A porous microcrystalline material immobilized chlorine dioxide solid gel, and a preparation method and application thereof

Abstract

This invention provides a porous microcrystalline material-supported chlorine dioxide solid gel, its preparation method, and its application. The porous microcrystalline material-supported chlorine dioxide solid gel comprises, by weight, the following raw materials: 0.2-10 parts of chlorine dioxide precursor, 0.5-20 parts of stabilizer, 0.5-25 parts of gelling agent, 0.1-10 parts of activator, and 0.1-25 parts of porous microcrystalline material. The preparation method is simple, and the resulting solid gel utilizes the slow-release and secondary storage functions of the porous microcrystalline material to achieve the safe and stable release of chlorine dioxide, making it suitable for use in the preparation of air purification products.

Description

Technical Field

[0001] This invention belongs to the field of air purification technology, specifically relating to a porous microcrystalline material-supported chlorine dioxide solid gel, its preparation method, and its application. Background Technology

[0002] Chlorine dioxide, as a gas with strong oxidizing properties, has a highly efficient, broad-spectrum, and safe bactericidal and formaldehyde-removing effect at low concentrations. It is recognized by the World Health Organization as a safe and non-toxic A1-level product, and has no "three-fold" effects (carcinogenic, teratogenic, and mutagenic) on humans. However, due to the instability and explosiveness of chlorine dioxide in liquid or gaseous states, its production, packaging, transportation, storage, and use are greatly restricted. Therefore, solid chlorine dioxide products have emerged.

[0003] CN111743072A discloses a chlorine dioxide-supported molecular sieve for formaldehyde removal, prepared as follows: A molecular sieve material is selected and processed with chlorine dioxide through calcination, modification, and multiple encapsulation to form a chlorine dioxide-supported molecular sieve. The chlorine dioxide-supported molecular sieve is characterized by stable storage and transportation, safe and convenient use, and good formaldehyde removal effect. However, its slow-release period is relatively short, lasting only about 7 hours.

[0004] CN112705159A discloses a slow-release chlorine dioxide gel-molecular sieve composite adsorbent, prepared as follows: the slow-release chlorine dioxide gel is obtained by reacting chlorite with inorganic or organic acids under reaction conditions of pH 1.4-4.5 and viscosity 30000-10000 cps; the molecular sieve is formed by colloidal SiO2 aqueous solution and organic cellulose compound, followed by plastic treatment to remove cellulose compounds, and treatment with alkaline metal aqueous solution and NaAlO2 to convert the silica in the inorganic binder component into X-type or Y-type molecular sieves. This slow-release chlorine dioxide gel-molecular sieve composite adsorbent utilizes the respective properties of the slow-release chlorine dioxide gel and molecular sieve to achieve long-term continuous adsorption of representative substances causing sickroom syndrome in confined spaces, achieving the effect of decomposing formaldehyde. However, this study does not disclose the stability and rate of chlorine dioxide release.

[0005] Based on the above research, it can be seen that solid chlorine dioxide products are currently widely used to absorb formaldehyde and achieve air purification. However, limitations remain, including the occurrence of explosive release phenomena in the initial stage of use and unstable release, and activation is required to trigger the release reaction. Therefore, finding a convenient, stable, safe, and effective solid chlorine dioxide product is of great importance to the field of air purification technology. Summary of the Invention

[0006] To address the shortcomings of existing technologies and practical needs, the present invention aims to provide a porous microcrystalline material-supported chlorine dioxide solid gel, its preparation method, and its applications. The chlorine dioxide slow-release gel is convenient to use and store, effectively controls the chlorine dioxide release rate, and allows for a release time of up to 3 months, significantly enhancing the formaldehyde removal effect.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a porous microcrystalline material-supported chlorine dioxide solid gel, wherein the porous microcrystalline material-supported chlorine dioxide solid gel comprises the following raw materials by weight: 0.2-10 parts of chlorine dioxide precursor, 0.5-20 parts of stabilizer, 0.5-25 parts of gelling agent, 0.1-10 parts of activator, and 0.1-25 parts of porous microcrystalline material.

[0009] The 0.2-10 parts can be 0.2 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, etc.

[0010] The 0.5-20 portions can be 0.5 portions, 1 portion, 2 portions, 3 portions, 5 portions, 7 portions, 9 portions, 10 portions, 12 portions, 14 portions, 15 portions, 17 portions, 19 portions, or 20 portions, etc.

