Compositions containing chlorine dioxide and method for preparing chlorine dioxide tablets

Abstract

The present application provides a composition containing chlorine dioxide and a method for preparing chlorine dioxide tablets. The composition comprises a chlorine dioxide precursor, a stabilizer, and a corrosion inhibitor. The stabilizer is selected from one or more of hydroxypropyl-β-cyclodextrin, sodium hexametaphosphate, sodium silicate, and boron nitride. After the composition is made into tablets and activated, the resulting solution has good stability and can be stored stably for 6 months, and has low corrosion to metals, which can well solve the problems that the solution after activation of existing chlorine dioxide tablets is not easy to store and has strong corrosion to metals.

Description

Technical Field

[0001] The present application relates to the field of disinfection technology, and particularly relates to a composition containing chlorine dioxide and a method for preparing chlorine dioxide tablets. Background Art

[0002] Chlorine dioxide was discovered by Sir Humphrey Davy in 1811, and reports on the use of chlorine dioxide for pulp bleaching and drinking water treatment began around 1940. When used at a pH level of 3.0 to 8.0, ClO2 does not form carcinogenic by-products such as dioxins, chloroform, and haloacetic acids. Its residues are H2O, NaCl, and CO2, and it does not combine with phenols to form toxic chlorophenol compounds. Low concentrations of chlorine dioxide are considered harmless to humans, animals, and plants. Moreover, the oxidation activity of chlorine dioxide is 2.63 times that of chlorine gas, and its effects of killing bacteria, germs, algae, zooplankton, etc. are all superior to those of liquid chlorine. Due to the characteristics of high efficiency and low toxicity of chlorine dioxide, it has now been recognized by the World Health Organization as a Class A high-efficiency fungicide and a fungicide with excellent performance. Currently, its application fields have covered industries such as water treatment, papermaking, food, medical and health care, and aquaculture.

[0003] Chlorine dioxide is a gas at room temperature. It is unstable by itself and has properties such as being easily decomposed by light and prone to low-level explosions, which brings inconvenience to its storage and transportation, and thus affects its wide popularization and use. Therefore, people began to search for methods to produce stable chlorine dioxide solutions and solid chlorine dioxide preparations.

[0004] Chlorine dioxide is unstable in aqueous solution and will decay by itself. Chen Bingqi reported that ClO2 can decay at room temperature, and the decay product of ClO2 is mainly Cl - under acidic conditions, mainly a small amount of ClO2 - under neutral conditions, and mainly ClO2 - and a small amount of ClO3 - under alkaline conditions. Moreover, there are also many external factors affecting the stability of chlorine dioxide, such as temperature, light, metal ions, pH value, microorganisms, etc. The short storage period of chlorine dioxide is the biggest factor restricting the wide promotion of chlorine dioxide. The emergence of chlorine dioxide tablets solves the problem of short storage period, and the storage period of chlorine dioxide tablets can reach more than two years. However, even after the chlorine dioxide tablets are formulated into a use solution, the storage period of the use solution generally does not exceed one month. Currently, most studies on chlorine dioxide tablets focus on ensuring the stability of the tablets, and less research has been done on the stability of the use solution after activation. In addition, chlorine dioxide has a certain corrosiveness to metals such as carbon steel, copper, and aluminum at different concentrations, especially strong corrosiveness to carbon steel. This also restricts the application of chlorine dioxide to a certain extent. Therefore, it is particularly important to reduce the corrosiveness of the chlorine dioxide use solution. Summary of the Invention

[0005] Based on the above existing problems, the present application provides a composition containing chlorine dioxide and a method for preparing chlorine dioxide tablets. After the composition containing chlorine dioxide is made into tablets and activated, the resulting solution has good stability and low corrosion to metals.

[0006] The specific technical solution of the present application is as follows:

[0007] The present application provides a composition containing chlorine dioxide, which comprises a chlorine dioxide precursor, a stabilizer, and a corrosion inhibitor. The stabilizer is selected from one or more of hydroxypropyl-β-cyclodextrin, sodium hexametaphosphate, sodium silicate, and boron nitride.

