WO2022003859A1 - 次亜塩素酸水溶液の製造方法及び製造装置 - Google Patents
次亜塩素酸水溶液の製造方法及び製造装置 Download PDFInfo
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- WO2022003859A1 WO2022003859A1 PCT/JP2020/025811 JP2020025811W WO2022003859A1 WO 2022003859 A1 WO2022003859 A1 WO 2022003859A1 JP 2020025811 W JP2020025811 W JP 2020025811W WO 2022003859 A1 WO2022003859 A1 WO 2022003859A1
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- aqueous solution
- hypochlorous acid
- value
- storage tank
- supply
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 146
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 claims abstract description 47
- 230000002378 acidificating effect Effects 0.000 claims abstract description 46
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 45
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000460 chlorine Substances 0.000 claims abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 17
- 238000003860 storage Methods 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 abstract 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000711573 Coronaviridae Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001263478 Norovirus Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 241000712461 unidentified influenza virus Species 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/04—Hypochlorous acid
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
Definitions
- the present invention relates to a method for producing an aqueous hypochlorous acid solution.
- the present invention also relates to an apparatus for producing an aqueous hypochlorous acid solution capable of carrying out this production method.
- hypochlorous acid aqueous solution has strong bactericidal action, deodorant action, bleaching action, etc., and is used in a wide range of fields such as medical equipment, daily necessities, sterilization and deodorization of human body and animals and plants.
- a slightly acidic (pH value: about 5.0 to 6.5) hypochlorous acid aqueous solution has a pH value similar to that of human skin, so that it has a high bactericidal action but is safe. It has the characteristic of being excellent.
- the chlorine odor peculiar to chlorine-based disinfectants does not remain.
- a slightly acidic aqueous solution of hypochlorous acid generally, a predetermined amount of sodium hypochlorite and an acid are supplied and mixed with raw water to adjust the pH value in the range of 5.0 to 6.5. Manufactured by. Alternatively, it is produced by electrolytically treating hydrochloric acid or an aqueous solution of hydrochloric acid with sodium chloride and then diluting the pH value to the range of 5.0 to 6.0.
- hypochlorous acid is a very unstable substance and is known to gradually decompose in an aqueous solution. Therefore, the hypochlorous acid aqueous solution has a problem that its action cannot be maintained for a long period of time.
- the hypochlorous acid aqueous solution is easily affected by weather conditions such as temperature and humidity, and it is difficult to control the pH value within a certain range even when the mixing ratio of the raw materials is the same.
- weather conditions such as temperature and humidity
- Japanese Patent Application Laid-Open No. 2002-273452 describes that when a sodium hypochlorite aqueous solution and an acidic aqueous solution are supplied and mixed with raw water to produce a hypochlorite aqueous solution, the flow rate and pH value of the raw water are determined.
- a method is disclosed in which the addition amounts of an aqueous sodium hypochlorite solution and an acidic aqueous solution are adjusted, and after each aqueous solution is added, the dilution reaction rate is gradually or stepwise increased.
- JP-A-2009-219984 in anticipation of a decrease in the concentration of sodium hypochlorite during use, sodium hypochlorite is added, the mixture is sufficiently stirred with a circulation pump, and then the primary concentration is measured with a pH meter.
- a method for producing an aqueous solution of hypochlorite in which an acid such as acetic acid or hydrochloric acid is dispersed and charged into a tank, sufficiently stirred by a circulation pump, and then the concentration of the finished product is controlled by a pH meter. ing.
- Japanese Patent Application Laid-Open No. 2011-56377 describes sodium hypochlorite and a pH adjuster composed of acetic acid and sodium acetate having a buffering action, in which the content of sodium hypochlorite is 76 ppm to 84 ppm and acetic acid is used.
- a hypochlorous acid aqueous solution having a pH value controlled in a specific range can be stably obtained.
- the pH value of the obtained aqueous hypochlorous acid solution is 5 to 6, and it cannot be said that the variation is sufficiently suppressed.
- the pH value of the hypochlorous acid aqueous solution obtained by the production methods described in these documents fluctuates with time, and the pH value of the hypochlorous acid aqueous solution varies over a long period of time. It is difficult to sustain the action.
