CN112335677A - Chlorine dioxide solution and preparation method thereof - Google Patents
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Abstract
The invention discloses a chlorine dioxide solution and a preparation method thereof, and belongs to the field of preparation methods of special-purpose chemical preparations. The chlorine dioxide solution provided by the invention is green and nontoxic, can be used for disinfecting pet environment and pet skin, can be diluted by deionized water and then used or directly used, has no stimulation to pet skin and respiratory tract mucosa, and does not cause poisoning or discomfort after a pet licks. And the proportion relation among the components is specified through a specific algorithm, so that the stable and long-acting disinfection function of the chlorine dioxide solution is realized.
Description
Technical Field
The invention relates to the field of preparation methods of special-purpose chemical preparations, in particular to a special-purpose chlorine dioxide solution and a preparation method thereof.
Background
Chlorine dioxide has been widely developed and applied as a main ingredient of mature disinfection products, and the traditional chlorine dioxide is mainly used for bleaching paper pulp, paper, fiber, wheat flour and starch, and refining and bleaching grease, beeswax and the like. The disinfection and sterilization treatment of the drinking water is a safe and nontoxic green disinfectant which is internationally recognized. Chlorine dioxide can efficiently and spectrally kill various bacteria, germs and other microorganisms, is non-toxic and stable in performance, can be naturally degraded without residue, and cannot cause the environmental bacteria, germs and other microorganisms to generate drug resistance, so that disinfection articles taking chlorine dioxide as a main component are particularly popular among consumers in daily life.
In the pet industry, because pets are susceptible to skin diseases and cross infection, and urine, excrement and the like of the pets pollute the environment and are easy to breed microbes such as pathogenic bacteria or germs, the environment and skin disinfection of the pets is very important.
In the current pet industry, due to factors such as cost control, 84 disinfectant is generally used for environmental disinfection, even if chlorine dioxide is used for disinfecting pet skin, the chlorine dioxide disinfection sheet is generally used for preparing water for use, the prepared disinfectant is not only unstable, but also the concentration of the obtained chlorine dioxide disinfectant is uncertain according to various ion contents, water temperatures and different pH values in water, and the problems of incomplete disinfection, damage to skin or nasal mucosa and the like are easily caused when the disinfectant is used for disinfecting, particularly the skin of a pet. At present, no particularly stable chlorine dioxide disinfectant for pets is available, and a stable chlorine dioxide solution is prepared in some work, but the adopted stabilizer is toxic components such as pyridine and the like, so that the stimulation to the skin of the pet is increased, and more importantly, due to the characteristics of the pet, the disinfectant used on the body of the pet needs to be a formula which can be eaten and is non-toxic and does not stimulate mucosal tissues, which is not seen in the market at present. Even though some work has been done with nontoxic stabilizers, the problem of solution instability when stored or used in more complex environments arises due to the stringent environmental requirements of a single specific stabilizer.
In addition, under the condition that the commonly used anthelmintic can repel insects for a long time, the action time of the disinfection product also attracts the attention of consumers, and the disinfection product for pets in the current market is influenced by factors such as high release speed or low use concentration, and the like, so that the long-time stable disinfection effect cannot be generally achieved.
Disclosure of Invention
Aiming at the problems, the invention provides a stable, non-toxic, harmless and long-acting chlorine dioxide solution suitable for pet environment and pet skin disinfection and a preparation method thereof, and the specific scheme is as follows:
first, the present invention provides a chlorine dioxide solution comprising chlorine dioxide, a chlorine dioxide/PVP (polyvinylpyrrolidone) complex, a chlorine dioxide/EDTA complex, sodium carbonate, and deionized water.
Preferably, the molar ratio of the chlorine dioxide/PVP complex and the chlorine dioxide/EDTA complex is (2-13) to (9-37), and the concentration of the chlorine dioxide/EDTA complex in the solution is 0.63-1.08% wt; the concentration of chlorine dioxide in the solution is 0.08-0.12% wt; the concentration of sodium carbonate in the solution is 0.05-0.1% wt.
More preferably, the concentrations of chlorine dioxide, chlorine dioxide/PVP complex, chlorine dioxide/EDTA complex and sodium carbonate in the solution are respectively C0、CP、CE、CNThen, there are: cPC0=CECN。
Preferably, the chlorine dioxide solution may further include an aminocarboxylic acid.
