KR102572086B1 - Circulating system using reverse electrodialysis(red) salinity power generation module - Google Patents

Abstract

A circulatory system using a RED salinity gradient power generation module is disclosed.
In the circulatory system using the RED salinity gradient power generation module according to the present invention, at least two or more influents are introduced, and the RED salinity gradient power generation module that produces power using the concentration difference of the inflow water flowing into the inside, seawater A seawater tank for accommodating, a first influent tank for receiving seawater from the seawater tank and supplying the received seawater to the RED salinity gradient power module as at least one of the first influent or electrode solution, and a salt concentration different from that of the first influent. A second influent tank for storing the second influent and supplying the second influent to the RED salinity gradient power module, and the seawater supplied to the first influent tank is supplied to the RED salinity gradient power module as an electrode solution, or the first Another part of the seawater supplied to the influent tank is provided to be supplied to at least one of the seawater tank and the first influent tank after being supplied to the RED salinity gradient power module as the first influent.

Description

Circulation system using RED salinity gradient power generation module {CIRCULATING SYSTEM USING REVERSE ELECTRODIALYSIS (RED) SALINITY POWER GENERATION MODULE}

The present invention relates to a circulation system using a RED salinity gradient power generation module, and relates to a circulation system using a RED salinity gradient power generation module capable of removing organic and inorganic pollutants in influent water such as seawater, fresh water, and wastewater.

Salinity gradient power generation is a system that generates electricity by recovering concentration energy generated in the mixing process of solutions (eg, salt water, fresh water) with different concentrations in the form of electrical energy.

In particular, in the RED (Reverse Electro Dialysis) salinity gradient power generation module, cations and anions move through a cation exchange membrane and an anion exchange membrane, respectively, due to a concentration difference between ions contained in seawater and fresh water. At this time, a chemical transition difference occurs between the cation exchange membrane and the anion exchange membrane, and at the electrodes (positive electrode (anode) and negative electrode (cathode)) located at both ends of which a plurality of cation exchange membranes and anion exchange membranes are alternately arranged, by the cation exchange membrane and the anion exchange membrane Electric energy is generated by the movement of electrons by the oxidation-reduction reaction using the generated potential difference.

As such, the RED salinity gradient power generation module refers to a power generation method in which chemical energy generated while ions dissolved in salt water move to fresh water through a cation exchange membrane and an anion exchange membrane is directly converted into electrical energy.

At this time, in the case of the conventional RED salinity gradient power generation module, since the volume of the reaction chamber in the RED salinity gradient power generation module is fixed, there is a problem that is not suitable for a circulating system.

In addition, there is a problem in that the RED salinity gradient power generation module is damaged because the gas generated by the reaction is not discharged from the inside of the reaction chamber.

On the other hand, when seawater and freshwater are used as influents generated in nature, there is no separate device for removing organic and inorganic contaminants contained in the influent, so organic contaminants flow directly into the RED salinity gradient power generation module, resulting in RED salinity difference There is a disadvantage that the flow path of the power generation module is blocked.

Accordingly, there is a need to develop a circulating system using a RED salinity differential power generation module suitable for circulating systems and easily removing organic/inorganic contaminants and reactive gases in influent such as seawater and fresh water.

Republic of Korea Patent Publication No. 10-2017-004579 (Publication date: 2017.04.24. Publication)

An object of the present invention is to provide a circulating system using a RED salinity gradient power generation module capable of removing organic and inorganic contaminants in influent water such as seawater, freshwater, and wastewater.

In addition, an object of the present invention is to provide a circulating system using a RED salinity gradient power generation module that may not use an electrode solution separately and can use seawater.

In addition, an object of the present invention is to conveniently fasten the electrode member and the current collector to the inside of the RED salinity gradient power module, change the volume of the reaction chamber, and discharge the gas generated in the reaction chamber to the outside. It is to provide a circulation system using a RED salinity gradient power generation module.

The problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

The above object is, according to the present invention, at least two types of inflow water are introduced, and a RED salinity differential power generation module that generates power using the concentration difference of the inflow water flowing into the inside, a seawater tank for accommodating seawater, A first influent tank for receiving seawater from the seawater tank and supplying the received seawater to the RED salinity differential power generation module as at least one of the first influent or an electrode solution, and a second influent having a salt concentration different from that of the first influent are stored. , It includes a second influent tank for supplying second influent to the RED salinity gradient power generation module, and the seawater supplied to the first influent tank is supplied to the RED salinity gradient power module as an electrode solution or the seawater supplied to the first influent tank is After being supplied to the RED salinity gradient power generation module as the first influent, it can be achieved by a circulation system using the RED salinity gradient power generation module, which is provided to be supplied to at least one of the seawater tank or the first influent tank.

A part of the seawater discharged from the first influent tank is supplied to the RED salinity gradient power generation module, and microorganisms present in the seawater are destroyed through an electrolysis reaction. 1 It may be arranged to flow into the influent tank and be recirculated.

The seawater after microorganisms are destroyed is supplied to the RED salinity gradient power generation module together with the seawater contained in the first influent tank, and the seawater after being supplied to the RED salinity gradient power module is supplied to at least one of the seawater tank and the first influent tank. can be provided.

The seawater tank may include a water treatment device capable of treating fish farms, purified water and wastewater.

On the other hand, in the RED salinity differential power generation module of the above-described circulating system, the RED salinity differential power module alternately forms a salt water channel and a fresh water channel, and an anode and a cathode are provided at both ends, respectively, but mutually It includes first and second end plates connected to a cation exchange membrane and an anion exchange membrane, a cathode and an anode, respectively, which are alternately disposed in a spaced apart state, and disposed at opposite positions, and inside the first and second end plates At least one electrode member is provided, and the electrode member is at least one of platinum/titanium mesh (Pt/Ti mesh), ruthenium (Ru), iridium (Ir), titanium (Ti), platinum (Pt), and carbon (C). can be provided.

