WO2022091381A1 - 次亜塩素酸水の製造方法及び製造装置 - Google Patents
次亜塩素酸水の製造方法及び製造装置 Download PDFInfo
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- WO2022091381A1 WO2022091381A1 PCT/JP2020/040946 JP2020040946W WO2022091381A1 WO 2022091381 A1 WO2022091381 A1 WO 2022091381A1 JP 2020040946 W JP2020040946 W JP 2020040946W WO 2022091381 A1 WO2022091381 A1 WO 2022091381A1
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- Prior art keywords
- aqueous solution
- hypochlorite
- water
- ppm
- hypochlorous acid
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title abstract description 22
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 161
- 239000007864 aqueous solution Substances 0.000 claims abstract description 105
- 230000002378 acidificating effect Effects 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 238000004519 manufacturing process Methods 0.000 claims description 50
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 31
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 31
- 238000005507 spraying Methods 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 32
- 239000000243 solution Substances 0.000 abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- 238000007792 addition Methods 0.000 description 25
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000001954 sterilising effect Effects 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- -1 hypochlorite ions Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 101100352919 Caenorhabditis elegans ppm-2 gene Proteins 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- BIVQBWSIGJFXLF-UHFFFAOYSA-N PPM-18 Chemical compound C=1C(=O)C2=CC=CC=C2C(=O)C=1NC(=O)C1=CC=CC=C1 BIVQBWSIGJFXLF-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
Images
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Definitions
- the present invention relates to a method for producing hypochlorite water and a production apparatus.
- hypochlorous acid water an aqueous solution of hypochlorous acid
- hypochlorous acid water an aqueous solution of hypochlorous acid
- the bactericidal or sterilizing effect of an aqueous solution of hypochlorous acid depends on the oxidizing power of hypochlorous acid molecules and hypochlorite ions.
- hypochlorite solution electrolyze the hypochlorite by electrolysis, and neutralize the aqueous solution of hypochlorite (sodium hypochlorite, etc.) and the acid aqueous solution (hydrochloric acid, etc.).
- hypochlorite sodium hypochlorite, etc.
- acid aqueous solution hydroochloric acid, etc.
- hypochlorite water For example, in the fields of food manufacturing factories and agriculture, it is necessary to use a large amount of hypochlorite water as sterilizing water, but in the electrolysis method, an expensive electrolytic device is required for mass production of hypochlorite water. .. The amount of hypochlorite water produced is insufficient and it is not practical.
- a high-concentration weakly acidic hypochlorous acid having a sterilizing or sterilizing effect is usually obtained by contacting and reacting a mixed solution of raw water such as tap water or well water with sodium hypochlorite with hydrochloric acid. Generates an acid aqueous solution (hypochlorous acid water).
- chlorine gas may be generated as a by-product.
- FIG. 3 is a schematic diagram of a manufacturing apparatus using the two-component method in the prior art. It is assumed that the illustrated manufacturing apparatus uses hydrochloric acid and sodium hypochlorite as raw materials.
- water for dilution reaches the flow rate proportional injection pump 33 from the faucet 31 through the flow meter 32.
- Hydrochloric acid is charged from the hydrochloric acid tank 34 into the flow rate proportional injection pump 33, and the hydrochloric acid is diluted with the above-mentioned water for dilution to reach the next flow rate proportional injection pump 36.
- a sodium hypochlorite aqueous solution is stored in the sodium hypochlorite tank 37, which is a tank separate from the hydrochloric acid tank 34, and the sodium hypochlorite aqueous solution is supplied to the flow rate proportional injection pump 36 described above. To. In this way, the hydrochloric acid supplied to the flow rate proportional injection pump 36 and the sodium hypochlorite aqueous solution are mixed by the mixer 38. As a result of mixing, hypochlorite water is produced, the pH of the product is measured by the pH measuring device 39, and the hypochlorite water obtained by the hypochlorite water spraying device 310 is sprayed.
- Patent Document 1 states that when the pH is 3.5 or higher, chlorine gas is substantially not generated, and the hypochlorite solution is allowed to pass therethrough.
- Invention of a manufacturing apparatus including a container filled with a weakly acidic ion exchanger and configured so that when the hypochlorite solution passes through the container, the pH does not drop below the pH at which chlorine gas is generated. Is disclosed.
- An object of the present invention is to provide a method and an apparatus for safely and easily producing hypochlorite water in a two-component method.
- An acidic aqueous solution having a pH of 1.5 to 5 and an aqueous solution containing hypochlorite are prepared separately and independently, and the two aqueous solutions are mixed.
- the pH is 5
- the production method of (1) to (3), wherein the hypochlorous acid concentration of the hypochlorous acid water is 2240 ppm or less.
