KR101220891B1 - A porous 3-dimensional bipolar electrode, an electrolyzer having the porous 3-dimensional bipolar electrode, and water treatment method using the electrolyzer having the porous 3-dimensional bipolar electrode - Google Patents

Abstract

The present invention is composed of a three-dimensional porous base material having a three-dimensional structure consisting of a metal material having a three-dimensional structure in which a plurality of pores are arranged in a multi-layer structure in communication with each other and composed of a metal material, and an electrode catalyst layer coated on the three-dimensional porous base material By using the three-dimensional porous bipolar electrode 140 to sterilize the microorganisms, etc. contained in the treated water, it is possible to minimize the energy required to remove the microorganisms, prevent secondary contamination, and ensure the durability of the electrode.

Description

A porous 3-dimensional bipolar electrode, an electrolyzer having the porous 3-dimensional bipolar electrode, and water treatment method using the electrolyzer having the porous 3-dimensional bipolar electrode}

The present invention relates to a water treatment technology for sterilizing microorganisms contained in the treated water, and more particularly, to a three-dimensional porous bipolar electrode configured to sterilize the microorganisms contained in the treated water by an environmentally friendly process, and Electrosterilization filter and a water treatment method using the same.

Ballast water, well water, tap water, industrial water, pure water, ultrapure water, bath water, swimming pool water, industrial drainage or domestic drainage, various microorganisms exist, and processes for removing them as necessary for health and hygiene purposes. This is being introduced.

Ballast water refers to seawater filled in a vessel in order to prevent the vessel from losing its balance when operating after unloading the vessel's cargo. In the United States, due to the problem of marine pollution caused by ballast water, the National Invasive Species Act was enacted in 1996 to define alien species as intruders, which required mandatory management and control of ballast water.The International Maritime Organization (IMO) In February 2004, the international agreement was signed, and from 2009, the ballast water disinfection treatment device should be installed on the ship in order to prohibit the entry of the ship in case of violation.

As a practical technology for the ballast water treatment device, various treatment devices such as ozone, electrolysis, ultraviolet light, and chemical treatment have been proposed, but are not satisfactory in terms of operation cost and investment cost. This is because of the zooplankton having a size of 50 µm or more present in the ballast water. That is, the size of the apparatus required for ballast water treatment and about three quarters of the energy consumed are used to sterilize zooplankton of 50 µm or more.

On the other hand, because the pool or bath water is inhabited with a lot of bacteria, such as harmful to the human body, these bacteria are likely to directly contact the eyes or wounds of the user to cause disease. Therefore, while disinfecting water by disinfecting water by adding drugs such as sodium hypochlorite, sodium hypochlorite, which has a strong sterilization effect, has a sterilizing effect by chemicals because the by-products are irritating by itself or after disinfection. Eye pain or dry skin side effects occur, especially in infants with low resistance has become a big problem.

Recently, as buildings such as multi-family houses or buildings such as apartments and mansions have increased, the number of installations of various air-conditioning and heating facilities installed in buildings has increased dramatically. In a building where such air conditioning and heating facilities are installed, a heat exchanger facility (for example, a cooling tower) and the like of the air conditioning and heating facilities are installed on the roof. If the cooling water of such heat exchanger equipment continues to be used for a long time, microorganisms such as bacteria grow and multiply on the heat exchanger surface of the heat exchanger to decrease the heat exchange performance, or biofilm (agglomerated microorganisms) is generated in the pipes. There is a serious problem of preventing or corroding pipes and equipment due to microbial by-products.

In addition, the amount of water used is increased in home bathtubs and hot springs, but since bath water is at a temperature of about 40 ° C., the microorganisms are most likely to multiply, and microorganisms multiply rapidly even if left alone and cannot continue to be used. Pollution is greatly increased by the time of human beings to provide a good environment for microorganisms to reproduce. Microorganisms thus propagated are difficult to remove by filtration.

As mentioned above, the demand for disinfecting water is increasing, and many water disinfection-related technologies have been introduced. Among them, representative processes are filtration and electrolysis.

Filtration processes aimed at disinfecting microorganisms (eg RO, MF, UF filtration filters) have the advantage of no secondary contamination, while microbial flocs or dissolved solids on the membrane surface. ) Has a disadvantage in that the cake layer is formed by the accumulation of membrane fouling phenomenon. Membrane fouling dramatically increases the permeation resistance of the membrane, which reduces the treatment efficiency. Therefore, the membrane fouling phenomenon should be suppressed or periodically removed. Therefore, the microbial treatment process using the separator is an environmentally friendly charm, but it is essential to minimize the contamination of the separator to microorganisms and contaminants.

The electrochemical method, which is one of other methods, is classified into a method of sterilizing a target treated water directly from an electrode and an indirect sterilization method in which a sterilant prepared after electrochemical preparation of a sterilant is supplied to the target treated water.

The indirect sterilization method consumes a lot of energy to electrolyze the brine to produce the disinfectant sodium hypochlorite (chlorine disinfectant), while the direct sterilization method suppresses or minimizes the generation of sodium hypochlorite, namely low voltage low The low energy of the electric current can kill microorganisms. Therefore, direct sterilization methods are of interest.

The principle of the direct sterilization method is to destroy cell membranes by using an electric field formed by flowing a DC current through water. A plurality of anodes and cathodes are installed in the outlet pipe at regular intervals, and a voltage is applied to the anodes and the cathodes. Electric current flows through the entire space between the cathodes, destroying all microorganisms and bacteria in the water with electrical energy.

As a technique for such a direct sterilization method there is Republic of Korea Patent Publication No. 2009-0109359. This technology separates and arranges positive and negative electrodes having a certain shape from each other in a specific direction, thereby forming a virtual electrode between the positive electrodes to penetrate the microbial membrane and perform electrochemical sterilization at the same time. A grating electrode having an improved structure and a water treatment system including the same. However, this technique has a disadvantage in that industrially treated water has a very fast flow rate in the piping, and thus, the contact time between the microorganism and the electrode is very short, and the killing effect of the microorganism is drastically reduced and the industrial application effect is very low. have.

