CN111226980A

CN111226980A - Reactive chlorine dioxide solid preparation and preparation method thereof

Info

Publication number: CN111226980A
Application number: CN202010232397.2A
Authority: CN
Inventors: 晋日亚; 贺增弟; 晋玮璘; 贺梓航
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-03-28
Filing date: 2020-03-28
Publication date: 2020-06-05

Abstract

The invention relates to a reactive chlorine dioxide solid preparation and a preparation method thereof, wherein the reactive chlorine dioxide solid preparation is prepared from the following raw materials in percentage by weight: 10-50 wt% of chlorine dioxide parent material, 10-50 wt% of solid acid activator, 10-30 wt% of water-absorbing passivator and 15-30 wt% of prepolymer forming agent, and the solid preparation is prepared by mixing and press forming. The reaction type chlorine dioxide solid preparation prepared by the invention has good product stability and high conversion rate, and is suitable for sterilization, air purification, deodorization and deodorization in different occasions.

Description

Reactive chlorine dioxide solid preparation and preparation method thereof

Technical Field

The invention belongs to the technical field of sterilizing disinfectants, relates to a chlorine dioxide sterilizing disinfectant, and particularly relates to a reactive chlorine dioxide solid preparation capable of slowly reacting to release chlorine dioxide gas.

Background

Chlorine dioxide is a strong oxidant, has high-efficiency and broad-spectrum sterilization capability, can oxidize and decompose microorganisms such as bacteria and viruses, amino acids and other reducing substances in protein, and can react with organic matters and various inorganic ions. Compared with other chlorine products, the chlorine dioxide does not generate organic halides such as chloroform and the like which cause distortion, canceration and mutation, the effects of killing viruses and bacteria, deodorizing, bleaching and the like are 2.5 times of those of the chlorine, and the safety of the chlorine dioxide is classified as A1 grade by the World Health Organization (WHO).

Based on the oxidation and sterilization characteristics of chlorine dioxide, the chlorine dioxide can also be used as a bleaching agent in the industries of paper pulp, textile and the like; sterilizing disinfectant for catering, sanitation, epidemic prevention, etc.; air purification fresheners for living rooms, toilets, automobiles, and the like; algicide and water treatment agent for industrial water treatment, drinking water treatment and sludge treatment.

However, in practical use, since the nature of the chlorine dioxide gas is unstable, it is difficult to produce a compressed gas, and it has explosive characteristics, which makes it inconvenient to transport and store, and the chlorine dioxide gas is easily volatilized and is not easily concentrated, thereby limiting the use of chlorine dioxide. The stable chlorine dioxide solution has large water content and low effective component of chlorine dioxide, and can be used only by adding an acid activating agent when in use. Meanwhile, different types and different usage amounts of the activating agents cause different activating effects and cause negative effects of different degrees on the sterilization and disinfection effects. Although chlorine dioxide generators exist in the market, the generators are high in cost, are not suitable for small occasions such as civil use and the like, and need special personnel to operate and maintain. Therefore, whether it is gaseous chlorine dioxide or stable chlorine dioxide solution, it brings many inconveniences in transportation, storage and use. To overcome this limitation, chlorine dioxide products in solid form have come into use.

The solid preparation of chlorine dioxide refers to a solid preparation capable of releasing chlorine dioxide gas under certain operating conditions, and the products can be in the forms of colloid, paste, powder, tablet, block and other solid forms with various shapes. The preparation is prepared by using chlorite or stable chlorine dioxide solution as a protogen and organic solid acid or inorganic acidic substance as a main raw material of an acidifier.

Compared with other forms of chlorine dioxide, solid chlorine dioxide has the advantages of simple operation, high chlorine dioxide content, stable property, convenient transportation and use and the like, and sometimes has some special functions, such as slow release function and the like.

According to the preparation method and principle and different functions of the preparation, the chlorine dioxide solid preparation can be generally divided into three types, namely an adsorption type, a reaction type and a sustained-release type.

1. Adsorption type solid chlorine dioxide.

The preparation of the adsorption type solid chlorine dioxide is simple, generally, chlorine dioxide gas with higher purity is prepared firstly, then the chlorine dioxide gas is absorbed by aqueous solution containing a stabilizing agent to obtain stable chlorine dioxide solution, and finally the solution is adsorbed by a solid adsorbent.

