KR101563179B1 - The bypass line through type electrolysis ballast water treatment method and device designed to disinfect fresh water and seawater - Google Patents

Abstract

The present invention relates to a method for reducing the pH of seawater and reducing the pH of the seawater by dissolving the carbon dioxide in seawater and converting the same into carbon dioxide microcapsule. When the pH of the seawater is lowered, the ratio of HOCl, The sterilization efficiency can be increased as compared with the conventional ballast water treatment system of the electrolytic water treatment method under the concentration condition, and only a part of the inflowed seawater is subjected to the microbubble treatment and the electrolytic treatment, The present invention also provides a method and apparatus for treating an electrolytic ship ballast water which can be sterilized by fresh water and sea water,

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic ship ballast water treatment method and apparatus capable of sterilizing fresh water and sea water,

The present invention relates to a method and apparatus for treating a non-electrolytic water electrolysis vessel ballast water capable of sterilizing fresh water and sea water. More specifically, it relates to a method and apparatus for dissolving carbon dioxide in seawater to lower the pH of seawater, (HOCl) or hypobromous acid (HOBr), which is excellent in the oxidizing power among the total oxidizing substances generated in the electrolysis, is increased. Therefore, compared to the existing electrolytic water treatment type ballast water treatment apparatus, It is possible to maximize the electrolysis efficiency against the installation area of the electrolytic processing means by performing only microbubble treatment and electrolytic treatment of only a part of the incoming seawater, The present invention relates to a method and an apparatus for dismantling ship ballast water.

In general, when there is no load on the ship and the propeller on the back of the ship floats on the surface of the water, the vessel is not steered properly. Therefore, in order to maintain the stability of the vessel, the center of gravity of the vessel must be lowered during operation.

However, since the gross weight of a ship is limited for safety, the vessel should be submerged under water by injecting ship equilibrium material in parallel to the center of the ship in accordance with the total weight of the cargo or passenger do. In addition, the ship equilibrium material is to be such that it can be easily discharged from the ship if necessary.

As a method for lowering the center of gravity of such a vessel, there has been traditionally a method of loading a solid material such as sand or lead as a ship equilibrium material under the vessel. However, such a solid material has a problem that it is not easy to discharge a solid material from a ship, and recently, water which is easy to inject and discharge into a ship is used as a parallel material. The water (seawater) used as such a ballast water balance material is called ballast water.

Injection and discharge of such ballast water are mostly carried out in ports or in the sea area where cargo or passengers ride.

Meanwhile, the ballast water is injected into or discharged from the ship by using a pump of the ship. At this time, the aquatic creatures included in the seawater are also injected or discharged into the ship. Therefore, seawater and aquatic organisms injected into the ship can be discharged to other places than the first place by moving long distance according to the operating distance of the ship.

Most of these aquatic organisms are unable to adapt to the new environment and die, but some of them may survive and disturb existing ecosystems or even destroy ecosystems in their area.

Therefore, the problem of disposal of ballast water has been highlighted by many countries, for example, by limiting the exchange of ballast water within the port through their own legal system or by forcing them to exchange in advance in places where water depth is high.

On the other hand, in the conventional electrolyzed vessel equilibrium water treatment method, when the water source to be electrolyzed is fresh water, the electrolytic substance necessary for electrolysis is generally lower than that of seawater, and thus the efficiency of generating sterilizing material is low.

In addition, in the existing electrolyzed vessel equilibrium water treatment method, all of the raw water to be treated is passed through the electrolytic treatment means, and the area for installing the electrolytic treatment means must be secured in order to increase the electrolytic efficiency. .

Korean Patent Registration No. 0883444

It is a main object of the present invention to provide a water tank which can increase the sterilization efficiency under the same total residual oxidant (TRO) concentration condition and can increase the electrolysis efficiency compared to the installation area of the electrolytic treatment means, The present invention also provides a method and apparatus for treating an electrolytic ship ballast water.

A non-electrolytic passing type electrolytic ship ballast water treatment apparatus capable of sterilizing fresh water and sea water according to the present invention comprises: a seawater inlet pipe for introducing seawater; A seawater inlet pipe for branching at the seawater inflow pipe and transferring 1 to 5% by weight of the main seawater inflow pipe and the inflowing seawater for transferring 95 to 99% by weight of the inflowed seawater; PH adjusting means for lowering the pH of seawater by injecting carbon dioxide gas into seawater flowing through the seawater inlet pipe for sterilization treatment; Micro-bubble generating means for atomizing the bubbles of the gas contained in the seawater whose pH is lowered and converting the bubbles into micro-bubbles; (HOCl) or hypobromous acid (HOBr) in the total oxidizing substances contained in the electrolyzed seawater by electrolyzing the seawater whose pH is lowered due to the dissolution of the microbubbles, An electrolytic treatment means for increasing the presence ratio of the microbubbles dissolved in the microbubbles to a ballast tank by sterilizing the microbubbles dissolved in the seawater with an excess of hypochlorous acid or hypobromic acid, An injector to which the main seawater inlet pipe and the sterilizing water discharge pipe extending from the rear of the electrolytic treatment means are joined; And a ballast tank disposed behind the injector, wherein the electrolytic processing means includes: a rectifier; An electrolytic module including at least one electrolytic module including an anode and an anode terminal connected to the rectifier, and an electrolytic part alternately disposed on the anode and the cathode terminals, the scale being removed by the carbon dioxide microbubbles, A reactor; And a control panel controlling the electrolysis driving time of the electrolytic reactor by controlling the DC rectification of the rectifier and the electrolytic driving time of the electrolytic unit; And a bypass line connected to the power supply line.

