JP4929430B2 - Electrolyzed water production apparatus and electrolyzed water production method - Google Patents

Description

  The present invention relates to an electrolyzed water production apparatus and electrolyzed water production method using a continuous flow type diaphragm electrolytic cell, and in particular, an electrolyzed water production apparatus that does not require disposal of either anode water or cathode water. And a method for producing electrolyzed water.

  In general, electrolyzed water production apparatuses include a diaphragm type electrolytic cell having a diaphragm between a pair of electrodes and a non-diaphragm type electrolytic cell without a diaphragm, which are used according to purposes.

  As the diaphragm of the diaphragm type electrolytic cell, an ion exchange membrane that is a charged membrane, a neutral membrane that is an uncharged membrane, or the like is used. Acidic electrolyzed water is generated on the anode side (anode chamber) of the electrolytic cell, and alkaline electrolyzed water is generated on the cathode side (cathode chamber). When using the apparatus using a diaphragm type electrolytic cell, normally, anode side electrolysis generated water (anode water) and cathode side electrolysis generated water (cathode water) are collected separately.

  When electrolysis is performed by adding a chloride such as sodium chloride to the raw electrolytic water as an electrolyte, hydrochloric acid, hypochlorous acid, dissolved oxygen, and active oxygen such as hydroxyl radicals are electrode reaction products on the anode side. Generate. Since hypochlorous acid exhibits a strong chlorination reaction and an oxidation reaction, anodized water is used for sterilization of fungi.

  On the other hand, cathodic water produced on the cathode side is widely known as drinking alkaline ionized water. Cathode water production apparatuses (see, for example, Patent Documents 1 to 3) are commercially available as medical instruments and the like, and are widely used with the spread of mineral water.

  Electrolyzed water produced by the diaphragm-type electrolytic cell is obtained as mixed electrolyzed water in which anode water and cathode water are mixed. Since the mixed electrolyzed water contains hypochlorous acid water because the anode water is mixed, it is mainly used for the purpose of controlling sterilization and bacterial growth.

  These electrolyzed water can be characterized by several parameters. As parameters, pH, redox potential, dissolved oxygen concentration, dissolved hydrogen concentration, hypochlorous acid concentration and the like are adopted. The values of these parameters are determined by the type and concentration of the solute contained in the electrolyzed raw water, the amount of electrolytic energy imparted to the electrolyzed water, and the like.

  When producing alkaline ionized water, hydroxide and dissolved hydrogen are produced on the cathode side, so that the pH of the cathode water increases and becomes alkaline, and the dissolved hydrogen concentration increases. For this reason, the redox potential of the alkaline ionized water is lowered, and sometimes it is −200 mV or less by direct reading of the reference electrode.

  A low oxidation-reduction potential means a reducing atmosphere. Since the solubility of dissolved hydrogen is very low and even if it is taken into the body, it is dissipated as a gas, so these are not important parameters when drinking alkaline ionized water.

  When drinking electrolyzed water, the most important parameters are hypochlorous acid concentration and pH values. In the case of cathodic water, hypochlorous acid is not included, so only the pH value becomes a problem. Since strongly alkaline or strongly acidic electrolyzed water is dangerous for a living body, electrolyzed water in a weak alkali to weakly acidic region is drunk. When the electrolysis energy is large, the anodic water tends to be strongly acidic and the cathodic water tends to be strongly alkaline, so that usually a large amount of electricity cannot be used during electrolysis.

In order to keep the pH of electrolyzed water obtained by using a high amount of electricity during electrolysis within a predetermined range, various methods have been conventionally used. For example, mixed electrolyzed water is obtained by electrolysis in a non-diaphragm electrolytic cell, or by mixing anodic water and cathodic water electrolyzed in a diaphragm electrolytic cell, and then a harmful substance such as hypochlorous acid is added. A method of removing, a method of controlling the pH of cathode water by adding a pH adjusting agent before or after electrolysis in a diaphragm type electrolytic cell (see Patent Document 4), and the like are known.
JP 2002-18439 A (FIG. 1) JP 2000-33377 A (FIGS. 1 and 2) JP-A-11-169856 (Claim 1) JP 2000-79391 A (Claim 1)

  Electrolysis using a diaphragm-type electrolytic cell and a method of obtaining mixed electrolyzed water after electrolysis using a membrane-type electrolytic cell are advantageous from the viewpoint of effective use of water because both positive and negative electrolyzed water are used. However, when electrolysis is performed using a diaphragm type electrolytic cell to obtain only anode water or cathode water, the electrolyzed water generated on the other electrode side is usually discarded. In fact, most commercially available alkaline ionized water production apparatuses have a structure in which anode water and cathode water are separately discharged from the diaphragm type electrolytic cell, and the cathode water discharged from the cathode side is used for drinking. On the other hand, the anode water is discarded. This is a huge loss based on the idea of effective use of water resources.