- a first container capable of containing an acidic aqueous solution
- a second container separate from the first container capable of containing an aqueous solution containing a hypochlorite
- a first and second container A mixer capable of mixing the acidic aqueous solution and the aqueous solution containing the hypochlorite by being connected via a pipe, and a pH measuring device capable of measuring the pH of the hydrochloric acid provided in the mixer.
- the pipe is configured so that the contents of the first container and the contents of the second container do not come into contact with each other before being provided to the mixer, and the acidic aqueous solution in the mixer is used.
- a device for producing hypochlorite water which produces hypochlorite water by mixing with the aqueous solution containing hypochlorite.
- the pH measuring device includes a storage means for storing a pH threshold value and a signal emitting means for emitting a signal when the measured pH of the acidic aqueous solution is lower than the pH threshold value.
- Device. (7) The manufacturing apparatus (5) or (6), further comprising a spraying device connected to the mixer, wherein the spraying device sprays hypochlorite water produced by the mixer.
- chlorine gas is substantially generated only when the pH environment of hypochlorite ion is lower than 1.35. Therefore, if the pH of the acidic aqueous solution is adjusted to 1.5 to 5 in advance and then brought into contact with hypochlorite ions, the concern about chlorine gas generation can be eliminated.
- the aqueous solution containing hypochlorite is mixed with an acidic aqueous solution adjusted to a pH value of 1.5 or more. In the neutralization reaction, the pH of the acidic aqueous solution before the reaction does not decrease and increases, so that the pH of hypochlorite does not fall below 1.5 in the production process. Therefore, the concern about chlorine gas generation in the entire manufacturing process is eliminated.
- substantially no chlorine gas means that no chlorine gas is substantially generated at a level dangerous to the living body, and chlorine bubbles from the solution when the pH of the hypochlorite solution is lowered. It means that it is not possible to confirm that chlorine is occurring, or that there is virtually no bleaching effect due to chlorine when the pH of the hypochlorite solution is lowered, which is one of the guidelines. Is a state in which the pungent odor peculiar to chlorine is hardly felt even when the generated hypochlorite aqueous solution is put into a cup or the like and the smell is directly smelled.
- hypochlorite water can be safely and easily obtained by the above-mentioned production method.
- FIG. 1 is a plot of measurement results in an embodiment of the present invention.
- FIG. 2 is a schematic diagram of the apparatus of the present invention.
- FIG. 3 is a schematic diagram of a manufacturing apparatus according to the prior art.
- a neutralization reaction is caused by contacting an aqueous solution of hypochlorite with an acidic aqueous solution, and hypochlorite is obtained from the hypochlorite.
- an acidic aqueous solution and an aqueous solution containing hypochlorite are prepared separately and independently. Preparing both aqueous solutions separately and independently means that the two aqueous solutions are not brought into contact with each other until the respective aqueous solutions have a predetermined pH and concentration. This makes it possible to suppress the generation of chlorine gas due to the contact between the aqueous solution having an undesirably low pH and the hypochlorite.
- the lower limit of the pH of the acidic aqueous solution to be prepared is 1.5, and preferable lower limit values include 1.75 and 2.0.
- a preferable upper limit of the pH of the acidic aqueous solution to be prepared is 2.1, and when the pH is 2.1 or less, hypochlorous acid water containing a significantly high concentration of hypochlorous acid can be obtained. Can be done.
- the pH of the acidic aqueous solution needs to be low, but on the other hand, from the viewpoint of preventing the generation of chlorine gas, a pH that is too low is inappropriate. .. From these points, the above pH range can be mentioned.
- the pH of the acidic aqueous solution to be prepared should be set based on the concentration and pH of the hypochlorite water finally obtained in consideration of the stoichiometry in the neutralization reaction described later. Can be done.
- FIG. 1 is a plot of the amount of sodium hypochlorite added and the pH of the product in the examples described later.
- the relationship between the addition amount and pH as shown in FIG. 1 can also be used. The specific contents of FIG. 1 will be described in detail in the column of Examples described later.
- the acid in the acidic aqueous solution is not particularly limited, and examples thereof include hydrochloric acid, acetic acid, and citric acid. Considering the use of the hypochlorite water to be finally obtained, it is preferable to use hydrochloric acid or citric acid, which have less adverse effect on the human body.
- the concentration of hypochlorite to be prepared can be set in consideration of the concentration of the hypochlorite water finally obtained. Specifically, if an aqueous solution containing 1 mol of hypochlorous acid ion is neutralized with an acid, an aqueous solution containing 1 mol of hypochlorous acid can be obtained. The concentration of hypochlorite can be determined in consideration of the stoichiometry.
- the hypochlorite is not particularly limited, and typically includes alkali metal salts, especially sodium salts, and the like.
