A dehumidifying and formaldehyde-removing attapulgite-based adsorbent material, preparation method and application

Abstract

The present invention belongs to the technical field of inorganic adsorption materials, and specifically relates to a dehumidification and formaldehyde removal attapulgite-based adsorbent material, a preparation method and an application thereof. The preparation method comprises the following steps: S1, preparing a attapulgite clay mixed solution; S2, dripping butyl titanate into anhydrous ethanol, adding acetylacetone and stirring, and mixing uniformly to obtain solution A; mixing anhydrous ethanol and deionized water, and stirring uniformly to obtain solution B; S3, adding solution B into solution A, and dripping Nd(NO3)3·5H2O solution and stirring uniformly to form Nd doped 3+ : TiO2 sol, adding TiO2 sol to the attapulgite clay mixed solution, adding acrylic emulsion, and stirring to form a mixed solution; S4, ultrasonically mixing the mixed solution, standing for aging, filtering, washing, drying, and calcining to obtain the attapulgite clay surface coated with Nd doped 3+ : TiO2 powder; S5, doping Nd 3+ TiO2 powder and graphite powder are mixed, and carboxymethyl cellulose is sprayed into the mixture to obtain a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material.

Description

Technical Field

[0001] The present invention belongs to the technical field of inorganic adsorption materials, and in particular relates to a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material, a preparation method and an application thereof. Background Art

[0002] Currently available indoor formaldehyde control technologies include adsorption, thermal destruction, absorption, photocatalysis, and photochemical oxidation. Among these, the adsorption method is the most widely used due to its relatively low cost and simple operation. Traditional adsorption materials often have titanium oxide photocatalysts added as adsorbents, but the photocatalytic efficiency of pure TiO2 is insufficient to meet actual needs, resulting in considerable energy consumption, poor visible light catalytic activity, low quantum efficiency, and high preparation costs. Therefore, ordinary adsorbents have problems in actual applications, such as poor adsorption effect, adsorbent saturation, and the need for desorption or renewal. Therefore, the development and application of high-efficiency formaldehyde adsorption materials and the solution to the adsorbent saturation problem in the process have become the focus of current research on indoor formaldehyde treatment. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the purpose of the present invention can be achieved through the following technical solutions:

[0004] A method for preparing a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material, the preparation method comprising the following steps:

[0005] S1, preparing an attapulgite clay mixed solution;

[0006] S2. Slowly drip butyl titanate into anhydrous ethanol, add acetylacetone, and stir until uniformly mixed to obtain solution A for standby use; mix anhydrous ethanol and deionized water, and stir until uniformly mixed to obtain solution B;

[0007] S3. Slowly add solution B into solution A, and gradually add Nd(NO3)3·5H2O solution and stir evenly to form Nd doped 3+ : TiO2 sol, adding TiO2 sol to the attapulgite clay mixed solution, adding acrylic emulsion, and then stirring to form a mixed solution;

[0008] S4, ultrasonically mixing the mixed solution, aging it, filtering it, washing it, drying it and calcining it to obtain the surface of the attapulgite clay coated with Nd doped 3+ : TiO2 powder;

[0009] S5, doping Nd 3+ TiO2 powder and graphite powder are put into a rotating disk for dry mixing, and carboxymethyl cellulose is sprayed into the mixture for mixing to obtain a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material.

[0010] Preferably, step S1 of preparing the attapulgite clay mixed solution comprises: weighing attapulgite clay with a fineness of 200-400 mesh, putting it into distilled water and stirring it for 2-4 hours, then adding sepiolite fiber and mixing it, and then adding polyacrylic acid amine active agent and stirring it to obtain the attapulgite clay mixed solution.

[0011] Preferably, the solid-liquid ratio of the attapulgite clay and distilled water is 1:8-10 g / ml, the mass ratio of the sepiolite fiber to the attapulgite clay is 1-2:10, and the volume ratio of the polyacrylic acid amine active agent to distilled water is 1-2:160-200.

[0012] Preferably, the stirring conditions when adding the polyacrylic acid amine active agent are: stirring temperature: 80-100° C., stirring speed: 1500-2000 rpm, and stirring time: 2-4 hours.

[0013] Preferably, in step S2, the volume ratio of butyl titanate, anhydrous ethanol and acetylacetone in solution A is 10-16:20-30:3-4, and the volume ratio of anhydrous ethanol and deionized water in solution B is 10-15:2-3. When preparing solution B, glacial acetic acid is added to adjust the pH of solution B to 2-3, and the concentration of glacial acetic acid is: 17.5 mol / L.