[0011] The 0.5-25 parts can be 0.5 parts, 0.8 parts, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 21 parts, 23 parts, or 25 parts, etc.

[0012] The 0.1-10 parts can be 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, etc.

[0013] The 0.1-25 parts can be 0.1 parts, 0.5 parts, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, or 25 parts, etc.

[0014] Other point values ​​within the above range can be selected, and will not be elaborated on here.

[0015] This invention employs a technique of separately immobilizing chlorine dioxide precursor and activator. The activator is immobilized in a stabilizer, and the chlorine dioxide precursor is adsorbed into a porous microcrystalline material. The adsorbed chlorine dioxide precursor / porous microcrystalline material is then mixed with the immobilized activator and gelling agent to prepare a porous microcrystalline material-immobilized chlorine dioxide solid gel. This gel is convenient to use and store, and can achieve safe and stable release of chlorine dioxide.

[0016] It should be noted that this invention utilizes porous microcrystalline materials to adsorb the chlorine dioxide precursor within the pores, blocking direct contact with the activator and providing a secondary storage function for the chlorine dioxide. This reduces the contact area with the immobilized activator, lowers the reaction rate, effectively controls the chlorine dioxide release rate, and allows for a release time of up to 3 months. Furthermore, it actively captures and decomposes formaldehyde and odor molecules in the air, increasing the reaction rate and enhancing the effects of formaldehyde removal, sterilization, and odor elimination.

[0017] The gel described in this invention is solid, non-flowing, and has good elasticity and toughness. When using it, consumers can simply open the cap and place it in a place that is not easily touched, such as a wardrobe or table.

[0018] In this invention, the chlorine dioxide precursor includes any one or a combination of at least two of calcium chlorite, potassium chlorite, magnesium chlorite, sodium chlorite, barium chlorite, sodium chlorate, sodium hypochlorite, or magnesium hypochlorite. The combination of at least two may be a combination of calcium chlorite and sodium chlorite, or a combination of sodium chlorite and potassium chlorite, etc. Any other combination is acceptable and will not be elaborated further here.

[0019] In this invention, the stabilizer includes any one or a combination of at least two of anhydrous calcium sulfate, anhydrous calcium chloride, anhydrous potassium sulfate, anhydrous barium sulfate, hydrogen peroxide, or anhydrous magnesium sulfate. The combination of at least two may be a combination of anhydrous calcium sulfate and anhydrous calcium chloride, or a combination of anhydrous calcium chloride and anhydrous potassium sulfate, etc. Any other combination is acceptable and will not be elaborated upon here.

[0020] In this invention, the gelling agent comprises any one or a combination of at least two of the following: carrageenan, agar, gelatin, gellan gum, xanthan gum, superabsorbent polymer, sodium alginate, polyethylene glycol 6000, polyethylene glycol, chitosan, acrylamide, sodium carboxymethyl cellulose, or potassium alginate. The combination of at least two can be a combination of carrageenan and agar, or agar and gelatin, etc., and any other combination is acceptable and will not be elaborated further. Preferably, it comprises any one or a combination of at least two of the following: carrageenan, agar, superabsorbent polymer, or sodium carboxymethyl cellulose.

[0021] The gelling agents used in this invention can all achieve the gelling effect. Carrageenan, agar, superabsorbent resin or sodium carboxymethyl cellulose, or any one or at least a combination of two of them, are preferred because they can make the final product have better performance and morphology.

[0022] In this invention, the activator includes any one or a combination of at least two of the following: citric acid, oxalic acid, tartaric acid, boric acid, aminosulfonic acid, phosphoric acid, stearic acid, maleic acid, malic acid, or acetic acid. The combination of at least two can be a combination of oxalic acid and tartaric acid, or a combination of tartaric acid and malic acid, etc. Any other combination is acceptable and will not be elaborated further here.

[0023] In this invention, the porous microcrystalline material includes any one or a combination of at least two of activated carbon, montmorillonite, kaolin, bentonite, porous ceramics, NaA molecular sieve, or maifanite, preferably a combination of NaA molecular sieve and activated carbon.

[0024] The components provided by this invention can all be used as porous microcrystalline materials for secondary storage of chlorine dioxide gas, thereby effectively controlling the release rate of chlorine dioxide. The combination of NaA molecular sieve and activated carbon is preferred because it can store abundant chlorine dioxide gas and prevent photodecomposition, and its complex pore structure slows down the release of chlorine dioxide gas.

