TWI423921B - Preparation method of hypochlorite solution like molecule by ionic exchange and hypochlorite solution like molecule - Google Patents

Description

Modulation of molecular hypochlorous acid solution by ion exchange and molecular hypochlorous acid solution

This invention relates to a technique for modulating a stable molecular hypochlorous acid solution. More specifically, the present invention relates to a technique for preparing a stable pure molecular hypochlorous acid solution by substituting a metal ion contained in a hypochlorite solution with a hydrogen ion and replacing the chloride ion with a hydroxide ion.

The hypochlorite solution, which is based on sodium hypochlorite, is the most widely used fungicide in the world for a long time and is used in a wide range of fields. The field of sodium hypochlorite is dominated by almost all areas of food production, distribution and supply, including water facilities, wastewater treatment, swimming pools, hot springs, public baths, medical care, nursing, agriculture and fisheries, and general households. In order to supply these demand, the annual shipments in Japan are about 1 million metric tons, and it is estimated that there are dozens of shipments in the world.

As such, it has been used in a very wide range of hypochlorite solutions, but until now, it has been pointed out. It is a series of trihalomethanes. It was confirmed that the trihalomethane was produced when the alkaline chlorine agent was in contact with the organic substance, and it was found that even if one of the trihalomethanes had a low concentration of chloroform, it was carcinogenic, and therefore, the world was a problem in the world. In an advanced country that sincerely blocks this part, restrict the use of food or drinking water.

The second problem is the problem of bromic acid or chloric acid. The bromic acid is derived from a bromine compound which is contained in the salt of the sodium hypochlorite raw material and becomes an impurity. On the other hand, since chloric acid is produced by the heterogeneous decomposition of hypochlorite itself, it is toxic to the human body. Therefore, in recent years, the upper limit concentration has been set in the tap water method and related regulations. Bromo acid is reduced by increasing the purity of the salt of the raw material. It is known that there are several acceleration factors in the formation reaction of chloric acid, but the cause of the greatest influence is the temperature and the concentration of hypochlorite. The ratio is increased in temperature and concentration to increase the rate of formation. Further, it is also known that the salt or heavy metal of the inclusions promotes the reaction. Therefore, sodium hypochlorite used for sterilization or food of tap water is used as a raw material, or is distributed at a low concentration, or needs to be stored at a low temperature, resulting in a large increase in cost.

The third problem is that the bactericidal power is insufficient. The hypochlorite solution is one of the reasons for utilizing a wide range of microorganisms and having an effect over a wide range of microorganisms, but it has no practical effect on bacterial spores and is not more than 1000 ppm for tuberculosis. At the high concentration, there is no weakness in the effect or the like. The 1000 ppm hypochlorite solution has a great adverse effect on people or objects and the environment, and there is a great limitation in the method or purpose of use. For this reason, the hypochlorite solution is strongly alkaline, so that hypochlorite is almost present as a hypochlorite ion. The bactericidal effect of the hypochlorite solution is almost lower than that of the molecular hypochlorous acid contained therein. However, when the liquidity is alkaline and ionized, the sterilizing power, particularly the sterilization rate, is greatly attenuated. In order to compensate for this, it is not only an effect that the effect is hardly increased as it is used at a high concentration, and, as described above, various disadvantages due to high concentration use also occur. For example, there are damage to objects, causes of abnormal odor, generation of harmful substances, rough surface, obstacles to wastewater treatment, environmental pollution, and the like.

Then, the final problem stems from the inclusion of salt. In the hypochlorite, a representative sodium hypochlorite solution contains, in addition to the sodium ion as the counter ion of the hypochlorite ion, a salt of a part of the raw material and sodium hydroxide added as a raw material of the process. Sodium hypochlorite is only allowed to separate, and it decomposes into salt, or changes to chloric acid due to the heterogeneous reaction. However, as described above, it is known that the salt promotes the reaction. Further, it is known that when sodium and free chlorine coexist, the effect of rusting of the metal becomes strong, and when the metal surface is dried, it is concentrated, and even if it is a corrosion-resistant material such as stainless steel, rust is generated. In addition, when sprayed for the purpose of sterilization or humidification or deodorization in the room, it also becomes a health disorder such as asthma due to inhalation of the fine powder salt of the residue into the lungs or accumulation of salt or electrical products in the room. the reason.