Preferably, the aminocarboxylic acid is carbamic acid or glycine; further preferably, the aminocarboxylic acid is added to the solution at a concentration of 0.4 to 0.7 times the concentration of the free chlorine dioxide species.
More preferably, when the aminocarboxylic acid is included in the solution, chlorine dioxide/PVP complex, dioxide in solutionThe concentrations of the chlorine/EDTA complex, sodium carbonate and aminocarboxylic acid are respectively C0、CP、CE、CNThen, there are: cPCN=μC0CEMu is a constant with a value of 0.3-0.6.
The invention provides a preparation method of the chlorine dioxide solution, which comprises the following steps:
(1) preparing chlorine dioxide/EDTA complex solution;
(2) preparing chlorine dioxide/PVP complex solution;
(3) uniformly mixing chlorine dioxide/EDTA complex solution and chlorine dioxide/PVP complex solution;
(4) and (4) adding sodium carbonate into the solution obtained in the step (3) and uniformly mixing to obtain the stable chlorine dioxide solution.
Preferably, step (1) is specifically: introducing chlorine dioxide gas into deionized water to prepare chlorine dioxide aqueous solution, adding EDTA disodium salt into the chlorine dioxide aqueous solution, uniformly mixing and chelating, and adjusting the pH of the solution to 4.0-6.0 to form chlorine dioxide/EDTA complex solution.
Preferably, the concentration of chlorine dioxide in the chlorine dioxide water solution is 0.1-0.17% wt; the molar ratio of EDTA disodium salt to chlorine dioxide in the aqueous solution is 0.5 (1-1.32).
Preferably, the step (2) is specifically: preparing PVP aqueous solution, introducing chlorine dioxide gas to saturate the PVP aqueous solution, and adjusting the pH value of the obtained solution to 4.0-6.0.
Preferably, the concentration of the aqueous solution of PVP is 40-60% wt, the degree of polymerization of PVP is 50-70.
Preferably, the molar ratio of the chlorine dioxide/PVP complex and the chlorine dioxide/EDTA complex is (2-13) to (9-37), and the concentration of the chlorine dioxide/EDTA complex in the solution is 0.63-1.08% wt; the concentration of chlorine dioxide in the solution is 0.08-0.12% wt; the concentration of sodium carbonate in the solution is 0.05-0.1% wt.
More preferably, the concentrations of chlorine dioxide, chlorine dioxide/PVP complex, chlorine dioxide/EDTA complex and sodium carbonate in the solution are respectively C0、CP、CE、CNThen, there are: cPC0=CECN。
Preferably, an aminocarboxylic acid may also be added to the chlorine dioxide solution in step (4).
Preferably, the aminocarboxylic acid is carbamic acid or glycine; further preferably, the aminocarboxylic acid is added to the solution at a concentration of 0.4 to 0.7 times the concentration of the free chlorine dioxide species.
More preferably, when the aminocarboxylic acid is added to the solution, the concentrations of chlorine dioxide, chlorine dioxide/PVP complex, chlorine dioxide/EDTA complex and sodium carbonate in the solution are C0、CP、CE、CNThen, there are: cPCN=μC0CEMu is a constant with a value of 0.3-0.6.
The chlorine dioxide gas used in the present invention has a chlorine content of not more than 5% by weight.
Advantageous effects
The invention has the beneficial effects that:
the chlorine dioxide solution provided by the invention is green and nontoxic, can be used for disinfecting pet environment and pet skin, can be diluted by deionized water and then used or directly used, has no stimulation to pet skin and respiratory tract mucosa, and does not cause poisoning or discomfort after a pet licks.
The chlorine dioxide solution provided by the invention does not contain a metal ion initiator, does not need metal ion initiation, and due to different intermolecular forces of aminocarboxylic acid, PVP, EDTA and chlorine dioxide complexing, the content relationship among the components is specified by the algorithm provided by the invention, so that under the conditions of different use time periods, temperatures, environmental humidity and other factors, when different microorganisms are combined with the complex, the three complexes are matched with each other to generate action, but the chlorine dioxide is quickly released after the initiation without a difference action in a short time, the action duration of the disinfectant is ensured while accurate sterilization is realized, and because the disinfectant is not processed in a simple stable manner, the requirements on storage and use environments are not strict, and the application range is wide. When the algorithm provided by the invention is not used for limiting the relationship among the components, even if the components in the disinfectant are the same, the intermittent disinfection and sterilization performance is weakened or even disappears, the effective time is greatly reduced, and the like.
