KR101368491B1 - Appliance for electrolysis attached ship and the method of sterilizing red tied using it - Google Patents

Abstract

The present invention relates to an electrolysis device for mounting on ships which includes a seawater inflow unit, an electrolysis electrode plate, an electrolysis tank, a diffusion/spraying unit, a sterilizing water concentration measuring sensor, a power supply device, and a controller. The electrolysis device is an electrolysis reaction tank which performs inflow of seawater, production of sterilizing water, and the diffusion and spraying of the sterilizing water in a single process in a single reaction tank; and does not need secondary facilities and devices including an insertion pump, a sterilizing water storage tank, a spraying pump, and a pipe. The electrolysis device is easy to be mounted on the ships, is capable of being mounted on small ships by having a small size, and is capable of being used regardless of the range of the waters with red tide. A user can easily install the electrolysis device and use the electrolysis device regardless of the size of the target waters.

Description

Appliance for electrolysis attached ship and the method of sterilizing red tied using it}

The present invention relates to a device for removing red tide phenomena occurring in the ocean, and more particularly to an electrolysis device that can be mounted on a ship and a method for removing red tide phenomenon using the same.

Red tide is a phenomenon in which seawater discolors and marine life is damaged by the explosive growth of marine microorganisms (animal phytoplankton, protozoa, bacteria). The most common cause of red tide is phytoplankton, which is found in Korea, including diatoms, dinoflagellates, blue-green algae, microalgae, and cilia. . Depending on the type of plankton, the color of the seawater is not limited to red, but may be dark brown, blue, or white. When we look at the creatures that cause red tide in Korea seasonally, there are diatoms belonging to the genus Skeletonema and Chetoceros in the spring, and in the heterosigma and Prorocentrum in the early summer. There are small flagella birds in the genus, and from late summer to autumn, there are large ceratium, Gymnodinium, and Cochlodinium. By 1995, Cochlodinium polykrikoides species have been causing red tide phenomena on the southern and eastern seas since 1995.

As a technique for preventing such a red tide phenomenon, the loess spreading method, ozone treatment method, chemical spraying method, biological method using the natural bacterium and electrolysis method are used.

The ocher spreading method aggregates and precipitates the red tide microorganisms in the loess by using the property of the ocher colloidal particles to aggregate and adsorb suspended solids such as nutrients and microplankton in seawater. The removal effect of toxic red algae by ocher spray was different according to species, but the removal effect of Cochlodinium red algae was 70-80% according to indoor and field survey. In the control of red tide microorganisms in acidic clay in Japan, experiments with 14 red tide-causing organisms including Cochlodinium confirmed the effects of adsorption, sedimentation and cell destruction.

As a literature on the red tide control method by the loess spreading method may be registered Patent No. 10-0325396, which is a powdered ocher (temperature condition 100 ~ 1000, crushing granularity condition; 1 ~ 1500) adsorbent Red tide microorganism removal, characterized in that the natural minerals such as slaked lime and tourmaline as additives (addition range: 1-7 wt%) to absorb and aggregate red tide organisms. It relates to the method is effective to remove the toxic red tide within 30 minutes ~ 1 hour.

However, the ocher spreading method as described above is merely a method of cohesive adhesion of red tide bacteria using cohesive force of ocher to settle to the bottom of the sea surface, and thus cannot be regarded as a fundamental solution of red tide. In addition, the spread of the ocher increases the floating matters cause side effects and clogging the gills of fish causes a problem of death. When spraying raw ocher to the ocean, loess and impurities are sedimented as it is, so there is no time for adsorption and aggregation of red tide organisms, thus reducing red tide removal efficiency and causing secondary environmental pollution of the seabed sediment.