In addition, if hypochlorous acid does not contain salt, it can also be used in industries that hate salt residues. Originally, hypochlorous acid is an extremely strong active oxygen, and therefore, it can be utilized for the purpose of oxidizing and removing pollution or impurities by using its oxidizing power. However, until now, it is inevitable to contain salt, and therefore cannot be utilized in these applications. Therefore, it is predicted that if a pure hypochlorous acid solution is formed, the field of use is further expanded.

Various efforts are made for the purpose of compensating for the disadvantages of such hypochlorite. Among them, a method of increasing the bactericidal power by adding various acids and lowering the pH value in the sodium hypochlorite solution to increase the ratio of the presence of the molecular hypochlorous acid has been carried out since ancient times, and many specialized devices are also commercially available. However, in this method, the bactericidal power is surely enhanced, but the sodium or the like contained in the system remains, and therefore, the disadvantage caused by the salt cannot be eliminated. In addition, there are reports of contraindications to the danger of mixing sodium hypochlorite solution and acid, so there are many accidents.

Further, in Japanese Laid-Open Patent Publication No. Hei 6-206076, it is shown that hypochlorite is reduced by ion exchange treatment with water of a hypochlorite solution or a diluted hypochlorite solution by a hydrogen-substituted ion exchange material. The method of pH of the solution. However, this method merely reduces the pH of the hypochlorite solution for the purpose, and as a result, the same method as the above-mentioned hypochlorite solution to add an acid retains most of the contained metal. Further, in this method, when a certain amount or more of metal ions contained in the hypochlorite solution is replaced by hydrogen ions, the pH is extremely low, chlorine gas is generated, which is dangerous, and becomes unstable without preservation. Therefore, it is not suitable for practical use.

Accordingly, the problem to be solved by the present invention is to provide a technique for preparing a pure molecular hypochlorous acid solution having minimal formation of trihalomethane or chloric acid, no salt, high stability, and high bactericidal power, and a pure molecular form. Hypochlorous acid solution.

The hypochlorite solution sold in the market contains, in addition to hypochlorite, a chloride salt or a hydroxide base as a regular component. The liquidity of the hypochlorite solution is a strong alkali which is a metal ion of a counter ion of a hypochlorite ion and a hydroxide of an alkali or an alkaline earth metal. Therefore, if all of the metal ions are replaced by hydrogen ions, the alkalinity is eliminated, and the residual salt in the dry state is not present. However, on the other hand, the chloride ion contained in the salt is bonded to the hydrogen ion which replaces the sodium ion, and becomes hydrochloric acid. Therefore, when treated only by the hydrogen-type cation exchange resin, the liquidity becomes strongly acidic, and the hypochlorous acid molecule becomes unstable and becomes chlorine to volatilize and diffuse.

Therefore, in order to stabilize hypochlorous acid, it is necessary to carry out treatment by a hydroxide-type anion exchange resin, and to replace a part of the chloride ion remaining in the solution with hydroxide ions. Further, the inclusion ions originally contained in the hypochlorite solution are also completely removed by these two-stage treatment, and thus a pure hypochlorous acid solution is obtained.

However, it is important that these ion exchange treatments are carried out by anion exchange resin treatment after the cation exchange resin treatment. Initially, since the hypochlorite solution is strongly alkaline, the hypochlorite is ionized, and metal ions are present as cations, and ions such as hypochlorous acid ions, chloride ions, and hydroxide ions become anions. Among them, the metal ion which becomes a cation is treated and removed by a hydrogen type cation exchange resin. However, when it is treated by an anion exchange resin at the beginning, the hypochlorite ion which becomes an anion is removed, and the active component is removed.

