A three-dimensional honeycomb adsorption material, preparation method and application

Abstract

The present invention relates to the technical field of inorganic adsorbent materials, and specifically to a three-dimensional honeycomb adsorbent material, a preparation method and an application thereof. The preparation method is as follows: S1. Spray silica sol on the surface of a three-dimensional honeycomb medium-efficiency filter cotton and set aside; S2. Dissolve tetrabutyl titanate in absolute ethanol, add acetylacetone to obtain solution A; add nitric acid and deionized water to absolute ethanol to obtain solution B; drop solution B into solution A to obtain nano-TiO2 sol; S3. Put Dy(OC3H7)3 and water in a reflux device to hydrolyze Dy(OC3H7)3 to obtain Dy(OH)3, and add Dy(OH)3 to the nano-TiO2 sol to prepare a mixed Dy 3+ TiO2 sol; S4. Mix acrylamide, N,N-methylenebisacrylamide and deionized water to prepare a premixed solution; S5. Add the mixed Dy 3+ TiO2 sol to the premixed solution, and add ammonium persulfate to obtain a mixed solution; S6. Completely immerse the silica sol-sprayed medium-efficiency filter cotton in the mixed solution. After immersion, wash the medium-efficiency filter cotton with deionized water, dry and calcine to obtain a three-dimensional honeycomb formaldehyde adsorbent material.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic adsorption materials, and particularly relates to a three-dimensional honeycomb adsorption material, a preparation method and an application thereof. Background Art

[0002] In modern family life, people pay more and more attention to indoor decoration pollution. During the decoration of new houses, various building materials adhesives will produce pollutants such as formaldehyde, benzene, and TVOC to a certain extent, which will constantly threaten our physical health. In addition to opening windows for ventilation, the traditional solution more often uses adsorbents prepared from TiO2 photocatalytic materials to solve formaldehyde and other pollution problems. Patent CN104888770A developed a visible light photocatalyst of C-doped TiO2 nanoparticles loaded with metal Ag. The process is relatively complex, and C and Ag formed by reducing glucose as a carbon source and silver nitrate as a silver source cannot form a uniform structure with TiO2 nanoparticles doping, and cannot fully stimulate the electron-hole pairs of TiO2; Patent CN107469822A developed a preparation method of a highly efficient electron transfer Cu-modified C / TiO2 photocatalytic reduction material. It is difficult to fully ensure that copper-containing compounds are completely converted into Cu deposited on the surface of the C / TiO2 material by photoreduction. The existing technology has problems such as low efficiency of TiO2 particles releasing electron-hole pairs, easy recombination of electron-hole pairs, resulting in low quantum efficiency of photocatalytic reactions, and insignificant degradation effect on pollutants such as formaldehyde. The present application develops a three-dimensional honeycomb structure adsorption material with TiO2 nanoparticles adsorbed on the surface, which can increase the contact surface between TiO2 nanoparticles and ultraviolet light, improve the quantum efficiency of photocatalytic reactions, and enhance the formaldehyde degradation effect. Summary of the Invention

[0003] In view of the deficiencies of the prior art, the present invention provides a three-dimensional honeycomb adsorption material, a preparation method and an application thereof.

[0004] The purpose of the present invention can be achieved by the following technical solutions:

[0005] A preparation method of a three-dimensional honeycomb adsorption material, characterized in that the preparation method includes the following steps:

[0006] S1. Take a three-dimensional honeycomb medium filter cotton, spray silica sol on the surface of the three-dimensional honeycomb medium filter cotton, and stand by;

[0007] S2. Slowly drop tetrabutyl titanate into absolute ethanol, add acetylacetone, and stir at room temperature to obtain solution A; add nitric acid and deionized water to absolute ethanol, then drop hydrochloric acid to adjust the pH to 3-4 and stir to obtain solution B; drop solution B into solution A and stir to obtain nano-TiO2 sol;

[0008] S3. Place Dy(OC3H7)3 and water in a reflux device, heat and stir to completely hydrolyze Dy(OC3H7)3. Filter the hydrolyzed precipitate to obtain Dy(OH)3. Add Dy(OH)3 to the nano-TiO2 sol, heat and stir to mix Dy(OH)3 and the nano-TiO2 sol evenly, and then cool to room temperature to prepare the mixed Dy 3+ TiO2 sol;

[0009] S4. Mix acrylamide, N,N'-methylenebisacrylamide and deionized water, and stir evenly to prepare a premixed solution;

[0010] S5. Add the mixed Dy 3+ TiO2 sol to the premixed solution, and add ammonium persulfate and stir to obtain a mixed solution;

[0011] S6. Completely immerse the medium-efficiency filter cotton sprayed with silica sol in the mixed solution. After immersion, take out the medium-efficiency filter cotton, wash it with deionized water, dry it in vacuum and calcine it to obtain the adsorbent material with a three-dimensional honeycomb structure.