[0025] Preferably, the specific surface area of ​​the porous microcrystalline material is 200-2000 m². 2 / g, pore size is

[0026] The 200-2000m 2 / g, which can be 200m 2 / g、400m 2 / g、600m 2 / g、800m 2 / g, 1000m 2 / g、1200m 2 / g, 1400m 2 / g, 1600m 2 / g、1800m 2 / g or 2000m 2 / g etc.

[0027] The It can be or wait.

[0028] Other point values ​​within the above range can be selected, and will not be elaborated on here.

[0029] Secondly, the present invention provides a method for preparing a porous microcrystalline material-supported chlorine dioxide solid gel, the preparation method comprising the following steps:

[0030] (1) The activator, stabilizer, first gelling agent and water are mixed to obtain a first mixture; the chlorine dioxide precursor is mixed with porous microcrystalline material to obtain a second mixture; the second gelling agent is mixed with water, heated to boiling, and then cooled to obtain a gel liquid;

[0031] (2) Mix the first mixture obtained in step (1) with the gel liquid to obtain the third mixture; mix the third gel agent and the second mixture obtained in step (1) to obtain the fourth mixture;

[0032] (3) Mix the third mixture and the fourth mixture obtained in step (2) to obtain the porous microcrystalline material supported on chlorine dioxide solid gel.

[0033] The mass ratio of the first gelling agent, the second gelling agent, and the third gelling agent is (2-15):(70-85):(2-15).

[0034] The numbers 2-15 can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15, etc.

[0035] The numbers 70-85 can be 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84 or 85, etc.

[0036] Other point values ​​within the above range can be selected, and will not be elaborated on here.

[0037] The first, second, and third gelling agents are all selected from any one or a combination of at least two of carrageenan, agar, gelatin, gellan gum, xanthan gum, superabsorbent polymer, sodium alginate, polyethylene glycol 6000, polyethylene glycol, chitosan, acrylamide, sodium carboxymethyl cellulose, or potassium alginate, preferably any one or a combination of at least two of carrageenan, agar, superabsorbent polymer, or sodium carboxymethyl cellulose.

[0038] The combination of at least two can be a combination of carrageenan and agar or agar and gelatin, etc. Any other combination can be selected, which will not be described in detail here.

[0039] It should be noted that the gelling agent described in this invention is added in three stages. This is because it can better support the gel skeleton, disperse it evenly, and improve the elasticity and toughness of the gel.

[0040] Preferably, the mixing temperature during the process of obtaining the first mixture is 80-90°C, and the mixing time during the process of obtaining the first mixture is 2-4 hours.

[0041] The 80-90℃ can be 80℃, 81℃, 82℃, 83℃, 84℃, 85℃, 86℃, 87℃, 88℃, 89℃, or 90℃, etc.

[0042] The 2-4h can be 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, or 4h, etc.

[0043] Other point values ​​within the above range can be selected, and will not be elaborated on here.

[0044] Preferably, the process of obtaining the first mixture further includes drying and cooling steps after mixing.

[0045] Preferably, the drying temperature is 100-120℃ and the drying time is 3-5 hours.

[0046] The 100-120℃ can be 100℃, 102℃, 104℃, 106℃, 108℃, 110℃, 112℃, 114℃, 116℃, 118℃, or 120℃, etc.

[0047] The 3-5h can be 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, or 5h, etc.

[0048] Other point values ​​within the above range can be selected, and will not be elaborated on here.

[0049] Preferably, the cooling to a temperature ≤25°C.

[0050] Preferably, the mixing temperature during the process of obtaining the second mixture is 18-25°C, and the mixing time during the process of obtaining the second mixture is 3-7 hours.

[0051] The 18-25℃ can be 18℃, 19℃, 20℃, 21℃, 22℃, 23℃, 24℃, or 25℃, etc.

[0052] The 3-7h can be 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, or 7h, etc.

[0053] Other point values ​​within the above range can be selected, and will not be elaborated on here.

[0054] Preferably, the process of obtaining the second mixture further includes a drying step after mixing.

[0055] Preferably, the drying temperature is 25-45℃; the drying time is 20-30h.

[0056] The 25-45℃ range can be 25℃, 27℃, 29℃, 31℃, 33℃, 35℃, 37℃, 39℃, 41℃, 43℃, or 45℃, etc.

[0057] The 20-30h can be 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, or 30h, etc.

[0058] Other point values ​​within the above range can be selected, and will not be elaborated on here.

