CN102847181B - Product capable of delaying generation and releasing of chlorine dioxide and preparation method thereof - Google Patents

Abstract

The invention relates to a product for delaying the production and release of chlorine dioxide and a preparation method thereof. The product includes a porous carrier, chlorite attached to the porous carrier, and alkaline substance attached to the porous carrier. Also provided is a method for preparing a stabilized chlorine dioxide product, comprising: (a) preparing an aqueous solution comprising chlorite and an alkaline substance; (b) preparing an aqueous suspension comprising an organic hydrocarbon, the aqueous suspension of the organic hydrocarbon may be formulated alone, or in a solution of step (a) together with chlorite and an alkaline substance; (c) adding the solution of steps (a) and (b) (if present) to the porous support , mix uniformly, so that the chlorite, alkaline substance and optional organic hydrocarbon and alkaline salt in the porous carrier adsorption solution; (d) make the mixture obtained in step (c) dry, make the moisture content be lower than 10% , sealed and packaged, ready to be obtained.

Description

Product for delaying generation and release of chlorine dioxide and preparation method thereof

technical field

The invention relates to a product for delaying the production and release of chlorine dioxide. The product can be used to purify the environment, and can also be used for deodorization, sterilization, virus removal, mildew prevention, and anticorrosion when transporting food. A chlorine dioxide stabilized product for these purposes, and a method involving the use of the product/product for the delayed and stable generation of chlorine dioxide gas at low concentrations.

Background technique

Chlorine dioxide is a strong oxidizing agent, which is considered to have good prospects in deodorization, sterilization, virus removal, mildew prevention, antisepsis, bleaching, etc. But because chlorine dioxide is very unstable, it is not suitable for long-term storage and transportation, and there will be problems such as explosion hazards in high concentrations. In order to solve these problems, people have tried to use many methods.

For example, CN1915041A (Chinese patent application number: 200610030912.9, publication date: 2007-2-21) discloses a vegetable and fruit preservative product and its application. The product consists of 5000ppm activated chlorine dioxide (ClO ₂ ) in the total composition 30-40% by weight, ultra-fine ore powder accounts for 20-30% of the total weight of the composition, and acacia gum powder accounts for 40% of the total weight of the composition, and then diluted with water. Described activated chlorine dioxide (ClO ₂ ) is a nontoxic, harmless disinfectant recognized worldwide; the ultrafine ore powder is derived from smectite, sepiolite, zeolite, limestone, medical stone, The granular material of porous rock is ultra-finely crushed, and its particle size is between 0.001-0.0001mm; natural gum powder extracted from the seeds of honey locust tree. The preservatives for vegetables and fruits formed by diluting these three substances by 50-100 times of water can solve the problems of disinfection, sterilization, insecticide, insect repelling, inhibition of breathing, elimination of ethylene, reduction of water loss, nutrient consumption, prevention of discoloration, Taste, rot and other issues. It can also achieve the advantages of harmlessness, non-toxicity, non-polluting environment, low cost, convenient use, and easy operation.

Although there is a proposal to make a gel-like substance composed of stabilized chlorine dioxide and a water-absorbent resin (see, for example, JP-A-61-181532), this method has a problem that chlorine dioxide gas is hardly generated. In order to solve this problem, although a method of irradiating a gel-like substance composed of chlorine dioxide and a water-absorbing resin with ultraviolet rays has been proposed (for example, see Japanese Patent Laid-Open No. 2000-202009), this method must be combined with an ultraviolet irradiation device. .

Although it is proposed to use chlorine dioxide gas solution, chlorite and acidic ph regulators to form pure chlorine dioxide products, and gel-like compositions containing superabsorbent resins (for example, see JP-A 11-278808 bulletin), but due to the decomposition of chlorine dioxide gas solution, it is not suitable for long-term preservation.

In addition, although it has been proposed to add an activator, a water-absorbent resin, and a water-retaining agent to an aqueous chlorite solution to gel it (for example, see JP-A-2007-1807), it is necessary to add Chemicals have the problem that the reaction after addition is uncontrollable, and high-concentration chlorine dioxide gas is produced several days after addition.

Therefore, it is desirable in the art to provide a method for stabilizing chlorine dioxide, which method is expected to delay the generation and release of chlorine dioxide from products.

Contents of the invention

It is an object of the present invention to provide a method for stabilizing chlorine dioxide which is expected to delay the generation and release of chlorine dioxide from products. The present inventors have found that by impregnating chlorite and specific substances into porous carriers, stable chlorine dioxide products/products can be obtained, which can use chlorine dioxide to purify the environment, or deodorize and sterilize when transporting food In terms of virus removal, anti-mildew, and anti-corrosion, provide stabilized chlorine dioxide products that do not generate chlorine dioxide during storage, but can delay and stably generate chlorine dioxide during use, and methods for stably generating chlorine dioxide .

The first aspect of the present invention provides a product capable of delaying and stably providing chlorine dioxide, which includes a porous carrier, chlorite attached to the porous carrier, and an alkaline substance attached to the porous carrier.

The product according to the first aspect of the present invention, wherein the porous carrier is selected from sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, and activated carbon. The porous carrier used in the stabilized chlorine dioxide product in the present invention can use sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, activated carbon, etc., but in order to make the Chlorate does not decompose, and the carrier that is alkaline when suspended in water is better, palygorskite and sepiolite are relatively better, and sepiolite is the best. Sepiolite is a natural mineral of magnesium silicate, and its chemical structure is shown below.

(OH ₂ ) ₄ (OH) ₄ Mg ₈ Si ₁₂ O ₃₀ 8H ₂ O

The surface of this crystal structure is fibrous, with many grooves on the surface and many voids of cylindrical tunnel structure inside, which is a substance with a very large surface area. In the present invention, regardless of whether it is the pulverized and refined sepiolite raw ore, or the sepiolite after molding, or any granular, powdery, fibrous, or formed body calcined at 100-800°C The material of the shape can be used according to the purpose. In addition, sepiolite has a great ability to absorb and retain water, even if it absorbs the same weight of water as itself, it can appear dry.

