JP6491010B2 - Equipment for producing sterilized water containing chlorine dioxide - Google Patents

Description

  The present invention is used to produce sterilized water (chlorine dioxide-containing sterilized water) that contains chlorine dioxide and is used for sterilization of water for food processing facilities and buildings, livestock production, fresh products, hospital sterilized water, purified water, waste water, etc. The present invention relates to a chlorine dioxide-containing sterilizing water generator.

  Water containing chlorine dioxide is used as a disinfectant with a sterilizing or deodorizing function by utilizing the strong oxidizing power of dissolved chlorine dioxide gas, and sterilizes fresh products such as vegetables, seafood and meat. It is widely used for sterilization, such as sterilization of reverse osmosis membranes of artificial dialysis machines, sterilization of drinking water, building water supply, etc., sterilization of livestock, and sterilization water of hospitals. And from the strong disinfection power of chlorine dioxide, chlorine dioxide gas can be used at a low concentration, and the concentration is adjusted depending on the sterilization application or the object of sterilization.

  As a method for producing water containing chlorine dioxide, for example, Japanese translations of PCT publication No. 2004-536761 (patent document 1) and JP 2013-144085 (patent document 2) include sodium chlorite sodium. A method is disclosed in which ions are ion exchanged with hydrogen ions to produce chlorous acid and then chlorite is oxidized by a catalytic reaction to obtain water containing chlorine dioxide.

Japanese translation of PCT publication No. 2004-536761 JP2013-1444085A

  Since chlorine dioxide-containing water used for sterilization usually has a low chlorine dioxide concentration, the present inventors have succeeded in efficiently and continuously performing sodium ionization and catalytic oxidation of sodium chlorite in an aqueous solution. In order to obtain chlorine dioxide-containing water, a sodium chlorite aqueous solution with a concentration of several percent is used as a raw material, which is supplied to a liquid feed pipe for supplying dilution water to the ion exchange means, and the liquid feed pipe A diluted sodium chlorite aqueous solution is obtained, and the resulting diluted sodium chlorite aqueous solution is subjected to ion exchange and catalytic oxidation to obtain chlorine dioxide-containing water, and the resulting chlorine dioxide-containing water is further diluted with diluted water. An attempt was made to obtain sterilized water containing chlorine dioxide by dilution.

  However, as a result of repeated studies by the present inventors, in this way, when obtaining sterilized water containing chlorine dioxide, the diluted sodium chlorite is ion-exchanged and converted to chlorite. When the concentration of the aqueous sodium chlorite solution is high, the pH of the aqueous chlorous acid solution generated by the ion exchange means is lowered. The pH of the aqueous chlorous acid solution obtained by the ion exchange means is the same as that of the chlorine dioxide-dissolved water obtained by the catalytic oxidation means. Here, when the chlorine dioxide-dissolved water has a high chlorine dioxide concentration and a low pH, there is a risk that chlorine dioxide gas dissolved in the chlorine dioxide-dissolved water is released from the water. Further, when the pH of chlorine dioxide-dissolved water is low and strongly acidic, the diluted solution becomes an acidic solution even when diluted and used.

  Accordingly, an object of the present invention is to provide an apparatus capable of producing sterilizing water containing chlorine dioxide without causing the pH of the aqueous solution of chlorous acid after ion exchange and the aqueous solution after catalytic oxidation to be too low. is there.

The problems in the above prior art are solved by the present invention described below.
That is, the present invention comprises an ion exchange means for obtaining a chlorite aqueous solution by ion-exchanging sodium ions of sodium chlorite in a diluted sodium chlorite aqueous solution to hydrogen ions,
Catalytic oxidation means for oxidizing chlorine acid in the aqueous chlorous acid solution with an oxidation catalyst to obtain chlorine dioxide-dissolved water;
Diluted water for diluting sodium chlorite aqueous solution is supplied from one end side, and the dilute sodium chlorite aqueous solution feed pipe connected to the ion exchange means at the other end side,
A high-concentration sodium chlorite aqueous solution feed pipe to which a high-concentration sodium chlorite aqueous solution is supplied from one end side and the other end side is connected to the diluted sodium chlorite aqueous solution feed pipe;
One end side is connected to the ion exchange means, the other end side is connected to the catalytic oxidation means, and a chlorous acid aqueous solution feeding pipe through which a chlorous acid aqueous solution is fed;
Dilution water for diluting chlorine dioxide dissolved water is supplied from one end side, and the other end side is a chlorine dioxide-containing sterilizing water feed pipe that leads to a use point,
One end side is connected to the catalytic oxidation means, the other end side is connected to a chlorine dioxide-containing sterilized water supply pipe, and a chlorine dioxide-dissolved water supply pipe through which chlorine dioxide-dissolved water is supplied;
The dilute sodium chlorite aqueous solution feed pipe branches off from the dilute sodium chlorite aqueous solution feed pipe, and the dilute sodium chlorite aqueous solution feed pipe in the dilute sodium chlorite aqueous solution feed pipe transfers the dilute sodium chlorite aqueous solution feed pipe. Dilute sodium chlorite aqueous solution bypass pipe for supplying to the liquid pipe;
A high-concentration sodium chlorite aqueous solution feed pump installed in the high-concentration sodium chlorite aqueous solution feed pipe, and for feeding the high-concentration sodium chlorite aqueous solution;
A bypass pipe installed in the dilute sodium chlorite aqueous solution bypass pipe for feeding a part of the dilute sodium chlorite aqueous solution in the dilute sodium chlorite aqueous solution feed pipe into the chlorite aqueous solution feed pipe A feed pump;
A chlorine dioxide-dissolved water feed pump installed in the chlorine dioxide-dissolved water feed pipe, for delivering chlorine dioxide-dissolved water;
A pH measuring means installed in the chlorous acid aqueous solution feeding pipe for measuring the pH of the chlorous acid aqueous solution;
Chlorine dioxide concentration measuring means installed in the chlorine dioxide-containing sterilized water feed pipe and measuring the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water;
Electrically connected to the pH measuring means and the bypass pipe liquid feeding pump, the management pH value is stored, the pH value sent from the pH measuring means is compared with the management pH value, and the pH measuring means If there is a difference between the pH value sent and the control pH value, the pH of the aqueous chlorous acid solution is determined from the difference between the pH value sent from the pH measuring means and the control pH value. Calculating a liquid feed flow rate of the bypass pipe liquid feed pump necessary for the control pH value, and sending a liquid feed flow rate change command to the bypass pipe liquid feed pump;
The chlorine dioxide concentration measuring means and the chlorine dioxide-dissolved water feed pump are electrically connected to store the management chlorine dioxide concentration value, and the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means and the management chlorine dioxide If there is a difference between the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means and the control chlorine dioxide concentration value, the dioxide dioxide sent from the chlorine dioxide concentration measuring means is compared. From the difference between the chlorine concentration value and the control chlorine dioxide concentration value, the chlorine dioxide-dissolved water feed pump required to make the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water the control chlorine dioxide concentration value Calculating a flow rate, and sending a liquid feed flow rate change command to the chlorine dioxide-dissolved water feed pump;
A device for producing chlorine dioxide-containing sterilizing water is provided.

