KR101219582B1 - Electrochemically sterilizing device and electrochemical cell comprising the same - Google Patents

Abstract

The present invention discloses a method for maximizing the utilization of salt in an electrolysis cell for electrolyzing brine and improving power consumption. In another aspect, the present invention provides a system for producing a hypochlorous acid concentration of 1% or more using the electrolysis cell to increase the concentration of the disinfectant to reduce the volume of the reservoir. In addition, the present invention provides a system using the electrolysis cell to maintain the presence of salt water in the disinfectant.

Description

Electrochemically sterilizing device and apparatus using same {Electrochemically sterilizing device and electrochemical cell comprising the same}

The present invention relates to an apparatus for producing hypochlorous acid by electrolysis of brine, to generate an electrochemical fungicide, and more particularly, to a structure of an electrolysis cell for producing high concentration hypochlorous acid and a system using the same.

Sodium hypochlorite (NaOCl), hypochlorous acid (OCl), and chlorine (Cl ₂ ) are the same chlorine-based components, different forms present in water according to pH, slightly different sterilization capacity, but applied in the same sense in the present invention I would like to.

Hypochlorite, as is widely known, is used for water purification plants, sterilizers in sewage treatment plants, cooling water boilers in general chemical plants, desalination process water, cooling water treatment in power plants, drinking water treatment, plants and vegetables, meat processing, off-pool washing and papermaking, and household It is a colorless transparent liquid with a strong chlorine odor used as bleach.

Conventional hypochlorous acid production apparatus is a salt electrolysis device in the form of a diaphragm, the schematic diagram is shown in FIG. In the figure, s denotes a separation pipe, m denotes a mixed pipe, and l denotes a general pipe. In FIG. 1, salt (NaCl) is added to the brine reservoir 120, and the brine is maintained at a salt concentration of about 25 wt% in the brine reservoir 120. The electrolysis cell is fed with l3 saturated brine and l1 sisu line mixed in a mixer (m1), adjusted to 3-4% brine, and then fed to l4. Since the current efficiency is reduced by the calcium and magnesium present in the city water, the electrolysis cell 130 removes the calcium and magnesium through the water softener 110. The softened water is branched from s1 to the brine reservoir 120 through l2, and is supplied to the electrolysis cell 130 through l1.

The brine introduced into the electrolysis cell 130 generates hypochlorous acid by the electrolysis reaction. In the electrolysis cell 130, salt water exists as sodium ions (Na ⁺ ) and chlorine ions (Chloride, Cl ⁻ ), and chlorine ions and water hydroxy ions at the anode (132, anode) Oxidation reactions occur.

Cl ^- → Cl ₂ + 1/2 e ^-

2H ₂ O → H ⁺ + O ₂ + 2e

In general, an electrode coated with a catalyst having a low chlorine overvoltage, such as palladium oxide, ruthenium oxide, titanium dioxide, platinum, or the like, is coated on the valve metal to effectively generate chlorine at the anode 132. use. Chlorine generation efficiency at this time is 60-80% level.

On the other hand, in the cathode 134, the hydrogen ions generated in the reaction 2 are reduced, and sodium reacts with the hydroxide ions of water to become caustic soda.

^{H + + e - → 1 /} 2H 2

OH ^- + Na ⁺ NaOH →

In the solution, chlorine (Cl ₂ ) and caustic soda (NaOH) generated at the positive electrode react to form hypochlorous acid (ClO) or sodium hypochlorite (NaClO), the presence of which is determined by the pH of the solution. The product sodium hypochlorite, hydrogen, unreacted brine, and the like produced by the electrolytic reaction are stored in the sterilant reservoir 140 via l5.

As described above, a disinfectant generating system for preparing a disinfectant such as hypochlorous acid by electrolyzing brine with a septum has the following problem.

First, the disinfectant discharged from l5 contains unreacted brine, so if the water treatment system is closed (for example, indoor swimming pool), salt water gradually increases in the pool's water, making it salty for pipe corrosion and swimming. It can give off an unpleasant taste.

Second, the concentration (or effective chlorine) of the disinfectant hypochlorous acid generated in the conventional electrolysis cell is about 0.8%, and the storage volume of the disinfectant (or hypochlorous acid) storage tank 140 is increased.

Third, the salt utilization of the existing electrolysis cell has a problem of wasting salt to about 50% level.

Fourth, the existing electrolysis cell is electrolyzed at the concentration of 3-4% of the brine to be electrolyzed, which is low in salt water, the conductivity of the electrolyte (salt water) is low, and there is a problem of voltage rise due to solution resistance there was.

The present invention discloses a method for maximizing the utilization of salt in an electrolysis cell for electrolyzing brine and improving power consumption. In another aspect, the present invention provides a system for producing a hypochlorous acid concentration of 1% or more using the electrolysis cell to increase the concentration of the disinfectant to reduce the volume of the reservoir. In addition, the present invention provides a system using the electrolysis cell to maintain the presence of salt water in the disinfectant.

The brine electrolysis cell of the present invention is characterized by consisting of a membrane, an anode, and a cathode, and more particularly, the membrane, the anode, and the cathode are physically chemically bonded, and are characterized by having a structure that is not generally separated. In addition, the fungicide generating system of the present invention is characterized by having a means for separating chlorine and brine solutions generated in the electrolysis cell.

