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CN1052957C - Method for production of stable chlorine dioxide - Google Patents

Method for production of stable chlorine dioxide Download PDF

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Publication number
CN1052957C
CN1052957C CN96118919A CN96118919A CN1052957C CN 1052957 C CN1052957 C CN 1052957C CN 96118919 A CN96118919 A CN 96118919A CN 96118919 A CN96118919 A CN 96118919A CN 1052957 C CN1052957 C CN 1052957C
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chlorine dioxide
sodium
solution
extracting agent
aqueous solution
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CN96118919A
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CN1185417A (en
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丁章迅
丁文洁
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Abstract

The present invention relates to a new method for producing stable chlorine dioxide, which is characterized in that the whole producing flow is carried out under the state of liquid phase, namely that reacting substance solutions capable of generating chlorine dioxide gas are matched, are added into a reactor containing liquid state paraffin hydrocarbon, or aromatic hydrocarbon, or solvent naphtha used as an extraction agent, are stirred for reaction, and the extraction agent directly absorbs chlorine dioxide; the mixture is stood and stratified after the reaction is finished, the solution of other reaction products is discharged, the solution of sodium carbonate, or sodium percarbonate, or sodium perborate tetrahydrate used as a stabilizing agent is added, hydrogen peroxide is added, the mixture is mixed and stirred to dissolve and absorb the chlorine dioxide in the extraction agent, the chlorine dioxide is separated from the extraction agent, and the product with a high concentration and long storage term can be prepared.