  According to the present invention, the pH of the aqueous chlorous acid solution after ion exchange and the aqueous solution after catalyst oxidation is not too low, specifically, the pH of the aqueous solution of chlorous acid after ion exchange and the aqueous solution after catalyst oxidation. 5 to 6.5, an apparatus capable of producing sterilizing water containing chlorine dioxide can be provided.

It is a flowchart of the example of the form of the production | generation apparatus of the chlorine dioxide containing disinfection water of this invention. It is a flowchart of the example of the form of the production | generation apparatus of the chlorine dioxide containing disinfection water of this invention. It is a flowchart of the example of the form of the production | generation apparatus of the chlorine dioxide containing disinfection water of this invention.

An apparatus for producing chlorine dioxide-containing sterilizing water according to a first aspect of the present invention is an ion for obtaining an aqueous solution of chlorite by ion-exchanging sodium ions of sodium chlorite in a diluted aqueous solution of sodium chlorite to hydrogen ions. Exchange means,
Catalytic oxidation means for oxidizing chlorine acid in the aqueous chlorous acid solution with an oxidation catalyst to obtain chlorine dioxide-dissolved water;
Diluted water for diluting sodium chlorite aqueous solution is supplied from one end side, and the dilute sodium chlorite aqueous solution feed pipe connected to the ion exchange means at the other end side,
A high-concentration sodium chlorite aqueous solution feed pipe to which a high-concentration sodium chlorite aqueous solution is supplied from one end side and the other end side is connected to the diluted sodium chlorite aqueous solution feed pipe;
One end side is connected to the ion exchange means, the other end side is connected to the catalytic oxidation means, and a chlorous acid aqueous solution feeding pipe through which a chlorous acid aqueous solution is fed;
Dilution water for diluting chlorine dioxide dissolved water is supplied from one end side, and the other end side is a chlorine dioxide-containing sterilizing water feed pipe that leads to a use point,
One end side is connected to the catalytic oxidation means, the other end side is connected to a chlorine dioxide-containing sterilized water supply pipe, and a chlorine dioxide-dissolved water supply pipe through which chlorine dioxide-dissolved water is supplied;
The dilute sodium chlorite aqueous solution feed pipe branches off from the dilute sodium chlorite aqueous solution feed pipe, and the dilute sodium chlorite aqueous solution feed pipe in the dilute sodium chlorite aqueous solution feed pipe transfers the dilute sodium chlorite aqueous solution feed pipe. Dilute sodium chlorite aqueous solution bypass pipe for supplying to the liquid pipe;
A high-concentration sodium chlorite aqueous solution feed pump installed in the high-concentration sodium chlorite aqueous solution feed pipe, and for feeding the high-concentration sodium chlorite aqueous solution;
A bypass pipe installed in the dilute sodium chlorite aqueous solution bypass pipe for feeding a part of the dilute sodium chlorite aqueous solution in the dilute sodium chlorite aqueous solution feed pipe into the chlorite aqueous solution feed pipe A feed pump;
A chlorine dioxide-dissolved water feed pump installed in the chlorine dioxide-dissolved water feed pipe, for delivering chlorine dioxide-dissolved water;
A pH measuring means installed in the chlorous acid aqueous solution feeding pipe for measuring the pH of the chlorous acid aqueous solution;
Chlorine dioxide concentration measuring means installed in the chlorine dioxide-containing sterilized water feed pipe and measuring the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water;
Electrically connected to the pH measuring means and the bypass pipe liquid feeding pump, the management pH value is stored, the pH value sent from the pH measuring means is compared with the management pH value, and the pH measuring means If there is a difference between the pH value sent and the control pH value, the pH of the aqueous chlorous acid solution is determined from the difference between the pH value sent from the pH measuring means and the control pH value. Calculating a liquid feed flow rate of the bypass pipe liquid feed pump necessary for the control pH value, and sending a liquid feed flow rate change command to the bypass pipe liquid feed pump;
The chlorine dioxide concentration measuring means and the chlorine dioxide-dissolved water feed pump are electrically connected to store the management chlorine dioxide concentration value, and the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means and the management chlorine dioxide If there is a difference between the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means and the control chlorine dioxide concentration value, the dioxide dioxide sent from the chlorine dioxide concentration measuring means is compared. From the difference between the chlorine concentration value and the control chlorine dioxide concentration value, the chlorine dioxide-dissolved water feed pump required to make the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water the control chlorine dioxide concentration value Calculating a flow rate, and sending a liquid feed flow rate change command to the chlorine dioxide-dissolved water feed pump;
A device for producing sterilizing water containing chlorine dioxide, characterized by comprising:

  The production | generation apparatus of the chlorine dioxide containing disinfection water of this invention is demonstrated with reference to FIG.

  FIG. 1 is a flow diagram of an embodiment of a chlorine dioxide-containing sterilizing water generator according to the present invention. The apparatus for producing chlorine dioxide-containing sterilizing water shown in FIG. 1 has an ion exchange means 2 and a catalytic oxidation means 5. 1 includes a high-concentration sodium chlorite aqueous solution feeding pipe 42, a diluted sodium chlorite aqueous solution feeding pipe 41, and a chlorite aqueous solution feeding pipe 43. , A chlorine dioxide-dissolved water feed pipe 44, a chlorine dioxide-containing sterilized water feed pipe 47, and a dilute sodium chlorite aqueous solution bypass pipe 48.

The ion exchange means 2 is means for obtaining a chlorite aqueous solution by ion exchange of sodium ions of sodium chlorite in the diluted sodium chlorite aqueous solution 51 to hydrogen ions. The ion exchange means is not particularly limited as long as it is an H ⁺ type ion exchanger capable of exchanging sodium ions in an aqueous sodium chlorite solution into hydrogen ions. Examples of the H ⁺ type ion exchanger include an H ⁺ type cation exchange resin having a cation exchange group, and the counter cation of the cation exchange group is a hydrogen ion, and an H ⁺ type inorganic ion exchange. Examples include the body. Examples of the H ⁺ type inorganic ion exchanger include H ⁺ type zeolites, H ⁺ type metal oxides such as H ⁺ type zirconium and antimony oxide, and ferrocyanide complexes.

