KR100883894B1 - Apparatus for manufacturing of weak-acidic hypochlorous acid water and manufacturing method of weak-acidic hypochlorous acid water - Google Patents

Abstract

An apparatus for manufacturing weak-acidic hypochlorous acid water is provided to generate hypochlorous acid water with high concentration, control acidity of the hypochlorous acid water, prevent blockage of a spray nozzle, and reduce the amount of univalent chloride to be used. An apparatus for manufacturing weak-acidic hypochlorous acid water comprises the following units. An electrolytic cell with a separating film(30) separates a cathode chamber(320) and an anode chamber(310) by an anion penetration diaphragm(34). Univalent chloride aqueous solution is circulated in the cathode chamber of the electrolytic cell with a separating film. The Univalent chloride aqueous solution is electrolyzed in the anode chamber of the electrolytic cell with a separating film.

Description

Apparatus for manufacturing of weak-acidic hypochlorous acid water and manufacturing method of weak-acidic hypochlorous acid water}

The present invention relates to a non-acidic hypochlorous acid production apparatus and a method for producing non-acidic hypochlorous acid, more specifically, a monovalent chloride aqueous solution in the cathode chamber of the membrane membrane electrolyte tank divided into a cathode chamber and an anode chamber by an anion permeable membrane By supplying and circulating the electrolysis, and by supplying only the raw water to the anode chamber to configure the electrolysis, the chlorine ion electrolytically generated in the cathode chamber is moved to the anode chamber through the anion permeable membrane to the chlorine ion at the anode of the anode chamber The present invention relates to a non-acidic hypochlorite-water production apparatus and a method for producing non-acidic hypochlorite-water to prevent the chloride from remaining in the hypochlorous acid generated by the generation of hypochlorous acid by anodization.

Hypochlorite water contains 10 to 80 ppm of hypochlorous acid (HOCl) produced by the oxidation of chlorine ions produced by the electrolysis of monochloride on the anode surface, and the pH is 2.2 or more and 6.5 or less, and the pH is 2.2 or more and 2.7 or less The hypochlorous acid water of the strong acid hypochlorite dissipative water, 2.7 or more and less than 5.0, the weakly acidic hypochlorous acid, 5.0 or more and less than 6.5 is called the non-acidic hypochlorous acid, any of which can be used as a disinfectant. Depending on the type of hypochlorous acid, the composition ratio of dissolved chlorine (Cl ₂ aq) and hypochlorous acid, which are effective chlorine components, is different, and the strong acid hypochlorous acid is composed of dissolved chlorine 15-20% and hypochlorous acid 80-85%. The weakly acidic hypochlorous acid is composed of 2 to 15% and 85 to 98%, respectively, and the non-acidic hypochlorous acid is composed of 0 to 15% of hypochlorite ions (OCl ⁻ ) and 85 to 100% of hypochlorous acid (integer technology, pp 98-107, Gibodang, 1985.). Strong acid hypochlorous acid water is prepared by using a membrane electrolyzer generating device using salt as electrolyte, and weak acid and micro acid hypochlorite water is prepared by using a solution of hydrochloric acid or a mixture of salt and hydrochloric acid as electrolyte. Are prepared using. Under the same effective chlorine concentration, strong acidic hypochlorite water showed higher sterilizing power than others due to low pH, high oxidation potential, etc., but the acidic hypochlorous acid water was excellent in the stability of effective chlorine.

Hypochlorite number while using bio-toxicity is low compared to the universally sodium hypochlorite (NaOCl) that is being used in an existing sterilizing power is practical and 5 to 10 times the river, sterilization resistance is greater Bacillus subtilis (Bacillus), cross-tree Stadium (Clostridium), etc. It has high sterilizing ability against subpopulations, and when disinfecting, it generates very little by-products such as trihalomethane, a carcinogenic substance.It is easily decomposed, leaving no food or odor in food materials, and less environmental load. It is a product that can make a great contribution as an efficient and environmentally friendly disinfectant in the future food hygiene management because it does not harm the skin.

