CN112493235B - Chlorine dioxide solid preparation, preparation method thereof and preparation method of high-purity chlorine dioxide solution - Google Patents
Chlorine dioxide solid preparation, preparation method thereof and preparation method of high-purity chlorine dioxide solution Download PDFInfo
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Abstract
The invention provides a chlorine dioxide solid preparation, a preparation method thereof and a preparation method of a high-purity chlorine dioxide solution, belonging to the technical field of chlorine dioxide preparation. The preparation method of the chlorine dioxide solid preparation comprises the following steps: soaking the adsorbent into a stable chlorine dioxide solution, and drying to obtain a chlorine dioxide solid preparation; the adsorbent is aluminum silicate or high-silicon active alumina balls; the molar ratio of silicon atoms to aluminum atoms of the aluminum silicate is 1 (1-1.5); the mass percentage of silicon in the high-silicon active alumina ball is 5-15%. The chlorine dioxide solid preparation can be directly used for preparing high-purity chlorine dioxide solution, activation and use of strong acid are not needed, the purity of the chlorine dioxide can reach more than 95 percent, higher concentration can be achieved in a short time, and the chlorine dioxide solid preparation is convenient to use, safe, reliable and suitable for civil or medical small-sized equipment and scenes.
Description
Technical Field
The invention relates to the technical field of chlorine dioxide preparation, in particular to a solid preparation of chlorine dioxide, a preparation method thereof and a preparation method of high-purity chlorine dioxide solution.
Background
Chlorine dioxide is a fourth-generation disinfectant, is the only high-efficiency disinfectant in the internationally recognized chlorine-containing disinfectants, and a large number of experiments and field sterilization tests at home and abroad prove that the chlorine dioxide can almost kill all microorganisms including viruses, fungi, mycobacteria, bacterial propagules, bacterial spores and the like, and has the advantages of broad spectrum, high efficiency, quickness, no residue, no drug resistance and the like. Since the beginning of the 19 th century, it has become one of the most widely used disinfecting articles in the world. The action mechanism of the chlorine dioxide determines that only microorganisms are killed, the safety of the chlorine dioxide is evaluated by a food additive expert committee (JECFA) which is formed by the World Health Organization (WHO) and the Food and Agriculture Organization (FAO) of the United nations, the safety level ADI (human body intake allowance standard) is A1 level, and the chlorine dioxide is understood as the only authenticator in the disinfectant, and the safety is guaranteed.
However, chlorine dioxide is extremely unstable, easy to decompose and disproportionate, inconvenient to store and transport and use, generally needs to be activated and prepared on site, the traditional preparation method has the problems of high cost, high risk, low purity and the like, and the high-purity chlorine dioxide product needs to be prepared on site by using strong acid, so that the use of the high-efficiency disinfectant which is judged as safe even if being eaten by the international most authoritative institution is greatly limited.
Disclosure of Invention
The invention aims to provide a chlorine dioxide solid preparation, a preparation method thereof and a preparation method of a high-purity chlorine dioxide solution, the chlorine dioxide solid preparation can be directly used for preparing the high-purity chlorine dioxide solution, activation and use of strong acid and strong base are not needed, the high-purity chlorine dioxide solution with higher concentration can be obtained in a short time, the purity of chlorine dioxide can reach more than 95%, and the chlorine dioxide solid preparation is convenient to use, safe and reliable and suitable for small-sized equipment and scenes in the civil or medical field.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a chlorine dioxide solid preparation, which comprises the following steps:
soaking the adsorbent into a stable chlorine dioxide solution, and drying to obtain a chlorine dioxide solid preparation; the adsorbent is aluminum silicate or high-silicon active alumina balls; the molar ratio of silicon atoms to aluminum atoms of the aluminum silicate is 1 (1-1.5); the mass percentage of silicon in the high-silicon active alumina ball is 5-15%.
Preferably, the stable chlorine dioxide solution is prepared by mixing sodium chlorite, sodium percarbonate, hydrogen peroxide and water, wherein the dosage ratio of the sodium chlorite to the sodium percarbonate to the hydrogen peroxide to the water is (10-40) g: 2 g:10 mL of: 200 mL; the mass concentration of the hydrogen peroxide is 20%.
Preferably, the pH value of the stable chlorine dioxide solution is 8.5-9.0.
Preferably, the dosage ratio of the adsorbent to the stable chlorine dioxide solution is (100-300) g:100 mL.
