Preparation method of broad-spectrum protective zirconium-based adsorption material

Abstract

The invention discloses a preparation method of a broad-spectrum protective zirconium-based adsorbing material, and belongs to the technical field of adsorbents, the preparation method comprises the following steps: adding a dispersing agent into a zirconium oxychloride aqueous solution, and stirring at normal temperature to obtain a suspended emulsion to obtain zirconium oxychloride suspension slurry; adding a composite surfactant into the zirconium oxychloride suspension slurry, and stirring at a high speed to obtain a suspension; dropwise adding a sodium hydroxide solution in a stirring state, hydrolyzing to generate a precipitate, standing the precipitate, filtering, washing, drying, and crushing to obtain a surface modified zirconium hydroxide particle sample; preparing an impregnation liquid: adding sodium bicarbonate, basic cupric carbonate, potassium carbonate, silver nitrate and ammonium molybdate into pure water, stirring and dissolving to obtain the impregnation liquid; and adding the obtained impregnation liquid into a modified zirconium hydroxide particle sample. After a substrate material is loaded with metal active components, ammonia gas and a copper reaction center are complexed, a coordination compound is formed through weak chemical adsorption, and the purpose of ammonia gas protection is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of protective materials, and specifically to a preparation method of a broad-spectrum protective zirconium-based adsorbent material. Background Art

[0003] CN 117963983 A discloses a production method of zirconium hydroxide. The method includes steps of adding zirconium salt solution and alkali solution into a reactor in a parallel-flow dropping manner to form a precipitate, and then hydrothermally aging and drying the precipitate, etc. This method adopts the traditional hydrothermal synthesis method, relies on a high-pressure reactor, has a long reaction time (from several hours to several days), high process energy consumption, and high equipment cost. Moreover, the particle size of the prepared zirconium hydroxide is distributed between 25 and 75 nm, without a microporous structure, which is not conducive to adsorbing small molecule substances such as ammonia and sulfur dioxide.

[0004] CN 117046449 A discloses a preparation method of a room-temperature renewable adsorbent material for CNCl; it is prepared by impregnating zirconium hydroxide with organic amine, sublimating, drying, tabletting, crushing, and sieving. Although this method has simple steps, it can only protect against a single gas, and the excessive impregnation amount of organic amine is likely to cause pore blockage, which is not conducive to the adsorption of toxic agents.

[0005] Therefore, in the process of synthesizing zirconium hydroxide at room temperature in the present invention, a surfactant is added. The surfactant binds to the metal precursor through hydrogen bonds or electrostatic interactions, inducing the formation of an ordered pore structure (such as hexagonal phase, cubic phase); at the same time, a dispersant is added to reduce the agglomeration between particles through electrostatic repulsion or steric hindrance effects, thereby increasing the specific surface area and pore volume of zirconium hydroxide. Moreover, without reducing the original toxic agent protection ability, metal active components beneficial to ammonia improvement are added to achieve the purpose of simultaneously protecting against multiple toxic gases. Summary of the Invention

[0006] The present invention discloses a preparation method of a zirconium-based adsorbent material added with a surfactant. The zirconium-based adsorbent material prepared by the present invention has comprehensive broad-spectrum protection capabilities against traditional chemical reagents such as HCN and CNCl, basic gases such as NH3, acidic gases such as SO2, and organic gases such as benzene vapor, and has good application prospects in the fields of chemical protection and air purification. To achieve the above object, the present invention adopts the following technical solutions: A preparation method of a broad-spectrum protective zirconium-based adsorbent material, the method comprising the following steps: (1) Adding a dispersant to an aqueous solution of zirconyl chloride, and stirring at room temperature until a suspension is obtained to obtain a zirconyl chloride suspension slurry; (2) Adding a composite surfactant to the zirconyl chloride suspension slurry, and stirring at high speed to obtain a suspension; (3) Under stirring, sodium hydroxide solution is dropped in to cause hydrolysis to form a precipitate. After the precipitate is allowed to stand, it is filtered, washed, dried, and crushed to obtain a sample of surface-modified zirconium hydroxide particles; (4) Prepare an impregnating solution: Sodium bicarbonate, basic copper carbonate, potassium carbonate, silver nitrate, and ammonium molybdate are added to pure water and stirred until dissolved to obtain the impregnating solution; (5) The impregnating solution obtained in step (4) is added to step (3), stirred evenly, left standing for a period of time, then taken out and dried; (6) The particulate zirconium-based material obtained in step (5) is sieved through a 12 - 35 mesh sieve, and the particles that do not meet this particle size are reground, pressed into tablets, crushed, and sieved again.