As a conventional hypochlorous acid water production apparatus, as shown in Figure 1, by the ion diaphragm 11 is separated into a cathode chamber 120 having a cathode 12 and a cathode chamber 130 having a cathode 130 An electrolyte solution 14, such as a salt solution or potassium chloride solution, is added to the raw water 15 in the gap membrane electrolyte tank 10, which is supplied through a supply pipe 16, to the positive electrode 12 and the negative electrode 13. When an electric current (D / C) is applied and electrolyzed, electrolyzed chlorine ions are oxidized to chlorine (Cl ₂ ) on the anode 12 side, which is represented by the following Chemical Formulas 1 (anode reaction) and Chemical Formula 2 (cathode reaction). Reaction with the raw water (15) produces a strongly acidic hypochlorous acid (17) having a pH of 2.7 or less, and in the cathode (13), the electrolytic sodium ions are reduced to react with water to form a strong alkaline electrolytic water (18). For example, the strong seawater manufacturing device in which the () is generated (the nature and sterilization of the strong seawater, See the Seminar on Electrolyzed Water Utilization Seminar, pp 16-36, Koji Electronic and Electrical Engineers' Association, 1997 (Japan).

^{NaCl → Na + + Cl -,} 2Cl - → Cl 2 + 2e

Cl ₂ + H ₂ O → HOCl + HCl

^{NaCl → Na + + Cl -,} Na + + e → Na

Na + H ₂ O → NaOH + 1 / 2H ₂

As described above, as shown in FIG. 1, an unelectrolyzed salt or potassium chloride remains in the strongly acidic hypochlorous acid water by adding an electrolyte to raw water and supplying it to the anode chamber to produce hypochlorous acid water. After disinfection, salt or potassium chloride precipitates in foodstuffs, utensils or containers, resulting in denaturation of foodstuffs, corrosion of utensils and the like, which causes clogging of spray holes when spraying, and weakens the stability of hypochlorous acid water. There was. After delivery by the addition of salt to the raw water 250㎎ 1ℓ, dissolved amount of chlorine in the anode chamber was 8%, the positive yarn feeding chlorine ion (Cl ^-) of the amount as added salt and out 20㎎ Within 20% of the amount of chloride The utilization efficiency is very low, so much unelectrolyzed salt remains in the produced hypochlorous acid (Review on Chemical Composition of Electrolytic Oxidized Dilute Saline for Disinfection and Disinfection 1-3, Chuckdae University Science and Engineering Annual Report 5 (4), See pp294-304, pp305-311, pp312-318, 1996).

As another conventional hypochlorous acid water production apparatus, as shown in FIG. 2, hydrochloric acid 23 is fed into the membrane-free electrolytic cell 20 in which the anode 21 and the cathode 22 are opposed to each other without an ion septum. In addition to (24), and supplied through the supply pipe 25, and applying a current (D / C) to both electrodes, and electrolytically to the following formula (3) (anode side reaction), formula (4) (cathode side reaction) and formula ( A non-acidic hypochlorous acid production apparatus for producing a non-acidic hypochlorous acid water 27 having a pH of 5.0 to 6.5 as shown in (mixing reaction) may be exemplified (see US Patent 6,217,741 B1, Japanese Patent No. 10-128336). ).