[0059] Preferably, the cooling to a temperature of 35-55°C in step (1) is 38-50°C.

[0060] The 35-55℃ can be 35℃, 37℃, 39℃, 41℃, 43℃, 45℃, 47℃, 49℃, 51℃, 53℃, or 55℃, etc.

[0061] Preferably, the mixing temperatures during the processes of obtaining the third mixture and the fourth mixture are each independently 23-28°C.

[0062] The 23-28℃ can be 23℃, 23.5℃, 24℃, 24.5℃, 25℃, 25.5℃, 26℃, 26.5℃, 27℃, 27.5℃, or 28℃, etc.

[0063] Preferably, the mixing temperature in step (3) is 38-45°C.

[0064] The 38-45℃ can be 38℃, 39℃, 40℃, 41℃, 42℃, 43℃, 44℃, or 45℃, etc.

[0065] Other point values ​​within the above range can be selected, and will not be elaborated on here.

[0066] Thirdly, the present invention provides an application of the porous microcrystalline material supported on chlorine dioxide solid gel according to the first aspect in the preparation of air purification products.

[0067] Compared with the prior art, the present invention has the following beneficial effects:

[0068] This invention utilizes porous microcrystalline materials to adsorb chlorine dioxide precursors within the pores, preventing direct contact with the activator and providing a secondary storage function for chlorine dioxide. This reduces the contact area with the immobilized activator, lowers the reaction rate, effectively controls the release rate of chlorine dioxide, prevents explosive release, and allows for a release time of up to 3 months. Furthermore, it actively captures and decomposes formaldehyde and odor molecules in the air, increasing the reaction rate and enhancing the effects of formaldehyde removal, sterilization, and deodorization. The resulting product is a pure solid gel, convenient to use and store, and enables safe and stable release of chlorine dioxide, superior to similar products on the market. Detailed Implementation

[0069] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0070] The sources of the materials and raw materials used in the following embodiments are as follows:

[0071] The NaA molecular sieve was purchased from Jiangxi Xintao Technology Co., Ltd., with a specific surface area of ​​450 m². 2 / g, bulk density 0.45g / mL; activated carbon purchased from Foshan Bashan Environmental Protection Chemical Co., Ltd., particle size 200 mesh, iodine value 1000mg / g; X-type molecular sieve purchased from Jiangxi Xintao Technology Co., Ltd., specific surface area 450m² 2 / g, bulk density 0.45g / mL; ZSM-5 zeolite was purchased from Shandong Dengzhuo Chemical Co., Ltd., bulk density 0.45g / mL, silica-alumina ratio 200; superabsorbent resin was purchased from Hebei Jinkai Environmental Protection Technology Co., Ltd., model 200-400 mesh; agar powder was purchased from Shandong Datang Biotechnology Co., Ltd. (food grade); carrageenan was purchased from Shandong Changxiao Bioengineering Co., Ltd., model XNB; sodium carboxymethyl cellulose was purchased from Henan Yuxing Biotechnology Co., Ltd., model FH9. Unless otherwise specified, all other materials and raw materials were obtained from other commercial sources.

[0072] Example 1

[0073] This embodiment provides a porous microcrystalline material immobilized with chlorine dioxide solid gel, the preparation method of which is as follows:

[0074] (1) Weigh 1.5g citric acid, 0.3g oxalic acid, 2g anhydrous calcium chloride, 3g anhydrous magnesium sulfate and 0.5g superabsorbent resin and dissolve them in 200mL deionized water. Control the temperature at 85℃ and stir for 3h. Then dry at 110℃ for 4h and cool to 25℃ in a desiccator to obtain the immobilized activator for later use.

[0075] (2) Weigh 2.1g sodium chlorite and dissolve it in 4mL of deionized water, and add 1.5g NaA molecular sieve. Mix at 20℃ and 500rad / min for 4h for chemical adsorption, and then dry in a desiccator at 30℃ for 24h to obtain porous microcrystalline material loaded with chlorine dioxide precursor for later use.

[0076] (3) Weigh 2g of agar powder and 1g of carrageenan into 100mL of deionized water, heat to boiling while stirring, then cool to 43℃, and continue stirring at a constant temperature to obtain a slightly viscous gel solution.