According to another preferred feature of the present invention, the apparatus further includes an aeration line for transferring the seawater whose pH is lowered by the microbubble generator to the disinfection process water discharge pipe without passing through the electrolytic treatment means.

According to another preferred aspect of the present invention, in the injector, the disinfection water discharge pipe is provided so as to communicate with one side of the main seawater inflow pipe, and an inner pipe installed in the inside is centered along the direction of the sea water And an end of the inner tube is formed with a vortex so as to have an inclined surface for facilitating mixing of the sterilizing treatment water in the seawater of the main seawater inflow pipe.

According to another preferred aspect of the present invention, the pH adjusting means comprises: a venturi injector; A concentrated carbon dioxide tank for injecting carbon dioxide into seawater introduced into the venturi injector; And a regulator for adjusting the amount of carbon dioxide injected in the concentrated carbon dioxide tank according to the pH and the flow rate of seawater flowing into the venturi injector; . ≪ / RTI >

According to another preferred feature of the present invention, the carbon dioxide injection line injects carbon dioxide in the concentrated carbon dioxide tank into the main seawater inflow pipe; A regulator provided on the carbon dioxide injection line for regulating an amount of carbon dioxide injected into the concentrated carbon dioxide tank; And an injector disposed at a portion where the main seawater inlet pipe and the carbon dioxide injection line are joined together; As shown in FIG.

At this time, in the injector, the carbon dioxide injection line is installed to communicate with one side of the main seawater inflow pipe, and the inner pipe installed inside is bent inside the main sea inflow pipe so as to be positioned in the center along the direction of the sea water And an end portion of the inner pipe may have a slope to form a vortex so that carbon dioxide can easily be mixed into seawater of the main seawater inflow pipe.

According to another preferred aspect of the present invention, the main seawater inlet pipe is provided with a mixing tank at the rear of the injector, and the mixing tank may be provided with a partition wall to increase the contact time between the gas and the seawater.

According to another preferred aspect of the present invention, the pH adjusting means comprises: a venturi injector; An air compressor for injecting air into seawater introduced into the venturi injector; And a regulator for adjusting an air injection amount of the air compressor according to a pH and a flow rate of seawater flowing into the venturi injector; . ≪ / RTI >

According to another preferred feature of the present invention, it is possible to further comprise salinity control means located in front of the electrolytic treatment means.

According to another preferred aspect of the present invention, the apparatus may further include a gas discharging means located behind the electrolytic processing means for discharging the gas deaerated from the seawater.

According to another preferred aspect of the present invention, the apparatus may further include a line line mixer located in front of the ballast tank.

According to another preferred aspect of the present invention, the apparatus may further include a neutralization line located behind the ballast tank and circulating the seawater toward the seawater inlet pipe when the TRO of the seawater discharged from the ballast tank is equal to or higher than the allowable concentration.

According to another preferred aspect of the present invention, the micro-bubble generating means may include a micro-bubble nozzle for atomizing the bubbles introduced from the mixing tank into micro-bubbles.

The non-electrolytic electrolytic ship ballast water treatment method according to the present invention is characterized in that 95 to 99% by weight of the seawater introduced through the seawater inlet pipe is transported toward the ballast tank, and 1 to 5% To the electrolytic treatment means; Lowering the pH of the seawater by injecting gas into the 1 to 5 wt% of seawater; Atomizing the bubbles of the gas contained in the seawater into microcapsules; (HOCl) or hypobromic acid (HOBr) among the total oxidizing substances contained in the electrolyzed seawater by electrolyzing the seawater whose pH is lowered by dissolving the microbubbles, Treating the seawater dissolved with the microbubbles with an excessive amount of hypochlorous acid or hypobromic acid and removing the scale generated in the electrolysis process using the microbubbles; Mixing 95 to 99% by weight of seawater transferred to the ballast tank with the sterilized treated water; And injecting the mixed seawater into a ballast tank; A bypass line is used.

According to an embodiment of the present invention, by dissolving carbon dioxide in seawater to lower the pH of seawater, and converting seawater having a low pH into a carbon dioxide microcavity, the ratio of the presence of highly oxidizable HOCl or HOBr among the total oxidizing substances contained in seawater is , The ratio of HOCl or HOBr is higher than that of conventional electrolytic ship ballast water treatment method under the same TRO concentration condition in the case of seawater, so that the sterilization efficiency can be increased, and accordingly, the size of the equipment can be reduced and the driving cost can be lowered There is an effect that can be.

Further, only 1 to 5% by weight of the incoming seawater is subjected to the microbubble treatment and the electrolytic treatment, thereby maximizing the electrolysis efficiency with respect to the installation area of the electrolytic treatment means.

Also, even when using fresh water as ballast water, it is possible to artificially set a pH lower than the pH of the fresh water condition by carbon dioxide microbubbles and further increase the amount of HOCl generated by using an appropriate salt control device, The sterilization efficiency can be secured.

Furthermore, it is possible to artificially control the pH of seawater to reduce the amount of generated hydrogen gas by suppressing the reaction of HOCl → H ⁺ + OCl ^- or HOBr → H ⁺ + OBr ^- .

1 is a schematic view showing the structure of a ship ballast water treatment apparatus according to an embodiment of the present invention.
FIG. 2 is a structural view showing a mixing tank in the pH adjusting means of FIG. 1; FIG.
Fig. 3 is an enlarged plan view of the electrolytic reactor in the electrolytic processing means of Fig. 1; Fig.
4 is a schematic view showing the internal structure of the electrolysis module in the electrolysis reactor of FIG.
Fig. 5 is a structural diagram of Fig. 4, which is shown rotated by 90 degrees in the transverse direction.
6 is a plan view showing an embodiment of the electrolysis unit in the electrolysis module of FIG.
7 is a plan view showing another embodiment of the electrolysis unit in the electrolysis module of FIG.
8 is a graph showing the distribution of hypochlorous acid, hypochlorous acid ion, hypobromic acid and hypobromite ion according to pH.
FIG. 9 is a structural view showing the injector located at A portion in FIG. 1; FIG.
10 is a structural view showing an injector located at a portion B in Fig.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the following embodiments.

