at 75 ℃; the drying process conditions are as follows: drying at 90 deg.C for 12 hr.
In the step (2), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 45 ℃ for 6 hours.
In the step (2), the drying process conditions are as follows: drying at 90 deg.C for 12 hr.
The preparation method of the modified hydroxyapatite comprises the following steps: firstly, adding 0.1kg of hydroquinone into 100kg of ethanol water solution with volume concentration of 85%, then dropwise adding glacial acetic acid until the pH is =4, then adding 4kg of 3- (N-diluted propylamino) propyl trimethoxy silane, stirring for 40 minutes, finally adding 1kg of hydroxyapatite, carrying out ultrasonic oscillation for 20 minutes, heating to 60 ℃, carrying out heat preservation and stirring for 3 hours, removing the solvent, washing and drying to obtain the modified hydroxyapatite. Alternately washing with anhydrous ethanol and deionized water for 3 times, and drying at 80 deg.C for 20 hr.
The preparation method of the modified silicon carbide comprises the following steps: mixing 1kg of absolute ethyl alcohol with 3kg of water, adding 0.01kg of 3-aminopropyltriethoxysilane and 0.01kg of silicon carbide, stirring for reaction in a nitrogen atmosphere, and centrifuging to obtain a solid; and adding the solid into 1kg of dimethylformamide, carrying out ultrasonic treatment, finally adding 0.2kg of glutaric anhydride, stirring at 100 ℃ for reacting for 70 minutes, centrifuging, washing and drying to obtain the modified silicon carbide. The technological conditions of the stirring reaction are as follows: the reaction was stirred at 75 ℃ for 12 hours. The process conditions of ultrasonic treatment are as follows: 500W ultrasonic oscillation is carried out for 60 minutes. Washed with deionized water 2 times and dried at 80 ℃ for 18 hours.
The preparation method of the acrylic acid premix comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then adding 0.01kg of cross-linking agent, stirring in water bath at 60 ℃ until the cross-linking agent is dissolved, and finally adding 0.001kg of initiator to obtain the acrylic acid premix; the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate.
The materials prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance evaluation as follows:
in a closed container, formaldehyde is generated by a formaldehyde generator, so that the initial concentrations are 120mg/L, 50mg/L and 1mg/L respectively, 8 comparison tests are set for each concentration respectively, the environment-friendly purification materials obtained in examples 1 to 3 or comparative examples 1 to 4 are used for treatment respectively, the dosage of the environment-friendly purification materials is 1mg/L, the room temperature is 28 ℃, the formaldehyde concentration is detected by a formaldehyde detector after standing for 30 minutes, and the formaldehyde removal rate is calculated, wherein the removal rate (%) = (concentration before treatment-concentration after treatment)/concentration before treatment multiplied by 100. The results are shown in Table 1.
