Composite molecular sieve material, method for preparing the same and use thereof

Abstract

This invention belongs to the field of inorganic non-metallic adsorbent materials, specifically relating to a composite molecular sieve material, its preparation method, and its application. The composite molecular sieve material includes a metal-loaded ZSM-5 molecular sieve, a metal-loaded high-silica Y-type molecular sieve, and a metal-loaded modified zeolite. The mass percentage of the loaded metal is 0.1%–5%, and the mass ratio of the metal-loaded ZSM-5 molecular sieve, the metal-loaded high-silica Y-type molecular sieve, and the metal-loaded modified zeolite is 1:1–2:0.5–2. The composite molecular sieve material provided by this invention involves metal loading of ZSM-5 molecular sieve, high-silica Y-type molecular sieve, and modified zeolite, followed by mixing, extrusion molding, or spraying or coating onto a carrier. The multiple metal-loaded molecular sieves in the composite molecular sieve material interact and work together to remove various air pollutants. The molecular sieve structure and the loaded carrier can reduce wind resistance and improve material performance in practical applications.

Description

Technical Field

[0001] This invention belongs to the field of inorganic non-metallic adsorption materials, specifically relating to a composite molecular sieve material, its preparation method, and its application. Background Technology

[0002] VOCs are a key concern in the field of air purification, representing harmful gaseous pollutants. With rising living standards, people have higher requirements for air quality and an increasing need for indoor odor elimination. Odors may originate from bathrooms, kitchens, building materials, pets, etc., and their components include inorganic substances such as ammonia and hydrogen sulfide, as well as organic compounds such as alkanes, aldehydes, ketones, acids, and aliphatic compounds. Molecular sieves, as excellent adsorbents, possess characteristics such as uniform pore size distribution, high selectivity, high thermal and chemical stability, and good regeneration performance. However, their uniform pore size and high selectivity mean that molecular sieves only adsorb and separate one type or class of pollutants during use.

[0003] Patent CN111250066A discloses a method for preparing a molecular sieve honeycomb carrier for adsorbing volatile organic compounds. The method involves preparing a molecular sieve honeycomb carrier by combining a composite molecular sieve, additives, and a binder. The composite molecular sieve is NaY molecular sieve, ZSM-5 molecular sieve, and β molecular sieve, synthesized in situ on a calcined plateau. Patent CN107583604B discloses a hydrophobic honeycomb zeolite material, its preparation method, and its applications. The material includes ZSM-5 type zeolite, Y-type zeolite, and a transcrystalline material. The preparation method is further disclosed. Both of these materials employ two or more molecular sieves in combination. However, the types of harmful substances they can adsorb are limited, the hydrophobic treatment steps are complex, and in practical industrial applications, VOCs gases often contain moisture, with some VOCs gases having a relative humidity as high as 80%. The strong hydrophilicity of Y-type molecular sieves greatly limits their application in the field of VOCs treatment. Summary of the Invention

[0004] Purpose of the invention: The technical problem to be solved by the present invention is to overcome the problems of limited adsorption of harmful substances, single pore size, and complex hydrophobic treatment steps in the prior art, so as to provide a composite molecular sieve material, its preparation method and application.

[0005] To achieve the above objectives, the technical solution provided by the present invention is as follows:

[0006] A composite molecular sieve material includes a metal-loaded ZSM-5 molecular sieve, a metal-loaded high-silica Y-type molecular sieve, and a metal-loaded modified zeolite. The mass percentage of the metal-loaded material is 0.1% to 5%, wherein the mass ratio of the metal-loaded ZSM-5 molecular sieve to the metal-loaded high-silica Y-type molecular sieve to the metal-loaded modified zeolite is 1:1 to 2:0.5 to 2.

[0007] The load metal is one or more of iron, manganese, copper, platinum, zinc, and cobalt.

[0008] The high-silicon Y-type molecular sieve is a high-silicon Y-type molecular sieve with a silicon-to-aluminum ratio of 50 to 200.

[0009] The modified zeolite with the loaded metal is prepared by impregnating artificial zeolite with a transition metal solution and then drying it. The artificial zeolite is Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50.

[0010] A method for preparing a composite molecular sieve material includes the following steps:

[0011] (1) Mix ZSM-5 molecular sieve loaded with metal, high-silica Y molecular sieve loaded with metal and modified zeolite loaded with metal in a mass ratio of 1:1 to 2:0.5 to 2 to obtain a mixed powder.