When preparing the adsorption type solid chlorine dioxide, the adsorbent used as the solid chlorine dioxide carrier has larger adsorption capacity, larger specific surface and larger particle size, and the pH value of the adsorbent is preferably controlled between 8.5 and 9.0 so as to avoid the premature decomposition of the adsorption solution to release the chlorine dioxide.

The adsorbent carriers can be divided into two categories, one category is inorganic adsorbent, and porous substances such as silica gel, calcium silicate, diatomite, talcum powder, molecular sieve, active carbon and the like can be adopted; another class is organic adsorbents such as super absorbent polyacrylic acid resins, agar, super absorbent resins, carboxymethyl cellulose, and the like.

In the process of preparing this type of solid preparation, it is necessary to prepare chlorine dioxide gas of high purity in advance. The high-concentration chlorine dioxide gas has strong oxidizing property, is easy to corrode equipment, has high requirements on the equipment, and seriously threatens the health of workers once equipment leakage occurs in industrial production.

When preparing the adsorption type chlorine dioxide preparation, the selection of proper adsorption media and stabilizers is also required to be considered so as to ensure that the prepared solid preparation meets the requirements.

The dosage form also requires the addition of an activating agent to facilitate the release of chlorine dioxide. The packaging of the product is required to adopt binary or multi-element packaging, the two components are respectively dissolved in water and then mixed for use, and once the two components are unsealed, the two components need to be used up at a time, otherwise the two components are easy to lose efficacy, the great waste of the product is caused, and the use concentration and the disinfection cost of the product are increased. In addition, the excessive amount of the activating agent added during the use can cause the pH value of the solution to be too low, thereby causing secondary pollution.

The adsorbent used in the preparation, especially the organic adsorbent, has large adsorption capacity and is easy to expand when meeting water. It is therefore desirable that formulations of this type be kept, stored and transported with strict control over their environment, particularly over ambient humidity, to prevent the product from failing when exposed to water (or large moisture) during storage.

2. Reactive solid chlorine dioxide.

The reactive solid chlorine dioxide is prepared by mixing different solid reaction raw materials together according to a certain proportion, so that the raw materials directly generate slow chemical reaction and release chlorine dioxide gas in a longer time. When the product is used, water in certain times is added or the product is placed in an environment with high relative humidity, so that chemical or activation reaction can be completed in a short time to release the effective component chlorine dioxide. If the stabilizer is added during the preparation, the chlorine dioxide solution can be prepared after water is added.

In the preparation of reactive solid preparations, it has been proposed to add alkali metal or alkaline earth metal chlorides as a passivating agent to the raw materials to achieve the drying purpose by utilizing their water-absorbing properties. The passivation means leads to unstable products and short storage time due to the strong water absorption of the passivating agent, and particularly, the products can be failed quickly after opening the bag.

The raw materials are coated by adopting an embedding mode, so that a better effect can be obtained. However, in practical production and application, special attention should be paid to the nature of the coating agent and the influence on the environment after embedding. In some processes, the coating material needs to be prepared firstly, and then the prepared material is coated on the surface of the sodium chlorite, so that the process is complex, and the equipment investment is high. And the solubility and the dissolution effect of the final product are influenced due to poor water solubility of the used coating agent. On the other hand, the insoluble solid content of the product is increased, and the dissolved coating agent causes water pollution.

3. Slow-release solid chlorine dioxide.

The sustained-release type chlorine dioxide solid preparation refers to a solid preparation capable of slowly releasing chlorine dioxide gas, the release rate of which is much less than that of adsorptive and reactive solid preparations, and the preparation is generally divided into gel type and powder type. In a strict sense, both the adsorption type and the reaction type chlorine dioxide solid preparation products have the function of slowly releasing chlorine dioxide gas.

The slow-release chlorine dioxide solid preparation (adsorbability) is characterized by that it utilizes the adsorption property of solid adsorbent to adsorb stable chlorine dioxide solution, then mixes it with solid acidifier, makes it react, slowly and continuously releases chlorine dioxide gas, and can be used for sterilizing, air-cleaning, deodorizing and fresh-keeping, etc. The solid acidifying agent may be a solid acid, or adsorb a compound that produces H⁺The acid or acid salt of (a) includes citric acid, ferric chloride, aluminum sulfate, tartaric acid, and the like. In the using process of the preparation, the release amount of chlorine dioxide gas can be controlled in various ways, for example, the addition amount of solid acid or the strength of the acid can be controlled, so as to achieve a certain using purpose.