TABLE 1 comparison of Formaldehyde removal
| Removal Rate (%, initial concentration 120 mg/L) | Removal Rate (%, initial concentration 50 mg/L) | Removal Rate (%, initial concentration 1 mg/L) | |
| Example 1 | 98.11 | 98.83 | 99.96 |
| Example 2 | 98.12 | 98.86 | 99.98 |
| Example 3 | 98.15 | 98.89 | 100 |
| Comparative example 1 | 71.22 | 72.37 | 74.02 |
| Comparative example 2 | 80.05 | 81.45 | 83.03 |
| Comparative example 3 | 69.33 | 70.04 | 71.18 |
| Comparative example 4 | 93.04 | 94.28 | 95.33 |
As can be seen from Table 1, the environment-friendly purification materials obtained in examples 1 to 3 had a high formaldehyde removal rate after 30 minutes of use, regardless of high-concentration or low-concentration formaldehyde. Comparative example 1 in step (1), hydroxyapatite and silicon carbide are used for replacing modified hydroxyapatite and modified silicon carbide, in comparative example 2, the formation process of manganese dioxide in step (2) is omitted, in comparative example 3, 3- (N-rare propyl amino) propyl trimethoxy silane is replaced by 3-aminopropyl triethoxy silane when modified hydroxyapatite is prepared, acrylic acid premix is omitted, the pore formation and the pore size distribution are influenced, and further the formaldehyde adsorption decomposition effect is influenced; comparative example 4 an intermediate product obtained by centrifugally drying the mixed solution obtained in the step (1) is added with a manganese sulfate aqueous solution, so that manganese dioxide is formed on the surface, and the distribution uniformity of the manganese dioxide on the surface of the material is poor, thereby influencing the absorption and decomposition of formaldehyde.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of an indoor formaldehyde purification material is characterized by comprising the following steps of:
(1) firstly, mixing 1 part of modified hydroxyapatite, 5-8 parts of modified silicon carbide and 0.5-0.7 part of acrylic acid premix for reaction to obtain a mixed solution;
(2) then adding 0.6-0.9 part of manganese sulfate monohydrate into the mixed solution, uniformly oscillating by ultrasonic waves, adding 10-12 parts of potassium permanganate solution with the mass concentration of 10-15% while stirring, reacting by stirring, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material;
wherein, the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on 3- (N-rare propyl amino) propyl trimethoxy silane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator.
2. The preparation method according to claim 1, wherein in the step (1), the process conditions of the stirring reaction are as follows: stirring and reacting for 4-6 hours at 70-75 ℃.
3. The preparation method according to claim 1, wherein in the step (2), the process conditions of the stirring reaction are as follows: stirring and reacting for 6-8 hours at 40-45 ℃.
4. The preparation method according to claim 1, wherein in the step (2), the drying process conditions are as follows: drying for 12-15 hours at 70-90 ℃.
5. The preparation method according to claim 1, wherein the modified hydroxyapatite is prepared by the following steps in parts by weight: firstly, 0.08-0.1 part of hydroquinone is added into 100 parts of ethanol water solution with volume concentration of 85-95%, then glacial acetic acid is dripped until the pH is = 3.5-4, then 4-6 parts of 3- (N-diluted propylamino) propyl trimethoxy silane is added, stirring is carried out for 30-40 minutes, finally 1-2 parts of hydroxyapatite is added, ultrasonic oscillation is carried out for 10-20 minutes, heating is carried out to 60-70 ℃, heat preservation stirring is carried out for 2-3 hours, a solvent is removed, washing and drying are carried out, and the modified hydroxyapatite is obtained.
6. The method according to claim 1, wherein the modified silicon carbide is prepared by the following steps in parts by weight: mixing 1 part of absolute ethyl alcohol and 2-3 parts of water, adding 0.01-0.02 part of 3-aminopropyltriethoxysilane and 0.008-0.01 part of silicon carbide, stirring for reaction in a nitrogen atmosphere, and centrifuging to obtain a solid; and adding the solid into 1-2 parts of dimethylformamide, carrying out ultrasonic treatment, finally adding 0.12-0.2 part of glutaric anhydride, stirring at 100-120 ℃ for reacting for 50-70 minutes, centrifuging, washing and drying to obtain the modified silicon carbide.
7. The preparation method according to claim 6, wherein the process conditions of the stirring reaction are as follows: stirring and reacting for 8-12 hours at 75-85 ℃.
8. The preparation method according to claim 6, wherein the ultrasonic treatment is carried out under the following process conditions: ultrasonic oscillation at 500-800W for 40-60 minutes.
9. The method according to claim 1, wherein the acrylic acid premix is prepared by the following method in parts by weight: stirring and dripping 1 part of acrylic acid into 2-3 parts of 25-30% sodium hydroxide solution under the condition of ice-water bath, then adding 0.008-0.01 part of cross-linking agent, stirring in water bath at 60 ℃ until the acrylic acid is dissolved, and finally adding 0.001-0.002 part of initiator to obtain the acrylic acid premix; the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate.
10. An indoor formaldehyde environment-friendly purification material prepared by the preparation method of any one of claims 1 to 9.
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