High-adsorbability silicon-zinc-based honeycomb molecular sieve and preparation method thereof

Abstract

The invention discloses a preparation method of a high-adsorbability silicon-zinc-based honeycomb molecular sieve. The preparation method comprises the following steps: (1) preparing matrix powder; (2) preparing modified powder; (3) preparing modified powder; and (4) uniformly mixing the modified powder, silica sol, a dispersing agent and deionized water to form mixed slurry, soaking a ceramic fiber honeycomb carrier in the mixed slurry, standing, taking out, drying and sintering to obtain the silicon-zinc-based honeycomb molecular sieve. The honeycomb molecular sieve prepared by the method is developed in internal pore structure and huge in specific surface area, so that the honeycomb molecular sieve has good adsorbability to volatile organic compounds.

Description

Technical Field

[0001] This invention relates to the field of adsorbent materials technology, and in particular to a highly adsorbent silicon-zinc based honeycomb molecular sieve and its preparation method. Background Technology

[0002] Molecular sieves are ordered porous materials with molecular-scale structures, their framework containing regular intracrystalline cavities and molecular-scale channel systems. As porous materials, they possess ordered pore structures and large specific surface areas, exhibiting excellent adsorption performance and finding wide applications in industry and agriculture. Furthermore, they possess good cation exchange capacity and can be modified to obtain more selective adsorption sites, thereby increasing their adsorption capacity. However, the pore size and surface state of molecular sieves limit their further applications. If the adsorption characteristics of active sites and pore structure can be adjusted, more applications will be available in the chemical and fine chemical industries. Summary of the Invention

[0003] Therefore, the present invention provides a method for preparing a highly adsorption-resistant silicon-zinc based honeycomb molecular sieve, comprising the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; add cuprous oxide powder and n-butylamine to the solution while stirring. After the addition is complete, continue stirring until uniform. Then add sodium silicate solution and zinc chloride solution while stirring. After the addition is complete, stir to form a suspension. Then seal the reaction vessel, heat to 110±10℃ and keep warm for more than 8 hours. Then air cool to room temperature, open the reaction vessel, separate the solid and liquid, wash the solid phase, dry, and calcine at 600~620℃ for 1~2 hours to obtain matrix powder. (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, stirred for 3-6 min, and then the solid and liquid are separated. The solid phase is washed with deionized water, dried, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60±5℃ in a water bath. After the addition is completed, the mixture is kept at 60±5℃ and stirred for more than 6 h, during which the mixture is refluxed. After stirring, the solid and liquid are separated, the solid phase is washed with deionized water, dried, and then added to ethanol and stirred to form a suspension. The suspension is then heated to 37±3℃ in a water bath and kept at that temperature. Glutaric anhydride is then added to the suspension while stirring. After the addition is completed, the mixture is kept at 37±3℃ and stirred for more than 2 h, during which the mixture is refluxed. Then the solid and liquid are separated, the solid phase is washed with deionized water, dried, and the modified powder is obtained. (3) Prepare an aqueous solution of cerium chloride and manganese chloride, heat the aqueous solution of cerium chloride and manganese chloride to 50±3℃ in a water bath and keep it at that temperature, and reflux during the holding process; then add the modified powder to the aqueous solution of cerium chloride and manganese chloride, and after the addition is completed, keep the solution at 50±3℃ and stir for more than 30 minutes, then separate the solid and liquid, dry the solid phase, and then calcine at 500~550℃ for 2~3 hours. After calcination, air cool to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant and deionized water are mixed evenly to form a mixed slurry. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand, then taken out and dried. After drying, it is sintered at 530-560℃ to obtain the silicon zinc-based honeycomb molecular sieve.

[0004] Further, in step (1), in the aqueous solution of sodium hydroxide and sodium aluminate, the concentration of sodium hydroxide is 5-8 g / 100 mL, the concentration of sodium aluminate is 1-2 g / 100 mL, and the solvent is water; in the sodium silicate solution, the concentration of sodium silicate is 5-7 g / 100 mL, and the solvent is water; in the zinc chloride solution, the concentration of zinc chloride is 10-12 g / 100 mL, and the solvent is water.

[0005] Further, in step (1), the ratio of cuprous oxide powder, n-butylamine, sodium silicate solution and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: cuprous oxide powder: n-butylamine: sodium silicate solution: zinc chloride solution = 30 mL: 0.7~0.9 g: 2.8~3.2 g: 40~50 mL: 20~25 mL.

[0006] Further, in step (2), the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is ammonium chloride: hydrochloric acid = 4-5 g / 100 mL, wherein the mass percentage of solute in the hydrochloric acid is 1%; the ratio of the matrix powder soaked in the aqueous solution of ammonium chloride and hydrogen chloride is matrix powder: aqueous solution of ammonium chloride and hydrogen chloride = 1 g: 20-30 mL.

[0007] Further, in step (2), the ethanol solution of γ-aminopropyltriethoxysilane contains 10% to 15% γ-aminopropyltriethoxysilane by mass, and the solvent is ethanol; the mass ratio of the dried solid phase added to the ethanol solution of γ-aminopropyltriethoxysilane is 1:30 to 50: the dried solid phase to the ethanol solution of γ-aminopropyltriethoxysilane = 1:30 to 50; the mass ratio of the dried solid phase to the ethanol suspension is 1:30 to 50: the solid phase to the ethanol suspension = 1:30 to 50; the mass ratio of the glutaric anhydride added to the suspension to the mass ratio of the solid phase added to prepare the suspension is 1 to 3:1.