The ozone treatment method has the advantage of minimizing the disturbance of the marine ecosystem without causing secondary pollution, but since the generator must be mounted on the ship separately with the ozone generator, which has a large power requirement and a large scale of equipment, the construction of a dedicated vessel is required. Since red tide occurs mainly during the summer, there is an excessive amount of idle facilities, or it is difficult to mount or dismantle a heavy ozone generator and generator on a ship in accordance with the red tide. In particular, since ozone is impossible to store, when red tide occurs excessively and the amount of ozone temporarily takes a large amount of oxygen, the amount of oxygen in the seawater is excessively increased, adversely affecting the ecosystem and insufficient red tide control ability.

Chemical spraying has been used in the past as a method of spreading copper sulfate (CuSO4), chlorine dioxide (ClO2), simazine, etc. Among them, copper sulfate, which is widely used because it is the least expensive, is specific to harmful flagella algae. Since it is not specific, it may affect other marine organisms besides the red tides, causing problems in terms of toxicity and corrosion to other organisms in the water, and copper sulfate should be used repeatedly because it shows only a temporary effect. The copper sulfate is unstable under the high alkaline environmental conditions that occur when red tide occurs, which is disadvantageous because it must be processed in large quantities.

Many biological methods have been tried as another method to control red tide. In particular, the use of natural zooplankton and marine bacteria or nutritional competition with harmful or toxic red tide organisms artificially induces less harmful red tide species to promote the consumption of nutrients. Biological method research is being actively conducted.

As a specific document, reference may be made to Patent Publication No. 10-0758997. The above document relates to a method for inhibiting flagella algae of Heterosigma genus using Pseudomonas genus microorganisms, specifically, Pseudomonas fluorescin strain HAK-13 capable of inhibiting genus hetero sigma and flagella algae using the same It is about a method to suppress. The method comprises the steps of: 1) selecting Pseudomonas genus microorganisms having the ability to inhibit flagella algae in hetero sigma; 2) culturing the Pseudomonas genus microorganism of step 1) to obtain a culture; 3) It is composed of the step of spraying the culture of step 2) in the red tide generation area.

Pseudomonas fluorescein HAK-13 strain was cultured in nutrient agar medium (Nutrient agar; 0.8% (w / v) Nutrient broth, 1.5% agar powder) at a culture temperature of 18-35 and culture conditions for 1-5 days. Inoculation into the heterologous growth stage of the heterosigma akashiwo D-075 culture resulted in a rapid inhibition of the growth of the cells of the heterosigma akashio D-075 strain 12 hours after the inoculation, which resulted in a reduction in cell numbers of more than 90% and inoculation 48 Not only did they completely die in time, but the Pseudomonas fluorescein HAK-13 strain treated group and the untreated control group were visually observed. It was shown a state. Since the Pseudomonas fluorescein has the ability to inhibit flagella algae, the algae using the strain can be usefully used to control the red tide phenomenon caused by flagella algae.

However, this has not yet been commercialized in that it is required to find and mass produce microorganisms that affect certain algae that cause red tide.

The method of using red algae's natural enemy is the method of using anti-microbial to ingest or inhibit activity of red algae, and it is difficult to dominate the natural necrosis, and it takes a long time to progress and is ineffective. It is a way.

The electrolysis method for preventing red tide has been introduced relatively recently. In this case, seawater is injected into an electrolysis reaction tank composed of a positive electrode and a negative electrode to produce disinfectant water such as hypochlorous acid and spray it to the ocean where red tide is generated. An inorganic or organic aqueous solution containing an electrolyte is flowed between the electrodes and an electric current is flowed from the outside to cause an electrolysis reaction to simultaneously remove the inorganic or organic contaminants in the aqueous solution. Through this, electrolysis reactions such as electrode reactions occurring at the interface between the electrode surface and the aqueous solution, and secondary reactions such as precipitation, flocculation, adsorption, and flotation separation caused by the reaction between the electrode reaction products and the suspensions and dissolved substances in the waste water solution are simultaneously performed. To get rid of red tide.