[0007] Preferably, in step (1), the dispersant is polyepoxysuccinic acid, and its added mass is 0.1 - 1.0% of the dry basis of zirconium oxychloride; the mass concentration of the zirconium oxychloride aqueous solution is 10 - 30%.

[0008] Preferably, in step (2), the composite surfactant is composed of sodium 3 - carboxybenzenesulfonate and polyoxyethylene lauryl ether carboxylic acid, and its added amount is 1.0 - 3.0% of the dry basis of zirconium oxychloride.

[0009] Preferably, in the composite surfactant of step (2), the mass ratio of sodium 3 - carboxybenzenesulfonate to polyoxyethylene lauryl ether carboxylic acid is 1:1 - 10.

[0010] Preferably, in step (2), the high - speed stirring means stirring is carried out under the condition of 800 - 1000 r / min.

[0011] Preferably, in step (3), the precipitate is first dried at 200 - 350 °C for 2 - 0.5 h, and then dried at 120 °C to constant weight.

[0012] Preferably, in step (3), the tablet pressing amount of zirconium hydroxide powder is 10 - 20 g, the tablet pressing thickness is 0.2 - 0.4 cm, and the tablet pressing pressure is 20 - 30 MPa.

[0013] Preferably, in step (4), basic copper carbonate can also be copper acetate or copper citrate; potassium carbonate can also be potassium acetate or potassium bromide; ammonium molybdate can also be sodium molybdate or magnesium molybdate.

[0014] Preferably, in step (4), the solid - liquid ratio of sodium bicarbonate, basic copper carbonate, potassium carbonate, silver nitrate, ammonium molybdate and pure water is (10 - 25):(25 - 40):(1 - 5):(0.1 - 0.5):(5 - 15):(100 - 150) (g / g / g / g / g / ml).

[0015] Preferably, in the step (5), the solid-liquid ratio of granular zirconium hydroxide to the impregnation solution is (100-150):(100-150) (g / ml), and they are stirred evenly at 40-60 °C and left standing for 1-5 h.

[0016] Preferably, in the step (5), the granular zirconium-based material is dried at 40-120 °C for 1-5 h.

[0017] The beneficial effects of the present invention are as follows: Compared with the traditional hydrothermal synthesis method, the room-temperature synthesis method is simple in operation, does not require complex equipment (only conventional steps such as stirring and filtration) and has a short reaction time (within several hours). The only drawback is that the products are mostly amorphous or low-crystallinity zirconium hydroxide, and the crystal structure and morphology cannot be regulated. To solve this problem, a surfactant is added during the synthesis process. The surfactant binds to the metal precursor through hydrogen bonds or electrostatic interactions, inducing the formation of an ordered pore structure (such as hexagonal phase, cubic phase). At the same time, the surfactant significantly optimizes the pore structure, specific surface area, surface functional groups and charge characteristics of zirconium hydroxide through structure guidance, dispersion stability and modification of surface active functional groups, thereby comprehensively improving its adsorption performance for chemical agents.

[0018] The doped metal zirconium-based material of the present invention is prepared by a solution impregnation method. The raw materials are widely available, and non-toxic and harmless pure water is used as the solvent, which has less harm to the human body and the ecological environment. The process is simple and easy to achieve large-scale production, and has good popularization and application value.