^{2HCl → 2H + + 2Cl -,} 2Cl - → Cl 2 + 2e

Cl ₂ + H ₂ O → HOCl + HCl

^{HCl → H + + Cl -,} 2H + + 2e → H 2

2HCl + H ₂ O → HOCl + HCl + H ₂

Since the conventional hypochlorous acid water production apparatus of FIG. 2 also adds an electrolyte which is hydrochloric acid to the raw water to electrolyze it to generate hypochlorous acid, there is a problem in that unelectrolyzed hydrochloric acid is mixed with the hypochlorous acid. That is, in the generation of hypochlorous acid water by the production method as shown in FIG. 2, when hydrochloric acid (reagent grade, 38%) is added to raw water to produce hypochlorous acid with 0.2 mol of dilute hydrochloric acid solution, dilution with raw water The pH of the previous electrolytic oxidation solution was 0.90, and the amount of dissolved chlorine generated was 3,500 ppm. Only 50% of the amount of chlorine ions charged was oxidized to become dissolved chlorine, and the remaining 50% was mixed in the generated water as unelectrolyzed hydrochloric acid. In particular, residual hydrochloric acid is dissolved chlorine (Cl ₂ In addition to hydrochloric acid generated when aq) reacts with raw water (H ₂ O) to produce hypochlorous acid (see Formula 3), the pH of the resulting hypochlorous acid water is further lowered. In order to achieve this, it must be diluted with a large amount of raw water, so it can generate high concentration of hypochlorous acid You will have a flaw without it (see Morinaga Engineering, Microacid Electrolyte Production Manual, 2002).

In the conventional hypochlorous acid water production apparatus, a chloride electrolyte is added to raw water and supplied to an anode chamber and an anode chamber in a membrane electrolyte tank, or a membrane electrolyte is supplied to a cathode electrolyte tank. In order to solve problems such as excessive consumption of chlorides due to electrolytic inefficiency, according to the present invention, only raw water without monovalent chloride is added to the anode chamber of the membrane electrolyte tank, and the monovalent chloride solution is separately added to the cathode chamber. The chlorine ions (Cl ⁻ ) of the monovalent chlorides ionized by electrolysis are permeated and transferred through the anion permeable membrane to the anode chamber to produce dissolved chlorine by anodization at the anode surface of the chlorine ion. Chloride is not mixed with the hypochlorous acid solution and the chloride can be used efficiently. As, to provide a hypochlorous acid can be a conventional non-acidic hypochlorite that can address the drawbacks of the manufacturing apparatus manufacturing apparatus, and non-acidic hypochlorite can manufacturing method for the purpose.

As described above, an apparatus for producing non-acidic hypochlorous acid water for achieving the object of the present invention includes an electrolytic cell separated into an anode chamber having an anode and a cathode chamber having a cathode by an ion diaphragm, and the anode and the cathode in the electrolyte tank. An electrolytic cell comprising a power supply for supplying a current for electrolysis, wherein the ion diaphragm is composed of an anion permeable membrane for selectively transmitting only anions, and the anode chamber is connected with a raw water supply pipe for supplying raw water, and the cathode chamber It characterized in that the aqueous solution supply pipe for supplying a monovalent chloride solution is made.

The anion permeable membrane may be one having a quaternary ammonium base (-NR ₃ OH) in the membrane.

The aqueous solution supply pipe is made by connecting an aqueous solution manufacturing room for preparing a monovalent chloride solution by mixing monochloride with raw water.

The aqueous solution production chamber is further connected to the circulation chamber for circulating the monovalent chloride solution by fluidly connecting the cathode chamber of the electrolytic cell and the aqueous solution production chamber.

The aqueous solution manufacturing chamber is further connected to a chloride supply chamber for maintaining the chloride concentration of the monovalent chloride solution prepared therein.

The electrolyzer may be configured to form a plurality of anode chambers and cathode chambers including two to six anodes, two to six cathodes, and a plurality of anion permeable membranes disposed between the anode and the cathodes.

A first manifold is connected between one end of the plurality of anode chambers and a raw water supply pipe, and a second manifold is connected to the other ends of the plurality of anode chambers so that the plurality of anode chambers are connected to the plurality of cathode chambers. Can be distinguished.

In addition, the method for producing non-acidic hypochlorite water according to the present invention includes an electrolytic cell separated into an anode chamber having an anode and a cathode chamber having a cathode by an ion diaphragm, and supplying a current for electrolysis to the anode and the cathode in the electrolyte tank. In the preparation of hypochlorous acid water using an electrolytic cell comprising a power source, (1) a direct current is applied to the positive electrode and the negative electrode in the electrolytic cell while supplying raw water to the anode chamber and supplying an aqueous monochloride solution to the cathode chamber. An electrolytic step of electrolysis; And (2) a circulation step of maintaining a constant chloride concentration of the monochloride chloride solution while circulating the monochloride chloride solution between the cathode chamber and the chloride supply chamber connected to the cathode chamber.

