CN113735064B - Preparation method of chlorine dioxide - Google Patents
Preparation method of chlorine dioxide Download PDFInfo
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- CN113735064B CN113735064B CN202111132954.4A CN202111132954A CN113735064B CN 113735064 B CN113735064 B CN 113735064B CN 202111132954 A CN202111132954 A CN 202111132954A CN 113735064 B CN113735064 B CN 113735064B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
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Abstract
The invention belongs to the technical field of disinfection and sterilization, and particularly relates to a preparation method of chlorine dioxide. A method for preparing chlorine dioxide, comprising the following steps: mixing chlorate, weak acid and water for oxidation-reduction reaction to obtain chlorine dioxide; the weak acid comprises one or more of citric acid, oxalic acid, boric acid, sorbic acid or tartaric acid; the mole ratio of chlorate to weak acid is 1: (0.5-2); the temperature of the oxidation-reduction reaction is 60-90 ℃, and the time of the oxidation-reduction reaction is 20-60 min. The method has the advantages of mild reaction conditions, high reaction yield and no generation of by-product chlorine, and has wide application prospect in the technical field of disinfection.
Description
Technical Field
The invention belongs to the technical field of disinfection and sterilization, and particularly relates to a preparation method of chlorine dioxide.
Background
In the prior art, after the chlorine is used for disinfecting water, a cancerogenic substance trihalomethane is generated; the chlorine dioxide can not generate trihalomethane after treating water, and the killing rate of the chlorine dioxide on single cell substances including bacteria, viruses and algae is up to 100 percent, and meanwhile, the chlorine dioxide can not generate any toxic or side effect on human beings and animals. Therefore, the world health organization WHO lists chlorine dioxide as the AI-level high-efficiency safe disinfectant, and has the advantages of environmental protection, high efficiency, rapidness, broad spectrum, no toxicity, long drug effect, no pH limit on sterilization effect and the like.
Currently, the preparation methods of chlorine dioxide mainly comprise an electrolytic method and a chemical method. The purity and yield of the chlorine dioxide prepared by the electrolytic method are low, so that the practical application is less. At present, the chemical method mainly takes chlorite or hypochlorite as a raw material, and reacts in a strong acid medium at a certain temperature to prepare the chlorine dioxide. However, the reaction is severe, and chlorine gas is generated as a byproduct in the reaction process, so that the yield of chlorine dioxide is low (generally, the yield of the chlorine dioxide is lower than 80 percent); meanwhile, the byproduct chlorine has strong corrosiveness, so that instruments and equipment are easy to corrode, and the application of the technology in the field of space disinfection in biosafety laboratories is limited.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of chlorine dioxide, which takes chlorate as a chlorine source and weak acid as a raw material to prepare the chlorine dioxide, and has the characteristics of mild reaction conditions, high chlorine dioxide yield and no generation of by-product chlorine.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of chlorine dioxide, which comprises the following steps:
mixing chlorate, weak acid and water for oxidation-reduction reaction to obtain chlorine dioxide;
the weak acid comprises one or more of citric acid, oxalic acid, boric acid, sorbic acid or tartaric acid;
the mole ratio of chlorate to weak acid is 1: (0.5-2);
the temperature of the oxidation-reduction reaction is 60-90 ℃, and the time of the oxidation-reduction reaction is 20-60 min.
Preferably, the chlorate comprises alkali metal chlorate.
Preferably, the mixing is carried out to obtain a reaction liquid, and the mass ratio of chlorate to water in the reaction liquid is (0.5-2): 10.
Preferably, the mixing is carried out to obtain a reaction feed liquid, and the concentration of weak acid in the reaction feed liquid is 0.2-1 mol/L.
Preferably, the redox reaction is carried out under stirring.
Preferably, the stirring speed is 300-800 rpm.
The invention provides a preparation method of chlorine dioxide, which comprises the following steps: mixing chlorate, weak acid and water to obtain reaction feed liquid, and carrying out oxidation-reduction reaction on the reaction feed liquid to obtain chlorine dioxide; the weak acid comprises one or more of citric acid, oxalic acid, boric acid, sorbic acid or tartaric acid; the mole ratio of chlorate to weak acid is 1: (0.5-2); the temperature of the oxidation-reduction reaction is 60-90 ℃, and the time of the oxidation-reduction reaction is 20-60 min. The method of the invention prepares chlorine dioxide by using chlorate and weak acid as raw materials, does not generate poisonous chlorine in the reaction process, can fully convert chlorine elements in the chlorate into chlorine dioxide by the reaction, and improves the yield of the chlorine dioxide. Meanwhile, the invention limits the dosage ratio of the raw materials, can ensure the full contact between the raw materials in the dosage range, and simultaneously combines with a certain reaction temperature, so that the reaction between the raw materials is more thorough, and the yield of the chlorine dioxide is improved. The preparation method provided by the invention has the advantages of reaction temperature lower than 100 ℃, mild condition, high chlorine dioxide yield and no generation of by-product chlorine, and has wide application prospect in the technical field of disinfection.