The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. Accordingly, the shapes and sizes of the elements in the drawings may be exaggerated for clarity of description, and the elements denoted by the same reference numerals in the drawings are the same elements. In the drawings, like reference numerals are used throughout the drawings.

In addition, to include an element throughout the specification does not exclude other elements unless specifically stated otherwise, but may include other elements.

1 is a schematic view showing the structure of a ship ballast water treatment apparatus according to an embodiment of the present invention.

1, the ballast water treatment apparatus according to the present embodiment includes a ballast tank 120, ballast water injection means and ballast water discharge means, pH adjusting means, fine bubble generating means, and electrolytic processing means .

The ballast tank 120 may vary depending on the size of the vessel, and in the case of a large-sized vessel, it may exceed 100,000 m 2, but the present invention is not limited thereto.

The ballast water injecting means includes a seawater inflow pump 10 and a seawater inflow pipe 21 into which seawater is introduced from the direction (I) by driving the seawater inflow pump 10. At this time, the sea water inflow pipe 21 may be provided with a flow meter 43 for measuring the amount of seawater inflow.

The ballast water discharging means includes a ballast water discharge pipe 232 connected to the ballast tank 120 to discharge the ballast water in the direction (D). At this time, a chemical neutralization device (not shown) may be installed in the ballast water discharge pipe 232 if necessary. A TRO sensor 47 for measuring the TRO concentration of the ballast water discharged from the ballast tank 120 may be provided at the end 22 of the ballast discharge pipe 232. The ballast water discharge pipe 232 may further include a ballast water inflow pump (not shown) and a dissolving tank (not shown).

The first and second branch pipes 23 and 24 are for sending the seawater introduced through the seawater inlet pipe 21 toward the ballast tank 120 or supplying a part of the seawater to the pH adjusting means and the fine bubble generating means .

The first branch pipe (23) is a main seawater inflow pipe and 95 to 99% by weight of seawater is moved toward the ballast tank (120) through the first branch pipe (23). The second branch pipe 24 is a seawater inflow pipe for sterilization treatment and 1 to 5% by weight of the seawater flowing through the seawater inflow pipe 21 flows into the pH adjusting means through the second branch pipe 24 . At this time, the first and second branch pipes (23, 24) may be provided with valves for regulating and supplying the supply amount of seawater. The second branch pipe (24) may be provided with a flow meter (44) for measuring the supply amount of the seawater flowing into the pH adjusting means.

The pH adjusting means is means for lowering the pH of seawater by injecting gas into the seawater introduced through the seawater inlet pipe 21 and the second branch pipe 24. This pH adjusting means may include one of a venturi injector 113 and a carbon dioxide injection means or an air injection means.

The carbon dioxide injection means includes a concentrated carbon dioxide tank 111 for injecting carbon dioxide gas into the seawater flowing into the venturi injector 113 and a carbon dioxide injection amount of the concentrated carbon dioxide tank 111 to the amount of the seawater introduced into the venturi injector 113 and a regulator 112 for adjusting the pH and the flow rate. Reference numerals 28 and 29 denote a supply pipe for supplying carbon dioxide in the concentrated carbon dioxide tank 111 to the venturi injector 113.

In addition, the carbon dioxide injection line 161 for injecting the carbon dioxide of the concentrated carbon dioxide tank 111 toward the main seawater inflow pipe 23 may be branched from the supply pipe 28. According to this embodiment, only 1 to 5 wt% of the fresh water or seawater flowing through the seawater inflow pipe 21 is sterilized and the pH is adjusted. That is, when the sterilized water and the sea water introduced through the main seawater inflow pipe 23 are mixed with each other in the injector A of FIG. 1, the pH of the mixed water is greatly increased again, and thus the presence of HOCl It is difficult to maintain the ratio to the level desired by the user. The carbon dioxide injection line 161 of this embodiment directly injects carbon dioxide into the main seawater inflow pipe 23 in order to solve this problem.

At this time, a regulator 160 is provided on the carbon dioxide injection line 161 so that the amount of carbon dioxide supplied from the concentrated carbon dioxide tank 111 to the main seawater inflow pipe 23 can be appropriately controlled.

An injector B may be provided at a portion where the main seawater inlet pipe 23 and the carbon dioxide injection line 161 are joined.

10, the injector B is provided with a carbon dioxide injection line 161 communicating with one side of the main seawater inflow pipe 23, and an inner pipe 162 provided inside the carbon dioxide injection line 161 is connected to the main The end portion 162a of the inner pipe 162 is formed with a vortex so that carbon dioxide is introduced into the seawater of the main seawater inflow pipe 23, And may be formed to have an inclined surface for facilitating mixing.

On the other hand, a carbon dioxide collecting device may be further provided in the vessel if necessary. The carbon dioxide collecting device can collect and concentrate carbon dioxide from the exhaust gas generated during the operation of the ship, and then send the concentrated carbon dioxide to the concentrated carbon dioxide tank 111 of the carbon dioxide injecting means.

The air injection means includes an air compressor 253 for injecting air into the seawater introduced into the venturi injector 113, a regulator 251 for regulating the amount of air injected in accordance with the pH and the flow rate of the seawater flowing into the venturi injector 113 ). Reference numerals 252 and 254 denote a supply pipe for supplying the air of the air compressor 253 to the venturi injector 113.