The slow-release chlorine dioxide solid preparation (reactivity) is prepared by putting solid chlorine dioxide or other protogenic agents and a solid acidifier together, and adding other auxiliary agents to slow down the release speed of the chlorine dioxide so as to achieve the aim of slow release. The product can be made into paste, gel and powder, can be placed in a proper place, and also has the functions of sterilization, air purification, deodorization, fresh keeping and the like.

The slow-release chlorine dioxide solid preparation has certain application value, can be used as a space disinfectant in living rooms, automobiles, toilets and other occasions in actual life, and has larger development space. In practice, however, special care should be taken to control the concentration of gaseous chlorine dioxide released by the formulation to ensure that it is within an effective threshold.

After researching the production method of the domestic chlorine dioxide solid preparation, the reactive chlorine dioxide solid preparation has the advantages of relatively simple production process and easy operation among several types of solid preparations. However, there are still some disadvantages of the type of formulations sold on the market, such as low conversion rate, difficulty in ensuring stability, etc.

Disclosure of Invention

The invention aims to provide a reactive chlorine dioxide solid preparation with good stability and high conversion rate.

The invention provides a preparation method of the reactive chlorine dioxide solid preparation, which is simple and easy to operate and relatively simple in production process, and is another aim of the invention.

The reactive chlorine dioxide solid preparation is prepared from the following raw materials in percentage by weight: 10-50 wt% of chlorine dioxide parent material, 10-50 wt% of solid acid activator, 10-30 wt% of water-absorbing passivator and 15-30 wt% of prepolymer forming agent, and the solid preparation is prepared by mixing and press forming.

The prepolymer forming agent is a liquid-state flowable polyurethane prepolymer forming agent or an epoxy resin prepolymer forming agent.

Specifically, the polyurethane prepolymer forming agent is formed by mixing liquid polyether, polyester or polybutadiene monomer, a liquid polyisocyanate-based crosslinking agent and a chain extender.

Further, the chain extender may be any conventional chain extender for polyurethane polymerization including, but not limited to, 1, 4-butanediol, ethylene glycol, propylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 4' -diaminodiphenylmethane, 3, 5-diethyltoluenediamine, diethanolamine, triethanolamine, triisopropanolamine.

More specifically, the liquid polyether monomer may include, but is not limited to, polyether diol, polyether triol, the liquid polyester monomer includes, but is not limited to, polyethylene adipate, polycaprolactone diol, and the liquid polybutadiene monomer includes, but is not limited to, hydroxyl-terminated polybutadiene, carboxyl-terminated polybutadiene.

The epoxy resin prepolymer forming agent is a mixture of liquid epoxy resin such as E44, E51 and the like, curing agent ethylenediamine and organic acid ester plasticizer.

The organic acid ester plasticizer includes, but is not limited to, dioctyl sebacate, dibutyl phthalate, and dioctyl phthalate.

In the reactive chlorine dioxide solid preparation, the chlorine dioxide parent material is one of alkali metal chlorate or chlorite or a mixture of the alkali metal chlorate and the chlorite in any proportion.

Alkali metal chlorates or chlorites that may be used as precursor materials for chlorine dioxide in the present invention include, but are not limited to: sodium chlorate, potassium chlorate, sodium chlorite, potassium chlorite.

In the reactive solid preparation of chlorine dioxide, the solid acid activator is one of sulfamic acid, citric acid, oxalic acid, tartaric acid and sodium bisulfate or a mixture of several of the sulfamic acid, the citric acid, the oxalic acid, the tartaric acid and the sodium bisulfate in any proportion.

In the reactive chlorine dioxide solid preparation, the water-absorbing passivating agent is selected from any one of anhydrous sodium sulfate, anhydrous calcium sulfate, anhydrous magnesium sulfate, sodium chloride, anhydrous calcium chloride, a molecular sieve and alumina, or a mixture of several of the anhydrous sodium sulfate, the anhydrous calcium sulfate, the anhydrous magnesium sulfate, the sodium chloride, the anhydrous calcium chloride, the molecular sieve and the alumina in any proportion.

In addition, 0.01-0.5 wt% of a release agent is further added to the reactive chlorine dioxide solid preparation.

Specifically, the release agent may be magnesium stearate and/or talc.

Further, the present invention can produce the reactive chlorine dioxide solid preparation by the following method.