  An object of the present invention is an electrolyzed water production apparatus for producing electrolyzed water using a diaphragm-type electrolytic cell, and discards the other of the anode water and the cathode water even when it is taken out and used. An object of the present invention is to provide an electrolyzed water production apparatus and electrolyzed water production method that are not necessary.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has obtained electrolyzed water obtained by flowing to either one of the anode chamber or the cathode chamber of the diaphragm type electrolytic cell and then flowing to the other. Was strongly influenced by the electrode chamber that passed last, and as a result, it was found that only anodic water or cathodic water was obtained.

  Furthermore, when electrolysis is performed by continuously supplying raw electrolytic water to both the anode chamber and the cathode chamber of the diaphragm type electrolytic cell, the electrolytic water circulated in either one is taken out and the electrolytic water circulated in the other is removed. It was found that only the anode water or the cathode water can be taken out by returning to the upstream side of the electrolytic cell, mixing with the raw electrolytic water, and electrolyzing again in the electrolytic cell.

  The present invention for achieving the above object is described below.

  [1] A flow-type electrolytic cell having a pair of electrodes, in which an anode chamber and a cathode chamber are formed by a diaphragm stretched between the electrodes, and electrolyzed raw water connected to the inlet side of the anode chamber are supplied to the anode chamber The electrolyzed raw water supply pipe, the electrolyzed water outlet pipe connected to the outlet side of the cathode chamber and taking out electrolyzed water in the cathode chamber out of the cathode chamber, and the electrolyzed water outlet side of the anode chamber and the electrolyzed water inlet side of the cathode chamber An electrolyzed water production apparatus having a distribution pipe.

  [2] A flow-type electrolytic cell having a pair of electrodes, in which an anode chamber and a cathode chamber are formed by a diaphragm stretched between the electrodes, and electrolyzed raw water connected to the inlet side of the cathode chamber is supplied to the cathode chamber The electrolytic raw water supply pipe is connected to the outlet side of the anode chamber, the electrolytic water outlet pipe for extracting the electrolytic water in the anode chamber to the outside of the anode chamber, and the electrolytic water outlet side of the cathode chamber and the electrolytic water inlet side of the anode chamber are connected. An electrolyzed water production apparatus having a distribution pipe.

  [3] A flow-type electrolytic cell comprising a pair of electrodes, in which an anode chamber and a cathode chamber are formed by a diaphragm stretched between the electrodes, and a downstream side branches, an inlet side of the anode chamber and an inlet side of the cathode chamber The electrolytic raw water supply branch pipe connected to the downstream end of each of the two, the electrolytic water take-off pipe connected to the outlet side of the cathode chamber, one end on the outlet side of the anode chamber, and the other end of the electrolytic raw water supply branch pipe An electrolyzed water production apparatus, comprising: a reflux pipe connected to the upstream side of the branch portion.

  [4] The electrolyzed water production apparatus according to [3], wherein the reflux pipe is provided with a pump.

  [5] A flow-type electrolytic cell comprising a pair of electrodes, in which an anode chamber and a cathode chamber are formed by a diaphragm stretched between the electrodes, and a downstream side branches, an inlet side of the cathode chamber and an inlet side of the anode chamber The electrolytic raw water supply branch pipe connected to the downstream end thereof, the electrolytic water outlet pipe connected to the outlet side of the anode chamber, one end on the outlet side of the cathode chamber, and the other end of the electrolytic raw water supply branch pipe An electrolyzed water production apparatus, comprising: a reflux pipe connected to the upstream side of the branch portion.

  [6] The electrolyzed water production apparatus according to [5], wherein the reflux pipe is provided with a pump.