Other methods include Japanese Patent Laid-Open Nos. Hei 3-224686, Hei 4-27488, and Hei 11-10156, which have improved contact efficiency by applying a fixed electrode made of carbon material. However, these techniques are due to the oxygen generated by side reactions during the electrolytic corrosion of the fixed electrode of a carbon material (i.e., react with the oxygen generated at the electrode erosion is switched are the materials of carbon in the electrode to the CO ₂ developed) rapidly up Durability is reduced and has a problem in industrial use.

Accordingly, the present invention has been made to solve the problems of the prior art as described above, a plurality of pores are arranged in a multi-layer structure has a three-dimensional structure in which one side and the other side is in communication with each other and is composed of a metal material dimensional stability By sterilizing microorganisms, etc. contained in the treated water using a three-dimensional porous bipolar electrode manufactured using a three-dimensional porous base material having a, the purpose is to minimize the energy required to remove the microorganisms.

In addition, the present invention is an environmentally friendly microbial sterilization process using a three-dimensional porous bipolar electrode to prevent or minimize the generation of excess fungicides (eg, sodium hypochlorite) during the electrolysis process to prevent secondary contamination. There is another purpose.

In addition, the present invention has another object to ensure the durability of the electrode that maintains the initial dimensions even after the period of use, as the base metal material is used in manufacturing the three-dimensional porous bipolar electrode.

The three-dimensional porous bipolar electrode of the present invention has a three-dimensional structure in which a plurality of pores are arranged in a multi-layered structure and one side and the other side communicate with each other, and composed of a metal material, having a dimensional stability and a three-dimensional porous base material. It is composed of an electrode catalyst layer to be coated, by adsorbing microorganisms contained in the treated water at the time of energization, it is characterized in that the sterilization is possible by generating an oxidizing agent and an electric sterilization.

The three-dimensional porous base material of the present invention may be configured by compressing entangled thin metal wires (Fiber) to a predetermined thickness, or by mixing a plurality of metal powders with a binder to form a predetermined shape and then sintering.

The three-dimensional porous base material of the present invention may have a pore of 0.1 ~ 60㎛, and a thickness of 0.5 ~ 5.0mm.

The three-dimensional porous base material of the present invention may be composed of carbon, nickel, cobalt, titanium, zirconium, niobium, tungsten, hafnium, hastelloy, stainless steel, iron or a mixture, oxide or alloy containing two or more thereof. .

The electrode catalyst layer of the present invention may be composed of platinum, palladium, rhodium, iridium, ruthenium, osmium, carbon, gold, tantalum, tin, indium, nickel, tungsten, manganese or a mixture, oxide or alloy containing two or more thereof. Can be.

The electrosterilization filter of the present invention comprises at least one of three or more constitutions as described above arranged between a flow path tube having a flow path, a pair of electrodes for feeding arranged at a predetermined interval in the flow path, and a pair of feeding electrodes. A plurality of spacers disposed between the dimensional porous bipolar electrode and the pair of feeding electrodes and the three-dimensional porous bipolar electrode and between the three-dimensional porous bipolar electrodes to control the spacing between the electrodes, and the first and second external parts. It characterized in that it comprises a DC power supply for supplying a DC current to a pair of electrodes for feeding through the wire.

In the water treatment method of the present invention, the treated water is passed through the electrosterilization filter configured as described above, and when passing through the treated water, the microorganisms contained in the treated water are applied to the pair of feeding electrodes to pass the three-dimensional porous bipolar electrode. Adsorption at and characterized in that the sterilization by generating an oxidant as well as electrosterilization.

The present invention can be sterilized while reversing the polarity of the applied current applied to the pair of power supply electrodes at regular cycles.

The present invention can be sterilized through an electrosterilization filter in the state where an electrolyte is added to the treated water.

The present invention mixes the direct sterilization process using an electrosterilization filter and the indirect sterilization process using an indirect sterilizer to produce hypochlorous acid at a concentration of 1000 ppm or more by electrolyzing salt water as a seawater component, and the plankton contained in the treated water. Microorganisms can be sterilized.

The ballast water treatment method of the present invention comprises a seawater supply pump for pumping and supplying seawater, an electrosterilization filter configured as described above in a system of a ballast water tank for seawater storage, and electrolysis of seawater to produce hypochlorous acid at a concentration of 1000 ppm or more. A water treatment method in a ballast water treatment system comprising an indirect sterilizer which further comprises an inert sterilizer, wherein seawater is passed through an electrosterilization filter, and when the seawater passes, a current is applied to a pair of electrodes for feeding the microorganisms contained in the Adsorption on the dimensional porous bipolar electrode is characterized in that the sterilization by generating an oxidant as well as electrosterilization.

The electrosterilization filter of this invention may be located at the front or rear of the indirect sterilizer.

The present invention is processed using a three-dimensional porous bipolar electrode manufactured using a three-dimensional porous base material having a three-dimensional structure in which a plurality of pores are arranged in a multi-layer structure, one side and the other side communicate with each other and composed of a metal material having a dimensional stability By sterilizing the microorganisms and the like contained in the water, it is possible to minimize the energy required to remove the microorganisms.

In addition, the present invention is an environmentally friendly microbial sterilization process using a three-dimensional porous bipolar electrode to prevent or minimize the generation of excess fungicides (eg, sodium hypochlorite) during the electrolysis process to prevent secondary contamination. have.

In addition, the present invention can ensure the durability of the electrode that maintains the initial dimensions even after the period of use as the base material of the metal material used in manufacturing the three-dimensional porous bipolar electrode.