1) And adding the chlorine dioxide parent material and part of the water-absorbing passivator in percentage by weight into a three-dimensional mixer, and uniformly mixing to obtain a first component.

2) And uniformly mixing the solid acid activator with the balance of the water-absorbing passivator in percentage by weight in a three-dimensional mixer to obtain a second component.

3) And uniformly mixing the first component and the second component in the three-dimensional mixer again, transferring the mixture into a kneading machine, adding the prepolymer forming agent, and kneading for 10-60 minutes to obtain a mixed material.

4) And (3) after the mixed material is formed in a forming die, standing and polymerizing for 5-12 hours to prepare the reactive chlorine dioxide solid preparation.

Further, the present invention mixes the release agent with a chlorine dioxide precursor material and a partial water-absorbing deactivator to obtain a first component.

The method is used for preparing various raw materials used for preparing the reactive chlorine dioxide solid preparation, wherein the solid raw materials are ground and then screened by a 100-120-mesh sieve, and raw material substances with intermediate granularity are left and dried until the water content is less than 0.5%; various liquid raw materials are heated and dehydrated to ensure that the water content is less than 0.05 percent.

Specifically, the molding of the mixed material of the invention can be a press-and-stretch molding.

More specifically, the mixed material is subjected to pressure-stretch forming, standing polymerization for 5-12 hours, cutting into sheet-shaped and columnar chlorine dioxide solid preparation profiles according to the required length, and standing polymerization for 6-10 hours to prepare the chlorine dioxide solid preparation.

Furthermore, the mixed material can be molded by compression molding, and the mixed material can be directly molded into various shapes such as sheets, cylinders, strips and the like.

The reactive chlorine dioxide solid preparation prepared by the invention needs to be sealed and packaged for storage, and the packaging material can adopt plastic films, aluminum plastic films, plastic tanks and the like.

The product prepared by the invention is convenient to store and has high product stability. When in use, the composition is prepared into different formulations according to different use occasions, and can realize the functions of sterilization, air purification, deodorization, peculiar smell removal and the like when being put into a required environment.

The product of the invention is suitable for being used in shoes, refrigerators, wardrobes, cabinets, semi-closed cabins of vehicles (such as trains, automobiles, airplanes, ships, submarines and the like), filters or air outlets of air conditioning systems (such as vehicles, household or office buildings, hospitals, waiting cars, waiting halls and the like), storage and transportation processes for preserving fruits and vegetables and degrading pesticide residues, storage and transportation of meat in slaughtering industries, and other space environments which need sterilization and disinfection processes in the processes of processing, storing and transportation of other foods and the like, and is applied to the technical fields of sterilization and disinfection, purification of harmful gas in air, preservation of fruits and vegetables, deodorization and the like.

Drawings

Fig. 1 is a graph showing the release of chlorine dioxide from the production of a solid chlorine dioxide formulation of example 1.

Fig. 2 is a partial magnified view of the release profile after day 26 in fig. 1.

Detailed Description

The following examples further describe embodiments of the present invention. The following examples are only for illustrating the technical solutions of the present invention more clearly, and do not limit the scope of the present invention. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.

In the following embodiment of the invention, various solid raw materials for preparing the reactive chlorine dioxide solid preparation are ground in advance and sieved by a 100-120-mesh sieve, and the raw materials with the intermediate granularity are left and dried until the water content is less than 0.5%. Heating and dehydrating various liquid raw materials until the water content is less than 0.05 percent.

Example 1.

Weighing 100g of sodium chlorite, 70g of anhydrous magnesium sulfate, 30g of anhydrous sodium sulfate and 8g of talcum powder, putting the materials into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing 150g of sodium bisulfate and 10g of anhydrous calcium chloride, putting the sodium bisulfate and the anhydrous calcium chloride into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing liquid epoxy resin E44130 g, 8g of dibutyl phthalate and 7g of ethylenediamine, uniformly mixing, and standing for 0.5 hour to obtain the epoxy resin prepolymer forming agent.

And (3) putting the two mixed solid materials into a three-dimensional mixer again, continuously mixing for 1 hour, discharging, putting into a stainless steel kneader, adding the prepared epoxy resin prepolymer forming agent, and kneading for 20 minutes.

And putting the kneaded material into a forming die, pressing and stretching the material into a long strip-shaped section, curing the section for 6 hours, cutting the section into a sheet shape or a cylindrical shape according to the required length, curing the section for 10 hours, and hermetically packaging the section by using a plastic tank to obtain the chlorine dioxide solid preparation product.