According to one aspect of the invention, (i) water softener, (ii) salt water reservoir 220,

(iii) a diaphragm type electrolysis cell, (iv) a diaphragm type fungicide generator comprising a sterilant reservoir; The diaphragm type electrolysis cell includes a diaphragm capable of passing sodium ions between the anode chamber and the cathode type; The diaphragm type sterilizer generator further comprises: (v) a liquid-gas separator capable of separating unreacted brine and chlorine from the discharge of the anode chamber and (vi) a chlorine dissolver; The unreacted brine separated in the liquid-gas separator is circulated back to the anode chamber, and the chlorine separated from the liquid-gas separator is introduced into the chlorine dissolver together with the caustic soda solution discharged from the cathode chamber. Disclosed is a diaphragm type fungicide generator characterized by the above-mentioned.

According to another aspect of the invention, (i) water softener, (ii) salt water reservoir 220,

(iii) a diaphragm type electrolysis cell, (iv) a diaphragm type fungicide generator comprising a sterilant reservoir; The diaphragm type electrolysis cell includes a diaphragm capable of passing sodium ions between the anode chamber and the cathode type; The diaphragm type sterilizer generator (v ') separates the discharge of the anode chamber into a first liquid-gas separator capable of separating unreacted brine and chlorine, and (vi') the discharge of the cathode chamber into hydrogen and caustic soda solution. A second liquid-gas separator, (vii ') caustic soda reservoir, and (viii') chlorine dissolver; The unreacted brine separated in the first liquid-gas separator is circulated back to the anode chamber, and the chlorine separated in the first liquid-gas separator together with the caustic soda solution discharged from the caustic soda storage tank. A caustic soda introduced into a chlorine dissolver, the caustic soda separated in the second liquid-gas separator is introduced into the caustic soda storage tank, and caustic soda is introduced into the cathode chamber from the caustic soda reservoir. Is disclosed.

According to one embodiment, the salt water electrolyte of the anode chamber is preferably circulated to the outside or inside of the electrolytic cell.

According to another embodiment, the diaphragm-type electrolysis cell includes (a) a porous reinforcing membrane, (b) an ion exchange membrane impregnated in the porous reinforcing membrane, and (c) first and second positions on both sides of the porous reinforcing membrane. A current distribution plate, and (d) first and second electrodes positioned at both sides of the ion exchange membrane; The ion exchange membrane may be located not only inside the porous reinforcement membrane but also on both surfaces thereof to integrate the porous reinforcement membrane, the ion exchange membrane, the first and second current distribution plates, and the first and second electrodes.

The porous reinforcing membrane is a polymer material selected from polysulfone, polyimide, polyamide, polycarbonate, polyacetal, nylon, ultra high molecular weight polyethylene, fluorine resin, PEEK, PBT, phenolic resin, ABS, PPS, polyacrylonitrile, alumina, Selected from inorganic materials selected from silica, zirconium dioxide, titanium dioxide, zinc dioxide, iron oxide (Fe ₂ O ₃ ), ruthenium oxide (RuO ₂ ), cesium oxide (CeO ₂ ), zeolite; The thickness of the reinforcing film is 1-50 μm, and the porosity is preferably 40-90%.

The ion exchange membrane is a hydrocarbon-based or fluorocarbon-based polymer containing acidic groups selected from sulfonic, carboxylic, and phosphoric systems. Is; The ion exchange membrane is preferably 5-500 μm thicker than the reinforcing membrane.

The first and second current distribution plates are the same or different materials from each other; Each independently is selected from a metal fiber sintered plate, a metal porous sintered plate, a metal mesh, and a screen pack laminated therewith; The metal is selected from titanium, nickel, molybdenum, tungsten, zinc, hastelloy, tin and alloys thereof; The current distribution plate preferably has a porosity of 40-80%.

The first and second electrodes are the same or different materials from each other; Each independently platinum, ruthenium, rhodium, palladium, osmium, iridium, gold, silver, chromium, iron, titanium, manganese, cobelt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, tin, alloys thereof and these Is selected from oxides of; It is preferable that the said 1st, 2nd catalyst is 1-10 micrometers in thickness.

According to another embodiment, the diaphragm-type electrolysis cell includes (i) an ion exchange membrane, (ii) first and second electrodes positioned on both sides of the ion exchange membrane, and (iii) outside of the first and second electrodes. An electrolysis cell comprising first and second current distribution plates respectively located on the side thereof, and (iv) first and second separation plates respectively located outside the first and second current distribution plates, wherein the electrolysis cell comprises: Any one of between the first current distribution plate and the first separation plate, between the second current distribution plate and the second separation plate, or between the first current distribution plate and the first separation plate, and the second current distribution plate; It is preferable to further include a pressure mat located between all of the second separator plates.

The pressure mat is preferably a foamed metal having a compression ratio of 50-90% and a porosity of 50-90%. The pressure mat is preferably a foam of a metal selected from copper, nickel, gold, silver, tin, aluminum, sus, cobalt, alloys thereof or oxides thereof. In particular, the pressure mat is preferably coated with a conductive material selected from platinum, silver, copper on the surface of the metal foam.

Accordingly, the present invention, the first manufacturing sterilizer is free of unreacted brine, salt water does not accumulate in the water of the pool in a closed water treatment system (for example, indoor swimming pool) can eliminate pipe corrosion and discomfort to the swimmers. Second, the concentration (or effective chlorine) of the disinfectant hypochlorous acid generated in the existing electrolysis cell can be reduced to 1 to 11 times the volume of the existing reservoir by storing the disinfectant at a concentration of 1-12 wt%.