In the circulating step, the monochloride solution may be circulated while maintaining the chloride concentration of the aqueous solution of monochloride at 0.05 to 0.2 molar concentration.

The apparatus for producing non-acidic hypochlorite water and the method for producing non-acidic hypochlorite water according to the present invention as described above are configured to electrolyze while supplying a monovalent chloride solution to the cathode chamber for circulation, and to supply only raw water to the anode chamber for electrolysis. Thus, chlorine ions electrolytically generated in the cathode chamber are transferred to the anode chamber through the anion permeable membrane so that the chloride remains in the hypochlorous acid water generated by the generation of hypochlorous acid by anodization of the chlorine ion at the anode of the anode chamber. This prevents precipitation of chlorides on the surface of the disinfectant and prevents clogging of the spray holes, economical use of monovalent chlorides, improvement of electrolytic efficiency, and proper pH control even when diluting the produced dissolved chlorine in low multiples. Therefore, there is an effect that can generate a high concentration of hypochlorous acid water.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

As shown in FIG. 3 and FIG. 4, the apparatus for producing non-acidic hypochlorite water for achieving the object of the present invention includes an anode chamber 310 having an anode 31 and an anode 32 by an ion diaphragm. An electrolytic cell 30 comprising an electrolytic cell 30 separated by a cathode chamber 320, and a power supply 33 for supplying current for electrolysis to the positive electrode 31 and the negative electrode 32 in the electrolytic cell 30 ( 30, wherein the ion diaphragm is composed of an anion permeable membrane 34 for selectively transmitting only anions, and the anode chamber 310 is connected to a raw water supply pipe 35 for supplying raw water 350, and the cathode Seal 320 is characterized in that the aqueous solution supply pipe 36 for supplying the monovalent chloride solution 360 is connected. That is, according to the present invention, the monochloride chloride solution 360 is supplied only to the cathode chamber 320, and only chlorine ions generated by electrolysis in the cathode chamber 320 are supplied through the anion permeable membrane 34. It moves to the chamber 310 and anodized by the anode 31 in the anode chamber 310 to produce chlorine, and the chlorine thus produced reacts with the raw water supplied into the anode chamber 310 to form hypochlorous acid water. (38) is characterized in that undissolved chloride does not remain in the generated hypochlorous acid water.

The anion permeable membrane 34 moves chlorine ions formed at the cathode toward the anode, and undecomposed chloride or the like functions to limit movement. As the anion permeable membrane 34, a polyester non-woven fabric (Polyester) non-woven fabric, a polyethylene sheet (Polyethylene sheet), vinylidene fluoride (Vinylidene-fluoride) coated with a sucrose ester Ester nonwoven sheets may be used, but any of them may have high anion permeability, low electrical resistance, high mechanical strength, chemical stability, high swelling stability due to low swelling under use conditions, and the like. Required. Especially in this invention, the thing of strong resistance to hydrochloric acid is preferable. In particular, the anion permeable membrane is produced by electrolysis (-) ions (e.g. Cl ^-, SO42 ^-) is transmitted, and (+) ions (e.g. Na ^+, Ca ₂ ⁺⁾ is a not-permeable membrane It may be one having a quaternary ammonium base (-NR ₃ OH) in the film.

In addition, the aqueous solution supply pipe 36 is made by connecting an aqueous solution production chamber 361 for mixing the monochloride chloride 362 with the raw water 350 to produce a monovalent chloride solution 360, whereby the aqueous solution production chamber ( The monovalent chloride solution 360 prepared in 361 is continuously supplied to the cathode chamber 320.

In particular, the aqueous solution manufacturing chamber (361) circulating the negative electrode chamber 320 of the electrolytic cell 30 and the aqueous solution production chamber 361 fluidly connected to circulate the monochloride chloride solution 360 to circulate This is further connected, thereby recovering the monovalent chloride solution 360 containing the undigested monovalent chloride 362 remaining in the cathode chamber 320 to be returned to the aqueous solution manufacturing chamber 361 It is characterized in that undissolved monochloride 362 can be continuously recycled. In the present invention, the hydrochloric acid concentration of the monovalent chloride solution is 0.05 to 0.2 molar concentration, and the water for preparing the dilute hydrochloric acid is preferably distilled water from which other anions, cations and the like are removed.