[0012] (2) The mixed powder is mixed evenly with additives, binders and water, wherein the mass ratio of the mixed powder, additives, binders and water is 1-1.5:0.01-0.05:0.1-1:20-30 to obtain a slurry;

[0013] (3) The slurry is sprayed or coated onto a carrier and dried to obtain a composite molecular sieve material, wherein the solid content of the slurry is 5-20% and the loading of molecular sieves on the carrier is 60-125 g / m³. 2 .

[0014] The carrier is one of fiberglass, skeleton cloth, metal mesh, or corrugated paper.

[0015] A method for preparing a composite molecular sieve material includes the following steps:

[0016] (1) Mix ZSM-5 molecular sieve loaded with metal, high-silica Y molecular sieve loaded with metal and modified zeolite loaded with metal in a mass ratio of 1:1 to 2:0.5 to 2 to obtain a mixed powder.

[0017] (2) The mixed powder is mixed evenly with additives, binders and water, wherein the mass ratio of the mixed powder, additives, binders and water is 1-1.5:0.01-0.2:0.3-0.6:0.5N2 to obtain mud material;

[0018] (3) Vacuum knead the clay, age it, extrude it into shape, and dry and roast it.

[0019] (4) The calcined molded carrier is placed in a reaction furnace and subjected to gas phase hydrophobic treatment under inert gas protection to obtain composite molecular sieve material.

[0020] The structure of the molded carrier is rod-shaped, spherical, or honeycomb-shaped.

[0021] The additive is one or more of hydroxypropyl methylcellulose, polyvinyl alcohol, dextrin, guar gum powder, and glycerin, and the binder is one or more of boehmite, silica sol, alumina sol, aluminosilicate glue, resin, polyacrylic acid, styrene-butadiene latex (SBR), and polycarboxylate.

[0022] The application of the composite molecular sieve material in devices for adsorbing odorous gases and VOCs.

[0023] Beneficial effects:

[0024] This invention provides a composite molecular sieve material, its preparation method, and its application. Compared with the prior art, this invention has the following advantages:

[0025] Composite molecular sieve materials include metal-loaded ZSM-5 molecular sieves, metal-loaded high-silica Y-type molecular sieves, and metal-loaded modified zeolites. The molecular sieves with various metal loads work together to remove a variety of air pollutants. The material's molded structure or loading on a carrier can reduce wind resistance and improve material performance in practical applications, while maintaining the high specific surface area of ​​the molecular sieve. This enhances the adsorption capacity of volatile organic compounds per unit time, providing a material basis for the development of related indoor air purifiers. Attached Figure Description

[0026] To more clearly illustrate the technical solution of this application, the drawings used in the embodiments will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This is a schematic diagram of the loaded composite molecular sieve material skeleton cloth filter media provided in the embodiments of this application;

[0028] Figure 2 This is a schematic diagram of the metal mesh of the loaded composite molecular sieve material provided in the embodiments of this application;

[0029] Figure 3 This is a schematic diagram of the honeycomb carrier of the composite molecular sieve material provided in the embodiments of this application. Detailed Implementation

[0030] The present invention will be further illustrated below with reference to specific embodiments. These embodiments are implemented under the premise of the technical solution of the present invention. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0031] Example 1

[0032] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g tetraethyl orthosilicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0033] 10g of the above ZSM-5 molecular sieve was impregnated with 4g of a 50% manganese nitrate precursor solution, then allowed to stand for 10h, and calcined at 500℃ for 6h. A ZSM-5 molecular sieve with a manganese loading of 5% was obtained.

[0034] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1100℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:10, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 500℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 100.

[0035] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% zinc nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a zinc loading of 3.1% was obtained.

[0036] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0037] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:1 to obtain a composite molecular sieve.

[0038] (5) Add 10g of composite molecular sieve, 2g of styrene-butadiene latex SBR binder with a mass fraction of 50%, and 0.4g of hydroxypropyl methylcellulose additive to 208g of water and mix evenly to obtain a slurry with a solid content of 5.2%.

[0039] (6) The above-mentioned slurry with a solid content of 5.2% is uniformly coated onto the skeleton fabric and dried at 120°C to obtain a composite molecular sieve filter material that can adsorb odor gases and VOC gases, such as... Figure 1As shown.

[0040] Example 2

[0041] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0042] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.4 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 0.6% was obtained.

[0043] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1100℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:10, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 500℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 100.

[0044] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% zinc nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a zinc loading of 3.1% was obtained.

[0045] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0046] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:1:1 to obtain a composite molecular sieve.

