CN108991007A - A kind of safe slow released ClO 2 disinfectant and preparation method thereof - Google Patents

Abstract

The invention provides a safe slow-release chlorine dioxide disinfectant, relates to the technical field of daily-use disinfectants, and comprises the following raw materials in parts by weight: 50-60 parts of slow-release passivation stabilizer, 10-60 parts of anhydrous sodium chlorite 20 parts, 10-18 parts of anhydrous sodium bisulfate, 7-12 parts of anhydrous magnesium sulfate, 0-13 parts of povidone K-30. The nano attapulgite in the nano formula of the present invention has the function of passivating strong oxidizing substances, and the special multi-channel structure can effectively absorb and control the water content, not only significantly reducing or avoiding the re-preparation and trial process of chlorine dioxide disinfectant products There is a moderate risk of fire or explosion, and it can play a slow-release role. It has the ability to stably produce low-concentration chlorine dioxide gas for six months, and is especially suitable for household disinfection and cleaning daily necessities.

Description

A kind of safe slow-release chlorine dioxide disinfectant and preparation method thereof

technical field

The invention relates to the technical field of daily-use disinfectants, in particular to a safe slow-release chlorine dioxide disinfectant suitable for daily household disinfection, sterilization and cleaning and a preparation method thereof.

Background technique

Disinfectants range from phenol to bleaching powder, from bleaching powder to sodium hypochlorite (such as 84 solution), and from Jie Er Mie (quaternary ammonium salts) to iodophor. Disinfectants have played a huge role in sterilization and ensuring people's healthy life. The problems of traditional disinfectants are: strong smell, corrosive, highly toxic and even carcinogenic substances.

Since chlorine dioxide has no teratogenicity and carcinogenicity, it is a new type of disinfectant with high efficiency, wide range, low toxicity, fast speed, no corrosion, and no irritating odor. It has been listed as AI level by the United Nations Health Organization (currently the highest level) safe disinfectant.

Currently, stabilized chlorine dioxide products mainly include liquid and solid forms. Solid products have become popular dosage forms because they are more convenient to use and transport than liquid products, and have better effects. But most of the solid chlorine dioxide disinfectant used at present is to pack sodium chlorite and solid acidifying agent separately, and this product has many inconveniences in use.

Chinese patent CN1104610A discloses a production method of stable chlorine dioxide. After melting stearic acid or beeswax as a coating agent, sodium chlorite is added to make microcapsule particles, and then mixed with dry tartaric acid or oxalic acid particles for bagging . The disadvantage of this product is that on the one hand, the poor water solubility of the coating agent affects the use effect, and on the other hand, the melting of the coating agent will pollute the water quality.

Chinese patent CN1415533A discloses a powdery chlorine dioxide disinfectant and its preparation method. The disinfectant prepared by the production method is one-package, which solves the problem of inconvenient use, but it uses highly reducing oxalic acid as a catalyst. Or prone to reaction and accidents when hit.

Chinese patent CN1439268A discloses a preparation method of a solid chlorine dioxide disinfectant. It uses organic polymers such as soluble polyvinyl alcohol to coat sodium chlorite. The biodegradability of the polymer is very poor, which does not meet the concept of eco-environmental protection.

Chinese patent CN11406208A discloses a production method of solid chlorine dioxide in block form, which adopts organic raw material sodium dichloroisocyanurate or sodium trichloroisocyanurate as auxiliary chlorine dioxide generating agent, although it improves The amount of gas produced by chlorine, but because it can be decomposed into hypochlorous acid to produce the pungent smell of chlorine, it does not meet the concept of green products.

It has been scientifically proven that chlorine dioxide with a low concentration of 3000μg/ ^m3 cannot be smelled by humans, but it can effectively eliminate odors and bacteria in the environment and protect the human body and the environment. However, the existing stabilized chlorine dioxide products mainly include liquid and solid products, which react rapidly during use and produce high-concentration chlorine dioxide in a short period of time, which is not only harmful to the human body, but also has the potential to cause fire, Risk of Explosion. Therefore, how to choose materials that can effectively control the release rate of chlorine dioxide and eliminate safety risks is a key technology. In the existing technology, some scientists use polyvinyl alcohol, sodium polyacrylate, dextrin, sodium alginate and other organic polymer gels to stabilize chlorine dioxide, but the user needs to mix the two components A and B on site , It is not only inconvenient to use, but also has certain potential safety hazards. The materials used contain polymer materials that are not easily biodegradable, which has secondary pollution to the environment.