The product according to the first aspect of the present invention, wherein the chlorite may be an alkali metal salt of chlorous acid or an alkaline earth metal salt of chlorous acid. The chlorite used in the present invention, specifically, the alkali metal salts that can be exemplified have sodium chlorite, potassium chlorite, lithium chlorite, etc., and sodium chlorite is the best in terms of economy and practicality. good. When preparing the stabilized chlorine dioxide product of the present invention, the concentration of chlorite used is usually more than 1% by weight, but it is not suitable for production control after exceeding 25% by weight, so when the chlorite is attached to When in a porous carrier, its concentration is usually 1% by weight to 25% by weight, more usually 5% to 20%. Although it is expected that relative to a fixed amount of porous carrier, the greater the amount of chlorite adsorption, the more beneficial the use of the article of the present invention, but the purpose of the present invention is to make chlorite more stably attached to the porous carrier, so that the The amount of chlorate adsorption is not the inventor’s concern. The inventor expects that the amount of chlorite adsorbed on 1000g of porous carrier can be 1g~500g, such as 10g~250g, such as 25g~250g, such as 50g~250g , for the purpose of the present invention, there is no need to specifically limit the amount of chlorite adsorbed on the porous carrier.

The product according to the first aspect of the present invention, wherein the alkaline substance can be an organic base or an inorganic base, preferably an inorganic base. The alkaline substance used in the present invention may be, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate and the like. From an economic point of view, sodium hydroxide and sodium carbonate are acceptable. From the perspective of storage stability of stabilized chlorine dioxide products, sodium hydroxide is better.

The product according to the first aspect of the present invention, wherein the ratio (R1) of the molar amount of alkaline substance to the molar amount of chlorite is 0.1~1:1, for example 0.1~0.7:1, for example 0.1~0.6:1 . When the amount is less than 0.1 times, the adsorbed chlorite is easy to decompose at normal temperature, and when it exceeds 0.7, although the stability is improved, it is difficult to generate chlorine dioxide, which is not ideal.

The stabilized chlorine dioxide product in the present invention is a material obtained by impregnating chlorite and alkali in a porous carrier and drying it, and the degree of drying (moisture content) has a great influence on the performance of the stabilized chlorine dioxide product. Impact. That is to say, the high water content of stabilized chlorine dioxide products will promote the decomposition reaction of chlorite to chlorate. In addition, although it is not clear whether the generated chlorine dioxide is blocked by water, but the higher the water content, the less chlorine dioxide is produced. Generally speaking, in the stabilized chlorine dioxide product of the present invention, the water content below 10% by weight is preferred, and can also be suitable for most use situations of the product of the present invention, and the water content below 7.5% by weight is more preferable. Preferably, the water content is more preferably below 5% by weight. Since the carrier material of the stabilized chlorine dioxide product of the present invention is porous, after it has adsorbed chlorite and alkaline substances, it can easily remove the moisture therein through a conventional heating and drying process, and reach 5% by weight The following water content is easy for those skilled in the art. Therefore, as far as the purpose of the present invention is concerned, the stabilized chlorine dioxide product of the present invention does not need to specifically limit the water content therein, and in the case of no special instructions, the water content in the stabilized chlorine dioxide product is below 10% by weight , 7.5% by weight or less, or 5% by weight or less.

In addition, it was unexpectedly found that adding an appropriate amount of basic salts, especially basic salts of inorganic acids, during the preparation of the stabilized chlorine dioxide product of the present invention can make the chlorite adsorbed on the carrier more stable. The above-mentioned basic salts are for example but not limited to phosphates, sulfates and carbonates, such as sodium phosphate, disodium hydrogen phosphate, sodium sulfate, sodium carbonate. Preferred basic salts are sodium phosphate and disodium hydrogen phosphate, more preferred basic salt is sodium phosphate. In particular, when basic salt is added, the ratio (R2) of the molar amount of basic salt to the molar amount of chlorite is 0.01-0.5:1, for example 0.01-0.25:1, for example 0.01-0.1:1. The above-mentioned basic salt can be added together with the basic substance such as sodium hydroxide, or can be fed before or after the basic substance is added. Generally speaking, it can be added under the condition that it can be added evenly, for example, the basic salt can be added before there is enough water but not completely dried, so the adding method of the basic salt in the present invention is not particularly limited.

In addition, it has also been unexpectedly found that adding an appropriate amount of organic hydrocarbon compound during the preparation of the stabilized chlorine dioxide product of the present invention can make the chlorite adsorbed on the carrier more stable. The aforementioned organic hydrocarbons are, for example but not limited to, alkanes, alkenes, esters of fatty alcohols and fatty carboxylic acids, fatty alcohols and fatty acids. In one embodiment, the organic hydrocarbon is an organic hydrocarbon containing 16-20 carbons. In one embodiment, the organic hydrocarbon is an organic hydrocarbon comprising 16 or 18 carbons. In one embodiment, the organic hydrocarbons are linear hydrocarbons. In one embodiment, the organic hydrocarbons are saturated hydrocarbons. In one embodiment, the organic hydrocarbon is selected from the group consisting of cetyl alcohol, stearyl alcohol, cetostearyl alcohol, hexadecane, octadecane, stearic acid, stearates such as stearic acid Magnesium, sodium stearate, and combinations thereof. Especially, when organic hydrocarbons are added, the ratio (R3) of the weight of organic hydrocarbons to the weight of chlorite is 0.01-0.5:1, for example, 0.01-0.2:1. The above-mentioned organic hydrocarbons can be added together with the basic substance such as sodium hydroxide, or can be fed before or after the basic substance is added. In general, it can be added under the condition that it can be added evenly, for example, the organic hydrocarbon can be added before there is enough water but not completely dried, so the method of adding the organic hydrocarbon in the present invention is not particularly limited. In addition, when added together with alkaline substances, the solubility of organic hydrocarbons may be insufficient, and at this time it can be added in the form of suspension.

According to the product according to the first aspect of the present invention, its aqueous solution exhibits basicity when suspended in water.

The product according to the first aspect of the present invention, wherein the porous carrier is palygorskite or sepiolite.

The product according to the first aspect of the present invention, wherein the moisture content is below 5%.