[0008] Preferably, for the above-mentioned composition, the corrosion inhibitor is selected from one or more of hydroxyethane-1,1-diphosphonic acid, sodium methylbenzotriazole, azabenzene ring polyaminohexanoic acid, tetrasodium iminodisuccinate, and organosiloxanone.

[0009] For the composition described in any one of the above, the composition further comprises an activator, a disintegrant, a binder, and a lubricant.

[0010] For the above-mentioned composition, by mass percentage in the composition, the chlorine dioxide precursor is 30 - 50%, the activator is 20 - 30%, the disintegrant is 2 - 8%, the binder is 8 - 15%, the stabilizer is 0.1 - 1%, the corrosion inhibitor is 0.05 - 0.5%, and the lubricant is 0.1 - 0.5%.

[0011] For the composition described in any one of the above, the activator is selected from one or more of citric acid, tartaric acid, sodium bisulfate, potassium dihydrogen phosphate, aluminum trichloride, and phytic acid; and / or

[0012] the disintegrant comprises sodium bicarbonate and citric acid, or comprises sodium bicarbonate and malic acid; and / or

[0013] the binder is selected from one or more of polyvinylpyrrolidone K30, sodium carboxymethylcellulose, hydroxypropyl methylcellulose, and polyethylene glycol; and / or

[0014] the lubricant is selected from one or more of talc powder, magnesium stearate, and microcrystalline silica gel.

[0015] For the composition described in any one of the above, the dosage form of the composition is a tablet.

[0016] The present application provides a method for preparing chlorine dioxide tablets, which includes:

[0017] Mix chlorine dioxide precursor, binder, stabilizer and lubricant, and pulverize them to obtain a first mixture;

[0018] Mix activator and disintegrant, and pulverize them to obtain a second mixture;

[0019] Mix the first mixture and the second mixture, and tablet them to obtain chlorine dioxide tablets;

[0020] The corrosion inhibitor is mixed and pulverized with the chlorine dioxide precursor, binder, stabilizer and lubricant to obtain a first mixture, or the corrosion inhibitor is mixed and pulverized with the activator and disintegrant to obtain a second mixture.

[0021] For the method described above, wherein, by mass percentage in the composition, the chlorine dioxide precursor is 30 - 50%, the activator is 20 - 30%, the disintegrant is 2 - 8%, the binder is 8 - 15%, the stabilizer is 0.1 - 1%, the corrosion inhibitor is 0.05 - 0.5%, and the lubricant is 0.1 - 0.5%.

[0022] For the method described above, wherein the activator is selected from one or more of citric acid, tartaric acid, sodium bisulfate, potassium dihydrogen phosphate, aluminum trichloride and phytic acid; and / or

[0023] The disintegrant contains sodium bicarbonate and citric acid, or contains sodium bicarbonate and malic acid; and / or

[0024] The binder is selected from one or more of polyvinylpyrrolidone K30, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose and polyethylene glycol; and / or

[0025] The lubricant is selected from one or more of talcum powder, magnesium stearate and colloidal silica; and / or

[0026] The stabilizer is selected from one or more of hydroxypropyl - β - cyclodextrin, sodium hexametaphosphate, sodium silicate and boron nitride; and / or

[0027] The corrosion inhibitor is selected from one or more of hydroxyethylidene diphosphonic acid, sodium salt of methylbenzotriazole, azabenzene ring polyaminohexanoic acid, tetrasodium iminodisuccinate and organosiloxanone.

[0028] Effects of the Invention

[0029] After the composition described in this application is made into tablets and activated, the resulting liquid has good stability and can be stored stably for 6 months, and has low corrosion to metals, which can well solve the problems that the liquid after activation of current chlorine dioxide tablets is not easy to store and has strong corrosion to metals. Detailed Embodiments

[0030] The present application will be described in detail below in conjunction with the described embodiments. Although specific embodiments of the present application are shown, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided so that the present application can be more thoroughly understood and the scope of the present application can be completely conveyed to those skilled in the art.