At this time, the first and second end plates include a body in which a reaction chamber for electrode reaction is formed, at least one electrode member coupled to one end of the body, a housing coupled to the other end of the body, and the inside of the housing. It may include a current collector for adjusting the volume of the reaction chamber formed between the main body and the housing through coupling.

A housing coupling portion is formed on the inner surface of the body, a body coupling portion is formed on an outer circumferential surface of the housing, and the housing coupling portion and the body coupling portion may be coupled.

A current collector fastening part is formed on the inner surface of the housing, and the current collector has a support part having one surface formed flat to be in contact with the electrode member, and a gap adjusting part extending along the axial direction from the support part and coupled to the current collector fastening part on the outer circumferential surface. Including, the volume of the reaction chamber may be provided to vary according to the coupling area of the gap control unit to the current collector fastening unit.

In the housing, at least one mounting auxiliary member may be additionally provided at a position adjacent to the current collector fastening part.

In the reaction chamber, at least one gap maintaining member is additionally provided to maintain a minimum volume for reaction in the reaction chamber, and the gap maintaining member may be positioned between the main body and the housing.

The main body is provided with at least one gas discharge hole through which gas generated in the reaction chamber is discharged, and the gas discharge hole may communicate with the reaction chamber.

Hydrogen gas may be generated in the reaction chamber of the main body, and the generated hydrogen gas may be discharged through a gas discharge hole and collected in a separate tank communicating with the reaction chamber.

On the other hand, the above object is, according to the present invention, at least two or more influents are introduced, and a RED salinity gradient power generation module that generates power using the concentration difference of the inflow water flowing into the inside, seawater that accommodates seawater A first influent tank receiving seawater from a tank and a seawater tank and supplying the received seawater to the RED salinity differential power generation module as at least one of first influent or electrode solution, and a second influent having a salt concentration different from that of the first influent It is stored, and includes a second influent tank that supplies second influent to the RED salinity gradient power module, and the seawater supplied to the first influent tank is supplied to the RED salinity gradient power module to generate an oxidizer through an electrolysis reaction, The generated oxidant can be achieved by a circulation system using a RED salinity gradient power generation module that is prepared to be stored in a separate oxidant tank.

At this time, the seawater tank is provided as a wastewater treatment device, and the oxidizer stored in the oxidizer tank is injected into the water treatment device and can be used to kill microorganisms included in the wastewater treatment device.

In addition, the RED salinity gradient power generation module may be provided to generate an electrolysis reaction by being connected to a renewable energy system and receiving power.

The circulation system using the RED salinity gradient power generation module of the present invention can effectively remove organic and inorganic contaminants in influent water through seawater electrolysis using a carbon electrode member.

In addition, the circulation system using the RED salinity gradient power generation module of the present invention can change the volume of the reaction chamber by securing the distance between the electrode member and the current collector inside the RED salinity gradient power module, and generated in the reaction chamber It may be easy to discharge the reaction gas to the outside of the RED salinity gradient power generation module. Moreover, as the structure of the RED salinity gradient power generation module is simplified, the fastening method between the electrode member and the current collector becomes convenient, and accordingly, there is an advantage in that maintenance and repair are easy.

In addition, the circulation system using the RED salinity gradient power module can reduce the output of the RED salinity gradient power module by using natural sea water as an electrode solution and salt water and recycling it. The internal pH of the secondary power generation module is also significantly reduced.

The effects of the present invention are not limited to those mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

1 is a block diagram of a circulation system using a RED salinity gradient power generation module according to an embodiment of the present invention.
FIG. 2 is a diagram for briefly explaining the principle of removing organic/inorganic contaminants from influent water such as seawater/freshwater in a circulating system using the RED salinity gradient power generation module shown in FIG. 1. Referring to FIG.
FIG. 3 is a view for explaining a modification of the circulatory system using the RED salinity gradient power generation module shown in FIG. 1;
4 is a view for explaining the internal structure of the first and second end plates of the RED salinity gradient power generation module shown in FIGS. 1 and 3;
FIG. 5 is an exploded perspective view of the first and second end plates shown in FIG. 3 .
FIG. 6(a) is a photograph showing the inside of the first and second end plates shown in FIG. 3 before being coupled, and FIG. 6(b) is a RED salinity gradient power module that has been coupled in FIG. 6(a) is a perspective view of
7 is a photograph showing an experimental configuration for examining performance according to the output, oxidant generation result, long-term operation result, water treatment sterilization, and seawater reuse number using a circulation system using the RED salinity gradient power generation module shown in FIG.
8 and 9 are graphs and photographs showing the output and oxidant generation results generated by the circulation system using the RED salinity gradient power generation module shown in FIG. 1.
Figure 10 (a) is a graph showing the results of long-term operation of the circulation system using the RED salinity gradient power generation module shown in FIG. It is a diagram showing the inside of the RED salt gradient power generation module according to the long-term operation of
11 is a graph showing sterilization results through a circulation system using the RED salinity gradient power generation module shown in FIG. 1.
12 is a graph showing the output and pH of the RED salinity gradient power generation module according to the number of times (cycles) of seawater reuse in the circulating system using the RED salinity gradient power generation module shown in FIG.
FIG. 13 is a view showing the result of long-term operation optimization through response surface analysis statistical modeling of the RED salinity gradient power generation module according to the long-term operation of the circulating system using the RED salinity gradient power generation module shown in FIGS. 9 and 10 .
14 is a graph showing the mortality rate of microorganisms in seawater according to a modified example of the circulatory system using the RED salinity gradient power generation module shown in FIG. 3.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. This invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

It is advised that the drawings are schematic and not drawn to scale. Relative dimensions and proportions of parts in the drawings are shown exaggerated or reduced in size for clarity and convenience in the drawings, and any dimensions are illustrative only and not limiting. And like structures, elements or parts appearing in two or more drawings, like reference numerals are used to indicate like features.