The mixing tank 150 may be disposed behind the injector B in the main seawater inlet pipe 23. In the present embodiment, the fine bubble generating means is disposed in the line for the bactericidal treatment seawater inflow pipe 24, whereas only the mixing tank 150 is disposed in the main seawater inflow pipe 23 in the case of the carbon dioxide, This is because the fine bubble generating means and the mixing tank 150 can sufficiently dissolve the injected carbon dioxide.

2, partition walls 152a and 152b may be formed in the mixing tank 150 to increase the contact time of the carbon dioxide or the air and the sea water in the body 151 so that the dissolution can be performed easily. Although two barrier ribs are illustrated and described in the present embodiment, the present invention is not limited thereto and only one barrier rib may be formed or three or more barrier ribs may be formed at predetermined intervals.

Also, the mixing tank 150 may be provided with a gas discharging unit 115 for mixing carbon dioxide or air and seawater into bubbles, and then discharging the remaining beauty zone gas or large-sized large bubbles into the atmosphere.

The micro-bubble generating means is means for atomizing the bubbles of the gas contained in the seawater whose pH is lowered and converting it into a micro-bubble. The use of the micro-bubble generating means in the bypass line means that the micro-bubble generating means requires a shorter time to travel to the electrolytic processing means located at the rear side and requires a faster mixing efficiency than that in the mixing tank, So that the bubbles of the gas are atomized so as to be suitable for the gas. In the main seawater inflow pipe 23 described above, since there is a margin to the injector A, the fine bubble generating means is omitted and the mixing tank 150 suitable for large-capacity flow rate treatment is used. However, the present invention is not limited thereto.

The fine bubble generating means may include fine bubble nozzles 116 that atomize the introduced bubbles into fine bubbles and mix them into seawater to make seawater having a low pH and then transfer the seawater to the electrolytic treatment means. The fine bubble nozzles 116 serve to atomize the bubbles introduced from the venturi injector 113 side to form more atomized fine bubbles.

Here, it means that the bubbles of about 30 탆 of the micropores are shrunk to about 10 탆 at a pressure of about 1.5 atm, and then compressed to about 0.1 to 10.0 탆 by shrinking to about 15 atm.

The venturi injector 113 and the fine bubble nozzles 116 are connected to the first mixing water pipe 25 and the amount of mixed sea water supplied to the fine bubble nozzle 116 is supplied to the first mixing water pipe 25 And a pH sensor 114 for measuring the pH of the mixed seawater may be installed. At this time, the venturi injector 113 may be replaced with a perforated plate or an orifice tube if necessary, and the present invention is not limited thereto. Reference numeral 27 denotes a supply line for supplying the electrolytic processing means with the sea water in which the minute bubbles are dissolved. At this time, the supply line 27 may be provided with a valve.

On the other hand, an aeration line for transferring the lowered pH of the seawater to the sterilizing treatment water discharge pipe 231 without passing through the electrolytic treatment means may be provided behind the minute bubbling means.

The electrolytic treatment means includes an electrolytic treatment means for sterilizing the electrolytically generated hypochlorous acid and dissolving the fine bubbles flowing through the fine bubble nozzle 116 into the ballast tank 120, ) Processing type of ballast water.

The electrolytic processing means includes a control panel (not shown) for controlling the DC rectification of the rectifier 130 and the rectifier 130 and for controlling the electrolytic driving time and the like of the electrolytic unit to be described later and at least one electrolytic module 141, And an electrolytic reactor (140).

FIG. 3 is a plan view showing an electrolysis reactor in the electrolysis processing means of FIG. 1 in an enlarged scale, FIG. 4 is a structural view schematically showing an internal structure of the electrolysis module in the electrolysis reactor of FIG. 3, And rotated 90 degrees in the horizontal direction.

3 to 5, one electrolytic module 141 is illustrated as one set in the present embodiment, but the present invention is not limited to this, and the number of electrolytic modules is not limited to the ballast water capacity Design can be changed by increasing or decreasing more than two if necessary.

The electrolysis module 141 includes a body 141a having a generally square shape and a cathode terminal 142 and a cathode terminal 143 connected to the body 141a so as to receive DC rectification from the rectifier 130 Lt; / RTI > The anode terminal 142 and the anode terminal 143 have a cathode bus bar 142a and a cathode bus bar 143a for receiving a cathode and an anode, respectively. In addition, the voltage of the rectifier 130 varies depending on the amount of applied current, and a voltage of 10 V or less for seawater or 15 V or less for fresh water can be applied, and the present invention is not limited thereto.

The anode and anode busbars 142a and 143a of the anode terminal 142 and the anode terminal 143 are alternately stacked in the body 141a so that the cathode and anode electrolysis units 144 and 145 are connected do. At this time, the cathode and anode electrolytic units 144 and 145 may be formed by coating ruthenium on a titanium base so as to have good corrosion resistance even in seawater and fresh water, but the present invention is not limited thereto.

As shown in FIG. 7, the cathode and anode electrolytic units 144 and 145 may be of a plate type as shown in FIG. 6, .