[0031] It should be noted that certain terms are used in the specification and claims to refer to specific components. Those skilled in the art should understand that technicians may use different nouns to refer to the same component. The specification and claims do not use the difference in nouns as a way to distinguish components, but use the difference in the functions of components as the criterion for distinction. For example, the terms "comprising" or "including" mentioned throughout the specification and claims are open-ended terms, so they should be interpreted as "including but not limited to". The subsequent description in the specification is the preferred embodiment for implementing the present application, but the description is for the purpose of the general principles of the specification and is not used to limit the scope of the present application. The protection scope of the present application shall be determined by the scope defined by the appended claims.

[0032] The present application provides a composition containing chlorine dioxide, which comprises a chlorine dioxide precursor, a stabilizer and a corrosion inhibitor, and the stabilizer is selected from one or more of hydroxypropyl-β-cyclodextrin, sodium hexametaphosphate, sodium silicate and boron nitride.

[0033] The chlorine dioxide precursor can be a substance commonly used in the art, for example, it can be sodium chlorite, potassium chlorite, calcium chlorite, magnesium chlorite, barium chlorite, etc., and preferably sodium chlorite.

[0034] In some embodiments, the corrosion inhibitor is selected from one or more of hydroxyethylidene diphosphonic acid, sodium salt of methylbenzotriazole, azabenzene ring polyaminohexanoic acid, tetrasodium iminodisuccinate and organosiloxanone.

[0035] In some embodiments, the composition further comprises an activator, a disintegrant, a binder and a lubricant.

[0036] In the present application, the activator, disintegrant, binder and lubricant are the commonly used activator, disintegrant, binder and lubricant in the art, and those skilled in the art are not restricted in any way and can make routine selections according to needs. For example, the activator can be citric acid, tartaric acid, sodium bisulfate, potassium dihydrogen phosphate, aluminum trichloride and phytic acid or a combination thereof;

[0037] The disintegrant can comprise sodium bicarbonate and citric acid, or comprise sodium bicarbonate and malic acid, etc.;

[0038] The binder can be polyvinylpyrrolidone K30, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, polyethylene glycol, etc. or a combination thereof;

[0039] The lubricant can be talc, magnesium stearate, colloidal silica, etc. or a combination thereof.

[0040] In some embodiments, based on the mass percentage in the composition, the chlorine dioxide precursor is 30 - 50%, the activator is 20 - 30%, the disintegrant is 2 - 8%, the binder is 8 - 15%, the stabilizer is 0.1 - 1%, the corrosion inhibitor is 0.05 - 0.5%, and the lubricant is 0.1 - 0.5%.

[0041] For example, based on the mass percentage in the composition, the chlorine dioxide precursor can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, etc.;

[0042] The activator can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.;

[0043] The disintegrant is 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, etc.;

[0044] The binder can be 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.;

[0045] The stabilizer is 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1%, etc.;

[0046] The corrosion inhibitor can be 0.05%, 006%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, etc.;

[0047] The lubricant can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, etc.

[0048] In this application, for the stabilizer, when two or more are selected from hydroxypropyl-β-cyclodextrin, sodium hexametaphosphate, sodium silicate, and boron nitride, any combination can be made, and one component in the combination shall not be less than one-tenth of the other component, as long as the content of the stabilizer is within the above range. For example, when using a combination of hydroxypropyl-β-cyclodextrin and sodium silicate as the stabilizer, the mass ratio (m 羟丙基-β-环糊精 :m 硅酸钠 ) can be from 10:1 to 1:10. Similarly, when using a combination of sodium hexametaphosphate and boron nitride as the stabilizer, the mass ratio (m 六偏磷酸钠 :m 氮化硼 ) can be from 10:1 to 1:10;

[0049] For example, the mass ratio (m 羟丙基-β-环糊精 :m 硅酸钠 ) of hydroxypropyl-β-cyclodextrin and sodium silicate can be 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.;

[0050] The mass ratio (m 六偏磷酸钠 :m 氮化硼 ) of sodium hexametaphosphate and boron nitride can be 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.

[0051] Similarly, for the corrosion inhibitor, when two or more are selected from hydroxyethylidene diphosphonic acid, sodium methylbenzotriazole, azabenzene ring polyaminohexanoic acid, tetrasodium iminodisuccinate, and organosiloxanone, any combination can be made, and one component in the combination shall not be less than one-tenth of the other component, as long as the content of the corrosion inhibitor is within the above range.