  The catalytic oxidation means 5 is a means for oxidizing the chlorous acid in the aqueous chlorous acid solution (after pH adjustment) 52 with an oxidation catalyst to obtain the chlorine dioxide-dissolved water 53. The catalyst oxidation means 5 is not particularly limited as long as it is an oxidation catalyst that can oxidize chlorous acid in an aqueous chlorous acid solution to generate chlorine dioxide-dissolved water. Examples of the catalytic oxidation means include alumina on which Pd, Pt and the like are supported, an zeolite on which Pd, Pt and the like are supported, and an oxidation catalyst such as manganese dioxide.

  The diluted sodium chlorite aqueous solution feeding pipe 41 is a liquid feeding pipe for feeding the dilution water 32 for diluting the high concentration sodium chlorite aqueous solution 31 from the outside of the apparatus to the ion exchange means 2. The dilution water 32 for diluting the sodium chlorite aqueous solution is supplied from the side, and the other end side is connected to the ion exchange means 2. In the middle of the diluted sodium chlorite aqueous solution feeding pipe 41, a high concentration sodium chlorite aqueous solution feeding pipe 42 is connected. The high concentration sodium chlorite aqueous solution feeding pipe 42 supplies the high concentration sodium chlorite aqueous solution 31 to the dilution water 32 for diluting the sodium chlorite aqueous solution in the diluted sodium chlorite aqueous solution feeding pipe 41. The high concentration sodium chlorite aqueous solution 31 is supplied from one end side, and the other end side is connected to the diluted sodium chlorite aqueous solution supply tube 41. Then, the dilute sodium chlorite aqueous solution 31 is supplied to the dilute water 32 for diluting the sodium chlorite aqueous solution in the dilute sodium chlorite aqueous solution feed pipe 41, thereby supplying the dilute sodium chlorite aqueous solution 31. In the tube 41, a diluted sodium chlorite aqueous solution 51 is prepared.

  The chlorous acid aqueous solution feeding pipe 43 connects the ion exchange means 2 and the catalytic oxidation means 5, and feeds the aqueous chlorous acid solution generated by the ion exchange means 2 to the catalytic oxidation means 5. One end side is connected to the ion exchange means 2, and the other end side is connected to the catalytic oxidation means 5.

  The chlorine dioxide-containing sterilizing water liquid feeding pipe 47 is a liquid feeding pipe for feeding the dilution water 33a for diluting the chlorine dioxide-dissolved water 53 from the outside of the apparatus to the use point, and chlorine dioxide-dissolved water from one end side. Dilution water 33a for dilution is supplied, and the other end is connected to a use point. A chlorine dioxide-dissolved water feeding pipe 44 is connected to the middle of the chlorine dioxide-containing sterilizing water feeding pipe 47. This chlorine dioxide-dissolved water feed pipe 44 is chlorine dioxide obtained by oxidizing chlorine dioxide with diluting water 33a for diluting chlorine dioxide-dissolved water in the chlorine dioxide-containing sterilizing water feed pipe 47 by the catalytic oxidation means 5. It is a liquid feed pipe for supplying the dissolved water 53, and one end side is connected to the catalytic oxidation means 5, and the other end side is connected to the chlorine dioxide containing sterilized water liquid feed pipe 47. Then, the chlorine dioxide-dissolved water 53 is supplied to the diluted water 33a for diluting chlorine dioxide-dissolved water in the chlorine dioxide-containing sterilized water feed pipe 47. Chlorine-containing sterilized water 36 is produced.

  The dilute sodium chlorite aqueous solution bypass pipe 48 does not pass a part of the dilute sodium chlorite aqueous solution 51 in the dilute sodium chlorite liquid feed pipe 41 without passing through the ion exchange means 2. 43 is a bypass pipe for supplying the liquid into the dilute sodium chlorite aqueous solution feed pipe 41 and is connected to the chlorite aqueous solution feed pipe 43. The branch position of the diluted sodium chlorite aqueous solution bypass pipe 48, that is, the position where the diluted sodium chlorite aqueous solution bypass pipe 48 is connected to the diluted sodium chlorite aqueous solution feed pipe 41 is a high-concentration sodium chlorite aqueous solution feed pipe. 42 is after the position connected to the diluted sodium chlorite aqueous solution feeding pipe 41 and before the ion exchange means 2. The position where the diluted sodium chlorite aqueous solution bypass pipe 48 is connected to the chlorite aqueous solution feeding pipe 43 is after the ion exchange means 2 and before the pH measurement means 3. Then, the diluted sodium chlorite aqueous solution 51 is added to the chlorous acid aqueous solution (before pH adjustment) 54 in the chlorous acid aqueous solution feeding pipe 43, that is, the chlorine dioxide aqueous solution immediately after the ion exchange treatment by the ion exchange means 2. By being supplied, the diluted sodium chlorite aqueous solution 51 is mixed with the chlorite aqueous solution (before pH adjustment) 54 in the chlorous acid aqueous solution feeding pipe 43, and the pH of the chlorite aqueous solution is adjusted, A chlorous acid aqueous solution (after pH adjustment) is obtained.

  In the device for generating chlorine dioxide-containing sterilizing water shown in FIG. 1, a high-concentration sodium chlorite aqueous solution feed pump 11 is installed in a high-concentration sodium chlorite aqueous solution feed pipe 42. The high-concentration sodium chlorite aqueous solution feed pump 11 is a feed pump for supplying the high-concentration sodium chlorite aqueous solution 31 in the diluted sodium chlorite aqueous solution feed pipe 41 by adjusting the supply amount. is there.

  In the chlorine dioxide-containing sterilizing water generator shown in FIG. 1, the chlorine dioxide-dissolved water feed pump 13 is installed in the chlorine dioxide-dissolved water feed pipe 44. The chlorine dioxide-dissolved water feed pump 13 is a feed pump for feeding the chlorine dioxide-dissolved water 53 obtained by the catalytic oxidation means 5 to the chlorine dioxide-containing sterilizing water feed pipe 47.

  Moreover, in the production apparatus for chlorine dioxide-containing sterilizing water shown in FIG. 1, the bypass pipe liquid feed pump 16 is installed in the diluted sodium chlorite aqueous solution bypass pipe 48. The bypass pipe liquid feed pump 16 extracts a part of the diluted sodium chlorite aqueous solution feed pipe 51 from the diluted sodium chlorite aqueous solution feed pipe 41, It is a liquid feed pump for supplying the sodium chlorate aqueous solution 51 by adjusting the supply amount.

  Further, in the chlorine dioxide-containing sterilizing water generator shown in FIG. 1, the pH of the chlorite aqueous solution is measured in the chlorite aqueous solution feeding pipe 43 after the position where the diluted sodium chlorite aqueous solution bypass pipe 48 is connected. PH measuring means 3 is provided for this purpose.