[0008] Further, in step (3), the concentration of cerium chloride in the aqueous solution of cerium chloride and manganese chloride is 12-15 g / 100 mL, the concentration of manganese chloride is 8-10 g / 100 mL, and the solvent is water; the mass ratio of the modified powder added to the aqueous solution of cerium chloride and manganese chloride is modified powder: aqueous solution of cerium chloride and manganese chloride = 1:20-100.

[0009] Further, in step (4), the mass percentage of the modified powder in the mixed slurry is 20% to 25%, the mass percentage of the silica sol is 9% to 10%, the mass percentage of the dispersant is 0.4% to 0.5%, and the remainder is deionized water.

[0010] Furthermore, the dispersant is polyacrylic acid.

[0011] The beneficial effects of this invention are as follows: the honeycomb molecular sieve prepared by the method described in this invention has a well-developed internal pore structure and a large specific surface area, thus exhibiting excellent adsorption capacity for volatile organic compounds. Doping the molecular sieve with cuprous oxide, modifying it, and altering it with cerium and manganese ions all significantly improve the adsorption capacity of the final honeycomb molecular sieve. This may be because: in this invention, the doping of the molecular sieve with cuprous oxide enhances the apparent adsorption potential of the molecular sieve through the combined effect of copper ions and the micro-mesoporous structure of the molecular sieve during sintering; simultaneously, during sintering, some cuprous oxide can capture oxygen from the crystal lattice, generating a large number of oxygen vacancies and acidic sites, which also improves the adsorption capacity of the molecular sieve. On the other hand, due to the antibacterial properties of cuprous oxide, its addition to the molecular sieve reduces the adsorption of microorganisms on the molecular sieve surface to a certain extent, reducing the impact of microorganisms on adsorption capacity. Further treatment with an aqueous solution of ammonium chloride and hydrogen chloride dissolves some aluminum, increasing the silicon-to-aluminum ratio. It is well known that the hydrophobic properties of molecular sieves are correlated with their silicon-to-aluminum ratio. A higher silicon-to-aluminum ratio results in better hydrophobicity. A hydrophobic surface reduces water adsorption under certain humidity conditions, increasing the adsorption of VOC molecules. Furthermore, dealumination of the molecular sieve exhibits a larger specific surface area and mesopore volume. Additionally, hydrochloric acid activation increases the surface hydroxyl density. Subsequent amino and carboxyl group modification enhances the adsorption and ion exchange of cerium and manganese ions on the molecular sieve surface, allowing the surface to be partially loaded with active cerium-manganese oxide components. This alters the surface physicochemical properties and polarity of the molecular sieve, thereby improving its adsorption capacity for xylene. Detailed Implementation

[0012] The present invention will be further described below with reference to the embodiments.

[0013] Example 1 A method for preparing a highly adsorption-resistant silicon-zinc based honeycomb molecular sieve, comprising the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 5 g / 100 mL, the concentration of sodium aluminate is 1 g / 100 mL, and the solvent is water; add cuprous oxide powder and n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of cuprous oxide powder, n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: cuprous oxide. Powder: n-Butylamine: Sodium silicate solution: Zinc chloride solution = 30mL: 0.7g: 2.8g: 40mL: 20mL; wherein the sodium silicate solution has a concentration of 5g / 100mL and is in water; the zinc chloride solution has a concentration of 10g / 100mL and is in water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8h, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1h, and calcined at 600℃ for 1h to obtain the matrix powder; (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is ammonium chloride: hydrochloric acid = 4g / 100mL, wherein the mass percentage of solute in the hydrochloric acid is 1%; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, wherein the mass ratio of matrix powder to aqueous solution of ammonium chloride and hydrogen chloride is 1g: 20mL; the mixture is stirred for 4min, and then the solid and liquid phases are separated. The solid phase is washed three times with deionized water, dried at 100℃ for 1h, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60℃ in a water bath, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution of γ-aminopropyltriethoxysilane is 10%, and the solvent is ethanol; the dried solid phase is then added to the γ-aminopropyltriethoxysilane... The mass ratio of the propyltriethoxysilane ethanol solution to the dried solid phase was 1:30. After addition, the mixture was kept at 60°C and stirred for 6 hours, with reflux during the heating process. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour. The dried solid phase was then added to ethanol and stirred to form a suspension. The mass ratio of the dried solid phase to ethanol in the suspension was 1:30. The suspension was then heated to 37°C in a water bath and kept at that temperature. Glutaric anhydride was added to the suspension while stirring, with the mass ratio of glutaric anhydride added to the solid phase in the suspension being 1:1. After addition, the mixture was kept at 37°C and stirred for 2 hours, with reflux during the heating process. The solid and liquid phases were then separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour to obtain the modified powder. (3) Prepare an aqueous solution of cerium chloride and manganese chloride, wherein the concentration of cerium chloride is 12 g / 100 mL and the concentration of manganese chloride is 8 g / 100 mL, and the solvent is water; heat the aqueous solution of cerium chloride and manganese chloride to 50°C in a water bath and keep it at that temperature, and reflux during the heat preservation process; then add the modified powder to the aqueous solution of cerium chloride and manganese chloride, wherein the mass ratio of the modified powder to the aqueous solution of cerium chloride and manganese chloride is 1:30; after the addition is completed, keep the solution at 50°C and stir for 30 min, then separate the solid and liquid phases, dry the solid phase at 100°C for 1 h, and then calcine it at 500°C for 3 h, and then air cool it to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 20%, the mass percentage of the silica sol is 9%, the mass percentage of the dispersant is 0.4%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the silicon zinc-based honeycomb molecular sieve.