The PVP with the specific degree of polymerization adopted by the invention is the PVP which is most suitable for being used in the pet environment, and years of experience shows that after the PVP in the degree of polymerization range is complexed with chlorine dioxide, the formed complex has the best effect of killing microorganisms in the pet environment and skin, can realize directional killing, and can not cause the reduction of effective concentration caused by the PVP with other degrees of polymerization contained in the disinfectant and the chlorine dioxide complex, and the disinfection effect is weakened.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The following examples and comparative examples are parallel runs, with the same processing steps and parameters, unless otherwise indicated.
Example 1 preparation of chlorine dioxide solution:
(1) preparing chlorine dioxide/EDTA complex solution;
(2) preparing chlorine dioxide/PVP complex solution;
(3) uniformly mixing chlorine dioxide/EDTA complex solution and chlorine dioxide/PVP complex solution;
(4) and (4) adding sodium carbonate into the solution obtained in the step (3) and uniformly mixing to obtain the stable chlorine dioxide solution.
The step (1) is specifically as follows: introducing chlorine dioxide gas into deionized water to prepare chlorine dioxide aqueous solution, adding EDTA disodium salt into the chlorine dioxide aqueous solution, uniformly mixing and chelating, and adjusting the pH of the solution to 4.0-6.0 to form chlorine dioxide/EDTA complex solution.
In the chlorine dioxide aqueous solution, the concentration of chlorine dioxide is 0.1 percent by weight; the molar ratio of EDTA disodium salt to chlorine dioxide in the aqueous solution was 0.5: 1.
The step (2) is specifically as follows: preparing PVP aqueous solution, introducing chlorine dioxide gas to saturate the PVP aqueous solution, and adjusting the pH value of the obtained solution to 4.0-6.0.
The concentration of PVP aqueous solution is 40 wt%, and the polymerization degree of PVP is 50-70.
The mol ratio of the chlorine dioxide/PVP complex to the chlorine dioxide/EDTA complex is 8:25, and the concentration of the chlorine dioxide/EDTA complex in the solution is 0.8 percent by weight; the concentration of chlorine dioxide in the solution is 0.1% wt; the concentration of sodium carbonate in the solution was 0.06% wt.
Example 2 preparation of chlorine dioxide solution:
(1) preparing chlorine dioxide/EDTA complex solution;
(2) preparing chlorine dioxide/PVP complex solution;
(3) uniformly mixing chlorine dioxide/EDTA complex solution and chlorine dioxide/PVP complex solution;
(4) and (4) adding sodium carbonate into the solution obtained in the step (3) and uniformly mixing to obtain the stable chlorine dioxide solution.
The step (1) is specifically as follows: introducing chlorine dioxide gas into deionized water to prepare chlorine dioxide aqueous solution, adding EDTA disodium salt into the chlorine dioxide aqueous solution, uniformly mixing and chelating, and adjusting the pH of the solution to 4.0-6.0 to form chlorine dioxide/EDTA complex solution.
In the chlorine dioxide aqueous solution, the concentration of chlorine dioxide is 0.1 percent by weight; the molar ratio of EDTA disodium salt to chlorine dioxide in the aqueous solution was 0.5: 1.
The step (2) is specifically as follows: preparing PVP aqueous solution, introducing chlorine dioxide gas to saturate the PVP aqueous solution, and adjusting the pH value of the obtained solution to 4.0-6.0.
The concentration of PVP aqueous solution is 40 wt%, and the polymerization degree of PVP is 50-70.
The concentration of chlorine dioxide/EDTA complex in the solution was 0.8% wt; the concentration of chlorine dioxide in the solution is 0.1% wt; the concentration of sodium carbonate in the solution was 0.06% wt.
In solution is provided with twoThe concentrations of the chlorine oxide, the chlorine dioxide/PVP complex, the chlorine dioxide/EDTA complex and the sodium carbonate are respectively C0、CP、CE、CNThen, there are: cPC0=CECN. The concentration of chlorine dioxide/PVP complex was calculated to be 0.48% wt.
Through performance detection (see details below), in the comparative example in which the proportion of each component is outside the range specified by the algorithm of the invention at 15 days after the pet skin disinfection operation by using the sample is finished, the time efficiency of the disinfectant is remarkably reduced, and the effects of the embodiment and the embodiment 4 are relatively stable, which shows that the proportion relation among the components specified by the algorithm provided by the invention plays a very important role in prolonging the effective time of the disinfectant.