  In the chlorine dioxide-containing sterilizing water generating apparatus shown in FIG. 1, chlorine dioxide concentration measuring means 7 for measuring the chlorine dioxide concentration in the chlorine dioxide-containing sterilizing water 36 is provided in the chlorine dioxide-containing sterilizing water feeding pipe 47. is set up.

  Then, the chlorine dioxide-containing sterilizing water generating device shown in FIG. 1 is electrically connected to the pH measuring means 3 and the bypass pipe liquid feeding pump 16, the management pH value is stored, and the pH is sent from the pH measuring means 3. If there is a difference between the pH value sent from the pH measuring means 3 and the managed pH value, the pH value sent from the pH measuring means 3 and the managed pH value are compared. From the difference, the flow rate of the dilute sodium chlorite aqueous solution 51 of the bypass pipe feed pump 16 necessary for setting the pH of the chlorite aqueous solution (after pH adjustment) to the control pH value is calculated and bypassed. It has the 1st calculating part 26 which sends a liquid sending flow rate change command to a pipe liquid feeding pump. The first calculation unit 26 stores the management pH value in the storage unit, and when there is a difference between the pH value sent from the pH measurement unit 3 and the management pH value, the first calculation unit 26 sends it from the pH measurement unit 3. From the difference between the incoming pH value and the control pH value, the dilute sodium chlorite aqueous solution 51 of the bypass pipe feed pump 16 required to bring the pH of the chlorite aqueous solution (after pH adjustment) to the control pH value. Is a computer in which a program for sending a liquid-feeding flow rate change command to the bypass pipe liquid-feeding pump 16 is incorporated so as to calculate the liquid-feeding flow rate. The management pH value refers to the set value of the pH value of the aqueous chlorous acid solution used for oxidation in the catalytic oxidation means 5. In addition, the flow rate of the dilute sodium chlorite aqueous solution of the bypass pipe feed pump, which is necessary to set the pH of the aqueous chlorous acid solution (after pH adjustment) to the control pH value, is calculated. When the pH value measured by the pH measuring unit is higher than the control pH value, the flow rate of the bypass pipe pump is decreased and the pH value measured by the pH measuring unit is controlled. Refers to adjustment to a pH value, and when the pH value measured by the pH measurement means is lower than the control pH value, the liquid flow rate of the bypass pipe liquid feed pump is increased to measure the pH. It means that the pH value measured by the means is adjusted to the control pH value. It should be noted that when there is a difference between the pH value measured by the pH measuring means and the management pH value, a pH difference that requires sending a command to change the flow rate of the bypass pipe liquid feed pump ( The effective pH difference is appropriately selected depending on the use of the sterilizing water, the set value of the chlorine dioxide concentration in the sterilizing water, and the like.

  In the apparatus for producing chlorine dioxide-containing sterilizing water shown in FIG. 1, the dilute sodium chlorite aqueous solution is mixed with the chlorous acid aqueous solution obtained by the ion exchange means 2 to be supplied to the catalytic oxidation means 5. The pH of the aqueous chlorous acid solution is adjusted. And the sodium chlorite between the outlet of the ion exchange means and the position where the dilute sodium chlorite aqueous solution bypass pipe is connected is the aqueous chlorous acid solution before pH adjustment. In the present invention, before this pH adjustment The aqueous chlorous acid solution is described as an aqueous chlorous acid solution (before pH adjustment) 54. Further, the sodium chlorite from the position where the dilute sodium chlorite aqueous solution bypass pipe is connected to the catalytic oxidation means 5 is the pH-adjusted chlorite aqueous solution. In the present invention, this pH-adjusted sub-chlorite solution is used. The aqueous chloric acid solution is referred to as an aqueous chlorous acid solution (after pH adjustment) 52.

  Further, in the chlorine dioxide-containing sterilizing water generator shown in FIG. 1, the chlorine dioxide concentration measuring means 7 and the chlorine dioxide-dissolved water feed pump 13 are electrically connected, the management chlorine dioxide concentration value is stored, and the chlorine dioxide concentration measurement is performed. When the chlorine dioxide concentration value sent from the means 7 is compared with the management chlorine dioxide concentration value, and there is a difference between the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means 7 and the management chlorine dioxide concentration value Is necessary to change the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water to the management chlorine dioxide concentration value from the difference between the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means 7 and the management chlorine dioxide concentration value. A second calculation unit is provided that calculates a liquid feed flow rate of the chlorine dioxide-dissolved water feed pump 13 and sends a liquid feed flow rate change command to the chlorine dioxide-dissolved water feed pump 13. The second arithmetic unit stores the management chlorine dioxide concentration in the storage unit, and if there is a difference between the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means 7 and the management chlorine dioxide concentration value, From the difference between the chlorine dioxide concentration value sent from the chlorine concentration measuring means 7 and the management chlorine dioxide concentration value, the chlorine dioxide necessary to change the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water to the management chlorine dioxide concentration value An electronic computer in which a program for sending a liquid feed flow rate change command to the chlorine dioxide dissolved water feed pump 13 is incorporated so that the liquid feed flow rate of the dissolved water feed pump 13 is calculated and changed to the liquid feed flow rate. is there. The management chlorine dioxide concentration value refers to a set value of the chlorine dioxide concentration of the chlorine dioxide-containing sterilizing water 36 for manufacturing purposes. In addition, the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water is calculated as the flow rate of the chlorine dioxide-dissolved water feed pump required to make the controlled chlorine dioxide concentration value, and changing to that feed rate is When the chlorine dioxide concentration value measured by the chlorine concentration measuring means is larger than the management chlorine dioxide concentration value, the chlorine dioxide concentration measuring means is measured by reducing the feed flow rate of the chlorine dioxide-dissolved water feed pump. This refers to adjustment so that the chlorine dioxide concentration value becomes the controlled chlorine dioxide concentration value. If the chlorine dioxide concentration value measured by the chlorine dioxide concentration measuring means is smaller than the controlled chlorine dioxide concentration value, Increase the flow rate of the chlorine-dissolved water pump to adjust the chlorine dioxide concentration value measured by the chlorine dioxide concentration measurement means to the controlled chlorine dioxide concentration value. It refers to the Rukoto. A command to change the flow rate of the chlorine dioxide-dissolved water feed pump when there is a difference between the chlorine dioxide concentration value measured by the chlorine dioxide concentration measuring means and the management chlorine dioxide concentration value Is selected as appropriate depending on the use of the sterilizing water, the set value of the chlorine dioxide concentration in the sterilizing water, and the like. Moreover, the program for a 1st calculating part and the 2nd calculating part may be integrated in the same electronic computer, and may each be integrated in a separate electronic computer.