[0052] For example, when using a combination of hydroxyethylidene diphosphonic acid and sodium methylbenzotriazole as the corrosion inhibitor, the mass ratio (m 羟基乙叉二膦酸 :m 甲基苯并三氮唑钠盐 ) can be from 10:1 to 1:10. Similarly, when using a combination of azabenzene ring polyaminohexanoic acid and organosiloxanone as the corrosion inhibitor, the mass ratio (m 氮杂苯环多氨基己酸 :m 有机硅氧烷酮 ) can be from 10:1 to 1:10;

[0053] For example, the mass ratio (m 羟基乙叉二膦酸 :m 甲基苯并三氮唑钠盐It can be 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.

[0054] The mass ratio (m 氮杂苯环多氨基己酸 :m 有机硅氧烷酮 )of pyridine ring polyaminohexanoic acid and organosiloxanone can be 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.

[0055] In some embodiments, the dosage form of the composition is a tablet.

[0056] After the composition described in the present application is made into a tablet and activated, the stability of the liquid for use is good, and it can be stored stably for more than 6 months, while in the prior art, the liquid for use can only be stored for about one month after activation; and it has low corrosion to metals, basically no corrosion to some metals, and only mild corrosion to some metals.

[0057] The present application provides a method for preparing chlorine dioxide tablets, which includes:

[0058] Mixing and pulverizing a chlorine dioxide precursor, a binder, a stabilizer, and a lubricant to obtain a first mixture;

[0059] Mixing and pulverizing an activator and a disintegrant to obtain a second mixture;

[0060] Mixing the first mixture and the second mixture and tableting to obtain chlorine dioxide tablets;

[0061] The corrosion inhibitor is mixed and pulverized with the chlorine dioxide precursor, the binder, the stabilizer, and the lubricant to obtain a first mixture, or the corrosion inhibitor is mixed and pulverized with the activator and the disintegrant to obtain a second mixture.

[0062] In the present application, the specific corrosion inhibitor can be mixed and pulverized with the chlorine dioxide precursor, the binder, the stabilizer, and the lubricant to obtain a first mixture according to its performance requirements, or mixed and pulverized with the activator and the disintegrant to obtain a second mixture.

[0063] For example, when the corrosion inhibitor is hydroxyethylidene diphosphonic acid and / or sodium methylbenzotriazole, it can be mixed and pulverized with the activator and the disintegrant to obtain a second mixture;

[0064] When the corrosion inhibitor is pyridine ring polyaminohexanoic acid and / or organosiloxanone, it can be mixed and pulverized with the chlorine dioxide precursor, the binder, the stabilizer, and the lubricant to obtain a first mixture.

[0065] In some embodiments, when preparing the second mixture, before comminution, the activator, disintegrant, and optionally the corrosion inhibitor are baked, preferably in an oven at 50 - 60 °C, and preferably baked for 12 - 24 h.

[0066] In some embodiments, during the process of preparing the chlorine dioxide tablets, the temperature is 20 - 30 °C, and / or the relative humidity is 20 - 40%.

[0067] For example, the temperature can be 20 °C, 21 °C, 22 °C, 23 °C, 24 °C, 25 °C, 26 °C, 27 °C, 28 °C, 29 °C, 30 °C, etc.;

[0068] The relative humidity can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, etc.

[0069] In some embodiments, based on the mass percentage in the composition, the chlorine dioxide precursor is 30 - 50%, the activator is 20 - 30%, the disintegrant is 2 - 8%, the binder is 8 - 15%, the stabilizer is 0.1 - 1%, the corrosion inhibitor is 0.05 - 0.5%, and the lubricant is 0.1 - 0.5%. In some embodiments, the activator is selected from one or more of citric acid, tartaric acid, sodium bisulfate, potassium dihydrogen phosphate, aluminum trichloride, and phytic acid; and / or

[0070] The disintegrant contains sodium bicarbonate and citric acid, or contains sodium bicarbonate and malic acid; and / or