[0014] Preferably, in step S3, the volume ratio of solution A, solution B and Nd(NO3)3·5H2O solution is 1.8-2:1:0.2, and the volume ratio of acrylic emulsion to Nd(NO3)3·5H2O solution is 1-2:4-6; the stirring conditions after adding the acrylic emulsion in step S3 are: temperature: 50-55°C, rotation speed: 350-500 rpm, and time: 30-40 min.

[0015] Preferably, in step S4, ammonia water is further added to the prepared mixed solution to adjust the pH of the mixed solution to 9-10. The temperature of ultrasonic mixing in step S4 is 50-55°C, the time is 30-40 min, the static aging temperature is 60-65°C, the time is 12-14 h, deionized water is used for washing, and the number of washings is at least three to remove unabsorbed TiO2 sol. The drying temperature is 80-90°C, the drying time is 24-30 h, the calcination temperature is 400-500°C, and the calcination time is 1-1.5 h.

[0016] Preferably, in step S5, the mass ratio of powder to graphite powder is 100:5-8, the mass percentage concentration of carboxymethyl cellulose is 20%, the temperature during mixing in the turntable is 30-60°C, the turntable speed is 50-100 rpm, and the mixing time is 2-4 hours.

[0017] Preferably, a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material is prepared by the preparation method.

[0018] Preferably, the dehumidifying and formaldehyde-removing attapulgite-based adsorbent material is used as an adsorbent to remove indoor formaldehyde.

[0019] Beneficial effects of the present invention:

[0020] 1. Prepare titanium-based photocatalytic materials by sol-gel, and dope rare earth element Nd into TiO2 nanopowder. 3+ , reducing the Ti ion band gap, promoting the migration and separation of photogenerated carriers, and forming a large number of oxygen vacancies.

[0021] 2. The present invention adopts a surface coating process to coat the surface of a porous attapulgite clay matrix material with a hydrophilic acrylic emulsion to form active functional groups such as hydroxyl groups, adsorb titanium-based photocatalytic materials, and prepare a high-performance adsorption material with physical adsorption and chemical decomposition functions to achieve the effects of removing formaldehyde and odor from the air. The adhesive is used to form a spherical adsorbent with high strength and high moisture absorption under a molding device, which is pollution-free and corrosive to the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present disclosure or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0023] Figure 1 This is a physical picture of the adsorbent material prepared according to the present invention. DETAILED DESCRIPTION

[0024] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0025] Example 1:

[0026] A method for preparing a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material comprises the following steps:

[0027] Step 1, weighing 100g of 200-mesh attapulgite clay, adding it into 800ml of distilled water and stirring it with a stirrer for 4 hours, adding 10g of sepiolite fiber and mixing it, adding 5ml of polyacrylic acid amine active agent and stirring it at 100°C, stirring it with a stirrer at 2000 rpm for 2 hours to obtain an attapulgite clay mixed solution;

[0028] Step 2: Slowly drop 50 ml of butyl titanate into 150 ml of anhydrous ethanol, add 20 ml of acetylacetone as an inhibitor, and stir for 15 minutes. After mixing evenly, obtain solution A for standby use; mix 150 ml of anhydrous ethanol and 30 ml of deionized water, drop glacial acetic acid to adjust the pH to 3, and stir evenly at room temperature to obtain solution B;

[0029] Step 3: Place solution A in a 70℃ constant temperature box, slowly add solution B into solution A, gradually add 30ml Nd(NO3)3·5H2O solution and stir evenly to form Nd doped 3+ : TiO2 sol, add the sol to the attapulgite clay mixed solution, add 5 ml of acrylic emulsion, stir in a constant temperature water bath, keep the speed at 500 rpm, maintain the system temperature at 55 ° C, and form a uniform mixed solution;

[0030] Step 4: Add ammonia water to the prepared mixture, adjust the system to pH 10, ultrasonically mix at 50°C for 30 minutes, and then stand for aging at 60°C for 12 hours. Cool to room temperature, filter, and wash with deionized water 5 times. Place in a vacuum drying oven at 80°C and dry for 24 hours. Calcined in the atmosphere at 400°C for 1 hour to obtain attapulgite clay surface coated with Nd doped 3+ : TiO2 powder;

[0031] Step 5: Add the powder to a 60° turntable and rotate it, add 8% by mass of graphite powder for dry mixing, mix for 3 hours, spray in 20% carboxymethyl cellulose for mixing, and rotate the turntable at 100 rpm for 2 hours to form a spherical adsorbent.