[0077] (4) Weigh 0.7g of the immobilized activator obtained in step (1) and add it to the gel solution, then stir and mix evenly;

[0078] (5) Weigh 0.5g of sodium carboxymethyl cellulose and the porous microcrystalline material loaded with chlorine dioxide precursor obtained in step (2), mix them evenly in a mixer at 25°C, add the mixture to the gel liquid, stir so that the material can be evenly suspended in the gel system, pour into a packaging bottle, seal it, and obtain the porous microcrystalline material loaded with chlorine dioxide solid gel.

[0079] Example 2

[0080] This embodiment provides a porous microcrystalline material immobilized with chlorine dioxide solid gel, the preparation method of which is as follows:

[0081] (1) Weigh 1.5g tartaric acid, 0.3g oxalic acid, 2g anhydrous magnesium sulfate, 3g anhydrous calcium sulfate and 0.5g superabsorbent resin and dissolve them in 200mL deionized water. Control the temperature at 80℃ and stir for 3.5h. Then dry at 100℃ for 5h and cool to 25℃ in a desiccator to obtain the immobilized activator for later use.

[0082] (2) Weigh 4.2g of sodium chlorite and dissolve it in 10mL of deionized water, and add 3g of activated carbon. Mix at 20℃ and 600rad / min for 3.5h for chemical adsorption, and then dry in a desiccator at 30℃ for 20h to obtain a porous microcrystalline material loaded with chlorine dioxide precursor for later use.

[0083] (3) Weigh 3g of agar powder and 2g of carrageenan into 250mL of deionized water, heat to boiling while stirring, then cool to 47℃, and continue stirring at a constant temperature to obtain a slightly viscous gel solution.

[0084] (4) Weigh 1.5g of the immobilized activator obtained in step (1) and add it to the gel solution, then stir and mix evenly;

[0085] (5) Weigh 1g of sodium carboxymethyl cellulose and the porous microcrystalline material loaded with chlorine dioxide precursor obtained in step (2), mix them evenly in a mixer at 25°C, add the mixture to the gel liquid, stir so that the material can be evenly suspended in the gel system, pour into a packaging bottle, seal it, and obtain the porous microcrystalline material loaded with chlorine dioxide solid gel.

[0086] Example 3

[0087] This embodiment provides a porous microcrystalline material immobilized with chlorine dioxide solid gel, the preparation method of which is as follows:

[0088] (1) Weigh 60g citric acid, 12g oxalic acid, 80g anhydrous calcium chloride, 120g anhydrous potassium sulfate and 20g superabsorbent resin and dissolve them in 8L deionized water. Control the temperature at 90℃ and stir for 2.5h. Then dry at 120℃ for 3h and cool to 25℃ in a desiccator to obtain the immobilized activator for later use.

[0089] (2) Weigh 420g of calcium chlorite and dissolve it in 1L of deionized water, and add 300g of NaA molecular sieve. Mix at 20℃ and 400rad / min for 7h for chemical adsorption, and then dry in a desiccator at 30℃ for 24h to obtain porous microcrystalline material loaded with chlorine dioxide precursor for later use.

[0090] (3) Weigh 350g of agar powder and 200g of carrageenan into 20L of deionized water, heat to boiling while stirring, then cool to 50℃, and continue stirring at a constant temperature to obtain a slightly viscous gel solution.

[0091] (4) Weigh 150g of the immobilized activator obtained in step (1) and add it to the gel solution, then stir and mix evenly;

[0092] (5) Weigh 100g of sodium carboxymethyl cellulose and the porous microcrystalline material loaded with chlorine dioxide precursor obtained in step (2), mix them evenly in a mixer at 25°C, add the mixture to the gel liquid, stir so that the material can be evenly suspended in the gel system, pour into a packaging bottle, seal it, and obtain the porous microcrystalline material loaded with chlorine dioxide solid gel.

[0093] Example 4

[0094] This embodiment provides a porous microcrystalline material-supported chlorine dioxide solid gel, which differs from Example 1 only in that the cooling temperature in step (3) is 35°C, while the other parameters remain the same as in Example 1. The preparation method is the same as in Example 1.

[0095] Example 5

[0096] This embodiment provides a porous microcrystalline material-supported chlorine dioxide solid gel, which differs from Example 1 only in that the cooling temperature in step (3) is 55°C, while the other parameters remain the same as in Example 1. The preparation method is the same as in Example 1.

[0097] Example 6

[0098] This embodiment provides a porous microcrystalline material-supported chlorine dioxide solid gel, differing from Example 1 only in that the NaA molecular sieve is replaced with an equal amount of activated carbon; all other parameters remain the same as in Example 1. The preparation method is the same as in Example 1.