In this case, for example, the cathode and anode electrolytic units 144 and 145 are formed such that a cathode and anode ports 146 and 147 are formed at one end and extended to the cathode and anode ports 146 and 147, Bolt coupling holes 146a and 147a are formed. Reference numerals 142b and 143b denote cathode and anode connection members. The cathode and anode connection members 142b and 143b are disposed so as to correspond to at least one surface of the upper surface or the lower surface of the cathode and anode ports 146 and 147, respectively, And the bolts 142c and 143c are coupled to the bolt holes 146a and 147a so as to pass through the anode ports 146 and 147, respectively. A plurality of cathode ports 146 and a plurality of anode ports 147 are electrically insulated from each other and a part of the cathode and anode connection members 142b and 143b is connected to the cathode and anode bus bars 142a and 143a The negative electrode (-) allows the negative electrode electrolysis unit 144, the negative electrode port 146, the negative electrode connection member 142b and the negative electrode bus bar 14a to be electrically connected to each other, and the positive electrode (+ The electrolytic unit 145, the anode port 147, the anode connection member 143b, and the anode bus bar 143a are electrically connected to each other.

Referring to FIG. 7, the cathode and anode electrolytic units 144 'and 145' may include a support 144a 'having a plurality of through holes 144b'. The mesh-type electrolytic units 144 'and 145' have the same size and larger specific surface area than the plate-type electrolysis units 144 and 145, The shape of the electrolysis part can be optionally used depending on the situation.

At this time, the size of the through hole 144b 'may be varied as required, but it is preferable that the ratio of the length L to the width W is about 6 (L): 3 (W). For example, the size of the through hole 144b 'of the mesh-type electrolytic units 144' and 145 'may be 6 * 3 mm (L * W), but it can be made smaller when a high concentration of TRO is required.

The electrolytic treatment means constructed as described above is one example in which when the carbon dioxide gas is introduced through the pH adjusting means, when the seawater passes through the electrolysis units 144 and 145 of the electrode disassembly module 141, And is electrolyzed through a potential difference.

[Reaction Scheme 1]

<Chlorination>

NaCl → Na ⁺ + Cl ^-

2Cl ^- ? Cl ₂ + 2e ^-

Cl ₂ + H ₂ O → HCl + HOCl

HOCl -> H ⁺ + OCl ^-

H ₂ O → H ⁺ + OH ^-

Na ⁺ + OH ^- &gt; NaOH

Cl ₂ + ₂ NaOH → NaOCl + NaCl + H ₂ O

<Bromination>

HOCl + Br- &gt; HOBr + Cl-

HOBr → H + + OBr-

Of the chemical species generated by the above reaction scheme 1, HOCl, OCl ^-? , OH ^- , NaOCl, HOBr, OBr ^-? And total oxidants (TRO) are called total residual oxidants (TRO), and microorganisms are sterilized by TRO. In particular, free available chlorine with high efficiency of disinfection with high oxidation resistance is HOCl and OCl ^- .

In electrolysis, HOCl and OCl ^- are irreversibly generated, and the ratio of the presence of HOCl and OCl ^- varies depending on the pH in the water as shown in FIG.

Referring to FIG. 8, the lower the pH is, the higher the presence ratio (%) of active acid of HOCl or HOBR and the lower the existence ratio (%) of active ion, and the higher the pH, the lower the ratio of active acid of HOCl or HOBR , And the presence ratio (%) of active ions is high.

In general, in the case of seawater, the pH is between 8 and 9, so the HOCl generated through the electrolysis reaction is decomposed and mostly exists as (HOCl → H ⁺ + OCl ^- ) OCl ^- form.

In general, HOCl has a higher oxidizing power than OCl ^- and its sterilization efficiency is about 80 times higher.

In this embodiment, a concentrated gas such as carbon dioxide is injected into the seawater introduced through the seawater inflow pipe to form carbon dioxide microbubbles, the pH of the seawater is lowered by dissolving the carbon dioxide micropores and the seawater, After sterilization with hypochlorous acid produced by decomposition, it can be injected into the ballast tank to increase the sterilization efficiency of the ballast water.

Here, the purpose of saturating the gas introduced into the seawater is to increase the dissolution efficiency so that the dissolution of the gas can be performed more easily.

That is, as in the present embodiment, if the pH of the seawater is adjusted by artificially controlling the pH of the seawater by dissolving the micro-saturated gas in the seawater, the presence of HOCl is increased and the sterilization effect is increased.

A gas discharging means 220 for discharging the gas deaerated from the seawater to the outside through the discharge pipe 222 may be located at the downstream end of the electrolytic processing means. When the air is injected to purify the air by the air instead of the carbon dioxide in the neutralization step, deaeration or OH radical in the gas discharging means 220 or physical force of micro bubbles such as high pressure and high temperature, The concentration can be kept below the concentration of the effluent (0.2 mg / L) notified by the IMO. The gas discharge means 220 is also connected to the rear end of the aeration line 234. Further, the gas discharging means 220 may be provided with a sensor 221 for measuring the amount of hydrogen gas or air to be degassed.

Hydrogen gas is known to cause explosion at a concentration of 5 ~ 27% under normal temperature and pressure. Hydrogen concentration during electrolysis occurs below the lower explosive limit (LEL), but it is highly likely that the hydrogen gas will stay in the pipe during the various piping operations until it moves to the ballast tank after passing through the electrolysis reactor. Concentration is likely to be concentrated above the explosion bottom line. In addition, hydrogen gas penetrates into various sensors including TRO sensor, and hydrogen gas is concentrated in a closed space, and there is a risk of explosion.

Therefore, even if the concentration of hydrogen gas generated in the electrolytic apparatus is equal to or lower than the LEL, it is necessary to reduce the hydrogen gas through gas-liquid separation after the electrolysis reactor. Hydrogen gas needs to be controlled with respect to the total flow rate of the gypsum in the conventional full-pass method, so that the facility for separating gas (liquid-liquid) (seawater-treated water)

However, in this embodiment, since the flow rate to be fed to the electrolytic treatment means is as small as 5% or less of the whole, the gas-liquid separator can be reduced and the gas discharge means 220 can be installed, .