Here, as a chlorine source for hypochlorous acid production, any of monovalent chlorides such as hydrochloric acid, salt and potassium chloride, or a mixture thereof (e.g. hydrochloric acid + salt) may be used, but in the present invention for circulating chlorides, Hydrochloric acid, which has no salt remaining and is released as hydrogen gas and has a high degree of ionization, is preferable. However, the present invention does not exclude other monochlorides or mixed chlorides thereof.

The aqueous solution manufacturing chamber 361 is further connected to the chloride supply chamber 363 to maintain the chloride concentration of the monovalent chloride solution 360 manufactured therein, thereby decomposed and consumed in the cathode chamber 320 Alternatively, it is possible to replenish more monovalent chlorides 362, thereby continuing to recycle undigested monochlorides 362, while maintaining the chloride concentration at the concentration necessary for the electrolysis of chlorides for the preparation of hypochlorous acid. It is characteristic in that it enables continuous production. As monovalent chloride 362 in the chloride supply chamber 363, hydrochloric acid (38% hydrochloric acid content) of reagent grade or food additive standard may be preferably used. The concentration of the monochloride chloride solution 360 in the aqueous solution manufacturing chamber 361 is gradually lowered by continuous circulation and electrolysis of the monochloride chloride solution 360, and the aqueous solution preparation chamber is not lower than an appropriate concentration (0.05 mol or less). It is also possible to continuously supply monovalent chloride into 361 or to exchange the entire amount of monovalent chloride solution 360 in the aqueous solution manufacturing chamber 361. The timing of the total amount exchange is equipped with a high water level sensor (S) in the upper part of the aqueous solution manufacturing chamber (361) and pumped by a control circuit (not shown for simplicity of the drawing) when the level of the dilute hydrochloric acid at the initial intermediate level reaches a high level. By stopping the operation of the device and the operation of the device and notifying the liquid crystal panel (not shown for simplicity of the drawings). In order to maintain a large amount of continuous production, the monovalent chloride 362 in the chloride supply chamber 363 is continuously supplied into the aqueous solution production chamber 361 so as to maintain the concentration of the monovalent chloride in the aqueous solution production chamber 361 at an appropriate concentration. It is desirable to.

The electrolytic voltage in the present invention can be within the range of 1.5 to 4.0V. This is possible because the electrolytic voltage of chlorine generation by ionization of chlorine ion of hydrochloric acid and oxidation in the anode chamber of chlorine ion is 1.5V or more, so that the electrolytic voltage of water is not exceeded 4.0V, which impairs the efficiency by electrolysis of water. It can be understood to the extent that does not occur. However, it will be understood by those skilled in the art that the electrolytic voltage can be appropriately adjusted according to the monovalent chloride or raw water used and the characteristics of the electrolytic cell and the electrode.

FIG. 4 is a schematic diagram illustrating an enlarged facility for mass production of an apparatus for producing non-acidic hypochlorous acid according to the present invention shown in FIG. 3. Reference numerals in FIG. 4 used the same or similar reference numerals, except that components corresponding to or similar to those of FIG. 3 are not provided or corresponding functions in FIG. 3.

As shown in Figure 4, the electrolytic bath of the non-acidic hypochlorous acid production apparatus according to the present invention may comprise a large-capacity electrolytic tank 40, two or more, preferably two to two in the large-capacity electrolytic tank 40 It can be composed of six even number of anodes 31 and one more cathodes 32 than the anodes 31, thereby maximizing the anodization area. When the number of the anodes 31 exceeds six, the size of the large-capacity electrolytic bath 40 becomes so large that it is difficult to design a structure that can support the internal pressure received by the outer wall of the large-capacity electrolytic bath 40, and many reinforcement devices are reinforced. In addition, the capacity of the rectifier for converting alternating current to direct current also increases in the power supply system, and the price rises beyond the proportional size of the capacity. have.