- Japanese Patent Application Laid-Open No. 2005-138001 and Japanese Patent Application Laid-Open No. 2007-283167 disclose a method for producing a slightly acidic hypochlorous acid aqueous solution by subjecting various treatments after electrolytic treatment of dilute hydrochloric acid. ing.
- the hypochlorous acid aqueous solution obtained by these production methods also has a wide pH value range of 5.0 to 6.5 at the time of production, and it cannot be evaluated that the variation is sufficiently suppressed. ..
- Japanese Unexamined Patent Publication No. 2002-273452 Japanese Unexamined Patent Publication No. 2009-219984 Japanese Unexamined Patent Publication No. 2011-56377 Japanese Unexamined Patent Publication No. 2005-138001 Japanese Unexamined Patent Publication No. 2007-283167
- the present invention is a slightly acidic hypochlorous acid aqueous solution capable of maintaining a constant pH value in the range of 5.5 to 6.5 for a long period of time and maintaining an effective chlorine concentration of 30 ppm or more. It is an object of the present invention to provide a manufacturing method and a manufacturing apparatus.
- an acidic aqueous solution and sodium hypochlorite are supplied to the storage tank while raw water is supplied to the storage tank and stirred, and the pH value of the hypochlorite solution is coarse.
- An aqueous solution is produced, after which the pH value of the hypochlorite aqueous solution is stably maintained at a constant value in the range of 5.5 to 6.5 for 1 minute or more, and the effective chlorine concentration is 30 ppm or more. It is characterized in that the supply of the acidic aqueous solution and the supply of the sodium hypochlorite are repeated until the temperature is maintained.
- the apparatus for producing a hypochlorite aqueous solution of the present invention includes a storage tank having a stirring means, a water supply means for supplying raw water to the storage tank, and a first supply means for supplying an acidic aqueous solution to the storage tank.
- a hypochlorite aqueous solution producing apparatus comprising a pH value controlling means for measuring and controlling the pH value of the hypochlorite solution and a chlorine effective concentration controlling means for measuring and controlling the effective concentration of chlorine in the hypochlorite aqueous solution.
- the value control means the pH value of the hypochlorite aqueous solution is stably maintained at a constant value in the range of 5.5 to 6.5 for 1 minute or more, and the effective chlorine concentration is maintained at 30 ppm or more.
- the device for producing an aqueous hypochlorite solution which is a means for repeatedly supplying the acidic aqueous solution by the first supply means and the sodium hypochlorite by the second supply means in this order.
- a slightly acidic hypochlorous acid aqueous solution capable of maintaining a constant pH value in the range of 5.5 to 6.5 for a long period of time and maintaining an effective chlorine concentration of 30 ppm or more.
- Production method can be provided. Further, according to the present invention, it is possible to provide an apparatus for producing a slightly acidic hypochlorous acid aqueous solution capable of carrying out such a production method. Therefore, the industrial significance of the present invention is extremely large.
- FIG. 1 is a flowchart showing a manufacturing process of the hypochlorous acid aqueous solution of the present invention.
- FIG. 2 is a schematic view for explaining the apparatus for producing the hypochlorous acid aqueous solution of the present invention.
- hypochlorous acid is an extremely unstable substance, but in the prior art, the influence of meteorological conditions such as temperature and humidity at the manufacturing stage is fully considered. It was not done, and (b) in the conventional technique, the pH value of the final product, the hypochlorous acid aqueous solution, is controlled only by measuring immediately after mixing of each component, and it is controlled for a certain period of time after mixing. It was concluded that the fluctuation of the pH value until the lapse of time was not controlled at all.
- hypochlorous acid aqueous solution once by supplying an acidic aqueous solution and sodium hypochlorite to the raw water, and then a certain period of time has passed.
- the above problems (a) and (b) can be solved simultaneously.
- the effective chlorine concentration needs to be 30 PPM or more, and this condition must be satisfied.
- the present invention has been completed based on this finding.