Reference numeral 231 denotes a sterilized water discharge pipe for transferring sterilized treated water discharged from the gas discharge means 220 to the ballast tank 120 side. At this time, the disinfection water discharge pipe 231 may be equipped with a valve and a TRO sensor 45 to detect the TRO concentration of the flow meter 46 and the sterilized seawater, if necessary.

On the other hand, in the case of the electrolysis method, the chemical is used to neutralize and discharge the chemical from the back of the ballast tank, resulting in problems such as maintenance of the chemical, consumption of the chemical cost, and release of the neutralizing agent in the marine environment. In this embodiment, the electrolytic treatment means is capable of stably maintaining the discharge allowable TRO concentration by deaeration of the residual TRO by using the aeration line 234, and there is an effect that the sodium thiosulfate is not used or saved.

In addition, the salt control means 211 may be disposed in front of the electrolytic treatment means. In the case of ballast water using electrolysis treatment, the treatment efficiency is higher than other technologies because the efficiency of TRO generation is high in a high salinity water environment such as seawater.

On the other hand, in a low-salt water environment, the efficiency of TRO generation is low and other auxiliary sterilization facilities such as ozone and UV are needed. In some electrolytic water treatment techniques, there is an attempt to raise the efficiency of TRO generation by raising the salinity by artificially using salt or sea water. However, in the case of the full-pass method, the use of salt is excessive, Electrolytic water treatment is not solved.

However, as in the present embodiment, in the case of the non-electrolytic water passing method, the treatment flow rate is small and the amount of salt used can be reduced, and in some cases, a high concentration of brine can be injected.

For example, when the salinity of the water quality exceeds 7.0 PSU in the electrolysis, the difference in the efficiency of TRO generation by the salinity is insignificant, so 7.0 PSU is set as the lower limit and the salinity of the salt cartridge above the lower limit is maintained .

In addition, before the ballast tank 120, the injector A is disposed at a point where the untreated water introduced from the main seawater inflow pipe 23 and the treated water sterilized by the electrolytic treatment means are mixed through the treatment inflow inlet 231, May be provided.

9, the injector A is connected to one side of the main seawater inflow pipe 23, and the inner pipe 232 installed inside the main inflow pipe 231 is connected to the inside of the main processing inflow pipe 231, And has a structure that is bent to be positioned at the center along the progress direction. At this time, an end of the inner pipe 232 is formed to have a slope so that a vortex is formed and seawater sterilized in the seawater of the main seawater inflow pipe 23 can be easily mixed.

Also, a line mixer 240 may be installed between the injector A and the ballast tank 120. The line mixer 240 is, for example, a liquid-liquid static type, which quickly mixes the high concentration of sterilized TRO and seawater introduced through the main seawater inlet pipe 23. Reference numeral 30 denotes an injection pipe for injecting seawater having passed through the line mixer 240 into the ballast tank 120. At this time, the injection pipe 30 may be provided with a TRO sensor 41 for detecting the TRO concentration of the flowmeter 42 and the sterilized seawater, if necessary.

The ballast tank 120 may further include a neutralization line 233 branched from the ballast water discharge pipe 232 at a rear end thereof. The neutralization line 233 is connected to the seawater inflow pipe 21 and circulates the seawater to the seawater inflow pipe 21 when the TRO of the seawater discharged from the ballast tank 120 is equal to or higher than the allowable concentration.

Table 1 below shows the amount of change in the pH of seawater due to the dissolution of CO2 in the ballast water treatment method. As shown in Table 1, as the dissolution amount of microbubbles increased, the pH was gradually lowered and the pH was measured as low as 3.7 ppm at a maximum of 1,500 ppm.

Co ₂ dissolution amount (concentration) PH 0 ppm 8.2 50 ppm 7.8 100 ppm 7.1 500 ppm 6.0 1,000 ppm 4.3 1,500 ppm 3.7

Table 2 below shows the rate of bio-degradation with changes in pH. As shown in Table 2, as the pH was lowered by carbon dioxide, the biological killing efficiency at the same TRO concentration was lowered from 8.2 to 3.7, and thus the bio-killing efficiency was 70% for the zooplankton, 50% for phytoplankton and 60% for other bacteria (E. coli).

PH TRO Biodegradation rate Zooplankton Phytoplankton E.Coli 8.2 5.0 mg / L 30% 50% 40% 7.8 5.0 mg / L 40% 60% 50% 7.1 5.0 mg / L 40% 60% 50% 6.0 5.0 mg / L 80% 90% 90% 4.3 5.0 mg / L 100% 100% 100% 3.7 5.0 mg / L 100% 100% 100

On the other hand, the condensed carbon dioxide can be separated and concentrated from the exhaust gas generated during the operation of the ship. . For this purpose, a carbon dioxide collecting device may be further provided in the vessel. The carbon dioxide collecting device is installed to the extent that it can collect about 65% of the carbon dioxide from the exhaust gas discharged during the operation of the ship.

Currently, the International Maritime Organization (IMO) regulates the warming gas among the exhaust gases generated from ships, such as ship ballast water regulations, so that if the regulations become effective in the future, carbon dioxide enrichment / capture technology in the ship's exhaust gas will be applied to ships , Which makes it easier to receive the necessary carbon dioxide.

Further, when the supply of carbon dioxide from the exhaust gas of the ship is not smooth, commercially available concentrated carbon dioxide can be stored in the concentrated carbon dioxide tank 111 and utilized.