The second aspect of the present invention provides a method for preparing the stabilized chlorine dioxide product described in the first aspect of the present invention, which includes the following steps:

(a) preparing an aqueous solution comprising chlorite and an alkaline substance;

(b) preparing an aqueous suspension comprising organic hydrocarbons, which may be prepared separately or in the solution of step (a) together with chlorite and an alkaline substance;

Optionally (b') formulating an aqueous solution comprising an alkaline salt, which may be formulated alone or in the solution of step (a) together with chlorite and an alkaline substance;

(c) adding the solution obtained in step (a) and step (b) (if present) and optional step (b') (if present) to the porous carrier, and mixing uniformly so that the porous carrier absorbs the solution in the solution Chlorite, alkaline substances and optional organic hydrocarbons and alkaline salts;

(d) drying the mixture obtained in step (c) so that the water content is lower than 10%, and sealing the mixture to obtain the final product.

According to the method of the second aspect of the present invention, wherein the porous carrier is selected from sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite. In one embodiment, the porous support is sepiolite. In the present invention, the sepiolite can be the powder or granule or its molded product after the sepiolite ore is directly pulverized (that is, the original powder or granule is processed to form a certain shape of material, such as granular, block), It can also be granular, powdery, fibrous or shaped products obtained by calcining sepiolite ore at 100-800°C.

According to the method of the second aspect of the present invention, wherein said chlorite can be an alkali metal salt of chlorite or an alkaline earth metal salt of chlorite, such as sodium chlorite, potassium chlorite, lithium chlorite.

According to the method according to the second aspect of the present invention, wherein the concentration of chlorite in step (a) is 1% to 25% by weight, such as 5% to 25% by weight, preferably 5% to 20%.

According to the method of the second aspect of the present invention, wherein said alkaline substance can be an organic base or an inorganic base, preferably an inorganic base, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, Lithium carbonate etc.

According to the method of the second aspect of the present invention, the organic hydrocarbons are, for example but not limited to, alkanes, alkenes, esters formed from fatty alcohols and fatty carboxylic acids, fatty alcohols and fatty acids. In one embodiment, the organic hydrocarbon is an organic hydrocarbon containing 16-20 carbons. In one embodiment, the organic hydrocarbon is an organic hydrocarbon comprising 16 or 18 carbons. In one embodiment, the organic hydrocarbons are linear hydrocarbons. In one embodiment, the organic hydrocarbons are saturated hydrocarbons. In one embodiment, the organic hydrocarbon is selected from the group consisting of cetyl alcohol, stearyl alcohol, hexadecane, octadecane, stearic acid, stearates such as magnesium stearate, sodium stearate and its combination.

According to the method of the second aspect of the present invention, wherein in the step (a), the molar ratio (R1) of the molar amount of alkaline substance to the molar amount of chlorite is 0.1~1:1, for example 0.1~0.7:1, for example 0.1~ 0.3:1.

According to the method of the second aspect of the present invention, wherein said basic salt is such as but not limited to phosphate, sulfate and carbonate, such as sodium phosphate, disodium hydrogen phosphate, sodium sulfate, sodium carbonate. Preferred basic salts are sodium phosphate and disodium hydrogen phosphate, more preferred basic salt is sodium phosphate.

According to the method of the second aspect of the present invention, wherein the amount of basic salt used in step (a) or step (b') is calculated relative to chlorite, specifically the molar amount of basic salt and chlorite The molar ratio (R2) of the acid salt is 0.01-0.5:1, for example 0.01-0.25:1, for example 0.05-0.2:1.

According to the method of the second aspect of the present invention, wherein the amount of organic hydrocarbon used in step (a) or step (b) is calculated relative to chlorite, specifically, when adding organic hydrocarbon, the weight of organic hydrocarbon The ratio (R3) to the weight of chlorite is 0.01~0.5:1, for example 0.01~0.2:1.

According to the method of the second aspect of the present invention, wherein the drying of step (d) is such that the water content in the stabilized chlorine dioxide product obtained in the present invention is below 10% by weight, more preferably below 7.5% by weight, containing The amount of water is more preferably 5% by weight or less.

A third aspect of the present invention provides a method of generating and/or releasing chlorine dioxide in a substantially controllable manner, the method comprising the steps of:

(i) The stabilized chlorine dioxide product described in any embodiment of the first aspect of the present invention is provided, and the product is wrapped in a packaging material (i.e. insulating material) container that can isolate moisture and air circulation before use, such as a bag such that the article substantially does not generate and/or release chlorine dioxide prior to use;

(ii) When using the product, the container is opened to allow moisture and air outside the container to contact the product and generate and/or release chlorine dioxide.

The method according to the third aspect of the present invention, wherein the rate of chlorine dioxide generation and/or release is controlled by controlling the amount of moisture and air in contact with the product by controlling the size of the opening of the container.

Any aspect of the present invention or any technical feature of any implementation of this any aspect is also applicable to any other implementation or any implementation of any other aspect, as long as they do not contradict each other, of course When applicable, the corresponding features can be appropriately modified if necessary. Various aspects and features of the present invention are further described below.

All the documents cited in the present invention are incorporated herein by reference in their entirety, and if the meaning expressed in these documents is inconsistent with the present invention, the expression of the present invention shall prevail. In addition, various terms and phrases used in the present invention have common meanings known to those skilled in the art. Even so, the present invention still hopes to make a more detailed description and explanation of these terms and phrases here. The terms and phrases mentioned are as follows: If there is any inconsistency with the known meaning, the meaning expressed in the present invention shall prevail.

Various aspects of the invention are further described below.

In the present invention, % is weight/weight percentage unless otherwise stated.

In the present invention, the term "stabilized chlorine dioxide product" refers to an artificial product that can control the release of chlorine dioxide substantially according to the expected needs of people. Since chlorine dioxide can be formed by reacting chlorite with carbon dioxide and water, the present invention attaches chlorite to a porous carrier, and the product thus obtained is called "stabilized chlorine dioxide product", It chemically reacts with water and carbon dioxide in the ambient air to release chlorine dioxide, a gas that can be used for disinfection and other purposes. Therefore, the "stabilized chlorine dioxide product" of the present invention can also be called a Artifacts that allow for the steady release of chlorine dioxide substantially for its intended purpose.

In the present invention, the term "porous carrier" is an adsorption carrier that can efficiently adsorb chlorite decomposing chlorine dioxide due to its high porosity. The apparent shape of the porous carrier is not particularly limited, for example, it may be granular, powdery, blocky, etc.