  Moreover, in the production | generation apparatus of chlorine dioxide containing sterilization water shown in FIG. 1, the pressurization pump 12 is installed in the diluted sodium chlorite aqueous solution feeding pipe 41 before this high concentration sodium chlorite aqueous solution supply position. . The pressurizing pump 12 is a pump that is installed to secure a hydraulic pressure from the ion exchange means 2 to the catalytic oxidation means 5, but the installation is optional. For example, the hydraulic pressure from the ion exchange means 2 to the catalytic oxidation means 5 can be secured by water pressure from the water supply without installing the pressurizing pump 12.

  Further, in the chlorine dioxide-containing sterilizing water generating device shown in FIG. 1, the pressurizing pump 15 is installed in the chlorine dioxide-containing sterilizing liquid feed pipe 47 before the supply position of the chlorine dioxide-dissolved water. The pressurizing pump 15 is a pump that is installed to ensure the liquid pressure of the chlorine dioxide-containing sterilizing water supplied to the use point, but the installation is arbitrary. For example, the hydraulic pressure of chlorine dioxide-containing sterilizing water can be maintained with the water pressure from the water supply without installing the pressurizing pump 15.

  Next, a method for producing chlorine dioxide-containing sterilized water using the chlorine dioxide-containing sterilized water generator shown in FIG. 1 will be described. First, a high concentration sodium chlorite aqueous solution is supplied to the high concentration sodium chlorite aqueous solution supply pipe 42 while supplying the diluted sodium chlorite aqueous solution dilution water 32 to the diluted sodium chlorite aqueous solution supply pipe 41. 31 is supplied. The high concentration sodium chlorite 31 is supplied to the high concentration sodium chlorite aqueous solution feeding pipe 42 while supplying the diluted sodium chlorite aqueous solution dilution water 32 to the diluted sodium chlorite aqueous solution feeding pipe 41. In the diluted sodium chlorite aqueous solution feed pipe 41, a diluted sodium chlorite aqueous solution 51 to be used for ion exchange is prepared and supplied to the ion exchange means 2. The concentration of sodium chlorite in the high-concentration sodium chlorite 31 is appropriately selected according to the set value of the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water for production purposes. For example, in the case of sterilizing water for food, the concentration of sodium chlorite in the high-concentration sodium chlorite aqueous solution 31 is 5 to 25% by mass, preferably 5 to 7.5% by mass. The dilution water 32 for diluting the sodium chlorite aqueous solution is not particularly limited, and examples thereof include tap water, ion exchange water, distilled water, treated water treated with activated carbon and reverse osmosis membrane, and sterilizing water. It is appropriately selected according to the application. Further, the concentration of sodium chlorite in the diluted sodium chlorite aqueous solution 51 is appropriately selected depending on the set value of the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water to be manufactured. The density | concentration of the sodium chlorite in the diluted sodium chlorite aqueous solution 31 is 0.1-0.4 mass% normally, Preferably it is 0.2-0.3 mass%.

  Next, sodium ion of sodium chlorite in the diluted sodium chlorite aqueous solution 51 is ion-exchanged with hydrogen ions by the ion exchange means 2 to obtain an aqueous chlorite solution (before pH adjustment) 54.

  Next, an appropriate amount of dilute sodium chlorite aqueous solution 51 is mixed from dilute sodium chlorite aqueous solution bypass pipe 48 to chlorous acid aqueous solution (before pH adjustment) 54 obtained by ion exchange means 2, and chlorous acid aqueous solution is fed. The pH in the tube 43 is adjusted to obtain an aqueous chlorous acid solution (after pH adjustment), and the resulting aqueous chlorous acid solution (after pH adjustment) is sent to the catalytic oxidation means 5, The chlorine dioxide dissolved water 53 is obtained by oxidizing the chlorous acid in the aqueous chlorous acid solution (after pH adjustment).

  Next, while supplying the diluted water 33a for diluting chlorine dioxide-dissolved water to the chlorine dioxide-containing sterilized water feed pipe 47, the chlorine dioxide-containing sterilized water feed pipe 47 in the chlorine dioxide-containing sterilized water feed pipe 47, Chlorine dioxide-dissolved water 53 obtained by the catalytic oxidation means 5 is supplied. And while supplying the diluted water 33a for diluting the chlorine dioxide-dissolved water to the chlorine dioxide-containing sterilized water feed pipe 47, the chlorine dioxide-containing sterilized water feed pipe 47 in the chlorine dioxide-containing sterilized water feed pipe 47, By supplying the chlorine dioxide-dissolved water 53 obtained by the catalytic oxidation means 5, the chlorine dioxide-containing sterilized water 36 is produced in the chlorine dioxide-containing sterilized water feed pipe 47 and supplied to the use point. The concentration of chlorine dioxide in the chlorine dioxide-containing sterilizing water 36 is appropriately selected according to the application. The concentration of chlorine dioxide in the chlorine dioxide-containing sterilizing water 36 is usually 0.1 to 200 mg / L, preferably 1 to 100 mg / L, particularly preferably 10 to 20 mg / L.

  Thus, in the chlorine dioxide containing sterilizing water production | generation apparatus shown in FIG. 1, chlorine dioxide containing sterilizing water is manufactured, and the manufactured chlorine dioxide containing sterilizing water is supplied to a use point, but chlorine dioxide containing sterilizing water is supplied. During the production of water, the concentration of chlorous acid in the aqueous chlorous acid solution coming out of the ion exchange means 2 does not change at exactly the same concentration, but always fluctuates. For some reason, the concentration of chlorous acid in the aqueous chlorous acid solution may be too low or too high than the desired concentration range. When a chlorous acid aqueous solution in which the chlorous acid concentration in the aqueous chlorous acid solution is too low or higher than the desired concentration range is sent to the catalytic oxidation means 5, the use point is finally reached. Variation of chlorine dioxide concentration in the chlorine dioxide-containing sterilized water supplied to the water becomes large. Therefore, by measuring the pH of the aqueous chlorous acid solution with the pH measuring means 3, it is determined whether or not the concentration of chlorous acid in the aqueous chlorous acid solution is within a desired concentration range. The management pH value of the chloric acid aqueous solution is determined in advance, and when there is a difference between the measured pH value and the managed pH value, from the difference between the pH value sent from the pH measuring means 3 and the managed pH value, The flow rate of the dilute sodium chlorite aqueous solution of the bypass pipe liquid feed pump 16 necessary for setting the pH of the chlorous acid aqueous solution (after pH adjustment) to the control pH value is calculated. The liquid supply flow rate of the bypass pipe liquid supply pump 16 is changed. As a result, in the chlorine dioxide-containing sterilizing water generator of the present invention, it is possible to reduce the variation in the concentration of the aqueous chlorite solution sent after the position where the diluted sodium chlorite aqueous solution bypass pipe 48 is connected. Thus, chlorine dioxide-containing sterilizing water with small variations in chlorine dioxide concentration can be produced. The first calculation unit performs control based on the acquisition of the pH measurement value from the pH measurement unit, the comparison between the pH measurement value and the management pH value, and the command to the bypass pipe liquid feeding pump based on the comparison result.