[0019] After the substrate material is loaded with metal active components in the present invention, ammonia is complexed with the copper reaction center and a coordination compound is formed through weak chemical adsorption to achieve the purpose of protecting ammonia. At the same time, the metal active components also have a certain protective effect on other chemical agents. Specific embodiments

[0020] The present invention will be described in detail below with reference to specific embodiments to make the technical solutions and their beneficial effects of the present invention clearer. It can be understood that the embodiments are only for reference and illustration, and are used to better explain the present invention rather than to limit the present invention. Unless otherwise specified, the technical terms described in the present invention have the same meanings and rights as those generally understood by those skilled in the art.

[0021] Example 1 (1) 60 g of zirconium oxychloride is added to 340 g of water and stirred evenly, and then 0.33 g of polyepoxysuccinic acid is added and stirred at room temperature until a suspension is obtained to obtain a zirconium oxychloride suspension slurry; (2) Add 0.2 g of sodium 3 - carboxybenzenesulfonate and 1.0 g of polyoxyethylene lauryl ether carboxylic acid to the zirconium oxychloride suspension, and stir at 900 r / min to obtain a suspension; (3) While stirring, drop 25 wt% NaOH into the mixed solution within 30 minutes to cause hydrolysis to form a precipitate. Stop adding NaOH when the pH of the suspension reaches 13. After standing for a period of time, filter and wash until the pH < 10. The precipitate is first dried at 200 °C for 2 h, and then dried at 120 °C to constant weight. Its specific surface area is shown in Table 1; (4) Weigh 15 g of zirconium hydroxide powder, press it into a sheet - shaped molding material with a diameter of 5.0 cm and a thickness of 0.3 cm under a pressure of 30 MPa, and then crush and screen it into particulate materials with a size of 0.5 - 1.6 mm. Repeat several times until the sample amount reaches 120 g; (5) Weigh 20 g of sodium bicarbonate, 30 g of basic copper carbonate, 3 g of potassium carbonate, 0.3 g of silver nitrate, and 10 g of ammonium molybdate, add 140 ml of pure water, and stir at 50 °C until dissolved; (6) Add the solution obtained in step (5) to step (4), stir evenly at 50 °C and let it stand for 3 h; (7) Take out the particulate zirconium hydroxide material in step (6), and dry it at 80 °C for 5 h to obtain a blue zirconium - based material; (8) Pass the particulate zirconium - based material obtained in step (7) through a 12 - 35 mesh sieve. Particles that do not meet this particle size are re - ground, pressed, crushed, and screened.

[0022] Example 2 (1) Add 60 g of zirconium oxychloride to 140 g of water, stir evenly, and then add 0.06 g of polyepoxysuccinic acid, and stir at room temperature until a suspension is obtained to get a zirconium oxychloride suspension; (2) Add 0.3 g of sodium 3 - carboxybenzenesulfonate and 0.3 g of polyoxyethylene lauryl ether carboxylic acid to the zirconium oxychloride suspension, and stir at 800 r / min to obtain a suspension; (3) While stirring, drop 25 wt% NaOH into the mixed solution within 30 minutes to cause hydrolysis to form a precipitate. Stop adding NaOH when the pH of the suspension reaches 13. After standing for a period of time, filter and wash until the pH < 10. The precipitate is first dried at 250 °C for 1.5 h, and then dried at 120 °C to constant weight. Its specific surface area is shown in Table 1; (4) Weigh 15 g of zirconium hydroxide powder, press it into a sheet - shaped molding material with a diameter of 5.0 cm and a thickness of 0.3 cm under a pressure of 30 MPa, and then crush and screen it into particulate materials with a size of 0.5 - 1.6 mm. Repeat several times until the sample amount reaches 120 g; (5) Weigh 20 g of sodium bicarbonate, 35 g of basic copper carbonate, 3 g of potassium carbonate, 0.3 g of silver nitrate, and 10 g of ammonium molybdate. Add 140 ml of pure water and stir at 50 °C until dissolved; (6) Add the solution obtained in step (5) to step (4), stir evenly at 50 °C and let it stand for 3 h; (7) Take out the granular zirconium hydroxide material from step (6) and dry it at 80 °C for 5 h to obtain the blue zirconium-based material; (8) Pass the granular zirconium-based material obtained in step (7) through a 12 - 35 mesh sieve. The particles that do not meet this particle size are re-ground, tableted, crushed, and screened again.