- An example of a method for setting the pH and concentration of an aqueous solution containing an acidic aqueous solution and a hypochlorite prepared separately and independently is as follows.
- the total amount of water and the amount of hypochlorite (ions) are determined from the target concentration of hypochlorous acid in the finally obtained hypochlorous acid water.
- the pH of the acidic aqueous solution prepared in advance is determined from the amount of acid required to neutralize hypochlorite to hypochlorous acid and the target pH of the finally obtained hypochlorous acid water.
- the examples described later can also be referred to.
- the pH of the obtained hypochlorite water is preferably 5 to 7, more preferably 5.5 to 6.5. Within the pH range, it can be safely used for foods and the like, and a suitable sterilizing / sterilizing effect can be obtained.
- the concentration of hypochlorous acid in the obtained hypochlorous acid water is not particularly limited, and as a preferable upper limit value, the upper limit value of the concentration of hypochlorous acid in this production method in which chlorine gas is not generated in principle is 2,440 ppm. Therefore, if the concentration is below the upper limit, it can be appropriately selected from the viewpoint of storage and transportation costs, sterilization and sterilization effects, and the like.
- the specific means for preparing the acidic aqueous solution and the aqueous solution containing hypochlorite separately and independently, and the specific method for mixing the two aqueous solutions are not particularly limited, and the methods in the prior art may be appropriately referred to. can.
- the present invention also provides a manufacturing apparatus capable of manufacturing hypochlorite water by implementing the above-mentioned usage.
- the device includes at least a first container, a second container, a mixer, a pipe connecting them, and a pH measuring device.
- FIG. 2 is a schematic diagram of the apparatus of the present invention.
- FIG. 2 is depicted on the premise that hydrochloric acid is used as the acidic aqueous solution and sodium hypochlorite is used as the hypochlorite.
- the invention is not limited to such uses.
- the first container is for accommodating an acidic aqueous solution having a pH of 1.5 to 5.
- the mixing tank indicated by reference numeral 26 corresponds to the “first container”.
- the first container may merely be able to contain a liquid, or may further include, for example, a mixing function with water for dilution as described below.
- the pH of the acidic aqueous solution is 1.5 to 5, chlorine gas is not generated, and the method for producing such an acidic aqueous solution and specific examples are as described above.
- the material, shape, and the like of the first container are not particularly limited as long as they can accommodate the acidic aqueous solution, and examples thereof include acid-resistant metal containers, glass containers, and acid-resistant plastic containers.
- a faucet 21, a flow meter 22, a flow rate proportional injection pump 23, and a raw material before dilution, which are sources of water for dilution, are used.
- a hydrochloric acid tank 24, which is a container for the acid, and a mixer 25 for diluting the acid with water are provided.
- the second container is for accommodating an aqueous solution containing hypochlorite.
- the sodium hypochlorite tank indicated by reference numeral 28 corresponds to the “second container”.
- the production method and properties of the aqueous solution containing hypochlorite are as described above.
- the material, shape, and the like of the second container are not particularly limited as long as they can accommodate the aqueous solution, and examples thereof include an alkali-resistant metal container, a glass container, and an alkali-resistant plastic container.
- the second container is designated by reference numeral 28.
- the first and second containers are provided separately and independently of each other. Being provided separately means that the contents of the first and second containers are separated to the extent that they do not mix without user intervention.
- the contents of the first and second containers are mixed in the mixer 29 indicated by reference numeral 29.
- the contents of the mixing tank 26 and the contents 28 of the sodium hypochlorite tank are supplied to the mixer 29 by using the flow rate proportional injection pump 27.
- the flow path from the two tanks 26 and 28 to the mixer 29 is connected by a pipe, and the flow rate proportional injection pump 27 described above constitutes all or a part of the pipe.
- the piping is configured so that the contents of the mixing tank 26 and the contents of the sodium hypochlorite tank 28 do not come into contact with each other before being provided to the mixer 29.
- the apparatus of the present invention is provided with a pH measuring apparatus for measuring the pH of an acidic aqueous solution before being supplied to a mixer.
- the pH measuring device is indicated by reference numeral 210.
- a pH measuring device a commercially available pH meter or the like can be appropriately used.
- the pH measuring device 210 includes a storage means (not shown) for storing the pH threshold and a signal emitting means (not shown) for emitting a signal when the measured pH of the acidic aqueous solution is lower than the pH threshold. It is preferable to provide with (1).
- a memory for storing information such as "the threshold value of pH is 1.4" in the pH measuring device 210 corresponds to the storage means.
- Examples of the signal emitted by the signal emitting means include a signal for stopping the driving of the entire device, a buzzer (sound) and a warning light (light) for notifying the user of an abnormality, and the like.