- the present invention will be described in detail by dividing into “1. Method for producing an aqueous solution of hypochlorous acid” and "2. Equipment for producing an aqueous solution of hypochlorous acid”.
- the present invention is not limited by the amount of the hypochlorous acid aqueous solution produced at one time, but in the following, 60 L at a time using a storage tank of 300 L to 500 L on the premise of industrial scale production.
- the present invention will be described in detail by taking as an example the case of producing a ⁇ 200 L hypochlorous acid aqueous solution.
- the method for producing the hypochlorous acid aqueous solution of the present invention will be described with reference to FIG.
- the steps are a) a first step (S01) of supplying raw water to the storage tank, and b) a first step of supplying an acidic aqueous solution while stirring the raw water in the storage tank to generate a mixed aqueous solution of the raw water and the acidic aqueous solution.
- the pH value of the hypochlorite aqueous solution is stably maintained at a constant value in the range of 5.5 to 6.5 for 1 minute or more, and the effective chlorine concentration is 30 ppm or more. It is characterized by comprising a fourth step (S04) in which the supply of the acidic aqueous solution and the supply of the sodium hypochlorite are repeated in this order so as to be maintained.
- the first step is a step of supplying raw water to the storage tank.
- the raw water is not particularly limited, but it is preferable to use pure water such as ion-exchanged water or distilled water in order to prevent impurities from being mixed.
- the total supply amount of raw water is preferably 20% to 40%, preferably 20% to 30% of the capacity of the storage tank, considering the ease of stirring and the supply amount of the acidic aqueous solution and sodium hypochlorite. More preferably, it is more preferably 20% to 25%.
- the first step (S01) in order to make the temperature and pH value of the raw water uniform, when the amount of raw water in the storage tank becomes 20% or more of the capacity of the storage tank, the inside of the storage tank is charged. It is preferable to start stirring the raw water.
- the stirring method is not particularly limited, and for example, a method of rotating a propeller-shaped stirring blade in a storage tank or a method of using a pump can be adopted.
- a method of drawing raw water from the lower part of the storage tank using a circulation pump and then resupplying the drawn raw water from the upper part of the storage tank is preferable.
- the raw water in the storage tank can be convected in the vertical direction, so that the raw water can be uniformly agitated.
- the discharge rate of the circulation pump is preferably 50 L / min or more, and more preferably 100 L / min or more. This is because if the discharge rate of the circulation pump is less than 50 L / min, the raw water may not sufficiently convection.
- the second step (S02) is a step of supplying an acidic aqueous solution while stirring the raw water in the storage tank after the completion of the first step to generate a mixed aqueous solution of the raw water and the acidic aqueous solution.
- the acidic aqueous solution supplied in the second step (S02) is not particularly limited, and dilute hydrochloric acid, acetic acid aqueous solution, dilute sulfuric acid and the like can be used.
- dilute hydrochloric acid more preferably 6% by mass to 8% by mass of dilute hydrochloric acid, and even more preferably 6% by mass to 7% by mass of dilute hydrochloric acid. ..
- the total supply amount of dilute hydrochloric acid in the second step is preferably 1/650 to 1/550, preferably 1/620 to 1/580, with the supply amount of raw water being 100. Is more preferable, and 1/600 is further preferable. If the total amount of dilute hydrochloric acid supplied is out of the above range, sufficient bactericidal action may not be obtained.
- the supply amount of dilute hydrochloric acid per unit time is preferably 28 mL / min to 38 mL / min, and more preferably 33 mL / min to 38 mL / min.
- the third step (S03) is a step of supplying sodium hypochlorite while stirring the mixed aqueous solution in the storage tank to generate the hypochlorous acid aqueous solution after the completion of the second step (S02).
- the generation of chlorine gas is reduced by supplying sodium hypochlorite after supplying an acidic aqueous solution to the raw water. That is, in the method of the present invention, by suppressing the above reaction, it is possible to reduce the generation of chlorine gas, ensure safety, and effectively prevent corrosion of manufacturing equipment.