1 is a schematic diagram showing the configuration of the electrosterilization filter according to an embodiment of the present invention,
2 is a conceptual diagram showing the principle of the three-dimensional porous bipolar electrode shown in FIG.
3 is a graph showing a method of inverting the polarity of the voltage applied to the electrode when the target treated water is electrosterilized in this embodiment,
4 is a schematic diagram of a water treatment system using the electrosterilization filter of this embodiment,
5 is a schematic diagram of another water treatment system using the electrosterilization filter of this embodiment,
6 is a schematic diagram of a ballast water treatment system using the electrosterilization filter of this embodiment,
7 is a schematic representation of another ballast water treatment system using the electrosterilization filter of this embodiment,
8 is a schematic diagram of a swimming pool water treatment system using the electrosterilization filter of this embodiment,
9 is a photograph of the surface of the three-dimensional porous bipolar electrode shown in FIG.
10 is a graph showing the relationship between residence time, current density, and A. salina killing rate,
11 is a graph showing the effect of sodium hypochlorite on A. salina killing,
12 is a graph showing the A. salina killing rate when neutralizing chlorine with sodium thiosulfate,
Figure 13 is a photograph showing the change in chromaticity before and after water treatment of pig sand wastewater.

Hereinafter, with reference to the accompanying drawings, a preferred embodiment of a three-dimensional porous bipolar electrode according to the present invention, an electrosterilization filter having the same and a water treatment method using the same will be described in detail.

1 is a schematic view showing the configuration of the electrosterilization filter according to an embodiment of the present invention, Figure 2 is a conceptual diagram showing the principle of the three-dimensional porous bipolar electrode shown in FIG.

As shown in FIG. 1, the electrosterilization filter 100 according to this embodiment has a structure in which the front and rear ends thereof are opened. That is, the electrosterilization filter 100 is configured to be discharged to the rear end after the treated water flows into the front end of the electrosterilization process.

The electrosterilization filter 100 includes a flow path tube 110 having a flow path having a predetermined width and length, a pair of electrodes for feeding 120 and 130 installed at a predetermined interval in the flow path pipe 110, and One or more three-dimensional porous bipolar electrodes 140 arranged between the pair of feeding electrodes 120 and 130, and the pair of feeding electrodes 120 and 130 and the three-dimensional porous bipolar electrodes 140. Between the spacers 150 and between the three-dimensional porous bipolar electrodes 140 to adjust the distance between the electrodes 120, 130, and 140, and the first and second external conductors 170 and 180. It is composed of a power supply DC power supply 160 for supplying a DC current to a pair of power supply electrodes (120, 130) through.

Here, the flow pipe 110 has a polygonal shape including a circular shape in cross section, and is made of a nonconductive material that does not pass electricity. The electrodes 120 and 130 for power supply have a mesh shape in which treated water can flow well, and the first and second external conductors 170 and 180 are connected to one side thereof. In this case, the first and second external conductors 170 and 180 form a hole in the flow path tube 110 and are connected to the electrodes for power feeding 120 and 130 there through.

Three-dimensional porous bipolar electrode (Bipolar Electrode) (140) refers to an electrode having both oxidative and cyclic properties when energized based on one electrode, it is configured to have a porosity. The three-dimensional porous bipolar electrode 140 of this embodiment has a three-dimensional structure in which a plurality of pores are arranged in a multi-layer structure and one side and the other side is in communication with each other and composed of a metal material having a dimensional stability and three-dimensional It is composed of an electrode catalyst layer coated on the porous base material, and serves to sterilize the microorganisms contained in the treated water at the time of energization to generate an oxidizing agent and to sterilize. Here, the three-dimensional porous base material is composed by squeezing the tangled thin metal wire to a certain thickness, or by mixing a plurality of metal powder with a binder to form a certain shape and then sintered.

The spacer 150 is installed between the electrodes 120, 130, and 140, respectively, to adjust the distance between the electrodes 120, 130, and 140, and is configured in a form in which water can flow smoothly. Meanwhile, the electrodes 120 and 130 and the three-dimensional porous bipolar electrode 140 of this embodiment are made of a conductive material.

Accordingly, the current is supplied from the power supply DC power supply 160 to the power supply electrode 120 on one side through the first external conductor 170, and then through the plurality of three-dimensional porous bipolar electrode 140 layers on the other side. The power supply 130 moves to the DC power supply 160 again through the power supply electrode 130 and the second external conductor 180.

Here, the 3D porous bipolar electrode 140 has a bipolar characteristic. That is, as shown in FIG. 2, two different polarities are formed in the three-dimensional porous bipolar electrode 140 based on one electrode.

The sterilization process in the electrosterilization filter 100 of this embodiment is as follows.

The first is a process of adsorbing microorganisms to the three-dimensional porous bipolar electrode 140. Second, as the microorganisms in contact with the three-dimensional porous bipolar electrode 140 loses electrons and is oxidized, enzymes necessary for their life activities are destroyed and are directly extinguished. Third, secondary sterilization by an oxidizing agent, for example, chlorine, ozone, hydrogen peroxide, and various radicals (hydroxyl, carbonate) generated through the redox reaction occurring in the three-dimensional porous bipolar electrode 140.

One feature of the three-dimensional porous bipolar electrode 140 as described above is to adsorb microorganisms at the electrode and to sterilize by the voltage applied to the electrode. This can be deduced from the process of microbial removal by Zimmerman. "If there is a potential difference of about 1 volt around the microbial cell membrane, the cell membrane will undergo a dielectric breakdown, the contents inside the cell will flow out of the cell and the microbe will be killed" (Zimmerman, U., G. Pilwat , and F. Riemann, "Dielectric breakdown of cell membranes ", Biophys. J. 1974 Nov; 14 (11): 88199).