[0014] Example 2 A method for preparing a highly adsorption-resistant silicon-zinc based honeycomb molecular sieve, comprising the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 6 g / 100 mL, the concentration of sodium aluminate is 1 g / 100 mL, and the solvent is water; add cuprous oxide powder and n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of cuprous oxide powder, n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: sodium aluminate and sodium aluminate. Copper powder: n-Butylamine: Sodium silicate solution: Zinc chloride solution = 30mL: 0.8g: 3g: 45mL: 20mL; wherein the sodium silicate solution has a concentration of 6g / 100mL and is in water; the zinc chloride solution has a concentration of 11g / 100mL and is in water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8 hours, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1 hour, and calcined at 610℃ for 1 hour to obtain the matrix powder; (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is ammonium chloride: hydrochloric acid = 4g / 100mL, wherein the mass percentage of solute in the hydrochloric acid is 1%; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, wherein the mass ratio of matrix powder to aqueous solution of ammonium chloride and hydrogen chloride is 1g: 20mL; the mixture is stirred for 4min, and then the solid and liquid phases are separated. The solid phase is washed three times with deionized water, dried at 100℃ for 1h, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60℃ in a water bath, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution of γ-aminopropyltriethoxysilane is 10%, and the solvent is ethanol; the dried solid phase is then added to the γ-aminopropyltriethoxysilane... The mass ratio of the propyltriethoxysilane ethanol solution to the dried solid phase was 1:30. After addition, the mixture was kept at 60°C and stirred for 6 hours, with reflux during the heating process. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour. The dried solid phase was then added to ethanol and stirred to form a suspension. The mass ratio of the dried solid phase to ethanol in the suspension was 1:30. The suspension was then heated to 37°C in a water bath and kept at that temperature. Glutaric anhydride was added to the suspension while stirring. The mass ratio of glutaric anhydride added to the suspension to the mass of the solid phase added to the suspension was 2:1. After addition, the mixture was kept at 37°C and stirred for 2 hours, with reflux during the heating process. The solid and liquid phases were then separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour to obtain the modified powder. (3) Prepare an aqueous solution of cerium chloride and manganese chloride, wherein the concentration of cerium chloride is 13 g / 100 mL and the concentration of manganese chloride is 9 g / 100 mL, and the solvent is water; heat the aqueous solution of cerium chloride and manganese chloride to 50°C in a water bath and keep it at that temperature, and reflux during the heat preservation process; then add the modified powder to the aqueous solution of cerium chloride and manganese chloride, wherein the mass ratio of the modified powder to the aqueous solution of cerium chloride and manganese chloride is 1:30; after the addition is completed, keep the solution at 50°C and stir for 30 min, then separate the solid and liquid phases, dry the solid phase at 100°C for 1 h, and then calcine it at 500°C for 3 h, and then air cool it to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 20%, the mass percentage of the silica sol is 9%, the mass percentage of the dispersant is 0.4%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the silicon zinc-based honeycomb molecular sieve.

[0015] Example 3 A method for preparing a highly adsorption-resistant silicon-zinc based honeycomb molecular sieve, comprising the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 7 g / 100 mL, the concentration of sodium aluminate is 2 g / 100 mL, and the solvent is water; add cuprous oxide powder and n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of cuprous oxide powder, n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: sodium aluminate and sodium aluminate. Copper powder: n-Butylamine: Sodium silicate solution: Zinc chloride solution = 30mL: 0.8g: 3g: 45mL: 25mL; wherein the sodium silicate solution has a concentration of 6g / 100mL and is in water; the zinc chloride solution has a concentration of 11g / 100mL and is in water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8 hours, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1 hour, and calcined at 610℃ for 1 hour to obtain the matrix powder; (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is 5 g / 100 mL, wherein the mass percentage of the solute in the hydrochloric acid is 1%; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, wherein the ratio of the matrix powder to the aqueous solution of ammonium chloride and hydrogen chloride is 1 g: 20 mL; the mixture is stirred for 4 min, and then the solid and liquid phases are separated. The solid phase is washed three times with deionized water, dried at 100°C for 1 h, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60°C in a water bath, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution of γ-aminopropyltriethoxysilane is 15%, and the solvent is ethanol; the dried solid phase is then added to the γ-aminopropyltriethoxysilane... The mass ratio of the propyltriethoxysilane ethanol solution to the dried solid phase was 1:30. After addition, the mixture was kept at 60°C and stirred for 6 hours, with reflux during the heating process. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour. The dried solid phase was then added to ethanol and stirred to form a suspension. The mass ratio of the dried solid phase to ethanol in the suspension was 1:30. The suspension was then heated to 37°C in a water bath and kept at that temperature. Glutaric anhydride was added to the suspension while stirring. The mass ratio of glutaric anhydride added to the suspension to the mass of the solid phase added to the suspension was 2:1. After addition, the mixture was kept at 37°C and stirred for 2 hours, with reflux during the heating process. The solid and liquid phases were then separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour to obtain the modified powder. (3) Prepare an aqueous solution of cerium chloride and manganese chloride, wherein the concentration of cerium chloride is 14 g / 100 mL and the concentration of manganese chloride is 9 g / 100 mL, and the solvent is water; heat the aqueous solution of cerium chloride and manganese chloride to 50°C in a water bath and keep it at that temperature, and reflux during the heat preservation process; then add the modified powder to the aqueous solution of cerium chloride and manganese chloride, wherein the mass ratio of the modified powder to the aqueous solution of cerium chloride and manganese chloride is 1:30; after the addition is completed, keep the solution at 50°C and stir for 30 min, then separate the solid and liquid phases, dry the solid phase at 100°C for 1 h, and then calcine it at 550°C for 2 h, and then air cool it to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 25%, the mass percentage of the silica sol is 10%, the mass percentage of the dispersant is 0.5%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the silicon zinc-based honeycomb molecular sieve.