Anion permeable membranes 34 are interposed between the electrodes in the large-capacity electrolytic cell 40 to distinguish them and form the cathode chambers 310 and the cathode chambers 320. Therefore, the number of the anode chamber 310 and the cathode chamber 320 formed by the anion permeable membranes 34 is the number of the anode 31 and / or the cathode 32 installed in the large capacity electrolytic cell 40. Will be proportional to

One end of the plurality of anode chambers 310 is connected to the first anode manifold 41 to allow only raw water 350 to flow into the anode chamber 310, and the other ends of the plurality of anode chambers 310. Are connected to the second anode manifold 42 and the hypochlorous acid water generated in the anode chamber 310 flows out of the large-capacity electrolyte tank 40 without being mixed with the monovalent chloride solution in the cathode chambers 320. You can. The positive electrode manifold 41 is connected between the plurality of positive electrode chambers 310 and the same or similar raw water supply pipe 35 to the raw water supply pipe 35 of FIG. Accordingly, by the use of the first positive electrode manifold 41 and the second positive electrode manifold 42, the plurality of negative electrode chambers 320 merely connect the aqueous solution supply pipe 36 to the large capacity electrolytic cell 40. As a result, the monovalent chloride solution 360 supplied through the aqueous solution supply pipe 36 may be supplied only to the cathode chambers 320. Conversely, it is obvious to those skilled in the art that a configuration of connecting a manifold to the cathode chambers 320 is also possible.

In addition, although not specifically described, the apparatus for producing non-acidic hypochlorous acid according to the present invention having the above-described configuration may be equipped with facilities for automated or mass production applied in a conventional hypochlorous acid production apparatus. For example, the aqueous solution production chamber 361 may be provided with a hydrogen automatic discharge valve (39). This may allow the discharge of hydrogen generated in the cathode chamber to be automatically discharged when hydrochloric acid is used as the monovalent chloride 362 in the aqueous solution manufacturing chamber 361, thereby preventing the risk of explosion due to hydrogen gas. .

The aqueous solution manufacturing chamber 361 may include a water level sensor, for example, a high level sensor (S), and a level sensor for automatic control such as high and low water level. In addition, the aqueous solution supply pipe (36) may be provided with a pump (P1) for supplying a monovalent chloride solution 360, the chloride connection in the conduit connecting the aqueous solution production chamber (361) and the chloride supply chamber (363) A pump P2 may be provided to supply the monovalent chloride 362 from the supply chamber 363 to the aqueous solution manufacturing chamber 361. In addition, the water level sensors may be applied to other sources, for example, a raw water source for supplying the raw water 350, pumps for transferring known liquid raw materials or products such as a metering pump to other conduits, and It will be understood by those skilled in the art that well-known control means for controlling these sensors or pumps may be included.

In addition, the method for producing non-acidic hypochlorous acid water according to the present invention includes an electrolytic cell 30 separated by an ion septum into an anode chamber 310 having an anode 31 and a cathode chamber 320 having a cathode 32. In the production of hypochlorous acid water using an electrolytic cell 30 comprising a power source 33 for supplying a current for electrolysis to the positive electrode 31 and the negative electrode 32 in the electrolytic cell 30, (1 An electrolysis step of supplying raw water to the anode chamber 310 and supplying a DC current to the anode and the cathode in the electrolytic cell 30 while supplying an aqueous monochloride solution to the cathode chamber 320 for electrolysis; And (2) a circulating step of circulating the monochloride chloride solution between the cathode chamber 320 and the chloride supply chamber connected to the cathode chamber 320 to maintain a constant chloride concentration of the monochloride chloride solution. It features.

The electrolysis step of (1) is the same as or similar to the conventional electrolysis, supplying raw water to the anode chamber 310, and supplying an aqueous monochloride solution to the cathode chamber 320 and the positive electrode in the electrolytic cell 30 It is made by applying a direct current to the cathode to electrolytically.