Third, the salt utilization of the electrolysis cell is about 99%, eliminating the problem of salt waste. Fourth, the operating energy of the electrolysis cell is drastically lowered to 3.5 kWh per 1kg production, thereby reducing operating costs.

Hereinafter, some embodiments of an electrolysis cell and a system having the same according to the present invention will be described in detail with reference to the accompanying drawings.

2 is a schematic diagram of the diaphragm type fungicide generating system 200 of the present invention, wherein the concentration of the fungicide is 1-3 wt%.

The electrolysis system 200 generating the sterilant concentration of 1-3 wt% according to the present invention includes a softener 210 for softening the time water, a salt water storage tank 220, and an electrolyte (salt water) in the anode chamber. Diaphragm-type electrolysis cell 230 having a circulating (or circulating inside) structure, liquid / gas separator 240 for separating chlorine and unreacted salt water generated in the anode chamber, chlorine generated in the anode chamber And a chlorine dissolver 250 and a sterilization storage tank 260 for mixing or reacting the product passed through the cathode chamber.

As shown in the figure, salt (NaCl) is introduced into the brine reservoir 220, and the brine is maintained at about 25 wt% salt concentration (saturated brine) in the brine reservoir 220. Saturated brine is supplied to the l203 by the brine pump 222, mixed with the circulation line l207 of the chlorine-salt water liquid / gas separator 240 in the mixing pipe m201 and the anode 232 of the electrolysis cell 230 through l204 Supplied by.

Calcium and magnesium present in the time water are removed from the softener 210. The softened water l201 is branched in the branch pipe s201, the branched l202 is used to dissolve the salt, and l208 is supplied to the cathode 234 of the electrolysis cell 230.

In the anode 232 of the electrolysis cell 230, the same reaction occurs as in the anode reaction in the non-capacity electrolysis cells shown in Schemes 1 and 2 (FIG. 1). In the negative electrode 234 of the electrolysis cell 230, the same reaction as in the non-diaphragm electrolysis cell shown in Schemes 3 and 4 (FIG. 1) occurs. The membrane 236 in the electrolysis cell 230 separates chlorine (Cl ₂ ) produced at the anode 232 and caustic soda (NaOH) generated at the cathode 234, and the sodium ions present at the anode are transferred to the cathode. Let it move

Chlorine (Cl ₂ ) and unreacted brine are present at the outlet l205 of the anode 232 side of the electrolysis cell 230, which is converted from chlorine-salt solution / gas separator 240 to chlorine (Cl ₂ ) and unreacted brine. Are separated. The separated chlorine (Cl ₂ ) is moved to the chlorine (Cl ₂ ) dissolver 250 along l206, the unreacted brine is moved to l207 phosphorus is mixed with the incoming brine l203 phosphorus in the mixing pipe m201.

In the pipe 209 of the cathode 234 side of the electrolysis cell 230, only a dilute caustic soda solution (1 wt% or less) is used, which is used as a medium to dissolve chlorine (Cl ₂ ) of l206.

The chlorine (Cl ₂ ) dissolver 250 may be of a function such as an ejector. After the chlorine (Cl ₂ ) dissolver 250, l210 is produced in a disinfectant (hypochlorite) concentration of 1-5 wt% and stored in the disinfectant reservoir 260, by the hypochlorous acid pump 270 where the disinfectant is needed. Supplied.

The material of the pipes and the device in the disinfectant generating system 200 of the present invention may be made of a plastic material including CPV, Teflon, etc., chemically resistant to hypochlorous acid, and titanium, hastelory, stainless steel, and the like.

The chlorine-salt liquid / gas separator 240 of the disinfectant generating system 200 of the present invention is designed within 2-60 minutes based on residence time and the level of gas and liquid is controlled by a level sensor (not shown). (Hereinafter, the liquid / gas separators of FIGS. 3 and 4 are also possible in the same configuration.)

The chlorine (Cl ₂ ) dissolver 250 of the disinfectant generation system 200 of the present invention has a structure such as an ejector or an orifice. The structure has a diameter change of diameter D1, diameter D2, diameter D1, and branch D2 has a branch pipe. At this time, l209 is connected to the D1 diameter of the chlorine dissolver 250, and l206 is connected to the D2 branch pipe. When the ratio of diameter D1 to diameter D2, D2 / D1 is 0.05-0.5, negative pressure is generated at l206, and the chlorine separated from the chlorine-salt water / gas separator 240 can be efficiently transferred without using a pump or the like. have. More preferably 0.1-0.2 is preferable. If it is less than 0.01, the feed rate (feed amount) of l209 should be large, and the auxiliary power cost for this increases, resulting in a large configuration of the device (which leads to an increase in investment cost). At 0.5 or more, the pressure is similar between D1 and D2 of D2, so that desired mixing cannot be achieved.

5 is a structural diagram of a unit electrolysis cell 500 of the present invention. As shown, the unit electrolysis cell 500 is composed of an electrochemical oxidation catalyst (anode catalyst, 530) and an electrode catalyst layer having a reduction catalyst (hydrogen catalyst, 520) of the ion exchange membrane 510 is physically combined do. An ion exchange membrane 210 and a structure in which electrode catalysts (oxidation catalysts and reduction catalysts) are physically or chemically integrated on both sides of the ion exchange membrane 210 are referred to as an electrode membrane assembly (hereinafter, referred to as an EMC).