Preferably, the drying comprises airing and vacuum drying which are sequentially carried out; the temperature of vacuum drying is 60-100 ℃.
Preferably, the impregnation process comprises: the adsorbent is immersed in a stable chlorine dioxide solution and kept stand, and then stirred for adsorption.
Preferably, the standing time is 30-60 min; the stirring and adsorbing time is 0.5-2 h.
The invention provides a chlorine dioxide solid preparation prepared by the preparation method in the scheme.
The invention provides a preparation method of a high-purity chlorine dioxide solution, which comprises the following steps:
placing the chlorine dioxide solid preparation in the scheme into a container filled with water, and absorbing chlorine dioxide gas released by the chlorine dioxide solid preparation by the water to obtain high-purity chlorine dioxide solution; the solid preparation of chlorine dioxide is positioned above the water.
Preferably, when preparing the high-purity chlorine dioxide solution, the chlorine dioxide solid preparation is under ultraviolet irradiation or ozone existence.
The invention provides a preparation method of a chlorine dioxide solid preparation, which comprises the following steps: soaking the adsorbent into a stable chlorine dioxide solution, and drying to obtain a chlorine dioxide solid preparation; the adsorbent is aluminum silicate or high-silicon active alumina balls; the molar ratio of silicon atoms to aluminum atoms of the aluminum silicate is 1 (1-1.5); the mass percentage of silicon in the high-silicon active alumina ball is 5-15%. According to the invention, aluminum silicate with a silicon-aluminum atomic molar ratio of 1 (1-1.5) or high-silicon activated alumina balls with silicon mass percent of 5-15% are selected as adsorbents, the internal pore structures of the adsorbents are rich in B acid capable of providing protons, strong acid centers are taken as main materials, and the adsorbents are matched with strong water absorption, so that water and acid environments for generating chlorine dioxide gas are completely provided after water molecules are adsorbed.
The solid preparation of chlorine dioxide prepared by the invention is placed in a container filled with water, the solid preparation of chlorine dioxide is positioned above the water, after the solid preparation of chlorine dioxide adsorbs water vapor, the center of active acid is activated to generate chlorine dioxide gas, the density of the chlorine dioxide gas is greater than that of air, the chlorine dioxide gas is very easy to disperse and dissolve in water, the chlorine dioxide gas is deposited towards the lower part and is absorbed by the water to form high-purity chlorine dioxide solution, and the purity of the prepared chlorine dioxide solution is up to more than 95%.
Furthermore, the chlorine dioxide solid preparation is placed under the ultraviolet irradiation or the environment with ozone, so that the chlorine dioxide gas release of the chlorine dioxide solid preparation can be accelerated, and the high-concentration and high-purity chlorine dioxide solution can be obtained in a short time.
The method for preparing the high-purity chlorine dioxide solution does not need activation treatment and strong acid and strong alkali, has simple steps, convenient use, safety and reliability, and is suitable for civil or medical small equipment and scenes.
Drawings
FIG. 1 is a schematic structural diagram of a container containing water according to the present invention;
FIG. 2 is a schematic structural view of the upper cover of the present invention;
FIG. 3 is a schematic view of the excitation device according to the present invention;
in the figure: 1-main body, 2-upper cover, 3-outer cylinder, 4-inner cylinder, 5-annular cavity, 6-excitation device, 7-air inlet, 8-air outlet, 9-perspective window, 10-color ribbon, 11-scale mark, 12-containing cavity, 13-battery chamber and 14-switch.
Detailed Description
The invention provides a preparation method of a chlorine dioxide solid preparation, which comprises the following steps:
soaking the adsorbent into a stable chlorine dioxide solution, and drying to obtain a chlorine dioxide solid preparation; the adsorbent is aluminum silicate or high-silicon active alumina balls; the molar ratio of silicon atoms to aluminum atoms of the aluminum silicate is 1 (1-1.5); the mass percentage of silicon in the high-silicon active alumina ball is 5-15%.
In the present invention, the starting materials used are all commercially available products well known to those skilled in the art, unless otherwise specified.