Another characteristic of the three-dimensional porous bipolar electrode 140 is a fungicide generated by an electrochemical catalysis of an electrolyte (water or chlorine ions are oxidized by the electrochemical reaction and thus ozone molecules, OH radicals, and HO ₂ (hydroperoxyl radicals)). , Carbonate radicals (Carbonate Radical, chlorine, etc.) can easily remove microorganisms ( E nv iron. S ci. & T echnol., Vol. 12, No. 1, pp. 79-84 , 1978 , Environ. Sci. & T echnol., Vol. 32, No. 1, pp. 63- 70, 1998).

The three-dimensional porous bipolar electrode 140 includes a three-dimensional porous base material and an electrode catalyst layer coated on the base material. The anode side (oxidation reaction side or + side) catalyst layer of the three-dimensional porous bipolar electrode 140 electrosterilizes microorganisms adsorbed on the porous base material, and electrolytic oxidation of water or salt water, which is electrolyte, is ozone, OH. It functions to generate radicals, chlorine and the like, and the cathode side (reduction reaction side or -side) catalyst layer reacts to generate hydrogen through a reduction reaction of water.

Suitable catalyst metals for the electrochemical oxidation and reduction processes simultaneously include platinum, palladium, rhodium, iridium, ruthenium, osmium, carbon, gold, tantalum, tin, indium, nickel, tungsten, manganese or two or more thereof. Mixtures, oxides, or alloys, and most preferably consists of a mixed catalyst of one or more platinum, iridium, ruthenium or the like.

The material of the three-dimensional porous base material is suitable as long as it has a conductive function and durability against an oxidation-reduction atmosphere in the electrolysis process. Preferably, carbon, nickel, cobalt, titanium, zirconium, niobium, tungsten, hafnium, ha Steroids, stainless steel, iron or mixtures comprising two or more thereof, oxides or alloys.

The shape of the three-dimensional porous base material is preferably a three-dimensional structure formed from metal wires, granules, granular metal powders and the like in the form of fibers. That is, the three-dimensional porous base material may be configured by pressing a thin metal wire entangled like fibers to a certain thickness, or by mixing a plurality of metal powders with a binder to form a predetermined shape and then sintering. Accordingly, the three-dimensional porous base material is a three-dimensional structure in which a plurality of pores formed between the thin metal wires or overlapped by the binders burned at the time of sintering are arranged in a multi-layered structure so that one side and the other side communicate with each other. Has In addition, since the three-dimensional porous base material is composed of a metal material has a dimensional stability to maintain the initial dimensions even after the period of use.

The three-dimensional porous base material may have a thickness of 10 mm or less, and preferably has a thickness of about 0.5 to about 5.0 mm. The reason is that the time required for adsorption of microorganisms is short at 0.5 mm or less, and the pressure drop at a single electrode layer becomes large at 5.0 mm or more.

Suitable porosity of the three-dimensional porous base material is at least about 10% by volume ratio, preferably about 40% to about 90%. The reason for this is that at 10% or less, pressure loss occurs when the treated water passes through the porous base material, and at 90% or more, adsorption of microorganisms present in the treated water on the porous base material becomes difficult, so it is difficult to expect the effect of sterilization purpose. Because.

The average pore of the three-dimensional porous base material may be used when less than about 100㎛, preferably 0.1㎛ to 60㎛. The reason is that the pressure loss occurs when the treated water passes through the three-dimensional porous substrate at 0.1 µm or less, and at 60 µm or more, adsorption of microorganisms present in the treated water on the three-dimensional porous substrate becomes difficult, which is an effect of sterilization. Because it is difficult to expect.

In the method of forming an electrochemical catalyst layer on a three-dimensional porous substrate, a three-dimensional porous substrate is dipped in a catalyst precursor solution composed of a precursor having a desired electrochemical catalyst component and a solvent capable of dissolving the same, and then sintered by sintering. To form an electrode. The electrochemical catalyst layer forming method of this embodiment is not limited to the above-described method.

The catalyst loading applied to the three-dimensional porous base material is preferably 0.24 to 24 mg / cm ² . This is because the loss of the noble metal catalyst does not increase the sterilizing effect occurs in the 0.24mg / cm ² or less, and is limited to a very low to kill bacteria, the activity of the catalyst, 24mg / cm ² or more.

The terminals of the power supply electrodes 120 and 130 for supplying electricity may be made of a platinum group oxide-coated titanium material, a platinum-coated titanium material, a nickel material, a stainless material, a Hastelloy material, or a metal material coated with a platinum group metal Is suitable.

The current applied to the three-dimensional porous bipolar electrode 140 of this embodiment is preferably 1 to 1000 mA / cm ² in terms of current density. The reason is that the 1mA / cm ² or less, because the it is difficult to sterilize the microorganisms, 1000mA / cm ² or more due to excess current may occur catalyst damage, and durability decreases.

The spacer 150 in the electrosterilization filter 100 of this embodiment is located between the power feeding electrodes 120 and 130 and / or adjacent three-dimensional porous bipolar electrodes 140, and may be made of glass, ceramic, resin, Non-conductive materials such as fibers and nonwovens are preferred, and the thickness is preferably 0.5 to 5 mm and the average pore diameter is 200 µm or more.

FIG. 3 is a graph illustrating a method of inverting the polarity of a voltage applied to an electrode when electrostatically treating a target treated water. FIG. 3 illustrates a second method of inverting the polarity of an applied voltage after applying a first applied voltage Vf to an electrolytic cell. The applied voltage Vr is lower than or equal to the first applied voltage Vf, and the polarity is to apply a reverse voltage. This method is based on the easy sterilization of microorganisms by the polarity reversal method. Microorganisms are adsorbed to the three-dimensional porous bipolar electrode 140, and the adsorbed microorganisms are sterilized by a voltage applied to the electrode or a sterilizing agent generated at the electrode. The bacteria sterilized in the three-dimensional porous bipolar electrode 140 may be easily peeled off the electrode, but if the polarity of the voltage is repeatedly reversed, the adsorbed microorganisms are more easily peeled off, and again, the new microorganism is easily on the three-dimensional porous bipolar electrode 140. Adsorption can increase the sterilization effect.