Contents of the invention

In order to solve the safety and slow-release technical problems of the above-mentioned chlorine dioxide disinfectant, the present invention provides a safe slow-release chlorine dioxide disinfectant and a preparation method thereof.

To achieve the above object, the present invention adopts the following technical solutions:

A safe slow-release chlorine dioxide disinfectant, comprising the following raw materials in parts by weight: 50-60 parts of a slow-release passivation stabilizer, 10-20 parts of anhydrous sodium chlorite, and 10-18 parts of anhydrous sodium bisulfate parts, 7-12 parts of anhydrous magnesium sulfate, and 13 parts of povidone K-300.

Further, the slow-release passivation stabilizer is nano attapulgite, the diameter of nano attapulgite is 10-50nm, and the length is 5000-200000nm.

Further, the nano-attapulgite is a white needle-like substance with dissociated crystal bundles and a diameter of 15-30 nm, and its mass fraction accounts for 50-60% of the total mass of the disinfectant.

Further, the mass fraction of the nano-attapulgite is 56% of the total mass of the disinfectant;

Further, the mass fraction of the anhydrous magnesium sulfate accounts for 7-12% of the total mass of the disinfectant.

Furthermore, the mass fraction of the anhydrous magnesium sulfate accounts for 9% of the total mass of the disinfectant.

Further, the mass fraction of the anhydrous sodium chlorite accounts for 10-20% of the total mass of the disinfectant.

Furthermore, the mass fraction of the anhydrous sodium chlorite accounts for 16% of the total mass of the disinfectant.

Further, the mass fraction of the anhydrous sodium bisulfate accounts for 10-18% of the total mass of the disinfectant.

Further, the mass fraction of the anhydrous sodium bisulfate accounts for 16% of the total mass of the disinfectant.

Further, the mass fraction of the povidone K-30 accounts for 0-13% of the total mass of the disinfectant.

Furthermore, the mass fraction of the povidone K-30 accounts for 3% of the total mass of the disinfectant.

A preparation method of a safe slow-release chlorine dioxide disinfectant, the preparation steps comprising:

(1) First, add a certain amount of nano-attapulgite to the food-grade stainless steel blending equipment, then add anhydrous sodium chlorite, start the equipment, and mix homogeneously for 30-40 minutes;

(2) Add a certain amount of anhydrous magnesium sulfate to the mixture of the above step (1), start the equipment, and mix homogeneously for 10-15min;

(3) Add a certain amount of anhydrous sodium bisulfate to the mixture of the above step (2), start the equipment, and mix homogeneously for 10-15min;

(4) Add a certain amount of povidone K-30 to the mixture of the above step (3), start the equipment, mix and homogenize for 30-40min, and prepare the blend master powder of the disinfectant product.

Further, the master powder of the blended material of the prepared disinfectant product is subjected to powder sealing and subpackaging or is made into tablets by compression molding equipment.

The slow-release passivation stabilizer in the present invention is selected from nano-attapulgite, which has a super-strong passivation and stabilizing effect of sodium chlorite, a strong oxidant, and nano-attapulgite can effectively prevent the explosion and fire of chlorous acid when it is hit. , so that this product has good safety; the dissociated nano-attapulgite also has a special multi-channel nanostructure, which has strong water absorption and water retention properties, and can control chlorine dioxide in compatibility. In addition, nano-attapulgite is a unique inorganic natural mineral in my country, which is rich in reserves, economical, environmentally friendly, green and safe, and is especially suitable for home disinfection and cleaning.

The beneficial effect of the present invention is,

1. Nano-attapulgite has the function of passivating strong oxidizing substances. The special multi-channel structure can effectively absorb and control the moisture content, which not only significantly reduces or avoids fire or explosion during the re-preparation and trial of chlorine dioxide disinfectant products risk, and can play a slow-release role, fully meeting the safety requirements of daily household products.