The anode chamber 532 is a place where an oxidation reaction (chlorine generation reaction) occurs, and an anode (catalyst) 530 in which an electrochemical reaction occurs, a frame 550 holding an electrolysis cell, and a separation separating a cell from a cell Plate 560, an anode chamber current distribution plate 570 for supplying current to the anode, and a gasket for preventing external leakage of reactants and products in the anode chamber 532 between the frame 550 and the separator plate 560 ( Packing 580).

The cathode chamber 522 is a cathode (catalyst) 520 where a reduction reaction (hydrogen generation reaction) takes place, a frame 552 holding an electrolysis cell, and a separator separating the cell from the cell. (The same material and structure as 562 and 560 are possible), a cathode chamber current distribution plate 572 for supplying current to the cathode, and between the frame 550 and the separator 562 in the cathode chamber 522 Gaskets (packing) 582 that prevent external leakage of reactants and products.

The ion exchange membrane 510 has a thickness of 50 to 200 μm and is a solid polymer electrolyte, in which cations such as sodium ions or hydrogen ions are movable, and are resistant to temperature and electrochemical redox atmospheres. It must be durable. In order to satisfy these functions and requirements, the ion transport groups sulfonic and carboxyl are used to selectively move cations to hydrocarbon-based or fluorocarbon-based polymers. Polymer structures having carboxylic and phosphoric acidic groups are preferred. The most preferable structure is a membrane having a strong acid resistance group of -SO ₃ type in a fluorocarbon polymer having excellent heat resistance and oxidation resistance. A representative film 310 of this series is the product name NAFION of DuPont (EI du Pont de Nemours and Company, Wilmington, Del.).

The electrode catalyst layers 520 and 530 of the electrolysis cell 500 in the present invention may be composed of only metal catalysts, respectively.

In the present invention, the catalysts included in the anode catalyst layer 530 and the cathode catalyst layer 520 may be the same or different, but a metal catalyst made of a platinum group or a platinum group alloy is preferable. Metal catalysts include gold, silver, chromium, iron, titanium, manganese, cobelt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, in addition to metals of the platinum group (platinum, ruthenium, rhodium, palladium, osmium, iridium) Preferred is one or one or more metal alloys selected from the group consisting of tin or oxides thereof.

In the present invention, the most preferred anode catalyst layer 530 is preferably a metal having a low chlorine overvoltage, such as platinum, ruthenium, iridium alone or a mixed metal thereof, or an oxide thereof.

In the present invention, the most preferable cathode catalyst layer 530 is preferably one or more metals, alloys or oxides thereof selected from the group consisting of platinum, palladium, nickel and tungsten having a low hydrogen overvoltage.

Although the thickness of EMC which consists of the electrode catalyst layers 520 and 530 and the ion exchange membrane 510 in this invention is not specifically limited, It is preferable that it is about 150-200 micrometers. If the thickness is too thin (50 μm or less), a short circuit may occur. If the thickness of the EMC is 200 μm or more, the ion resistance becomes large and the voltage rises sharply. Therefore, the thickness is preferably 50 μm to 200 μm.

The thickness of the electrode catalyst layers 520 and 530 (thickness of both electrode catalyst layers) in the configuration of the EMC is preferably 1 to 15 µm. At 15 μm or more, the loss of the catalyst due to excessive use of the catalyst becomes a problem, and when the thickness of the catalyst layer is less than 1 μm, the amount of catalyst present per unit area is small and thus does not have high reaction activity. The best thickness range in the present invention is 5-10 μm.

EMC is not particularly limited to the method of fabricating EMC by physically or chemically integrating the hydrogen ion exchange membrane 510 and the electrode catalyst layers 520 and 530, but specifically, a method of depositing a catalyst directly on an ion exchange membrane and a catalyst layer. There is a method for pressing the film into a film, and the production method thereof is well known. Representative examples include the application No. 10-2005-0016642 (method of manufacturing a membrane electrode assembly having a porous electrode catalyst layer), the application No. 10-2005-0016639 (method of manufacturing a membrane electrode assembly) and the application number 10- 2005-0016637 and the like.

The feeders 570 and 572 should have the ability to transfer reactants and products to or from EMC and to distribute currents smoothly to the EMC surface. For this function, EMC must be configured to have appropriate pores. The preferred porosity is 40-80%. Above 80%, the mass transfer of the reactants or products is smooth, but the contact point with EMC is too small, resulting in uneven current distribution. As a result, the mass movement is not smooth.

In order to secure the porosity in order to have such a function, a metal fiber sintered plate, a porous sintered plate, a metal mesh, or a stacked screen pack may be configured.

The material of the feeder should be conductive and suitable for the environmental and electrochemical redox conditions of the reactants and products present in the electrolysis cell. Possible materials in such an environment are preferably alloys with one or more metals selected from the group consisting of titanium, nickel, molybdenum, tungsten, zinc, hastelloy and tin.

Since the cathode chamber feeder 570 should have chemical resistance in a salt water and chlorine atmosphere, titanium, hastelloy, and the like are preferable, and the cathode chamber feeder 572 is selected from the group consisting of nickel, molybdenum, tungsten, zinc, and Hastelloy. Preference is given to species or alloys with at least one metal.