The embodiments of the present invention specifically represent ideal embodiments of the present invention. As a result, various modifications of the drawings are expected. Therefore, the embodiment is not limited to the specific shape of the illustrated area, and includes, for example, modification of the shape by manufacturing.

Hereinafter, with reference to FIGS. 1 to 14, a circulatory system (100, hereinafter referred to as a 'circulatory system') using a RED salinity differential power generation module according to an embodiment of the present invention will be described.

First, referring to FIGS. 1 and 2, the circulation system 100 according to an embodiment of the present invention includes a RED salinity differential power generation module 140, a seawater tank 110, a first influent tank 120, and a second It includes an influent tank 130.

The RED salinity gradient power generation module 140 generates power by using a difference in salt concentration of two or more influents.

At least two or more types of inflow water may flow into the RED salinity gradient power generation module 140, and for example, the first inflow water may be salt water (HC) and the second inflow water may be fresh water (LC).

Salt water means a solution with a relatively high concentration of salt, and fresh water means a solution with a relatively low concentration of salt compared to salt water.

The RED salinity gradient power generation module 140 receives first influent and second influent having different salt concentrations, and generates power using a difference in salt concentration between the first influent and the second influent.

For reference, in the RED salinity gradient power generation module 140 according to the present invention, the first influent may be influent having a higher pH than the second influent.

The seawater tank 110 is a part where seawater is accommodated.

Seawater accommodated in the seawater tank 110 is supplied to the first inlet water tank 120 .

The first inlet water tank 120 stores seawater supplied from the seawater tank 110 . At this time, the first influent tank 120 is connected to the RED salinity gradient power generation module 140.

In other words, seawater from which seawater is taken from the seawater tank 110 using the pump 112 and solids are removed through the housing filter 114 having a thickness of about 5 μm is stored in the first inlet water tank 120 .

The seawater stored in the first influent tank 120 is supplied to the RED salinity gradient power generation module 140 as at least one of the first influent HC and the electrode solution ERS using the pump 122.

The second influent tank 130 stores second influent having a salt concentration lower than that of the influent received in the first influent tank 120 .

The second influent tank 130 is connected to the RED salinity gradient generation module 140 and supplies the second influent LC to the inside of the RED salinity gradient generation module 140 using the pump 132 .

For reference, the second influent tank 130 collects fresh water (LC) such as river water or tap water using a pump (not shown), and stores fresh water from which solids are removed through a housing filter (not shown) of about 5 μm. do.

Meanwhile, as described above, part of the seawater stored in the first influent tank 120 is influent into the RED salinity gradient power generation module 140 as the electrode solution ERS.

Referring to FIG. 2, a high-concentration electrode solution (ERS) is supplied between the electrode members of the RED salinity gradient power generation module 140, that is, between the cation exchange membrane 143 and the anion exchange membrane 144 to generate electricity through oxidation and reduction reactions. After the decomposition reaction, it is effluent from the RED salt gradient power generation module 140 and circulated.

At this time, the seawater supplied to the electrode solution (ERS) is disinfected by generating an oxidizing agent by an electrolysis reaction, and flows into the first influent tank 120 in a disinfected state to be mixed with seawater stored in the first influent tank 120. do.

For reference, seawater supplied as an electrode solution (ERS) kills microorganisms, reduces total organic carbon and turbidity, and maintains a pH of about 7 to 8.

In addition, another part of the seawater stored in the first influent tank 120 is introduced into the RED salinity gradient power generation module 140 as the first influent, that is, brine (HC).

At this time, the first influent flowing into the RED salinity gradient power generation module 140 from the first influent tank 120 may include seawater in which microorganisms are killed by an electrolysis reaction inside the RED salinity gradient power generation module 140. .

The first inflow water introduced into the RED salinity gradient power generation module 140 as salt water circulates through the RED salinity gradient power generation module 140 . At this time, a part of the first influent that has passed through the RED salinity gradient power generation module 140 is recycled and flows back into the first influent tank 120, and the remaining part of the first influent flows into the seawater tank 110.

As described above, the circulation system 100 according to an embodiment of the present invention is a circulation-filtering type, and can have a closed type circulation structure.

The electrode solution (ERS) supplied to the RED salinity gradient power generation module 140 and the first influent are supplied to the RED salinity gradient power generation module 140 after using seawater introduced from the seawater tank 110 and removing microorganisms in the seawater By doing so, there is an effect of stabilizing the water quality of the first influent tank 120 . Moreover, as recycling and discharge are possible after being introduced into the RED salinity gradient power generation module 140, there is an effect of significantly reducing the water used in the RED salinity gradient power generation module 140.

Moreover, since the electrode solution (ERS) supplied to the RED salinity gradient power generation module 140 is not used separately from the first inflow water, but seawater contained in the seawater tank 110 is used, there is an advantage in energy saving.

Meanwhile, in the circulating system 100 according to an embodiment of the present invention, the seawater tank 110 may include various water treatment devices.

For example, the water treatment device may be any one of an indoor/outdoor aquaculture system, an indoor/outdoor smart-farm, an indoor/outdoor microalgae culturing system, and various upper/lower wastewater treatment devices, but is not necessarily limited thereto. For reference, the wastewater applicable to the wastewater treatment device may be domestic sewage, industrial wastewater, livestock wastewater, food wastewater, and the like.

