CN1196881A - High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. - Google Patents
High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. Download PDFInfo
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- CN1196881A CN1196881A CN 97106395 CN97106395A CN1196881A CN 1196881 A CN1196881 A CN 1196881A CN 97106395 CN97106395 CN 97106395 CN 97106395 A CN97106395 A CN 97106395A CN 1196881 A CN1196881 A CN 1196881A
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Abstract
A high-concentration stable disinfecting tablet of ClO2 is prepared through preparing gas of ClO2, suction, concentration, crystallization and tabletting, and features high active component content up to more than 50%, high concentration increased by at least 25 times compared with liquid product, and stable storage period (longer than 2 years).
Description
The invention relates to a broad-spectrum and high-efficiency disinfectant and a preparation method thereof, in particular to a high-concentration stable chlorine dioxide solid disinfection tablet and a preparation method thereof.
Chlorine dioxide is an ideal disinfectant with broad spectrum and high efficiency, can be widely used in the fields of water treatment, sterilization, bleaching, food preservation, air purification and the like, and is classified as A1 grade safe disinfectant by the world health organization. However, the substance is a yellow-green or orange gaseous substance, has a strong pungent smell similar to chlorine gas, is explosive, has high solubility in water but is unstable, and is a dangerous substance which is difficult to store and transport. The characteristics make it only be prepared and used on site for a long time, and the popularization and application of the product are severely restricted. In order to solve this conflict, experts in various countries have conducted intensive research and have developed technologies for preparing stable aqueous solutions of chlorine dioxide and solid chlorine dioxide. However, although there are many reports on the articles and patent documents in this field, the content of the prepared product is not high. (environmental protection 1995 3 rd stage P34 ~ 36.)
Currently, there are several methods for producing chlorine dioxide, the main raw material being sodium chlorate. The earliest production method was the Mathieson method, which uses SO2As reducing agent, also using H2SO4The disadvantage of this process is the low yield. Rapson in CanadaR for teaching invention1Method adopts NaClO3、SO2And H2Production of ClO from O2R of the invention2Method adopts NaClO3NaCl and H2SO4As a starting material, R2Simple operation, high yield, more sulfuric acid and by-product Na2SO4Recovery is difficult. The Solvey method is a process developed by Allied, USA, and uses NaClO3H2SO4And CH3OH as starting material, process for preparing ClO2The yield is improved to 85-90%. Subsequently, on the basis of the above-mentioned various processes, the Allied company has successively developed a series of new processes of R series, named R respectively3Method, R3H method, R4Method, R5Method, R6Method, R7Methods and R developed in the early 1980 s8The method is a method widely adopted in the process. R3Reaction principle of the process and R2The method mainly changes the used equipment and the circulation of the solution, and improves the concentration of the chlorine dioxide aqueous solution. R3H method and R3The method is characterized in that sodium chloride is partially or completely replaced by aqueous hypochlorous acid or anhydrous hydrochloric acid, and acid is added to reduce the amount of sulfuric acid and byproduct Na2SO4The amount of (c). R4The process aims to convert the screen sodium chloride by metathesis and recycle the acid to the generator, but is not economically valuable. R5Also known as hydrochloric acid method, namely NaClO3Reaction with HCl to form ClO2The process equipment and process conditions are similar to those of R3The method generates chlorine dioxide under vacuum and reaction temperature, and is characterized by recovering pure sodium chloride crystal, but it uses anhydrous hydrochloric acid as raw material, and its cost is high. R6By the process of R5The method process is combined with a sodium chlorate electrolysis production device. The reactor feed is sodium chlorate bath from the electrolyzer, which contains sodium dichromate, sodium chloride and sodium chlorate. R6The method comprises a sodium chloride electrolysis device, so the investment cost is high. R in the early 1980 s7The method is first industrialized in North America, and it uses SO2As a reducing agent, the total reaction is as follows:
wherein the by-product Na2SO4Is greatly reduced.