- the above signal is emitted to automatically or manually operate the device to stop the drive of the device and prevent the generation of chlorine gas. be able to.
- hypochlorous acid water is produced by mixing an acidic aqueous solution and an aqueous solution containing hypochlorite in the above-mentioned mixer 29.
- the generated hypochlorite water can be used arbitrarily.
- a spraying device is connected to the mixer 29, from which hypochlorite water can be sprayed.
- the spraying device corresponds to the hypochlorous acid spraying device indicated by reference numeral 211 in the device of FIG.
- the spraying device conventionally known materials and forms can be appropriately selected and used.
- hydrochloric acid was diluted with pure water to prepare dilute hydrochloric acid having a pH of 4.03.
- a 100,000 ppm sodium hypochlorite aqueous solution was prepared separately from the dilute hydrochloric acid.
- To 1 liter of the dilute hydrochloric acid 0.2 ml of the sodium hypochlorite aqueous solution was added, and the pH and the hypochlorous acid concentration were measured.
- the amount of sodium hypochlorite aqueous solution added (denoted as "addition amount"), the pH measured as described above (denoted as "pH"), and the concentration of hypochlorous acid (referred to as "hypochlorous acid concentration"). Notation) is summarized below.
- Example 2 Approximately 1 liter of hypochlorite water (pH 6.77, concentration 62 ppm) was treated in the same manner as in Example 1 except that the pH of the dilute hydrochloric acid prepared first was adjusted to 3.45 instead of 4.03. Got As in the case of Example 1, the "addition amount”, "pH” and “hypochlorous acid concentration” were measured. The measurement results are summarized below, and further plotted with the addition amount on the horizontal axis and pH on the vertical axis as FIG. 1, “B”. No odor of chlorine gas was generated from the start of production to during and after production.
- Example 3 Approximately 1 liter of hypochlorite water (pH 6.68, concentration 88 ppm) was treated in the same manner as in Example 1 except that the pH of the dilute hydrochloric acid prepared first was adjusted to 3.02 instead of 4.03. Got As in the case of Example 1, the "addition amount”, "pH” and “hypochlorous acid concentration” were measured. The measurement results are summarized below, and further plotted with the addition amount on the horizontal axis and pH on the vertical axis as FIG. 1, “C”. No odor of chlorine gas was generated from the start of production to during and after production.
- hydrochloric acid was diluted with pure water to prepare dilute hydrochloric acid having a pH of 2.51.
- a 100,000 ppm sodium hypochlorite aqueous solution was prepared separately from the dilute hydrochloric acid.
- To 1 liter of the dilute hydrochloric acid 1 ml of the sodium hypochlorite aqueous solution was added, and the pH and the hypochlorous acid concentration were measured.
- the amount of sodium hypochlorite aqueous solution added (denoted as "addition amount"), the pH measured as described above (denoted as "pH”), and the concentration of hypochlorite (referred to as "hypochlorite concentration").
- Example 5 Approximately 1 liter of hypochlorite water (pH 6.55, concentration 930 ppm) was treated in the same manner as in Example 4, except that the pH of the dilute hydrochloric acid prepared first was adjusted to 2.02 instead of 2.51. Got As in the case of Example 4, the "addition amount”, “pH” and “hypochlorous acid concentration” were measured. The measurement results are summarized below, and further plotted with the addition amount on the horizontal axis and pH on the vertical axis as FIG. 1, “E”. No odor of chlorine gas was generated from the start of production to during and after production.
- Example 6 Approximately 1 liter of hypochlorite water (pH 6.52, concentration 1150 ppm) was treated in the same manner as in Example 4, except that the pH of the dilute hydrochloric acid prepared first was adjusted to 1.75 instead of 2.51. Got As in the case of Example 4, the "addition amount”, "pH” and “hypochlorous acid concentration” were measured. The measurement results are summarized below, and further plotted with the addition amount on the horizontal axis and pH on the vertical axis as FIG. 1, “F”. No odor of chlorine gas was generated from the start of production to during and after production.
- Example 7 Approximately 1 liter of hypochlorite water (pH 6.65, concentration 2240 ppm) was treated in the same manner as in Example 4, except that the pH of the dilute hydrochloric acid prepared first was adjusted to 1.50 instead of 2.51. Got As in the case of Example 4, the "addition amount”, “pH” and “hypochlorous acid concentration” were measured. The measurement results are summarized below, and further plotted with the addition amount on the horizontal axis and pH on the vertical axis as FIG. 1, “G”. No odor of chlorine gas was generated from the start of production to during and after production.
- hydrochloric acid was diluted with pure water to prepare dilute hydrochloric acid having a pH of 1.35.