In addition, in the conventional electrolysis, a scale including MgCO ₃ and CaCO ₃ in the electrode may be generated due to a problem other than the reduction of the treatment efficiency in the generation of the hydrogen gas and the fresh water in the electrolysis, so that the electrolysis efficiency may be reduced.

However, according to the present embodiment, the scale attached to the electrodes of the electrolytic processing means due to the physical force and the adsorption effect of the carbon dioxide microbubbles at the front end of the electrolytic treatment means or at the front end of the salt control means, So that the reduction of the electrolysis efficiency can be effectively suppressed.

Hereinafter, the operation of the bypass line 234 of the present embodiment will be described.

According to this embodiment, the electrolytic treatment means generates a high TRO concentration of up to 1,000 mg / L by applying an amount of current equal to that of the whole-passing system (hereinafter referred to as comparative example) The desired level of TRO concentration can be set by mixing with the seawater. At this time, the total TRO concentration of the ballast tank 120 can be kept constant.

In the comparative example, the TRO concentration formula in the main seawater inflow pipe leading to the ballast water tank is expressed by the following equation 1.

<Formula 1>

C _t = Q _M C _m / Q _m

Here, C _t = Total TRO concentration (mg / L), Q _M = Flow rate at the main seawater inlet pipe (m ³ / hr), C _m = TRO concentration at the main seawater inlet pipe (mg / L).

In the present embodiment, which is a non-electrolytic water passing method, the TRO concentration equation at the time of complete mixing of the TRO at the point (A) where the main sea inflow pipe 23 and the treatment inflow inlet 231 meet is expressed by the following Equation 2.

<Formula 2>

C _t = Q _M C _M + Q _B C _B / Q _M + Q _B

here, C _t = Total TRO concentration (mg / L), Q _M (M ³ / hr) at the main sea feeding inflow pipe 23, Q _B = flow rate at the seawater inflow pipe 24 for sterilization treatment (m ³ / hr), C _m = TRO concentration (mg / L) in the main seawater inflow pipe 23, and C _B = TRO concentration (mg / L) in the seawater inflow pipe 24 for sterilization treatment.

As shown in Equations (1) and (2) above, since the total flow rate is the same in the comparative example and the embodiment, the amount of TRO generated for the total flow rate is also the same. Are the same. That is, it can be seen that the TRO concentration of a relatively high concentration is generated in the embodiment, while the amount of power is consumed as in the comparative example.

Therefore, the non-electrolytic passing method using the bypass line as in the present embodiment is equal to the existing capacity (size) in the case of the rectifier, but the size of all the equipment except the rectifier can be reduced. Particularly, since the size of the chamber of the electrolytic processing means can be greatly reduced, it is not necessary to provide a separate space (ballast room) for the ship ballast water treatment apparatus in the ship.

Further, even if the size of the electrolysis module is reduced in the electrolytic processing means, the size of the electrolysis module is difficult to reduce in order to maintain the allowable current density since the size of the applied current does not change.

However, in the comparative example, the electrode interval was maintained at 5 to 6 mm for smooth flow rate due to the fast flow rate through the electrolytic reactor. However, in this embodiment, the flow rate through the electrolytic reactor is slow, have. By reducing the electrode interval in this way, the size of the electrolysis module can be reduced and the size of the electrolysis reactor as a whole can be reduced.

If the reactants A and B are well mixed in the general chemical reaction (A + B → C), they can participate in the reaction regardless of where the reactants are located in the reactor. However, in electrochemical reactions such as electrolytic water treatment, only reactants that are close to the electrodes can participate in the reaction. The range of the solution near the electrode where the reactant capable of participating in the electrochemical reaction exists is called a diffusion layer, and the portion away from the electrode is called a bulk solution.

In theory, the diffusion layer has a thickness of about 1 to 10 mm. This embodiment maximizes the surface area of the electrode in a certain reactor volume through one modularization using a plurality of anodes and cathodes instead of electrolyzing the solution between the anode and the cathode using a single electrode, Is the technology to increase

In this case, the interval of the diffusion layers can be reduced within the theoretical range to increase the electrolysis efficiency and reduce the size of the electrolysis processing means. Thus, it is possible to secure additional equipment installation area due to the reduction of the entire equipment, so it is possible to install the auxiliary device, so that the auxiliary device can be prepared, for example, in case of equipment failure. In addition, as the auxiliary equipment can be operated, scale removal is facilitated and there is an advantage that maintenance can be performed regardless of ballasting operation.

The present invention is not limited by the above-described embodiment and the accompanying drawings, but is intended to be limited by the appended claims.

It will be apparent to those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. something to do.

21; A seawater inlet pipe 22; Ballast water discharge pipe
23, 24; First and second branch pipes 111; Carbon dioxide tank
112; A regulator 113; Venturi injector
114; pH sensor 116; Fine bubble nozzle
120; Ballast tank
130; Rectifier 140; The electrolytic processing means
141; An electrolysis module 150; Mixing tank
151; Bodies 152a, 152b; septum
211; Salinity control means
220; Gas discharge means
233; Neutralization line

Claims (15)