2. In the preparation method of the present invention, the nano-attapulgite can first coat and passivate the strong oxidant sodium chlorite that causes fire and explosion, and isolate the direct contact with other components, which can minimize the impact frequency, and Under the action of heat, sodium chlorite reacts instantaneously with other components to cause fire and then explode.

3. Since during the preparation process, the rotation of the mixing machine or the mechanical impact of the tablet press can easily lead to fires during the preparation process, the present invention not only improves the safety of the product, but also the passivation of the nano-attapulgite makes The safety of the product production process can also be guaranteed.

To sum up, using nano-attapulgite as a slow-release passivation stabilizer has dual functions of slow release and safety and explosion protection. It can not only eliminate the risk of fire and explosion of solid chlorine dioxide disinfectant, but also has the ability to stably generate low-concentration chlorine dioxide gas for six months, especially suitable for household disinfection and cleaning daily necessities.

Description of drawings

Fig. 1 is the TEM figure of slow-release passivation stabilizer among the present invention.

Detailed ways

Example 1

A safe slow-release chlorine dioxide disinfectant, the preparation steps comprising:

(1) First, add 56Kg nano-attapulgite to the food-grade stainless steel blending equipment, then add 16Kg anhydrous sodium chlorite, start the equipment, and mix and homogenize for 30 minutes;

(2) Add 9Kg anhydrous magnesium sulfate to the mixture of the above step (1), start the equipment, and mix homogeneously for 10min;

(3) Add 16Kg of anhydrous sodium bisulfate to the mixture of the above step (2), start the equipment, and mix homogeneously for 10 minutes;

(4) Finally, add 3Kg povidone K-30 to the mixture of the above-mentioned step (3), start the equipment, mix and homogenize for 30min, and obtain the blend master powder of the disinfectant product.

(5) The master powder of the blended material is measured and packaged according to the product demand with a bag packing machine, and a safe slow-release chlorine dioxide disinfectant powder product 1 of different quality sub-packages is obtained.

(6) The master powder of the blend is metered and pressed into tablets by the product demand with a tablet press, and packaged to obtain the safe slow-release chlorine dioxide disinfectant tablet product 2 of different quality subpackages.

Safety inspection: Take samples from the powder and tablet products prepared above, and determine whether the products are qualified by the following detection methods.

Example 2

A safe slow-release chlorine dioxide disinfectant, the preparation steps comprising:

(1) First, add 50Kg nano-attapulgite to the food-grade stainless steel blending equipment, then add 20Kg anhydrous sodium chlorite, start the equipment, and mix and homogenize for 35 minutes;

(2) Add 12Kg anhydrous magnesium sulfate to the mixture of the above step (1), start the equipment, and mix homogeneously for 12min;

(3) Add 18Kg of anhydrous sodium bisulfate to the mixture of the above-mentioned step (2), start the equipment, mix homogeneously for 35min, and obtain the blend master powder of the disinfectant product.

(4) The master powder of the blended material is measured and packaged according to the product demand with a bag packaging machine, and the safe slow-release chlorine dioxide disinfectant powder product three of different quality subpackages is obtained.

(5) The master powder of the blend is metered and compressed by the product demand with a tablet press, and packaged to obtain the safety slow-release chlorine dioxide disinfectant tablet product four of different quality subpackages.

Safety inspection: Take samples from the powder and tablet products prepared above, and determine whether the products are qualified by the following detection methods.

Example 3

A safe slow-release chlorine dioxide disinfectant, the preparation steps comprising:

(1) First, add 60Kg nano-attapulgite to the food-grade stainless steel blending equipment, then add 10Kg anhydrous sodium chlorite, start the equipment, and mix and homogenize for 40 minutes;

(2) Add 7Kg anhydrous magnesium sulfate to the mixture of the above step (1), start the equipment, and mix homogeneously for 15min;

(3) Add 10Kg of anhydrous sodium bisulfate to the mixture of the above step (2), start the equipment, and mix homogeneously for 15min;

(4) Finally, add 13Kg povidone K-30 to the mixture of the above-mentioned step (3), start the equipment, mix homogeneously for 40min, and obtain the blend master powder of the disinfectant product.