In the present invention, the term "chlorite attached to the porous carrier" means that because there are many pores inside the porous carrier, chlorite can be attached to the surface of these pores, and the larger the surface area of the pores inside the porous carrier, the greater the chlorite can be. The larger the area available for chlorite adsorption. Similarly, the term "basic substance attached to the porous carrier" also has a similar meaning.

In the present invention, the "moisture content" of the stabilized chlorine dioxide product of the present invention refers to the amount of moisture contained in the finished product of the present invention, which is usually difficult to completely remove the finished product during the drying process, such as moisture When the water content is reduced to below 5%, the cost of continuing to reduce the water content will increase greatly. However, in the field of products of the present invention, stabilized chlorine dioxide products of the present invention having a moisture content of less than 7.5% by weight are generally acceptable in order to control chlorite decomposition.

In the present invention, when packaging the stabilized chlorine dioxide products of the present invention, packaging materials that can isolate moisture and air circulation are usually used, which can be called insulating materials, such as packaging formed by composite aluminum-plastic film, composite paper-plastic film, etc. Containers such as bags or such as plastic bottles or glass bottles, such packaging containers can provide a good storage and transportation environment for the stabilized chlorine dioxide product of the present invention without continuous reaction and decomposition with moisture and air in the air. When the stabilized chlorine dioxide product of the present invention needs to be used, the above-mentioned packaging material that can isolate moisture and air circulation can be opened. Of course, inside the above-mentioned packaging container that can isolate moisture and air circulation of the present invention, an inner packaging container such as an inner packaging bag can also be included, which can allow moisture and air in a gaseous state and chlorine dioxide produced by decomposition to enter and exit the inner packaging container. A packaging container such as an inner packaging bag, but the stabilized chlorine dioxide product of the present invention in the form of granules, powder or other states cannot freely pass through the inner packaging container such as an inner packaging bag. Like this, when the stabilized chlorine dioxide product of the present invention is used, open the inner packing container such as the inner packing bag that is made of insulating material layer, the moisture and air that are gaseous state can pass through inner packing material and enter the stabilized chlorine dioxide of the present invention. Inside the pores of the product, it reacts with the chlorite attached to it to generate gaseous chlorine dioxide and escapes from the inner packaging material into the external environment for disinfection and other purposes.

In the process of preparing the stabilized chlorine dioxide product of the present invention, the alkaline salt can be prepared separately, or can be prepared in the same solution with chlorite and alkaline substances.

In the process of preparing the stabilized chlorine dioxide product of the present invention, the organic hydrocarbon can be prepared separately, or can be prepared in the same solution with chlorite, alkaline substance and optional alkaline salt.

In the process of preparing the stabilized chlorine dioxide product of the present invention, the moisture is dried to leave the porous carrier. The drying process may be natural air drying, vacuum drying, heating drying, etc. or a combination of these drying methods. Because the porous carrier of the present invention has a fairly strong water absorption capacity, after absorbing a large amount of dissolved chlorite, alkaline substances and alkaline salt aqueous solution, the appearance can still be in a dry or semi-dry state, so the subsequent drying process is easy to dry by natural air , Realized by drying under reduced pressure. Of course, in terms of production efficiency, heat drying is usually adopted. Generally speaking, when preparing the product of the present invention, the temperature used for heating and drying is usually lower than 100°C, more usually lower than 80°C, such as about 50°C, about 60°C, about 70°C, about 80°C °C. Those skilled in the art understand that the drying process of the present invention is usually carried out at a temperature of 50°C to 80°C.

In the present invention, impregnating chlorite and alkali into the porous carrier and drying it is a feature of the stabilized chlorine dioxide product. The porous carrier used is alkaline when suspended in water. The concentration of alkali used is higher than 0.1 times the amount and lower than 0.7 times the amount per mol of chlorite. The moisture content in this stabilized chlorine dioxide product is 10% by weight or less. In addition, this stabilized chlorine dioxide product should be isolated from carbon dioxide and water vapor when it is stored, and it is a feature of the method to stably generate chlorine dioxide gas by making it contact with carbon dioxide and water vapor when it is used.

In the present invention, for the purpose of utilizing chlorine dioxide to purify the environment or deodorize, sterilize, remove viruses, prevent mildew, and prevent corrosion during food transportation, a stable amount (no more, no less) of stable chlorine dioxide can be provided. Chlorine dioxide products, especially for the purpose of providing a method that does not generate chlorine dioxide during storage and generates chlorine dioxide during use.

In the present invention, in the stabilized chlorine dioxide product obtained by impregnating chlorite and alkaline substances into the porous carrier and drying, the amount of alkali used is higher than 0.1 times the amount per mol of chlorite. 0.7 times the amount. A stabilized chlorine dioxide product having a water content after drying of 10% by weight or less.

In the present invention, when the stabilized chlorine dioxide product is preserved, it is isolated from carbon dioxide and water vapor, and when in use, chlorine dioxide gas is generated by making it contact with carbon dioxide and water vapor in the air to stably produce chlorine dioxide gas method.

The stabilized chlorine dioxide product of the present invention can produce chlorine dioxide in an appropriate amount and stably. In addition, through the method for generating chlorine dioxide gas of the present invention, chlorine dioxide can not be produced during storage, and only chlorine dioxide can be produced during use. Chlorine oxide. In addition, the chlorine dioxide production method utilizing the stabilized chlorine dioxide products of the present invention does not produce chlorine dioxide during preservation, is suitable for long-term storage and handling, and can stably produce chlorine dioxide gas during use without the risk of explosion. Very low, which is quite satisfactory.

In addition, the stabilized chlorine dioxide product of the present invention is basically in the appearance of the porous carrier used in the present invention, that is, in the form of powder, granules or lumps. These forms are quite beneficial for the production, transportation, use and other disposal processes of the product.

In the present invention, the stabilized chlorine dioxide product refers to a substance capable of stably releasing chlorine dioxide, which is a substance impregnated with chlorite and alkaline substances into a porous carrier and dried.

In the present invention, the stabilized chlorine dioxide product is to add fully dried porous carrier to the mixture of chlorite aqueous solution and alkali and optional basic salt and hydrocarbon, and then mix and dry; The carrier is obtained by adding mixed alkali, adding mixed chlorite aqueous solution and drying. In addition, a stabilized chlorine dioxide product with a high content of chlorite can be obtained by repeating the above operations. The drying method and equipment are not particularly limited, and a vacuum dryer, flow dryer, shelf dryer, rotary dryer, etc. may be used.