- the method of supplying sodium hypochlorite is not particularly limited, but it is usually supplied as an aqueous solution of sodium hypochlorite. At this time, it is preferable to adjust the concentration of the sodium hypochlorite aqueous solution to 6% by mass to 7% by mass, and more preferably to 6% by mass to 6.5% by mass.
- the supply amount of sodium hypochlorite in the third step (S03) is preferably 1/650 to 1/550, preferably 1/620 to 1/580, with the total supply amount of raw water as 100. It is more preferable, and it is further preferable to set it to 1/600. If the total supply of hypochlorous acid is out of the above range, sufficient bactericidal action may not be obtained.
- the supply amount of the hypochlorous acid aqueous solution per unit time is preferably 28 mL / min to 38 mL / min, and more preferably 33 mL / min to 38 mL / min.
- Step (S04) In the fourth step (S04), after the completion of the third step (S03), the pH value of the hypochlorous acid aqueous solution generated in the storage tank is stably 5.5 to 6.5 for 1 minute or more. This is a step in which the supply of the acidic aqueous solution and the supply of sodium hypochlorite are repeated in this order until the constant value in the range is maintained.
- the pH value is stably maintained in a specific range for a certain period of time.
- the acidic aqueous solution and sodium hypochlorite are supplied in this order a plurality of times, preferably 5 to 15 times, more preferably 8 to 12 times, while stirring the hypochlorous acid aqueous solution. It is supposed to be.
- the final product, the hypochlorous acid aqueous solution is controlled not by the supply amount of the acidic aqueous solution or sodium hypochlorite, but by the pH value from the mixing of these to the lapse of a certain time.
- each component constituting the hypochlorous acid aqueous solution is in a state of being uniformly dispersed at the molecular level, so that the fluctuation of the pH value with time can be significantly suppressed.
- the present invention since it is not necessary to use a special device when producing such an aqueous solution of hypochlorous acid, it can be widely applied to industrial-scale production.
- the time (measurement time) for measuring the fluctuation of the pH value is 1 minute or more, preferably 2 minutes or more, and more preferably 3 minutes or more. If this measurement time is less than 1 minute, variations in the pH value of the obtained hypochlorous acid aqueous solution and variations over time cannot be sufficiently suppressed.
- the upper limit of the measurement time is not particularly limited, but even if the measurement time is too long, no further effect can be obtained, which leads to deterioration of productivity. Therefore, it is generally preferably within 5 minutes, and more preferably within 4 minutes.
- the pH value of the finally obtained hypochlorous acid aqueous solution is a constant value in the range of 5.5 to 6.5, preferably a constant value in the range of 6.0 to 6.5, more preferably. It will be necessary to adjust to 6.5. In addition, it is necessary to ensure an effective bactericidal action by maintaining the effective chlorine concentration at 30 ppm or more. By adjusting the pH value of the hypochlorous acid aqueous solution to a constant value in such a range, it is possible to suppress the variation in quality while ensuring high safety and bactericidal action.
- hypochlorous acid aqueous solution obtained as described above has a pH value of a constant value in the range of 5.5 to 6.5, preferably 6.0 to 6. It is controlled to a constant value in the range of 5, more preferably to 6.5. That is, since the pH value of the hypochlorous acid aqueous solution obtained by the present invention is almost the same as the pH value of human skin, it can be evaluated that the influence on the human body is extremely small and the safety is excellent. ..
- the abundance of effective chlorine which is a sterilizing and deodorizing component in a hypochlorous acid aqueous solution, varies depending on the pH value. Since the pH value is in the above range and the abundance rate of effective chlorine is 90% or more, the effective chlorine concentration is maintained at 30 ppm or more, and it can be evaluated that it is excellent in bactericidal action and deodorizing action.
- each component is uniformly dispersed at the molecular level as described above, so that the pH value can be maintained for a long period of time.
- the hypochlorous acid aqueous solution obtained by the production method of the present invention has a pH value in the range of 5.5 to 6.5 after storage under normal temperature and pressure for 7 days, preferably 6 It can be maintained at a constant value in the range of 0.0 to 6.5, more preferably 6.5.
- the effective chlorine concentration is maintained at 30 ppm or more.