As described above, seawater supplied from the seawater tank 110 to the RED salinity gradient power generation module 140 through the first influent tank 120 is electrolyzed for electrode reaction inside the RED salinity gradient power generation module 140 After being used, it may be introduced into the seawater tank 110 and circulated to be recycled.

Meanwhile, at least one meter (150, potentiostat) may be connected to the RED salinity gradient power generation module 140.

The meter 150 is for testing and observing the electrochemical reaction by applying an electrochemical constant potential and a constant current to the electrochemical sample during the electrolysis reaction in the RED salinity gradient power generation module 140 to measure the current or voltage.

For reference, the instrument 150 is mainly applied to a small RED salinity gradient power module, a potentiostat that performs reaction voltage/current/resistance monitoring after applying a fixed voltage/current/resistance, and a large RED salinity gradient power module. applied and may be a source meter that performs monitoring of the reaction voltage/current/resistance after applying a fixed voltage/current/resistance, but is not necessarily limited thereto.

In addition, a controller 160 may be additionally connected to the meter 150 . The control device 160 may be for controlling the meter 150 and controlling the operation of the RED salinity gradient power generation module 140 .

In other words, the control device 160 can control the instrument 150 or monitor the result, can determine the degree of contamination of the RED salinity differential power generation module 140, and can record the data of the entire circulation system 100. may be

To this end, the control device 160 may be provided as a PC (personal computer) capable of recording data, but is not necessarily limited thereto.

Meanwhile, an oxidizing agent tank (not shown) may be connected to the circulation system 100 according to an embodiment of the present invention.

For reference, the oxidant tank may be connected to the RED salinity gradient power generation module 140, but is not necessarily limited thereto.

Referring to FIG. 3 , when seawater supplied to the RED salinity gradient power generation module 140 through the first influent tank 120 undergoes an electrolysis reaction, an oxidizing agent is generated. At this time, the generated oxidizing agent may be stored in a separately connected oxidizing agent tank (not shown).

The resulting oxidizing agent may be HOCl ^- (hypochlorous acid) or OCl (hypochlorite), but is not necessarily limited thereto.

The oxidizing agent stored in the oxidizing agent tank may flow into the seawater tank 110 as needed.

If the seawater tank 110 is provided as an upper/lower wastewater treatment device, when the oxidizing agent stored in the oxidant tank is injected into the seawater tank 110, it can be used to kill microorganisms included in the upper/lower wastewater treatment device. .

Here, the oxidizing agent stored in the oxidizing agent tank may be used to kill microorganisms using a method of separately injecting into the upper and lower wastewater treatment devices, but is not necessarily limited thereto.

Meanwhile, with reference to FIGS. 2, 4 and 5, the structure of the RED salinity gradient power generation module 140 used in the circulation system 100 according to an embodiment of the present invention will be briefly described.

Referring to FIG. 2, the RED salinity gradient power generation module 140 includes at least one cation exchange membrane 143, an anion exchange membrane 144, a cation exchange membrane 143, and an anion exchange membrane 144. It includes first and second end plates 141 and 142 connected thereto.

The RED salinity gradient power generation module 140 has a form in which at least one cation exchange membrane 143 and an anion exchange membrane 144 are alternately disposed.

The cation exchange membrane 143 selectively passes only cations, and the anion exchange membrane 144 selectively passes only anions.

The cation exchange membrane 143 and the anion exchange membrane 144 are alternately disposed one by one to form a plurality of channels (not shown).

For reference, although not shown in the drawings, at least one gasket (not shown) may be provided between the cation exchange membrane 143 and the anion exchange membrane 144.

In general, the gasket may be used to change the flow of salt water (HC, or first influent) and fresh water (LC, or second influent).

In addition, at least one spacer (not shown) may be provided on an inner portion of the gasket. At least a portion of the spacer may be provided in a mesh form, but is not necessarily limited thereto.

In the case of the gasket and the spacer, it is possible to prevent the cation exchange membrane 143 and the anion exchange membrane 144 from contacting each other while forming a channel through which salt water (HC) and fresh water (LC) can flow.

At this time, at least one end plate 141 or 142 is provided at both ends of the cation exchange membrane 143 and the anion exchange membrane 144 .

The first end plate 141 and the second end plate 142 are provided at opposite positions. For reference, the first end plate 141 is connected to an anode, and the second end plate 142 is connected to a cathode (not shown).

Meanwhile, the first influent (or salt water, HC) and the second influent (or fresh water, LC) flowing into the RED salinity gradient power generation module 140 may have a co-flow form.

In the case of having a co-flow form, the first influent and the second influent flow in the same direction.

That is, the first influent and the second influent flow into the RED salinity gradient power generation module 140 in the same direction, react with the electrode inside through the electrode member 1420, and then change the flow direction together and discharge to the outside.

Since the first influent and the second influent flowing into the RED salinity gradient power generation module 140 have different salt concentration differences, a mixture of the second influent of the low-concentration solution and the high-concentration solution is formed between the cation exchange membrane 143 and the anion exchange membrane 144. The first influent passes alternately. Exchange of cations or anions is performed by the first influent and the second influent having different concentrations flowing into the cation exchange membrane 143 or the anion exchange membrane 144.

In other words, sodium ions (Na ⁺ ) of the first influent pass through the cation exchange membrane 143 that selectively passes only cations and diffuse from the first influent to the second influent, and the chloride ions (Cl ⁻ ) of the first influent are After passing through the anion exchange membrane 144 that selectively passes only negative ions, sodium ions diffuse from the first influent to the second influent in the opposite direction to that of sodium ions. As a result, voltage is generated as the side where sodium ions are concentrated is positive (+) and the side where chloride ions are concentrated is negative (-).