  [7] Electrolyzed raw water containing 0.1 mM or more of a water-soluble inorganic salt is continuously supplied to and circulated into either the anode chamber or the cathode chamber in the diaphragm type electrolytic cell, and then the other chamber. A method for producing electrolyzed water that is continuously electrolyzed by being introduced into and distributed.

  [8] Electrolyzed raw water containing 0.1 mM or more of a water-soluble inorganic salt is continuously supplied to the anode chamber and the cathode chamber in the diaphragm type electrolytic cell, and is circulated through either the anode chamber or the cathode chamber for electrolysis. A method for producing electrolyzed water, characterized in that the electrolyzed water taken out to the outside and recirculated to the other side to be electrolyzed is refluxed upstream of the electrolyzer and mixed with the electrolyzed raw water.

  [9] The ratio of the flow rate of the electrolyzed water taken out from either the anode chamber or the cathode chamber to the upstream side of the electrolyzer from the other is 1:50 to 50: 1. [8] The method for producing electrolyzed water as described in 1. above.

  According to the present invention, the electrolytic raw water is supplied to one of the anode chamber and the cathode chamber of the diaphragm type electrolytic cell and then introduced into the other, or the electrolytic raw water is supplied to both the anode chamber and the cathode chamber. Only the anode water or the cathode water can be taken out by taking out the electrolyzed water from one of them and refluxing the electrolyzed water flowing through the other to the upstream side of the electrolytic cell. Therefore, even when only anode water or cathode water is taken out using the diaphragm type electrolyzed water production apparatus, it is not necessary to discard the other.

  The electrolyzed water production apparatus of the present invention can take out all of the electrolyzed raw water as anode water or cathodic water, and the use efficiency of the electrolyzed raw water is extremely high as compared with the conventional diaphragm type electrolyzed water producing apparatus. Moreover, even if a high electrolysis current is applied, the pH of the resulting electrolyzed water can be kept near neutral by using a pH adjuster. Furthermore, compared with the conventional manufacturing apparatus in which the electrolytic raw water passes once through the electrolytic cell, the apparatus of the present invention has a high rate of electrolytic raw water passing a plurality of times through the electrolytic tank. Obtainable.

  FIG. 1 is a schematic configuration diagram showing an example of the electrolyzed water production apparatus of the present invention.

  In FIG. 1, 100 is an electrolyzed water production apparatus, and 1 is a flow-through diaphragm type electrolytic cell. Inside the electrolytic cell 1 having a quadrangular cross section, a pair of electrodes 3 and 5 are disposed along a pair of opposing side walls 15 and 16. In FIG. 1, the electrode 5 is an anode and the electrode 3 is a cathode.

  A diaphragm 6 is stretched between the electrodes 3 and 5 in parallel with the electrodes 3 and 5. The inner space of the electrolytic cell 1 is divided into two by the diaphragm 6, and the anode chamber 4 and the cathode chamber 2 are formed in the electrolytic cell 1.

  In FIG. 1, 17 and 18 indicate the side walls of the electrolytic cell 1 perpendicular to the electrodes 3 and 5. An electrolytic raw water supply port 11 is formed on the side of the anode chamber on the side wall 17, and an electrolytic water outlet 12 is formed on the side of the side wall 17 on the side of the cathode chamber electrolytic water. An electrolytic raw water supply pipe 9 is connected to the electrolytic raw water supply port 11, and an electrolytic water outlet pipe 10 is connected to the electrolytic water outlet 12. The electrolyzed raw water supply pipe 9 includes a pH adjusting agent supply tank 8.

  An anode water outlet 13 is formed on the side of the anode chamber electrolytic water outlet of the side wall 18, and an anode water supply port 14 is formed on the side of the cathode chamber electrolytic water inlet of the side wall 18. Both ends of the flow pipe 7 are connected to the anode water outlet 13 and the anode water supply port 14, respectively. The anode chamber 4 and the cathode chamber 2 are communicated with each other by the flow pipe 7.

  Electrolyzed raw water such as tap water or sodium chloride aqueous solution is fed into the anode chamber 4 of the electrolytic cell 1 through the electrolytic raw water supply pipe 9 after a pH adjusting agent is added by the pH adjusting agent supply tank 8 as desired. After being electrolyzed in the anode chamber 4, it is supplied into the cathode chamber 2 through the flow pipe 7. After being electrolyzed again in the cathode chamber 2, it is taken out as electrolyzed water through the electrolyzed water extraction pipe 10.