When the first applied voltage is Vf and the second applied voltage is Vr, the ratio of Vr / Vf is preferably 1 to 0.5, and the change period of the supply time (tf, tr) is about 15 to 60 minutes, respectively. It is preferable that the supply time tf of the first applied voltage Yf is larger than the supply time tr of the second applied voltage Vr. The inversion method is preferably inverted to + Vf → -Vr → + Vf. By this method, high sterilization efficiency can be obtained for a long time.

4 is a schematic view of a water treatment system using the electrosterilization filter of this embodiment. As shown in FIG. 4, the water treatment system 400 of this embodiment is a water treatment using the electrosterilization filter 100 configured as described above, and includes a first reservoir 410 for storing the target treated water, and a first reservoir. A supply pump 420 for supplying the target treated water in the reservoir 410, an electrosterilization filter 100 configured as described above for electrosterilizing the target treated water supplied by the supply pump 420, and the electrosterilized treatment It consists of a second reservoir 430 for storing the number.

5 is a schematic diagram of another water treatment system using the electrosterilization filter of this embodiment. As shown in FIG. 5, the water treatment system 500 of this embodiment is a water treatment using the electrosterilization filter 100 configured as described above, and is configured to add and treat an electrolyte to the treated water. That is, the water treatment system 500 includes a storage tank 510 for storing target treatment water, a supply pump 520 for supplying target treatment water in the storage tank 510, and target treatment water supplied by the supply pump 520. Electrosterilization filter 100 configured as described above, and a storage tank 530 for storing the electrosterilized treated water. Here, the electrolyte added to the treated water is salt (NaCl), potassium chloride (KCl), acid or alkali, and the concentration of the electrolyte is preferably 0.1 to 3%. When the concentration of the electrolyte is 3% or more, an excess of chlorine may be generated to react with organic materials in the treated water, thereby generating byproducts.

The water treatment system 500 of FIG. 5 may be applied for the purpose of electrolysis of organic matter, not for the purpose of electrosterilization by the electrosterilization filter 100. That is, when a large amount of organic matter is contained in water, by adding chloride to the target treated water and electrolyzing, efficient organic matter removal, chromaticity removal, and the like can be performed.

6 is a schematic diagram of a ballast water treatment system using the electrosterilization filter of this embodiment. As shown in FIG. 6, the ballast water treatment system 600 of this embodiment is configured to simultaneously apply the direct sterilization method using the electrosterilization filter 100 configured as described above and the indirect sterilization method by an indirect sterilizer. That is, the ballast water treatment system 600 of the present embodiment is a seawater supply pump 610 for pumping and supplying seawater, and the electrosterilization filter 100 configured as described above in existing systems such as a ballast water tank 640 for seawater storage. ), An indirect sterilizer 620 and a hydrogen separator 630 are further provided.

Here, the electrosterilization filter 100 is located at the front end of the indirect sterilizer 610, and the sterilization removal by adsorbing plankton of 50㎛ or more, and the indirect sterilizer 620 is electrolyzed salt of seawater components to more than 1000ppm hypochlorous acid It is manufactured in concentration and supplied to the ballast mainline. The ballast water treatment system 600 of this embodiment configured as described above can maintain the chlorine concentration of the ballast main stream at 5 ppm or less, and when treated alone with the existing indirect sterilizer 620 (the chlorine concentration of the ballast main stream is 20 ppm chlorine concentration). The concentration can be kept lower, so that the by-products by the reaction with the organic material is less, the energy consumption can be reduced by 75%.

7 is a schematic representation of another ballast water treatment system using the electrosterilization filter of this embodiment. As shown in FIG. 7, the ballast water treatment system 700 of this embodiment is the same as the ballast water treatment system 600 of FIG. 6 except that the electrosterilization filter 100 is installed at the rear end of the indirect sterilizer 720. It is configured. That is, the ballast water treatment system 700 of the present embodiment is an electrosterilization filter 100, an indirect sterilizer, to an existing system such as a seawater supply pump 710 for pumping and supplying seawater and a ballast water tank 740 for seawater storage. 720 and a hydrogen separator 730 are further provided.

8 is a schematic diagram of a swimming pool water treatment system using the electrosterilization filter of this embodiment. As shown in FIG. 8, the pool water treatment system 800 of this embodiment is configured to treat the water in the pool using the electrosterilization filter 100 configured as described above. That is, the pool water treatment system 800 of this embodiment is configured to remove contaminants and bacteria entering the pool pool 810 through a circulation process.

The pool water treatment system 800 includes a balance tank 820 which is an intermediate tank for adjusting the flow rate of the circulating water, a circulation pump 830 for pumping and circulating water in the balance tank 820, and a circulation pump 830. Filter 840 for removing contaminants contained in the water circulated by the sodium hypochlorite liquid chlorine injector or on-site electrolysis of the brine to produce sodium hypochlorite to flow through the filter 840 flows The sterilization apparatus (850, which is the structure of the field type sodium hypochlorite generator in FIG. 8) to supply, the electrosterilization filter 100 which electrosterilizes the water containing sodium hypochlorite, and the electric sterilization filter 100 It consists of a heat exchanger 860 to heat exchange the sterilized water.

Here, the electrosterilization filter 100 is installed at the rear end of the filter 840 to effectively decompose organic and inorganic substances contained in the water in addition to the sterilization function to lower the pollutant load of the filter 840 to maintain a longer backwash cycle of water In addition, the amount of water needed to warm the water can be saved by reducing the pool's water consumption. On the other hand, the electrosterilization filter 100 may be installed at the front end of the filter 840 to perform the same function as above.

Although this invention is demonstrated based on various experiment examples below, embodiment of this invention is not limited to this.