Description

Production method of stable chlorine dioxide
The invention relates to a process for producing stable chlorine dioxide.
Chlorine dioxide, as a novel disinfectant, is gaining importance and popularity in people's daily life. However, chlorine dioxide is an unstable gas, which is soluble in water, easily decomposed and difficult to store, and is prepared into liquid stable chlorine dioxide for storage and application except for on-site use, and is acidified (also called activated) by adding organic acid or inorganic acid to release chlorine dioxide gas when the chlorine dioxide is used.
The existing technology for producing stable chlorine dioxide generally adopts a chemical reaction method, pure chlorine dioxide gas is firstly prepared, and then the prepared gas is introduced into liquid serving as a stabilizer to be absorbed to form liquid stable chlorine dioxide. For example, the invention of patent application No. 9311608.2 entitled "method for producing stable chlorine dioxide" is created by reacting sodium chlorate with sulfuric acid, using hydrogen peroxide as a reducing agent to produce chlorine dioxide gas, and then introducing 5% sodium carbonate solution as a stabilizing agent to absorb the chlorine dioxide gas to produce stable chlorine dioxide. Since chlorine dioxide is soluble in water, it is difficult and not completely removed to remove chlorine dioxide gas during the reaction. Meanwhile, chlorine dioxide gas is extremely unstable, and the explosion is possible when the content of the chlorine dioxide gas in the air exceeds 10 percent, and the production condition and the process technical requirement of the production method for preparing stable chlorine dioxide by dissolving gaseous chlorine dioxide in stabilizer liquid are very strict.
The invention aims to disclose a method for producing stable chlorine dioxide, which has simple production process, safety, reliability and high product concentration.
The technological key points of the present invention are that the whole production process of the product is carried out in liquid phase, that is, reactant solution capable of generating chlorine dioxide gas is mixed and added into a reactor containing liquid alkane or liquid arene or solvent gasoline to stir and react, after the reaction is finished, the liquid benzene-taking agent in the container is changed from colorless to yellow green, and is layered with other reaction product solution, other reaction product solution is discharged, then sodium carbonate solution, sodium percarbonate solution or perboric acid solution as stabilizer is added with hydrogen peroxide, and is added into a container containing the extracting agent which is dissolved and absorbed with chlorine dioxide to stir, when the yellow green extracting agent is changed to colorless, that is, the original dissolved and absorbed chlorine dioxide is absorbed by the stabilizer, stirring is stopped, after standing and layering, the original stabilizer which is absorbed by chlorine dioxide is made into stable, separating the extract from the extractant, and storing in a lightproof sealed container to obtain the product.
The whole production process of the stable chlorine dioxide is carried out in a liquid phase state, so that the generation of gaseous chlorine dioxide is avoided, and the selected extracting agent can not dissolve reactants participating in the generation of chlorine dioxide and other reaction products except the chlorine dioxide, can not dissolve non-aqueous phase substances in the stabilizing agent participating in the absorption of the chlorine dioxide, and can not chemically react with the substances. The purity of the chlorine dioxide dissolved in the extracting agent is high, and the chlorine dioxide dissolved in the extracting agent can be completely absorbed by the selected stabilizing agent and a proper amount of hydrogen peroxide as an accelerating agent. More particularly, the samepart of stabilizing agent can absorb chlorine dioxide from the extracting agent dissolved with chlorine dioxide for a plurality of times, thereby preparing high-concentration stable chlorine dioxide with the concentration of more than 6 percent, which is incomparable with other prior stable chlorine dioxide production process methods. The preservation period can reach more than one year.
Specific embodiments of the invention are detailed below:
the chemical reactions that produce chlorine dioxide that meet the hygiene standards are several:
1. the reaction equation of sodium chlorite and hydrochloric acid is as follows:
2. the reaction equation of sodium chlorite and sulfuric acid is:
3. sodium chloride and sulfuric acid are used for reducing sodium chlorate to generate chlorine dioxide, and the reaction equation is as follows:
4. the chlorine dioxide is generated by reducing sodium chlorate with hydrochloric acid, and the inverse equation is as follows:
5. oxidizing sodium chlorite with sodium hypochlorite to produce chlorine dioxide, the reaction equation of which is:
among them, a chemical reaction in which sodium chlorite reacts with hydrochloric acid to generate chlorine dioxide is preferable. By using
In the present invention, all reactants are used after being prepared into an aqueous solution. For example, sodium chlorite and water are prepared into a solution with the concentration of 10-20%, and the concentration of hydrochloric acid is 7.5-20% generally; firstly, putting the prepared hydrochloric acid and an extracting agent into an inverter provided with a stirrer according to the ratio of the solution amount of 1: 1-4, starting the stirrer, then pouring chlorous acid steel solution with the same amount as the hydrochloric acid into the reactor for 3-5 times at intervals of 2-3 minutes every time, after the sodium chlorite solution is put for the last time, continuing stirring for 5-10 minutes, and then dissolving chlorine dioxide generated by the reaction of the sodium chlorite and the hydrochloric acid into the extracting agent, wherein the extracting agent is changed from colorless to yellowish green. Stopping stirring, allowing the liquid in the reactor to stand for layering, and allowing the extracting agent dissolved with chlorine dioxide to float on the reaction product liquid. The separated reaction product liquid can be placed in a sealed lightproof container to be extracted for the second time. The liquid alkane in the extractant can be cyclohexane or cyclopentane, and the liquid arene can be xylene, chlorobenzene and the like, so long as the working condition that the liquid alkane is always liquid is ensured. Of course, solvent gasoline is the most economical and most suitable extractant.
The preparation of the stabilizer is ideally carried out by three schemes:
firstly, dissolving sodium carbonate in water to prepare a 3-12% aqueous solution, taking the amount according to the proportion of the sodium carbonate aqueous solution to an extracting agent of 2-1/2: 1, mixing the sodium carbonate aqueous solution with the extracting agent absorbing chlorine dioxide, adding 1/2-3/4 of hydrogen peroxide, starting a stirrer, if the extracting agent is changed from yellow green to colorless, pouring the rest of hydrogen peroxide, or adding 1/4-1/3 of hydrogen peroxide successively until the extracting agent is completely colorless, stopping stirring, standing for layering, and then releasing stable chlorine dioxide.
The second scheme is that sodium percarbonate is dissolved in water to prepare an aqueous solution with the concentration of 5-18% before use, the amount of the aqueous solution of the sodium percarbonate is also taken according to the proportion of 2-1/2: 1 of the extracting agent, hydrogen peroxide with the weight equal to that of pure sodium percarbonate is prepared, the aqueous solution of the sodium percarbonate is mixed with the extracting agent absorbing chlorine dioxide, the mixture is stirred until the extracting agent absorbing chlorine dioxide is changed from yellow green to colorless, and standby hydrogen peroxide is not required to be added, otherwise, a proper amount of hydrogen peroxide is gradually added until the extracting agent is completely colorless.
Dissolving sodium perborate in water to prepare an aqueous solution with the concentration of 5-20% before use, taking the amount according to the proportion of the sodium perborate aqueous solution to the extracting agent of 2-1/2: 1, and preparing hydrogen peroxide with the same amount as the pure sodium perborate, mixing and stirring, if the extracting agent absorbing chlorine dioxide is changed from yellow green to colorless, adding the hydrogen peroxide, or gradually pouring a proper amount of hydrogen peroxide, and stirring until the extracting agent is completely colorless.
The same stabilizer is matched with hydrogen peroxide to absorb chlorine dioxide from the extracting agent absorbing chlorine dioxide for many times so as to prepare a high-concentration stable chlorine dioxide product. Two or more reactors provided with stirrers can be connected into a production line, and each reactor is fixed to work with a dose of extractant, so that continuous reaction and production are realized.
When in use, the chlorine dioxide can be released by adding organic acid or inorganic acid into the stable chlorine dioxide to acidify the stable chlorine dioxide, thereby achieving the purpose of disinfection and sterilization.