In addition, the preparation method of the invention has no generation of by-product chlorine and can not cause corrosion to experimental instruments and equipment. Therefore, the generated chlorine dioxide gas can be directly used for sterilizing and disinfecting microorganisms in various space environments such as biosafety laboratories.
Detailed Description
The invention provides a preparation method of chlorine dioxide, which comprises the following steps:
mixing chlorate, weak acid and water to obtain reaction feed liquid, and carrying out oxidation-reduction reaction on the reaction feed liquid to obtain chlorine dioxide.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
In the present invention, the chlorate preferably comprises alkali metal chlorate; the alkali metal chlorate preferably comprises sodium chlorate or potassium chlorate. In the present invention, the mass ratio of chlorate to water in the reaction solution is preferably (0.5 to 2): 10, more preferably (0.55 to 1.5): 10.
In the present invention, the weak acid includes one or more of citric acid, oxalic acid, boric acid, sorbic acid or tartaric acid, preferably citric acid, oxalic acid, boric acid, sorbic acid or tartaric acid. In the present invention, the concentration of the weak acid in the reaction liquid is 0.2 to 1mol/L, more preferably 0.2 to 0.8mol/L, still more preferably 0.5 to 0.8mol/L.
In the invention, the mole ratio of the chlorate to the weak acid is 1: (0.5 to 2), preferably 1: (0.5-1.6). In the invention, the mass ratio of chlorate to weak acid is set as the above parameter, which is helpful for complete reaction of chlorate and improves the yield of chlorine dioxide.
In the present invention, the temperature of the redox reaction is 60 to 90 ℃, preferably 60 to 80 ℃, more preferably 65 to 80 ℃. In the present invention, the time for the redox reaction is 20 to 60 minutes, preferably 30 to 40 minutes, more preferably 30 to 35 minutes. In the present invention, the rate of the uniform temperature rise to the temperature of the redox reaction is preferably 4 to 6 ℃/min.
In the present invention, the redox reaction is preferably carried out under stirring, and the stirring speed is preferably 300 to 800rpm, more preferably 400 to 600rpm. In the present invention, the redox reaction is preferably carried out in a stirred reactor.
The following is a detailed description of the method for producing chlorine dioxide provided by the present invention with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
Adding 10g of sodium chlorate, 90g of water and 10.53g of citric acid into a reactor with stirring at room temperature to obtain a reaction feed liquid, wherein the concentration of the citric acid is 0.55mol/L; then, the temperature was increased to 75℃at a constant rate of 5℃per minute, and oxidation-reduction reaction was carried out at a rotation speed of 500rpm for 30 minutes, to thereby obtain 6.26g of chlorine dioxide gas, the yield of which was 98.3%.
The reaction equation that occurs in this example is:
18NaClO 3 +7H 8 C 6 O 7 ＝18ClO 2 ↑+6CO 2 ↑+13H 2 O+6Na 3 H 5 C 6 O 7
example 2
10g of sodium chlorate, 190g of water and 13.32g of oxalic acid are added into a reactor with stirring at room temperature to obtain a reaction liquid, and the concentration of the citric acid is 0.74mol/L. Then, the temperature is increased to 60 ℃ at a constant speed of 5 ℃/min, oxidation-reduction reaction is carried out under the condition of the rotating speed of 700rpm, and the reaction is carried out for 50min, so that 6.14g of chlorine dioxide gas is obtained, and the yield of the chlorine dioxide gas is 96.4%.
The reaction equation that occurs in this example is:
2NaClO 3 +3H 2 C 2 O 4 ＝2ClO 2 ↑+2CO 2 ↑+2H 2 O+2NaHC 2 O 4
example 3
10g of sodium chlorate, 80g of water and 4.26g of boric acid are added into a reactor with stirring at room temperature to obtain a reaction liquid, and the concentration of the citric acid is 0.78mol/L. Then, the temperature is increased to 65 ℃ at a constant speed of 5 ℃ per minute, oxidation-reduction reaction is carried out under the condition of the rotating speed of 450rpm, and the reaction is carried out for 35 minutes, so that 6.22g of chlorine dioxide gas is obtained, and the yield of the chlorine dioxide gas is 97.6%.
The reaction equation that occurs in this example is:
3NaClO 3 +2H 3 BO 3 ＝3ClO 2 ↑+3H 2 O+NaH 2 BO 3 +Na 2 HBO 3
example 4
10g of potassium chlorate, 140g of water and 11.2g of sorbic acid are added into a reactor with stirring at room temperature to obtain a reaction liquid, and the concentration of citric acid is 0.67mol/L. Then, the temperature is increased to 90 ℃ at a constant speed of 5 ℃/min, oxidation-reduction reaction is carried out under the condition of the rotating speed of 350rpm, the reaction is carried out for 25min, 5.35g of chlorine dioxide gas is obtained, and the yield of the chlorine dioxide gas is 96.7%.
