KR20170036997A - An Electrode for Electrolysis of Ballast Water - Google Patents

An Electrode for Electrolysis of Ballast Water Download PDF

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KR20170036997A
KR20170036997A KR1020150136003A KR20150136003A KR20170036997A KR 20170036997 A KR20170036997 A KR 20170036997A KR 1020150136003 A KR1020150136003 A KR 1020150136003A KR 20150136003 A KR20150136003 A KR 20150136003A KR 20170036997 A KR20170036997 A KR 20170036997A
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metal oxide
electrode
present
ballast water
metal
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KR1020150136003A
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Korean (ko)
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KR101898536B1 (en
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김용태
박신애
이은경
신종혁
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(주)엘켐텍
부산대학교 산학협력단
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Priority to KR1020150136003A priority Critical patent/KR101898536B1/en
Priority to PCT/KR2016/010345 priority patent/WO2017052137A1/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B13/00—Conduits for emptying or ballasting; Self-bailing equipment; Scuppers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63J—AUXILIARIES ON VESSELS
    • B63J4/00—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63J—AUXILIARIES ON VESSELS
    • B63J4/00—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for
    • B63J4/002—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for for treating ballast water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/008—Originating from marine vessels, ships and boats, e.g. bilge water or ballast water

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Ocean & Marine Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Toxicology (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The present invention relates to a base electrode, And a catalyst layer disposed on the upper portion of the base electrode, wherein the catalyst layer is a first metal-second metal oxide alloy, and the first metal-second metal oxide alloy is used as a catalyst layer. By using the bifunctional effect, which is an interaction between the metal and the metal oxide, it is possible to promote the chlorine generating reaction by improving the activity.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an Electrode for Electrolysis of Ballast Water

The present invention relates to an electrode for ballast water electrolysis, and more particularly to a ballast water electrolysis electrode including a catalyst layer capable of promoting a chlorine generating reaction.

In general, ballast water refers to seawater filled in a ship for safe and efficient operation of the ship. When the cargo that the boat is loading is lowered, it floats on the water as much as the reduced weight, and accordingly, the higher the center of gravity, the more the left and right shake increase. When operating in this condition, it may lead to rollover accidents.

1 is a schematic view for explaining general ship equilibrium.

1, the ship 10 is provided with a water tank 12 in addition to the cargo tank 11 inside the hull, and is immersed in the water to some extent by keeping the center of gravity of the ship in the lower side with the ship ballast water .

Also, if there is a lot of cargo on one side of the vessel, the opposite ballast tank may be filled with water to balance the balance. Furthermore, ship equilibrium is also needed to improve the efficiency of the ship's operation, since the ship must be locked to a certain extent so that the propeller can operate below the surface of the water.

Such ballast water is essential for ship operation, but it is stigmatized as the main cause of destruction of marine ecosystems today, and various marine organisms contained in ship equilibrium can move to other coasts and disturb ecosystems.

For example, after unloading cargo from country A and then loading the country's seawater and discharging the sea water that has been loaded as ship equilibrium on the coast of country B, various creatures living in coast A move to the coast of country B , The marine life of exotic species from other countries disturb and destroy indigenous ecosystems.

Due to these problems, it has become mandatory to install a ship equilibrium water treatment system in new vessels built after 2012 and all vessels currently in operation after 2017. Effective technologies for ship equilibrium water treatment are therefore required.

Various treatment methods such as electrolysis (straight tube type, side stream type), ultraviolet ray (UV), ozone, filter method, centrifugation, heat treatment and the like have been proposed as common ship ballast water treatment technologies.

Recently, the most widely adopted method is the electrolysis method. In the direct direct electrolysis method, the ballast water is sterilized by direct disinfection by the hypochlorite (HClO, NaClO), OH radical or potential difference generated by electrolysis of seawater It is sterilized.

Conventional direct electrolysis uses an electrolytic process in which oxygen or chlorine is generated as in a seawater decomposition process, and uses an electrode active material such as iridium (Ir) or ruthenium (Ru), which is an oxide of a platinum group metal, A catalyst layer) is deposited on the surface of the electrode.