Comparative example 1 preparation of chlorine dioxide solution:
(1) preparing chlorine dioxide/EDTA complex solution;
(2) preparing chlorine dioxide/PVP complex solution;
(3) uniformly mixing chlorine dioxide/EDTA complex solution and chlorine dioxide/PVP complex solution;
(4) and (4) adding sodium carbonate into the solution obtained in the step (3) and uniformly mixing to obtain the stable chlorine dioxide solution.
The step (1) is specifically as follows: introducing chlorine dioxide gas into deionized water to prepare chlorine dioxide aqueous solution, adding EDTA disodium salt into the chlorine dioxide aqueous solution, uniformly mixing and chelating, and adjusting the pH of the solution to 4.0-6.0 to form chlorine dioxide/EDTA complex solution.
In the chlorine dioxide aqueous solution, the concentration of chlorine dioxide is 0.1 percent by weight; the molar ratio of EDTA disodium salt to chlorine dioxide in the aqueous solution was 0.5: 1.
The step (2) is specifically as follows: preparing PVP aqueous solution, introducing chlorine dioxide gas to saturate the PVP aqueous solution, and adjusting the pH value of the obtained solution to 4.0-6.0.
The concentration of PVP aqueous solution is 40 wt%, and the polymerization degree of PVP is 50-70.
The concentration of chlorine dioxide/EDTA complex in the solution was 0.8% wt; the concentration of chlorine dioxide in the solution is 0.1% wt; the concentration of sodium carbonate in the solution was 0.06% wt. The concentration of the chlorine dioxide/PVP complex was 0.6% wt.
Example 3 preparation of chlorine dioxide solution:
(1) preparing chlorine dioxide/EDTA complex solution;
(2) preparing chlorine dioxide/PVP complex solution;
(3) uniformly mixing chlorine dioxide/EDTA complex solution and chlorine dioxide/PVP complex solution;
(4) and (4) adding sodium carbonate into the solution obtained in the step (3) and uniformly mixing to obtain the stable chlorine dioxide solution.
The step (1) is specifically as follows: introducing chlorine dioxide gas into deionized water to prepare chlorine dioxide aqueous solution, adding EDTA disodium salt into the chlorine dioxide aqueous solution, uniformly mixing and chelating, and adjusting the pH of the solution to 4.0-6.0 to form chlorine dioxide/EDTA complex solution.
In the chlorine dioxide aqueous solution, the concentration of chlorine dioxide is 0.1 percent by weight; the molar ratio of EDTA disodium salt to chlorine dioxide in the aqueous solution was 0.5: 1.
The step (2) is specifically as follows: preparing PVP aqueous solution, introducing chlorine dioxide gas to saturate the PVP aqueous solution, and adjusting the pH value of the obtained solution to 4.0-6.0.
The concentration of PVP aqueous solution is 40 wt%, and the polymerization degree of PVP is 50-70.
The mol ratio of the chlorine dioxide/PVP complex to the chlorine dioxide/EDTA complex is 8:25, and the concentration of the chlorine dioxide/EDTA complex in the solution is 0.8 percent by weight; the concentration of chlorine dioxide in the solution is 0.1% wt; the concentration of sodium carbonate in the solution was 0.06% wt.
And (4) adding aminocarboxylic acid into the chlorine dioxide solution.
The aminocarboxylic acid is carbamic acid; the aminocarboxylic acid is added to the solution at a concentration of 0.5 times the concentration of the free chlorine dioxide species.
Example 4 preparation of chlorine dioxide solution:
(1) preparing chlorine dioxide/EDTA complex solution;
(2) preparing chlorine dioxide/PVP complex solution;
(3) uniformly mixing chlorine dioxide/EDTA complex solution and chlorine dioxide/PVP complex solution;
(4) and (4) adding sodium carbonate into the solution obtained in the step (3) and uniformly mixing to obtain the stable chlorine dioxide solution.
The step (1) is specifically as follows: introducing chlorine dioxide gas into deionized water to prepare chlorine dioxide aqueous solution, adding EDTA disodium salt into the chlorine dioxide aqueous solution, uniformly mixing and chelating, and adjusting the pH of the solution to 4.0-6.0 to form chlorine dioxide/EDTA complex solution.
In the chlorine dioxide aqueous solution, the concentration of chlorine dioxide is 0.1 percent by weight; the molar ratio of EDTA disodium salt to chlorine dioxide in the aqueous solution was 0.5: 1.