[0016] Example 4 A method for preparing a highly adsorption-resistant silicon-zinc based honeycomb molecular sieve, comprising the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 8 g / 100 mL, the concentration of sodium aluminate is 2 g / 100 mL, and the solvent is water; add cuprous oxide powder and n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of cuprous oxide powder, n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: cuprous oxide. Powder: n-Butylamine: Sodium silicate solution: Zinc chloride solution = 30mL: 0.9g: 3.2g: 50mL: 25mL; wherein the sodium silicate solution has a concentration of 7g / 100mL and is in water; the zinc chloride solution has a concentration of 12g / 100mL and is in water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8 hours, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1 hour, and calcined at 620℃ for 1 hour to obtain the matrix powder; (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is 5 g / 100 mL, wherein the mass percentage of the solute in the hydrochloric acid is 1%; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, wherein the ratio of the matrix powder to the aqueous solution of ammonium chloride and hydrogen chloride is 1 g: 20 mL; the mixture is stirred for 4 min, and then the solid and liquid phases are separated. The solid phase is washed three times with deionized water, dried at 100°C for 1 h, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60°C in a water bath, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution of γ-aminopropyltriethoxysilane is 15%, and the solvent is ethanol; the dried solid phase is then added to the γ-aminopropyltriethoxysilane... The mass ratio of the propyltriethoxysilane ethanol solution to the dried solid phase was 1:30. After addition, the mixture was kept at 60°C and stirred for 6 hours, with reflux during the heating process. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour. The dried solid phase was then added to ethanol and stirred to form a suspension. The mass ratio of the dried solid phase to ethanol in the suspension was 1:30. The suspension was then heated to 37°C in a water bath and kept at that temperature. Glutaric anhydride was added to the suspension while stirring. The mass ratio of glutaric anhydride added to the suspension to the mass of the solid phase added to the suspension was 3:1. After addition, the mixture was kept at 37°C and stirred for 2 hours, with reflux during the heating process. The solid and liquid phases were then separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour to obtain the modified powder. (3) Prepare an aqueous solution of cerium chloride and manganese chloride, wherein the concentration of cerium chloride is 15 g / 100 mL and the concentration of manganese chloride is 10 g / 100 mL, and the solvent is water; heat the aqueous solution of cerium chloride and manganese chloride to 50°C in a water bath and keep it at that temperature, and reflux during the heat preservation process; then add the modified powder to the aqueous solution of cerium chloride and manganese chloride, wherein the mass ratio of the modified powder to the aqueous solution of cerium chloride and manganese chloride is 1:30; after the addition is completed, keep the solution at 50°C and stir for 30 min, then separate the solid and liquid phases, dry the solid phase at 100°C for 1 h, and then calcine it at 550°C for 2 h, and then air cool it to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 25%, the mass percentage of the silica sol is 10%, the mass percentage of the dispersant is 0.5%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the silicon zinc-based honeycomb molecular sieve.

[0017] Comparative Example 1 A comparative method for preparing molecular sieves includes the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 7 g / 100 mL, the concentration of sodium aluminate is 2 g / 100 mL, and the solvent is water; add n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: n-butylamine Sodium silicate solution: zinc chloride solution = 30mL: 3g: 45mL: 25mL; wherein the concentration of sodium silicate in the sodium silicate solution is 6g / 100mL, and the solvent is water; the concentration of zinc chloride in the zinc chloride solution is 11g / 100mL, and the solvent is water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8h, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1h, and calcined at 610℃ for 1h to obtain the matrix powder; (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is 5 g / 100 mL, wherein the mass percentage of the solute in the hydrochloric acid is 1%; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, wherein the ratio of the matrix powder to the aqueous solution of ammonium chloride and hydrogen chloride is 1 g: 20 mL; the mixture is stirred for 4 min, and then the solid and liquid phases are separated. The solid phase is washed three times with deionized water, dried at 100°C for 1 h, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60°C in a water bath, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution of γ-aminopropyltriethoxysilane is 15%, and the solvent is ethanol; the dried solid phase is then added to the γ-aminopropyltriethoxysilane... The mass ratio of the propyltriethoxysilane ethanol solution to the dried solid phase was 1:30. After addition, the mixture was kept at 60°C and stirred for 6 hours, with reflux during the heating process. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour. The dried solid phase was then added to ethanol and stirred to form a suspension. The mass ratio of the dried solid phase to ethanol in the suspension was 1:30. The suspension was then heated to 37°C in a water bath and kept at that temperature. Glutaric anhydride was added to the suspension while stirring. The mass ratio of glutaric anhydride added to the suspension to the mass of the solid phase added to the suspension was 2:1. After addition, the mixture was kept at 37°C and stirred for 2 hours, with reflux during the heating process. The solid and liquid phases were then separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour to obtain the modified powder. (3) Prepare an aqueous solution of cerium chloride and manganese chloride, wherein the concentration of cerium chloride is 14 g / 100 mL and the concentration of manganese chloride is 9 g / 100 mL, and the solvent is water; heat the aqueous solution of cerium chloride and manganese chloride to 50°C in a water bath and keep it at that temperature, and reflux during the heat preservation process; then add the modified powder to the aqueous solution of cerium chloride and manganese chloride, wherein the mass ratio of the modified powder to the aqueous solution of cerium chloride and manganese chloride is 1:30; after the addition is completed, keep the solution at 50°C and stir for 30 min, then separate the solid and liquid phases, dry the solid phase at 100°C for 1 h, and then calcine it at 550°C for 2 h, and then air cool it to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 25%, the mass percentage of the silica sol is 10%, the mass percentage of the dispersant is 0.5%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the molecular sieve of this comparative example.