In the present invention, the method for producing chlorine dioxide from stabilized chlorine dioxide products includes the method of mixing the stabilized chlorine dioxide products with acidic substances or oxidizing substances and allowing the stabilized chlorine dioxide products to contact with air. In terms of stabilizing the production of chlorine dioxide and releasing it within a certain period of time, it is better to let the stabilized chlorine dioxide product come into contact with the air.

In the present invention, chlorine dioxide can be produced by contacting chlorine dioxide products with air. Therefore, the inventors of the present invention compared the introduction of ordinary air into the chlorine dioxide product of the present invention, the introduction of air from which carbon dioxide has been removed by an aqueous solution of sodium hydroxide, and the introduction of an aqueous solution of sodium hydroxide and calcium chloride. Chlorine dioxide production for the three methods of air with carbon dioxide and water vapor removed (see below). Compared with ordinary air, the production of chlorine dioxide is greatly reduced when the air with carbon dioxide removed is introduced, and the production of chlorine dioxide is basically zero when the air with carbon dioxide and water vapor is introduced. It can be considered that this is because water vapor and carbon dioxide are absorbed through the pores of the stabilized chlorine dioxide product to produce carbonic acid as shown in the following chemical equation. Since carbonic acid is a weak acid with the first dissociation constant pk1=6.4, this carbonic acid acts as an acid and chlorine dioxide Chlorine dioxide is produced by the interaction of acid salts.

CO ₂ +2H ₂ O→H ₂ CO ₃

Through this phenomenon, it does not need to be mixed with acidic substances, and chlorine dioxide can be produced by contacting with air, specifically carbon dioxide and water vapor in the air. Conversely, chlorine dioxide production can be suppressed by avoiding contact with carbon dioxide and water vapor. Therefore, when not in use, put chlorine dioxide products into containers that are difficult to permeate carbon dioxide and water vapor, or use methods such as packaging to suppress the generation of chlorine dioxide when not in use, and use it to contact the outside air ( Remove from the container, open the container cap, remove the packaging material, etc.) to slowly release chlorine dioxide gas.

In 81kg of sepiolite particles (particle diameter 1-3mm) formed by calcining at 700°C for 3 hours, add an aqueous solution containing 25% sodium chlorite and 25% sodium hydroxide (the aqueous solution contains chlorous acid After the amount of sodium is 16 kg and the amount of sodium hydroxide is 1 kg), vacuum-dry at 70° C. for 5 hours to obtain a chlorine dioxide-releasing product adsorbed with sodium chlorite. The product is dried at 105° C. to measure its moisture content , with a moisture content of about 2%. Put 40g of the chlorine dioxide product thus obtained into a 300ml glass-made packed tower (diameter 50×height 150mm), at a temperature of 25°C and a humidity of 60%, feed it with ordinary air at a rate of 1L/min for 5 hours (gas 1), pass through the air (gas 2) that removes carbon dioxide from 25% sodium hydroxide aqueous solution, pass through the air (gas 3) that removes carbon dioxide and water vapor from 25% sodium hydroxide aqueous solution and calcium chloride tube, and measure The amount of chlorine dioxide produced under these three methods. The results show that compared with the normal air (gas 1, the gas generation rate is 10 mg/hr/kg), when the air with carbon dioxide removed (gas 2, the gas generation rate is 3 mg/hr/kg) is two The production of chlorine oxide is greatly reduced; when the air that removes carbon dioxide and water vapor is introduced (gas 3, the gas production is 0.15mg/hr/kg), the production of chlorine dioxide can be basically suppressed below 0.2%.

In the present invention, sodium chlorite purity detection method can use following method (can be referred to as iodine titration in the present invention):

Reagents and solutions: 1. Sulfuric acid solution (1+8): absorb 20mL of sulfuric acid, slowly add it to 160mL of water, and keep stirring.

2. Potassium iodide solution (100g/L): Weigh 20g of potassium iodide, dissolve it in 200mL of water, and make it fresh.

3. Starch indicator solution (5g/L): weigh 0.5g of starch, dissolve it in 100mL of boiling water, and make it fresh.

4. Standard solution of sodium thiosulfate [c(Na ₂ S ₂ O ₃ )=0.100mol/L]: Weigh 26g of sodium thiosulfate and 0.2g of sodium carbonate, add appropriate amount of freshly boiled cold water to dissolve them, and Dilute to 1000mL, mix well, transfer to a brown reagent bottle, filter after standing for one month, and set aside after accurate calibration.

Calibration of sodium thiosulfate standard solution: Accurately weigh about 0.15g of potassium dichromate (national standard substance GBW 06105c) dried to constant weight at 120°C, place it in a 500mL iodine bottle, add 50mL of water to dissolve it . Add 2g of potassium iodide, shake gently to dissolve it, then add 20mL of sulfuric acid solution (1), seal it, and shake well. Place in the dark for 10 minutes and then dilute with 250mL of water. Add sodium thiosulfate standard titration solution until the solution turns light yellow, then add 3mL starch indicator solution (3), and continue titration until the blue color disappears and turns bright green. The temperature of the reaction solution and dilution water should not be higher than 20°C. At the same time, do a reagent blank test.

Determination steps: Weigh a sample containing approximately 3g of sodium chlorite, accurate to 0.0002g, put it in a 100mL beaker, add water to dissolve it, transfer it all into a 500mL volumetric flask, dilute with water to the mark, and shake well.

Measure 10mL of the test solution, place it in a 250mL iodine measuring bottle previously added with 20mL of potassium iodide solution (2), add 20mL of sulfuric acid solution (1), and shake well. Place in the dark for 10min. Add 100mL of water, titrate with sodium thiosulfate standard solution (4) until the solution turns light yellow, add about 3mL of starch indicator solution (3), continue titration until the blue color disappears, which is the end point, and do a blank test at the same time. Calculate the content of sodium chlorite in the sample. The difference between the two parallel measurement results is not more than 0.2%, and the arithmetic mean value is taken as the measurement result.