  The electrolyzed water obtained by this apparatus is electrolyzed water electrolyzed in the anode chamber 4 and the cathode chamber 2, but is strongly affected by electrolysis in the cathode chamber that has passed through last. The electrolyzed water obtained by the electrolyzed water production apparatus 100 is cathodic water.

  Since the electrolyzed water is electrolyzed twice in the anode chamber and the cathode chamber, the electrolyzed water producing apparatus 100 is a conventional manufacturing apparatus in which electrolysis energy per unit flow rate given to the electrolyzed water circulates only in the anode chamber or the cathode chamber. Twice as much.

  In the electrolyzed water production, a direct current voltage current is applied between the electrodes 3 and 5.

  In addition, 0.5A-10A are preferable with respect to the electrolyzed raw water which has the flow rate of 1 L / min, and, as for the electric current applied to electrolyzed raw water, 1A-5A is especially preferable. If it is less than 0.5 A, the amount of dissolved oxygen and dissolved hydrogen in the electrolyzed water cannot be made higher than that of the electrolyzed raw water, and if it exceeds 10 A, a large current flows, so that the fatigue of the electrode increases and the electrolytic efficiency becomes extremely high. Tend to fall.

  The electrodes 3 and 5 are made of an electrochemically inactive metal material. As the electrode material, platinum, a platinum alloy or the like is preferable.

  The distance between the electrodes 3 and 5 is 3 to 1 mm, preferably 2 to 1 mm.

  As the diaphragm 6, what is conventionally used as an electrolytic diaphragm, such as an ion exchange membrane or an uncharged membrane, can be used as appropriate.

  The flow rate of the raw electrolytic water supplied to the electrolytic cell 1 is preferably 0.5 to 10 L / min, more preferably 1 to 5 L / min.

The ionic strength of the water-soluble inorganic salt or the like of the electrolyzed raw water is preferably 0.1 mM or more, more preferably 0.1 to 0.5 mM in total for each water-soluble inorganic electrolyte. The electrolyzed raw water usually uses tap water or water to which sodium chloride is added as an electrolyte, and contains chlorine in the form of Cl ⁻ , HCl or the like.

  In order to adjust the pH of the obtained electrolyzed water to a desired pH, a basic electrolyte aqueous solution such as sodium hydroxide or sodium bicarbonate or an acidic electrolyte aqueous solution such as hydrochloric acid or phosphoric acid is used by the pH adjuster supply tank 8. Can be easily performed by adding to the raw electrolytic water. The use of the pH adjusting agent is optional, and the pH adjusting agent may not be used depending on the purpose of use of the electrolyzed water.

  In the above description, the case where the pH adjusting agent supply tank 8 is attached to the electrolyzed raw water supply pipe 9 has been described, but the pH adjusting agent supply tank may be attached to the electrolyzed water extraction pipe 10 or the flow pipe 7.

  When the obtained electrolyzed water is used for drinking purposes, etc., when the concentration of free chlorine such as hypochlorous acid or chlorine gas contained in the electrolyzed water is high, it can be easily treated by treating the electrolyzed water with activated carbon or the like. Can be removed. In this case, the electrolyzed water extraction pipe 10 may be provided with a free chlorine removing device filled with an adsorbent such as activated carbon.

  FIG. 2 shows a schematic configuration diagram of an example of an apparatus for producing anodized water, which is an electrolyzed water producing apparatus of the present invention. In FIG. 2, since it is the same structure as FIG. 1 except the polarity of an electrode being reverse, the same code | symbol is attached | subjected to the same part and the description is abbreviate | omitted. In FIG. 2, 200 is an electrolyzed water production apparatus, 20 is a cathode water outlet, and 21 is a cathode water supply port.

  In FIG. 2, the raw electrolytic water is first supplied into the cathode chamber 2, electrolyzed in the cathode chamber 2, then supplied into the anode chamber 4 through the flow pipe 7, and electrolyzed in the anode chamber 4. .