[0023] Example 3 (1) Add 60 g of zirconium oxychloride to 340 g of water and stir evenly. Then add 0.46 g of polyepoxysuccinic acid and stir at room temperature until a suspension is obtained, resulting in a zirconium oxychloride suspension slurry; (2) Add 0.1 g of sodium 3 - carboxybenzenesulfonate and 0.8 g of polyoxyethylene lauryl ether carboxylic acid to the zirconium oxychloride suspension slurry and stir at 900 r / min to obtain a suspension; (3) While stirring, slowly add 25 wt% NaOH dropwise to the mixed solution within 30 minutes to cause hydrolysis and form a precipitate. Stop adding NaOH when the pH of the suspension reaches 13. After standing for a period of time, filter and wash until the pH < 10. First, dry the precipitate at 300 °C for 1 h, and then dry it at 120 °C to constant weight. Its specific surface area is shown in Table 1; (4) Weigh 15 g of zirconium hydroxide powder and press it into a sheet-shaped formed material with a diameter of 5.0 cm and a thickness of 0.3 cm under a pressure of 30 MPa. Then crush and screen it into granular materials with a particle size of 0.5 - 1.6 mm, and repeat several times until the sample amount reaches 120 g; (5) Weigh 15 g of sodium bicarbonate, 30 g of basic copper carbonate, 3 g of potassium carbonate, 0.3 g of silver nitrate, and 10 g of ammonium molybdate. Add 140 ml of pure water and stir at 50 °C until dissolved; (6) Add the solution obtained in step (5) to step (4), stir evenly at 50 °C and let it stand for 3 h; (7) Take out the granular zirconium hydroxide material from step (6) and dry it at 80 °C for 5 h to obtain the blue zirconium-based material; (8) Pass the granular zirconium-based material obtained in step (7) through a 12 - 35 mesh sieve. The particles that do not meet this particle size are re-ground, tableted, crushed, and screened again.

[0024] Example 4 (1) Add 60 g of zirconium oxychloride to 340 g of water, stir evenly, then add 0.46 g of polyepoxysuccinic acid, and stir at room temperature until a suspension is obtained to get a zirconium oxychloride suspension slurry; (2) Add 0.9 g of sodium 3-carboxybenzenesulfonate to the zirconium oxychloride suspension slurry, and stir at 900 r / min to obtain a suspension; (3) While stirring, drop 25 wt% NaOH into the mixed solution within 30 minutes to hydrolyze and form a precipitate. Stop adding NaOH when the pH of the suspension reaches 13. After standing for a period of time, filter and wash until the pH < 10. The precipitate is first dried at 300 °C for 2 h, and then dried at 120 °C to constant weight. Its specific surface area is shown in Table 1; (4) Weigh 15 g of zirconium hydroxide powder, press it into a sheet-shaped molding material with a diameter of 5.0 cm and a thickness of 0.3 cm under a pressure of 30 MPa, and then crush and screen it into granular materials with a size of 0.5 - 1.6 mm. Repeat multiple times until the sample amount reaches 120 g; (5) Weigh 20 g of sodium bicarbonate, 30 g of basic copper carbonate, 2 g of potassium carbonate, 0.3 g of silver nitrate, and 10 g of ammonium molybdate, add 140 ml of pure water, and stir at 50 °C until dissolved; (6) Add the solution obtained in step (5) to step (4), stir evenly at 50 °C and let it stand for 3 h; (7) Take out the granular zirconium hydroxide material in step (6), and dry it at 80 °C for 5 h to obtain a blue zirconium-based material; (8) Pass the granular zirconium-based material obtained in step (7) through a 12 - 35 mesh sieve, and re-grind, press, crush, and screen the particles that do not meet this particle size.