A seawater inlet pipe for introducing seawater;
A seawater inlet pipe for branching at the seawater inflow pipe and transferring 1 to 5% by weight of the main seawater inflow pipe and the inflowing seawater for transferring 95 to 99% by weight of the inflowed seawater;
PH adjusting means for lowering the pH of the seawater by injecting gas into the seawater flowing through the seawater inlet pipe for sterilization treatment;
Micro-bubble generating means for atomizing the bubbles of the gas contained in the seawater whose pH is lowered and converting the bubbles into micro-bubbles;
(HOCl) or hypobromic acid (HOBr) in the total oxidizing substances contained in the electrolyzed seawater by electrolyzing the seawater whose pH is lowered due to the dissolution of the microbubbles, An electrolytic treatment means for increasing the presence ratio of the microbubbles dissolved in the microbubbles to a ballast tank by sterilizing the microbubbles dissolved in the seawater with an excess of hypochlorous acid or hypobromic acid,
An injector to which the main seawater inlet pipe and the sterilizing water discharge pipe extending from the rear of the electrolytic treatment means are joined; And
And a ballast tank located behind the injector,
The electrolytic processing means includes a rectifier; An electrolytic reactor including at least one electrolytic module including an anode and an anode terminal connected to the rectifier, and an electrolytic part alternately disposed on the anode and the cathode, the scale being removed by carbon dioxide microbubbles, ; And a control panel controlling the electrolysis driving time of the electrolytic reactor by controlling the DC rectification of the rectifier and the electrolytic driving time of the electrolytic unit; Which is capable of sterilizing fresh water and sea water, including an electrolytic vessel, 2. The water treatment system according to claim 1, further comprising an aeration line for transferring the seawater whose pH is lowered by the microbubble generator to the disinfection water discharge pipe without passing through the electrolytic treatment means. Electrolysis vessel ballast water treatment system for non - electrolytic water treatment system capable of disinfection of sea water. The method according to claim 1, wherein in the injector, the disinfection water discharge pipe is provided so as to communicate with one side of the main seawater inflow pipe, and an inner pipe installed in the inner side is positioned in the center Wherein the end portion of the inner pipe has an inclined surface to form a vortex so that the sterilizing treatment water can be easily mixed into the seawater of the main seawater inflow pipe. A ballast water treatment system. The apparatus of claim 1, wherein the pH adjusting means comprises: a venturi injector; A concentrated carbon dioxide tank for injecting carbon dioxide into seawater introduced into the venturi injector; And a regulator for adjusting the amount of carbon dioxide injected in the concentrated carbon dioxide tank according to the pH and the flow rate of seawater flowing into the venturi injector; Wherein the electrolytic vessel is provided with an electrolytic vessel, The electrolytic apparatus according to claim 4, further comprising a carbon dioxide collecting device for collecting carbon dioxide from the exhaust gas generated during the operation of the ship, and concentrating the carbon dioxide to the concentrated carbon dioxide tank, Processing device. The method according to claim 4, further comprising: a carbon dioxide injection line for injecting carbon dioxide in the concentrated carbon dioxide tank into the main seawater inflow pipe; A regulator provided on the carbon dioxide injection line for regulating an amount of carbon dioxide injected into the concentrated carbon dioxide tank; And an injector disposed at a portion where the main seawater inlet pipe and the carbon dioxide injection line are joined together; And further comprising an electrolytic water treatment apparatus for desalination, which is capable of sterilizing seawater. The method according to claim 6, wherein in the injector, the carbon dioxide injection line is provided so as to communicate with one side of the main seawater inflow pipe, and an inner pipe installed in the inner side is positioned in the middle of the main sea inflow pipe along the traveling direction of the seawater Wherein the end portion of the inner pipe has a curved structure and has an inclined surface to form a vortex so that carbon dioxide can be easily mixed into seawater of the main seawater inflow pipe. A ballast water treatment system. [7] The method of claim 6, wherein the main seawater inlet pipe is provided with a mixing tank at the rear of the injector, and the mixing tank is provided with a partition wall for increasing the contact time between the gas and the seawater. Capable of passing through a non - electrolytic vessel ballast water treatment system. The apparatus of claim 1, wherein the pH adjusting means comprises: a venturi injector; An air compressor for injecting air into seawater introduced into the venturi injector; And a regulator for adjusting an air injection amount of the air compressor according to a pH and a flow rate of seawater flowing into the venturi injector; Wherein the electrolytic vessel is provided with an electrolytic vessel, The electrolytic apparatus of claim 1, further comprising salinity control means located in front of the electrolytic treatment means. The electrolytic water treatment system according to claim 1, further comprising a gas discharging means located behind the electrolytic treatment means for discharging the gas deaerated from the seawater. A ballast water treatment system. The apparatus of claim 1, further comprising a static line mixer located in front of the ballast tank. The apparatus according to claim 1, further comprising a neutralization line located behind the ballast tank and circulating the seawater toward the seawater inlet pipe when the TRO of the seawater discharged from the ballast tank is equal to or higher than an allowable concentration, Electrolysis vessel ballast water treatment system which can be sterilized. The method according to claim 1,
Wherein the micro-bubble generating means includes a micro-bubble nozzle for atomizing the bubbles introduced from the mixing tank disposed in the rear of the injector in the main seawater inflow pipe to form micro-bubbles. Electrolytic vessel ballast water treatment system. Transferring 95 to 99% by weight of the seawater introduced through the seawater inlet pipe to the ballast tank and 1 to 5% by weight to the electrolytic treatment means;
Lowering the pH of the seawater by injecting gas into the 1 to 5 wt% of seawater;
Atomizing the bubbles of the gas contained in the seawater into microcapsules;
(HOCl) or hypobromic acid (HOBr) among the total oxidizing substances contained in the electrolyzed seawater by electrolyzing the seawater whose pH is lowered by dissolving the microbubbles, Treating the seawater dissolved with the microbubbles with an excessive amount of hypochlorous acid or hypobromic acid and removing the scale generated in the electrolysis process using the microbubbles;
Mixing 95 to 99% by weight of seawater transferred to the ballast tank with the sterilized treated water; And
Injecting the mixed seawater into a ballast tank; A method of treating an electrolytic ship ballast water, which is capable of sterilizing fresh water and sea water, comprising a non-electrolytic water passing method.

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