(5) The master powder of the blended material is measured and packaged according to the product demand with a bag packaging machine, and the safe slow-release chlorine dioxide disinfectant powder product five of different quality subpackages is obtained.

(6) The master powder of the blend is metered and compressed by the product demand with a tablet press, and packed to obtain the safe slow-release chlorine dioxide disinfectant tablet product six of different quality subpackages.

Safety quality inspection: take a sample and measure it through the following detection method, which is a qualified product.

The nano-attapulgite used in the above examples is shown in Figure 1, and the TEM photos show that the nano-attapulgite is a one-dimensional nanomaterial with a diameter of 20-50 nm and a length of 50-150 μm, which has been dissociated from crystal beams.

Safety inspection: Take samples from the powder and tablet products prepared above, and determine whether the products are qualified by the following detection methods.

Select Examples 1-3 as representative examples, and evaluate the safety of the product through the control sample.

In view of the fact that there is no national standard for reference for the safety evaluation of this product, two extreme tests of impact and heat are specially set up. The experimental methods and test results are as follows:

Evaluation method: Simulate the experimental phenomenon when the product is impacted and subjected to high heat.

(1) Sample preparation

Weigh 30 mg each of the powder and tablet of the self-made samples in the above examples, pack them tightly with tin foil respectively, and mark them as product one, product two, product three, product four, product five and product six respectively.

Control sample: commercially available solid chlorine dioxide disinfectant powder, tablet, does not contain attapulgite composition, weighs 30mg of sample equally, packs tightly with tin foil respectively, and marks as product seven and product eight respectively.

(2) Impact test

Place the experimental samples tightly packed in tin foil on the center of the granite slab (length x width x thickness = 50cm x 50cm x 10cm), hit the sample hard (about 75Kg) with a 200g iron hammer at a height of 70cm, and observe whether the sample is burn or explode.

(3) Heating experiment

Place the above-mentioned test samples tightly packed with tin foil in stainless steel pans in an oven, and gradually raise the temperature to 80°C (considering that the ambient temperature during product storage and transportation is generally at room temperature, under the hot sun or under heavy impact The limit temperature is set to 80°C), keep the temperature for 60 minutes, observe whether the sample burns or explodes, and record the experimental results. See Table 1 for the results.

Table 1 Safety experiment results

sample crash test Heating experiment Total Chlorine Dioxide % safety rating product one no change no change 5.8 five star product two no change no change 5.2 five star product three fuming unburned smoke, burn 6.3 Three Star product four fuming unburned smoke, burn 5.4 Three Star product five no change no change 4.8 five star product six no change no change 4.3 five star product seven explosion, fire smoke, burn 2.8 one star product eight explosion, fire smoke, burn 2.3 one star

Note: The safety rating is based on five-star evaluation, the more stars, the better the safety.

The above experimental results show that the addition of nano-attapulgite can significantly improve the safety and stability of chlorine dioxide disinfectant, and can effectively eliminate the risk of fire and explosion.

Select Examples 1-3 as representative examples, and evaluate the sustained-release property of the product through the control sample.

In view of the fact that there is no national standard for the sustained release evaluation of this product, a constant humidity method is specially set. The experimental methods and test results are as follows:

Evaluation method: constant humidity and temperature, measure the amount of chlorine dioxide produced by the quantitative sample and the time for releasing chlorine dioxide. The longer the time to reach the specified amount, the better the slow-release effect.

(1) Sample preparation

Weigh each 1g of the self-made sample powder and tablet of the above-mentioned examples, pack them tightly with non-woven bags (length and width=5×3cm) respectively, and mark them as product one, product two, product three, product four, product five and product respectively six.

Control sample: commercially available solid chlorine dioxide disinfectant powder, tablet, does not contain attapulgite composition, takes sample 1g equally, packs tightly with non-woven bag (length and width=5 * 3cm) respectively, marks respectively Product Seven and Product Eight.