The chlorine dioxide solid preparation product prepared by the embodiment is placed in an environment with the relative humidity of 50-70% and the temperature of 20-30 ℃ to slowly release chlorine dioxide.

The amount of chlorine dioxide gas released per day was collected and measured for 30 consecutive days to obtain the chlorine dioxide release profile shown in fig. 1.

In fig. 1, the release amount of chlorine dioxide is relatively large in the first 3 days, the release amount per day is more than 3g, and the release amount per day is relatively stable and flat from 2.5g in the 4 th day to 1.05g in the 26 th day. After 26 days, the amount of chlorine dioxide released tended to decrease, indicating that the release was essentially complete.

The map of the release amount of chlorine dioxide after day 26 is shown in fig. 2. From the trend of the curve in fig. 2, chlorine dioxide is actually released after 30 days, but the release after 30 days is rejected as not detectable by the existing test conditions, since less than 0.01g has been released.

The total amount of the chlorine dioxide released by the chlorine dioxide solid preparation product in the embodiment in 30 days is 53.17g, which is 89.1% of the theoretical release amount, and the conversion rate is high.

Example 2.

80g of sodium chlorite, 40g of anhydrous magnesium sulfate and 6g of magnesium stearate are weighed and placed into a three-dimensional mixer, and the mixture is discharged after being mixed for 1 hour.

Weighing 80g of sodium bisulfate, 40g of sulfamic acid, 10g of anhydrous calcium chloride and 45g of anhydrous sodium sulfate, putting the materials into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing 70g of hydroxyl-terminated butadiene, 6g of 2, 4-toluene diisocyanate and 0.7g of triethanolamine, uniformly mixing, and standing for 2 hours to obtain the liquid viscous polyurethane prepolymer forming agent.

And (3) putting the two mixed solid materials into a three-dimensional mixer again, continuously mixing for 1 hour, discharging, putting into a stainless steel kneader, adding the prepared polyurethane prepolymer forming agent, and kneading for 20 minutes.

And putting the kneaded material into a forming die, pressing and stretching the material into a long strip-shaped section, polymerizing for 5 hours, cutting the section into a sheet shape or a cylindrical shape according to the required length, polymerizing for 10 hours, and hermetically packaging by using a plastic tank to obtain the chlorine dioxide solid preparation product.

The total amount of the chlorine dioxide released by the chlorine dioxide solid preparation product in the embodiment cumulatively for 30 days is 40 plus or minus 0.5g, which is 84.4 percent of the theoretical release amount, and the conversion rate is higher.

Example 3.

Weighing 100g of sodium chlorite, 60g of anhydrous magnesium sulfate, 30g of anhydrous sodium sulfate and 8g of talcum powder, putting the materials into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing 130g of sodium bisulfate, 50g of tartaric acid and 20g of anhydrous calcium chloride, putting into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing liquid epoxy resin E44140 g, dibutyl phthalate 9g and ethylenediamine 9g, uniformly mixing, and standing for 0.5 hour to obtain the epoxy resin prepolymer forming agent.

And (3) putting the two mixed solid materials into a three-dimensional mixer again, continuously mixing for 1 hour, discharging, putting into a stainless steel kneader, adding the prepared epoxy resin prepolymer forming agent, and kneading for 30 minutes.

And (3) putting the kneaded material into a compression molding die to mold a profile, curing for 5 hours, taking out the profile from the die, curing for 10 hours, and hermetically packaging by using a plastic tank to obtain the chlorine dioxide solid preparation product.

The total amount of the chlorine dioxide released by the chlorine dioxide solid preparation product in the embodiment cumulatively within 30 days is 52 +/-1 g, which is 86.7 percent of the theoretical release amount, and the conversion rate is higher.

Example 4.

Weighing 80g of sodium chlorite, 50g of anhydrous magnesium sulfate and 7g of talcum powder, putting the materials into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing 70g of sodium bisulfate, 40g of oxalic acid, 10g of anhydrous calcium chloride and 40g of anhydrous sodium sulfate, putting the materials into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing 80g of hydroxyl-terminated butadiene, 6g of 2, 4-toluene diisocyanate and 0.7g of triethanolamine, uniformly mixing, and standing for 2 hours to obtain the liquid viscous polyurethane prepolymer forming agent.