- hypochlorite aqueous solution obtained by the production method of the present invention does not oxidize (rust) the metal, so that the load on the production equipment is small, and the running cost and maintenance cost are reduced. It can be reduced.
- hypochlorous acid aqueous solution obtained by the production method of the present invention is not limited in its usage method, and its effect can be exhibited by any usage method such as spraying, dipping, and coating. can.
- hypochlorous acid aqueous solution obtained by the production method of the present invention can exert a high bactericidal action against various bacteria and viruses.
- bacteria such as Escherichia coli (O157: H7), Staphylococcus aureus, and Bacillus subtilis
- viruses such as influenza virus, norovirus, and coronavirus.
- the equipment for producing hypochlorous acid aqueous solution of the present invention is particularly limited as long as the above-mentioned production method can be carried out. However, assuming industrial-scale production, it is preferable to have the configuration shown in FIG. That is, the apparatus 1 for producing an aqueous hypochlorite solution of the present invention has a storage tank 2 having a stirring means 3, a water supply means 5 for supplying raw water to the storage tank 2, and a first method for supplying an acidic aqueous solution to the storage tank 2.
- a pH value control means for measuring and controlling the pH value of the supply means 7, the second supply means 9 for supplying sodium hypochlorite to the storage tank 2, and the hypochlorite aqueous solution 11 generated in the storage tank 2.
- the pH value controlling means 12 is provided with the above 12 so that the pH value of the hypochlorite aqueous solution 11 is stably maintained at a constant value in the range of 5.5 to 6.5, and the effective chlorine concentration is 30 ppm or more. It is characterized in that the supply of the acidic aqueous solution by the first supply means 7 and the supply of sodium hypochlorite by the second supply means 9 are repeated in this order so as to be maintained. It is preferable that the pH value control means 12 is automated by a microcontroller, a sequencer, or the like.
- hypochlorous acid aqueous solution 11 is produced using this production apparatus 1
- this production apparatus 1 which is the same as the above-mentioned method for producing the hypochlorous acid aqueous solution. Will be abbreviated or simplified.
- the water supply valve 6 of the water supply means 5 is opened to supply raw water into the storage tank 2.
- the stirring means 3 (circulation pump in the illustrated example) is started to operate and the circulation valves 4a and 4b are opened. ..
- the water supply valve 6 is closed and the supply of raw water is stopped (first step).
- the first supply valve 8 of the first supply means 7 is opened to start supplying the acidic aqueous solution. After supplying a predetermined amount of the acidic aqueous solution, the first supply valve 8 is closed and the supply of the acidic aqueous solution is stopped (second step).
- the second supply valve 10 of the second supply means 9 is opened to start supplying the sodium hypochlorite aqueous solution. Similarly, after supplying a predetermined amount of the sodium hypochlorite aqueous solution, the second supply valve 10 is closed and the supply of the sodium hypochlorite aqueous solution is stopped (third step).
- the hypochlorous acid aqueous solution 11 is generated in the storage tank 2.
- the pH value of the hypochlorite aqueous solution 11 is measured for 1 minute or more by the pH sensor 13 provided in the pH value control means 12, and the chlorine sensor 15 provided in the effective chlorine concentration control means 14 is used.
- the effective chlorine concentration of the hypochlorite aqueous solution 11 is measured over 1 minute or longer.
- the acidic aqueous solution and the sodium hypochlorite aqueous solution are supplied to the hypochlorous acid aqueous solution 11 in this order based on the fluctuation range of the measured pH value and the effective chlorine concentration.
- this operation is repeated a plurality of times, preferably 5 to 15 times, and the pH value of the final product hypochlorous acid aqueous solution 11 is stably in the range of 5.5 to 6.5 for 1 minute or more.
- the supply of all the aqueous solutions is stopped (fourth step (S04)).
- the water supply valve 6 of the water supply means 5 was opened, and the supply of raw water to the storage tank 2 (volume: 500 L) was started at 100 L / min.
- the operation of the stirring means 3 was started and the circulation valves 4a and 4b were opened.