[Experimental Example 1]

Experimental Example 1 is an example of performing the electrosterilization of microorganisms using the three-dimensional porous bipolar electrode 140.

end. Electrosterilization filter and water treatment system using the same (see FIGS. 1 and 4)

(1) three-dimensional porous bipolar electrode 140

○ Base material: Fibrous titanium with porosity of 60%, average pore diameter of 51㎛, diameter of 10cm, and thickness of 0.5mm

○ Catalyst layer: The catalyst layer was formed by chemically cleaning the base material with an acid, dipping the solution containing chloride and alcohol containing palladium, iridium, and ruthenium (1: 0.1: 0.5 by weight) and sintering it. The surface photograph of the electrode obtained through this process is shown in FIG. 9.

○ Number: 1

(2) Power supply electrodes (120, 130): Manufactured by coating palladium, iridium, and ruthenium on a mesh-type base material made of titanium

(3) Operation conditions of the water treatment system (Fig. 4)

The system is configured as shown in FIG. 4, and water including Pseudomonas diminuta is prepared in the first reservoir 410, and the treated water is supplied to the electrosterilization filter 100 using the feed pump 420 in an amount of 2 L / min. And the experiment was performed by applying a current. At this time, the main driving factors are as follows.

○ Current supply: Apply 0.1A / cm ² constant current based on electrode area

○ Electrosterilization filter passing speed: 1sec

Water was collected from the first reservoir 410 storing the target treated water and the second reservoir 430 holding the electrosterilized treated water, respectively, and the number of live bacteria was measured.

I. Analysis method

(1) Microorganism measuring method

The measurement method was agar plate method using agar medium (Aiken Chemical). After incubating Pseudomonas diminuta for one day using a liquid culture medium, the cells were centrifuged at 5,000 rpm, washed with pure water and centrifuged again. This was added to tap water (residual chlorine concentration of 0.01 ppm or less) to obtain the treated water.

(2) Chlorine analysis method

Residual chlorine was measured by standard method 4500 Cl-B method I and salinity was measured by Crison microCM 2002 conductivity meter.

All. result

The measurement results are shown in Table 1. From Table 1, it was clear that the system using the three-dimensional porous bipolar electrode of this experimental example was excellent in the sterilization efficiency.

[Experimental Example 2]

Under the same configuration and experimental conditions as in Experimental Example 1, the applied current (voltage) was supplied in a pulse form to compare the bactericidal performance.

end. Electrosterilization filter and water treatment system using the same (see FIGS. 1 and 4)

(1) three-dimensional porous bipolar electrode 140: same as Experimental Example 1

(2) electrodes for power feeding (120, 130): same as Experimental Example 1

(3) Operation conditions of the water treatment system (Fig. 4)

Same as Experimental Example 1, and the current application conditions were different.

○ Current supply: Pulse applied at 0.1A / cm ² constant current based on electrode area (30 minutes in the forward direction and 30 minutes in the reverse direction)

I. Analysis method: same as Experimental Example 1

All. result

The experimental results are shown in Table 1. It is clear from Table 1 that the system using the three-dimensional porous bipolar electrode of this example is clearly excellent in sterilization efficiency.

[Comparison of Experimental Example 1 and Experimental Example 2]

As can be seen from Table 1, the electrosterilization filter 100 using the three-dimensional porous bipolar electrode 140 of this embodiment and the electrosterilization filter process using the pulsed electric application of Experimental Example 2, as in Experimental Examples 1 and 2 It was found to be excellent in efficiency and, in particular, at low power, excellent in disinfection efficiency.

[Experimental Example 3]

Experimental Example 3 is an example of electrosterilizing microorganisms having a size of 50 μm or more in order to grasp the applicability of the three-dimensional porous bipolar electrode 140 of this embodiment to a ballast water treatment process. The actual ballast water treatment process is the same as FIG. 6 and 7, but was configured and evaluated as shown in Figure 4 to examine the effect of the electrosterilization filter only for the purpose of removing microorganism of the size of 50㎛ or more.

end. Electrosterilization filter and water treatment system using the same (see FIGS. 1 and 4)

(1) three-dimensional porous bipolar electrode 140: same as Experimental Example 1

(2) electrodes for power feeding (120, 130): same as Experimental Example 1

(3) Target microorganisms: Artemia salina (hereinafter referred to as A. salina)

Artemia salina was purchased in the form of dehydrated cysts and stored in the dark at 4 ° C. At the time of hatching for use, 25 mL of the cyst was placed in 1 L of artificial seawater and maintained at 28 ° C, followed by continuous aeration with air. Incubation of artemia salina was completed after 24 hours. After that, the hatched Artemia salina was added to 200L of artificial seawater used as the treated water, and aeration was continuously performed.

I. System configuration and operation

4, the artificial brine having a final concentration of 30 ‰ salinity was prepared by adding unrefined salt to tap water, about 30 gpl of artificial seawater. A. salina is added to the artificial brine thus prepared and stored in the first storage tank 410, and the treated water is supplied using four feed pumps 420 at 50 L / h for four different flow conditions (65.5 sec based on residence time). ), 100 L / h (32.8 sec based on the dwell time), 20 L / h (16.4 sec based on the dwell time), and 300 L / h (10.9 sec based on the dwell time) are supplied to the electrosterilization filter 100, and the voltage is It supplied in the range of 0-20V (current value 0-47A) under flow conditions.

The samples of the artificial seawater sterilized while continuously running were taken from the second reservoir 430 in which the electrosterilized artificial seawater was stored to measure the number of live bacteria. That is, after collecting 500 mL of water in the second reservoir 430 in two sample beakers, 2 mL of sodium thiosulfate solution (1N) was added to one beaker to decompose free chlorine generated during electrolysis. No sodium thiosulfate solution was added to the other beakers. The primary sample was used to determine the viable A. salina microorganisms, and the other secondary sample was used to determine the total residual chlorine. Sampling was repeated 3 times at the given flow and current conditions.