- a 100,000 ppm sodium hypochlorite aqueous solution was prepared separately from the dilute hydrochloric acid.
- To 1 liter of the dilute hydrochloric acid 1 ml of the sodium hypochlorite aqueous solution was added.
- the reaction solution was stirred while continuing to measure the pH of the reaction solution. The pH gradually increased and became stable, but the odor of chlorine gas was generated after about 1 hour. In consideration of safety, the process was terminated at this stage. As a result, in this example, hypochlorite water could not be obtained in a safe process.
- citric acid was diluted with pure water to prepare an aqueous citric acid solution having a pH of 1.88.
- a 100,000 ppm sodium hypochlorite aqueous solution was prepared separately from the citric acid aqueous solution.
- 40 ml of the sodium hypochlorite aqueous solution was added to 50 ml of the citric acid aqueous solution.
- the hypochlorous acid concentration obtained by the neutralization reaction at this time corresponds to 44,400 ppm. In this way, about 90 ml of hypochlorite water (pH 6.00) was obtained. No odor of chlorine gas was generated during and after this production. Therefore, this example is also an embodiment of the present invention.
- Example 9 The pH of the initially prepared citric acid aqueous solution was adjusted to 2.01 instead of 1.88, and the amount of 100,000 ppm sodium hypochlorite aqueous solution prepared separately was added to 50 ml of this citric acid aqueous solution. Approximately 61 ml of hypochlorous acid water was obtained by the same treatment as in Example 8 except that the value was changed to 11 ml. The hypochlorous acid concentration obtained by the neutralization reaction at this time corresponds to 18,000 ppm. The measured value of the pH of this hypochlorite water was 6.19, and no odor of chlorine gas was generated during and after the production. Therefore, this example is also an embodiment of the present invention.
- Example 10 The pH of the initially prepared citric acid aqueous solution was adjusted to 2.75 instead of 1.88, and the amount of 100,000 ppm sodium hypochlorite aqueous solution prepared separately was added to 50 ml of this citric acid aqueous solution. About 51 ml of hypochlorous acid water was obtained by the same treatment as in Example 8 except that the value was changed to 1 ml. The hypochlorous acid concentration obtained by the neutralization reaction at this time corresponds to 1900 ppm. The measured value of the pH of this hypochlorite water was 6.04, and no odor of chlorine gas was generated during and after the production. Therefore, this example is also an embodiment of the present invention.