That is, an oxidation reaction occurs at the anode connected to the first end plate 141 to generate electrons, and the generated electrons move to the cathode connected to the second end plate 142 . A reduction reaction occurs at the cathode connected to the second end plate 142 and electrons are absorbed, resulting in a flow of electrons and current (I, in the shape of a fluorescent lamp in FIG. 2 ) is generated. A value obtained by multiplying the generated current (I) by the voltage (V) generated inside the RED salinity gradient generation module 140 may be the magnitude of electrical energy produced by the RED salinity gradient generation module 140.

An oxidation electrode reaction occurs in the first end plate 141 .

Here, the oxidation electrode reaction is divided into an electrode surface reaction (electrochemical reaction) and an electrode solution phase reaction, and the reaction equation generated at the interface in the first end plate 141, that is, the electrode surface reaction (electrochemical reaction) is same.

[Scheme 1]

2H ₂ O -> O ₂ + 4OH ⁺ + 4e ^-

2Cl ^- -> Cl ₂ + 2e ^-

A reaction formula by chemicals generated at the interface of the first end plate 141, that is, an electrode solution phase reaction (chemical equilibrium reaction) is as follows. At this time, the electrode solution phase reaction (chemical equilibrium reaction) refers to a reaction that occurs when a product generated after an electrode reaction is diffused into a solution.

[Scheme 2]

Cl ₂ + 2NaOH -> NaOCl + Cl ^_ + Na ⁺ + H ₂ O

NaOCl + H ₂ O -> HOCl <-> H ⁺ + OCl ^-

2OCl ^- -> O ₂ + 2Cl ^-

Here, the electrode member used for the oxidation reaction may be a noble metal such as platinum/titanium mesh (Pt/Ti mesh), ruthenium (Ru), iridium (Ir), titanium (Ti), and platinum (Pt), but is necessarily limited thereto. it is not going to be

As such, the chlorine-based disinfectant is generated by the oxidation reaction occurring in the first end plate 141 .

That is, sodium hypochlorite (NaOCl) is generated by an oxidation reaction in the first end plate 141, the site can be disinfected, and ammonia nitrogen can be removed.

In addition, a cathode reaction occurs in the second end plate 142 . At this time, the reaction formula is as follows.

[Scheme 3]

O ₂ + 2H ⁺ + 2e ^- -> H ₂ O ₂ (Carbon)

2H ₂ O + 2e ^- -> H ₂ + 2OH ^-

OCl ^- + H ₂ O + 2e ^- -> Cl ^- + 2OH ^-

Here, the electrode member used in the oxidation electrode reaction is selected from precious metals such as platinum/titanium mesh (Pt/Ti mesh), ruthenium (Ru), iridium (Ir), titanium (Ti), and platinum (Pt) or carbon (C). At least one may be provided, but is not necessarily limited thereto.

Hydrogen peroxide (H ₂ O ₂ ) is generated in the seawater by the reduction electrode reaction occurring at the second end plate 141, chlorine (Cl) remaining in the seawater can be removed, and the site can be disinfected.

Moreover, it has the advantage of filtering particulate organic matter in seawater and neutralizing pH.

Referring to FIGS. 4 and 5 , the first and second end plates 141 and 142 include a body 1410 , an electrode member 1420 , a housing 1440 and a current collector 1430 .

The body 1410 has a reaction chamber 1414 for electrode reaction formed therein.

In addition, at least one electrode member 1420 is coupled to one end of the main body 1410 .

To this end, an electrode member seating groove 1415 may be formed at one end of the main body 1410 .

At least one electrode member 1420 may be provided, and the number of electrode members 1420 positioned inside the main body 1410 may vary according to the required number.

When a plurality of electrode members 1420 are provided, the plurality of electrode members 1420 may overlap one end of the main body 1410 .

For reference, the electrode member 1420 may have a thickness of several tens of millimeters (mm) to several tens of centimeters (cm), and accordingly, the number of electrode members 1420 may vary.

For example, the electrode member 1420 may be provided as a multi-electrode of about 1 to 10 sheets, and accordingly, the number of electrode members 1420 may vary.

Furthermore, the electrode member 1420 may include contaminated electrodes such as organic/inorganic contamination, damage, or old electrodes, and accordingly, the number of electrode members 1420 may vary.

As described above, the shape of the electrode member seating groove 1415 formed in the main body 1410 may vary depending on the number of electrode members 1420, and the shape of the electrode member seating groove 1415 is not limited thereto. .

That is, the electrode member 1420 can be conveniently replaced and removed during operation/stop of the RED salinity differential power generation module 140 according to the material, thickness, number of electrodes (multi-electrode) or number of contaminated electrodes (contaminated electrode), etc. There are possible advantages.

A gas discharge hole 1412 may be provided in the main body 1410 .

The gas discharge hole 1412 is for discharging a reaction gas generated during an electrode reaction within the reaction chamber 1414 from the reaction chamber 1414 .

Accordingly, the gas discharge hole 1412 is provided to communicate with the reaction chamber 1414, so that the gas generated inside the reaction chamber 1414 can be more quickly discharged to the outside of the reaction chamber 1414.

Here, in the reaction chamber 1414 of the main body 1410, the reaction gas generated during the electrode reaction process may include hydrogen gas. In particular, hydrogen gas is generated on the reduction reaction side of the electrode reaction of the main body 1410 .

Although not shown in the drawing, the generated hydrogen gas may be separately collected in a collection tank (not shown) connected to the reaction chamber 1410 through the gas discharge hole 1412 . There is an advantage in that the hydrogen gas collected in the collection tank can be used as an energy source.