And (3) putting the two mixed solid materials into a three-dimensional mixer again, continuously mixing for 1 hour, discharging, putting into a stainless steel kneader, adding the prepared polyurethane prepolymer forming agent, and kneading for 30 minutes.

The total amount of the chlorine dioxide released by the chlorine dioxide solid preparation product in the embodiment cumulatively within 30 days is 40 +/-0.2 g, which is 83.7 percent of the theoretical release amount, and the conversion rate is higher.

Example 5.

Weighing 100g of sodium chlorite, 50g of anhydrous magnesium sulfate, 30g of anhydrous sodium sulfate and 8g of talcum powder, putting the materials into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing 125g of sodium bisulfate, 30g of citric acid, 10g of anhydrous calcium chloride and 20g of anhydrous sodium sulfate, putting the materials into a three-dimensional mixer, mixing for 1 hour, and discharging.

Weighing 80g of hydroxyl-terminated butadiene, 7g of 2, 4-toluene diisocyanate and 0.8g of triethanolamine, uniformly mixing, and standing for 3 hours to obtain the liquid viscous polyurethane prepolymer forming agent.

And putting the kneaded material into a forming die, pressing and stretching the material into a long strip-shaped section, polymerizing for 6 hours, cutting the section into a sheet shape or a cylindrical shape according to the required length, polymerizing for 10 hours, and hermetically packaging by using a plastic tank to obtain the chlorine dioxide solid preparation product.

The total amount of the chlorine dioxide released by the chlorine dioxide solid preparation product in the embodiment cumulatively within 30 days is 52 +/-0.8 g, which is 88% of the theoretical release amount, and the conversion rate is higher.

Claims

1. A reactive solid preparation of chlorine dioxide is prepared from the following raw materials in percentage by weight: 10-50 wt% of chlorine dioxide matrix material, 10-50 wt% of solid acid activator, 10-30 wt% of water-absorbing passivator and 15-30 wt% of prepolymer forming agent, and mixing and then performing compression molding to obtain the solid preparation, wherein the prepolymer forming agent is a liquid-state flowable polyurethane prepolymer forming agent or epoxy resin prepolymer forming agent.

2. The reactive solid chlorine dioxide preparation of claim 1, wherein the polyurethane prepolymer forming agent is prepared by mixing liquid polyether, polyester or polybutadiene monomer with liquid isocyanate-based crosslinking agent and chain extender.

3. The reactive chlorine dioxide solid preparation as claimed in claim 1, wherein the epoxy resin prepolymer forming agent is a mixture of liquid epoxy resin, curing agent ethylenediamine and organic acid ester plasticizer.

4. The reactive solid preparation of chlorine dioxide as claimed in claim 1, wherein the chlorine dioxide precursor material is one of alkali metal chlorate or chlorite, or a mixture of alkali metal chlorate and chlorite.

5. The reactive solid preparation of chlorine dioxide according to claim 1, wherein the solid acid activator is one of sulfamic acid, citric acid, oxalic acid, tartaric acid, sodium bisulfate, or a mixture of several of them in any proportion.

6. The reactive solid preparation of chlorine dioxide according to claim 1, wherein the water-absorbing passivating agent is one or more of anhydrous sodium sulfate, anhydrous calcium sulfate, anhydrous magnesium sulfate, sodium chloride, anhydrous calcium chloride, molecular sieve and alumina.

7. The reactive solid chlorine dioxide preparation according to claim 1, further comprising 0.01 to 0.5wt% of a release agent, wherein the release agent is magnesium stearate and/or talc.

8. A method of preparing a reactive solid formulation of chlorine dioxide as claimed in claim 1, said method comprising:

1) adding the chlorine dioxide parent material and part of the water-absorbing passivator in percentage by weight into a three-dimensional mixer, and uniformly mixing to obtain a first component;

2) uniformly mixing the solid acid activator with the balance of the water-absorbing passivator in percentage by weight in a three-dimensional mixer to obtain a second component;

3) uniformly mixing the first component and the second component in a three-dimensional mixer again, transferring the mixture into a kneading machine, adding the prepolymer forming agent, and kneading for 10-60 minutes to obtain a mixed material;

9. The method for preparing a reactive solid preparation of chlorine dioxide as claimed in claim 8, wherein a release agent is added to the first component.

10. The method for preparing a reactive solid preparation of chlorine dioxide as claimed in claim 8 or 9, wherein the forming of the mixed material is compression molding or compression molding.