However, the above-mentioned electrolysis method requires a facility such as a seawater inflow pump, a hypochlorous acid production water storage tank, a pump for spraying, and is not suitable for large-scale due to excessive size of the reactor and power supply to remove red tides in a wide range of sea areas. Low effectiveness In addition, if the electrolysis device is used continuously for a long time, Ca adhesion occurs on the negative electrode, which causes the electrolytic voltage to rise or the electrolytic current to be difficult to flow, and the water flow resistance increases, resulting in a decrease in yield, resulting in continuous electrolysis. There is a problem that can not proceed.

In order to solve the red tide generated in a wide range of waters in a short time more effectively, the present inventors have completed the present invention which can simultaneously perform seawater inflow, hypochlorous acid generation and spraying.

Patent Registration No. 10-0325396, Publication No. 10-2001-10139, Registration Patent No. 10-0758997

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The present invention has been devised to solve the above problems and is equipped with a vessel that can be carried out without additional equipment such as seawater inflow and hypochlorous acid generation and spraying, and a ship mounting electrolysis device and a method for removing red tide phenomenon using the same The main purpose is to solve the problem.

The present invention to solve the above problems more effectively
In the electrolysis device for ship mounting,
The electrolytic apparatus
Located on one side of the ship, the seawater inlet is attached to the screen of the net-shaped screen for filtering the suspended matter inside the seawater flows;
An electrolysis tank connected to the sea water inlet and provided with a baffle-shaped inclined plate for vertical diffusion of sterile disinfectant water generated by electrolysis;
An electrolysis electrode plate formed inside the electrolysis tank, the electrolysis electrode plate comprising an anode and a cathode installed to maintain an interval of 1 mm to 30 mm;
A diffusion / spreading part connected to a rear surface of the electrolysis tank to induce diffusion of disinfectant water;
A disinfectant water concentration sensor installed adjacent to the diffusion / spray part and measuring a disinfectant water concentration generated during an electrolysis process and supplying a measured value to a controller installed on the vessel;
A control unit connected to the concentration measuring sensor and controlling power supply according to the concentration value of the disinfecting water measured at the upper portion of the vessel;
A power supply device connected adjacent to the control unit and receiving a control signal from the control unit to supply power;
The anode of the electrolytic electrode plate is selected from electrodes in which iridium dioxide (IrO 2), ruthenium (Ru) or platinum (Pt) is electrodeposited on titanium (Ti),

The negative electrode is the same as the positive electrode or provides a ship mounting electrolysis device, characterized in that selected from among the titanium or stainless steel electrodes.

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The present invention is characterized in that the sterilized sterilized water to be treated using the vessel-mounted electrolysis device is maintained at 10 ~ 8,000ppm and the concentration of sterilized sterilized water of the discharged seawater is maintained at 0.1 ~ 6.0ppm.

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The sterile sodoksu is hypochlorous acid (HOCl), hypochlorite ion (OCl ^-) is characterized in that the selection from, chlorine dioxide (ClO _2).

The ship-mounted electrolysis device of the present invention is characterized by an electrolysis reaction tank comprising seawater inflow, sterilization water production process, and diffusion and spreading of sterilization water in a single reactor in a single process. Therefore, there is no need for additional facilities and equipment, such as an inflow pump, a sterilization water storage tank, a spraying pump, and a pipe, which are required in the conventional electrolysis device to prevent red tide.

In addition, it is easy to mount the vessel, the small size can be mounted on a small ship, as well as has the advantage that can be used regardless of the area of the red tide occurs.

1 is a view showing the configuration of the electrolysis device of the present invention.
Figure 2 is a flow chart showing a process of preventing red tide phenomenon using the electrolysis device of the present invention.
Figure 3 is a plan view and side view showing the inflow of seawater, the generation, dispersal and spraying of sterilized water according to the direction of ship movement.
Figure 4 shows the form of the electrolysis device of the present invention attached to the vessel.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings and examples. The terms and descriptions set forth below are merely illustrative to clearly explain the present invention, and the scope of the present invention should not be construed as being limited thereto.

The terms first, second, etc. used in the description of the present invention are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component. And / or < / RTI > includes any combination of a plurality of related listed items or any of a plurality of related listed items.