[0018] Comparative Example 2 A comparative method for preparing molecular sieves includes the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 7 g / 100 mL, the concentration of sodium aluminate is 2 g / 100 mL, and the solvent is water; add cuprous oxide powder and n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of cuprous oxide powder, n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: sodium aluminate and sodium aluminate. Copper powder: n-Butylamine: Sodium silicate solution: Zinc chloride solution = 30mL: 0.8g: 3g: 45mL: 25mL; wherein the sodium silicate solution has a concentration of 6g / 100mL and is in water; the zinc chloride solution has a concentration of 11g / 100mL and is in water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8 hours, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1 hour, and calcined at 610℃ for 1 hour to obtain the matrix powder; (2) Ammonium chloride was added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride was 5 g / 100 mL, wherein the mass percentage of solute in the hydrochloric acid was 1%; the matrix powder was then soaked in the aqueous solution of ammonium chloride and hydrogen chloride, the ratio of matrix powder to aqueous solution of ammonium chloride and hydrogen chloride was 1 g: 20 mL; the mixture was stirred for 4 min, and then the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100 °C for 1 h to obtain the modified powder of this comparative example. (3) Prepare an aqueous solution of cerium chloride and manganese chloride, wherein the concentration of cerium chloride is 14 g / 100 mL and the concentration of manganese chloride is 9 g / 100 mL, and the solvent is water; heat the aqueous solution of cerium chloride and manganese chloride to 50°C in a water bath and keep it at that temperature, and reflux during the heat preservation process; then add the modified powder to the aqueous solution of cerium chloride and manganese chloride, wherein the mass ratio of the modified powder to the aqueous solution of cerium chloride and manganese chloride is 1:30; after the addition is completed, keep the solution at 50°C and stir for 30 min, then separate the solid and liquid phases, dry the solid phase at 100°C for 1 h, and then calcine it at 550°C for 2 h, and then air cool it to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 25%, the mass percentage of the silica sol is 10%, the mass percentage of the dispersant is 0.5%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the molecular sieve of this comparative example.

[0019] Comparative Example 3 A comparative method for preparing molecular sieves includes the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 7 g / 100 mL, the concentration of sodium aluminate is 2 g / 100 mL, and the solvent is water; add cuprous oxide powder and n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of cuprous oxide powder, n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: sodium aluminate and sodium aluminate. Copper powder: n-Butylamine: Sodium silicate solution: Zinc chloride solution = 30mL: 0.8g: 3g: 45mL: 25mL; wherein the sodium silicate solution has a concentration of 6g / 100mL and is in water; the zinc chloride solution has a concentration of 11g / 100mL and is in water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8 hours, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1 hour, and calcined at 610℃ for 1 hour to obtain the matrix powder; (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is 5 g / 100 mL, wherein the mass percentage of the solute in the hydrochloric acid is 1%; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, wherein the ratio of the matrix powder to the aqueous solution of ammonium chloride and hydrogen chloride is 1 g: 20 mL; the mixture is stirred for 4 min, and then the solid and liquid phases are separated. The solid phase is washed three times with deionized water, dried at 100°C for 1 h, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60°C in a water bath, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution of γ-aminopropyltriethoxysilane is 15%, and the solvent is ethanol; the dried solid phase is then added to the γ-aminopropyltriethoxysilane... The mass ratio of the propyltriethoxysilane ethanol solution to the dried solid phase was 1:30. After addition, the mixture was kept at 60°C and stirred for 6 hours, with reflux during the heating process. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour. The dried solid phase was then added to ethanol and stirred to form a suspension. The mass ratio of the dried solid phase to ethanol in the suspension was 1:30. The suspension was then heated to 37°C in a water bath and kept at that temperature. Glutaric anhydride was added to the suspension while stirring. The mass ratio of glutaric anhydride added to the suspension to the mass of the solid phase added to the suspension was 2:1. After addition, the mixture was kept at 37°C and stirred for 2 hours, with reflux during the heating process. The solid and liquid phases were then separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour to obtain the modified powder. (3) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 25%, the mass percentage of the silica sol is 10%, the mass percentage of the dispersant is 0.5%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the molecular sieve of this comparative example.