  In addition, when sodium chlorite is treated by ion exchange means, chlorous acid, which is an acid, is produced, so the aqueous chlorite solution after the ion exchange treatment is acidic, but the pH of the aqueous chlorite solution is If it is lower than 5, chlorine gas is likely to be generated in the aqueous solution. For this reason, it is not preferable to send an aqueous solution of chlorous acid whose pH is too low after the ion exchange means. Therefore, the diluted sodium chlorite aqueous solution is mixed from the diluted sodium chlorite aqueous solution bypass pipe into the chlorous acid aqueous solution (before pH adjustment) immediately after the ion exchange treatment. This can prevent the pH of the diluted sodium chlorite aqueous solution from becoming too low.

  Further, in the apparatus for producing chlorine dioxide-containing sterilizing water shown in FIG. 1, the chlorine dioxide concentration measuring means 7 measures the chlorine dioxide concentration in the chlorine dioxide-containing sterilizing water 36 during the production of chlorine dioxide-containing sterilizing water, and chlorine dioxide Concentration measurement value and management chlorine dioxide concentration value are compared. If there is a difference between the chlorine dioxide concentration measurement value and the management chlorine dioxide concentration value, the chlorine dioxide sent from the chlorine dioxide concentration measuring means 7 From the difference between the concentration value and the managed chlorine dioxide concentration value, the liquid feed flow rate of the chlorine dioxide-dissolved water feed pump 13 required to change the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water to the managed chlorine dioxide concentration value is calculated. Then, the liquid feed flow rate of the chlorine dioxide-dissolved water liquid feed pump 13 is changed to the liquid feed flow rate. Thus, the chlorine dioxide-containing sterilizing water producing apparatus of the present invention can produce chlorine dioxide-containing sterilizing water with small variations in chlorine dioxide concentration. Such acquisition of chlorine dioxide concentration value from chlorine dioxide concentration measuring means, comparison of measured value of chlorine dioxide concentration and management chlorine dioxide concentration value, calculation of liquid feeding flow rate from comparison result, based on liquid feeding flow rate, Control by a command to the chlorine-dissolved water feed pump is performed by the second arithmetic unit.

  In addition, the chlorine dioxide-containing sterilizing water generator of the present invention can have an intermediate tank installed in a chlorous acid aqueous solution feeding pipe between the pH measuring means and the catalytic oxidation means.

  FIG. 2 is a flow diagram of an embodiment of the chlorine dioxide-containing sterilizing water generator of the present invention having an intermediate tank. In the chlorine dioxide-containing sterilizing water generator shown in FIG. 2, an intermediate tank 4 is further installed in the chlorine dioxide-containing sterilizing water generator shown in FIG. 1, and the ion exchange means 2 and the catalytic oxidation means 5 are provided. An intermediate tank 4 is installed in the middle of the chlorous acid aqueous solution feeding pipe 43 to be connected. In the intermediate tank 4, in order to adjust the pressure in the intermediate tank 4, a pressurized gas supply pipe 37 that supplies pressurized gas into the intermediate tank 4 and a pressurized gas discharge that discharges gas in the intermediate tank 4. A tube 39 is attached. Note that the installation of the pressurized gas supply pipe 37 and the pressurized gas discharge pipe 39 to the intermediate tank 4 is optional. The chlorous acid aqueous solution feeding pipe 43 is a liquid feeding pipe that connects the ion exchange means 2 and the catalytic oxidation means 5 through the intermediate tank 4, one end side is connected to the ion exchange means 2, and the other end side is the catalytic oxidation means 5. It is connected to. An intermediate tank 4 is installed in the middle of the chlorous acid aqueous solution feeding pipe 43. The chlorous acid aqueous solution feeding pipe 43 is a liquid feeding pipe for feeding the chlorous acid aqueous solution generated by the ion exchange means 2 to the catalytic oxidation means 5 through the intermediate tank 4.

  In the method for producing chlorine dioxide-containing sterilized water using the chlorine dioxide-containing sterilized water generator shown in FIG. 2, the diluted sodium chlorite aqueous solution 51 is ion-exchanged by the ion exchange means 2 and further diluted. A chlorous acid aqueous solution (after pH adjustment) 52 mixed with the chlorous acid aqueous solution 51 and adjusted in pH is sent to the intermediate tank 4. Next, the chlorous acid aqueous solution (after pH adjustment) 52 in the intermediate tank 4 is sent to the catalyst oxidation means 5, and the catalyst oxidization means 5 causes the chlorite in the chlorite aqueous solution (after pH adjustment) 52. Is oxidized to obtain chlorine dioxide-dissolved water 53.

  The chlorine dioxide-containing sterilizing water generator of the present invention includes a switching valve installed in a chlorine dioxide sterilizing water feeding pipe between the chlorine dioxide concentration measuring means and the use point, and a chlorine dioxide-containing sterilizing water connected to the switching valve. And a water blow tube.

  FIG. 3 is a flow diagram of an embodiment of the chlorine dioxide-containing sterilizing water generator of the present invention having a switching valve and a chlorine dioxide-containing sterilizing water blow pipe. In the chlorine dioxide-containing sterilizing water generating device shown in FIG. 3, the chlorine dioxide-containing sterilizing water feeding device between the chlorine dioxide concentration measuring means 7 and the use point is added to the chlorine dioxide-containing sterilizing water generating device shown in FIG. A switching valve 28 is installed in the pipe 47, and a chlorine dioxide-containing sterilizing water blow pipe 49 is connected to the switching valve 28. The switching valve 28 is a valve for switching the flow direction so that the chlorine dioxide-containing sterilized water flows to either the direction toward the use point or the chlorine dioxide-containing sterilized water blow pipe 49.