[0047] (5) Add 13g of composite molecular sieve, 2.5g of styrene-butadiene latex SBR binder with a mass fraction of 50%, and 0.4g of additive guar gum powder to 208g of water, mix evenly, and obtain a slurry with a solid content of 6.5%.

[0048] (6) The above-mentioned slurry with a solid content of 6.5% is uniformly coated on the skeleton cloth and dried at 120°C to obtain a composite molecular sieve filter material that can adsorb odor gases and VOC gases.

[0049] Example 3

[0050] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0051] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.8 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 1.2% was obtained.

[0052] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1200℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:15, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 550℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 120.

[0053] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% manganese nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a manganese loading of 2.8% was obtained.

[0054] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0055] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:1 to obtain a composite molecular sieve.

[0056] (5) Add 10g of composite molecular sieve, 2g of styrene-butadiene latex SBR binder with a mass fraction of 50%, and 0.4g of additive guar powder to 208g of water and mix evenly to obtain a slurry with a solid content of 5.2%.

[0057] (6) The above-mentioned slurry with a solid content of 5.2% is uniformly coated onto nickel foam metal mesh and dried at 120°C to obtain a composite molecular sieve filter material that can adsorb odor gases and VOC gases, such as... Figure 2 As shown.

[0058] Example 4

[0059] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0060] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.8 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 1.2% was obtained.

[0061] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1200℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:15, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 550℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 120.

[0062] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% manganese nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a manganese loading of 2.8% was obtained.

[0063] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0064] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:0.5 to obtain a composite molecular sieve.

[0065] (5) Add 15g of composite molecular sieve, 10g of styrene-butadiene latex SBR binder with a mass fraction of 50%, and 0.5g of additive guar gum powder to 300g of water and mix evenly to obtain a slurry with a solid content of 6.3%.

[0066] (6) The above-mentioned slurry with a solid content of 6.3% is uniformly coated on the nickel foam metal mesh and dried at 120°C to obtain a composite molecular sieve filter material that can adsorb odor gases and VOC gases.

[0067] Example 5

[0068] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0069] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.8 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 1.2% was obtained.

[0070] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1200℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:15, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 550℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 120.

[0071] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% manganese nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a manganese loading of 2.8% was obtained.

[0072] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0073] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:2 to obtain a composite molecular sieve.

[0074] (5) Add 10g of composite molecular sieve, 1g of styrene-butadiene latex SBR binder with a mass fraction of 50%, and 0.1g of additive guar gum powder to 200g of water and mix evenly to obtain a slurry with a solid content of 5.0%.

[0075] (6) The above-mentioned slurry with a solid content of 5.0% is uniformly coated on the nickel foam metal mesh and dried at 120°C to obtain a composite molecular sieve filter material that can adsorb odor gases and VOC gases.

[0076] Example 6

[0077] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0078] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.8 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 1.2% was obtained.

[0079] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1200℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:15, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 550℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 120.

[0080] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% zinc nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a zinc loading of 3.1% was obtained.

[0081] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0082] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:1 to obtain a composite molecular sieve.

[0083] (5) 140g of composite molecular sieve, 60g of pseudoboehmite SB powder, 4g of guar gum powder, and 94g of water (water-to-powder ratio of 0.46, mass ratio of water to total powder after mixing) were mixed evenly, shaped, and calcined. The calcined shaped carrier was placed in a reactor, and under nitrogen protection, SiCl4 was used for vapor-phase hydrophobic treatment to obtain a 200-mesh composite molecular sieve honeycomb structure material. Figure 3 As shown.

[0084] Example 7

[0085] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0086] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.8 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 1.2% was obtained.

[0087] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1200℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:15, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 550℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 120.

[0088] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% zinc nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a zinc loading of 3.1% was obtained.

[0089] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0090] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:1 to obtain a composite molecular sieve.

[0091] (5) Mix 150g of composite molecular sieve, 60g of polyacrylic acid, 20g of dextrin, and 200g of water with a water-to-powder ratio of 0.87 (the mass ratio of water to the total powder after mixing) evenly, shape, and calcine. Place the calcined shaped carrier in a reaction furnace and perform gas-phase hydrophobic treatment with SiCl4 under argon protection to obtain 200-mesh composite molecular sieve honeycomb structure material.

[0092] Example 8

[0093] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0094] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.8 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 1.2% was obtained.

[0095] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1200℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:15, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 550℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 120.

[0096] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% zinc nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a zinc loading of 3.1% was obtained.

[0097] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0098] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:1 to obtain a composite molecular sieve.