[0099] Example 7

[0100] This embodiment provides a porous microcrystalline material-supported chlorine dioxide solid gel, differing from Embodiment 1 only in that the 1.5g NaA molecular sieve is replaced with "1g NaA molecular sieve and 0.5g activated carbon," while the remaining parameters remain the same as in Embodiment 1. The preparation method is the same as in Embodiment 1.

[0101] Example 8

[0102] This embodiment provides a porous microcrystalline material-supported chlorine dioxide solid gel, differing from Example 1 only in that the 1.5g NaA molecular sieve is replaced with "0.9g X-type molecular sieve and 0.6g ZSM-5 zeolite", while the other parameters remain the same as in Example 1. The preparation method is the same as in Example 1.

[0103] Example 9

[0104] This embodiment provides a porous microcrystalline material-supported chlorine dioxide solid gel, differing from Example 1 only in that the agar powder is replaced with an equal amount of carrageenan; all other parameters remain the same as in Example 1. The preparation method is the same as in Example 1.

[0105] Example 10

[0106] This embodiment provides a porous microcrystalline material immobilized with chlorine dioxide solid gel. The only difference from Example 1 is that the carrageenan is replaced with an equal amount of agar powder, while the other parameters remain the same as in Example 1. The preparation method is the same as in Example 1.

[0107] Example 11

[0108] This embodiment provides a porous microcrystalline material-supported chlorine dioxide solid gel, differing from Embodiment 1 only in that the agar powder is replaced with an equal amount of resin, while the remaining parameters remain the same as in Embodiment 1. The preparation method is the same as in Embodiment 1.

[0109] Example 12

[0110] This embodiment provides a porous microcrystalline material immobilized with chlorine dioxide solid gel, the preparation method of which is as follows:

[0111] (1) Weigh 1.5g citric acid, 0.3g oxalic acid, 2g anhydrous calcium chloride and 3g anhydrous magnesium sulfate and dissolve them in 200mL deionized water. Control the temperature at 85℃ and stir for 3h. Then dry at 110℃ for 4h and cool to 25℃ in a desiccator to obtain the immobilized activator for later use.

[0112] (2) Weigh 2.1g sodium chlorite and dissolve it in 4mL of deionized water, and add 1.5g NaA molecular sieve. Mix at 20℃ and 500rad / min for 4h for chemical adsorption, and then dry in a desiccator at 30℃ for 24h to obtain porous microcrystalline material loaded with chlorine dioxide precursor for later use.

[0113] (3) Weigh 2g agar powder, 1g carrageenan, 0.5g superabsorbent resin and 0.5g sodium carboxymethyl cellulose and place them in 100mL of deionized water. Stir and heat to boiling, then cool to 43℃ and stir continuously at a constant temperature to obtain a slightly viscous gel.

[0114] (4) Weigh 0.7g of the immobilized activator obtained in step (1) and add it to the gel solution, then stir and mix evenly;

[0115] (5) Add the porous microcrystalline material loaded with chlorine dioxide precursor obtained in step (2) to the gel liquid, stir so that the material can be uniformly suspended in the gel system, pour into the packaging bottle, seal the bottle, and obtain the porous microcrystalline material loaded with chlorine dioxide solid gel.

[0116] Comparative Example 1

[0117] This comparative example provides a chlorine dioxide gel, which, compared to Example 1, does not use NaA molecular sieves to support sodium chlorite. Its preparation method is as follows:

[0118] (1) Weigh 1.5g citric acid, 0.3g oxalic acid, 2g anhydrous calcium chloride, 3g anhydrous magnesium sulfate and 0.5g superabsorbent resin and dissolve them in 200mL deionized water. Control the temperature at 85℃ and stir for 3h. Then dry at 110℃ for 4h and cool to 25℃ in a desiccator to obtain the immobilized activator for later use.

[0119] (2) Weigh 2g of agar powder and 1g of carrageenan into 100mL of deionized water, heat to boiling while stirring, then cool to 43℃, and continue stirring at a constant temperature to obtain a slightly viscous gel solution.

[0120] (3) Weigh 0.7g of the immobilized activator obtained in step (1) and add it to the gel solution, then stir and mix evenly;

[0121] (4) Weigh 0.5g of sodium carboxymethyl cellulose and the porous microcrystalline material loaded with chlorine dioxide precursor obtained in step (2), mix them evenly in a mixer at 25°C, add the mixture to the gel liquid, stir so that the material can be evenly suspended in the gel system, pour into a packaging bottle, seal it, and obtain the chlorine dioxide gel.