The R8 method has been put into operation in the United states in 1985, and is currently being expanded because of its easy control of the process operation and high production efficiency, which is well appreciated by operators.
The raw materials for the R8 process are the same as in the Solvay process described above, and the main reactions are as follows:
the method adopts a high-acidity reaction medium, the main reaction can be continuously carried out, the conversion rate reaches 99-100%, and a small amount of chlorine byproducts can be generated in the side reaction. The R8 process uses a reaction-evaporation-crystallization unit reactor. The reaction is carried out under the pressure of 100-400 mmHg and the boiling temperature of the reactant, and then the product ClO is obtained2The gas is absorbed by cold water in an absorption tower to become a solution, wherein ClO2The concentration of (b) is 10-12 g/L. The method can be operated smoothly and continuously. For the purpose of efficient mixing of the acid with the reactants, the acid-containing gas stream should have a relatively high injection velocity into the recycle stream. The acid should be as highly atomized as possible before entering the recycle stream and a large flow circulation pump is required to circulate the reaction liquid between the reactor and reboiler. The R8 method has the disadvantages of reaction under higher negative pressure and boiling state, complicated equipment and the likeAnd the obtained ClO2The concentration of the solution is low.
U.S. Pat. No. 5,416,88, Japanese patent application laid-open No. 4, 231304, Japanese patent application laid-open No. 60, 161307, European patent application laid-open No. EP 581,550 and JP58,161904 disclose solid chlorine dioxide products, which are generally produced by adsorbing and solidifying the chlorine dioxide products by an adsorbent based on liquid phase absorption. Common adsorbents comprise calcium silicate, granular silicon dioxide, talc, diatomite, volcanic ash and the like, and the pH value of the absorption liquid is generally controlled to be 8.5-9; and if an acidic absorbent is used, the pH value of the absorption liquid is usually lower than 3, and when the absorbent is used, an alkaline solution is added, the pH value of the solution is adjusted to be 8.5-9, and the chlorine dioxide is slowly released to form liquid for application. In addition, a binary solid composite reaction type powder chlorine dioxide product formed by binary vacuum packaging is also provided, the product is P11-12 in No. 1 of 1995 in Henan preventive medicine journal, and a chlorine dioxide tablet which is prepared by preparing microcapsules by related components and pressing the microcapsules into a tablet can be used for personal drinking water disinfection (Chinese invention patent CN 1094698). However, the content of the components of the solid chlorine dioxide product is not high.
The invention aims to provide a high-concentration steady-state chlorine dioxide solid disinfection tablet and a preparation method thereof.
The above object of the present invention is achieved by:
a stable chlorine dioxide tablet comprising:
60-80 parts by weight of steady chlorine dioxide powder with effective components of at least 50%,
2 parts by weight of sodium carboxymethylcellulose,
15 to 32 parts by weight of sodium bicarbonate,
3-7 parts by weight of citric acid to form the effervescent tablet.
Characterized in that it further comprises
1-10 parts of a material A consisting of potassium percarbonate and 3-10 parts of chloroisocyanuric acid by weight of citric acid 50-90 parts by weight; and uniformly mixing the material B consisting of 8-30 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethyl cellulose, and tabletting to form the composite functional tablet.