[0025] Example 5 (1) Add 60 g of zirconium oxychloride to 340 g of water, stir evenly, and stir at room temperature until a suspension is obtained to get a zirconium oxychloride suspension slurry; (2) Add 0.3 g of sodium 3-carboxybenzenesulfonate and 1.2 g of polyoxyethylene lauryl ether carboxylic acid to the zirconium oxychloride suspension slurry, and stir at 1000 r / min to obtain a suspension; (3) While stirring, drop 25 wt% NaOH into the mixed solution within 30 minutes to hydrolyze and form a precipitate. Stop adding NaOH when the pH of the suspension reaches 13. After standing for a period of time, filter and wash until the pH < 10. The precipitate is first dried at 350 °C for 0.5 h, and then dried at 120 °C to constant weight. Its specific surface area is shown in Table 1; (4)Weigh 15 g of zirconium hydroxide powder and press it into a sheet-shaped forming material with a diameter of 5.0 cm and a thickness of 0.3 cm under a pressure of 30 MPa. Then crush and screen it to obtain granular materials with a size of 0.5 - 1.6 mm. Repeat this process multiple times until the sample amount reaches 120 g. (5)Weigh 20 g of sodium bicarbonate, 30 g of basic copper carbonate, 3 g of potassium carbonate, 0.2 g of silver nitrate, and 10 g of ammonium molybdate. Add 140 ml of pure water and stir at 50 °C until dissolved. (6)Add the solution obtained in step (5) to step (4), stir evenly at 50 °C, and let it stand for 3 h. (7)Take out the granular zirconium hydroxide material obtained in step (6) and dry it at 80 °C for 5 h to obtain a blue zirconium-based material. (8)Pass the granular zirconium-based material obtained in step (7) through a 12 - 35 mesh sieve. The particles that do not meet this particle size are re-ground, pressed, crushed, and screened.

[0026] Comparative Example 1 Prepare the zirconium-based adsorbent material according to the method of Example 1, except that no surfactant is added. That is, the granular zirconium-based material is obtained by the scheme of steps 4 - 8, and its specific surface area is shown in Table 1.

[0027] Test and evaluate the protection time of ammonia, sulfur dioxide, benzene, hydrogen cyanide, and cyanogen chloride for the materials prepared in Examples 1 - 5 and Comparative Example 1. During the test, the specific velocity is 0.25 L / min·cm 2 , the carbon height is 2 cm, the initial concentration of ammonia is 2.1 mg / L, the initial concentration of cyanogen chloride is 9 mg / L, the initial concentration of hydrogen cyanide is 8 mg / L, the initial concentration of sulfur dioxide is 8.0 mg / L, and the initial concentration of benzene is 18 mg / L.

[0028] Table 1 Protection time for organic, inorganic, acidic, and basic gases

[0029] As can be seen from Table 1, after adding the composite surfactant, the prepared novel zirconium-based adsorbent material can maintain the protection ability against sulfur dioxide, cyanogen chloride, and benzene vapor, while significantly improving the protection effect against ammonia and hydrogen cyanide, ultimately enabling the prepared novel zirconium-based adsorbent material to achieve the purpose of efficiently protecting against acid-base industrial gases and traditional chemical reagents simultaneously.

[0030] The present invention first adds a dispersant to reduce the agglomeration between particles through electrostatic repulsion or steric hindrance effects; secondly, a composite surfactant is added, and zirconium hydroxide with a high specific surface area is successfully synthesized by means of micelle self-assembly and pore retention at room temperature. Finally, the substrate material is loaded with metal active components, and the prepared zirconium hydroxide modified material has uniformly dispersed active sites and excellent poison protection ability. The raw materials and solvents used in this preparation method are non-toxic and harmless, providing a useful exploration for the research and development of future new broad-spectrum protection materials.