 When a component is referred to as being "connected" or "connected" to another component, it may be directly connected to or connected to that other component, but it may be understood that other components may be present in between. Should be. On the other hand, when an element is referred to as being "directly connected" or "directly connected" to another element, it should be understood that there are no other elements in between.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Red tide removal device of the present invention is characterized in that it is mounted on the ship at the same time the inflow of sea water and the generation and spreading of hypochlorous acid.

In addition, the device of the present invention is attached to the side or the rear of the ship can be adjusted to the depth of 0 ~ 3m below the water surface, the seawater inflow is automatically made according to the operation of the ship, generated by direct or indirect reaction in the electrolysis reactor It is characterized by an electrolysis device and method that generates sterilized sterilized water (hypochlorite, etc.) and can be automatically diffused and sprayed from the rear of the ship according to the ship's movement path to remove red tide.

1 is a view showing the configuration of the electrolysis device of the present invention. Electrolysis device of the present invention as shown is a seawater inlet; Electrolysis electrode plate; Electrolysis bath; Diffusion / spray; Disinfectant concentration measuring sensor; Power supply; It consists of a control unit.

The seawater inflow portion of the electrolysis device is gently larger than the interval of the electrode plate to be electrolyzed to facilitate the inflow of seawater, so that seawater flows smoothly, and to the front of the electrode plate in order to exclude colloids or suspended matter in the seawater. The screen is installed.

The electrolytic electrode plate is provided with a positive electrode and a negative electrode. The positive electrode and the negative electrode are installed to maintain a predetermined interval in the form facing each other, the electrode interval is preferably maintained to 1mm ~ 30mm, but is not necessarily limited to those skilled in the art in consideration of the concentration and flow rate of sterilization water production, such as hypochlorous acid It can be designed and changed.

The positive electrode and the negative electrode use an insoluble electrode.

As the anode, an electrode in which iridium dioxide (IrO 2) is electrodeposited on titanium (Ti), an electrode in which ruthenium (Ru) or platinum (Pt) is electrodeposited on titanium may be used.

As the negative electrode, the same electrode as the positive electrode may be used, and titanium or stainless steel may be used.

The positive electrode and the negative electrode may be formed in the form of a net electrode and a plate electrode, but are not necessarily limited thereto. Those skilled in the art may appropriately select the type of electrode according to the flow of the seawater and the spraying direction.

The electrolysis tank maintains a constant gap between the positive electrode and the negative electrode, and is configured to be free from vibration or shaking without being disturbed by the flow of the inflowing seawater, and, if necessary, a baffle type inclined plate may be installed at the rear end for proper diffusion of the disinfectant water. This allows the ship to operate, leading to the proper vertical diffusion of disinfectant water, depending on depth.

The diffusion / spreading portion may gently widen the diffusion spreading range to facilitate diffusion and spreading, and may operate to spread to a depth of depth according to the diffusion flow of hypochlorous acid or the like.

The power supply device serves to supply DC power to the positive and negative poles installed in the electrolysis tank, and is a device capable of producing DC power using the ship's own power, so that there is no problem in power supply and generation of DC power. The anode and cathode connections of the decomposition are made of durable materials for ships and seawater so that they do not become a problem for long-term use.

The disinfectant concentration measurement sensor serves to measure the concentration of disinfectant water such as hypochlorous acid generated during the electrolysis process and supply the value to the controller.

The control unit recognizes the concentration value received through the disinfectant concentration measurement sensor to adjust the power supply range of the electrolysis, and if necessary to adjust the ship operating speed.