A housing 1440 is coupled to the other end of the body 1410.

The housing 1440 is coupled to the inside of the other end of the body 1410.

To this end, the housing coupling part 1411 is formed on the inner surface of the main body 1410, and the main body coupling part 1441 is formed on the outer circumferential surface of the housing 1440.

The housing coupling portion 1411 formed on the main body 1410 and the body coupling portion 1441 formed on the outer circumferential surface of the housing 1440 are formed in the form of a screw thread and coupled to each other.

Meanwhile, at least one mounting auxiliary member 1446 may be coupled to an outer circumferential surface of the housing 1440 .

The mounting auxiliary member 1446 is provided at a position adjacent to the body coupling part 1441 formed on the outer circumferential surface of the housing 1440 .

As shown in (a) of FIG. 6, when the housing 1440 is coupled to the main body 1410, the mounting auxiliary member 1446 is primarily pressed and coupled to the main body 1410, and after coupling, the main body ( The housing coupling portion 1411 of the housing 1410 is coupled to the main body coupling portion 1441 of the housing 1440 . Due to this, coupling of the housing 1440 to the main body 1410 can be made more convenient.

As shown in (b) of FIG. 6, since the mounting auxiliary member 1446 is provided at a position adjacent to the body coupling part 1441 on the outer circumferential surface of the housing 1440, the housing 1440 is attached to the body 1410. After being coupled, the gap between the housing 1440 and the main body 1410 can be covered.

At least one or more flow channels 1443 and 1444 may be formed in the housing 1440 .

The flow passages 1443 and 1444 formed in the housing 1440 include an inflow passage 1443 and a reaction chamber 1414 for allowing at least one inflow water to flow in for an electrode reaction with the electrode member 1420 inside the reaction chamber 1414. ) Includes a discharge passage 1444 for discharging the influent after the reaction from the inside.

In this case, the inlet passage 1443 and the outlet passage 1444 may be formed at a predetermined interval from each other along the longitudinal direction of the housing 1440 .

A gap maintaining member 1450 may be additionally provided inside the main body 1410 .

The gap maintaining member 1450 is for maintaining a minimum volume of the reaction chamber 1414 and may be provided between the housing 1440 coupled to the main body 1410 and the main body 1410 .

Although at least one space maintaining member 1450 may be included, it is preferable to provide one each on the upper and lower sides along the width direction of the reaction chamber 1414 .

In this way, even when the housing 1440 is coupled to the main body 1410 by using at least two space maintaining members 1450, the minimum volume of the reaction chamber 1414 for the electrode reaction may be maintained.

For reference, the minimum volume of the reaction chamber 1414 may vary according to the length of the gap maintaining member 1450 .

A current collector 1430 is positioned inside the main body 1410 .

The current collector 1430 is for adjusting the volume of the reaction chamber 1414 formed inside the main body 1410 .

The current collector 1430 passes through the inside of the housing 1440 and is coupled to adjust the volume of the reaction chamber 1414 formed between the body 1410 and the housing 1440 .

The current collector 1430 includes a support part 1432 and a space adjusting part 1434 .

One surface of the support portion 1432 is formed to be flat so as to come into contact with the electrode member 1420 stacked in an overlapping manner on the inside of the main body 1410 .

An end of the support portion 1432 has a shape that pushes the electrode member 1420 , and whether or not it contacts the electrode member 1420 may vary depending on a contact area with the housing 1440 .

The spacing adjusting part 1434 extends from the support part 1432 along the axial direction. The gap adjusting unit 1434 is a part coupled to the housing 1440 .

To this end, a current collector fastening part 1442 is formed on an inner surface of the housing 1440, and a gap adjusting part 1434 is coupled to the current collector fastening part 1442.

The volume of the reaction chamber 1414 of the main body 1410 may vary according to the fastening area of the gap control unit 1434 and the current collector fastening unit 1442 .

The gap control part 1434 is formed in the form of a screw thread on the outer circumferential surface of the current collector 1430 and the current collector fastening part 1442 is formed in the form of a screw thread inside the housing 1440, so that they are coupled to each other.

In addition, at least one O-ring 1460 may be provided at an end of the current collector 1430 .

Accordingly, it is possible to cover a gap between the gap adjusting part 1434 of the current collector 1430 and the current collector fastening part 1442 of the housing 1440 .

Experimental example

Output in the circulation system (100, hereinafter referred to as 'circulation system') using the RED salinity gradient power generation module, oxidant generation result, long-term operation result, performance according to the number of times of water treatment sterilization and seawater reuse, and RED salinity gradient power module ( 140) was used, and an experiment was conducted to find out the performance according to the results.

For reference, the experiment was conducted in a state set as shown in FIG. 7 .

8 and 9 are graphs showing output and oxidizing agent (SW) generation results generated by the circulation system 100 according to an embodiment of the present invention.

Tests on the output and oxidant generation of the circulating system 100 were performed when the electrode solution was 20% Pt/C/CC and acid-plasma/CC, respectively.

For reference, the experimental values are shown as experimental values consistent with the predicted level by RSM.

Comparison of time (time/hr) between the circulating system 100 including an electrode solution of 20% Pt/C/CC Ac and the circulating system 100 including an electrode solution of acid-plasma/CC In terms of short-term stability, the output was found to be higher in the circulating system 100 including the acid-plasma/CC electrode solution.

In addition, the time (time/hr) of the circulating system 100 including an electrode solution of 20% Pt/C/CC Ac and the circulating system 100 including an electrode solution of acid-plasma (Acid-plasma/CC) ), the concentration of hypochlorous acid (HClO concentration, mg/L) was found to be higher in the circulating system 100 containing the electrode solution, which is acid-plasma/CC.