The step of circulating (2) is newly implemented in the present invention, wherein the chloride concentration of the monovalent chloride solution is circulated while circulating the monochloride solution between the cathode chamber 320 and the chloride supply chamber connected to the cathode chamber 320. It is made to maintain a constant, thereby continuously replenishing the monochloride chloride consumed by the electrolysis in the cathode chamber 320 to enable the electrolysis continuously under the appropriate conditions for electrolysis, thereby to maintain the hypochlorous acid water Make it possible to produce.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example  One

Dialysis electrolytic tank  Composition and Electrodes

As shown in Fig. 4, the self-produced electrolytic cell was composed of two anode chambers and three cathode chambers, with three anode plates and two anode plates each having a negative electrode permeable membrane. The electrode was manufactured by Heesung Metal Co., Ltd. in Korea. The cathode was made of platinum plated titanium plate, and the anode was coated and sintered with iridium oxide on titanium plate. 130 mm (thickness 0.5 mm) and the distance between electrodes were 3.5 mm. The negative ion permeable diaphragm used NEOSEPTA-AHA of Tokuyama, Japan, and the electrodes were connected in series to the power supply.

Of dilute hydrochloric acid  pharmacy

332 ml of reagent grade hydrochloric acid (concentration 38%) was taken as a dilute hydrochloric acid to be supplied to the cathode chamber, and dissolved in distilled water to prepare a 20 L 0.2 mol hydrochloric acid solution (pH 0.74).

Hypochlorous acid  Produce

Electric dilute hydrochloric acid solution was supplied to the cathode chamber at 1.0ℓ per minute, and raw water (water: 60ppm hardness, pH 7.2) was supplied at 1.0ℓ per minute, and the electrolytic voltage was 3.5V and the DC current was 10A. The dissolved chlorine concentration of the electrolyte in the anode chamber was 3,500 ppm and the pH was 1.32.

As a result of diluting the oxidizing electrolyte solution 100 times with the original raw water, hypochlorous acid water having a pH of 3.8 and an effective chlorine concentration of 24 ppm was obtained. The pH of the dilute hydrochloric acid solution recovered through the circulating recovery tube 37 in the cathode chamber was 1.14. Compared to the pH 0.74 of the hydrochloric acid solution supplied, 40% of the hydrochloric acid supplied was recovered and 60% was ionized to permeate into the anode chamber. I could confirm it. The dissolved chlorine concentration of the electrolytic oxidation solution was measured to be 3,400 ppm, and 80% of the chlorine ion permeately transferred was calculated as oxidized at the anode surface.

The concentration of the formed hypochlorous acid is lower than the dissolved chlorine concentration because the dissolved chlorine reacts with the raw water to produce the same molar hydrochloric acid as the hypochlorous acid, as shown in Formula 3.

In the above example, the pH of the solution was measured using Tongyang Propagation pH HM-124, and the effective chlorine concentration was measured by urea titration by diluting the electrolytic oxidation solution 10 times with distilled water and finally diluting 100 times with raw water. The effective chlorine concentration of the hypochlorous acid water was determined by the urea titration method.

As shown in the above embodiment, the non-acidic hypochlorous acid water production apparatus according to the present invention by supplying the dilute hydrochloric acid and the raw water by electrolysis, because the electroless hydrochloric acid is recovered and resupply, it is possible to economically use a chlorine ion source The anodization rate of chlorine ions reached 80%, indicating higher generation efficiency than 20% of conventional strong electrolyzed water production apparatus and 50% of non-acidic electrolyzed water production apparatus. The effective chlorine concentration and final pH of the final hypochlorous acid water are lower than or higher than the calculated value of 25 ppm, 3.4, or higher than the calculated value of the hypochlorous acid because of the reaction of chemical species such as hydroxides, carbonates and bicarbonates in the raw water.