[0099] (5) Mix 100g of composite molecular sieve, 30g of styrene-butadiene latex (SBR), 1g of polyvinyl alcohol, and 50g of water. The water-to-powder ratio is 0.37 (the mass ratio of water to the total powder after mixing). The mixture is shaped, calcined, and the calcined shaped carrier is placed in a reaction furnace. Under argon protection, SiCl4 is subjected to vapor-phase hydrophobic treatment to obtain a 200-mesh composite molecular sieve honeycomb structure material.

[0100] Example 9

[0101] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0102] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.08 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 0.1% was obtained.

[0103] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1200℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:15, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 550℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 120.

[0104] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% zinc nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a zinc loading of 3.1% was obtained.

[0105] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0106] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:0.5 to obtain a composite molecular sieve.

[0107] (5) Mix 100g of composite molecular sieve, 30g of styrene-butadiene latex (SBR), 1g of polyvinyl alcohol, and 50g of water. The water-to-powder ratio is 0.37 (the mass ratio of water to the total powder after mixing). The mixture is shaped, calcined, and the calcined shaped carrier is placed in a reaction furnace. Under nitrogen protection, SiCl4 is used for vapor-phase hydrophobic treatment to obtain 200-mesh composite molecular sieve honeycomb structure material.

[0108] Example 10

[0109] (1) Mix 1g aluminum isopropoxide, 0.2g sodium hydroxide, and 63g tetrapropylammonium hydroxide, and stir at room temperature until the solution is clear. Then, add 30g ethyl silicate dropwise while stirring to form a uniform gel. Add 4g lysine to the gel system, stir at room temperature for 3 hours, and then transfer the gel to a stainless steel high-pressure reactor with a polytetrafluoroethylene liner. Crystallize at 80°C for 2 days, and then at 200°C for 2 days. Then, centrifuge and wash the obtained product 5 times with water, dry at 80°C for 12 hours, and calcine at 600°C for 5 hours to obtain Na-type ZSM-5. Then, ion exchange in an ammonia solution at 80°C for 6 hours, centrifuge and wash with water 3 times, and dry at 80°C to obtain H-type ZSM-5.

[0110] 10 g of the above ZSM-5 molecular sieve was impregnated with 0.08 g of a 50% manganese nitrate precursor solution, then allowed to stand for 10 h, and calcined at 500 °C for 6 h. A ZSM-5 molecular sieve with a manganese loading of 0.1% was obtained.

[0111] (2) Take 2g of Y-type parent molecular sieve, calcine it at 1200℃, and simultaneously introduce an air-water vapor mixture for high-temperature treatment for 3h. Add 1mol / L hydrochloric acid to the sample, with a solid mass: liquid mass = 1:15, treat it in a water bath for 2h, wash it thoroughly until neutral, dry it at 120℃ for 12h, and calcine it at 550℃ for 6h. Repeat the above dealuminization process for the obtained solid powder, and perform acid dealuminization 5 times to obtain a high-silicon Y-type molecular sieve with a silicon-aluminum ratio of 120.

[0112] 10g of the above-mentioned Y-type molecular sieve was impregnated with 2g of a 50% zinc nitrate precursor solution, then allowed to stand for 10h, and calcined at 550℃ for 8h. A high-silica Y-type molecular sieve with a zinc loading of 3.1% was obtained.

[0113] (3) Take 20g of Na2O-Al2O3-mSiO2-nH2O artificial zeolite, where m is 50-200 and n is 10-50, add 20% CuCl2 solution, soak for 12h, and then dry the zeolite at 105℃ to obtain modified zeolite with a copper loading of 4%.

[0114] (4) The above three molecular sieves are mixed evenly in a mass ratio of 1:2:2 to obtain a composite molecular sieve.

[0115] (5) Mix 100g of composite molecular sieve, 30g of styrene-butadiene latex (SBR), 1g of polyvinyl alcohol, and 50g of water. The water-to-powder ratio is 0.37 (the mass ratio of water to the total powder after mixing). The mixture is shaped, calcined, and the calcined shaped carrier is placed in a reaction furnace. Under nitrogen protection, SiCl4 is used for vapor-phase hydrophobic treatment to obtain 200-mesh composite molecular sieve honeycomb structure material.