10 to 13 are graphs showing the results of long-term operation of the circulation type system 100 according to an embodiment of the present invention.

For reference, when using natural seawater, stable power production was found to be more than 90%, and power generation was possible for approximately 60 days.

Referring to the graph of FIG. 10 (a), the first influent (salt water, HC) was found to have a stable output (black circled part in the graph) and pressure (bar) value (blue circled part in the graph).

In addition, referring to (b) of FIG. 10, even if the circulatory system 100 is operated for a long time, the inside of the RED salinity differential power generation module 140 is initially, 100h, 300h, 400h, 500h and 680h time It can be seen that even after this elapsed time, the inside is not contaminated and remains relatively clean.

Disinfection efficiency (%) through the circulation system 100 according to an embodiment of the present invention can be calculated through the following equation.

Referring to FIG. 11, the disinfection efficiency was ≧99.5±0.2% within 5 minutes, indicating that microorganisms were almost completely killed.

At this time, it was confirmed that the concentration of the generated chlorine-based oxidizing agent remained approximately 400 g/mL or less after about 600 hours.

12, according to the use and recycling (5 cycle) of natural seawater in the circulation system 100 according to an embodiment of the present invention, the output used in the RED salinity differential power generation module 140 is circulated It was found that it decreased sequentially according to the cycle, and the pH of the first influent also decreased sequentially.

On the other hand, in the circulation system 100 according to an embodiment of the present invention, the water quality change was tested when the electrolysis disinfection mode was maintained and the seawater circulation cycle was increased to 5 cycles.

The experimental results showed the pH, conductivity, microbial count, turbidity, and total organic carbon (TOC) of the first influent as shown in [Table 1]. For reference, the pH and conductivity of the second influent were shown in [Table 2].

The flow rate of the first influent HC flowing into the RED salinity gradient power generation module 140 is 100 ml/min, and the flow rate of the second influent LC is 100 ml/min.

Referring to [Table 1], it was found that the pH of the water quality of the seawater used as the first influent of the RED salinity gradient power generation module 140 was well maintained in neutral, and the conductivity was maintained at each cycle according to ion exchange It has been shown to decrease in the range of 10 to 30%.

The most important concentration of microorganisms in seawater was initially 2275 CFUs/mL, but was reduced by more than 99% with on-site electrolytic disinfection.

Turbidity was reduced within 50% at the time of 5 cycles, and total organic carbon was found to be reduced within 5%.

For reference, referring to [Table 2], in the case of fresh water (LC) used as the first influent of the RED salinity gradient power module 140, the pH is neutral and similar to that of seawater (HC) used as the first influent. and the conductivity was about 3.0 ~ 5.0 (ms/cm) for each cycle.

As shown in [Table 1] and [Table 2], the pH, conductivity, number of microorganisms, turbidity, and total organic carbon of the first influent decreased according to circulation and recycling after sterilization, but the second influent It was found that the pH and conductivity did not significantly decrease even if circulation and recycling were performed after sterilization.

Referring to FIG. 13, it is a diagram showing the result of statistical modeling of response surface analysis for optimization of the circulatory system 100 using the RED salinity gradient power generation module.

The predicted levels optimized by response surface analysis statistical modeling are shown in Table 3 below.

As shown in [Table 3], response surface analysis statistical modeling was performed using the circulation system 100 under operating conditions to derive maximum output, maximum disinfection efficiency, and shortest treatment time. As a result, the current density of the circulating system 100 was 30 A/m ² , the flow rate was 424 mL/min, and the treatment time was 6.7 min. In addition, the maximum output of the circulating system 100 under the conditions was 0.24 W, the pH was 8, the disinfection efficiency was 99.5%, and the chlorine oxidizing agent showed performance of 38 mg/L.

On the other hand, referring to FIG. 14, the disinfection efficiency in the circulation system 100 according to the embodiment of the present invention shown in FIG. appear. In addition, the microbial death rate was found to continuously maintain 99% or more from 20% or more.

According to the above configuration, according to the present invention The circulation system 100 using the RED salinity gradient power generation module can effectively remove organic and inorganic contaminants in influent water through seawater electrolysis using a carbon electrode member.

In addition, the circulation system 100 using the RED salinity gradient power generation module of the present invention can change the volume of the reaction chamber by securing a gap between the electrode member and the current collector inside the RED salinity gradient power module, and in the reaction chamber It may be easy to discharge the reaction gas generated in RED to the outside of the salinity gradient power generation module. Moreover, as the structure of the RED salinity gradient power generation module is simplified, the fastening method between the electrode member and the current collector becomes convenient, and accordingly, there is an advantage in that maintenance and repair are easy.

In addition, the circulation system 100 using the RED salinity gradient power generation module of the present invention uses natural sea water as an electrode solution and brine and recycles it, thereby reducing the output of the RED salinity gradient power module and the internal pH of the RED salinity gradient power generation module is also significantly reduced.

As described above, in one embodiment of the present invention, specific details such as specific components and limited embodiments and drawings have been described, but this is only provided to help a more general understanding of the present invention, and the present invention is based on the above embodiments. It is not limited, and those skilled in the art can make various modifications and variations from these descriptions. Therefore, the spirit of the present invention should not be limited to the described embodiments and should not be determined, and all things equivalent or equivalent to the claims as well as the following claims belong to the scope of the present invention.