[0012] Preferably, in step S1, the mass of the sprayed silica sol is 30-50% of the mass of the medium-efficiency filter cotton, and the standing time is 10-12 h.

[0013] Preferably, in step S2, the volume ratio of tetrabutyl titanate, absolute ethanol and acetylacetone in solution A is (5-10):(20-30):(2-5); the volume ratio of absolute ethanol, nitric acid and deionized water in solution B is (10-15):(2-5):(5-10); the volume ratio of solution B to solution A is (0.3-0.5):1.

[0014] Preferably, in step S3, the molar ratio of Dy(OC3H7)3 to water is (5-8):(50-100), the heating temperature in the reflux device is 100°C-150°C, and the stirring time in the reflux device is 2-4 h; the mass ratio of Dy(OH)3 to the nano-TiO2 sol is 1:(50-60), the heating temperature after adding Dy(OH)3 to the nano-TiO2 sol is 90-100°C, and the stirring conditions are: the rotation speed is 350-500 rpm and the time is 30-40 min.

[0015] Preferably, in step S4, the volume ratio of acrylamide to N,N'-methylenebisacrylamide is (30-35):(200-250), and the sum of the masses of acrylamide and N,N'-methylenebisacrylamide accounts for 10%-15% of the total mass of the premixed solution; the stirring conditions are: the rotation speed is 150-200 rpm and the time is 30-40 min.

[0016] Preferably, in step S5, the mixed Dy3+ The TiO2 sol accounts for 20% of the total mass of the mixed solution, and ammonium persulfate accounts for 5-10% of the total mass of the mixed solution; the stirring conditions are: the rotation speed is 150-200 rpm, and the time is 30-40 min.

[0017] Preferably, in step S6, the soaking time is 24-26 h, washed with deionized water 1-3 times, the vacuum drying temperature is 70-80 °C, the drying time is 24-26 h, the calcination temperature is 400-500 °C, and the calcination time is 1-1.5 h.

[0018] A three-dimensional honeycomb adsorption material is prepared by the preparation method of the above-mentioned three-dimensional honeycomb adsorption material.

[0019] The application of the above-mentioned three-dimensional honeycomb adsorption material in the preparation of formaldehyde removal adsorption products.

[0020] Advantages of the present invention:

[0021] 1. The present invention uses the coprecipitation method to dope Dy 3+ compounds in the TiO2 sol. Under photocatalysis, rare earth elements fully excite the electron-hole pairs of TiO2, improve the adsorption effect of the adsorption material prepared in this application, reduce the environmental formaldehyde concentration, and have broad application prospects;

[0022] 2. In this application, the medium-effect filter cotton is wrapped with silica sol inside and outside, has a three-dimensional honeycomb structure, changes the hydrophobic property of the medium-effect filter cotton, immerses the medium-effect filter cotton in an acrylamide gel system, and the organic monomers acrylamide and N,N-methylenebisacrylamide are dried in a vacuum drying oven at 70-80 °C for 24 h under the action of ammonium persulfate to achieve in-situ curing, forming a three-dimensional network structure, and removed during the calcination of the medium-effect filter cotton in the atmosphere at 400 °C - 500 °C. The doped Dy 3+ adsorbed on the surface of the three-dimensional network structure formed by the acrylamide gel system. The TiO2 sol forms nanoparticles in the atmosphere at 400 °C - 500 °C, having excellent photocatalytic effects. Specific embodiments

[0023] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0024] Example 1

[0025] A preparation method of a three-dimensional honeycomb structure adsorption material, the preparation method is:

[0026] S1. Take a three-dimensional honeycomb medium-effect filter cotton with a size of 12 cm × 12 cm × 12 cm, soak the filter cotton in silica sol, and let it stand for 12 h for later use;