Due to the configuration described above, when the electrolysis device of the present invention is mounted on the rear or side of the ship, sterilization water is diffused / spreaded as opposed to the ship movement path to remove red tide in the red tide occurrence area. The inflow and diffusion / spreading of sea water is automatically introduced and spread / sprayed according to the ship's operating speed, and according to the concentration of sterilized sterilized water such as hypochlorous acid, the ship's operating speed and electrolysis operation conditions are adjusted to adjust the proper sterilized water concentration. To prevent excessive disinfectant spraying. In addition, the electrolysis device of the present invention can be easily attached or detached to any vessel regardless of size, use, fishing, working conditions, height can be adjusted below the depth in consideration of the height of the ship structure and sea level. .

In the conventional electrolysis device, the reaction tank is mounted on a vessel, and in order to produce sterilized sterilized water such as hypochlorous acid, seawater must be introduced through an inflow pump, and the produced sterilized sterilized water is stored in a tank having a predetermined capacity and sprayed again in the sea area. The hassle and accessories required. In addition, a separate device for fixing on the ship is required to prevent movement, such as vibration, depending on the ship operation. However, the present invention solved this problem.

Figure 2 is a flow chart showing a process of preventing red tide phenomenon using the electrolysis device of the present invention. As shown in the drawing, the electrolysis device mounted on the ship is supplied with power to the electrolytic cell electrode plate through a power supply device to electrolyze seawater passing through the screen. Hypo-produced in the electrolysis process hypochlorite (HOCl), hypochlorite ion (OCl ^-), sterilization sodoksu such as chlorine dioxide (ClO ₂₎ is being sprayed diffuse into the area through the inclined plate of the electrolyzer trailing measured by a sensor The operation proceeds in the order of adjusting the operating conditions and operating speed in the control unit according to the concentration of the disinfectant water.

Figure 3 is a plan view and a side view showing the inflow of seawater, the generation, dispersal and spreading of the sterilized water according to the ship moving direction, Figure 4 shows the form of the electrolysis device of the present invention attached to the vessel.

An electrolysis device is installed on the rear or side of the ship to disinfect sterilized water in the opposite direction of the ship's movement. The number of times of the ship speed and the flight is hypochlorous acid (HOCl) generated in the electrolyzer, hypochlorite ion (OCl ^-), chlorine dioxide (ClO ₂₎ determined in accordance with the disinfection concentration such as is sterilization that is end-processed exhaust Adjust ship operations to ensure that the concentration of disinfectant water is 0.16 ppm. Also, for vertical diffusion, a steep plate such as baffle is placed at the rear end of the electrolysis tank to disinfect sterilized water below sea level.

The concentration of sterilized water is measured by placing a sensor in the diffusion part of the sterilized water and the electrolytic operation conditions and the speed of the ship's operation are controlled through the controller roll according to the concentration, so that the concentration of the sterilized water is kept constant according to the range of the sea area where red tide occurs.

In a port or port of a red tide cluster, the red tide sinks at night and floats during the day, causing red tide to occur throughout the sea.At this time, a ship equipped with this electrolysis device operates a ship equipped with this electrolysis device. Spray.

Sterilization water spraying around aquaculture farms operates in the same way as yellow soil spraying, but automatically sprays sterilizing water generated from the electrolysis device installed on the ship according to the ship's operation.

As shown, the present invention provides the operation of a vessel equipped with an electrolysis device for the removal of red tide around the sea area and the aquaculture farm where red tide has occurred, and thus, hypochlorous acid (HOCl), hypochlorite ion (OCl ⁻ ), and chlorine dioxide. Prediction and spread of disinfectant water, such as (ClO ₂ ).

Sterilization water generation concentration of the electrolysis tank is preferably maintained in the range of 10 ~ 8,000 ppm, the concentration of the sterilized sterilized water discharged from the final treatment is treated to maintain 0.1 ~ 6.0 ppm. The operating conditions that can be controlled can be controlled by changing conditions such as current density, contact time, electrode interval, etc., and control the concentration of sterilized water.The concentration of sterilized water in the target sea area where red tide has occurred can be adjusted according to the ship's operating speed and frequency. I can regulate it.