In the invention, the particle size of the adsorbent is preferably 2-3 mm; the mole ratio of silicon atoms to aluminum atoms of the aluminum silicate is preferably 1 (1-1.3), and more preferably 1: 1; the mass percentage of silicon in the high-silicon active alumina ball is 10-15%. The invention ensures the purity of chlorine dioxide and obtains chlorine dioxide solution with high concentration by optimizing the silicon and aluminum atom mol ratio of aluminum silicate and the mass percentage of silicon in the high-silicon active alumina balls to be in the range. In the invention, the stable chlorine dioxide solution is preferably prepared by mixing sodium chlorite, sodium percarbonate, hydrogen peroxide and water, and the dosage ratio of the sodium chlorite, the sodium percarbonate, the hydrogen peroxide and the water is preferably (10-40) g: 2 g:10 mL of: 200mL, more preferably 20 g: 2 g:10 mL of: 200 mL; the mass concentration of the hydrogen peroxide is preferably 20%. In the invention, the pH value of the stable chlorine dioxide solution is preferably 8.5-9.0. The pH value of the stable chlorine dioxide solution is preferably adjusted to 8.5-9.0 by adopting sulfuric acid. In the present invention, the mass concentration of the sulfuric acid is preferably 2%. The invention controls the pH value of the stable chlorine dioxide solution in the range, and is beneficial to improving the stability of the stable chlorine dioxide solution. In the invention, the dosage ratio of the adsorbent to the stable chlorine dioxide solution is preferably (100-300) g:100mL, and more preferably 100g:100 mL.
In the present invention, the process of impregnation preferably comprises: the adsorbent is immersed in a stable chlorine dioxide solution and kept stand, and then stirred for adsorption. In the invention, the standing time is preferably 30-60 min, more preferably 30min, and the stirring and adsorbing time is preferably 0.5-2 h, more preferably 1 h. The invention has no special requirement on the stirring speed during stirring and adsorption, and liquid splashing is not caused. In the impregnation process, the stable chlorine dioxide solution is adsorbed on the surface and/or in the pore channels of the adsorbent.
After the impregnation is finished, the system obtained after the impregnation is dried to obtain the chlorine dioxide solid preparation. In the present invention, the drying preferably includes airing and vacuum drying, which are performed in this order. In the invention, the airing time is preferably 1 h; the invention preferably adopts a fan to assist in airing so as to be beneficial to the evaporation of water on the surface. In the invention, the temperature of the vacuum drying is preferably 60-100 ℃, more preferably 80 ℃, and the time is preferably 3-8 h, more preferably 4 h.
According to the invention, aluminum silicate with a silicon-aluminum atomic molar ratio of 1 (1-1.5) or high-silicon activated alumina balls with silicon mass percent of 5-15% are selected as adsorbents, the internal pore structures of the adsorbents are rich in B acid capable of providing protons, strong acid centers are taken as main materials, and the adsorbents are matched with strong water absorption, so that water and acid environments for generating chlorine dioxide gas are completely provided after water molecules are adsorbed.
The invention provides a chlorine dioxide solid preparation prepared by the preparation method in the scheme. The chlorine dioxide solid preparation adsorbs water vapor in the water vapor-containing environment, and then the active acid center is activated to generate chlorine dioxide gas.
The invention provides a preparation method of a high-purity chlorine dioxide solution, which comprises the following steps:
placing the chlorine dioxide solid preparation in the scheme into a container filled with water, and absorbing chlorine dioxide gas released by the chlorine dioxide solid preparation by the water to obtain high-purity chlorine dioxide solution; the solid preparation of chlorine dioxide is positioned above the water.
The chlorine dioxide solid preparation is placed in a container filled with water, water vapor in air can be adsorbed, after the water vapor is adsorbed, the active acid center is activated to generate chlorine dioxide gas, the density of the chlorine dioxide gas is greater than that of the air, the chlorine dioxide gas is very easy to disperse and dissolve in the water, the chlorine dioxide gas is deposited towards the lower part and is absorbed by the water to form high-purity chlorine dioxide solution, and the purity of the prepared chlorine dioxide solution is as high as more than 95%.
The amount of the water used in the invention has no special requirements, and the skilled person can adjust the amount according to the actual needs. The invention can regulate and control the concentration of the high-purity chlorine dioxide solution by controlling the consumption of water.