In addition, the sodium chlorite purity/content detection method is also carried out with reference to the method recorded in the chemical industry standard HG3250-2001 of the People's Republic of China.

Because the stabilized chlorine dioxide product related to the present invention can produce a stable amount of chlorine dioxide within a certain period of time, it is very suitable for use as a bactericide, deodorant, antiseptic, and antifungal agent.

The carbon dioxide and water vapor transmission rates of packaging materials or containers used in the method for stably generating chlorine dioxide of the present invention are as follows. The permeability of carbon dioxide should be controlled below 2.5×10 ^-11 cc(STP)/cm ² ·sec·cmHg, if the thickness of the packaging film is 50μm, it should be controlled at 5×10 ^-11 cc(STP)/cm ² · It is preferably below sec·cmHg. In addition, the water vapor transmission rate should be controlled below 5×10 ^-9 cc(STP)/cm ² ·sec·cmHg, if the thickness of the packaging film is 50μm, it should be controlled at 1000×10 ^-10 cc(STP)/ It is preferably below cm ² ·sec·cmHg. Metal, glass, etc. are considered as materials that make it difficult for carbon dioxide and water vapor to pass through. Especially, plastic films are widely used when used as packaging materials and container lids. In that case, vacuum aluminized polyethylene film can be used. , Vinylidene chloride, polychlorotrifluoroethylene, etc.

Detailed ways

The present invention is further illustrated below through specific embodiments/experimental examples, but it should be understood that these embodiments and experimental examples are only used for more detailed description, and should not be interpreted as being used to limit the present invention in any form. invention.

The present invention provides general and/or specific descriptions of the materials and test methods used in the tests. While many of the materials and methods of manipulation which are employed for the purposes of the invention are well known in the art, the invention has been described here in as much detail as possible. It will be clear to those skilled in the art that in the following, unless otherwise specified, the materials and operation methods used in the present invention are well known in the art.

In the products obtained in the following tests, when they are sealed and packaged to isolate carbon dioxide and moisture, if not otherwise stated, the packaging material used to isolate carbon dioxide and moisture is a vacuum aluminized polyethylene film bag, which is allowed to be in a gas state. The inner packaging material for the entry and exit of moisture, air, and chlorine dioxide produced by decomposition is a non-woven bag; unless otherwise specified, the packaging volume of each bag is 50 grams. In the following, unless otherwise stated, the sepiolite used is the granules produced by calcining the sepiolite ore produced in Neixiang County, Henan Province at 700°C for 3 hours, and the particle diameter is 1-3mm.

Example 1:

In the sepiolite (particle diameter 1-3mm) formed by calcining at 700°C for 3 hours, add sodium chlorite and sodium hydroxide (preformed into an aqueous solution, the concentration is respectively 25%) in the following proportions, After mixing and making the adsorption uniform, vacuum-dry for 5 hours at 70° C. to obtain chlorine dioxide products 1A to 1G of the composition shown below (in the table, the unit of each numerical value is parts by weight, and it can also be understood as weight in most cases. Percentage; the value in the brackets in the NaOH column is relative to the molar weight of _NaClO2 , for example, in product 1A, the molar weight of _NaOH is 0.14 based on 1 mole of NaClO2 in 8 parts by weight; the numerical value in the water column indicates The water content in the final product shows that the water content in the product 1G reaches 15 parts by weight/107 parts by weight).

NaClO ₂ NaOH water Sepiolite Product 1A 8 0.5(0.14) 2 89.5 Product 1B 16 1(0.14) 2 81 Product 1C 16 1(0.14) 4 79 Product 1D 16 4(0.56) 2 78 Product 1E 16 0.5(0.07) 2 81.5 Product 1F 16 8(1.12) 2 74 Product 1G 16 1(0.14) 15 75

Put each 10g of stabilized chlorine dioxide products 1A to 1G into a glass sample bottle in a sealed manner, place it for 3 months at a temperature of 45°C and a humidity of 75%, and use iodine titration to analyze the chlorine dioxide before and after high temperature treatment. The concentration of sodium chlorite is calculated by calculating the percentage of sodium chlorite concentration change in the product after high-temperature treatment relative to the sample without high-temperature treatment, that is, the percentage change of sodium chlorite concentration = concentration of sodium chlorite in high-temperature-treated samples Divide by the concentration of sodium chlorite in the untreated sample and multiply by 100%. The results are shown in the table below.

In addition, each 40g of the stabilized chlorine dioxide products prepared above is dropped into a 300ml glass-made packed tower (diameter 50×high 150mm), at a temperature of 25° C., and at a humidity of 60%, pass into it for 5 hours at a speed of 1L/min. Air, the gas at the outlet is fed into the potassium iodide solution adjusted to pH = 7 with phosphate buffer solution. Since chlorine dioxide can free iodine, the generation of chlorine dioxide gas can be calculated by iodine titration with sodium thiosulfate solution , the results are shown in the table below. The unit of measurement is the chlorine dioxide gas produced by 1 kg of stabilized chlorine dioxide products, expressed in mg/hr.

sample Percent change in sodium chlorite concentration Gas production (mg/hr/kg) Product 1A 93.2% 7.3 Product 1B 91.7% 8.9 Product 1C 94.1% 8.2 Product 1D 95.2% 7.1 Product 1E 29.4% 30.8 Product 1F 93.8% 0.53 Product 1G 26.6% 4.2

The results showed that after the amount of sodium hydroxide was reduced, the sodium chlorite in the product could not be kept more stably in the adsorbent material; in addition, the sodium chlorite was also unfavorable when the water content in the product was high. Specifically, the reductions of chlorite in stabilized chlorine dioxide products 1A to 1D and 1F are all below 10%. The stabilized chlorine dioxide product 1E decomposes due to the small amount of alkaline substances, and the stabilized chlorine dioxide product 1E decomposes. In product 1G, due to the high water content, the decomposition reaction of chlorite to chlorate is caused, and the concentration of sodium chlorite is lower than 1/3 of the initial stage.

In addition, as shown in the results in the table, the stabilized chlorine dioxide products 1A to 1D all produced an appropriate amount of chlorine dioxide gas, and the stabilized chlorine dioxide product 1E produced too much chlorine dioxide gas due to the small amount of alkaline substances. Chlorine gas, stabilized chlorine dioxide product 1F has insufficient chlorine dioxide gas due to the large amount of alkaline substances.