[Example: Red Tide Experiment Results]

In June 2013, the electrolysis device of the present invention was operated for 5 hours using the electrolysis device of the present invention on the left rear of a 10-ton fishing boat in Tongyeong, Gyeongnam. Then, chlorella, which is a kind of Frankton around the ocean, was collected and its concentration was measured using a spectrophotometer (UV-1601, Shimadzu, Japan) at a wavelength of 660 nm with a 1 cm × 1 cm quartz square cell using an absorbance spectrometer. Was measured.

The concentration of chlorella in seawater was 52.1%, expressed as transmittance (%). The seawater having such chlorella concentration was passed through the electrolysis device of the present invention.

The effective volume of the electrolysis device of the present invention was a square reactor having a size of 18 cm x 12 cm x 6 cm, the volume was 1296 cm ³ , and the effective area (16 cm x 6 cm x 2 cm) of one electrode plate was 192 cm ³ . Two cathodes were installed in one set centering on one cathode plate.

Electrolysis conditions were compared for transmittance by varying the treatment flow rate according to the current density residence time of 1.0 A / dm ² . It was compared with experiments using the electrodes and the electrode plate (Ti / IrO ₂₎ of the present invention, using the prior art.

The experiment was performed once again using a conventional electrolysis apparatus and the results are shown in Table 2.

Treatment flow rate (ml / min) 0 1296 185 144 86.4 43.2 Residence time (min) 0 One 7 9 15 30 Transmittance (%) 52.1 18.2 9.4 0.1 0.005 0.0005 Removal efficiency (%) - 62.1 82.0 99.8 99.99 99.99

Treatment flow rate (ml / min) 0 1296 185 144 86.4 43.2 Residence time (min) 0 One 7 9 15 30 Transmittance (%) 52.1 35.5 20.1 12.4 1.5 0.1 Removal efficiency (%) - 31.8 61.4 76.2 97.1 99.8

As confirmed in Tables 1 and 2, the effect of red tide prevention using the electrolysis device of the present invention was found to be superior to the conventional method. This is due to the fact that the generation concentration of sterilizing sterilized water differs according to the characteristics of the electrode plate, and the sterilization efficiency increases as the electrode interval is narrow.

Although the above description has been made with reference to the drawings and embodiments, the present invention is not limited thereto and various modifications can be made. Of course, it can also have a number of embodiments. On the other hand, the present invention is not limited to the specific embodiments, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

100: sea water inlet (screen) 101: electrolysis electrode plate (anode / cathode)
102: electrolysis tank (electrode plate frame) 103: diffusion / spreading portion (vertical / horizontal diffusion)
104: disinfectant concentration measurement (sensor) 105: power supply device
106: control unit

Claims (5)

In the electrolysis device for ship mounting,
The electrolytic apparatus
Located on one side of the ship, the seawater inlet is attached to the screen of the net-shaped screen for filtering the suspended matter inside the seawater flows;
An electrolysis tank connected to the sea water inlet and provided with a baffle-shaped inclined plate for vertical diffusion of sterile disinfectant water generated by electrolysis;
An electrolysis electrode plate formed inside the electrolysis tank, the electrolysis electrode plate comprising an anode and a cathode installed to maintain an interval of 1 mm to 30 mm;
A diffusion / spreading part connected to a rear surface of the electrolysis tank to induce diffusion of disinfectant water;
A disinfectant water concentration sensor installed adjacent to the diffusion / spray part and measuring a disinfectant water concentration generated during an electrolysis process and supplying a measured value to a controller installed on the vessel;
A control unit connected to the concentration measuring sensor and controlling power supply according to the concentration value of the disinfecting water measured at the upper portion of the vessel;
A power supply device connected adjacent to the control unit and receiving a control signal from the control unit to supply power;
The anode of the electrolytic electrode plate is selected from electrodes in which iridium dioxide (IrO 2), ruthenium (Ru) or platinum (Pt) is electrodeposited on titanium (Ti),
The negative electrode is the same as the positive electrode or shipboard electrolysis device, characterized in that selected from among titanium or stainless steel electrodes delete delete delete delete

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