[0071] The binder is selected from one or more of polyvinylpyrrolidone K30, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, and polyethylene glycol; and / or

[0072] The lubricant is selected from one or more of talc, magnesium stearate, and colloidal silica; and / or

[0073] The stabilizer is selected from one or more of hydroxypropyl - β - cyclodextrin, sodium hexametaphosphate, sodium silicate, and boron nitride; and / or

[0074] The corrosion inhibitor is selected from one or more of hydroxyethylidene diphosphonic acid, sodium methylbenzotriazole, azabenzene ring polyaminohexanoic acid, tetrasodium iminodisuccinate, and organosiloxanone.

[0075] The chlorine dioxide tablets prepared by the method described above in this application are very stable in the use solution after activation, can be stored stably for 6 months, and have little corrosion to metals.

[0076] Examples

[0077] This application provides a general and / or specific description of the materials and test methods used in the experiments. In the following examples, unless otherwise specified, % represents wt%, i.e., weight percentage. Reagents or instruments without indicating the manufacturer can be obtained as conventional reagent products through commercial purchase.

[0078] Example 1

[0079] (1) Add the chlorine dioxide precursor, binder, stabilizer, and lubricant to a pulverizer for pulverization. The powder is passed through a 100-mesh sieve to obtain the first mixture.

[0080] The chlorine dioxide precursor is sodium chlorite, with a dosage of 500 g.

[0081] The binder is polyvinylpyrrolidone K30, with a dosage of 80 g.

[0082] The stabilizer is a mixture of hydroxypropyl-β-cyclodextrin and sodium silicate. The dosage of hydroxypropyl-β-cyclodextrin is 1 g, and the dosage of sodium silicate is 5 g.

[0083] The lubricant is talcum powder, with a dosage of 5 g.

[0084] (2) Place the activator, disintegrant, and corrosion inhibitor in an oven at 50 °C for baking for 24 hours. After cooling, take them out and pulverize them with a pulverizer. The powder is passed through a 100-mesh sieve to obtain the second mixture.

[0085] The activator is tartaric acid, with a dosage of 300 g.

[0086] The disintegrant is a mixture of citric acid and sodium bicarbonate. The dosage of citric acid is 30 g, and the dosage of sodium bicarbonate is 100 g.

[0087] The corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid and sodium methylbenzotriazole. The dosage of hydroxyethylidene diphosphonic acid is 1 g, and the dosage of sodium methylbenzotriazole is 1.5 g.

[0088] (3) Mix the first mixture and the second mixture evenly and directly press tablets to obtain chlorine dioxide tablets.

[0089] The entire preparation process is carried out under the conditions of a temperature of 20 °C to 30 °C and a relative humidity of 20% to 40%.

[0090] Example 2

[0091] (1) Add the chlorine dioxide precursor, corrosion inhibitor, binder, stabilizer, and lubricant to a pulverizer for pulverization. The powder is passed through a 100-mesh sieve to obtain the first mixture.

[0092] The chlorine dioxide precursor is sodium chlorite, with a dosage of 300 g.

[0093] The corrosion inhibitor is a mixture of azabenzene ring polyaminohexanoic acid and organosiloxanone, with the dosage of azabenzene ring polyaminohexanoic acid being 3 g and the dosage of organosiloxanone being 2 g.

[0094] The binder is a mixture of hydroxypropyl methylcellulose and polyethylene glycol, with the dosage of hydroxypropyl methylcellulose being 50 g and the dosage of polyethylene glycol being 100 g.

[0095] The stabilizer is a mixture of sodium hexametaphosphate and boron nitride, with the dosage of sodium hexametaphosphate being 10 g and the dosage of boron nitride being 1 g.

[0096] The lubricant is microcrystalline silica gel, with the dosage being 3 g.

[0097] (2) Put the activator and disintegrant into an oven at 60 °C and bake for 12 hours, then take them out and crush with a pulverizer. Pass the powder through a 100-mesh sieve to obtain the second mixture.

[0098] The activator is a mixture of potassium dihydrogen phosphate and aluminum trichloride, with the dosage of potassium dihydrogen phosphate being 150 g and the dosage of aluminum trichloride being 150 g.