[0027] S2. Slowly drip 5 ml of tetrabutyl titanate into 20 ml of absolute ethanol, add 2 ml of inhibitor acetylacetone, and strongly stir with a stirrer for 30 min to mix evenly to obtain solution A for later use; Take 10 ml of absolute ethanol, add 2 ml of nitric acid with a concentration of 68% and 5 ml of deionized water, drip in hydrochloric acid to adjust the pH = 3, stir at room temperature for 15 - 30 min to obtain solution B, then place solution A in a constant temperature water bath, slowly add solution B to solution A, drip 3 ml of solution B into every 10 ml of solution A, and stir for 4 h after dripping to obtain nano-TiO₂ sol;

[0028] S3. Load 5 ml of Dy(OC₃H₇)₃ and 50 ml of water into a reflux device, heat and stir to completely hydrolyze Dy(OC₃H₇)₃, filter the hydrolyzed precipitate to obtain Dy(OH)₃, add Dy(OH)₃ to the nano-TiO₂ sol, add 1 ml of Dy(OH)₃ to every 50 ml of nano-TiO₂ sol, heat and stir to mix Dy(OH)₃ and nano-TiO₂ sol evenly, and then cool to room temperature to prepare the mixed Dy 3+ TiO₂ sol; The heating temperature in the reflux device is 150 °C, and the stirring time in the reflux device is 4 h; The heating temperature after adding Dy(OH)₃ to the nano-TiO₂ sol is 90 °C, and the stirring conditions are: rotation speed is 350 rpm, and time is 30 min.

[0029] S4. Mix 30 ml of acrylamide, 5 ml of N,N'-methylenebisacrylamide and 250 ml of deionized water, and stir evenly to prepare a premixed solution; The stirring conditions are: rotation speed is 150 rpm, and time is 30 min.

[0030] S5. Add the mixed Dy 3+ TiO₂ sol to the premixed solution. The mixed Dy 3+ TiO₂ sol accounts for 20% of the total mass of the mixed solution, and add ammonium persulfate and stir to obtain a mixed solution; Ammonium persulfate accounts for 5% of the total mass of the mixed solution, and the stirring conditions are: rotation speed is 150 rpm, and time is 30 min.

[0031] S6. Completely soak the medium-effect filter cotton sprayed with silica sol in the mixed solution for 24 h. After soaking, take out the medium-effect filter cotton and wash it 3 times with deionized water, then put the medium-effect filter cotton into a vacuum drying oven and dry it in vacuum at 70 °C for 24 h, and then calcine it in the atmosphere at 400 °C for 1 h to obtain a three-dimensional honeycomb structure adsorption material.

[0032] Example 2

[0033] A preparation method of a three-dimensional honeycomb structure adsorption material, the preparation method is as follows:

[0034] S1. Take a three-dimensional honeycomb medium filter cotton with a size of 12 cm × 12 cm × 12 cm, soak the filter cotton in silica sol, and let it stand for 12 h for standby;

[0035] S2. Slowly drip 10 ml of tetrabutyl titanate into 30 ml of absolute ethanol, add 5 ml of inhibitor acetylacetone, and stir strongly with a stirrer for 30 min to mix evenly to obtain solution A for use; Take 12 ml of absolute ethanol, add 5 ml of nitric acid with a concentration of 68% and 10 ml of deionized water, drip hydrochloric acid to adjust the pH = 3, stir at room temperature for 30 min to obtain solution B, then place solution A in a constant temperature water bath, and slowly add solution B to solution A. Drop 3 ml of solution B into every 10 ml of solution A, and stir for 4 h after dropping to obtain nano-TiO2 sol;

[0036] S3. Load 8 ml of Dy(OC3H7)3 and 80 ml of water into a reflux device, heat and stir to completely hydrolyze Dy(OC3H7)3, filter the hydrolyzed precipitate to obtain Dy(OH)3, add Dy(OH)3 to the nano-TiO2 sol, add 1 ml of Dy(OH)3 to every 50 ml of nano-TiO2 sol, heat and stir to mix Dy(OH)3 and nano-TiO2 sol evenly, and then cool to room temperature to prepare a mixed Dy 3+ TiO2 sol; The heating temperature in the reflux device is 100 °C, and the stirring time in the reflux device is 6 h; The heating temperature after adding Dy(OH)3 to the nano-TiO2 sol is 100 °C, and the stirring conditions are: the rotation speed is 500 rpm and the time is 30 min.