  In the anode chamber 4, if chlorine ions are present in the electrolyte solution, it is oxidized to chlorine gas, and a part of the chlorine gas dissolved in water becomes hypochlorous acid. The rate at which hypochlorous acid and chlorine gas are produced from chlorine ions varies depending on the pH of the solution. In order to increase the concentration of free chlorine in the anode water when used for sterilization or the like, the chlorine ion concentration of the electrolytic raw water is increased and the pH is adjusted to the acidic side. Specifically, by adding a mixed solution of a chloride electrolyte such as sodium chloride or potassium chloride and hydrochloric acid from the pH adjuster supply tank 8 to the electrolytic raw water, electrolyzed water containing strongly acidic hypochlorous acid is obtained. Obtainable.

  FIG. 3 is a schematic configuration diagram showing another example of the electrolyzed water production apparatus of the present invention.

  In FIG. 3, 300 is an electrolyzed water production apparatus. The configuration of the electrolytic cell 1 is the same as the configuration of the electrolytic cell shown in FIG.

  Electrolytic raw water supply ports 30 and 31 are formed on the side of the cathode chamber inlet side and the side of the anode chamber inlet side of the side wall 17, respectively. The electrolyzed raw water supply ports 30 and 31 are respectively attached with downstream ends of electrolytic raw water supply branch pipes 37 branched to 37a and 37b on the downstream side from the branch portion 37c.

  A cathode water outlet 32 is formed at the cathode chamber outlet side of the side wall 18, and an anode water outlet 33 is formed at the anode chamber outlet side. A cathode water outlet 34 is connected to the cathode water outlet 32, and a reflux pipe 38 is connected to the anode water outlet 33. A three-way valve 36 is interposed in the reflux pipe 38. One end of an anodic water extraction pipe 35 is connected to the three-way valve 36, and the anodic water can be discharged to the outside of the apparatus by switching the three-way valve 36.

  The other end of the reflux pipe 38 is connected to the upstream side of the branch part 37 c of the electrolytic raw water supply branch pipe 37. A pump 39 is interposed in the reflux pipe 38.

  The electrolytic raw water supply branch pipe 37 includes a pH adjuster supply tank 8. A free chlorine removing device 40 is interposed in the downstream branch pipe 37a.

  After the pH adjusting agent is added by the pH adjusting agent supply tank 8, a part of the electrolytic raw water is sent into the cathode chamber 2 of the electrolytic cell 1 through the electrolytic raw water supply branch pipe 37 a. Thereafter, it is electrolyzed in the cathode chamber 2 to become cathodic water, and is taken out from the cathodic water extraction pipe 34 to the outside.

  A part of the electrolytic raw water is introduced into the anode chamber 4 through the electrolytic raw water supply branch pipe 37b by operating the pump 39, and is electrolytically decomposed to become anode water. After the anode water is taken out from the reflux pipe 38, it is returned to the upstream side from the branch portion 37c of the electrolytic raw water supply branch pipe 37. The anode water is mixed with the electrolytic raw water in the electrolytic raw water supply branch pipe 37, again becomes a part of the electrolytic raw water, passes through the pH adjuster supply tank 8, and is sent to the cathode chamber 2 or the anode chamber 4.

  The free chlorine generated in the anode chamber 4 is removed by the free chlorine removing device 40 when introduced into the cathode chamber 2.

  The free chlorine removing device 40 can be filled with a known material capable of removing free chlorine, and examples thereof include activated carbon, activated carbon fiber, and zeolite.

  In addition, when the obtained cathode water is not intended for drinking, the use of the free chlorine removing device 40 is optional.

  In order to adjust the pH of the obtained cathode water to a desired value, an aqueous electrolyte solution similar to that in FIG. 1 is added as a pH adjuster.

  Since the anode water is mixed with the electrolytic raw water, the pH of the electrolytic raw water flowing through the downstream side of the electrolytic raw water supply branch pipe 37 is inclined to the acidic side from the original electrolytic raw water. Since the cathode water in the cathode chamber 2 is inclined to the alkaline side, the cathode water obtained by mixing them is neutralized to some extent.

  When the electrolyzed water production apparatus 300 is used, the ratio of the flow rate of the cathode water taken out from the outlet side of the cathode chamber to the flow rate of the anodic water refluxed from the outlet side of the anode chamber to the upstream side of the branch portion 37c is 1: 50-50: 1 are preferable, 1: 20-20: 1 are more preferable, and 1: 10-10: 1 are still more preferable.