- Example 11 The pH of the initially prepared citric acid aqueous solution was adjusted to 3.05 instead of 1.88, and the amount of 100,000 ppm sodium hypochlorite aqueous solution prepared separately was added to 50 ml of this citric acid aqueous solution. Approximately 50.3 ml of hypochlorous acid water was obtained by the same treatment as in Example 8 except that the value was changed to 0.3 ml. The hypochlorous acid concentration obtained by the neutralization reaction at this time corresponds to 596 ppm. The measured value of the pH of this hypochlorite water was 6.24, and no odor of chlorine gas was generated during and after the production. Therefore, this example is also an embodiment of the present invention.
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Abstract
Description
(1)pHが1.5~5である酸性水溶液と、次亜塩素酸塩を含む水溶液とを、別個独立にそれぞれ調製して、前記両水溶液を混合することを特徴とする、pHが5~7である次亜塩素酸水の製造方法。
(2)前記酸性水溶液が塩酸水溶液である(1)の製造方法。
(3)前記次亜塩素酸塩が次亜塩素酸ナトリウムである(1)又は(2)の製造方法。
(4)前記次亜塩素酸水の次亜塩素酸濃度が2240ppm以下である(1)~(3)の製造方法。
(5)酸性水溶液を収容し得る第1の容器と、次亜塩素酸塩を含む水溶液を収容し得る第1の容器とは別個独立の第2の容器と、第1及び第2の容器と配管を介して連結して前記酸性水溶液と前記次亜塩素酸塩を含む水溶液とを混合させることができる混合機と、前記混合機に供される前記塩酸のpHを測定し得るpH測定装置と、を備え、前記配管は第1の容器の内容物と第2の容器の内容物とが前記混合機に供される前には接触しないよう構成されており、前記混合機における前記酸性水溶液と前記次亜塩素酸塩を含む水溶液との混合により次亜塩素酸水が生成する、次亜塩素酸水の製造装置。
(6)前記pH測定装置はpHの閾値を格納する記憶手段と、測定された前記酸性水溶液のpHが前記pHの閾値より低いときに信号を発する信号発出手段と、を備える(5)の製造装置。
(7)前記混合機に連結された噴霧装置をさらに備え、前記噴霧装置は前記混合機で生成する次亜塩素酸水を噴霧するものである、(5)又は(6)製造装置。
最終的に得る次亜塩素酸水における次亜塩素酸の目標濃度から、水の総量及び次亜塩素酸塩(イオン)の量を決定する。次亜塩素酸塩を次亜塩素酸へと中和するために必要な酸の量および最終的に得る次亜塩素酸水における目標pHから、予め調製する酸性水溶液のpHが決定される。これらの具体的な数値例は後述の実施例などを参照することもできる。
pH:東亜DKK製ポータブルpH計HM-30Pにて反応系中のpHを連続的に測定し続けた。
次亜塩素酸濃度:柴田科学株式会社製有効塩素濃度測定キットAQ-202P型により有効塩素濃度を測定して次亜塩素酸濃度に換算した。
塩素ガス:官能検査(臭い)により塩素ガス発生の有無を判定した。
まず、塩酸を純水で希釈して、pHが4.03である希塩酸を調製した。上記希塩酸とは別個独立に100,000ppmの次亜塩素酸ナトリウム水溶液を調製した。1リットルの上記希塩酸に対して、上記次亜塩素酸ナトリウム水溶液を0.2mlずつ添加し、pH及び次亜塩素酸濃度を測定した。次亜塩素酸ナトリウム水溶液の添加量(「添加量」と表記)と、前記のようにして測定したpH(「pH」と表記)及び次亜塩素酸の濃度(「次亜塩素酸濃度」と表記)を以下にまとめる。さらに、添加量を横軸とし、pHを縦軸として、図1、「A」として、プロットした。このようにして、約1リットルの次亜塩素酸水(pH6.56、濃度42ppm)を得た。製造開始から製造中及び製造後に至るまで、塩素ガスの臭いは一切発生しなかった。
0ml 4.03 0ppm
0.2ml 5.90 26ppm
0.4ml 6.56 42ppm
最初に調製する希塩酸のpHを4.03ではなく3.45に調節したことの他は、実施例1と同様の処理により、約1リットルの次亜塩素酸水(pH6.77、濃度62ppm)を得た。実施例1の場合と同様に、「添加量」、「pH」及び「次亜塩素酸濃度」を測定した。測定結果を、以下にまとめ、さらに、添加量を横軸とし、pHを縦軸として、図1、「B」として、プロットした。製造開始から製造中及び製造後に至るまで、塩素ガスの臭いは一切発生しなかった。
0ml 3.45 0ppm