[0099] The disintegrant is a mixture of malic acid and sodium bicarbonate, with the dosage of malic acid being 50 g and the dosage of sodium bicarbonate being 100 g.

[0100] (3) Mix the first mixture and the second mixture evenly and directly press tablets to obtain chlorine dioxide tablets.

[0101] The whole preparation process is carried out under the conditions of a temperature of 20 °C to 30 °C and a relative humidity of 20% to 40%.

[0102] Example 3

[0103] The difference between Example 3 and Example 1 is that only hydroxypropyl-β-cyclodextrin is used, with the dosage being 6 g to prepare chlorine dioxide tablets.

[0104] Example 4

[0105] The difference between Example 4 and Example 3 is that the dosage of hydroxypropyl-β-cyclodextrin used is 1 g to prepare chlorine dioxide tablets.

[0106] Example 5

[0107] The difference between Example 5 and Example 3 is that the dosage of hydroxypropyl-β-cyclodextrin used is 10 g to prepare chlorine dioxide tablets.

[0108] Example 6

[0109] The difference between Example 6 and Example 3 is that the dosage of hydroxypropyl-β-cyclodextrin used is 4 g to prepare chlorine dioxide tablets.

[0110] Example 7

[0111] The difference between Example 6 and Example 3 is that 15 g of hydroxypropyl-β-cyclodextrin is used to prepare the chlorine dioxide tablets.

[0112] Example 8

[0113] The difference between Example 8 and Example 1 is that only sodium silicate is used, and the amount of sodium silicate is 6 g to prepare the chlorine dioxide tablets.

[0114] Example 9

[0115] The difference between Example 9 and Example 3 is that 6 g of magnesium sulfate, a conventional stabilizer in the art, is used to prepare the chlorine dioxide tablets.

[0116] Example 10

[0117] The difference between Example 10 and Example 1 is that only sodium methylbenzotriazole is used to prepare the chlorine dioxide tablets.

[0118] Example 11

[0119] The difference between Example 11 and Example 10 is that the amount of sodium methylbenzotriazole is 1 g to prepare the chlorine dioxide tablets.

[0120] Example 12

[0121] The difference between Example 12 and Example 10 is that the amount of sodium methylbenzotriazole is 5 g to prepare the chlorine dioxide tablets.

[0122] Example 13

[0123] The difference between Example 13 and Example 10 is that 2.5 g of sodium phosphate, a conventional corrosion inhibitor in the art, is used to prepare the chlorine dioxide tablets.

[0124] Example 14

[0125] The difference between Example 14 and Example 1 is that only hydroxyethane-1,1-diphosphonic acid is used, and the amount of hydroxyethane-1,1-diphosphonic acid is 2.5 g to prepare the chlorine dioxide tablets.

[0126] Example 15

[0127] The difference between Example 15 and Example 2 is that only sodium hexametaphosphate is used, and the amount of sodium hexametaphosphate is 11 g to prepare the chlorine dioxide tablets.

[0128] Example 16

[0129] The difference between Example 16 and Example 2 is that only boron nitride is used, and the amount of boron nitride is 11 g to prepare the chlorine dioxide tablets.

[0130] Example 17

[0131] The difference between Example 17 and Example 2 is that only polyaminocaproic acid with an azobenzene ring is used, and the dosage of polyaminocaproic acid with an azobenzene ring is 5 g to prepare the chlorine dioxide tablets.

[0132] Example 18

[0133] The difference between Example 18 and Example 2 is that only silicone oxanone is used, and the dosage of silicone oxanone is 5 g to prepare the chlorine dioxide tablets.

[0134] Example 19

[0135] The difference between Example 19 and Example 1 is that the dosage of hydroxypropyl-β-cyclodextrin is 0.1 g and the dosage of sodium silicate is 5 g to prepare the chlorine dioxide tablets.

[0136] Example 20

[0137] The difference between Example 20 and Example 1 is that the dosage of hydroxypropyl-β-cyclodextrin is 5 g and the dosage of sodium silicate is 1 g to prepare the chlorine dioxide tablets.