  The attachment position of the pH adjusting agent supply tank 8 is not limited to the case of FIG. 3, and can be set to an arbitrary position. The free chlorine removing device 40 may be attached to the cathode water extraction pipe 34.

  Preferred values of the raw electrolytic water, pH adjuster, electrolytic current, interelectrode distance, electrolytic raw water flow rate, etc. used are the same as in FIG.

  In the apparatus shown in FIG. 3, the reflux pipe 38 is provided with a pump 39, but the pump 39 may not be used.

  When the pump 39 is not used, a part of the raw electrolytic water is introduced from the anode chamber 4 to the cathode chamber 2 through the path indicated by the broken-line arrow. That is, after electrolysis in the anode chamber 4 from the electrolytic raw water supply pipe 37 through the reflux pipe 38, electrolysis is performed in the cathode chamber 2 through the electrolytic water supply branch pipes 37b and 37a. Also in this case, free chlorine generated in the anode chamber 4 can be removed by the free chlorine removing device 40. Further, the pH adjusting agent supply tank 8 can set the pH of the cathode water to a desired value.

  FIG. 4 is a schematic configuration diagram showing an example of the electrolyzed water production apparatus of the present invention for producing anodized water. The electrolyzed water production apparatus 400 shown in FIG. 4 has the same configuration as the apparatus shown in FIG. 3 except that the polarities of the electrodes are reversed and the free chlorine removing apparatus 40 is not provided. Therefore, the description is omitted. In FIG. 4, 42 is an anode water extraction tube, and 41 is a cathode water extraction tube.

  The electrolytic raw water is added with the pH adjusting agent by the pH adjusting agent supply tank 8, and a part thereof is sent into the anode chamber 4 of the electrolytic cell 1 through the electrolytic raw water supply branch pipe 37a. After being electrolyzed in the anode chamber 4, it is taken out from the anode water extraction pipe 42.

  The electrolyzed raw water flowing through the electrolyzed raw water supply branch pipe 37 b is electrolytically decomposed in the cathode chamber 2, taken out from the reflux pipe 38, and returned to the upstream side from the branch part 37 c by the pump 39.

  Also in FIG. 4, the broken line arrows indicate the path of the electrolytic raw water that flows through the cathode chamber 2 and is supplied to the anode chamber when the pump 39 is not used.

  The pH adjusting agent added by the pH adjusting agent supply tank 8 is the same as in the case of FIG.

Example 1
Using the electrolyzed water production apparatus 300 shown in FIG. 3, tap water was electrolyzed to produce cathodic water. However, the internal space of the electrolytic cell is a rectangular parallelepiped of 15 cm × 10 cm × 0.2 cm, and two platinum electrodes formed in a plate shape of 140 mm × 100 mm are inserted into the electrolytic cell at intervals of 2 mm, and an anode and a cathode are arranged. . An uncharged membrane was used as the diaphragm. Tap water (total chlorine concentration 15 mg / L) was supplied to this electrolytic cell at a flow rate of 3 L / min, and the current flowing between the electrodes was set to 1.5 A with respect to the flow rate of 1 L / min of water flowing through the cathode chamber. A sodium hydrogen carbonate aqueous solution was used as the pH adjuster, and activated carbon was used as the adsorbent of the free chlorine removing device 40. Pump 39 was not used. The flow rate of the electrolytic raw water flowing through the reflux pipe 38 was 1.5 L / min.

Comparative Example 1
Cathode water was produced under the same conditions as in Example 1 by switching the three-way valve 36 of the electrolyzed water production apparatus 300 shown in FIG. 3 so that the anode water was discharged to the outside from the anode water extraction pipe 35. The flow rate of the electrolytic raw water flowing through the branch pipes 37a and 37b was 1: 1.

  Table 2 shows the results of measuring the pH, redox potential (ORP), dissolved oxygen content (DO), and electrical conductivity (EC) of the cathode water obtained in Example 1 and Comparative Example 1.

  In Example 1, although the amount of electricity with respect to the flow rate per unit time is larger than that of Comparative Example 1, the pH of the cathode water is lower than that of Comparative Example 1 and is neutral. Further, the ORP value is higher in Example 1 than in Comparative Example 1, and considering the result of dissolved oxygen amount in Table 1 together, in Example 1, dissolved oxygen and dissolved hydrogen coexist. I can guess.