Therefore, compared with the stabilized chlorine dioxide products 1E to 1G, 1A to 1D of the stabilized chlorine dioxide products 1A to 1D of the present invention can stably produce an appropriate amount of chlorine dioxide gas within a certain period of time.

In another test, the sepiolite ore produced in Neixiang County, Henan Province was directly crushed into fine particles (1~3mm) as the adsorbent, and the stabilized chlorine dioxide products were prepared according to the methods of the above products 1A to 1D. The results showed that Essentially the same results shown in the table above as for Preparations 1A to 1D. In another test, particles (particle diameter 0.2-1 mm) produced by sepiolite ore produced in Yixian County, Hebei Province were calcined for 3 hours at 700 ° C for 3 hours as an adsorbent, and stabilized according to the methods of the above-mentioned products 1A to 1D. Chlorine dioxide formulations, the results showed essentially the same results as shown in the table above as formulations 1A to 1D. In another test, referring to the preparation process of product 1B, only the concentration of chlorite was designed to be 5%, 10%, 15% and 20%, respectively, and the concentration of sodium hydroxide was set to be the same as that of sodium chlorite; The 4 stabilized chlorine dioxide products thus obtained showed essentially the same results as shown in the table above as Product 1B.

In another test, the particles (0.5-2mm in particle diameter) produced by palygorskite (palygorskite) ore produced in Hebei Province were calcined at 700°C for 3 hours were used as adsorbents, prepared according to the methods of the above-mentioned products 1A to 1D Stabilized chlorine dioxide preparations, the results showed essentially the same results as shown in the table above for preparations 1A to 1D.

Example 2:

To the sepiolite (particle diameter 1-3mm) that was calcined at 700°C for 3 hours, add sodium chlorite, sodium hydroxide and sodium phosphate (prepared to aqueous solution, the concentration is 20% respectively), after mixing and making the adsorption uniform, vacuum-dry at 70°C for 5 hours, so that the water content in the product is 2% (± 0.5%), and the following composition is obtained: Chlorine Products 2A to 2P. Each product designed and prepared contained 80 parts by weight of sepiolite and 15 parts by weight of NaClO ₂ . In each formula shown in the table, the numerical value in the NaOH column represents the mole fraction of NaOH relative to every 1 mole of sodium chlorite contained in the formula; similarly, the numerical value in the sodium phosphate column represents the relative Molar parts of sodium phosphate in terms of parts of sodium chlorite.

Put each 20g of the above-prepared stabilized chlorine dioxide products 2A to 2P into a non-woven bag that can pass through water vapor and air, place it for 1 month at a temperature of 40°C and a humidity of 60%, and analyze it by iodine titration The concentration of sodium chlorite before and after high-temperature treatment, calculate the percentage change of sodium chlorite concentration in the product after high-temperature treatment, relative to the sample without high-temperature treatment, that is, the percentage change of sodium chlorite concentration = Divide the concentration of sodium chlorite in the high temperature treated sample by the concentration of sodium chlorite in the sample without high temperature treatment and multiply by 100%. The results show that the stabilized chlorine dioxide products can still maintain a high content after high temperature treatment when the molar ratio (R2) of the molar amount of alkaline salt to the molar amount of chlorite is 0.05~0.2:1. The chlorite is above 50%; when the concentration is too low or the concentration is high, the chlorite retention is reduced to less than 15%.

sample NaClO ₂ NaOH Sodium Phosphate Percent change in concentration Product 2A 15 copies 0.15mol parts 0mol parts 2% Product 2B 15 copies 0.15mol parts 0.01mol parts 9% Product 2C 15 copies 0.15mol parts 0.05mol parts 58% Product 2D 15 copies 0.15mol parts 0.1mol parts 71% Product 2E 15 copies 0.15mol parts 0.15mol parts 65% Product 2F 15 copies 0.15mol parts 0.2mol parts 55% Product 2G 15 copies 0.15mol parts 0.3mol parts twenty one% Product 2H 15 copies 0.15mol parts 0.5mol parts 13% Product 2I 15 copies 0.5mol parts 0mol parts 1% Product 2J 15 copies 0.5mol parts 0.01mol parts 6% Product 2K 15 copies 0.5mol parts 0.05mol parts 62% Product 2L 15 copies 0.5mol parts 0.1mol parts 76% Product 2M 15 copies 0.5mol parts 0.15mol parts 71% Product 2N 15 copies 0.5mol parts 0.2mol parts 58% Product 2O 15 copies 0.5mol parts 0.3mol parts 27% Product 2P 15 copies 0.5mol parts 0.5mol parts 11%

In addition, refer to the above product 2C, product 2D, product 2F, product 2K, product 2L, and product 2N, but the basic salt used is disodium hydrogen phosphate, and products with different formulations are prepared respectively, and tested according to the above method, the result The percent change of chlorite concentration is in the range of 50% to 75%. For example, the percent change of chlorite concentration of the products obtained by referring to product 2D and product 2L are 64% and 71% respectively. However, using disodium hydrogen phosphate as the basic salt reference product 2B and product 2H and product 2J and product 2P, the percentage change of its chlorite concentration of the obtained product is all below 10%.

Example 3:

In the sepiolite (particle diameter 1-3mm) formed by calcining at 700°C for 3 hours, add sodium chlorite, sodium hydroxide and organic hydrocarbon compound (according to concentration Design requirements, make the three dissolve/disperse together in water), mix and make the adsorption uniform, then vacuum dry at 70°C for 5 hours, so that the water content in the product is 2% (± 0.5%), as shown below Composition of chlorine dioxide products 3-1 to 3-18. Each product designed and prepared contained 80 parts by weight of sepiolite and 15 parts by weight of NaClO ₂ . In each formula shown in the table, the numerical value in the column of NaOH represents the mole fraction of NaOH relative to every 1 mole part of sodium chlorite contained in the formula; Parts by weight of organic hydrocarbon compound in terms of parts sodium chlorite.