When it is treated by a hydrogen-type cation exchange resin, the metal ions are replaced by hydrogen ions. Therefore, the liquidity becomes acidic to strong acid, and the main chemical species contained in the solution are molecular hypochlorous acid and hydrogen ions. ,Chloride. Then, when this treatment is carried out by the hydroxide ion-type anion exchange resin, the chloride ion is substituted into the hydroxide ion and reacts with the hydrogen ion to become water. Therefore, the chemical species remaining in the solution become only the molecular hypochlorous acid. . However, when the treatment by the hydroxide ion-type anion exchange resin is excessively performed, the hydroxide ions become excessive in the near future, and the liquidity changes from neutral to alkaline. As a result, the molecular hypochlorous acid is again an anionic hypochlorite ion, and is adsorbed to the anion exchange resin to be removed. Therefore, it is important to properly manage the reaction end point system by the treatment of the anion exchange resin. The liquidity after the end of the treatment can be made weakly acidic by appropriately managing these processes. It is confirmed that a pure molecular hypochlorous acid solution is produced by this method. Therefore, each form of the means for solving the problem is as follows.

First, the treatment liquid is treated with a hydrogen-oxygen anion exchange resin after the hypochlorite solution is treated with a hydrogen-type cation exchange resin and the metal ions are replaced by hydrogen ions, and the chloride ions are replaced by hydroxide ions. The method of modulating the molecular hypochlorous acid solution is the first aspect of the means for solving the problem.

Further, in the first embodiment, the exchange capacity of the hydrogen-type cation exchange resin is A (equivalent), the cation exchange treatment time is T (sec), and the effective chlorine amount of the hypochlorite solution treated in T seconds is C (mol) The method of preparing a molecular hypochlorous acid solution having a value of (A × T) ÷ C of 200 or more or 350 or more is the second aspect of the means for solving the problem.

Further, in the first or second embodiment, the exchange capacity of the hydroxide-type anion exchange resin is B (equivalent), the anion exchange treatment time is T (second), and the effective chlorine amount of the hypochlorite solution treated in T seconds The method of preparing a molecular hypochlorous acid solution having a value of (B × T) ÷ C of C (mol) of 5 or more, 100 or less, or 5 or more, 50 or less, is the third means for solving the problem. form.

Further, in the first embodiment, the hypochlorite solution is prepared by treating the hypochlorite solution with a hydrogen-type cation exchange resin and replacing the metal ions with hydrogen ions at a pH of 6.5 or less or 4 or less. The method is the fourth aspect of the means for solving the problem.

Further, in the first or fourth aspect, after the hypochlorite solution is treated with a hydrogen-type cation exchange resin and the metal ions are replaced by hydrogen ions, the treatment liquid is treated with a hydroxide-type anion exchange resin and A method of preparing a molecular hypochlorous acid solution having a pH of 4 or more, 8 or less, or 5 or more and 6.5 or less in which the hydroxide ion is replaced by a hydroxide ion is the fifth aspect of the means for solving the problem.

In addition, a method of preparing a molecular hypochlorous acid solution of a molecular hypochlorous acid solution obtained by diluting the form of any one of the first to fifth forms by water is used as the sixth means for solving the problem. form.

Further, in the form of any one of the first to sixth aspects, the hypochlorite is a method of preparing a molecular hypochlorous acid solution of sodium hypochlorite, and is a seventh aspect of a means for solving the problem.

Next, the molecular hypochlorous acid solution obtained by the form of any one of the first to seventh aspects is the eighth aspect of the means for solving the problem.

The effects by the present invention are as follows. First, after treating the hypochlorite solution with a hydrogen-type cation exchange resin and replacing the metal ions with hydrogen ions, the treatment liquid is treated with a hydrogen-oxygen anion exchange resin, and replaced with hydroxide ions. The chloride ion is such that the chlorine which is originally contained in the hypochlorite solution is not wasted, and the metal ions contained therein are removed to obtain a molecular hypochlorous acid solution of desired liquidity.