Claims (2)

1. A method for producing stabilized chlorine dioxide, comprising: preparing reactant solution capable of generating chlorine dioxide gas, successively adding the reactant solution into a reactor containing liquid alkane or aromatic hydrocarbon or solvent gasoline as an extracting agent, stirring and reacting, changing the colorless liquid extracting agent in the reactor into yellow-green after the reaction is finished, layering the extracting agent with other reaction product solution, and then discharging other reaction product solution; the preparation scheme of the stabilizer is as follows:
a. dissolving sodium carbonate in water to prepare a 3-12% aqueous solution, taking the aqueous solution of the sodium carbonate and an extracting agent according to the ratio of 2-1/2: 1, and preparing hydrogen peroxide with the same amount as the net weight of the sodium carbonate;
b. dissolving sodium percarbonate in water to prepare an aqueous solution with the concentration of 5-18%, taking the amount according to the ratio of the aqueous solution of the sodium percarbonate to an extracting agent of 2-1/2: 1, and preparing hydrogen peroxide with the same amount as the net weight of the sodium percarbonate;
c. dissolving sodium perborate in water to prepare an aqueous solution with the concentration of 5-20%, taking the amount of the aqueous solution of sodium perborate and an extracting agent according to the ratio of 2-1/2: 1, and preparing hydrogen peroxide with the same amount as the pure sodium perborate; then adding sodium carbonate solution or sodium percarbonate solution or sodium perborate solution as stabilizer and hydrogen peroxide into a reactor containing chlorine dioxide-absorbed extractant, stirring until the extractant turns from yellow green to colorless, standing for layering, absorbing the original stabilizer of chlorine dioxide to obtain stabilized chlorine dioxide, separating the stabilized chlorine dioxide from the extractant, and filling into a light-tight sealed container.
2. The method for producing stabilized chlorine dioxide as claimed in claim 1, wherein: the reactant capable of generating chlorine dioxide gas can be sodium chlorite and hydrochloric acid, or sodium chlorite and sulfuric acid, or sodium chlorate can be reduced by sodium chloride and sulfuric acid, or sodium chlorate can be reduced by hydrochloric acid, or sodium chlorite can be oxidized by sodium hypochlorite.
CN96118919A 1996-12-18 1996-12-18 Method for production of stable chlorine dioxide Expired - Fee Related CN1052957C (en)

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8992831B2 (en) 2009-09-25 2015-03-31 E. I. Du Pont De Nemours And Company Stabilized chlorine dioxide to preserve carbohydrate feedstocks
CN102390813A (en) * 2011-07-19 2012-03-28 贵州大学 Preparation method and product of stable chlorine dioxide
CN104585231B (en) * 2014-04-29 2018-01-23 深圳市格易通消毒药械科技有限公司 A kind of sterilized disinfectant preparation and its application method for hospital sewage
CN105036083A (en) * 2015-07-08 2015-11-11 优尼克生技股份有限公司 A kind of preservation method of chlorine dioxide aqueous solution
CN106074692A (en) * 2016-07-06 2016-11-09 李光新 A kind of compound recipe stable ClO 2 solution and its preparation method and application
CN111436456A (en) * 2020-05-09 2020-07-24 南京协心健康科技有限公司 Chlorine dioxide solution spray and preparation method thereof
CN112741109A (en) * 2021-02-22 2021-05-04 卫溯源(北京)生物医药科技有限公司 Preparation method of chlorine dioxide sterilizing gas
CN112956492A (en) * 2021-03-01 2021-06-15 昆明火木生物科技有限公司 Stable chlorine dioxide disinfectant and preparation method thereof
CN117401649B (en) * 2023-12-15 2024-03-08 山东华实药业有限公司 Pure activation-free stable chlorine dioxide solution

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1075298A (en) * 1992-02-13 1993-08-18 青岛海洋大学 A kind of method of producing chlorine dioxide of high concentration and stable state
CN1097716A (en) * 1993-07-17 1995-01-25 湖南省劳动卫生职业病防治研究所 The production method of stability chlorine dioxide
CN1107438A (en) * 1994-12-16 1995-08-30 关文志 Process for producing stable chlorine dioxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1075298A (en) * 1992-02-13 1993-08-18 青岛海洋大学 A kind of method of producing chlorine dioxide of high concentration and stable state
CN1097716A (en) * 1993-07-17 1995-01-25 湖南省劳动卫生职业病防治研究所 The production method of stability chlorine dioxide
CN1107438A (en) * 1994-12-16 1995-08-30 关文志 Process for producing stable chlorine dioxide

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