  The chlorine dioxide-containing sterilizing water generating device of the present invention shown in FIG. 3 is electrically connected to the chlorine dioxide concentration measuring means 7 and the switching valve 28, and the management chlorine dioxide concentration range is stored, and the chlorine dioxide concentration measuring means 7 The chlorine dioxide concentration value sent from the control chlorine dioxide concentration range is compared with the management chlorine dioxide concentration range, and when the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means is out of the management chlorine dioxide concentration range, When a command to switch the liquid flow to the blow side is sent and the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means 7 returns to the management chlorine dioxide concentration range, the liquid flow is switched to the normal flow side to the switching valve 28. A third operation unit 29 for sending an instruction to switch to The third arithmetic unit 29 stores the management chlorine dioxide concentration range in the storage unit, compares the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means 7 with the management chlorine dioxide concentration range, and compares them. Depending on the result, the electronic computer incorporates a program for sending a command for switching the liquid flow to the blow side to the switching valve 28 or sending a command for switching the liquid flow to the normal flow side for the switching valve 28. The management chlorine dioxide concentration value indicates a range of chlorine dioxide concentration that is allowed as a variation range of the chlorine dioxide concentration of the chlorine dioxide-containing sterilizing water 36. The management chlorine dioxide concentration value is appropriately selected depending on the use of the sterilizing water, the set value of the chlorine dioxide concentration in the sterilizing water, and the like. Further, switching the liquid flow to the blow side means that the chlorine dioxide-containing sterilized water 36 being sent to the use point is not sent to the chlorine dioxide-containing sterilized water feed pipe 47 toward the use point, and It refers to switching so that the solution is sent to the chlorine dioxide-containing sterilizing water blow pipe 49. Further, when the liquid flow is switched to the normal flow side, the chlorine dioxide-containing sterilizing water 36 sent to the chlorine dioxide-containing sterilizing water blow pipe 49 is not sent to the chlorine dioxide-containing sterilizing water blow pipe 49, And it refers to switching so that the chlorine dioxide-containing sterilized water liquid feeding pipe 47 is directed to the use point. The program for the third arithmetic unit may be incorporated in the same computer as the program for the first arithmetic unit or the program for the second arithmetic unit, or may be incorporated in a separate electronic computer. Also good.

  In the method for producing chlorine dioxide-containing sterilized water using the chlorine dioxide-containing sterilized water generating device shown in FIG. 3, the chlorine dioxide concentration of the chlorine dioxide-containing sterilized water 36 is controlled during the production of chlorine dioxide-containing sterilized water. When it is out of the chlorine dioxide concentration range, the switching valve 28 switches the flow direction of the chlorine dioxide-containing sterilizing water, and the chlorine dioxide-containing sterilizing water that is out of the management chlorine dioxide concentration range is replaced with the chlorine dioxide-containing sterilization water. It is discharged out of the apparatus as water drainage 57.

Sodium chlorite is dissociated into Na ⁺ and ClO ₂ ⁻ in an aqueous solution as shown in formula (1), and the sodium ion of sodium chlorite is hydrogenated as shown in formula (2). When ion exchanged into ions, chlorous acid is produced.
NaClO ₂ → Na ⁺ + ClO ₂ ⁻ (1)
Na ⁺ + ClO ₂ ⁻ → H ⁺ + ClO ₂ ⁻ → HClO ₂ (2)
Next, as shown in the formula (3), when chlorous acid is oxidized, chlorine dioxide is generated.
5HClO ₂ → 4ClO ₂ + HCl + 2H ₂ O (3)
For this reason, if the sodium chlorite is simply ion-exchanged and then oxidized, a strongly acidic chlorine dioxide-dissolved water can be obtained.
Here, when sodium chlorite is added to the aqueous solution obtained by the formula (3), the aqueous solution is neutralized with sodium chlorite as shown in the formula (4). 5 to 6.5.
4ClO ₂ + HCl + NaClO ₂ → 4ClO ₂ + NaCl + HClO ₂ (4)

  In the apparatus for producing sterilized water containing chlorine dioxide according to the present invention, the aqueous chlorite solution in the chlorous acid aqueous solution feeding pipe immediately after the ion exchange becomes strongly acidic, but alkaline sodium chlorite is injected from the bypass pipe. It becomes weakly acidic. And in the manufacturing apparatus of the chlorine dioxide containing sterilization water of this invention, the aqueous solution after oxidation is shown by Formula (4) by mixing sodium chlorite with the chlorite aqueous solution before oxidation, and strongly acidic. Chlorine dioxide-dissolved water can be brought into the same state as an aqueous solution neutralized with sodium chlorite, and chlorine dioxide-dissolved water having a pH of 5 to 6.5 is obtained.

  Chlorine dioxide-dissolved water that has been weakly acidified to a pH of 5 to 6.5 is safe to handle despite the high concentration of dissolved chlorine dioxide. And in the manufacturing apparatus of chlorine dioxide containing sterilizing water of this invention, since it can handle the chlorine dioxide melt | dissolving water in which chlorine dioxide is melt | dissolving by pH 5-6.5, manufacture of the chlorine dioxide containing sterilizing water of this invention According to the apparatus, chlorine dioxide-containing sterilized water can be produced safely.

  In addition, when installing an intermediate tank, if the pH of the aqueous chlorous acid solution is 2 or less, chlorine dioxide is produced from chlorous acid over time while the aqueous solution is being stored in the intermediate tank. As time goes on, there is a risk of chlorine dioxide being released from the aqueous solution. In the apparatus for producing sterilized water containing chlorine dioxide of the present invention, the aqueous chlorous acid solution can be transferred to an intermediate tank after adjusting the pH to 5 to 6.5. According to this, it is possible to avoid the danger of chlorine dioxide being released from the aqueous solution during storage in the intermediate tank.

In this way, chlorine dioxide-containing sterilizing water is obtained in the chlorine dioxide-containing sterilizing water manufacturing apparatus of the present invention. And the chlorine dioxide containing sterilizing water obtained by the chlorine dioxide containing sterilizing water manufacturing apparatus of the present invention contains chlorine dioxide (ClO ₂ ) and chlorous acid (HClO ₂ ) as main sterilizing components, and as other components. , Sodium ion, and by-product containing chlorite ion, chlorate ion and chlorine. That is, the device for producing sterilized water containing chlorine dioxide of the present invention is a device for producing sterilized water containing chlorine dioxide and chlorous acid.

  In the apparatus for producing chlorine dioxide-containing sterilizing water of the present invention, sodium chlorite is mixed with an aqueous chlorite solution to make the aqueous solution weakly acidic, but the aqueous chlorous acid solution or aqueous chlorine dioxide solution is made weakly acidic. Since the chlorine dioxide concentration in the obtained chlorine dioxide-containing sterilized water does not change, the sterilizing power is not lowered by making it weakly acidic. Then, in the chlorine dioxide-containing sterilizing water production apparatus of the present invention, chlorine dioxide-dissolved water, which is weakly acidified chlorine dioxide-containing water, is diluted with dilution water according to the requirements at the point of use, thereby producing chlorine dioxide. A chlorine dioxide-containing sterilized water whose concentration is adjusted to the concentration required at the point of use is obtained.