Figure 3 is a fungicide generation system 300 of the present invention is possible concentration of the fungicide is 4-8 wt%.

The configuration of the electrolysis system 300 to generate a 4-8 wt% disinfectant concentration consists of a water softener 310, a brine reservoir 320, a diaphragm type electrolysis cell 330, and chlorine and unreacted brine produced at the anode. A first liquid / gas separator 340 for separating, a second liquid / gas separator 350 for separating caustic soda and hydrogen generated from the cathode, a caustic soda tank 360, and a final concentration of 5 wt% sterilizer for preparing Chlorine dissolver 370, sterilizing agent made of 380.

As shown in the figure, salt (NaCl) is added to the brine reservoir 320, and the brine reservoir 320 is maintained at a concentration of about 25% by weight. Saturated brine is supplied to the l303 by the brine pump (p301) and mixed with the circulation line l307 of the chlorine-salt liquid / gas separator 340 and supplied to the anode 332 of the electrolysis cell 330 through l304. .

Calcium and magnesium, which are present in the water, are removed from the softener 310. The softened water line l301 is branched from the branch pipe s301 so that l202 is used to dissolve the salt and l308 is supplied to the caustic soda solution reservoir 360.

The electrolysis cell 330 is composed of an anode 332, a cathode 334, and a film 336, and each function is the same as described above with reference to FIG. 2.

Chlorine and unreacted salt are present at the anode 332 side l305, which is separated in the chlorine-salt first liquid / gas separator 340. The separated chlorine moves to the chlorine dissolver 370 along l306, and the flow rate flowing through the l306 line is controlled through the chlorine flow rate control valve v301.

Hydrogen and caustic soda solution exists at the cathode 234 side l310, which is separated and discharged from the second gas-liquid separator 350, and then the caustic soda solution is supplied to the caustic soda solution reservoir 360 through l312. . Caustic solution reservoir 360 is maintained at a pH of 10 or more to increase the reaction efficiency with chlorine. 4% NaOH in the caustic soda reservoir 360 is moved to the chlorine dissolver 370 with l313, the flow rate flowing through the l313 line is controlled through the caustic soda flow control valve (v302).

The chlorine supplied through l306 and the caustic soda solution supplied through l313 dissolve-react in the chlorine dissolver 370, and the chlorine dissolver 370 operates in the same manner as the chlorine dissolver principle mentioned in FIG. The negative pressure media of l306 and l312 are controlled by a circulating hypochlorous acid solution supplied through l317.

The hypochlorous acid synthesized through the chlorine dissolver 370 is stored in the hypochlorous acid storage tank 380 through l315. The stored hypochlorous acid is circulated through the circulation pipe l317 in the hypochlorous acid storage tank 380 to increase the concentration, and some of the hypochlorous acid is discharged to l306 for the purpose of use.

The chlorine dissolver 370 has a diameter change of diameter D1, diameter D2, diameter D3, and diameter D1, and branch pipes are installed at diameters D2 and D3. At this time, the circulation pipe l317 of hypochlorous acid is connected to the main pipe D1 of the chlorine dissolver 370, l306 is connected to the D2 branch pipe, and l313 is connected to the D3 branch pipe.

The ratio D2 / D1 of the diameter D1 to the diameter D2 is negative pressure generated at l306 at 0.05-0.5 to transfer chlorine, and D2 / D1 is most preferably 0.1-0.2. If less than 0.01, the feed rate (supply amount) of l370 should be large, and the auxiliary power ratio (pump p303) for this will be large. Above 0.5, the pressure is similar between D1 and D2 of D2, so that desired mixing cannot be achieved.

In the ratio D3 / D1 of the diameter D1 and the diameter D3, negative pressure is generated at l313 at 0.05-0.5 so that the caustic soda solution can be efficiently transferred from the caustic soda storage tank 360 without using a pump or the like. D2 / D1 is most preferably 0.1-0.2. If it is less than 0.01, the feed rate (feed amount) of l317 should be large, and the auxiliary power cost (capacity increase of p303) is required for this. Above 0.5, the pressure is similar between D1 and D3 of D2, so that a desired purpose of mixing cannot be achieved.

Figure 4 is a disinfectant generation system 400 of the present invention possible concentration of the disinfectant is 8-12 wt%.

The composition of the electrolysis system 400 to generate a disinfectant concentration of 8-12 wt% comprises the water softener 410, the brine reservoir 420, the diaphragm electrolysis cell 430, and the chlorine and unreacted brine produced at the anode. A first liquid / gas separator 440 for separating, a caustic soda generated from the cathode and a second liquid / gas separator 460 for separating hydrogen, and a first caustic soda tank 462 for circulating caustic soda generated at the cathode. A first hypochlorous acid reservoir 470 storing a 5 wt% medium disinfectant, a first chlorine dissolver 450, a second chlorine dissolver 482 for producing a sterilant concentration of 12 wt% final, A second hypochlorous acid reservoir 480 for storage of a disinfectant at a final concentration of 12 wt%.

As shown in the figure, salt (NaCl) is introduced into the brine reservoir 420, and the brine is maintained at a concentration of about 25% by weight in the brine reservoir 420. Saturated brine is supplied to the l403 by the brine pump (p401), mixed with the circulation line l407 of the chlorine-salt first liquid / gas separator 440 and supplied to the anode 432 of the electrolysis cell 430 through l404. do.