When preparing the high-purity chlorine dioxide solution, the chlorine dioxide solid preparation is preferably under ultraviolet irradiation or in the presence of ozone. The invention has no special requirement on the wavelength of the ultraviolet light, and the ultraviolet light with any wavelength can be used. But the short band uv light generates chlorine dioxide gas at a faster rate than the medium and long band uv light. The invention has no special requirement on the concentration of the ozone, and the ozone is only required to be contained. The chlorine dioxide solid preparation is placed under the ultraviolet irradiation or the environment with ozone, so that the chlorine dioxide gas release of the chlorine dioxide solid preparation can be accelerated, and the high-purity chlorine dioxide solution can be obtained in a short time.
The invention has no special requirements on the structure of the container filled with water. In the embodiment of the present invention, the structure of the container containing water is preferably as shown in fig. 1, and includes a housing, water for absorbing chlorine dioxide gas, a gas-permeable cylinder for containing a solid preparation of chlorine dioxide, and an excitation device 6 for exciting the solid preparation of chlorine dioxide, the housing has a closed containing cavity 12 inside, and the water, the gas-permeable cylinder, and the excitation device 6 are all disposed in the containing cavity 12. In this embodiment, the excitation device 6 is specifically an ultraviolet lamp or an ozone generator, a battery compartment 13 for installing a battery is disposed at the upper end of the excitation device 6, a switch 14 is disposed at the upper end of the battery compartment 13, the switch 14, the battery and the excitation device 6 are electrically connected in sequence, and the switch 14 is disposed outside the housing so as to be convenient for a user to use; the ventilative barrel is seted up and is used for getting the feed inlet of putting chlorine dioxide solid preparation and a plurality of bleeder vent that are used for ventilative, and ventilative barrel is cylinder structure or sawtooth structure to improve the air permeability of ventilative barrel. In the specific using process, the excitation device 6 works to excite the chlorine dioxide solid preparation to release chlorine dioxide gas, and the chlorine dioxide gas is absorbed by water to prepare high-purity chlorine dioxide solution.
In order to facilitate the disassembly and the use of the device, the shell comprises a main body 1 and an upper cover 2, a containing cavity 12 is formed in the main body 1, an opening communicated with the containing cavity 12 is formed in the upper portion of the main body 1, the upper cover 2 seals the opening and is detachably connected with the main body 1, and the ventilating cylinder and the excitation device 6 are detachably connected with the upper cover 2. Specifically, the upper cover 2 is in threaded connection with the main body 1, and the air-permeable cylinder and the excitation device 6 are both in threaded connection with the upper cover 2.
In order to save space and improve the excitation effect, the ventilation cylinder body comprises an outer cylinder 3 and an inner cylinder 4 which are coaxially nested from outside to inside, an annular cavity 5 for containing a chlorine dioxide solid preparation is formed between the outer cylinder 3 and the inner cylinder 4, an excitation device 6 is arranged in the inner cylinder 4, and in the embodiment, ventilation holes are formed in the inner cylinder 4 and the outer cylinder 3.
In order to facilitate the replacement of the gas in the accommodating cavity 12, the upper cover 2 is provided with a gas inlet 7 and a gas outlet 8 which are communicated with the accommodating cavity 12, and the gas inlet 7 and the gas outlet 8 are both provided with a block. In a specific use process, the plugging block is taken out, and the containing cavity 12 can conveniently intake and exhaust air.
In order to facilitate the judgment of the concentration of the high-purity chlorine dioxide solution, a perspective window 9 and a colorimetric belt 10 are arranged on the main body 1 side by side, and the perspective window 9 and the colorimetric belt 10 are both arranged along the height direction of the main body 1. In the specific use process, a user can preliminarily judge the concentration of the high-purity chlorine dioxide solution by comparing the solution color with the colorimetric belt 10 after observing the solution color through the perspective window 9.
In order to facilitate the determination of the volume of water, the body 1 is further provided with scale lines 11 along the height direction of the body 1.
In order to prevent the chlorine dioxide solid preparation from being stimulated and decomposed by an external light source, the shell is made of opaque materials. In this embodiment, the housing is made of high boron glass, corrosion-resistant stainless steel or PVC.