0.2ml 5.34 25ppm
0.4ml 6.23 39ppm
0.6ml 6.77 62ppm
最初に調製する希塩酸のpHを4.03ではなく3.02に調節したことの他は、実施例1と同様の処理により、約1リットルの次亜塩素酸水(pH6.68、濃度88ppm)を得た。実施例1の場合と同様に、「添加量」、「pH」及び「次亜塩素酸濃度」を測定した。測定結果を、以下にまとめ、さらに、添加量を横軸とし、pHを縦軸として、図1、「C」として、プロットした。製造開始から製造中及び製造後に至るまで、塩素ガスの臭いは一切発生しなかった。
0ml 3.02 0ppm
0.2ml 3.34 22ppm
0.4ml 4.92 48ppm
0.6ml 6.16 67ppm
0.6ml 6.68 88ppm
まず、塩酸を純水で希釈して、pHが2.51である希塩酸を調製した。上記希塩酸とは別個独立に100,000ppmの次亜塩素酸ナトリウム水溶液を調製した。1リットルの上記希塩酸に対して、上記次亜塩素酸ナトリウム水溶液を1mlずつ添加し、pH及び次亜塩素酸濃度を測定した。次亜塩素酸ナトリウム水溶液の添加量(「添加量」と表記)と、前記のようにして測定したpH(「pH」と表記)及び次亜塩素酸の濃度(「次亜塩素酸濃度」と表記)を以下にまとめ、さらに、添加量を横軸とし、pHを縦軸として、図1、「D」として、プロットした。このようにして、約1リットルの次亜塩素酸水(pH6.53、濃度300ppm)を得た。製造開始から製造中及び製造後に至るまで、塩素ガスの臭いは一切発生しなかった。
0ml 2.51 0ppm
1ml 2.74 142ppm
2ml 3.24 218ppm
3ml 6.53 300ppm
最初に調製する希塩酸のpHを2.51ではなく2.02に調節したことの他は、実施例4と同様の処理により、約1リットルの次亜塩素酸水(pH6.55、濃度930ppm)を得た。実施例4の場合と同様に、「添加量」、「pH」及び「次亜塩素酸濃度」を測定した。測定結果を、以下にまとめ、さらに、添加量を横軸とし、pHを縦軸として、図1、「E」として、プロットした。製造開始から製造中及び製造後に至るまで、塩素ガスの臭いは一切発生しなかった。
0ml 2.02 0ppm
1ml 2.10 73ppm
2ml 2.17 215ppm
3ml 2.24 327ppm
4ml 2.35 368ppm
5ml 2.49 464ppm
6ml 2.69 522ppm
7ml 3.01 585ppm
8ml 5.49 645ppm
9ml 6.55 930ppm
最初に調製する希塩酸のpHを2.51ではなく1.75に調節したことの他は、実施例4と同様の処理により、約1リットルの次亜塩素酸水(pH6.52、濃度1150ppm)を得た。実施例4の場合と同様に、「添加量」、「pH」及び「次亜塩素酸濃度」を測定した。測定結果を、以下にまとめ、さらに、添加量を横軸とし、pHを縦軸として、図1、「F」として、プロットした。製造開始から製造中及び製造後に至るまで、塩素ガスの臭いは一切発生しなかった。
0ml 1.75 0ppm
1ml 1.83 133ppm
2ml 1.88 254ppm
3ml 1.97 312ppm
4ml 2.05 388ppm
5ml 2.14 440ppm
6ml 2.26 468ppm
7ml 2.41 585ppm
8ml 2.64 666ppm
9ml 3.19 788ppm
10ml 6.00 844ppm
11ml 6.52 1150ppm
最初に調製する希塩酸のpHを2.51ではなく1.50に調節したことの他は、実施例4と同様の処理により、約1リットルの次亜塩素酸水(pH6.65、濃度2240ppm)を得た。実施例4の場合と同様に、「添加量」、「pH」及び「次亜塩素酸濃度」を測定した。測定結果を、以下にまとめ、さらに、添加量を横軸とし、pHを縦軸として、図1、「G」として、プロットした。製造開始から製造中及び製造後に至るまで、塩素ガスの臭いは一切発生しなかった。
0ml 1.50 0ppm
1ml 1.55 111pm
2ml 1.58 211pm
3ml 1.62 294pm
4ml 1.68 336pm
5ml 1.70 405pm
6ml 1.74 460pm
7ml 1.78 496pm
8ml 1.83 612pm
9ml 1.88 696pm
10ml 1.95 732pm
11ml 2.02 768pm
12ml 2.09 844pm
13ml 2.18 872pm
14ml 2.28 1056ppm
15ml 2.42 1215ppm
16ml 2.56 1386ppm
17ml 2.79 1519ppm
18ml 3.19 1544ppm
19ml 5.42 1680ppm
20ml 6.19 1850ppm
21ml 6.48 1930ppm
22ml 6.65 2240ppm
まず、塩酸を純水で希釈して、pHが1.35である希塩酸を調製した。上記希塩酸とは別個独立に100,000ppmの次亜塩素酸ナトリウム水溶液を調製した。1リットルの上記希塩酸に対して、1mlの上記次亜塩素酸ナトリウム水溶液を添加した。添加後、反応液のpHを測定し続けながら、反応液を撹拌したところ、徐々にpHが上昇してやがて安定したが、約1時間経過後に塩素ガスの臭いが発生した。安全性を考慮して、この段階で処理を終了した。結果として、この例では、安全な工程で次亜塩素酸水を得ることができなかった。
最初に調製する希塩酸のpHを1.35ではなく1.30に調節したことの他は、比較例1と同様の処理を試みた。1リットルの上記希塩酸に対して、1mlの上記次亜塩素酸ナトリウム水溶液を添加したところ、数分後には反応液が黄変し、塩素ガスの臭いが発生した。安全性を考慮して、この段階で処理を終了した。結果として、この例では、安全な工程で次亜塩素酸水を得ることができなかった。