100: circulation system
110: sea water tank
120: first influent tank
130: second influent tank
140: RED salinity gradient power generation module
141, 142: first and second end plates
143,144: cation exchange membrane, anion exchange membrane
1410: body
1420: electrode member
1430: entire collector
1440: housing
1450: spacing maintaining member
1460: O-ring
150: instrument
160: control device

Claims (15)

A RED salinity gradient power generation module for generating electric power using a concentration difference of at least two kinds of inflow water and a concentration difference of the inflow water flowing into the inside;
a seawater tank for accommodating seawater;
A first influent tank for receiving seawater from the seawater tank and supplying the received seawater to the RED salinity gradient power module as at least one of the first influent or an electrode solution; and
a second influent tank for storing second influent having a salt concentration different from that of the first influent and supplying the second influent to the RED salinity gradient power generation module;
Including,
The seawater supplied to the first influent tank is supplied to the RED salinity gradient power module as an electrode solution, or the seawater supplied to the first influent tank is supplied to the RED salinity gradient power module as the first influent, and then the seawater tank or the first influent tank Arranged to be supplied with at least one of them, a circulating system using a RED salinity gradient power generation module.
According to claim 1,
Part of the seawater discharged from the first influent tank is supplied to the RED salinity gradient power generation module, and microorganisms present in the seawater are destroyed through an electrolysis reaction,
A circulating system using a RED salinity gradient power module, in which seawater after microorganisms are destroyed is discharged from the RED salinity gradient power module and introduced into the first influent tank to be recycled.
According to claim 2,
The seawater after microorganisms are destroyed is supplied to the RED salinity gradient power generation module together with the seawater contained in the first influent tank, and the seawater after being supplied to the RED salinity gradient power module is supplied to at least one of the seawater tank and the first influent tank. Circulation system using RED salinity gradient power generation module.
According to claim 1,
The seawater tank is a circulatory system using a RED salinity gradient power generation module, including a water treatment device capable of processing farms, purified water and wastewater.
According to claim 1,
The RED salinity gradient power generation module,
A cation exchange membrane and an anion exchange membrane alternately forming salt water channels and fresh water channels, and having anodes and cathodes provided at both ends, but spaced apart from each other, alternately disposed; and
It includes first and second end plates connected to the cathode and the anode, respectively, and disposed opposite to each other;
At least one electrode member is provided inside the first and second end plates,
The electrode member is provided with at least one of platinum / titanium mesh (Pt / Ti mesh), ruthenium (Ru), iridium (Ir), titanium (Ti), platinum (Pt) and carbon (C), RED salinity differential power generation module circulatory system used.
According to claim 5,
The first and second end plates,
A main body in which a reaction chamber for electrode reaction is formed therein;
At least one electrode member coupled to one end of the body;
a housing coupled to the other end of the main body; and
A circulation system using a RED salinity differential power generation module, including a current collector coupled to the inside of the housing to adjust the volume of the reaction chamber formed between the body and the housing.
◈Claim 7 was abandoned when the registration fee was paid.◈ According to claim 6,
A housing coupling part is formed on the inner surface of the main body,
A body coupling portion is formed on the outer circumferential surface of the housing,
A circulation system using a RED salt gradient power generation module in which a housing joint and a main body joint are coupled.
According to claim 6,
A current collector fastening portion is formed on the inner surface of the housing,
the whole house,
a support portion having one surface flat to be in contact with the electrode member; and
It extends from the support part along the axial direction and includes a gap adjusting part coupled to the current collector fastening part on the outer circumferential surface,
A circulation system using a RED salinity gradient power generation module, in which the volume of the reaction chamber is prepared to vary according to the area of the gap control unit coupled to the current collector fastening unit.
◈Claim 9 was abandoned when the registration fee was paid.◈ According to claim 8,
in the housing,
At least one mounting auxiliary member is additionally provided at a location adjacent to the current collector fastening unit, a circulation system using a RED salinity gradient power generation module.
◈Claim 10 was abandoned when the registration fee was paid.◈ According to claim 6,
In the reaction chamber, at least one gap maintaining member is additionally provided so that a minimum volume for reaction in the reaction chamber is maintained,
The distance maintaining member is located between the main body and the housing, a circulation system using a RED salt gradient power generation module.
◈Claim 11 was abandoned when the registration fee was paid.◈ According to claim 6,
In the body,
At least one gas discharge hole is provided to allow gas generated in the reaction chamber to be discharged;
The gas discharge hole communicates with the reaction chamber, a circulating system using a RED salinity gradient power generation module.
◈Claim 12 was abandoned when the registration fee was paid.◈ According to claim 11,
Hydrogen gas is generated in the reaction chamber of the main body,
The generated hydrogen gas is discharged through the gas discharge hole and is arranged to be collected in a separate tank communicated with the reaction chamber.
A RED salinity gradient power generation module for generating electric power using a concentration difference of at least two kinds of inflow water and a concentration difference of the inflow water flowing into the inside;
a seawater tank for accommodating seawater;
A first influent tank for receiving seawater from the seawater tank and supplying the received seawater to the RED salinity gradient power module as at least one of the first influent or an electrode solution; and
a second influent tank for storing second influent having a salt concentration different from that of the first influent and supplying the second influent to the RED salinity gradient power generation module;
Including,
The seawater supplied to the first influent tank is supplied to the RED salinity gradient power generation module to generate an oxidizer through an electrolysis reaction,
The generated oxidant is prepared to be stored in a separate oxidant tank, a circulating system using a RED salinity gradient power generation module.
According to claim 13,
The seawater tank is provided as a wastewater treatment device,
The oxidizing agent stored in the oxidizing agent tank is injected into the water treatment device and used to kill microorganisms included in the wastewater treatment device, a circulation system using a RED salinity differential power generation module.
According to claim 13,
The RED salinity gradient power generation module is a circulatory system using the RED salinity gradient power generation module, which is connected to a renewable energy system to receive power and generate an electrolysis reaction.

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