[0031] The above embodiments are only the preferred technical solutions of the present invention, but the protection scope of the present invention is not limited thereto. The embodiments and the features in the embodiments in this application can be arbitrarily combined with each other without conflict. The protection scope of the present invention should be the technical solutions recorded in the claims, including the equivalent replacement solutions of the technical features in the technical solutions recorded in the claims. Any changes or replacement improvements that can be easily thought of by any person skilled in the art within the technical scope disclosed by the present invention are also covered by the protection scope of the present invention.

Claims

1. A method for preparing a broad-spectrum protective zirconium-based adsorption material, characterized in that: The method comprises the following steps: (1) adding a dispersant to an aqueous zirconium oxychloride solution, stirring at room temperature to form a suspension emulsion, and obtaining a zirconium oxychloride suspension slurry; (2) adding a composite surfactant to the zirconium oxychloride suspension slurry and stirring at high speed to obtain a suspension; (3) Under stirring, a sodium hydroxide solution is added dropwise to hydrolyze the solution to generate a precipitate, and the precipitate is allowed to stand for filtration, washing, drying, and crushing to obtain a surface-modified zirconium hydroxide particle sample; (4) preparing an impregnation solution: adding sodium bicarbonate, basic copper carbonate, potassium carbonate, silver nitrate and ammonium molybdate into pure water, stirring and dissolving to obtain an impregnation solution; (5) Add the impregnation solution obtained in step (4) to step (3), stir evenly and let it stand for a period of time, then take it out and dry, crush and sieve to obtain a broad-spectrum protective zirconium-based adsorption material.

2. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 1, characterized in that: In the step (1), the dispersant is polyepoxysuccinic acid, and the added mass thereof is 0.1-1.0% of the dry basis of zirconium oxychloride; and the mass concentration of the zirconium oxychloride aqueous solution is 10-30%.

3. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 1, characterized in that: In the step (2), the composite surfactant is composed of sodium 3-carboxybenzenesulfonate and polyoxyethylene lauryl ether carboxylic acid, and the added amount thereof is 1.0-3.0% of the dry basis of zirconium oxychloride.

4. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 3, characterized in that: The mass ratio of sodium 3-carboxybenzenesulfonate to polyoxyethylene lauryl ether carboxylic acid in the composite surfactant of step (2) is 1: 1-10.

5. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 1, characterized in that: In the step (2), the high-speed stirring refers to stirring at 800-1000 r / min.

6. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 1, characterized in that: In the step (3), the precipitate is first dried at 200-350° C. for 2-0.5 h, and then dried at 120° C. to constant weight.

7. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 1, characterized in that: In the step (3), the amount of zirconium hydroxide powder pressed into tablets is 10 to 20 g, the thickness of the pressed tablets is 0.2 to 0.4 cm, and the pressing pressure is 20 to 30 MPa.

8. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 1, characterized in that: In the step (4), the basic copper carbonate may also be copper acetate or copper citrate; the potassium carbonate may also be potassium acetate or potassium bromide; and the ammonium molybdate may also be sodium molybdate or magnesium molybdate.

9. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 1, characterized in that: In the step (4), the solid-to-liquid ratio of sodium bicarbonate, basic copper carbonate, potassium carbonate, silver nitrate, ammonium molybdate and pure water is (10-25): (25-40): (1-5): (0.1-0.5): (5-15): (100-150) (g / g / g / g / g / ml).

10. The method for preparing the broad-spectrum protective zirconium-based adsorption material according to claim 1, characterized in that: In the step (5), the solid-liquid ratio of the granular zirconium hydroxide and the impregnation solution is (100-150): (100-150) (g / ml), and the mixture is stirred evenly at 40-60° C. and left for 1-5 hours.

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