All. Analysis method

(1) Microbial analysis

Sampling and measurement of A. salina before and after electrolysis was repeated three times. A. The volume of each sample used in the measurement of the salina is 5 mL. Each sample was transferred to a Petri dish (90 mm in diameter) and measured using a colony counter apparatus. The determination of whether or not to survive was judged as whether the organism was moving. The number of A. salinas is expressed as the number of organisms per liter.

la. result

10 is a graph showing the relationship between residence time, current density, and A. salina killing rate. As shown in Figure 10, the higher the residence time and the current density, the higher the killing rate of A. salina. On the other hand, A. salina was completely killed under the residence time of 65.5 sec and current density of 135 mA / cm ² . As can be seen in Figure 10, the electrosterilization process is a very effective process even if the residence time is very short, such as 1 minute.

Comparative Example 1

end. Experimental Method

Comparative Example 1 is an inactivating agent distributed in the market to test the effect of hypochlorous acid on Artemia salina was performed in a 500 mL conical flask. After adding hypochlorite chemicals to artificial seawater, hatched Artemia salina was added. At this time, the residual chlorine concentration was adjusted to 50, 100 and 200 mg / L level. Samples were measured for live Artemia salina at 5, 10, 15, 30 and 45 minutes.

I. result

The effect of sodium hypochlorite (free residual chlorine) on A. salina killing is shown in FIG. Residual chlorine levels were 50, 100 and 200 mg / L and chlorine contact time was from 0 to 45 minutes. In general, the killing of A. salina was larger as the chlorine dose and contact time increased. The highest A. salina killing rate (more than 75%) was obtained at high chlorine concentrations (200 mg / L) and contact time of more than 15 minutes.

Comparative Example 2

end. Experimental Method

In Comparative Example 2, an experiment was performed to determine the effect of residual chlorine and sodium thiosulfate on the proliferation of artemia salina.

Add 2 mL of 1N sodium thiosulfate solution (Na ₂ S ₂ O ₃ · 5H ₂ O) to the conical flask. This amount is sufficient to remove 200 mg / L residual chlorine.

I. result

12 shows the A. salina killing rate when neutralizing chlorine with sodium thiosulfate. As shown in FIG. 12, A. salina killing rate does not exceed 14% even under any chlorine dosing conditions and contact time conditions. This means that the killing rate of A. salina is reduced by the dechlorination process of the sample.

[Comparison Review of Experimental Example 3, Comparative Example 1, and Comparative Example 2]

Comparing the concentration levels of residual chlorine during electrolysis, high concentrations are obtained at very short residence times. For example, at 135 mA / cm ² and a residence time of 66.5 seconds, the chlorine level is 475 mg / L, and electrochemical treatment based on the same chlorine concentration is more effective than sodium hypochlorite. On the other hand, A. salina killing is greater in the electrochemical treatment than in the case of using sodium hypochlorite. This means that the inactivation mechanism is due to the direct oxidation at the anode surface as well as the coupling effect with hypochlorous acid occurring at the electrode.

The conclusion obtained from the above result is as follows.

First, sodium hypochlorite is an effective fungicide, but at a high concentration of 200 mg / L chlorine and a contact time of more than 1.5 min, the mortality is 75%.

Second, electrochemical treatment provides high mortality. That is, A. salina is killed at 100% even at a current density of 135 mA / cm ² and a residence time of about 1 minute. Under these conditions, the concentration of residual chlorine is about 400 mg / L.

Third, the electricity consumption is 0.07 ~ 19.2 kWh / m ³ level. Therefore, the optimum treatment conditions are current density 135mA / cm ² , residence time 65.5sec, and electricity consumption is 3.6kWh / m ³ at 100% A. salina killing rate.

[Experimental Example 4]

In Experimental Example 4, the applicability of the three-dimensional porous bipolar electrode 140 of this example to the general water treatment process was grasped.

end. Preparation of 3D porous bipolar electrode 140: same as Experimental Example 1

I. Electrolysis Experiment

500 ml of pig wastewater was placed in a beaker, a three-dimensional porous bipolar electrode 140 was installed, and a batch method (Batch) was performed for 40 minutes under 0.2 A / cm ² operating conditions. The property of the pig wastewater used for the experiment is the value at time 0 of Table 2.

All. Analysis method

For physicochemical characterization of raw water and treated water, the absorbance method was applied for chromaticity, the ammonia nitrogen (NH3-N) was applied with Salicylate method, and the electrolytic voltage in the electrochemical reaction was applied with a multimeter. The efficiency was applied to the iodine titration method.

la. result

The experimental results are shown in Table 2. When using the three-dimensional porous bipolar electrode 140 with time as shown in Table 2, the chromaticity was easily removed.

[Comparative Example 3]

The chromaticity of the pig wastewater in Table 2 was removed under the same size and the same current density conditions using the existing two-dimensional flat electrode (DSA electrode). At this time, the electrode catalyst loading, the experimental apparatus, the analysis method was applied in the same manner as in Example 1.

[Comparison Result of Experimental Example 4 and Comparative Example 3]

As can be seen from Table 2, when the three-dimensional porous bipolar electrode 140 of Experimental Example 4 is used, chromaticity and ammonia are easily removed with time, whereas the conventional flat electrode of Comparative Example 3 has ammonia but with increased chromaticity. You can see that. This cause associated with chromaticity is, in the case of the flat electrode, in the case of the three-dimensional porous bipolar electrode 140, whereas the by-product of increasing the chromaticity is formed by the reaction of the color-related organisms and chlorine generated in the electrochemical reaction It is estimated that the amount of color-related organisms adsorbed and decomposed onto the three-dimensional porous bipolar electrode 140 is greater than the amount participating in the reaction with chlorine, thereby decreasing the chromaticity.