The reaction equation that occurs in this example is:
6KClO 3 +7H 8 C 6 O 2 ＝6ClO 2 ↑+2H 2 O+6KH 7 C 6 O 2 +CH 3 CHO+2HCHO+CHOCOOH
example 5
10g of potassium chlorate, 180g of water and 6.73g of tartaric acid are added into a reactor with stirring at room temperature to obtain a reaction liquid, and the concentration of the citric acid is 0.24mol/L. Then, the temperature is increased to 80 ℃ at a constant speed of 5 ℃/min, oxidation-reduction reaction is carried out under the condition of 650rpm, the reaction is carried out for 40min, 5.36g of chlorine dioxide gas is obtained, and the yield of the chlorine dioxide gas is 96.9%.
The reaction equation that occurs in this example is:
4KClO 3 +2H 6 C 4 O 6 ＝4ClO 2 ↑+4H 2 O+K 2 H 4 C 4 O 6 +K 2 C 4 O 6
comparative example 1
10g of sodium chlorite, 17.36g of hydrochloric acid (37% strength) and 140g of water were added to a stirred reactor at room temperature, and then reacted at room temperature for 20 minutes to obtain 3.75g of chlorine dioxide gas, the yield of which was 75.7%, to obtain 1.97g of chlorine gas.
Comparative example 2
10g of sodium chlorite, 15.91g of hydrochloric acid (37% by mass) and 90g of water were charged into a stirred reactor at room temperature, and then reacted at room temperature for 30 minutes to obtain 3.53g of chlorine dioxide gas, the yield of which was 71.3% and 1.85g of chlorine gas.
Comparative example 3
Adding 10g of sodium chlorate, 60g of water and 10.53g of citric acid into a reactor with stirring at room temperature to obtain a reaction feed liquid, wherein the concentration of the citric acid is 0.91mol/L; then, the temperature was increased to 75℃at a constant rate of 5℃per minute, and oxidation-reduction reaction was carried out at a rotation speed of 500rpm for 30 minutes, to obtain 5.11g of chlorine dioxide gas, the yield of which was 80.6%.
Comparative example 4
10g of sodium chlorate, 90g of water and 8.53g of citric acid are added into a reactor with stirring at room temperature to obtain reaction feed liquid, and the concentration of the citric acid is 0.44mol/L; then, the temperature was increased to 75℃at a constant rate of 5℃per minute, and oxidation-reduction reaction was carried out at a rotation speed of 500rpm for 30 minutes, to thereby obtain 4.64g of chlorine dioxide gas, the yield of which was 73.2%.
Comparative example 5
Adding 10g of sodium chlorate, 90g of water and 25.53g of citric acid into a reactor with stirring at room temperature to obtain a reaction feed liquid, wherein the concentration of the citric acid is 1.3mol/L; then, the temperature was increased to 75℃at a constant rate of 5℃per minute, and oxidation-reduction reaction was carried out at a rotation speed of 500rpm for 30 minutes, to obtain 4.91g of chlorine dioxide gas, the yield of which was 77.4%.
TABLE 1 yields of chlorine dioxide from examples 1 to 5 and comparative examples 1 to 5
As can be seen from Table 1, the chlorine dioxide prepared by the preparation method of chlorine dioxide provided by the application has higher yield.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. The preparation method of the chlorine dioxide is characterized by comprising the following steps of:
adding 10g of sodium chlorate, 90g of water and 10.53g of citric acid into a reactor with stirring at room temperature to obtain a reaction feed liquid, wherein the concentration of the citric acid is 0.55mol/L; then, the temperature was raised to 75℃at a constant rate of 5℃per minute, and oxidation-reduction reaction was carried out at a rotation speed of 500rpm for 30 minutes, to thereby obtain 6.26g of chlorine dioxide gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB849816A (en) * | 1956-04-06 | 1960-09-28 | Tennants Cons Ltd | Production of chlorine dioxide |
| CN101357752B (en) * | 2008-09-02 | 2012-01-11 | 艾雪莉 | Process for producing chlorine dioxide using chlorate method |
| CN101844747A (en) * | 2010-06-18 | 2010-09-29 | 钱校忠 | Novel preparation method of chlorine dioxide |
| FI126250B (en) * | 2012-01-31 | 2016-08-31 | Kemira Oyj | Method for the production of chlorine dioxide |
| CN110200011A (en) * | 2019-07-05 | 2019-09-06 | 四川齐力绿源水处理科技有限公司 | A kind of preparation method of composite chlorine dioxide |
| CN112616851A (en) * | 2020-12-04 | 2021-04-09 | 湖南喜爱迪生物科技有限责任公司 | Preparation method of chlorine dioxide disinfectant |
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