A preparation method of a stable chlorine dioxide tablet comprises the steps of preparing a 4-6% stable chlorine dioxide solution by taking sodium chlorate, sulfuric acid and methanol as raw materials and sodium percarbonate as a stabilizer, and is characterized in that the stable chlorine dioxide solution with low concentration is further taken as an absorption liquid, the generated chlorine dioxide is introduced into the absorption liquid by adopting negative pressure, and 8-20% of compound stabilizing liquid in weight is added into the absorption liquid in batches according to the following proportion:
sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate and sodium hydroxide in a ratio of 1: 3-20: 0.1-5: 1-20: 5-40
Simultaneously, adjusting the pH value of the absorption liquid to 7.5-9 by using sodium carbonate, controlling the reaction to 0-2 ℃ to prepare 15-20% of stable chlorine dioxide solution, filtering to remove inorganic salt, performing vacuum evaporation concentration to obtain chlorine dioxide with the concentration of at least 25%, performing cooling crystallization, and uniformly mixing 60-80 parts by weight of the crushed solid, 2 parts by weight of sodium carboxymethylcellulose, 15-32 parts by weight of sodium bicarbonate and 3-7 parts by weight of citric acid at the cooling temperature of-1 ℃ -10 ℃ to obtain solid with the effective component of the chlorine dioxide of at least 50%, and performing dry tabletting to obtain the effervescent tablet.
The method is characterized by further comprising the steps of adding 1-10 parts by weight of potassium percarbonate into a material A before mixing and tabletting, and uniformly mixing the material A with a material B consisting of 50-90 parts by weight of citric acid, 3-10 parts by weight of chloroisocyanuric acid, 8-30 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethylcellulose, and tabletting to prepare the composite functional tablet.
The advantages of the invention are obvious: the effective concentration of the chlorine dioxide solid product with the effective components of more than 50 percent is at least 25 times higher than that of the existing solution product, the transportation and the use are convenient, the stable period can reach more than two years, the process of the product is simple, the cost is lower, the sale price is only one third of that of the solution, the social demand of the chlorine dioxide disinfectant is extremely large, the successful development of the stabilized solid chlorine dioxide tablet is a great contribution to the disinfection science, and the economic benefit is also considerable. In addition, the action product of the chlorine dioxide as the disinfectant is harmless substances such as sodium chloride, water, carbon oxides and the like, carcinogens are not formed, and the chlorine dioxide can oxidize carcinogens without polluting the environment, so that the environmental benefit is also influenced profoundly.
Hereinafter, the present invention will be described in further detail by way of specific examples. Example 1:
the R8 method is adopted, andthe main reaction is as follows:
h is put into the reactor according to the ratio of 20: 30: 72SO4、NaClO3And CH3Adding some water into the OH, uniformly mixing, heating to 75-80 ℃ to generate yellow ClO2The gas, which is withdrawn from the upper outlet of the reactor, passes through an absorption column containing a sodium percarbonate solution having a pH of around 9, which is connected to an evacuation system which maintains the pressure at the upper outlet of the reactor at around 700 mmHg. Analyzing the obtained ClO2Solutions containing free radicalsClO26.5%, discharging the precipitate from the lower part of the reactor, evaporating by an evaporator to obtain byproduct Na3H(SO4)2。
Then using the above-mentioned ClO26.5% solution as absorption liquid, ClO will be generated2While introducing the mixture into the absorption liquid for negative pressure absorption, adding 8-20% of stable aqueous solution of the following formula in batches:
sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate, sodium hydroxide in a ratio of 1: 5: 1: 10: 5,
adjusting the pH value to be 7.5-9 by using sodium carbonate until the concentration of chlorine dioxide is at least 18%, filtering after the reaction is finished, removing inorganic salt, carrying out vacuum evaporation and concentration until the concentration of chlorine dioxide is at least 25%, cooling and crystallizing in a crystallizer, and controlling the temperature to be below-8 to-10 ℃ to obtain a steady solid containing 52% of chlorine dioxide. Example 2
The procedure of example 1 was repeated as described aboveClO26.5% of the solution as an absorption solution, ClO to be generated2While this solution was pumped in for negative pressure absorption, a 15% stable aqueous solution of the formulation was fed in batch:
sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate and sodium hydroxide are aqueous solutions of 1: 10: 3: 20: 10, the pH value is adjusted to be 7.5-9 by using sodium carbonate until the concentration of chlorine dioxide is 20%, inorganic salts are removed by filtration after the reaction is finished, the inorganic salts are concentrated in vacuum until the concentration of the chlorine dioxide reaches 25%, and then the mixture is cooled and crystallized in a crystallizer, and the temperature is controlled to be below-5 ℃ to-8 ℃, so that stable solid containing 55% of chlorine dioxide is obtained. Example 3
The procedure of example 1 was repeated with ClO as described above2ClO generated by using 6.5% solution as absorption liquid2While this solution was passed through for negative pressure absorption, a 20% stable aqueous solution of the following formulation was added in portions.
Sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate and sodium hydroxide are aqueous solutions of 1: 20: 5: 15: 40, the pH value is adjusted to be 7.5-9 by using sodium carbonate until the concentration of chlorine dioxide is 15%, inorganic salts are removed by filtration after the reaction is finished, the inorganic salts are concentrated in vacuum until the concentration of the chlorine dioxide reaches 26%, and then the mixture is cooled and crystallized in a crystallizer, and the temperature is controlled to be below-1 to-8 ℃, so that stable solid containing 50% of chlorine dioxide is obtained. Example 4
The procedure of example 1 was repeated using the R7 method to obtain a steady state solid containing 52% chlorine dioxide, the main reaction of which was as follows:
wherein the by-product Na2SO4Is greatly reduced.Example 5
The procedure of example 2 was repeated using the R7 method to obtain a steady state solid containing 55% chlorine dioxide. Example 6
The procedure of example 3 was repeated using the R7 method to obtain a steady-state solid containing 50% chlorine dichloride. Example 7
ClO was prepared using the following starting materials2The main reaction is as follows:
the procedure of example 1 was repeated to obtain a steady solid containing 52% chlorine dioxide. Example 8
ClO was prepared by performing the reaction using the starting materials of example 72The procedure of example 2 was repeated to obtain a steady solid containing 55% chlorine dioxide. Example 9
ClO was prepared by performing the reaction using the starting materials of example 72The procedure of example2 was repeated to obtain a steady-state solid containing 50% chlorine dichloride. Examples 10 to 12
An effervescent instant tablet (example 10) was obtained by mixing 70 parts by weight of the steady state solid containing 52% chlorine dioxide obtained in example 1 or example 4 or example 7, 2 parts by weight of sodium carboxymethylcellulose, 25 parts by weight of sodium bicarbonate, and 5 parts by weight of citric acid, and then compressing the mixture into a tablet by a dry method.
Tablets were dry-compressed using 60 parts by weight of the steady state solid containing 55% of chlorine dichloride obtained in example 2 or example 5 or example 8, 2 parts by weight of sodium carboxymethylcellulose, 32 parts by weight of sodium bicarbonate and 7 parts by weight of lemon (example 11).
Tablets were dry-compressed using 80 parts by weight of 20 steady-state solids containing 50% of chlorous dichloride prepared in example 3 or example 6 or example 9, 2 parts by weight of sodium carboxymethylcellulose, 15 parts by weight of sodium bicarbonate and 3 parts by weight of citric acid (example 12). Examples 13 to 15
Using the uniformly mixed powder obtained in example 10, 1 part by weight of potassium percarbonate was added to prepare a material A, and after uniformly mixing with a material B comprising 70 parts by weight of citric acid, 15 parts by weight of sodium bicarbonate, 2 parts by weight of sodium carboxymethylcellulose and 7 parts by weight of chloroisocyanuric acid, an AB material double-layer composite tablet was prepared by dry tableting (example 13).
Using the uniformly mixed powder obtained in example 11, 20 parts by weight of potassium percarbonate was added to prepare a material A, and after uniformly mixing with 50 parts by weight of citric acid, 30 parts by weight of sodium bicarbonate, 2 parts by weight of sodium carboxymethylcellulose and 10 parts by weight of chloroisocyanuric acid, an AB material bilayer complex function tablet was prepared by dry tableting (example 13).