[0037] S4. Mix 35 ml of acrylamide, 10 ml of N,N-methylenebisacrylamide and 250 ml of deionized water, and stir evenly to obtain a premixed solution; The stirring conditions are: the rotation speed is 150 rpm and the time is 30 min.

[0038] S5. Add the mixed Dy 3+ TiO2 sol to the premixed solution. The mixed Dy 3+ TiO2 sol accounts for 20% of the total mass of the mixed solution, and add ammonium persulfate and stir to obtain a mixed solution; Ammonium persulfate accounts for 5% of the total mass of the mixed solution, and the stirring conditions are: the rotation speed is 150 rpm and the time is 30 min.

[0039] S6. Immerse the medium - efficiency filter cotton sprayed with silica sol completely in the mixed solution for 24 h. After immersion, take out the medium - efficiency filter cotton and wash it 4 times with deionized water. Then put the medium - efficiency filter cotton into a vacuum drying oven and dry it in vacuum at 80 °C for 12 h, and then calcine it in the atmosphere at 400 °C for 3 h to obtain an adsorption material with a three - dimensional honeycomb structure.

[0040] Comparative Example 1

[0041] S1. Take a three - dimensional honeycomb medium - efficiency filter cotton with a size of 12 cm×12 cm×12 cm, immerse the filter cotton in silica sol, and let it stand for 12 h for standby;

[0042] S2. Slowly drip 5 ml of tetrabutyl titanate into 20 ml of absolute ethanol, and add 2 ml of inhibitor acetylacetone. Stir strongly with a stirrer for 30 min to mix evenly to obtain solution A for later use. Take 10 ml of absolute ethanol, add 2 ml of nitric acid with a concentration of 68% and 5 ml of deionized water, drip in hydrochloric acid to adjust the pH = 3, and stir at room temperature for 15 - 30 min to obtain solution B. Then place solution A in a constant - temperature water bath, and slowly add solution B to solution A. Drop 3 ml of solution B into every 10 ml of solution A. After dropping, stir for 4 h to obtain nano - TiO₂ sol;

[0043] S3. Immerse the medium - efficiency filter cotton sprayed with silica sol completely in nano - TiO₂ sol for 24 h. After immersion, take out the medium - efficiency filter cotton and wash it 4 times with deionized water. Then put the medium - efficiency filter cotton into a vacuum drying oven and dry it in vacuum at 80 °C for 12 h, and then calcine it in the atmosphere at 400 °C for 3 h to obtain an adsorption material with a three - dimensional honeycomb structure.

[0044] Test

[0045] In measuring the ability of the sample prepared in this application to adsorb formaldehyde, measure the formaldehyde adsorption effect of sample 1 prepared in Example 1, sample 2 prepared in Example 2, and sample 3 prepared in Comparative Example 1. The experiment selects a closed space of 1 m 3 . Drop 2 drops of formaldehyde solution (0.05 ml / drop) with a concentration of 100% into it. After standing for 4 h, put the sample in, set the adsorption time to 12 h, and measure the remaining formaldehyde concentration in the space again to illustrate the formaldehyde absorption effect of the black adsorbent prepared in this application.

[0046] Table 1 Formaldehyde content adsorbed by the adsorbent

[0047] Sample number Initial formaldehyde content / % Adsorbed formaldehyde content / % Remaining formaldehyde content / % Sample 1 100 95.1 4.9％ Sample 2 100 94.6 5.4％ Sample 3 100 50.4 49.6

[0048] After 12 h, the formaldehyde adsorption amounts of sample 1 and sample 2 reach more than 94%. Sample 1 is heat - treated at 400 °C, while sample 2 is heat - treated at 500 °C. With the increase in temperature, the mixed Dy3+ The change in the nanostructure formed by heat-treating the TiO2 sol reduces the adsorption effect of the adsorbent.

[0049] Dy was not doped into the adsorption material during the preparation of Sample 3 3+ , resulting in a significant reduction in the effect of the prepared adsorption material on adsorbing formaldehyde.