Electrode coated with a platinum group metal complex oxide such as iridium oxide as a catalyst layer has a relatively low overvoltage for oxygen generation and oxidizes the electrode toxic organic substance itself on the surface of the electrode and can maintain the integrity for a long time in an oxygen or chlorine solution atmosphere It is known as an insoluble electrode.

Such an insoluble electrode means an insoluble anode used in an atmosphere in which oxygen or chlorine is generated. Since it does not dissolve in a solution, it can be called a DSA (Dimensionally Stable Anode) electrode. It is also referred to as MMO (Mixed Metal Oxide) electrode.

At this time, catalyst layers such as the above-mentioned oxides of platinum group metals such as iridium (Ir) and ruthenium (Ru) are used for inducing high chlorine formation and reduction reaction, and therefore studies for improving the activity of these catalyst layers have been carried out There is no satisfactory outcome.

Therefore, it is necessary to develop a catalyst capable of promoting chlorine generation reaction through improvement of activity.

Korean Patent Publication No. 10-2013-0130504

It is an object of the present invention to provide a ballast water electrolysis electrode comprising a catalyst layer capable of promoting a chlorine generating reaction through activity improvement.

The objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

In order to solve the above-mentioned problems, the present invention provides a plasma display panel comprising: a base electrode; And a catalyst layer located above the base electrode, wherein the catalyst layer is a first metal oxide-second metal oxide alloy, and provides an electrode for ballast water electrolysis.

The first metal oxide may be selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Nb, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au, In, Sb and Pb The second metal oxide is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Cd, Hf, Ta, At least one selected from the group consisting of Pb, Bi, Sc, Y, Sr, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, An electrode for ship ballast water electrolysis, which is an oxide of one metal, is provided.

The present invention also provides an electrode for ballast water electrolysis wherein the first metal oxide is IrO 2 or RuO 2 and the second metal oxide is TiO 2 .

The present invention also provides a method of manufacturing a ship ballast water electrolysis electrode comprising a first metal oxide-second metal oxide alloy comprising a first metal oxide layer and a second metal oxide layer located above the first metal oxide layer, to provide.

The first metal oxide-second metal oxide alloy further comprises a first metal oxide layer and a second metal oxide island pattern located above the first metal oxide layer, wherein the first metal oxide- .

The first metal oxide-second metal oxide alloy may further comprise a first metal oxide island pattern and a second metal oxide island located above the first metal oxide island pattern. Thereby providing an electrode for ballast water electrolysis.

According to the present invention, by using the first metal oxide-second metal oxide alloy such as IrO 2 / TiO 2 alloy or RuO 2 / TiO 2 alloy as the catalyst layer, the interaction between the metal oxide and the metal oxide Bifunctional effect can be used to promote the chlorination reaction through improved activity.

1 is a schematic view for explaining general ship equilibrium.
2 is a cross-sectional view showing an electrode for ship ballast water electrolysis according to the first embodiment of the present invention.
3 is a cross-sectional view showing an electrode for ship ballast water electrolysis according to a second embodiment of the present invention.
4 is a cross-sectional view showing an electrode for ship ballast water electrolysis according to a third embodiment of the present invention.
5 is a view showing a catalyst layer according to an embodiment of the present invention.
6 is a graph showing the chlorine evolution reaction (ClER) of the catalyst layer according to Examples and Comparative Examples of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings. &Quot; and / or "include each and every combination of one or more of the mentioned items. ≪ RTI ID = 0.0 >

Although the first, second, etc. are used to describe various components, it goes without saying that these components are not limited by these terms. These terms are used only to distinguish one component from another. Therefore, it goes without saying that the first component mentioned below may be the second component within the technical scope of the present invention.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. The terms " comprises "and / or" comprising "used in the specification do not exclude the presence or addition of one or more other elements in addition to the stated element.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

The terms spatially relative, "below", "beneath", "lower", "above", "upper" And can be used to easily describe a correlation between an element and other elements. Spatially relative terms should be understood in terms of the directions shown in the drawings, including the different directions of components at the time of use or operation. For example, when inverting an element shown in the figures, an element described as "below" or "beneath" of another element may be placed "above" another element . Thus, the exemplary term "below" can include both downward and upward directions. The components can also be oriented in different directions, so that spatially relative terms can be interpreted according to orientation.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

2 is a cross-sectional view showing an electrode for ship ballast water electrolysis according to the first embodiment of the present invention.