  Moreover, in the apparatus for producing chlorine dioxide-containing sterilizing water of the present invention, an aqueous solution containing chlorine dioxide and hydrochloric acid is neutralized with sodium chlorite, as shown in formula (4), by oxidation with catalytic oxidation means. In other words, it has obtained chlorine dioxide-dissolved water similar to that which has been weakly acidified, but in other words, alkaline sodium chlorite has been weakly acidified with an aqueous solution containing acidic chlorine dioxide and hydrochloric acid. It can be said that an acidified sodium chlorite aqueous solution is obtained. That is, the apparatus for producing chlorine dioxide-containing sterilizing water of the present invention can be said to be an apparatus for producing a weakly acidified sodium chlorite aqueous solution.

2 ion exchange means 3 pH measuring means 4 intermediate tank 5 catalytic oxidation means 6 carbon dioxide dissolving means 7 chlorine dioxide concentration measuring means 11 high concentration sodium chlorite aqueous solution feed pump 12 pressure pump 13 chlorine dioxide dissolved water feed pump 14 Pressurizing pump 15 Pressurizing pump 16 Bypass pipe liquid feeding pump 22 Gas flow controller 26 First computing unit 27 Second computing unit 28 Switching valve 29 Third computing unit 31 High-concentration sodium chlorite aqueous solution 32 Diluted water 33a, 33b Dilution water 34 Water for dissolving carbon dioxide 36 Chlorine dioxide-containing sterilizing water 37 Pressurized gas supply pipe 38 Carbon dioxide 39 Pressurized gas discharge pipe 41 Diluted sodium chlorite aqueous solution feed pipe 42 High-concentration sodium chlorite aqueous solution feed Tube 43 Chlorous acid aqueous solution feed tube 44 Chlorine dioxide dissolved water feed tube 45 Carbon dioxide supply tube 46 Carbon dioxide dissolving water Liquid feed pipe 47 Chlorine dioxide-containing sterilized water liquid pipe 48 Diluted sodium chlorite aqueous solution bypass pipe 49 Chlorine dioxide-containing sterilized water blow pipe 51 Diluted sodium chlorite aqueous solution 52 Chlorous acid aqueous solution (after pH adjustment)
53 Chlorine dioxide-dissolved water 54 Chlorous acid aqueous solution (before pH adjustment)
56 Wastewater containing chlorous acid 57 Wastewater containing chlorine dioxide

Claims (3)

Ion exchange means for obtaining sodium chlorite aqueous solution by ion exchange of sodium ion of sodium chlorite in dilute sodium chlorite aqueous solution to hydrogen ion;
Catalytic oxidation means for oxidizing chlorine acid in the aqueous chlorous acid solution with an oxidation catalyst to obtain chlorine dioxide-dissolved water;
Diluted water for diluting sodium chlorite aqueous solution is supplied from one end side, and the dilute sodium chlorite aqueous solution feed pipe connected to the ion exchange means at the other end side,
A high-concentration sodium chlorite aqueous solution feed pipe to which a high-concentration sodium chlorite aqueous solution is supplied from one end side and the other end side is connected to the diluted sodium chlorite aqueous solution feed pipe;
One end side is connected to the ion exchange means, the other end side is connected to the catalytic oxidation means, and a chlorous acid aqueous solution feeding pipe through which a chlorous acid aqueous solution is fed;
Dilution water for diluting chlorine dioxide dissolved water is supplied from one end side, and the other end side is a chlorine dioxide-containing sterilizing water feed pipe that leads to a use point,
One end side is connected to the catalytic oxidation means, the other end side is connected to a chlorine dioxide-containing sterilized water supply pipe, and a chlorine dioxide-dissolved water supply pipe through which chlorine dioxide-dissolved water is supplied;
The dilute sodium chlorite aqueous solution feed pipe branches off from the dilute sodium chlorite aqueous solution feed pipe, and the dilute sodium chlorite aqueous solution feed pipe in the dilute sodium chlorite aqueous solution feed pipe transfers the dilute sodium chlorite aqueous solution feed pipe. Dilute sodium chlorite aqueous solution bypass pipe for supplying to the liquid pipe;
A high-concentration sodium chlorite aqueous solution feed pump installed in the high-concentration sodium chlorite aqueous solution feed pipe, and for feeding the high-concentration sodium chlorite aqueous solution;
A bypass pipe installed in the dilute sodium chlorite aqueous solution bypass pipe for feeding a part of the dilute sodium chlorite aqueous solution in the dilute sodium chlorite aqueous solution feed pipe into the chlorite aqueous solution feed pipe A feed pump;
A chlorine dioxide-dissolved water feed pump installed in the chlorine dioxide-dissolved water feed pipe, for delivering chlorine dioxide-dissolved water;
A pH measuring means installed in the chlorous acid aqueous solution feeding pipe for measuring the pH of the chlorous acid aqueous solution;
Chlorine dioxide concentration measuring means installed in the chlorine dioxide-containing sterilized water feed pipe and measuring the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water;
Electrically connected to the pH measuring means and the bypass pipe liquid feeding pump, the management pH value is stored, the pH value sent from the pH measuring means is compared with the management pH value, and the pH measuring means If there is a difference between the pH value sent and the control pH value, the pH of the aqueous chlorous acid solution is determined from the difference between the pH value sent from the pH measuring means and the control pH value. Calculating a liquid feed flow rate of the bypass pipe liquid feed pump necessary for the control pH value, and sending a liquid feed flow rate change command to the bypass pipe liquid feed pump;
The chlorine dioxide concentration measuring means and the chlorine dioxide-dissolved water feed pump are electrically connected to store the management chlorine dioxide concentration value, and the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means and the management chlorine dioxide If there is a difference between the chlorine dioxide concentration value sent from the chlorine dioxide concentration measuring means and the control chlorine dioxide concentration value, the dioxide dioxide sent from the chlorine dioxide concentration measuring means is compared. From the difference between the chlorine concentration value and the control chlorine dioxide concentration value, the chlorine dioxide-dissolved water feed pump required to make the chlorine dioxide concentration in the chlorine dioxide-containing sterilized water the control chlorine dioxide concentration value Calculating a flow rate, and sending a liquid feed flow rate change command to the chlorine dioxide-dissolved water feed pump;
A device for producing chlorine dioxide-containing sterilizing water, comprising:   2. The chlorine dioxide-containing sterilizing water generator according to claim 1, further comprising an intermediate tank installed in the chlorous acid aqueous solution feeding pipe between the pH measuring means and the catalytic oxidation means. A switching valve installed in the chlorine dioxide-containing sterilizing water feed pipe between the chlorine dioxide concentration measuring means and the use point;
A chlorine dioxide-containing sterilizing water blow pipe connected to the switching valve;
The apparatus for producing sterilized water containing chlorine dioxide according to claim 1 or 2, characterized by comprising:

Images