最初に調製する希塩酸のpHを1.35ではなく1.15に調節したことの他は、比較例1と同様の処理を試みた。1リットルの上記希塩酸に対して、1mlの上記次亜塩素酸ナトリウム水溶液を添加したところ、数分後には反応液が黄変し、塩素ガスの臭いが発生した。安全性を考慮して、この段階で処理を終了した。結果として、この例では、安全な工程で次亜塩素酸水を得ることができなかった。
まず、クエン酸を純水で希釈して、pHが1.88であるクエン酸水溶液を調製した。上記クエン酸水溶液とは別個独立に100,000ppmの次亜塩素酸ナトリウム水溶液を調製した。50mlの上記クエン酸水溶液に対して、40mlの上記次亜塩素酸ナトリウム水溶液を添加した。添加後、反応液のpHを測定し続けながら、反応液を撹拌したところ、徐々にpHが上昇し、pHの値が6.00で安定した。このときの中和反応により得られる次亜塩素酸濃度は44400ppmに相当する。このようにして、約90mlの次亜塩素酸水(pH6.00)を得た。この製造中及び製造後に、塩素ガスの臭いは一切発生しなかった。よって、この例もまた本発明の実施の一形態である。
最初に調製するクエン酸水溶液のpHを1.88ではなく2.01に調節し、このクエン酸水溶液50mlに対して、別個独立に調製した100,000ppmの次亜塩素酸ナトリウム水溶液の添加量を11mlに変更したことの他は、実施例8と同様の処理にて、約61mlの次亜塩素酸水を得た。このときの中和反応により得られる次亜塩素酸濃度は18000ppmに相当する。この次亜塩素酸水のpHの測定値は6.19であり、この製造中及び製造後に、塩素ガスの臭いは一切発生しなかった。よって、この例もまた本発明の実施の一形態である。
最初に調製するクエン酸水溶液のpHを1.88ではなく2.75に調節し、このクエン酸水溶液50mlに対して、別個独立に調製した100,000ppmの次亜塩素酸ナトリウム水溶液の添加量を1mlに変更したことの他は、実施例8と同様の処理にて、約51mlの次亜塩素酸水を得た。このときの中和反応により得られる次亜塩素酸濃度は1900ppmに相当する。この次亜塩素酸水のpHの測定値は6.04であり、この製造中及び製造後に、塩素ガスの臭いは一切発生しなかった。よって、この例もまた本発明の実施の一形態である。
最初に調製するクエン酸水溶液のpHを1.88ではなく3.05に調節し、このクエン酸水溶液50mlに対して、別個独立に調製した100,000ppmの次亜塩素酸ナトリウム水溶液の添加量を0.3mlに変更したことの他は、実施例8と同様の処理にて、約50.3mlの次亜塩素酸水を得た。このときの中和反応により得られる次亜塩素酸濃度は596ppmに相当する。この次亜塩素酸水のpHの測定値は6.24であり、この製造中及び製造後に、塩素ガスの臭いは一切発生しなかった。よって、この例もまた本発明の実施の一形態である。
23 流量比例注入ポンプ 24 塩酸タンク
25 混合機 26 混合タンク
27 流量比例注入ポンプ 28 次亜塩素酸ナトリウムタンク
29 混合機 210 pH測定装置
211 次亜塩素酸噴霧装置
31 水栓 32 流量計
33 流量比例注入ポンプ 34 塩酸タンク
36 流量比例注入ポンプ 37 次亜塩素酸ナトリウムタンク
38 混合機 39 pH測定装置
310 次亜塩素酸噴霧装置
Claims (7)
- pHが1.5~5である酸性水溶液と、次亜塩素酸塩を含む水溶液とを、別個独立にそれぞれ調製して、前記両水溶液を混合することを特徴とする、pHが5~7である次亜塩素酸水の製造方法。
- 前記酸性水溶液が塩酸水溶液である請求項1記載の製造方法。
- 前記次亜塩素酸塩が次亜塩素酸ナトリウムである請求項1又は2記載の製造方法。
- 前記次亜塩素酸水の次亜塩素酸濃度が2240ppm以下である請求項1~3のいずれか1項記載の製造方法。
- 酸性水溶液を収容し得る第1の容器と、次亜塩素酸塩を含む水溶液を収容し得る第1の容器とは別個独立の第2の容器と、第1及び第2の容器と配管を介して連結して前記酸性水溶液と前記次亜塩素酸塩を含む水溶液とを混合させることができる混合機と、前記混合機に供される前記塩酸のpHを測定し得るpH測定装置と、を備え、前記配管は第1の容器の内容物と第2の容器の内容物とが前記混合機に供される前には接触しないよう構成されており、前記混合機における前記酸性水溶液と前記次亜塩素酸塩を含む水溶液との混合により次亜塩素酸水が生成する、次亜塩素酸水の製造装置。
- 前記pH測定装置はpHの閾値を格納する記憶手段と、測定された前記酸性水溶液のpHが前記pHの閾値より低いときに信号を発する信号発出手段と、を備える請求項5記載の製造装置。
- 前記混合機に連結された噴霧装置をさらに備え、前記噴霧装置は前記混合機で生成する次亜塩素酸水を噴霧するものである、請求項5又は6記載の製造装置。
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JP2010167375A (ja) * | 2009-01-23 | 2010-08-05 | Shinmeiwa:Kk | 殺菌用の残留有効塩素含有水の製造方法およびその製造装置 |
CN103004871A (zh) * | 2013-01-08 | 2013-04-03 | 邵鹏飞 | 一种低腐蚀性的氧化电位杀菌水及其制备方法 |
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JP2006334450A (ja) * | 2005-05-31 | 2006-12-14 | Hsp:Kk | 殺菌水生成装置の制御方法 |
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