[0020] Comparative Example 4 A comparative method for preparing molecular sieves includes the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 7 g / 100 mL, the concentration of sodium aluminate is 2 g / 100 mL, and the solvent is water; add cuprous oxide powder and n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of cuprous oxide powder, n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: sodium aluminate and sodium aluminate. Copper powder: n-Butylamine: Sodium silicate solution: Zinc chloride solution = 30mL: 0.8g: 3g: 45mL: 25mL; wherein the sodium silicate solution has a concentration of 6g / 100mL and is in water; the zinc chloride solution has a concentration of 11g / 100mL and is in water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8 hours, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1 hour, and calcined at 610℃ for 1 hour to obtain the matrix powder; (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is 5 g / 100 mL, wherein the mass percentage of the solute in the hydrochloric acid is 1%; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, wherein the ratio of the matrix powder to the aqueous solution of ammonium chloride and hydrogen chloride is 1 g: 20 mL; the mixture is stirred for 4 min, and then the solid and liquid phases are separated. The solid phase is washed three times with deionized water, dried at 100°C for 1 h, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60°C in a water bath, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution of γ-aminopropyltriethoxysilane is 15%, and the solvent is ethanol; the dried solid phase is then added to the γ-aminopropyltriethoxysilane... The mass ratio of the propyltriethoxysilane ethanol solution to the dried solid phase was 1:30. After addition, the mixture was kept at 60°C and stirred for 6 hours, with reflux during the heating process. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour. The dried solid phase was then added to ethanol and stirred to form a suspension. The mass ratio of the dried solid phase to ethanol in the suspension was 1:30. The suspension was then heated to 37°C in a water bath and kept at that temperature. Glutaric anhydride was added to the suspension while stirring. The mass ratio of glutaric anhydride added to the suspension to the mass of the solid phase added to the suspension was 2:1. After addition, the mixture was kept at 37°C and stirred for 2 hours, with reflux during the heating process. The solid and liquid phases were then separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour to obtain the modified powder. (3) Prepare an aqueous solution of cerium chloride, wherein the concentration of cerium chloride in the aqueous solution of cerium chloride is 14 g / 100 mL and the solvent is water; heat the aqueous solution of cerium chloride to 50 °C in a water bath and keep it at that temperature, and reflux during the heat preservation process; then add the modified powder to the aqueous solution of cerium chloride, wherein the mass ratio of the modified powder to the aqueous solution of cerium chloride is 1:30; after the addition is completed, keep the solution at 50 °C and stir for 30 min, then separate the solid and liquid phases, dry the solid phase at 100 °C for 1 h, and then calcine it at 550 °C for 2 h, and then air cool it to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 25%, the mass percentage of the silica sol is 10%, the mass percentage of the dispersant is 0.5%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the molecular sieve of this comparative example.

[0021] Comparative Example 5 A comparative method for preparing molecular sieves includes the following steps: (1) Prepare an aqueous solution of sodium hydroxide and sodium aluminate in a reaction vessel; the concentration of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium aluminate is 7 g / 100 mL, the concentration of sodium aluminate is 2 g / 100 mL, and the solvent is water; add cuprous oxide powder and n-butylamine to the solution while stirring, and continue stirring until homogeneous after the addition is complete. Then, add sodium silicate solution and zinc chloride solution while stirring. The ratio of cuprous oxide powder, n-butylamine, sodium silicate solution, and zinc chloride solution added to the aqueous solution of sodium hydroxide and sodium aluminate is: aqueous solution of sodium hydroxide and sodium aluminate: sodium aluminate and sodium aluminate. Copper powder: n-Butylamine: Sodium silicate solution: Zinc chloride solution = 30mL: 0.8g: 3g: 45mL: 25mL; wherein the sodium silicate solution has a concentration of 6g / 100mL and is in water; the zinc chloride solution has a concentration of 11g / 100mL and is in water; after adding the materials, the mixture is stirred to form a suspension, then the reaction vessel is sealed, heated to 110℃ and kept at that temperature for 8 hours, then cooled to room temperature, the reaction vessel is opened, solid and liquid are separated, the solid phase is washed three times with deionized water, dried at 80℃ for 1 hour, and calcined at 610℃ for 1 hour to obtain the matrix powder; (2) Ammonium chloride is added to hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the ratio of ammonium chloride to hydrochloric acid in the aqueous solution of ammonium chloride and hydrogen chloride is 5 g / 100 mL, wherein the mass percentage of the solute in the hydrochloric acid is 1%; the matrix powder is then immersed in the aqueous solution of ammonium chloride and hydrogen chloride, wherein the ratio of the matrix powder to the aqueous solution of ammonium chloride and hydrogen chloride is 1 g: 20 mL; the mixture is stirred for 4 min, and then the solid and liquid phases are separated. The solid phase is washed three times with deionized water, dried at 100°C for 1 h, and then added to an ethanol solution of γ-aminopropyltriethoxysilane kept at 60°C in a water bath, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution of γ-aminopropyltriethoxysilane is 15%, and the solvent is ethanol; the dried solid phase is then added to the γ-aminopropyltriethoxysilane... The mass ratio of the propyltriethoxysilane ethanol solution to the dried solid phase was 1:30. After addition, the mixture was kept at 60°C and stirred for 6 hours, with reflux during the heating process. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour. The dried solid phase was then added to ethanol and stirred to form a suspension. The mass ratio of the dried solid phase to ethanol in the suspension was 1:30. The suspension was then heated to 37°C in a water bath and kept at that temperature. Glutaric anhydride was added to the suspension while stirring. The mass ratio of glutaric anhydride added to the suspension to the mass of the solid phase added to the suspension was 2:1. After addition, the mixture was kept at 37°C and stirred for 2 hours, with reflux during the heating process. The solid and liquid phases were then separated. The solid phase was washed three times with deionized water and dried at 100°C for 1 hour to obtain the modified powder. (3) Prepare an aqueous solution of manganese chloride, wherein the concentration of manganese chloride in the aqueous solution of manganese chloride is 9 g / 100 mL and the solvent is water; heat the aqueous solution of manganese chloride to 50°C in a water bath and keep it at that temperature, and reflux during the heat preservation process; then add the modified powder to the aqueous solution of manganese chloride, wherein the mass ratio of the modified powder to the aqueous solution of manganese chloride is 1:30; after the addition is completed, keep the solution at 50°C and stir for 30 min, then separate the solid and liquid phases, dry the solid phase at 100°C for 1 h, and then calcine it at 550°C for 2 h, and then air cool it to room temperature to obtain the modified powder; (4) The modified powder, silica sol, dispersant (polyacrylic acid Mw=3000) and deionized water are mixed evenly to form a mixed slurry. In the mixed slurry, the mass percentage of the modified powder is 25%, the mass percentage of the silica sol is 10%, the mass percentage of the dispersant is 0.5%, and the remainder is deionized water. Then, the ceramic fiber honeycomb carrier is immersed in the mixed slurry, left to stand for 30 minutes, then taken out and dried at 80°C for 1 hour. After drying, it is sintered at 550°C for 3 hours to obtain the molecular sieve of this comparative example.