2, the electrode 100 for ship ballast water according to the first embodiment of the present invention includes a base electrode 110 and catalyst layers 120 and 130 located above the base electrode 110, And the catalyst layers 120 and 130 are the first metal oxide-second metal oxide alloy.

At this time, the base electrode 110 is preferably a general Ti electrode, but the material of the base electrode is not limited in the present invention.

The first metal oxide-second metal oxide alloy 120, 130 is made of an alloy including a first metal oxide 120 and a second metal oxide 130, and the first metal oxide- Is an oxide of at least one metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Nb, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au, In, Sb, And the second metal oxide 130 may be at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Cd, Hf, Ta, W, In, An oxide of at least one metal selected from the group consisting of Sc, Y, Sr, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lt; / RTI >

At this time, the first metal oxide 120 is preferably IrO 2 or RuO 2 , and the second metal oxide 130 is preferably TiO 2 .

In addition, in the present invention, the first metal oxide-second metal oxide alloy 120, 130 may be manufactured by a heat treatment method using an inert gas, an arc melting method, an electroplating method, a synthesis method using an organic surfactant, However, the method of manufacturing the first metal oxide-second metal oxide alloy in the present invention is not limited thereto.

2, the first metal oxide-second metal oxide alloy of the electrode 100 for ship ballast water electrolysis according to the first embodiment of the present invention includes the first metal oxide layer 120 and the second metal oxide- And a second metal oxide layer 130 located on top of the first metal oxide layer 120.

That is, in the first embodiment of the present invention, the first metal oxide and the second metal oxide may be configured as a plate type.

As described above, in the conventional case, it is general to use an electrode manufactured by depositing an electrode active material (catalyst layer), which is an oxide of a platinum group metal such as iridium (Ir) or ruthenium (Ru), on the surface of a substrate made of metal titanium to be.

That is, catalyst layers such as iridium (Ir) and ruthenium (Ru), which are used for inducing high chlorine generation and reduction reactions, are unsatisfactory in improving the activity of the catalyst layer.

However, in the present invention, by using the first metal oxide-second metal oxide alloy such as IrO 2 / TiO 2 alloy or RuO 2 / TiO 2 alloy as the catalyst layer, the bifunctional effect of the interaction between the metal oxide and the metal oxide Can be used to promote the chlorine generation reaction through improvement of the activity.

3 is a cross-sectional view showing an electrode for ship ballast water electrolysis according to a second embodiment of the present invention. The electrode for ship ballast water electrolysis according to the second embodiment of the present invention may be the same as the first embodiment described above except for the following.

3, the ballast water electrolysis electrode 200 according to the second embodiment of the present invention includes a base electrode 210 and catalyst layers 220 and 230 located above the base electrode 210, And the catalyst layers 220 and 230 are a first metal oxide-second metal oxide alloy.

Since this is the same as described above, a detailed description will be omitted.

3, the first metal oxide-second metal oxide alloy of the electrode 200 for ship ballast water electrolysis according to the second embodiment of the present invention includes a first metal oxide layer 220 and a second metal oxide- And a second metal oxide island pattern 130 located on top of the first metal oxide layer 220.

That is, in the second embodiment of the present invention, the first metal oxide may be of a plate type, and the second metal oxide may be of an island type located on the first metal oxide layer.

4 is a cross-sectional view showing an electrode for ship ballast water electrolysis according to a third embodiment of the present invention. The electrode for ballast water electrolysis according to the third embodiment of the present invention may be the same as the first embodiment described above, except as described below.