The solid chlorine dioxide preparation and the method for producing the same and the method for producing a high-purity chlorine dioxide solution according to the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Preparation of solid preparation of chlorine dioxide
Example 1
1. Weighing 100g of aluminum silicate (the molar ratio of silicon atoms to aluminum atoms is 1:1) with the particle size of 2-3 mm, and placing the aluminum silicate in a triangular flask;
2. preparing a stable chlorine dioxide solution: adding 20g of sodium chlorite, 2g of sodium percarbonate and 10mL of 20% hydrogen peroxide into 200mL of distilled water in sequence, and adjusting the pH value of the solution to 8.5-9 by using 2% sulfuric acid;
3. soaking a catalyst carrier in a stable chlorine dioxide solution according to a ratio of 1:1 (100g of aluminum silicate: 100mL of the stable chlorine dioxide solution), standing for 30min, then pouring the solution into a reaction kettle, stirring and adsorbing for 1h, airing for 1h, and then drying for 4h under vacuum at the temperature of 80 ℃ to prepare the solid preparation of chlorine dioxide.
Example 2
The difference from example 1 is that the molar ratio of silicon to aluminum atoms of aluminum silicate is 1:1.3, and the rest is the same as example 1, to obtain a solid preparation of chlorine dioxide.
Example 3
The difference from example 1 is that the molar ratio of silicon to aluminum atoms of aluminum silicate is 1:1.5, and the rest is the same as example 1, to obtain a solid preparation of chlorine dioxide.
Comparative example 1
The difference from example 1 is that the molar ratio of silicon to aluminum atoms of aluminum silicate is 1:0.8, and the rest is the same as example 1, to obtain a solid preparation of chlorine dioxide.
Comparative example 2
The difference from example 1 is that the molar ratio of silicon to aluminum atoms of aluminum silicate is 1:1.8, and the rest is the same as example 1, to obtain a solid preparation of chlorine dioxide.
Preparing high-purity chlorine dioxide solution by using chlorine dioxide solid:
application example 1
The preparation of high-purity chlorine dioxide solution adopts a structure of a container filled with water as shown in figure 1.
100g of the chlorine dioxide solid preparation prepared in the embodiments 1-3 and the comparative examples 1-2 is placed in an annular cavity 5, and the volume of water is 200 mL; the activation device 6 is not switched on. After the reaction was carried out for 1 hour and 2 hours, the purity and the contents of each substance of the high-purity chlorine dioxide solution were measured by a five-step iodometry, and the results are shown in table 1.
Application example 2
The preparation of a high-purity chlorine dioxide solution was different from that of application example 1 in that the excitation device 6 was turned on, the excitation device 6 was irradiated with ultraviolet rays (having a wavelength of 253.7nm and a model of ZW8S15W), and after the reaction was carried out for 1 hour and 2 hours, the purity and the content of each substance of the high-purity chlorine dioxide solution were measured by a five-step iodometry, and the results are shown in table 1.
Application example 3
The preparation of high-purity chlorine dioxide solution is different from that of application example 1 in that the excitation device 6 is turned on, the excitation device 6 is an ultraviolet ozone generator (model ZW8S15W) with the wavelength of 185nm, and the ozone generation concentration is 0.02-0.1mg/m 3 After the reaction was carried out for 1 hour and 2 hours, the purity and the contents of each substance of the high-purity chlorine dioxide solution were measured by a five-step iodometric method, and the results are shown in table 1.
In table 1, the test dates of example 1 and comparative example 1 were 19 days in 2019, 6 months, 20 days in 2019, and 21 days in 2019, 6 months and 2, respectively.
Table 1 chlorine dioxide solution generation (adsorbent is aluminum silicate) unit of the chlorine dioxide solid preparations of examples 1 to 3 and comparative examples 1 to 2: mg/L
The results in table 1 show that the purity of chlorine dioxide in absorption liquid of each group of samples is greater than 95%, and no obvious difference exists between purity groups, which indicates that the chlorine dioxide solid preparation can generate high-purity chlorine dioxide liquid; however, when the silica-alumina ratio is 1:0.8 (comparative example 1) and 1:1.8 (comparative example 2), the concentration of the chlorine dioxide solid preparation for preparing a high-purity chlorine dioxide solution is too low to meet the requirements of practical application. When the silicon-aluminum ratio is 1: (1-1.5), the high-purity chlorine dioxide solution with high concentration can be obtained in a short time, the requirement of convenient use of civil or medical small equipment and scenes can be met, and the method has wide application value. In examples 1 to 3, the concentration of the chlorine dioxide solution is similar to that of the chlorine dioxide solution with the silicon-aluminum ratio of 1:1 (example 1) and the silicon-aluminum ratio of 1:1.3 (example 2), and the concentration of the chlorine dioxide solution is obviously higher than that of the chlorine dioxide solution with the silicon-aluminum ratio of 1:1.5 (example 3), so that the silicon-aluminum ratio of 1:1-1.3 is the optimal ratio. In addition, the experimental result also shows that the exciting device is used for obviously accelerating the release rate of the chlorine dioxide gas, and the ozone generator is more obvious.