Experimental Example 5 (Electrolysis of Electrolyte with Salt Added)

In Experimental Example 5, the applicability of the three-dimensional porous bipolar electrode 140 of this embodiment to the wastewater having an electrolyte brine 1% was grasped.

end. Preparation of 3D porous bipolar electrode 140: same as Experimental Example 1

I. Electrolysis Experiment

Salt was put in a beaker so that 500 ml of pig waste water and 1% of brine concentration were prepared, and a three-dimensional porous dimensional stable electrode 140 was installed, and it was carried out for 40 minutes under a batch method (Batch) at 0.2 A / cm ² operating conditions. The properties of pig wastewater used in the experiment are the values at time 0 in Table 3.

All. Analysis method: same as Experimental Example 4

la. result

The experimental results are shown in Table 3. As shown in Table 3, when the three-dimensional porous bipolar electrode 140 was used, chromaticity was easily removed.

[Comparative Example 4]

In Comparative Example 4, salt was added to pig wastewater so that the salt concentration was 1% in the electrolyte under the conditions of Comparative Example 3, and the same current density, electrode catalyst loading, experimental apparatus, and analytical method were applied. The experimental results are shown in Table 3.

[Comparison Result of Experimental Example 4, Experimental Example 5, Comparative Example 3, Comparative Example 4]

As can be seen from Table 2 and Table 3, the three-dimensional porous bipolar electrode 140 of Experimental Example 4, Experimental Example 5 was larger than the conventional flat electrode of Comparative Example 3, Comparative Example 4, the chromaticity removal rate over time. According to Experimental Example 4 and Example 5, it can be seen that chromaticity and ammonia removal rate are increased by the addition of electrolyte.

FIG. 13 is a photograph showing chromaticity changes before and after treatment as a result of the study performed in Experimental Example 5. FIG.

The technical details of the three-dimensional porous bipolar electrode of the present invention, the electrosterilization filter having the same, and the water treatment method using the same have been described together with the accompanying drawings, which are illustrative examples of the best embodiments of the present invention. It is not limited.

In addition, it is obvious that any person skilled in the art can make various modifications and imitations within the scope of the appended claims without departing from the scope of the technical idea of the present invention.

100: electrosterilization filter 120, 130: electrode for feeding
140: three-dimensional porous bipolar electrode 150: spacer
160: DC power supply 170: the first external lead
180: second external lead

Claims (13)

delete A plurality of pores are arranged in a multi-layer structure has a three-dimensional structure in which one side and the other side is in communication with each other, consisting of a metal material consisting of a three-dimensional porous base material having a dimensional stability, and an electrode catalyst layer coated on the three-dimensional porous base material, At the time of energization, the microorganisms contained in the treated water can be adsorbed and sterilized by generating oxidizing agent and electric sterilization.
The three-dimensional porous base material is a three-dimensional porous bipolar electrode, characterized in that by forming a tangled thin metal wire to a certain thickness or by mixing a plurality of metal powders with a binder to form a predetermined shape and then sintering. The method according to claim 2,
The three-dimensional porous base material is a three-dimensional porous bipolar electrode, characterized in that having a pore of 0.1 ~ 60㎛, and a thickness of 0.5 ~ 5.0mm. The method according to claim 2,
The three-dimensional porous base material is composed of carbon, nickel, cobalt, titanium, zirconium, niobium, tungsten, hafnium, Hastelloy, stainless steel, iron or a mixture containing two or more thereof, oxides or alloys Three-dimensional porous bipolar electrode. The method according to claim 2,
The electrode catalyst layer is composed of platinum, palladium, rhodium, iridium, ruthenium, osmium, carbon, gold, tantalum, tin, indium, nickel, tungsten, manganese or a mixture, oxide or alloy containing two or more thereof. A three-dimensional porous bipolar electrode. A flow path tube having a flow path, a pair of electrodes for feeding arranged at predetermined intervals in the flow path, one or more three-dimensional porous bipolar electrodes arranged between the pair of feeding electrodes, and the pair A plurality of spacers disposed between the power feeding electrode and the three-dimensional porous bipolar electrode and between the three-dimensional porous bipolar electrodes to adjust the distance between the electrodes, and the first and second external wires. It includes a power supply DC power supply for supplying a DC current to the pair of power supply electrodes,
The three-dimensional porous bipolar electrode is an electrosterilization filter according to any one of claims 2 to 5. Pass the treated water through the electrosterilization filter as set forth in claim 6, and when passing the treated water, an electric current is applied to the pair of feeding electrodes to adsorb microorganisms contained in the treated water at the three-dimensional porous bipolar electrode. Water treatment method characterized in that the sterilization by generating an oxidizing agent in addition to the electrosterilization. The method of claim 7,
And sterilizing while inverting the polarity of the applied current applied to the pair of power supply electrodes at a predetermined cycle. The method of claim 7,
The water treatment method characterized in that the sterilization through the electrosterilization filter in the state in which the electrolyte is added to the treated water. The method of claim 7,
Plankton contained in the treated water by mixing the treated water with the direct sterilization process using the electrosterilization filter, and an indirect sterilization process using an indirect sterilizer to produce hypochlorous acid at a concentration of 1000 ppm or more by electrolyzing salt water as a seawater component; A water treatment method characterized by sterilizing microorganisms. Further comprising a seawater supply pump for pumping and supplying seawater, an electrosterilization filter according to claim 6 and an indirect sterilizer for electrolysis of the seawater to produce hypochlorous acid at a concentration of 1000 ppm or more in a system of a ballast water tank for seawater storage. As a water treatment method in the configured ballast water treatment system,
The seawater is passed through the electrosterilization filter, and when passing through the seawater, electric current is applied to the pair of power supply electrodes to adsorb the microorganisms contained in the seawater at the three-dimensional porous bipolar electrode to electrosterilize and Ballast water treatment method characterized in that the sterilization by generating an oxidizing agent. The method of claim 11,
The electrosterilization filter is ballast water treatment method, characterized in that located in the front end of the indirect sterilizer. The method of claim 11,
The electrosterilization filter is ballast water treatment method, characterized in that located in the rear end of the indirect sterilizer.

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