Test example 1
After desalting 800 mL of the cathodic water obtained in Example 1 and Comparative Example 1 with a reverse osmosis membrane, adjusting the pH of Comparative Example 1 to the same value as that of Example 1, 10 μL of 0.1 M hydrochloric acid was added. The electrical conductivity was measured. The results are shown in FIG.

  In FIG. 5, the inflection point indicates the end point of the neutralization reaction. The amount of 0.1M hydrochloric acid added at the inflection point is about 100 μL for the cathodic water of Comparative Example 1, while about 40 μL for the cathodic water of Example 1.

The dissociation coefficient of the cathode water of Comparative Example 1 is Kw ₁ , the titration amount by neutralization titration is V ₁ , the dissociation coefficient of the cathodic water of Example 1 is Kw ₂ , and the titration amount by neutralization titration is V ₂ . Comparing the water dissociation index pKw = −logKw, the dissociation index of Comparative Example 1 is pKw ₁ = 14 + log (V ₁ / V ₀ ), and the dissociation index of Example 1 is pKw ₂ = 14 + log (V ₂ / log (V ₂ / V ₀ ). Since titre V ₂ of Example 1 less than the drop amount V ₁ of the Comparative Example 1, PKW ₂ <PKW ₁ next, it can be seen that towards the cathode water of Example 1 is large dissociation constant Kw of water. However, V ₀ is a control titration under 1 atm at 25 ° C. and is the titration required to adjust the pH of the electrolyzed raw water to the same value as the pH of the cathode water. In general, it is known that when the water dissociation coefficient Kw increases, the solute is dissolved well and the reactivity of the solute increases, and it can be seen that the cathode water of Example 1 is superior in these properties.

Example 2
An electrolyzed water production apparatus 400 shown in FIG. 4 was used to electrolyze a 0.2% aqueous sodium chloride solution to produce anodic water. However, the same electrolytic cell and electrode as in Example 1 were used. An aqueous sodium chloride solution was supplied to the electrolytic cell at a flow rate of 3 L / min, and the current flowing between the electrodes was set to 3 A with respect to the flow rate of 1 L / min of water flowing through the anode chamber. Hydrochloric acid was used as the pH adjuster. Pump 39 was not used. The flow rate of the electrolytic raw water flowing through the reflux pipe 38 was 1 L / min.

Comparative Example 2
Anode water was produced under the same conditions as in Example 2 except that the three-way valve 36 of the electrolyzed water production apparatus 400 shown in FIG. 4 was switched so that the cathode water was discharged from the cathode water extraction pipe 41 to the outside. The flow rate of the electrolytic raw water flowing through the branch pipes 37a and 37b was 1: 1.

  Table 2 shows the pH, ORP, DO, and free chlorine concentration of the anode water obtained in Example 2 and Comparative Example 2.

  In Example 2, the cathode water was mixed with the electrolytic raw water and introduced into the anode chamber, so that the cathode water could be regenerated as anode water without being discarded.

It is a schematic block diagram which shows an example of the electrolyzed water manufacturing apparatus of this invention. It is a schematic block diagram which shows the other example of the electrolyzed water manufacturing apparatus of this invention. It is a schematic block diagram which shows the other example of the electrolyzed water manufacturing apparatus of this invention. It is a schematic block diagram which shows the other example of the electrolyzed water manufacturing apparatus of this invention. 2 is a graph showing electric conductivity curves of cathodic water obtained in Example 1 and Comparative Example 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrolysis tank 2 Cathode chamber 3 Cathode 4 Anode chamber 5 Anode 6 Diaphragm 7 Supply pipe 8 pH adjuster supply tank 9 Electrolyzed raw water supply pipe 10 Electrolyzed water extraction pipe 11, 30, 31 Electrolytic raw water supply port 12 Electrolyzed water outlet 13 33 Anode water outlet 14 Anode water supply port 15, 16, 17, 18 Side wall 20, 32 Cathode water outlet 21 Cathode water supply port 34, 41 Cathode water outlet pipe 35, 42 Anode water outlet pipe 36 Three-way valve 37, 37a 37b Electrolytic raw water supply branch pipe 37c Branch section 38 Reflux pipe 39 Pump 40 Free chlorine removing apparatus 100, 200, 300, 400 Electrolyzed water production apparatus