- a circulation pump having a discharge rate of 50 L / min is used as the stirring means 3, and the raw water is drawn from the lower part of the storage tank 2 and then supplied from the upper part to supply the raw water in the storage tank 2.
- the water supply valve 6 was closed, the supply of raw water was stopped, and the first step (S01) was completed.
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Abstract
Description
(1)次亜塩素酸水溶液の製造方法
図1を参照しながら、本発明の次亜塩素酸水溶液の製造方法を説明する。その工程は、a)貯留タンクに原水を供給する第1工程(S01)と、b)前記貯留タンク内の原水を撹拌しながら酸性水溶液を供給し、原水と酸性水溶液の混合水溶液を生成する第2工程(S02)と、c)第2工程後に、前記貯留タンク内の混合水溶液を撹拌しながら次亜塩素酸ナトリウムを供給し、次亜塩素酸水溶液を生成する第3工程(S03)と、d)第3工程後に、前記次亜塩素酸水溶液のpH値が、1分以上、安定して5.5~6.5の範囲の一定値に維持され、かつ、有効塩素濃度が30ppm以上に維持されるように、前記酸性水溶液の供給と前記次亜塩素酸ナトリウムの供給を、この順序で繰り返し行う第4工程(S04)とを備えることを特徴とする。
第1工程は、貯留タンクに原水を供給する工程である。
第2工程(S02)は、第1工程の終了後に、貯留タンク内の原水を撹拌しながら酸性水溶液を供給し、原水と酸性水溶液の混合水溶液を生成する工程である。
第3工程(S03)は、第2工程(S02)の終了後に、貯留タンク内の混合水溶液を撹拌しながら次亜塩素酸ナトリウムを供給し、次亜塩素酸水溶液を生成する工程である。
NaClO+2HCl→NaCl+H2O+Cl2
第4工程(S04)は、第3工程(S03)の終了後に、貯留タンク内に生成された次亜塩素酸水溶液のpH値が、1分以上、安定して5.5~6.5の範囲の一定値に維持されるまで、酸性水溶液の供給と次亜塩素酸ナトリウムの供給を、この順序で繰り返し行う工程である。
a)特性
上述のようにして得られる次亜塩素酸水溶液は、pH値が5.5~6.5の範囲の一定値に、好ましくは6.0~6.5の範囲の一定値に、より好ましくは6.5に制御される。すなわち、本発明により得られる次亜塩素酸水溶液のpH値は、人間の肌のpH値とほぼ同程度であるため、人体に対する影響がきわめて少なく、安全性に優れていると評価することができる。
本発明の製造方法によって得られる次亜塩素酸水溶液は、その使用方法が制限されることはなく、噴霧、浸漬、塗布などのいずれの使用方法によっても、その効果を発揮することができる。
a)次亜塩素酸水溶液の製造装置の構成
本発明の次亜塩素酸水溶液の製造装置は、上述した製造方法を実施することができる限り、特に制限されることはないが、工業規模の生産を前提とした場合、図2に示すような構成を備えることが好ましい。すなわち、本発明の次亜塩素酸水溶液の製造装置1は、撹拌手段3を有する貯留タンク2と、貯留タンク2に原水を供給する給水手段5と、貯留タンク2に酸性水溶液を供給する第1供給手段7と、貯留タンク2に次亜塩素酸ナトリウムを供給する第2供給手段9と、貯留タンク2内に生成される次亜塩素酸水溶液11のpH値を測定および制御するpH値制御手段12とを備え、pH値制御手段12が、次亜塩素酸水溶液11のpH値が、安定して5.5~6.5の範囲の一定値に維持され、かつ、有効塩素濃度が30ppm以上に維持されるように、第1供給手段7による酸性水溶液の供給と第2供給手段9による次亜塩素酸ナトリウムの供給を、この順序で繰り返し行うように構成されていることを特徴とする。このようなpH値制御手段12は、マイクロコントローラやシーケンサなどによって自動化されていることが好ましい。