Preparation of a chlorine dioxide solid preparation:
example 4
1. Weighing 100g of high-silicon active alumina balls with the particle size of 2-3 mm (the mass percent of silicon is 10 percent and placing the balls in a triangular flask;
2. preparing a stable chlorine dioxide solution: adding 20g of sodium chlorite, 2g of sodium percarbonate and 10mL of 20% hydrogen peroxide into 200mL of distilled water in sequence, and adjusting the pH value of the solution to 8.5-9 by using 2% sulfuric acid;
3. soaking a catalyst carrier in a stable chlorine dioxide solution according to a ratio of 1:1 (100g of high-silicon activated alumina balls: 100mL of the stable chlorine dioxide solution), standing for 30min, then pouring the solution into a reaction kettle, stirring and adsorbing for 1h, airing for 1h, and then drying for 4h in vacuum at 80 ℃ to prepare the chlorine dioxide solid preparation.
Example 5
The difference from example 4 is that the mass percentage of silicon in the high-silicon activated alumina spheres is 15%, and the rest is the same as example 4 to obtain the chlorine dioxide solid preparation.
Example 6
The difference from the example 4 is that the mass percent of silicon in the high-silicon activated alumina ball is 5%, and the chlorine dioxide solid preparation is obtained in the same way as the example 4.
Comparative example 3
The difference from the example 4 is that the mass percent of silicon in the high-silicon activated alumina ball is 3%, and the chlorine dioxide solid preparation is obtained in the same way as the example 4.
Preparing high-purity chlorine dioxide solution by using chlorine dioxide solid:
application example 4
The preparation of high-purity chlorine dioxide solution adopts a structure of a container filled with water as shown in figure 1.
100g of the chlorine dioxide solid preparation prepared in the embodiments 4-6 and the comparative example 3 is placed in an annular cavity 5, and the volume of water is 200 mL; the activation device 6 is not switched on. After the reaction was carried out for 1 hour and 2 hours, the purity and the contents of each substance of the high-purity chlorine dioxide solution were measured by a five-step iodometry, and the results are shown in table 2.
Application example 5
The preparation of a high-purity chlorine dioxide solution was different from application example 4 in that the excitation device 6 was turned on, the excitation device 6 was irradiated with ultraviolet rays (having a wavelength of 253.7nm and a model of ZW8S15W), and after the reaction was carried out for 1 hour and 2 hours, the purity and the content of each substance of the high-purity chlorine dioxide solution were measured by a five-step iodometric method, and the results are shown in table 2.
Application example 6
The preparation of high-purity chlorine dioxide solution is different from application example 4 in that the excitation device 6 is turned on, the excitation device 6 is an ultraviolet ozone generator (model ZW8S15W) with the wavelength of 185nm, and the ozone generation concentration is 0.02-0.1mg/m 3 After the reaction was carried out for 1 hour and 2 hours, the purity and the contents of each substance of the high-purity chlorine dioxide solution were measured by a five-step iodometric method, and the results are shown in table 2.
In table 2, the test dates of example 6 and comparative example 2 were 12 days at 6 months in 2019, 13 days at 6 months in 2019, and 14 days at 6 months in 2019 in example 5.
Table 2 chlorine dioxide liquid generation (adsorbent is high silica activated alumina ball) unit for chlorine dioxide solid formulations of examples 4 to 6 and comparative example 3: mg/L
The results in table 2 show that the purity of the chlorine dioxide in the absorption liquid of each group of samples is greater than 95%, and no obvious difference exists between purity groups, which indicates that the chlorine dioxide solid preparation can generate high-purity chlorine dioxide liquid; however, when the mass content of silicon in the activated alumina spheres is 3% (comparative example 2), the concentration of the chlorine dioxide solid preparation for preparing a high-purity chlorine dioxide solution is too low to meet the requirements of practical application. When the silicon content is 5-15%, a high-purity chlorine dioxide solution with high concentration can be obtained in a short time, and the requirement of convenient use of civil or medical small equipment and scenes can be met. In examples 4 to 6, the concentration of the 10% silicon content (example 4) and the 15% silicon content (example 5) absorption solution chlorine dioxide solution was similar and was significantly higher than that of the 5% silicon content (example 6) when the 1 hour detection was performed, but the concentration of the 15% silicon content (example 5) was lower than that of the 10% silicon content (example 4) absorption solution chlorine dioxide solution when the 2 hour detection was performed, and the concentration of the chlorine dioxide solution obtained from the 15% silicon content (example 5) was reduced when the time reached 5 hours as the time elapsed, so the 10% silicon content was the best ratio. In addition, the experimental result also shows that the exciting device is used for obviously accelerating the release rate of the chlorine dioxide gas, and the ozone generator is more obvious.