Comparative example  1 and 2

According to the same method as in Example 1, the chloride consumption of the conventional method 1 (the diaphragm electrolyzer method; Comparative Example 1) and the conventional method 2 (the non-membrane electrolysis method; Comparative Example 2) and the present invention as described in the background art The hypochlorous acid production for the comparison was compared, the results are shown in Table 1 below. Here, in Comparative Example 1, a diaphragm was used as the diaphragm in the same electrolytic cell as in Example 1, and the positive and negative chambers were supplied with a salt solution of 0.05%. In Comparative Example 2, 0.2 mol of hydrochloric acid was supplied to the non-deposited membrane using an electrolytic cell having an electrode-to-electrode distance of 2.0 mm. The electrode area and supply charge were the same as in Example 1, and the raw water of Example 1 was used as dilution water.

chloride Chloride Consumption (A) (mg / L) Hypochlorous acid production amount (B) (mg / L) Dilution drainage   Final generation Production rate (B / A) (%) pH Effective chlorine concentration (mg / ℓ) Comparative Example 1 Comparative Example 2 Example 1 Salt hydrochloric acid 500 7,300 4,370 40 2,600 2,500 1 200 100 2.5 3.8 3.8 40 12 24 8.0 35.6 57.2

As shown in Table 1, the hypochlorous acid production rate of the present invention was found to be 57.2%, showing higher efficiency than 8.0% of Comparative Example 1, 35.6% of Comparative Example 2. In comparison with Comparative Example 2 and the present invention, Comparative Example 2 had to be diluted with 200 times the raw water in order to produce the weakly acidic hypochlorous acid water of the same pH 3.8 as the present invention, the effective chlorine concentration of the final product water 12 mg / It was confirmed that the production of hypochlorous acid water having high sterilizing power was difficult because it was only 1/2 of the present invention 24 mg / L.

Therefore, the present invention is configured to supply and circulate electrolytically by supplying monohydride aqueous solution to the cathode chamber of the membrane membrane electrolyte tank in which the inside is divided into the cathode chamber and the anode chamber by anion permeable membrane, and to supply and feed only the raw water separately to the anode chamber, Chlorine ions electrolytically generated in the cathode chamber are transferred to the anode chamber through the anion permeable membrane so that the chloride remains in the hypochlorous acid water generated by the generation of hypochlorous acid by anodization of the chlorine ion at the anode of the anode chamber. It provides a non-acidic hypochlorite water production apparatus and a non-acidic hypochlorite water production method to prevent.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications belong to the appended claims.

1 is a block diagram of a conventional diaphragm type hypochlorous acid production apparatus.

2 is a block diagram of a conventional diaphragm-type hypochlorous acid water production apparatus.

3 is a block diagram of an apparatus for producing non-acidic hypochlorous acid water of the present invention.

4 is a block diagram of a large-capacity electrolytic cell according to the present invention.

Claims (9)

An electrolytic cell comprising an electrolytic cell separated into an anode chamber having an anode and a cathode chamber having a cathode by an ion diaphragm, and a power supply for supplying current for electrolysis to the anode and the cathode in the electrolytic cell, The ion diaphragm is made of an anion permeable membrane that selectively permeates only anions, the anode chamber is connected to a raw water supply pipe for supplying raw water, the cathode chamber is made of an aqueous solution supply tube for supplying an aqueous hydrochloric acid solution, Here, the aqueous solution supply pipe is connected to an aqueous solution production chamber for preparing hydrochloric acid by mixing hydrochloric acid with raw water, and the aqueous solution production chamber is circulated to circulate the aqueous hydrochloric acid solution by fluidly connecting the cathode chamber of the electrolytic cell and the aqueous solution production chamber. A recovery pipe is further connected, and the aqueous acid production chamber is characterized in that the hydrochloric acid supply chamber for maintaining the concentration of the aqueous hydrochloric acid solution produced therein is further connected to the acidic hypochlorous acid production apparatus. delete delete delete delete The method of claim 1, The acid tank is characterized in that a plurality of anode chambers and cathode chambers are formed, including two to six anodes, three to seven cathodes, and a plurality of anion permeable membranes mounted between the anodes and cathodes. Hypochlorite water production apparatus. The method of claim 6, A first manifold is connected between one end of the plurality of anode chambers and a raw water supply pipe, and a second manifold is connected to the other ends of the plurality of anode chambers so that the plurality of anode chambers are connected to the plurality of cathode chambers. Miacidic hypochlorous acid water production apparatus characterized in that it is made to distinguish. delete delete

Images