The softened water l401 which has passed through the water softener 410 is branched in the branch pipe s401 and used to dissolve the salt, and the branch l402 is branched in the branch pipe s402. The branched l409 supplies water to the primary chlorine dissolver 450 to dissolve the chlorine of l408 firstly, and the separated l419 is supplied to the secondary caustic soda storage tank 470.

The electrolysis cell 430 is composed of a positive electrode 432, a negative electrode 434, the film 436, each function is the same as described above in FIG.

Chlorine (Cl ₂ ) and unreacted salt are present in the positive electrode 432 side l405 of the electrolysis cell 430, which is separated in the chlorine-salt liquid / gas separator 440. The separated chlorine (Cl ₂ ) moves along l406 and branches to l408 and l407 in branch pipe s403 and again to l417 and l425 in branch pipe s404. Branched l408 is fed to the primary chlorine dissolver 450. The branched l417 is mixed with l416 (caustic soda solution) in the mixed pipe m402 to l418, which is then mixed in l420 and mixed pipe m402 to l421.

The branched l425 is controlled by the chlorine flow valve v401 and supplied to the mixing pipe m403.

The caustic soda solution (including some hypochlorous acid) is supplied from the caustic soda electrolyzer 462 through the negative electrode 436 side l411, and the caustic soda solution is electrolyzed at the cathode 436 of the electrolysis cell 430. Concentrate to 4 wt% NaOH.

At the cathode 436 side, there are electrolyzed caustic soda, hypochlorous acid and hydrogen gas, and hydrogen-caustic soda is separated in the second liquid / gas separator 460. The liquid separated in the hydrogen-caustic second liquid / gas separator 460 is transferred to caustic soda reservoir 462 via l414. The primary caustic soda storage tank 462 is supplied with a solution in which chlorine is dissolved in the primary chlorine dissolver 450 through l410.

The 4 wt% caustic soda, 1 wt% hypochlorous acid solution stored in caustic soda reservoir 462 branches to l416 and l424 in l415 and branch piping s405. The branched 1424 is controlled by the caustic soda solution flow valve v402, and is supplied to the mixing pipe m403, and the branched l416 is supplied to the mixing pipe m402.

The first hypochlorous acid reservoir 470 stores a 5 wt% hypochlorous acid solution. To prepare a 5 wt% hypochlorous acid solution, a 5 wt% hypochlorous acid solution is circulated through the l420 circulation pipe using a pump p403. l420 is mixed with l418 containing hypochlorous acid from l403 to l421 in the mixed pipe and then branches back to l422 and l423 in branch pipe s406. l422 is circulated back to the first hypochlorous acid reservoir 470, and l423 is moved to the second hypochlorous acid reservoir 480 at a final concentration of 12 wt%.

The second hypochlorous acid storage tank 480 is a storage tank for storing 12 wt% hypochlorous acid, and is manufactured by circulating and concentrating 5 wt% moved from the first hypochlorous acid storage tank 470 to produce 12 wt% hypochlorous acid.

In the second hypochlorous acid reservoir 480, some of the solution is controlled by the hypochlorous acid flow valve v403 at l426, and is supplied to the mixing pipe m403.

The hypochlorous acid solution of the second hypochlorous acid reservoir 480 is circulated through the l430 circulation pipe by using the pump p403. Some of the l430's are supplied through l429 to destinations that use them.

The mixture l427 mixed in the circulation pipe l430 and the mixing pipe m403 is supplied to the second chlorine dissolver 482 to increase the concentration of hypochlorous acid and recycled to the second hypochlorous acid storage tank 480 through l428.

The structures of the first chlorine dissolver 450 and the second chlorine dissolver 482 are the same as those described above with reference to FIGS. 2 and 3.

Hereinafter, some embodiments of the present invention will be described based on examples. However, the following examples should not be construed to reduce or limit the scope of the present invention.

Example  1-3

1. Configuration of the electrolysis cell (see FIG. 5)

Parameter Specifications Number of unit cells One Unit cell area (active area) 314 cm ² Unit cell composition



Ion Exchange Membrane (510) Nafion 117 (180 μm) Anode Catalyst Layer 530 IrO ₂ -Pt Cathode Catalyst Layer 520 Pt Feeder (540,542) Titanium Metal Fiber Sintered Plate (70% Porosity, 0.5mm Thickness) Separator (560) A flow path was formed in the Ti plate (4 mm)

2. Operation condition of electrolysis cell

Parameter value Current density 1 A / cm2 Operating temperature Room temperature Operating pressure Atmospheric pressure Electrolyte
anode 25 wt% NaCl solution cathode pure

3. System Configuration

(1) Example 1: FIG. 2

(2) Example 2: FIG. 3

(3) Example 3: FIG. 4

4. Performance Analysis

Parameter Analysis method Analysis interval
(time) result Voltage Measure with multimeter 1 hours 6; Marked as Examples 1, 2, 3 Chlorine concentration in the reservoir Iodine titration 1 hours 7; Marked as Examples 1, 2, 3 Brine concentration in the reservoir 1 day 8; Marked as Examples 1, 2, 3 Power consumption required to generate 1 kg of chlorine Calculation based on current and voltage values 1 day Table 1; Marked as Examples 1, 2, 3 Salt consumption required to generate 1 kg of chlorine Calculated as the amount of salt consumed to produce 1kg 1 day Table 1; Marked as Examples 1, 2, 3 Current efficiency
(System efficiency) Calculated by the following formula 1 1 day Table 1; Marked as Examples 1, 2, 3

Reference Current Efficiency Calculation Formula

The current efficiency is obtained by dividing the actual value of hypochlorous acid generated with respect to the applied current (I) by the theoretical amount.