[0050] The adsorbent prepared in this application can effectively remove odors in an air environment, without adding any chemical fungicides, reducing pollution, meeting the deodorization and odor removal requirements of enclosed spaces, physically adsorbing formaldehyde to remove odors and moisture, and can be reused after being irradiated by sunlight, which is more environmentally friendly;

[0051] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0052] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and what is described in the above embodiments and the specification only illustrates the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. A preparation method of a three-dimensional honeycomb adsorption material, characterized in that, The preparation method includes the following steps: S1. Take a three-dimensional honeycomb medium-effect filter cotton, spray silica sol on the surface of the three-dimensional honeycomb medium-effect filter cotton, and let it stand for later use; S2. Slowly drop tetrabutyl titanate into absolute ethanol, add acetylacetone, and stir at room temperature to obtain solution A; add nitric acid and deionized water to absolute ethanol, then drop hydrochloric acid to adjust the pH to 3-4 and stir to obtain solution B; drop solution B into solution A and stir to obtain nano-TiO2 sol; S3. Place Dy(OC3H7)3 and water in a reflux apparatus, heat and stir to completely hydrolyze Dy(OC3H7)3. Filter the precipitate after hydrolysis to obtain Dy(OH)3. Add Dy(OH)3 to the nano-TiO2 sol, heat and stir to mix Dy(OH)3 and the nano-TiO2 sol evenly, and then cool to room temperature to prepare the mixed TiO2 sol containing Dy. 3+ sol of TiO2; S4. Mix acrylamide, N,N'-methylenebisacrylamide with deionized water, and stir evenly to prepare a premixed solution; S5. Add the mixed Dy 3+ TiO2 sol to the premixed solution, and add ammonium persulfate and stir to obtain a mixed solution; S6. Completely immerse the medium-effect filter cotton sprayed with silica sol in the mixed solution, take out the medium-effect filter cotton after immersion, wash it with deionized water, dry it under vacuum, and calcine it to obtain an adsorption material with a three-dimensional honeycomb structure.

2. The preparation method of a three-dimensional honeycomb adsorption material according to claim 1, characterized in that, In step S1, the mass of the sprayed silica sol is 30-50% of the mass of the medium-effect filter cotton, and the standing time is 10-12 h.

3. The preparation method of a three-dimensional honeycomb adsorption material according to claim 1, characterized in that In step S2, the volume ratio of tetrabutyl titanate, absolute ethanol, and acetylacetone in solution A is (5-10):(20-30):(2-5); the volume ratio of absolute ethanol, nitric acid, and deionized water in solution B is (10-15):(2-5):(5-10); the volume ratio of solution B to solution A is (0.3-0.5):

1.

4. The preparation method of a three-dimensional honeycomb adsorption material according to claim 1, characterized in that, In step S3, the molar ratio of Dy(OC3H7)3 to water is (5-8):(50-100), the heating temperature in the reflux device is 100°C-150°C, and the stirring time in the reflux device is 2-4 h; the mass ratio of Dy(OH)3 to nano-TiO2 sol is 1:(50-60), the heating temperature after adding Dy(OH)3 to the nano-TiO2 sol is 90-100°C, and the stirring conditions are: the rotation speed is 350-500 rpm, and the time is 30-40 min.

5. The preparation method of a three-dimensional honeycomb adsorption material according to claim 1, characterized in that, In step S4, the volume ratio of acrylamide to N,N'-methylenebisacrylamide is (30-35):(200-250), and the sum of the masses of acrylamide and N,N'-methylenebisacrylamide accounts for 10%-15% of the total mass of the premixed solution; the stirring conditions are: the rotation speed is 150-200 rpm, and the time is 30-40 min.

6. The preparation method of a three-dimensional honeycomb adsorption material according to claim 1, characterized in that, Step S5, mixing Dy 3+ The TiO2 sol containing 3+ accounts for 20% of the total mass of the mixed solution, and ammonium persulfate accounts for 5-10% of the total mass of the mixed solution; the stirring conditions are: the rotation speed is 150-200 rpm, and the time is 30-40 min.

7. The preparation method of a three-dimensional honeycomb adsorption material according to claim 1, wherein In step S6, the immersion time is 24-26 h, wash with deionized water 1-3 times, the vacuum drying temperature is 70-80°C, the drying time is 24-26 h, the calcination temperature is 400-500°C, and the calcination time is 1-1.5 h.

8. A three-dimensional honeycomb adsorption material is prepared by the preparation method of a three-dimensional honeycomb adsorption material according to any one of claims 1-7.

9. Use of a three-dimensional honeycomb adsorption material according to claim 8 in the preparation of a formaldehyde-removing adsorption product.