(2) Sustained release test

Place the above samples in the sample room (10L volume) of constant humidity (select two kinds of relative humidity (RH) 100% and 50%) and constant temperature (select temperature 25°C) box respectively, after timing, select 5 days, 10 days , 30 days, 60 days, 90 days, 120 days, 150 days, 180 days, and 210 days in nine time periods, use a syringe to draw 0.1L of sample chamber gas into the standard sodium thiosulfate solution for absorption, and use the iodometric method Measure the volume content (mg/L) of chlorine dioxide, and record the experimental results. The experimental results are shown in Table 2 and Table 3.

Table 2 Sustained release test results (25°C, RH50%)

Table 3 Sustained release test results (25°C, RH100%)

The above experimental results show that the addition of nano-attapulgite can significantly improve the slow-release stability of chlorine dioxide disinfectant, and can continuously produce low-concentration chlorine dioxide gas for six months. However, commercially available chlorine dioxide disinfectant products that do not contain nano-attapulgite can only last for two months at low humidity, but cannot last for one month at high humidity, and the concentration of chlorine dioxide is too high to release low concentrations of safe chlorine dioxide.

Of course, the above descriptions are not intended to limit the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or replacements made by those skilled in the art within the scope of the present invention shall also belong to the present invention. protection scope of the invention.

Claims (9)

1. A safe slow-release chlorine dioxide disinfectant, is characterized in that, comprises the raw material that following weight portion forms: 50-60 parts of slow-release passivation stabilizer, 10-20 parts of anhydrous sodium chlorite, anhydrous 10-18 parts of sodium bisulfate, 7-12 parts of anhydrous magnesium sulfate, 0-13 parts of povidone K-30. 2. a kind of safe slow-release chlorine dioxide disinfectant as claimed in claim 1, is characterized in that, described slow-release passivation stabilizer is nano attapulgite, and the diameter of nano attapulgite is 10-50nm, The length is 5000-200000nm. 3. a kind of safe slow-release type chlorine dioxide disinfectant as claimed in claim 2, is characterized in that, described nano-attapulgite is crystal beam dissociated and the white needle-like substance that diameter is 15-30nm, and its The parts by mass account for 44-50% of the total mass of the disinfectant. 4. a kind of safe slow-release chlorine dioxide disinfectant as claimed in claim 1, is characterized in that, the mass fraction of described anhydrous magnesium sulfate accounts for 7-12% of disinfectant gross mass. 5. A kind of safe slow-release chlorine dioxide disinfectant as claimed in claim 1, is characterized in that, the mass fraction of described anhydrous sodium chlorite accounts for 10-20% of disinfectant gross mass. 6. A kind of safe slow-release chlorine dioxide disinfectant as claimed in claim 1, is characterized in that, the mass fraction of described anhydrous sodium bisulfate accounts for 10-18% of disinfectant gross mass. 7. A kind of safe slow-release chlorine dioxide disinfectant as claimed in claim 1, is characterized in that, the mass fraction of described povidone K-30 accounts for 0-13% of disinfectant gross mass. 8. as the preparation method of the arbitrary described safe slow-release type chlorine dioxide disinfectant of claim 1-8, it is characterized in that, preparation step comprises: (1) First, add a certain amount of nano-attapulgite to the food-grade stainless steel blending equipment, then add anhydrous sodium chlorite, start the equipment, and mix homogeneously for 30-40 minutes; (2) Add a certain amount of anhydrous magnesium sulfate to the mixture of the above step (1), start the equipment, and mix homogeneously for 10-15min; (3) Add a certain amount of anhydrous sodium bisulfate to the mixture of the above step (2), start the equipment, and mix homogeneously for 10-15min; (4) Add a certain amount of povidone K-30 to the mixture of the above step (3), start the equipment, mix and homogenize for 30-40min, and prepare the blend master powder of the disinfectant product. 9. the preparation method of safe slow-release type chlorine dioxide disinfectant as claimed in claim 8 is characterized in that, the blend master powder of the disinfectant product that makes is carried out powder sealing sub-package or is made by compression molding equipment into tablets.