[0032] Example 2:

[0033] A method for preparing a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material comprises the following steps:

[0034] Step 1, weighing 100g of 300-mesh attapulgite and adding it into 800ml of distilled water and stirring it with a stirrer for 4 hours, adding 20g of sepiolite fiber and mixing it, adding 10ml of polyacrylic acid amine active agent and stirring it at 80°C and 2000 rpm for 2 hours to obtain an attapulgite mixed solution;

[0035] Step 2: Slowly drop 70 ml of butyl titanate into 150 ml of anhydrous ethanol, add 15 ml of acetylacetone as an inhibitor, and stir for 30 minutes. After mixing evenly, obtain solution A for standby use; mix 150 ml of anhydrous ethanol and 20 ml of deionized water, drop glacial acetic acid to adjust the pH to 2, and stir evenly at room temperature to obtain solution B;

[0036] Step 3: Place solution A in a constant temperature box at 80℃, slowly add solution B into solution A, gradually add 30ml Nd(NO3)3·5H2O solution and stir evenly to form Nd doped 3+ : TiO2 sol, add the sol to the attapulgite clay mixed solution, add 8 ml of acrylic emulsion, stir in a constant temperature water bath, keep the speed at 500 rpm, maintain the system temperature at 55 ° C, and form a uniform mixed solution;

[0037] Step 4: Ammonia water was added dropwise to the prepared mixed solution, and the pH of the system was adjusted to 10. The mixture was ultrasonically mixed at 50°C for 30 minutes, and then aged at 60°C for 12 hours. The mixture was cooled to room temperature, filtered, and washed with deionized water 5 times. The mixture was dried in a vacuum drying oven at 80°C for 24 hours. The mixture was calcined in the atmosphere at 500°C for 1 hour to obtain the attapulgite clay surface coated with Nd doped 3+ : TiO2 powder;

[0038] Step 5: Add the powder to a 60° turntable and rotate it, add 8% by mass of graphite powder for dry mixing, mix for 3 hours, spray in 20% carboxymethyl cellulose for mixing, and rotate the turntable at 100 rpm for 4 hours to form a spherical adsorbent.

[0039] Comparative Example 1

[0040] The difference between Comparative Example 1 and Example 1 is that when preparing the spherical adsorbent, Nd(NO3)3·5H2O is not added to the raw materials, and other materials are the same as those in Example 1, thereby preparing the spherical adsorbent.

[0041] Comparative Example 2

[0042] The difference between Comparative Example 2 and Example 1 is that when preparing the spherical adsorbent, no acrylic emulsion is added to the raw materials, and other materials are the same as those in Example 1, thereby preparing the spherical adsorbent.

[0043] test:

[0044] The dehumidification and formaldehyde removal black adsorbent prepared in Example 1 is as Figure 1 As shown, the adsorbent has a size of about 1.5 to 2.5 mm and is relatively uniform in size. Performance testing has shown that the adsorbent prepared by the present invention has excellent drying properties. When the air humidity is 66%, the moisture absorption rate reaches 39.8%, and the moisture content is less than 5.3%. The adsorbent has good strength under the action of carboxymethyl cellulose adhesive, the surface can withstand a pressure of 32.9N, and the structure is stable. After being immersed in water for 7 days, the adsorbent does not dissipate, and the weighed moisture absorption reaches more than 87%, which has good water absorption and good air purification effect.

[0045] In measuring the ability of the samples prepared in this application to adsorb formaldehyde, the formaldehyde adsorption effect test was carried out on sample 1 prepared in Example 1, sample 2 prepared in Example 2, sample 3 prepared in Comparative Example 1, and sample 4 prepared in Comparative Example 2. 3 In a confined space, every 1m 3 Two drops of formaldehyde solution (0.05 ml / drop) were dripped into a confined space at a concentration of 100%. After standing for 4 hours, Samples 1, 2, 3, and 4 were placed into each confined space, with one sample placed in each space. The adsorption time was set to 12 hours. After 12 hours, the amount of residual formaldehyde in each space was measured. The amount of residual formaldehyde was used to judge the effectiveness of the black adsorbent in absorbing formaldehyde. The measured data are shown in Table 1.

[0046] Table 1 shows the formaldehyde content of each sample adsorbent

[0047] Sample number Initial formaldehyde content / % Adsorbed formaldehyde amount / % Residual formaldehyde content / % Sample 1 100 96.4 3.6 Sample 2 100 94.2 6.8 Sample 3 100 60.3 39.7 Sample 4 100 48.6 51.4

[0048] It can be seen from the data in Table 1 that after 12 hours, the formaldehyde adsorption amount of Sample 1 and Sample 2 reached more than 94%. Sample 1 was heat-treated at 400°C, while Sample 2 was heat-treated at 500°C. The increase in temperature removed some of the structural water inside the attapulgite clay, causing the structure to change, which reduced the adsorption effect of the adsorbent.