[0116] The composite molecular sieve materials prepared in Examples 1-10 were subjected to NH3 adsorption and VOC adsorption performance tests (9 VOC mixed solutions, including benzene, toluene, n-butyl acetate, ethylbenzene, p-xylene, o-xylene, m-xylene, styrene, and n-undecane). Examples 6-10 were prepared by extrusion molding, drying, and calcination, without the need for carrier adsorption. The results are shown in Table 1 below:

[0117] Table 1 Performance indicators of composite molecular sieve materials prepared in different embodiments

[0118]

[0119] As shown in Table 1, the NH3 adsorption capacity and VOCs adsorption performance were significantly improved after different metal loadings, powder mixing, further calcination, and carrier treatment. The optimal matching of metal-loaded ZSM-5 and Y-type molecular sieves and artificial zeolite materials made it easier for the mixed powder materials to be adsorbed onto the carrier or calcined into shape. The added metals catalyzed the decomposition of organic matter in the form of oxides, improving the material's adsorption and purification capacity. The loading or shaping structure resulted in a greater improvement in NH3 and VOCs adsorption and purification capacity compared to rod-shaped and spherical molecular sieves on the market, especially in indoor air purification applications with high wind speeds.

[0120] The above specific embodiments further illustrate the purpose, technical solution and beneficial effects of this application. It should be understood that the above are only specific embodiments of this application and are not intended to limit the scope of protection of this application. Any modifications, equivalent substitutions, improvements, etc., made on the basis of the technical solution of this application should be included within the scope of protection of this application.

Claims

1. A composite molecular sieve material, characterized in that, It includes ZSM-5 type molecular sieve loaded with metal, high-silica Y-type molecular sieve loaded with metal, and modified zeolite loaded with metal. The mass percentage of loaded metal is 0.1% to 5%, and the mass ratio of ZSM-5 type molecular sieve loaded with metal: high-silica Y-type molecular sieve loaded with metal: modified zeolite loaded with metal is 1:1 to 2:0.5 to 2.

2. The composite molecular sieve material according to claim 1, characterized in that, The load metal is one or more of iron, manganese, copper, platinum, zinc, and cobalt.

3. The composite molecular sieve material according to claim 1, characterized in that, The high-silicon Y-type molecular sieve is a high-silicon Y-type molecular sieve with a silicon-to-aluminum ratio of 50 to 200.

4. The composite molecular sieve material according to claim 1, characterized in that, The modified zeolite with the loaded metal is prepared by impregnating artificial zeolite with a transition metal solution and then drying it.

5. A method for preparing a composite molecular sieve material, characterized in that, Includes the following steps: (1) Mix ZSM-5 molecular sieve loaded with metal, high-silica Y molecular sieve loaded with metal and modified zeolite loaded with metal in a mass ratio of 1:1~2:0.5~2 to obtain a mixed powder; (2) The mixed powder is mixed evenly with additives, binders and water, wherein the mass ratio of the mixed powder, additives, binders and water is 1-1.5:0.01-0.05:0.1-1:20-30 to obtain a slurry; (3) The slurry is sprayed or coated onto a carrier and dried to obtain a composite molecular sieve material, wherein the solid content of the slurry is 5-20% and the loading of molecular sieves on the carrier is 60-125 g / m³. 2 .

6. The method for preparing the composite molecular sieve material according to claim 5, characterized in that, The carrier is one of fiberglass, skeleton cloth, metal mesh, or corrugated paper.

7. A method for preparing a composite molecular sieve material, characterized in that, Includes the following steps: (1) Mix ZSM-5 molecular sieve loaded with metal, high-silica Y molecular sieve loaded with metal and modified zeolite loaded with metal in a mass ratio of 1:1~2:0.5~2 to obtain a mixed powder; (2) The mixed powder is mixed evenly with additives, binders and water, wherein the mass ratio of the mixed powder, additives, binders and water is 1-1.5:0.01-0.2:0.3-0.6:0.5-2, to obtain mud; (3) Vacuum knead the clay, age it, extrude it into shape, and dry and roast it. (4) The calcined molded carrier is placed in a reaction furnace and subjected to gas phase hydrophobic treatment under inert gas protection to obtain composite molecular sieve material.

8. The method for preparing the composite molecular sieve material according to claim 7, characterized in that, The structure of the molded carrier is rod-shaped, spherical, or honeycomb-shaped.

9. The method for preparing the composite molecular sieve material according to claim 5 or 7, characterized in that, The additive is one or more of hydroxypropyl methylcellulose, polyvinyl alcohol, dextrin, guar gum powder, and glycerin, and the binder is one or more of boehmite, silica sol, alumina sol, aluminosilicate glue, resin, polyacrylic acid, styrene-butadiene latex (SBR), and polycarboxylate.

10. The application of the composite molecular sieve material according to any one of claims 1-4 or the composite molecular sieve material prepared by the preparation method according to any one of claims 5-9 in a device for adsorbing odor gases and VOCs gases.

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