Current efficiency (%) = (F × ρ × V) / (35500 (mg) × I × t)｝ × 100

Where F is the Faraday constant, 96500 (C), ρ is the actual residual chlorine concentration (ppm, mg / L), V is the quantity of water supplied to the electrolysis cell (L), I is the current carrying current (A), and t is Electrolysis time (s).

Comparative example  1, 2

1. Configuration of the electrolysis cell (see FIG. 2)

Parameter Specifications Number of unit cells One Unit cell area (active area) 314 cm ² Unit cell composition Ion Exchange Membrane 310 none Anode (132) Formation of the electrode catalyst RuO ₂ -IrO ₂ on titanium Cathode (134) Platinum (Pt) plating on titanium Distance between anode and cathode 2 mm Electrolyzer frame Chlorinated PVC

2. Operation condition of electrolysis cell

(1) Comparative Example 1

Parameter value Current density 0.1 A / cm2 (actual operating condition value) Operating temperature Room temperature Operating pressure Atmospheric pressure Electrolyte 4 wt% NaCl

(1) Comparative Example 2

Parameter value Current density 1 A / cm2 (operating conditions same as the present invention) Operating temperature Room temperature Operating pressure Atmospheric pressure Electrolyte 4 wt% NaCl

3. Configuration of the system: Fig. 2

4. Performance Analysis

Parameter Analysis method Analysis interval
(time) result Voltage Measure with multimeter 1 hours 6; Displayed as Comparative Examples 1 and 2 Chlorine concentration in reservoir 140 Iodine titration 1 hours 7; Displayed as Comparative Examples 1 and 2 Brine concentration in the reservoir 140 1 day 8; Displayed as Comparative Examples 1 and 2 Power consumption required to generate 1 kg of chlorine Calculation based on current and voltage values 1 day Table 1; Displayed as Comparative Examples 1 and 2 Salt consumption required to generate 1 kg of chlorine Calculated as the amount of salt consumed to produce 1kg 1 day Table 1; Displayed as Comparative Examples 1 and 2 Current efficiency
(System efficiency) Calculated by the following formula 1 1 day Table 1; Displayed as Comparative Examples 1 and 2

Example was applied to the electrolytic cell of Figure 5 of the present invention and Figure 2 (Example 1), Figure 3 (Example 2), Figure 4 (Example 3) and the comparative example is the conventional fungicide generating system of Figure 2 ( Comparative Example 1) and the existing system were operated under the same conditions as the operating conditions of Example (Comparative Example 2).

The voltage comparison of FIG. 6 has a value of about 3 volts in Example, about 4 volts in Comparative Example 1, and about 6.5 volts in Comparative Example 2.

In the concentration comparison of FIG. 7, Example 1 is about 2.5 wt% in Example, about 5 wt% in Example 2, about 11.8 wt% in Example 3, about 0.7 wt% in Comparative Example 1, and Comparative Example 2 has a value of about 0.45%. In the case of Comparative Example 2, it is considered that the temperature of the electrolyte due to the increase in the current density increases, and thus, hypochlorous acid causes side reactions with perchloric acid and the like, and the efficiency is drastically lowered.

FIG. 8 compares the concentrations of brine in hypochlorous acid (sterilizer) reservoirs, with values of about 100 ppm in the embodiment of the present invention, while in the examples, about 13,000-15,000 ppm are maintained. The 100 ppm level of the present invention is estimated as the amount contained in the water, so the system of the present invention can be seen that the unreacted brine does not migrate to the fungicide.

The table below compares the present Example with a comparative example.

Parameter Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Power consumption required to generate 1 kg of chlorine
(Lower is preferable) 4.3 kWh 3.9 kWh 3.7 kWh 5.5 kWh 10.6 kWh Salt consumption required to generate 1 kg of chlorine
(Lower is preferable) 1.9 kg 1.9 kg 1.9 kg 3.5 kg 4.8 kg Current efficiency
(System efficiency) 88% 88% 88% 67% 44%

1 is a schematic diagram of a conventional membrane-free hypochlorous acid production apparatus.

Figure 2 is a schematic diagram of a diaphragm type fungicide generating system according to an embodiment of the present invention.

3 is a schematic diagram of a bactericide generating system according to another embodiment of the present invention.

4 is a schematic diagram of a bactericide generating system according to another embodiment of the present invention.

5 is a structural diagram of a unit electrolysis cell according to an embodiment of the present invention.

6 is a graph showing a change in voltage over time.

7 is a graph showing the change of the fungicide concentration over time.

8 is a graph showing the change in salt concentration over time.