Further, when the exchange capacity of the hydrogen type cation exchange resin is A (equivalent), the cation exchange treatment time is T (second), and the effective chlorine amount of the hypochlorite solution treated in T seconds is C (mol) The value of (A × T) ÷ C is 200 or more, and a molecular hypochlorous acid solution which can still be used as a sterilizing agent is obtained, or it is also possible to obtain a molecular state in which almost all metal ions are removed by being 350 or more. Chloric acid solution.

Further, the amount of available chlorine in the hypochlorite solution treated by the exchange capacity of the hydroxide-type anion exchange resin is B (equivalent), the anion exchange treatment time is T (second), and T seconds is C (mol). When the value of (B × T) ÷ C is 5 or more and 100 or less, molecular hypochlorous acid is stably present, and a liquid molecular hypochlorous acid solution which is still usable can be obtained, or it can be made into 5 In the state of 50 or less, it is also diluted with water to obtain a liquid hypochlorous acid solution which is liquid-like in the presence of molecular hypochlorous acid.

Further, a molecule containing a strong bactericidal effect can be obtained at a high ratio by treating the hypochlorite solution with a hydrogen-type cation exchange resin and replacing the metal ion with a hydrogen ion at a pH of 6.5 or less. A molecular hypochlorous acid solution of hypochlorous acid or a molecular hypochlorous acid solution having a strong bactericidal effect of molecular hypochlorous acid can be obtained at a high ratio by 4 or less.

Further, after treating the hypochlorite solution with a hydrogen-type cation exchange resin and replacing the metal ions with hydrogen ions, the treatment liquid is treated with a hydroxide-type anion exchange resin and replaced with hydroxide ions. The pH of the treatment liquid after the chloride ion is 4 or more and 8 or less, and a stable molecular hypochlorous acid solution containing a molecularly-produced hypochlorous acid having a strong bactericidal effect is obtained at a high ratio, or may be obtained by From 5 or more and 6.5 or less, a stable molecular hypochlorous acid solution which is still directly usable and which contains a strong bactericidal effect of molecular hypochlorous acid is obtained at a high ratio.

Further, by forming a molecular hypochlorous acid solution which is diluted with water to prepare a molecular hypochlorous acid solution, it is possible to directly utilize the produced molecular hypochlorous acid without taking a time such as dilution. Solution.

Further, since hypochlorite can be used as the most widely distributed hypochlorite by using hypochlorite, it is easy to stably obtain a raw material and become a liquid. Therefore, it is possible to improve the production of a molecular hypochlorous acid solution. The industrialization of production is carried out with ease of handling.

Next, the molecular hypochlorous acid solution obtained by any of the foregoing methods can be provided without using a generating device, and can be utilized for various purposes.

The minimum equipment for carrying out the present invention is constituted by an anion exchange cylinder, a cation exchange cylinder, a hypochlorite solution supply means, a dilution water supply means, a flow path switching means, and a mixing and agitating means. Hypochlorite or a resin having chlorine durability or alkali durability is recommended for the material of the wetted parts of each part. Any type of ion exchange resin may be used. However, the resin material of the substrate is durable to chlorine and is convenient for long-term use. If there is no ion exchange energy, regeneration can be carried out by a conventional method, and it can be used repeatedly. It is possible to regenerate the ion exchange resin, and it is also possible to use a regeneration device by using the production device.

The sodium hypochlorite solution or the like used in the present invention is preferably low in salt content, but any of these may be used. In addition, it is best to have fewer days after manufacture. There is no particular limitation on the chlorine concentration. In the state where the storage period of the hypochlorous acid solution to be produced must be lengthened, it is preferable to adjust the pH to approximately 7 as much as possible, and it can be arbitrarily adjusted between 4 and 7 in the state of immediate use. It is predicted that when the pH is lower than 4, the preservability of the effect due to the generation of chlorine gas is lowered or the influence on the surroundings is not recommended.