The step (2) is specifically as follows: preparing PVP aqueous solution, introducing chlorine dioxide gas to saturate the PVP aqueous solution, and adjusting the pH value of the obtained solution to 4.0-6.0.
The concentration of PVP aqueous solution is 40 wt%, and the polymerization degree of PVP is 50-70.
And (4) adding aminocarboxylic acid into the chlorine dioxide solution.
The amino carboxylic acid is carbamic acid or glycine; further preferably, the aminocarboxylic acid is added to the solution at a concentration of 0.5 times the concentration of the free chlorine dioxide species.
The concentration of chlorine dioxide/EDTA complex in the solution was 0.8% wt; the concentration of chlorine dioxide in the solution is 0.1% wt; the concentration of sodium carbonate in the solution was 0.06% wt.
The concentrations of chlorine dioxide, chlorine dioxide/PVP complex, chlorine dioxide/EDTA complex, sodium carbonate and aminocarboxylic acid in the solution are respectively C0、CP、CE、CNThen, there are: cPCN=μC0CEMu is a constant, and the value is 0.6. The concentration of chlorine dioxide/PVP complex was calculated to be 0.8% wt.
Comparative example 2 preparation of chlorine dioxide solution:
(1) preparing chlorine dioxide/EDTA complex solution;
(2) preparing chlorine dioxide/PVP complex solution;
(3) uniformly mixing chlorine dioxide/EDTA complex solution and chlorine dioxide/PVP complex solution;
(4) and (4) adding sodium carbonate into the solution obtained in the step (3) and uniformly mixing to obtain the stable chlorine dioxide solution.
The step (1) is specifically as follows: introducing chlorine dioxide gas into deionized water to prepare chlorine dioxide aqueous solution, adding EDTA disodium salt into the chlorine dioxide aqueous solution, uniformly mixing and chelating, and adjusting the pH of the solution to 4.0-6.0 to form chlorine dioxide/EDTA complex solution.
In the chlorine dioxide aqueous solution, the concentration of chlorine dioxide is 0.1 percent by weight; the molar ratio of EDTA disodium salt to chlorine dioxide in the aqueous solution was 0.5: 1.
The step (2) is specifically as follows: preparing PVP aqueous solution, introducing chlorine dioxide gas to saturate the PVP aqueous solution, and adjusting the pH value of the obtained solution to 4.0-6.0.
The concentration of PVP aqueous solution is 40 wt%, and the polymerization degree of PVP is 50-70.
And (4) adding aminocarboxylic acid into the chlorine dioxide solution.
The amino carboxylic acid is carbamic acid or glycine; further preferably, the aminocarboxylic acid is added to the solution at a concentration of 0.5 times the concentration of the free chlorine dioxide species.
The concentration of chlorine dioxide/EDTA complex in the solution was 0.8% wt; the concentration of chlorine dioxide in the solution is 0.1% wt; the concentration of sodium carbonate in the solution was 0.06% wt. The concentration of the chlorine dioxide/PVP complex was 0.9% wt.
The product performance is as follows:
taking 21 pet dogs of the same breed under the same feeding environment, detecting and recording the microbial condition of the neck skin, randomly dividing the pet dogs into 7 groups, respectively corresponding to the products obtained in examples 1-4, comparative examples 1 and 2 and a blank group (the test sample is equal to deionized water), respectively spraying the test sample on the whole body skin surface of the pet dog of the corresponding group according to the dosage of 5mL/Kg and massaging, repeating the operation once every three days, then detecting and recording the microbial condition of the same position of the neck skin every three days, and obtaining the result:
on the third day after the operation is finished, the types and the number of blank groups of microorganisms are increased; on the third day after the operation is finished, the microbial killing rates of other groups are respectively from high to low in example 2 (97%), example 1 (95%), comparative example 1 (97%), example 4 (94%), example 3 (95%) and comparative example 2 (91%), so that the relatively simple formula provided by the invention can achieve very high killing effect only in terms of the microbial killing rate in a short period, and the pet using the sample does not have the symptoms of frequent scratching, diarrhea, sneezing and the like, and the product is non-irritant and has no toxic or side effect.