[0022] Example 5 The adsorption rate of o-xylene by the molecular sieves prepared by the methods described in Appendix B of standard T / CAEPI 52-2022 was determined, and the results are shown in Table 1.

[0023] Table 1 As shown in Table 1, the honeycomb molecular sieve prepared by the method described in this invention has a well-developed internal pore structure and a large specific surface area, thus exhibiting good adsorption capacity for volatile organic compounds. Comparison of Example 3 and various comparative examples shows that incorporating cuprous oxide into the molecular sieve, modifying it, and modifying it with cerium and manganese ions all significantly improve the adsorption capacity of the final honeycomb molecular sieve. This may be because: in this invention, incorporating cuprous oxide into the molecular sieve enhances the apparent adsorption potential of the molecular sieve through the combined effect of copper ions and the micro-mesoporous structure of the molecular sieve during sintering; simultaneously, during sintering, some cuprous oxide can capture oxygen from the crystal lattice, generating a large number of oxygen vacancies and acidic sites, which also improves the adsorption capacity of the molecular sieve. On the other hand, due to the antibacterial properties of cuprous oxide, its addition to the molecular sieve reduces the adsorption of microorganisms on the molecular sieve surface to a certain extent, reducing the impact of microorganisms on adsorption capacity. Further treatment with an aqueous solution of ammonium chloride and hydrogen chloride dissolves some aluminum, increasing the silicon-to-aluminum ratio. It is well known that the hydrophobic properties of molecular sieves are correlated with their silicon-to-aluminum ratio. A higher silicon-to-aluminum ratio results in better hydrophobicity. A hydrophobic surface reduces water adsorption under certain humidity conditions, increasing the adsorption of VOC molecules. Furthermore, dealumination of the molecular sieve exhibits a larger specific surface area and mesopore volume. Additionally, hydrochloric acid activation increases the surface hydroxyl density. Subsequent amino and carboxyl group modification enhances the adsorption and ion exchange of cerium and manganese ions on the molecular sieve surface, allowing the surface to be partially loaded with active cerium-manganese oxide components. This alters the surface physicochemical properties and polarity of the molecular sieve, thereby improving its adsorption capacity for xylene.