The uniformly mixed powder obtained in example 12 was added with 10 parts by weight of potassium percarbonate to prepare a material a, and the uniformly mixed material a was dry-compressed with 90 parts by weight of citric acid, 8 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethylcellulose to prepare an AB material double-layer composite functional tablet.
The above-described embodiments are for illustrative purposes only, and the scope of the present invention will be indicated in the claims.
Claims (4)
1. A stable chlorine dioxide tablet comprising:
60-80 parts by weight of steady chlorine dioxide powder with effective components of at least 50%,
2 parts by weight of sodium carboxymethylcellulose,
15 to 32 parts by weight of sodium bicarbonate,
3-7 parts by weight of citric acid to form the effervescent tablet.
2. A stable chlorine dioxide tablet as claimed in claim 1, further comprising a material a consisting of 1-10 parts by weight of potassium percarbonate and 3-10 parts by weight of chloroisochlorouric acid with 50-90 parts by weight of citric acid; and uniformly mixing the material B consisting of 8-30 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethyl cellulose, and performing double-layer tabletting by adopting the material AB to form the composite functional tablet.
3. A preparation method of a stable chlorine dioxide tablet comprises the steps of preparing a 4-6% stable chlorine dioxide solution by taking sodium chlorate, sulfuric acid and methanol as raw materials and sodium percarbonate as a stabilizer, and is characterized in that the stable chlorine dioxide solution with low concentration is further taken as an absorption liquid, the generated chlorine dioxide is introduced into the absorption liquid by adopting negative pressure, and 8-20% of compound stabilizing liquid in weight is added into the absorption liquid in batches according to the following proportion:
sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate and sodium hydroxide in a ratio of 1: 3-20: 0.1-5: 1-20: 5-40
Simultaneously, adjusting the pH value of the absorption liquid to 7.5-9 by using sodium carbonate, controlling the reaction to 0-2 ℃ to prepare 15-20% of stable chlorine dioxide solution, filtering to remove inorganic salt, performing vacuum evaporation concentration to obtain chlorine dioxide with the concentration of at least 25%, performing cooling crystallization, and uniformly mixing 60-80 parts by weight of the crushed solid, 2 parts by weight of sodium carboxymethylcellulose, 15-32 parts by weight of sodium bicarbonate and 3-7 parts by weight of citric acid at the cooling temperature of-1 ℃ -8 ℃ to obtain solid with the effective component of the chlorine dioxide of at least 50%, and performing dry tabletting to obtain the effervescent tablet.
4. The method of claim 3, further comprising adding potassium percarbonate 1-10 parts by weight to form a material A before mixing and tabletting, and uniformly mixing with a material B consisting of 50-90 parts by weight of citric acid, 3-10 parts by weight of chloroisocyanuric acid, 8-30 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethylcellulose, and tabletting to form A, B double-layer composite functional tablets.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 97106395 CN1196881A (en) | 1997-04-21 | 1997-04-21 | High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. |
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| CN 97106395 CN1196881A (en) | 1997-04-21 | 1997-04-21 | High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436308C (en) * | 2004-12-08 | 2008-11-26 | 龙膺厚 | Long-effective instant aqueous chlorine solution |
| CN101300993B (en) * | 2008-06-06 | 2010-07-14 | 浙江省农业科学院 | Fresh-keeping method for seafood |
| WO2021242225A1 (en) * | 2020-05-26 | 2021-12-02 | Spectrum Doxyicide Llc | Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability |
-
1997
- 1997-04-21 CN CN 97106395 patent/CN1196881A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436308C (en) * | 2004-12-08 | 2008-11-26 | 龙膺厚 | Long-effective instant aqueous chlorine solution |
| CN101300993B (en) * | 2008-06-06 | 2010-07-14 | 浙江省农业科学院 | Fresh-keeping method for seafood |
| WO2021242225A1 (en) * | 2020-05-26 | 2021-12-02 | Spectrum Doxyicide Llc | Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability |
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