The method of flowing the liquid down to the respective tubes during the ion exchange treatment may be an upflow or a downflow. In order to avoid the stagnation or drift or short-cut of the bubble, the upward flow is convenient. In particular, in the anion exchange cylinder, the amount of the resin is generally reduced with respect to the amount of liquid flow, and therefore, in order to accurately control the contact time, the upward flow becomes convenient.

Embodiment 1

Next, the preparation process of the molecular hypochlorous acid solution will be described in detail using FIG. 1 of the display embodiment. The raw water system is supplied to the device from the raw water inlet 1. In the raw water supply piping, the solenoid valve 2 and the flow rate setting valve 3 are arranged to control the supply of raw water and the quantitative supply. One part of the raw water supplied is divided by the dilution of the hypochlorite solution by the quantitative pump 4, and the residual portion is passed through the pipe 13 for the final dilution of the molecular hypochlorous acid solution.

The raw water for diluting the hypochlorite solution is stored in the hypochlorite solution tank 5, and is mixed with the hypochlorite solution quantitatively pulled out by the hypochlorite solution quantitative pump 6 and The mixture is uniformly mixed by the static mixer 7, and supplied to the bottom of the cation exchange cylinder 8 filled with the hydrogen-type cation exchange resin through the flow switching valve 17.

In the cation exchange cylinder, the metal ions contained in the solution are replaced by hydrogen ions, and therefore, the liquidity of the discharged solution is biased toward the acidic side. The pH of the discharge liquid from the cation exchange resin cartridge was measured by the on-line pH meter 20, and the deviation from the target value was adjusted by adjusting the flow rates of the two pumps 4 and 6.

The liquid system discharged from the cation exchange resin cylinder is temporarily stored in the balance tank 9 via the switching valve 18, and is supplied to the anion exchange cylinder 11 through the supply valve 9 via the switching valve 19. The anion exchange cylinder is filled with a hydroxide ion anion exchange resin, and the chloride ion contained therein is replaced by hydroxide ions to raise the pH. The liquidity of the discharged liquid can be determined by the time when the liquid contacts the anion exchange resin, and therefore, the liquidity of the discharged liquid is controlled by supplying the supply amount of the pump and the filling amount of the anion exchange resin.

The solution discharged from the anion exchange cylinder passes through the pipe 12, is mixed with the dilution water flowing down from the pipe 13, is diluted, and is uniformly mixed in the final static mixer 14 and discharged through the discharge port 15. In the vicinity of the discharge port, an in-line type pH meter 21 is arranged to check the pH of the final discharge liquid. Further, the amount of dilution water is appropriately adjusted in accordance with the intended concentration of the final solution discharge liquid.

The effective chlorine system is hardly consumed on the way, and can be determined by the supply amount of the raw material and the amount of the diluted water. The ion exchange rate is managed by two pH meters arranged to prepare a pure hypochlorous acid solution having a concentration suitable for the purpose.

In the apparatus, 100 liters of Muromac C501-H manufactured by MUROMACHI TECHNOS Co., Ltd., and 10 liters of Muromac A7002-0H manufactured by MUROMACHI TECHNOS Co., Ltd. were used for the cation exchange resin, and the ultra-filtered water was used for the raw water system. The 6% sodium hypochlorite solution was treated as a raw material, and as a result, a pure molecular hypochlorous acid solution having a pH of 4.9 to 5.1 and an effective chlorine concentration of 970 to 1000 ppm was continuously obtained at about 1 metric ton per hour.

The present invention provides a bactericidal agent which does not contain a strong bactericidal power of a salt and a method for adjusting the same. The bactericide is used in the fields of the food industry, the medical care industry, tap water treatment, sewer treatment, public baths, swimming pools, semiconductor industries, building air conditioners, and the like. It is more suitable for applications such as the use of sprays, particularly the use of salts.