The embodiment of the invention provides a chlorine dioxide solid preparation, a preparation method thereof and a preparation method of a high-purity chlorine dioxide solution, the chlorine dioxide solid preparation can be directly used for preparing the high-purity chlorine dioxide solution, activation and use of strong acid and strong alkali are not needed, the purity of chlorine dioxide can reach more than 95%, a high concentration can be reached in a short time, and the chlorine dioxide solid preparation is convenient to use, safe and reliable, and is suitable for small-sized civil or medical equipment and scenes.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The preparation method of the chlorine dioxide solid preparation is characterized by comprising the following steps:
soaking the adsorbent into a stable chlorine dioxide solution, and drying to obtain a chlorine dioxide solid preparation; the adsorbent is aluminum silicate; the molar ratio of silicon atoms to aluminum atoms of the aluminum silicate is 1 (1-1.5);
the stable chlorine dioxide solution is prepared by mixing sodium chlorite, sodium percarbonate, hydrogen peroxide and water, wherein the dosage ratio of the sodium chlorite to the sodium percarbonate to the hydrogen peroxide to the water is (10-40) g: 2 g:10 mL of: 200 mL; the mass concentration of the hydrogen peroxide is 20%.
2. The method according to claim 1, wherein the stable chlorine dioxide solution has a pH of 8.5 to 9.0.
3. The method according to any one of claims 1 to 2, wherein the amount ratio of the adsorbent to the stable chlorine dioxide solution is (100 to 300) g:100 mL.
4. The method according to claim 1, wherein the drying comprises air drying and vacuum drying in this order; the temperature of vacuum drying is 60-100 ℃.
5. The method of claim 1, wherein the impregnating comprises: the adsorbent is immersed in a stable chlorine dioxide solution and kept stand, and then stirred for adsorption.
6. The preparation method according to claim 5, wherein the standing time is 30-60 min; the stirring and adsorbing time is 0.5-2 h.
7. The solid preparation of chlorine dioxide prepared by the preparation method of any one of claims 1 to 6.
8. The preparation method of the high-purity chlorine dioxide solution is characterized by comprising the following steps of:
placing the solid preparation of chlorine dioxide as defined in claim 7 in a container with water, and absorbing the chlorine dioxide gas released from the solid preparation of chlorine dioxide by water to obtain a high-purity chlorine dioxide solution; the solid preparation of chlorine dioxide is positioned above the water.
9. The method according to claim 8, wherein the chlorine dioxide solid preparation is exposed to ultraviolet light or ozone in the presence of ozone when the high-purity chlorine dioxide solution is prepared.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2000048612A1 (en) * | 1999-02-18 | 2000-08-24 | Bio-Cide International, Inc. | Method for producing chlorine dioxide using chemically impregnated expanded amorphous aluminum silicate |
| CN108439341A (en) * | 2018-05-18 | 2018-08-24 | 广西大学 | A kind of method and device producing chlorine dioxide with high purity gas |
| CN110449000A (en) * | 2019-09-11 | 2019-11-15 | 上海朗彤环境科技发展有限公司 | Absorbent-type solid preparation of chlorine dioxide generating device and detection method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2000048612A1 (en) * | 1999-02-18 | 2000-08-24 | Bio-Cide International, Inc. | Method for producing chlorine dioxide using chemically impregnated expanded amorphous aluminum silicate |
| CN108439341A (en) * | 2018-05-18 | 2018-08-24 | 广西大学 | A kind of method and device producing chlorine dioxide with high purity gas |
| CN110449000A (en) * | 2019-09-11 | 2019-11-15 | 上海朗彤环境科技发展有限公司 | Absorbent-type solid preparation of chlorine dioxide generating device and detection method |
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