[0122] Test Example 1

[0123] This test example examines the average release rate and release time of chlorine dioxide gels obtained in Examples 1-12 and Comparative Example 1. The test method is as follows:

[0124] Add 40 mL of potassium iodide solution (2.5% by mass), 4 mL of sulfuric acid solution (1 mol / L), and 0.4 mL of starch solution (0.5% by mass) to the testing apparatus, mix thoroughly to obtain the indicator solution. Place the prepared chlorine dioxide slow-release gel in the middle of the testing apparatus, seal the apparatus, and move it to a dark place. At the specified time, open the testing apparatus, take 5 mL of the indicator solution and place it in an Erlenmeyer flask, slowly add sodium thiosulfate solution (0.01 mol / L), and record the volume V1 of sodium thiosulfate solution consumed when the indicator solution turns colorless. The blank sample in this experiment is the same system of test solution. Seal the testing apparatus and move it to a dark place. After the same time, take 5 mL of the indicator solution and place it in an Erlenmeyer flask, slowly add sodium thiosulfate solution (0.01 mol / L), and record the volume V0 of sodium thiosulfate solution consumed when the indicator solution turns colorless.

[0125] The formula for calculating the chlorine dioxide release rate is as follows:

[0126] V(ClO2)=C×V 总 ×(V1-V0)×M / (5×V 样 ×t)

[0127] Wherein, V(ClO2) — average release rate of chlorine dioxide, mg / h;

[0128] The concentration of the C-sodium thiosulfate solution is 0.01 mol / L;

[0129] V 总 —Total volume of solution used in the test, mL;

[0130] V1—The volume of sodium thiosulfate solution consumed by the experimental group, in mL;

[0131] V0—The volume of sodium thiosulfate solution consumed by the blank group, in mL;

[0132] V 样 —Titration sample volume, mL;

[0133] t—the time of the test reaction, in hours.

[0134] The test results are shown in Table 1 below:

[0135] Table 1

[0136]

[0137]

[0138] The data above show that, compared with Examples 1-3, the porous microcrystalline material-supported chlorine dioxide solid gel provided by this invention effectively controls the release rate of chlorine dioxide, prevents explosive release, and allows for a release time of up to 3 months. Data from Examples 4-5 shows that excessively low or high cooling temperatures affect the gel's ability to slowly release chlorine dioxide. Data from Examples 6-8 shows that when the porous microcrystalline material is a combination of NaA molecular sieve and activated carbon, the resulting gel exhibits better slow-release properties for chlorine dioxide. Data from Examples 9-11 shows that when the gelling agent in step (3) is not a combination of agar powder and carrageenan, the prepared gel's slow-release effect on chlorine dioxide deteriorates. Data from Example 12 shows that when the gelling agent is added all at once, the prepared gel's slow-release effect on chlorine dioxide deteriorates.

[0139] In summary, this invention utilizes porous microcrystalline materials to adsorb the chlorine dioxide precursor within the pores, preventing direct contact with the activator and providing a secondary storage function for the chlorine dioxide. This reduces the contact area with the immobilized activator, lowers the reaction rate, effectively controls the release rate of chlorine dioxide, prevents explosive release, and allows for a release time of up to 3 months. Furthermore, it actively captures and decomposes formaldehyde and odor molecules in the air, increasing the reaction rate and enhancing the effects of formaldehyde removal, sterilization, and deodorization. The resulting product is a pure solid gel, convenient to use and store, and enables the safe and stable release of chlorine dioxide, superior to similar products on the market.