1‧‧‧ raw water inlet

2‧‧‧ solenoid valve

3‧‧‧ fixed flow valve

4‧‧‧Dilution quantitative pump

5‧‧‧ hypochlorite solution tank

6‧‧‧ hypochlorite solution quantitative pump

7‧‧‧Static mixer

8‧‧‧Cy cation exchange cylinder

9‧‧‧Balance trough

10‧‧‧ Anion exchange cylinder supply pump

11‧‧‧Anion exchange cylinder

12‧‧‧ Anion exchange cylinder discharge piping

13‧‧‧Dilution water piping

14‧‧‧Final static mixer

15‧‧‧Pure hypochlorous acid solution discharge

16‧‧‧Dilution water switching valve

17‧‧‧Switching valve

18‧‧‧Switching valve

19‧‧‧Switching valve

20‧‧‧pH meter for cation exchange

21‧‧‧ final pH meter

22‧‧‧Regeneration bypass piping

1 is a flow chart of an embodiment of the present invention.

1. . . Raw water inlet

2. . . The electromagnetic valve

3. . . Constant flow valve

4. . . Dilution quantitative pump

5. . . Hypochlorite solution tank

6. . . Hypochlorite solution quantitative pump

7. . . Static mixer

8. . . Cation exchange cartridge

9. . . Balance slot

10. . . Anion exchange cylinder supply pump

11. . . Anion exchange cylinder

12. . . Anion exchange cylinder discharge piping

13. . . Dilution water piping

14. . . Final static mixer

15. . . Pure hypochlorous acid solution discharge

16. . . Dilution water switching valve

17. . . Switching valve

18. . . Switching valve

19. . . Switching valve

20. . . Cation exchange cation meter

twenty one. . . Final pH meter

twenty two. . . Regenerative bypass piping

Claims (8)

A method for preparing a molecular hypochlorous acid solution, which comprises: treating a hypochlorite solution with a hydrogen-type cation exchange resin, replacing a metal ion with a hydrogen ion, and then using a hydrogen-oxygen anion exchange resin, The treatment liquid described above is treated, and the chloride ion is replaced by hydroxide ions to prepare a molecular hypochlorous acid solution. The method for preparing a molecular hypochlorous acid solution according to claim 1, wherein the exchange capacity of the hydrogen-type cation exchange resin is A (equivalent), the cation exchange treatment time is T (second), and the treatment is T seconds. When the effective chlorine amount of the hypochlorite solution is C (mol), the value of (A × T) ÷ C is 200 or more or 350 or more. The method for preparing a molecular hypochlorous acid solution according to claim 1 or 2, wherein the exchange capacity of the hydroxide-type anion exchange resin is B (equivalent), and the anion exchange treatment time is T (second) and T seconds. When the amount of available chlorine in the clock-treated hypochlorite solution is C (mol), the value of (B × T) ÷ C is 5 or more, 100 or less, or 5 or more, 50 or less. The method for preparing a molecular hypochlorous acid solution according to claim 1, wherein the pH of the solution after treating the hypochlorite solution with a hydrogen type cation exchange resin and replacing the metal ions with hydrogen ions is 6.5. Below or below 4. A method for preparing a molecular hypochlorous acid solution according to claim 1 or 4, wherein after treating the hypochlorite solution with a hydrogen type cation exchange resin and replacing the metal ion with hydrogen ions, the hydrogen and oxygen are used. The pH of the treatment liquid after treating the above-mentioned treatment liquid and replacing the chlorine ions with hydroxide ions is 4 or more, 8 or less, or 5 or more and 6.5 or less. A method for modulating a molecular hypochlorous acid solution, which is characterized by further diluting a molecular hypochlorous acid solution obtained by the method according to any one of claims 1 to 5 by water. The method for preparing a molecular hypochlorous acid solution according to any one of claims 1 to 6, wherein the hypochlorite is sodium hypochlorite. A molecular hypochlorous acid solution obtained by the method according to any one of claims 1 to 7.