次に、この製造装置1を用いて、次亜塩素酸水溶液11を製造する場合について説明するが、上述した次亜塩素酸水溶液の製造方法と同様である部分については、省略ないしは
簡略化して説明する。
a)第1工程(S01)
はじめに、図1に示す次亜塩素酸水溶液の製造装置1の給水手段5に原水(イオン交換水)を、第1供給手段7に6質量%の希塩酸を、第2供給手段9に6質量%の次亜塩素酸ナトリウム水溶液をそれぞれセットした。
第1工程(S01)終了後、撹拌手段3を稼働した状態のまま、第1供給手段7の第1供給弁8を開け、貯留タンク2内に、38mL/分で希塩酸の供給を開始した。14分間の供給後、第1供給弁8を閉じ、希塩酸の供給を停止し(総供給量:0.53L)、第2工程(S02)を終了した。
第2工程(S02)終了後、同様に、撹拌手段3を稼働した状態のまま、第2供給手段9の第2供給弁10を開け、貯留タンク2内に、38mL/分で次亜塩素酸ナトリウム水溶液の供給を開始した。11分間の供給後、第2供給弁10を閉じ、次亜塩素酸ナトリウム水溶液の供給を停止し(総供給量:0.42L)、第3工程(S03)を終了した。
第3工程(S03)の終了後、pH値制御手段12に備え付けられたpHセンサ13により、貯留タンク2内に生成された次亜塩素酸水溶液11のpH値を30分間にわたって測定したところ、5.5~6.5の範囲で変動していることが確認された。このため、次亜塩素酸水溶液11に、再度、第1供給手段7による希塩酸の供給と、第2供給手段9による次亜塩素酸ナトリウム水溶液の供給を、この順序で行った後、同様にして、次亜塩素酸水溶液11のpH値の測定をしたところ、5.5~6.5の範囲で変動し、また、有効塩素濃度が30ppm以上に維持されていることが確認された。以降、この操作を10回繰り返して行い、最終的に、pH値が3分間(180秒間)にわたって、安定して6.5に維持され、かつ、有効塩素濃度が30ppm以上に維持されたことを確認した後、第4工程(S04)を終了した。
S02 第2工程
S03 第3工程
S04 第4工程
1 次亜塩素酸水溶液の製造装置
2 貯留タンク
3 撹拌手段
4a、4b 循環弁
5 給水手段
6 給水弁
7 第1供給手段
8 第1供給弁
9 第2供給手段
10 第2供給弁
11 次亜塩素酸水溶液
12 pH値制御手段
13 pHセンサ
14 有効塩素濃度制御手段
15 塩素センサ
Claims (2)
- 貯留タンクに原水を供給し撹拌しながら、該貯留タンクに酸性水溶液と次亜塩素酸ナトリウムを供給し、pH値が粗調の次亜塩素酸水溶液を生成し、
その後に、前記次亜塩素酸水溶液のpH値が、1分以上、安定して5.5~6.5の範囲の一定値に維持され、かつ、有効塩素濃度が30ppm以上に維持されるように、前記酸性水溶液の供給と前記次亜塩素酸ナトリウムの供給を繰り返し行う次亜塩素酸水溶液の製造方法。 - 撹拌手段を有する貯留タンクと、該貯留タンクに原水を供給する給水手段と、該貯留タンクに酸性水溶液を供給する第1供給手段と、該貯留タンクに次亜塩素酸ナトリウムを供給する第2供給手段と、該貯留タンク内に、前記原水と前記酸性水溶液との混合水溶液と前記次亜塩素酸ナトリウムとの混合により生成された次亜塩素酸水溶液のpH値を測定および制御するpH値制御手段と、前記次亜塩素酸水溶液の塩素の有効存在率を測定および制御する塩素有効存在率制御手段とを備える次亜塩素酸水溶液製造装置であって、
前記pH値制御手段は、前記次亜塩素酸水溶液のpH値が、1分以上、安定して5.5~6.5の範囲の一定値に維持され、かつ、有効塩素濃度が30ppm以上に維持されるように、第1供給手段による酸性水溶液の供給と第2供給手段による次亜塩素酸ナトリウムの供給を、この順序で繰り返し行う手段である、次亜塩素酸水溶液の製造装置。
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