4, the ballast water electrolysis electrode 300 according to the third embodiment of the present invention includes a base electrode 310 and catalyst layers 320 and 330 located above the base electrode 310, And the catalyst layers 320 and 330 are a first metal oxide-second metal oxide alloy.

Since this is the same as described above, a detailed description will be omitted.

4, the first metal oxide-second metal oxide alloy of the electrode 300 for ship ballast water electrolysis according to the third embodiment of the present invention has a first metal oxide island pattern And a second metal oxide island pattern 130 located on top of the first metal oxide island pattern 220.

That is, in the third embodiment of the present invention, the first metal oxide is of an island pattern type, and the second metal oxide is an island (e.g., Island) type.

Hereinafter, preferred experimental examples according to the present invention will be described.

[Example]

Iridium polycrystalline was used as the first metal of the first metal oxide and titanium isopropoxide was used as the second metal oxide. 20 mu l of the 0.05 M solution of the second metal oxide precursor was loaded on the surface of the first metal and dried.

Thereafter, the catalyst layer was heat-treated with a H 2 Ar mixed gas to obtain a catalyst layer in which the second metal oxide was located on the first metal oxide.

[Comparative Example]

As the catalyst layer, an IrO 2 plate was used.

5 is a view showing a catalyst layer according to an embodiment of the present invention.

As shown in FIG. 5, it can be seen that TiO 2 is loaded on the upper part of the IrO 2 plate as an island type.

6 is a graph showing the chlorine evolution reaction (ClER) of the catalyst layer according to Examples and Comparative Examples of the present invention.

First, in the case of a catalyst layer in which TiO 2 is loaded in an island type on the top of an IrO 2 plate in the embodiment of the present invention, the interaction between the first metal oxide and the second metal oxide And the bifunctional effect is observed.

That is, as can be seen from FIG. 6, in the case of the embodiment according to the present invention, the chlorine evolution reaction is performed as compared with the comparative example according to the present invention, that is, the IrO 2 plate is used as the catalyst layer. It can be confirmed that the activity is remarkably improved.

As described above, in the present invention, by using the first metal oxide-second metal oxide alloy such as IrO 2 / TiO 2 alloy or RuO 2 / TiO 2 alloy as the catalyst layer, Using the bifunctional effect, it is possible to promote the chlorine generation reaction by improving the activity.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (6)

A base electrode; And
And a catalyst layer located above the base electrode,
Wherein the catalyst layer is a first metal oxide-second metal oxide alloy. The method according to claim 1,
The first metal oxide may be at least one selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Nb, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au, In, Sb, Of an oxide of a metal,
Wherein the second metal oxide is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Cd, Hf, Ta, W, In, Sb, Pb, Bi, Which is an oxide of at least one metal selected from the group consisting of Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Electrode. 3. The method of claim 2,
Wherein the first metal is IrO 2 or RuO 2 and the second metal oxide is TiO 2 . The method according to claim 1,
Wherein the first metal oxide-second metal oxide alloy comprises a first metal oxide layer and a second metal oxide layer located on top of the first metal oxide layer. The method according to claim 1,
Wherein the first metal oxide-second metal oxide alloy comprises a first metal oxide layer and a second metal oxide island pattern located on top of the first metal oxide layer. The method according to claim 1,
Wherein the first metal oxide-second metal oxide alloy comprises a first metal oxide island pattern and a second metal oxide island pattern located on top of the first metal oxide island pattern. Electrodes for ballast water electrolysis.
KR1020150136003A 2015-09-25 2015-09-25 An Electrode for Electrolysis of Ballast Water KR101898536B1 (en)

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KR1020150136003A KR101898536B1 (en) 2015-09-25 2015-09-25 An Electrode for Electrolysis of Ballast Water
PCT/KR2016/010345 WO2017052137A1 (en) 2015-09-25 2016-09-13 Electrode for ballast water electrolysis

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Publication number Priority date Publication date Assignee Title
KR20210064728A (en) * 2019-11-26 2021-06-03 (주) 테크로스 Ruthenium-zirconium based catalytic electrode for electrolysis of ballast water and preparation method thereof

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