[0024] The technical solutions provided by the present invention have been described in detail above. For those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of the embodiments of the present invention. Therefore, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A method for preparing a high adsorptive silicon-zinc-based honeycomb molecular sieve, characterized by the steps of The application relates to a preparation method of a silicon-zinc-based honeycomb molecular sieve. (1) an aqueous solution of sodium hydroxide and sodium metaaluminate is arranged in a reaction kettle; cuprous oxide powder and n-butylamine are added into the solution under stirring; after the feeding is completed, the solution is continuously stirred until uniform; then sodium silicate solution and zinc chloride solution are added into the solution under stirring; after the feeding, the solution is stirred to form a suspension; then the reaction kettle is closed; the solution is heated to 110+ / -10 DEG C and kept for more than 8h; then the solution is naturally cooled to normal temperature; the reaction kettle is opened; solid-liquid separation is carried out; the solid phase is washed; the solid phase is dried; the dried solid phase is calcined at 600-620 DEG C for 1-2h; and the base powder is obtained; (2) ammonium chloride is added into hydrochloric acid to prepare an aqueous solution of ammonium chloride and hydrogen chloride; the base powder is soaked in the aqueous solution of ammonium chloride and hydrogen chloride; the solution is stirred for 3-6min; then solid-liquid separation is carried out; the solid phase is washed with deionized water; the solid phase is dried; the dried solid phase is added into an ethanol solution of gamma-aminopropyl triethoxysilane in a water bath with a temperature of 60+ / -5 DEG C; after the feeding is completed, the solution is continuously kept in the water bath with a temperature of 60+ / -5 DEG C and stirred for more than 6h; during the keeping process, the solution is condensed and refluxed; after the stirring is completed, solid-liquid separation is carried out; the solid phase is washed with deionized water; the solid phase is dried; the dried solid phase is added into ethanol; the solution is stirred to form a suspension; then the suspension is heated in a water bath to 37+ / -3 DEG C and kept; under stirring, glutaric anhydride is added into the suspension; after the feeding is completed, the solution is kept in the water bath with a temperature of 37+ / -3 DEG C and stirred for more than 2h; during the keeping process, the solution is condensed and refluxed; then solid-liquid separation is carried out; the solid phase is washed with deionized water; the solid phase is dried; and the modified powder is obtained; (3) an aqueous solution of cerium chloride and manganese chloride is prepared; the aqueous solution of cerium chloride and manganese chloride is heated in a water bath to 50+ / -3 DEG C and kept; during the keeping process, the solution is condensed and refluxed; then the modified powder is added into the aqueous solution of cerium chloride and manganese chloride; after the feeding is completed, the solution is kept in the water bath with a temperature of 50+ / -3 DEG C and stirred for more than 30min; then solid-liquid separation is carried out; the solid phase is dried; the dried solid phase is calcined at 500-550 DEG C for 2-3h; after the calcination, the solution is naturally cooled to normal temperature; and the modified powder is obtained; (4) the modified powder, silica sol, dispersant and deionized water are uniformly mixed to form a mixed slurry; then a ceramic fiber honeycomb carrier is immersed in the mixed slurry; the solution is left to stand; then the solution is taken out and dried; after the drying, the solution is sintered at 530-560 DEG C; and the silicon-zinc-based honeycomb molecular sieve is obtained.

2. The method for preparing a highly adsorption-oriented silicon-zinc based honeycomb molecular sieve according to claim 1, characterized in that, In the step (1), in the aqueous solution of sodium hydroxide and sodium metaaluminate, the solubility of sodium hydroxide is 5-8g / 100mL, the concentration of sodium metaaluminate is 1-2g / 100mL, and the solvent is water; in the sodium silicate solution, the concentration of sodium silicate is 5-7g / 100mL, and the solvent is water; in the zinc chloride solution, the concentration of zinc chloride is 10-12g / 100mL, and the solvent is water.

3. The method for preparing a highly adsorption-oriented silicon-zinc based honeycomb molecular sieve according to claim 2, characterized in that, In the step (1), the amount ratio of the aqueous solution of sodium hydroxide and sodium metaaluminate, cuprous oxide powder, n-butylamine, sodium silicate solution and zinc chloride solution is as follows: the aqueous solution of sodium hydroxide and sodium metaaluminate: cuprous oxide powder: n-butylamine: sodium silicate solution: zinc chloride solution=30mL: 0.7-0.9g: 2.8-3.2g: 40-50mL: 20-25mL.

4. The method for preparing a highly adsorption-oriented silicon-zinc based honeycomb molecular sieve according to claim 1, characterized in that, In the step (2), the amount of the ammonium chloride added into the hydrochloric acid to configure the aqueous solution of ammonium chloride and hydrogen chloride is 4-5 g / 100 mL of the hydrochloric acid, wherein the mass percentage of the solute in the hydrochloric acid is 1%; the amount of the substrate powder immersed in the aqueous solution of ammonium chloride and hydrogen chloride is 1 g: 20-30 mL of the aqueous solution of ammonium chloride and hydrogen chloride.

5. The method for preparing a highly adsorption-oriented silicon-zinc based honeycomb molecular sieve according to claim 1, characterized in that, In the step (2), the mass percentage of the γ-aminopropyltriethoxysilane in the ethanol solution of the γ-aminopropyltriethoxysilane is 10%-15%, and the solvent is ethanol; the mass ratio of the dried solid phase to the ethanol solution of the γ-aminopropyltriethoxysilane after the dried solid phase is added to the ethanol solution of the γ-aminopropyltriethoxysilane is 1:30-50; the mass ratio of the solid phase to ethanol after the dried solid phase is added to ethanol to form a suspension is 1:30-50; and the mass ratio of glutaric anhydride to the solid phase after the glutaric anhydride is added to the suspension is 1-3:

1.

6. The method for preparing a highly adsorption-oriented silicon-zinc based honeycomb molecular sieve according to claim 1, characterized in that, In the step (3), the concentration of cerium chloride in the aqueous solution of cerium chloride and manganese chloride is 12-15 g / 100 mL, the concentration of manganese chloride is 8-10 g / 100 mL, and the solvent is water; and the mass ratio of the modified powder to the aqueous solution of cerium chloride and manganese chloride after the modified powder is added to the aqueous solution of cerium chloride and manganese chloride is 1:20-100.

7. The method for preparing a highly adsorption-oriented silicon-zinc based honeycomb molecular sieve according to claim 1, characterized in that, In the step (4), the mass percentage of the modified powder in the mixed slurry is 20%-25%, the mass percentage of the silica sol is 9%-10%, the mass percentage of the dispersant is 0.4%-0.5%, and the rest is deionized water.

8. The method for preparing a highly adsorption-oriented silicon-zinc based honeycomb molecular sieve according to claim 1, characterized in that, The dispersant is polyacrylic acid.

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