Claims (12)

(i) a water softener, (ii) brine reservoir 220, (iii) diaphragm electrolysis cells, (iv) a diaphragm type fungicide generator comprising a fungicide reservoir; The diaphragm electrolysis cell comprises a diaphragm capable of passing sodium ions between the anode chamber and the cathode chamber; The diaphragm type sterilizer generator further comprises: (v) a liquid-gas separator capable of separating unreacted brine and chlorine from the discharge of the anode chamber and (vi) a chlorine dissolver; The unreacted brine separated in the liquid-gas separator is circulated back to the anode chamber, and the chlorine separated from the liquid-gas separator is introduced into the chlorine dissolver together with the caustic soda solution discharged from the cathode chamber. A diaphragm type fungicide generator, characterized in that: (i) a water softener, (ii) brine reservoir 220, (iii) diaphragm electrolysis cells, (iv) a diaphragm type fungicide generator comprising a fungicide reservoir; The diaphragm electrolysis cell comprises a diaphragm capable of passing sodium ions between the anode chamber and the cathode chamber; The diaphragm type sterilizer generator (v ') separates the discharge of the anode chamber into a first liquid-gas separator capable of separating unreacted brine and chlorine, and (vi') the discharge of the cathode chamber into hydrogen and caustic soda solution. A second liquid-gas separator, (vii ') caustic soda reservoir, and (viii') chlorine dissolver; The unreacted brine separated in the first liquid-gas separator is circulated back to the anode chamber, and the chlorine separated in the first liquid-gas separator is combined with the caustic soda solution discharged from the caustic soda tank. A caustic soda is introduced into the dissolving unit, the caustic soda separated in the second liquid-gas separator is introduced into the caustic soda storage tank, caustic soda is introduced into the cathode chamber from the caustic soda reservoir. The diaphragm type fungicide generator according to claim 1 or 2, wherein the brine electrolyte of the anode chamber is circulated to the outside or the inside of the electrolytic cell. The method of claim 3, wherein the diaphragm-type electrolysis cell comprises: (a) a porous reinforcing membrane, (b) an ion exchange membrane impregnated in the porous reinforcing membrane, and (c) first and second electrodes located on both sides of the porous reinforcing membrane. A current distribution plate, and (d) first and second electrodes positioned at both sides of the ion exchange membrane; The ion exchange membrane is located not only inside the porous reinforcing membrane but also on both surfaces thereof, and thus, the porous reinforcing membrane, the ion exchange membrane, the first and second current distribution plates, and the first and second electrodes are all characterized in that the diaphragm is integrated. Mold sterilizer generator. The method of claim 4, wherein the porous reinforcing membrane is selected from polysulfone, polyimide, polyamide, polycarbonate, polyacetal, nylon, ultra high molecular weight polyethylene, fluorine resin, PEEK, PBT, phenol resin, ABS, PPS, polyacrylonitrile. Selected polymer materials and inorganic materials selected from alumina, silica, zirconium dioxide, titanium dioxide, zinc dioxide, iron oxide (Fe ₂ O ₃ ), ruthenium oxide (RuO ₂ ), cesium oxide (CeO ₂ ), zeolite; The thickness of the porous reinforcing membrane is 1-50 ㎛, porosity is a diaphragm type sterilizer generator, characterized in that 40-90%. The method of claim 4, wherein the ion exchange membrane is a hydrocarbon-based material or fluorocarbon including acidic groups selected from sulfonic, carboxylic and phosphoric systems. A polymer of) -based material; The ion exchange membrane is a diaphragm type sterilizer generator, characterized in that 5-500 ㎛ thicker than the porous reinforcing membrane. 4. The method of claim 3, wherein the first and second current distribution plates are the same or different materials from each other; Each independently is selected from a metal fiber sintered plate, a metal porous sintered plate, a metal mesh, and a screen pack laminated therewith; The metal is selected from titanium, nickel, molybdenum, tungsten, zinc, hastelloy, tin and alloys thereof; The current distribution plate is a diaphragm type sterilizer generator, characterized in that having a porosity of 40-80%. The method of claim 3, wherein the first and second electrodes are the same or different materials from each other; Each independently platinum, ruthenium, rhodium, palladium, osmium, iridium, gold, silver, chromium, iron, titanium, manganese, cobelt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, tin, alloys thereof and these Is selected from oxides of; The first and second catalysts are diaphragm type sterilizer generator, characterized in that the thickness of 1-10 ㎛. 4. The diaphragm electrolysis cell of claim 3, wherein the diaphragm electrolysis cell comprises (i) an ion exchange membrane, (ii) first and second electrodes located on both sides of the ion exchange membrane, and (iii) outside the first and second electrodes. An electrolysis cell comprising first and second current distribution plates respectively positioned, and (iv) first and second separation plates respectively positioned outside the first and second current distribution plates, wherein the electrolysis cell is the Any one of the first current distribution plate and the first separation plate and between the second current distribution plate and the second separation plate or between the first current distribution plate and the first separation plate and the second current distribution plate and the first 2. A diaphragm type sterilizer generator further comprising a pressure mat positioned between all of the two separation plates. 10. The diaphragm type fungicide generator according to claim 9, wherein the pressure mat is a foamed metal having a compression ratio of 50-90% and a porosity of 50-90%. The diaphragm type fungicide generator according to claim 9, wherein the pressure mat is a foam of a metal selected from copper, nickel, gold, silver, tin, aluminum, sus, cobalt, alloys thereof or oxides thereof. The diaphragm type sterilizer generator according to claim 10, wherein the pressure mat is further coated with a conductive material selected from platinum, silver and copper on the surface of the metal foam.

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