[0049] However, Sample 3 was not prepared by adding Nd(NO3)3·5H2O, which resulted in a significant reduction in the effectiveness of the prepared adsorbent in adsorbing formaldehyde. Similarly, Sample 3 was not prepared by adding acrylic emulsion, which resulted in a significant reduction in the effectiveness of the prepared adsorbent in adsorbing formaldehyde.

[0050] The attapulgite-based adsorbent prepared in the present application can effectively remove odors in the air environment without adding any chemical fungicides, reducing pollution, meeting the deodorization needs of confined spaces, etc., physically adsorbing formaldehyde to remove odor and moisture, and can be reused after exposure to sunlight, which is more ecological and environmentally friendly.

[0051] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0052] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the invention as claimed.

Claims

1. A method for preparing a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material, characterized in that: The preparation method comprises the following steps: S1, preparing an attapulgite clay mixed solution; S2. Slowly drip butyl titanate into anhydrous ethanol, add acetylacetone, and stir until uniformly mixed to obtain solution A for standby use; mix anhydrous ethanol and deionized water, and stir until uniformly mixed to obtain solution B; S3. Slowly add solution B into solution A, and gradually add Nd(NO3)3·5H2O solution and stir evenly to form Nd doped 3 + : TiO2 sol, adding TiO2 sol to the attapulgite clay mixed solution, adding acrylic emulsion, and then stirring to form a mixed solution; S4, ultrasonically mixing the mixed solution, aging it, filtering it, washing it, drying it and calcining it to obtain the surface of the attapulgite clay coated with Nd doped 3+ : TiO2 powder, wherein the calcination temperature is 400-500°C; S5, doping Nd 3+ : TiO2 powder and graphite powder are placed in a rotating disk for dry mixing, and carboxymethyl cellulose is sprayed into the mixture to obtain a dehumidifying and formaldehyde-removing attapulgite-based adsorbent material; In step S5, the mass ratio of powder to graphite powder is 100:5-8, the mass percentage concentration of carboxymethyl cellulose is 20%, the temperature during mixing in the turntable is 30-60° C., the turntable speed is 50-100 rpm, and the mixing time is 2-4 h.

2. The preparation method according to claim 1, characterized in that Step S1 of preparing the attapulgite clay mixed solution comprises: weighing attapulgite clay with a fineness of 200-400 mesh and adding it into distilled water and stirring for 2-4 hours; then adding sepiolite fiber and mixing; and finally adding polyacrylic acid amine active agent and stirring to obtain the attapulgite clay mixed solution.

3. The preparation method according to claim 2, characterized in that The solid-liquid ratio of the attapulgite clay and distilled water is 1:8-10 g / ml, the mass ratio of the sepiolite fiber to the attapulgite clay is 1-2:10, and the volume ratio of the polyacrylic acid amine active agent to distilled water is 1-2:160-200.

4. The preparation method according to claim 2, characterized in that The stirring conditions when adding the polyacrylic acid amine active agent are: stirring temperature: 80-100° C., stirring speed: 1500-2000 rpm, and stirring time: 2-4 hours.

5. The preparation method according to claim 1, characterized in that In step S2, the volume ratio of butyl titanate, anhydrous ethanol, and acetylacetone in solution A is 10-16:20-30:3-4, and the volume ratio of anhydrous ethanol to deionized water in solution B is 10-15:2-3. When preparing solution B, glacial acetic acid is added to adjust the pH of solution B to 2-3. The concentration of glacial acetic acid is 17.5 mol / L.

6. The preparation method according to claim 1, characterized in that In step S3, the volume ratio of solution A, solution B and Nd(NO3)3·5H2O solution is 1.8-2:1:0.2, and the volume ratio of acrylic emulsion to Nd(NO3)3·5H2O solution is 1-2:4-6; the stirring conditions after adding the acrylic emulsion in step S3 are: temperature: 50-55°C, rotation speed: 350-500 rpm, and time: 30-40 min.

7. The preparation method according to claim 1, characterized in that In step S4, ammonia water is added dropwise to the prepared mixed solution to adjust the pH of the mixed solution to 9-10. The ultrasonic mixing temperature in step S4 is 50-55°C, the time is 30-40 min, the static aging temperature is 60-65°C, the time is 12-14 h, and deionized water is used for washing, and the number of washings is at least three to remove unabsorbed TiO2 sol. The drying temperature is 80-90°C, the drying time is 24-30 h, and the calcination time is 1-1.5 h.

8. A dehumidifying and formaldehyde-removing attapulgite-based adsorbent material prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the dehumidifying and formaldehyde-removing attapulgite-based adsorbent material according to any one of claims 1 to 7 as an adsorbent in removing indoor formaldehyde.

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