Claims (7)

A diaphragm- type electrolytic cell having a pair of electrodes, in which an anode chamber and a cathode chamber are formed by a diaphragm stretched between the electrodes, and a downstream side is branched, on the inlet side of the anode chamber and the inlet side of the cathode chamber The electrolyzed raw water supply branch pipe connected at the downstream end thereof, the electrolyzed water outlet pipe connected to the outlet side of the cathode chamber, the one end at the outlet side of the anode chamber, and the other end branched from the electrolytic raw water supply branch pipe a reflux condenser coupled to the upstream side of the part, met electrolyzed water production apparatus having a PH adjusting agent supply portion between the branch portion and the connection portion between the return pipe of the electrolyte raw water supply branch pipe And
The electrolyzed water production apparatus has a first anodic water introduction path and a second anodic water introduction path that can be arbitrarily switched to introduce anodic water taken out from the anodic chamber into the cathodic chamber,
The first anode water introduction path is composed of the reflux pipe and a downstream portion of the connection portion of the electrolytic raw water supply branch pipe, and includes the PH adjuster supply section.
Said 2nd anode water introduction path | route is an electrolyzed water manufacturing apparatus which consists of a downstream part from the said branch part of the said electrolyzed raw water supply branch pipe . A diaphragm- type electrolytic cell having a pair of electrodes and having an anode chamber and a cathode chamber formed by a diaphragm stretched between the electrodes; The electrolyzed raw water supply branch pipe connected at the downstream end thereof, the electrolyzed water outlet pipe connected to the outlet side of the anode chamber, one end at the outlet side of the cathode chamber, and the other end branched from the electrolytic raw water supply branch pipe a reflux condenser coupled to the upstream side of the part, met electrolyzed water production apparatus having a PH adjusting agent supply portion between the branch portion and the connection portion between the return pipe of the electrolyte raw water supply branch pipe And
The electrolyzed water production apparatus has a first cathodic water introduction path and a second cathodic water introduction path that can be arbitrarily switched to introduce the cathodic water taken out from the cathodic chamber into the anode chamber,
The first cathodic water introduction path includes the reflux pipe and a downstream portion of the connection portion of the electrolytic raw water supply branch pipe, and includes the PH adjusting agent supply section.
Said 2nd cathodic water introduction path | route is an electrolyzed water manufacturing apparatus which consists of a downstream part from the said branch part of the said electrolyzed raw water supply branch pipe . The reflux pipe is provided with a pump, and the first anodic water flow path or the first cathodic water introduction path is selected by operating the pump, and the second anodic water is not operated by operating the pump. The operating method of the electrolyzed water manufacturing apparatus according to claim 1, wherein an introduction path or a second cathode water introduction / circulation path is selected. A three-way valve is provided between one end connected to the outlet side of the anode chamber or one end connected to the outlet side of the cathode chamber in the reflux pipe and a pump interposed in the reflux pipe, through the three-way valve. The electrolyzed water production apparatus according to claim 3, wherein the electrolyzed water discharge pipe is connected to the reflux pipe. 5. Electrolyzed raw water containing 0.1 mM or more of a water-soluble inorganic salt is continuously supplied to either one of the anode chamber and the cathode chamber in the diaphragm type electrolytic cell according to any one of claims 1 to 4. A method for producing electrolyzed water that is continuously electrolyzed after being distributed and then introduced into the other and distributed. Electrolytic raw water containing 0.1 mM or more of a water-soluble inorganic salt is continuously supplied to the anode chamber and the cathode chamber in the diaphragm type electrolytic cell according to any one of claims 1 to 4, and the anode chamber And the electrolyzed water electrolyzed by flowing through either the cathode chamber or the cathode chamber, and the electrolyzed water electrolyzed by flowing through the other is refluxed to the upstream side of the electrolytic cell and mixed with the electrolyzed raw water. A method for producing electrolyzed water. And electrolyzed water taken out from either the anode chamber and the cathode chamber, the flow rate ratio of the electrolytic water to be recirculated to the upstream side of the electrolytic cell from the other, 1: 50 to 50: according to claim 6 which is 1 A method for producing electrolyzed water.

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