[0138] Example 21

[0139] The difference between Example 21 and Example 1 is that the dosage of hydroxyethane-1,1-diphosphonic acid is 0.1 g and the dosage of sodium methylbenzotriazole is 1.5 g to prepare the chlorine dioxide tablets.

[0140] Example 22

[0141] The difference between Example 22 and Example 1 is that the dosage of hydroxyethane-1,1-diphosphonic acid is 1.5 g and the dosage of sodium methylbenzotriazole is 1 g to prepare the chlorine dioxide tablets.

[0142] Example 23

[0143] The difference between Example 23 and Example 2 is that the dosage of sodium hexametaphosphate is 1 g and the dosage of boron nitride is 10 g to prepare the chlorine dioxide tablets.

[0144] Example 24

[0145] The difference between Example 24 and Example 2 is that the dosage of polyaminocaproic acid with an azobenzene ring is 2 g and the dosage of silicone oxanone is 3 g to prepare the chlorine dioxide tablets.

[0146] Comparative Example 1

[0147] (1) Add the chlorine dioxide precursor, binder and lubricant to a crusher for crushing, and pass the powder through a 100-mesh sieve to obtain the first mixture.

[0148] Among them, the chlorine dioxide precursor is sodium chlorite, and the dosage is 500 g.

[0149] Among them, the binder is polyvinylpyrrolidone K30, and the dosage is 80 g.

[0150] Among them, the lubricant is talc powder, and the dosage is 5 g.

[0151] (2) Put the activator and disintegrant into an oven at 50 °C and bake for 24 hours. After cooling, take them out and crush them with a pulverizer. Sieve the powder through a 100-mesh sieve to obtain the second mixture.

[0152] Among them, the activator is tartaric acid, and the dosage is 300 g.

[0153] Among them, the disintegrant is a mixture of citric acid and sodium bicarbonate. The dosage of citric acid is 30 g, and the dosage of sodium bicarbonate is 100 g.

[0154] (3) Mix the first mixture and the second mixture evenly and directly press tablets to obtain chlorine dioxide tablets.

[0155] The whole preparation process is carried out under the conditions of a temperature of 20 °C to 30 °C and a relative humidity of 20% to 40%.

[0156] Comparative Example 2

[0157] (1) Add the chlorine dioxide precursor, binder and lubricant into a pulverizer and crush them. Sieve the powder through a 100-mesh sieve to obtain the first mixture.

[0158] Among them, the chlorine dioxide precursor is sodium chlorite, and the dosage is 300 g.

[0159] Among them, the binder is a mixture of hydroxypropyl methylcellulose and polyethylene glycol. The dosage of hydroxypropyl methylcellulose is 50 g, and the dosage of polyethylene glycol is 100 g.

[0160] Among them, the lubricant is microcrystalline silica gel, and the dosage is 3 g.

[0161] (2) Put the activator and disintegrant into an oven at 60 °C and bake for 12 hours. Then take them out and crush them with a pulverizer. Sieve the powder through a 100-mesh sieve to obtain the second mixture.

[0162] Among them, the activator is a mixture of potassium dihydrogen phosphate and aluminum trichloride. The dosage of potassium dihydrogen phosphate is 150 g, and the dosage of aluminum trichloride is 150 g.

[0163] Among them, the disintegrant is a mixture of malic acid and sodium bicarbonate. The dosage of malic acid is 50 g, and the dosage of sodium bicarbonate is 100 g.

[0164] (3) Mix the first mixture and the second mixture evenly and directly press tablets to obtain chlorine dioxide tablets.

[0165] The entire preparation process is carried out under the conditions of a temperature of 20°C to 30°C and a relative humidity of 20% to 40%.

[0166] Table 1

[0167] ;

[0168] 。

[0169] Experimental Example: Stability and Metal Corrosion Test

[0170] Take 1 g of the chlorine dioxide tablets in Examples 1-12 and Comparative Examples 1-2 respectively, dissolve them in 1 L of purified water, and obtain a chlorine dioxide working solution of 50-200 mg / L after activation. Test the stability and metal corrosion of the working solution, and determine it according to the methods in Sections 2.2.3 and 2.2.4 of the "Disinfection Technical Specifications" (2002 Edition). The results are shown in Table 2.