With each 20g of the stabilized chlorine dioxide products 3-1 to 3-18 prepared above, pack in the non-woven bag that can pass through water vapor and air, place 1 month under 40 ℃ of temperature, humidity 60%, use The iodine titration method analyzes the concentration of sodium chlorite before and after high temperature treatment, and calculates the percentage change of sodium chlorite concentration in the product after high temperature treatment compared with the sample without high temperature treatment, that is, sodium chlorite Percent change in concentration = concentration of sodium chlorite in high temperature treated samples divided by concentration of sodium chlorite in non-high temperature treated samples multiplied by 100%. The results show that in the range of 0.01~0.2:1 ratio (R3) between the amount of organic hydrocarbon compound and the amount of chlorite, the stabilized chlorine dioxide products can still maintain a high content of chlorite after high temperature treatment. Chlorate, all above 45%; and when the concentration is too low or the concentration is high, the chlorite retention is reduced to below 20%.

sample NaOH Octadecanol stearic acid Percent change in concentration Product 3-1 0.15 0 3% Product 3-2 0.15 0.01 49% Product 3-3 0.15 0.1 67% Products 3-4 0.15 0.2 53% Products 3-5 0.15 0.5 18% Products 3-6 0.15 1.0 11%

Products 3-7 0.5 0 4% Products 3-8 0.5 0.01 51% Products 3-9 0.5 0.1 71% Products 3-10 0.5 0.2 62% Products 3-11 0.5 0.5 16% Products 3-12 0.5 1.0 7% Products 3-13 0.25 0 5% Products 3-14 0.25 0.01 47% Products 3-15 0.25 0.1 69% Products 3-16 0.25 0.2 73% Products 3-17 0.25 0.5 18% Products 3-18 0.25 1.0 11%

In addition, with reference to the above product 3-2, product 3-3, and product 3-4, but the organic hydrocarbon compound used is cetearyl alcohol, octadecane, or magnesium stearate, different formulations are prepared respectively Products, tested according to the above method, the result of the change percentage of chlorite concentration is in the range of 45% ~ 75%, for example, refer to the method of product 3-3 with cetostearyl alcohol, octadecane, and magnesium stearate Obtained goods, its chlorite concentration change percentage is respectively 61%, 71%, and 68%; But the consumption ratio (R3) of the amount of using these three kinds of organic hydrocarbon compounds and the amount of chlorite is lower than When it is 0.01 or higher than 0.5, the percent change of chlorite concentration is lower than 15%.

In addition, in the above product 3-2, product 3-3, product 3-4, product 3-8, product 3-9, product 3-10, product 3-14, product 3-15, product 3-16, Add alkaline salt sodium phosphate (the molar ratio (R2) of the molar amount added to the molar amount of chlorite is 0.1:1, the results show that the percentage change of the concentration of chlorite is higher than that without the basic salt The corresponding formula is more than 10% higher; for example, when sodium phosphate with R2=0.1:1 is added to product 3-3, the percentage change of chlorite concentration in the product obtained is 81%.

Claims (1)

1. can delay ground, the goods of chlorine dioxide are stably provided, it comprises porous carrier, be attached to chlorite on this porous carrier, be attached to the alkaline matter on this porous carrier, and organic hydrocarbon compound and basic salt; Wherein:

Described porous carrier is selected from: meerschaum, Paligorskite, Montmorillonitum, silica gel, kieselguhr, zeolite, perlite, active carbon,

Described chlorite is sodium chlorite,

Described alkaline matter is selected from: sodium hydroxide, potassium hydroxide,

Described organic hydrocarbon compound is selected from: esters, aliphatic alcohols and fatty acid that paraffinic, chain alkene, fatty alcohol and aliphatic carboxylic acid generate,

Described basic salt is selected from: sodium phosphate, sodium hydrogen phosphate;

On every 1000g porous carrier, adsorbing chloritic amount is 10g ~ 250g, the mole of alkaline matter is 0.1 ~ 1:1 with the ratio of chloritic mole, the weight of organic hydrocarbon is 0.01 ~ 0.2:1 with the ratio of chlorite weight, and the mole of basic salt is 0.05 ~ 0.2:1 with the ratio of chloritic mole.

2. according to the goods of claim 1, wherein said porous carrier is selected from meerschaum, Paligorskite.

3. according to the goods of claim 1, wherein on every 1000g porous carrier, adsorbing chloritic amount is 50g ~ 250g.

4. according to the goods of claim 1, wherein said alkaline matter is sodium hydroxide.

5. according to the goods of claim 1, the mole of wherein said alkaline matter is 0.1 ~ 0.6:1 with the ratio of chloritic mole.

6. according to the goods of claim 1, wherein water content is below 5 % by weight.

7. according to the goods of claim 1, described organic hydrocarbon is the straight chain organic hydrocarbon that comprises 16 or 18 carbon.

8. according to the goods of claim 1, wherein organic hydrocarbon is selected from hexadecanol, octadecanol, 16 octadecanols, hexadecane, octadecane, stearic acid, stearate and combination thereof.

9. goods according to Claim 8, wherein said stearate is selected from: magnesium stearate, sodium stearate.

10. according to the goods of claim 1, its in water when suspendible aqueous solution be shown as alkalescence.

The method of the goods of 11. preparation claim 1 to 10 any one, it comprises the following steps:

(a) aqueous solution that preparation comprises chlorite and alkaline matter;

(b) aqueous suspensions that preparation comprises organic hydrocarbon;

The aqueous solution that (b ') preparation comprises basic salt;

(c) to the solution and the suspension that add step (a), step (b) and step (b ') gained in porous carrier, mix homogeneously, so that chlorite, alkaline matter, organic hydrocarbon and the basic salt in porous carrier adsorbent solution and suspension;

(d) make step (c) gained mixture dry, make water content lower than 5%, pack, to obtain final product.

12. produce and/or discharge the method for chlorine dioxide in substantially controlled mode, and the method comprises the following steps:

(i) provide the goods of claim 1 to 10 any one, before using, these goods are wrapped in the container of the packaging material that can completely cut off moisture and circulation of air, so that these goods did not substantially produce and/or discharge chlorine dioxide before using;

(ii) in the time using these goods, described container is opened, to allow that the moisture outside container contacts with these goods with air, and produced and/or release chlorine dioxide.

13. according to the method for claim 12, wherein opens by control the amount that the mode control moisture of described vessel port size contacts with these goods with air, thereby controls the speed that chlorine dioxide produces and/or discharges.