[0140] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A porous microcrystalline material immobilized chlorine dioxide solid gel, characterized in that, The porous microcrystalline material-supported chlorine dioxide solid gel comprises the following raw materials by weight: 0.2-10 parts of chlorine dioxide precursor, 0.5-20 parts of stabilizer, 0.5-25 parts of gelling agent, 0.1-10 parts of activator, and 0.1-25 parts of porous microcrystalline material. The gelling agent includes a first gelling agent, a second gelling agent, and a third gelling agent. The first gelling agent is a superabsorbent resin, the second gelling agent is carrageenan and agar powder, and the third gelling agent is sodium carboxymethyl cellulose. The stabilizer includes any one or a combination of at least two of anhydrous calcium sulfate, anhydrous calcium chloride, anhydrous potassium sulfate, anhydrous barium sulfate, hydrogen peroxide, or anhydrous magnesium sulfate. The porous microcrystalline material is a combination of NaA molecular sieve and activated carbon; The porous microcrystalline material-supported chlorine dioxide solid gel is prepared by the following method, which includes the following steps: (1) Mix the activator, stabilizer, first gelling agent and water to obtain a first mixture; mix the chlorine dioxide precursor with the porous microcrystalline material to obtain a second mixture; mix the second gelling agent with water, heat to boiling, and then cool to obtain a gel solution; (2) Mix the first mixture obtained in step (1) with the gel liquid to obtain the third mixture; mix the third gel agent and the second mixture obtained in step (1) to obtain the fourth mixture; (3) Mix the third mixture and the fourth mixture obtained in step (2) to obtain the porous microcrystalline material supported on chlorine dioxide solid gel.

2. The porous microcrystalline material immobilized with chlorine dioxide solid gel according to claim 1, characterized in that, The chlorine dioxide precursor includes any one or a combination of at least two of calcium chlorite, potassium chlorite, magnesium chlorite, sodium chlorite, barium chlorite, sodium chlorate, sodium hypochlorite, or magnesium hypochlorite.

3. The porous microcrystalline material immobilized with chlorine dioxide solid gel according to claim 1, characterized in that, The activator includes any one or a combination of at least two of the following: citric acid, oxalic acid, tartaric acid, boric acid, aminosulfonic acid, phosphoric acid, stearic acid, maleic acid, malic acid, or acetic acid.

4. The porous microcrystalline material immobilized with chlorine dioxide solid gel according to claim 1, characterized in that, The specific surface area of the porous microcrystalline material is 200-2000 m 2 / g, and the pore size is 2-30 A.

5. The method for preparing porous microcrystalline material-supported chlorine dioxide solid gel according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: (1) Mix the activator, stabilizer, first gelling agent and water to obtain a first mixture; mix the chlorine dioxide precursor with the porous microcrystalline material to obtain a second mixture; mix the second gelling agent with water, heat to boiling, and then cool to obtain a gel solution; (2) Mix the first mixture obtained in step (1) with the gel liquid to obtain the third mixture; mix the third gel agent and the second mixture obtained in step (1) to obtain the fourth mixture; (3) Mix the third mixture and the fourth mixture obtained in step (2) to obtain the porous microcrystalline material-supported chlorine dioxide solid gel; The mass ratio of the first gelling agent, the second gelling agent, and the third gelling agent is (2-15):(70-85):(2-15); The first gelling agent is a superabsorbent resin, the second gelling agent is carrageenan and agar powder, and the third gelling agent is sodium carboxymethyl cellulose.

6. The preparation method according to claim 5, characterized in that, The mixing temperature during the process of obtaining the first mixture is 80-90℃, and the mixing time during the process of obtaining the first mixture is 2-4 h.

7. The preparation method according to claim 5, characterized in that, The process of obtaining the first mixture includes drying and cooling steps in sequence after mixing.

8. The preparation method according to claim 7, characterized in that, The drying temperature is 100-120℃, and the drying time is 3-5 hours.

9. The preparation method according to claim 7, characterized in that, The cooling step following the drying step in the process of obtaining the first mixture is to cool it to a temperature ≤25℃.

10. The preparation method according to claim 5, characterized in that, The mixing temperature during the process of obtaining the second mixture is 18-25℃, and the mixing time during the process of obtaining the second mixture is 3-7 h.

11. The preparation method according to claim 5, characterized in that, The process of obtaining the second mixture also includes a drying step after mixing.

12. The preparation method according to claim 11, characterized in that, The drying temperature is 25-45℃, and the drying time is 20-30 h.

13. The preparation method according to claim 5, characterized in that, Step (1) involves cooling to a temperature of 35-55℃.

14. The preparation method according to claim 13, characterized in that, Step (1) involves cooling to a temperature of 38-50°C.

15. The preparation method according to claim 5, characterized in that, The mixing temperatures during the processes of obtaining the third mixture and the fourth mixture are each independently 23-28°C.

16. The preparation method according to claim 5, characterized in that, The mixing temperature in step (3) is 38-45℃.

17. The application of porous microcrystalline material-supported chlorine dioxide solid gel according to any one of claims 1-4 in the preparation of air purification products.

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