[0171] Table 2

[0172] 。

[0173] In summary, due to the addition of a stabilizer and a corrosion inhibitor in the composition described in the present application, and the stabilizer and the corrosion inhibitor being specific stabilizers and corrosion inhibitors, after the tablets prepared are activated, the stability of the working solution is greatly improved, and the corrosion of metals is greatly reduced, which is beneficial to the large-scale popularization and application of chlorine dioxide.

[0174] The above are only the preferred embodiments of the present application, and are not intended to limit the present application in other forms. Any person skilled in the art may use the technical content disclosed above to make changes or modifications into equivalent embodiments with equivalent changes. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present application without departing from the technical solution content of the present application still fall within the protection scope of the technical solution of the present application.

Claims

1. A composition containing chlorine dioxide, which comprises a chlorine dioxide precursor, a stabilizer, and a corrosion inhibitor; The stabilizer is a mixture of hydroxypropyl-β-cyclodextrin and sodium silicate; The corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid and sodium methylbenzotriazole; The chlorine dioxide precursor is sodium chlorite; Calculated by mass percentage in the composition, the chlorine dioxide precursor is 30-50%, the stabilizer is 0.1-1%, and the corrosion inhibitor is 0.05-0.5%.

2. The composition according to claim 1, wherein The composition further comprises an activator, a disintegrant, a binder, and a lubricant.

3. The composition according to claim 2, wherein, Calculated by mass percentage in the composition, the activator is 20-30%, the disintegrant is 2-8%, the binder is 8-15%, and the lubricant is 0.1-0.5%.

4. The composition according to claim 2, wherein, The activator is selected from one or more of citric acid, tartaric acid, sodium bisulfate, potassium dihydrogen phosphate, aluminum trichloride, and phytic acid; and / or The disintegrant is sodium bicarbonate and citric acid, or sodium bicarbonate and malic acid; and / or The binder is selected from one or more of polyvinylpyrrolidone K30, sodium carboxymethylcellulose, hydroxypropyl methylcellulose, and polyethylene glycol; and / or The lubricant is selected from one or more of talc, magnesium stearate, and colloidal silica.

5. The composition according to any one of claims 1-2, wherein the dosage form of the composition is a tablet.

6. A method for preparing chlorine dioxide tablets, which comprises: Mixing and pulverizing a chlorine dioxide precursor, a binder, a stabilizer, and a lubricant to obtain a first mixture; Mixing and pulverizing an activator and a disintegrant to obtain a second mixture; Mixing the first mixture and the second mixture, and tableting to obtain chlorine dioxide tablets; The corrosion inhibitor is mixed and pulverized with the chlorine dioxide precursor, the binder, the stabilizer, and the lubricant to obtain a first mixture or the corrosion inhibitor is mixed and pulverized with the activator and the disintegrant to obtain a second mixture; The stabilizer is a mixture of hydroxypropyl-β-cyclodextrin and sodium silicate; The corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid and sodium methylbenzotriazole; The chlorine dioxide precursor is sodium chlorite; Calculated by mass percentage in the composition, the chlorine dioxide precursor is 30-50%, the stabilizer is 0.1-1%, and the corrosion inhibitor is 0.05-0.5%.

7. The method according to claim 6, wherein, Calculated by mass percentage in the composition, the activator is 20-30%, the disintegrant is 2-8%, the binder is 8-15%, and the lubricant is 0.1-0.5%.

8. The method according to claim 6 or 7, wherein The activator is selected from one or more of citric acid, tartaric acid, sodium bisulfate, potassium dihydrogen phosphate, aluminum trichloride, and phytic acid; and / or The disintegrant is sodium bicarbonate and citric acid, or sodium bicarbonate and malic acid; and / or The binder is selected from one or more of polyvinylpyrrolidone K30, sodium carboxymethylcellulose, hydroxypropyl methylcellulose, and polyethylene glycol; and / or The lubricant is selected from one or more of talc, magnesium stearate, and colloidal silica.