On the 15 th day after the operation is finished, the types of the blank group microorganisms are increased by 3 compared with the third day, and the number of the blank group microorganisms is also increased; on the 15 th day after the operation is finished, the killing rates of other groups of microorganisms are respectively example 2 (86%), example 1 (83%), comparative example 1 (58%), example 4 (91%), example 3 (89%) and comparative example 2 (62%), and it can be seen that after the aminocarboxylic acid is added into the formula, the effective time of the disinfectant is prolonged, and when the proportion of each component adopted in the comparative example is out of the range specified by the algorithm of the invention, the aging of the disinfectant is remarkably reduced, which shows that the proportion relation among the components specified by the algorithm provided by the invention plays a very important role in prolonging the effective time of the disinfectant.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A chlorine dioxide solution characterized by: comprises chlorine dioxide, chlorine dioxide/PVP complex, chlorine dioxide/EDTA complex, sodium carbonate and deionized water.
2. A chlorine dioxide solution as claimed in claim 1, characterized in that: the mol ratio of the chlorine dioxide/PVP complex and the chlorine dioxide/EDTA complex is (2-13): (9-37), and the concentration of the chlorine dioxide/EDTA complex in the solution is 0.63-1.08 percent by weight; the concentration of chlorine dioxide in the solution is 0.08-0.12% wt; the concentration of sodium carbonate in the solution is 0.05-0.1% wt.
3. A preferred chlorine dioxide solution according to claim 2, characterized in that: the chlorine dioxide solution also comprises aminocarboxylic acid; the amount concentration of the substance added into the amino carboxylic acid in the solution is 0.4-0.7 times of that of the free chlorine dioxide substance.
4. A method for producing a chlorine dioxide solution as claimed in any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) preparing chlorine dioxide/EDTA complex solution;
(2) preparing chlorine dioxide/PVP complex solution;
(3) uniformly mixing chlorine dioxide/EDTA complex solution and chlorine dioxide/PVP complex solution;
(4) and (4) adding sodium carbonate into the solution obtained in the step (3) and uniformly mixing to obtain the stable chlorine dioxide solution.
5. The method for producing a chlorine dioxide solution according to claim 4, characterized in that: the step (1) is specifically as follows: introducing chlorine dioxide gas into deionized water to prepare chlorine dioxide aqueous solution, adding EDTA disodium salt into the chlorine dioxide aqueous solution, uniformly mixing and chelating, and adjusting the pH of the solution to 4.0-6.0 to form chlorine dioxide/EDTA complex solution.
6. The method for producing a chlorine dioxide solution according to claim 5, characterized in that: in the step (1), the concentration of chlorine dioxide in the chlorine dioxide water solution is 0.1-0.17 wt%; the molar ratio of EDTA disodium salt to chlorine dioxide in the aqueous solution is 0.5 (1-1.32).
7. The method for producing a chlorine dioxide solution according to claim 4, characterized in that: the step (2) is specifically as follows: preparing PVP aqueous solution, introducing chlorine dioxide gas to saturate the PVP aqueous solution, and adjusting the pH value of the obtained solution to 4.0-6.0.
8. The method for producing a chlorine dioxide solution according to claim 7, characterized in that: in the step (2), the concentration of the PVP aqueous solution is 40-60% wt, and the polymerization degree of the PVP is 50-70.
9. The method for producing a chlorine dioxide solution according to claim 4, characterized in that: the concentration of the chlorine dioxide/EDTA complex in the solution is 0.63-1.08% wt; the concentration of chlorine dioxide in the solution is 0.08-0.12% wt; the concentration of sodium carbonate in the solution is 0.05-0.1% wt; the concentrations of chlorine dioxide, chlorine dioxide/PVP complex, chlorine dioxide/EDTA complex and sodium carbonate in the solution are respectively C0、CP、CE、CNThen, there are: cPC0=CECN。
10. The method for producing a chlorine dioxide solution according to claim 4, characterized in that: adding aminocarboxylic acid into the chlorine dioxide solution in the step (4); the amino carboxylic acid is carbamic acid or glycine; the quantity concentration of the substance added into the amino carboxylic acid in the solution is 0.4 to 0.7 time of the quantity concentration of the free chlorine dioxide substance; the concentration of the chlorine dioxide/EDTA complex in the solution is 0.63-1.08% wt; the concentration of chlorine dioxide in the solution is 0.08-0.12% wt; the concentration of sodium carbonate in the solution is 0.05-0.1% wt; the concentrations of chlorine dioxide, chlorine dioxide/PVP complex, chlorine dioxide/EDTA complex, sodium carbonate and aminocarboxylic acid in the solution are respectively C0、CP、CE、CNThen, there are: cPCN=μC0CEMu is a constant with a value of 0.3-0.6.
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