TW201442917A - Layered structure for use as anode on a carrier submerged surface - Google Patents

Abstract

The present invention relates to a layered structure for use as anode on a carrier submerged surface, mainly comprising an electro catalyst layer to be disposed on the carrier submerged surface (such as the hull portion located below the waterline), the material of the electro catalyst layer is selected from one of the following groups: ruthenium doped oxide, manganese mixed oxide or bismuth mixed oxide. When such a layered structure is provided on the submerged surface of a carrier and used as an anode, in conjunction with a cathode provided on the submerged surface and a power supply, it can provide electro catalyst gassing to produce hydrogen and oxygen gases, or chlorine and hydrogen gases on the surface. The gas micro-bubbles may be used to cover the surface of the hull to form a hydrophobic layer, so as to achieve stealth effects of reducing the sailing resistance and suppressing cabin noise. The electro catalyst catalysis can also generate hydroxyl free radicals of strong oxidizing power on the anode surface in order to prevent marine organism from attaching to the surface, without having to apply anti-rust coatings or marine organism prevention coatings.

Description

a layered structure that can be placed on the surface of the vehicle submerged portion as an anode

The present invention relates to a layered structure, and more particularly to a layered structure which can be provided on the surface of the water immersion portion of the carrier as an anode.

Although the annual fuel consumption of maritime transport accounts for only 5% of the world, but also accounted for 10% of global emissions (about 12.57x10 ⁶ and 10.54x10 ⁶ tons / year) of nitrogen oxides (NO _X) and sulfur compounds (SO _X) And 1.8% (4.38x10 ⁶ tons / year) of carbon dioxide. Ship energy conservation and control of exhaust emissions has been one of the main topics of continuous efforts of the maritime transport industry in the past decade. This issue is closely related to the resistance of the ship movement. Since the resistance of the ship's movement mainly includes frictional resistance and wave-making resistance, the two together account for 85%~95% of the resistance, and a small amount of eddy current loss is about 3%~5%, and the air resistance is about 2% (low speed ship). ) or 10% (high-speed boat), in which the frictional resistance can affect up to 90% of low-speed ships (15 mph), which shows that frictional resistance has a very important impact on the energy consumption of the ship.
For a long time, reducing the frictional resistance of ships during the movement to reduce the energy consumption required for ship propulsion has been an extremely important issue in ship fluid dynamics research. Various ways to reduce the frictional resistance of the hull are also the most environmentally friendly with the effect of reducing the resistance of the microbubbles. The microbubble drag reduction technology was first proposed by M. McCormick and R. Bhattacharya in the United States in 1973. The experiment was conducted to reduce the resistance of hydrogen by copper wire electrolysis. In 1985, N. Madavan applied compressed air through microbubbles of porous gas permeable plates. The resistance experiment obtained a drag reduction effect of up to 80%; later, H. Kato (1994) confirmed that the drag reduction effect of up to 80% was also achieved by the microbubble drag reduction study of the same experimental device.
Although the pioneering experiment of M. McCormick's electrolysis of hydrogen drag reduction in the United States has achieved a drag reduction effect of up to 80%, the electrolysis efficiency (electrochemical hydrogen evolution chemical energy and input electrical energy) is due to the use of non-electrocatalytic copper wire as the electrode material. The ratio is only about 4.3%, only the electrolysis hydrogen is used to reduce the resistance in the hull, and the energy of oxygen evolution is discarded, and the area of gas production (hydrogen) only accounts for less than 0.2% of the water immersion area, resulting in higher ship speed and more drag reduction effect. Low; while Chinese scholar Wu Shengru uses electrochemistry to synchronize hydrogen production between the anode and the cathode, which greatly increases the gas supply rate, but uses a disposable electrode material and the electrode coverage is low, resulting in low drag reduction effect and low commercial applicability. . In addition, if traditional electrolysis or electrochemical methods want to generate a large number of microbubbles, it is bound to greatly increase the heat convection effect and low electrolysis efficiency derived from energy consumption and current enhancement.
Nevertheless, the experimental results of M. McCormick prove that the effect of hydrogen evolution of hydrogen evolution is proportional to the hydrogen production rate and coverage area. This is because the electrolysis of hydrogen can stay in the boundary layer of the hull to effectively reduce the resistance. The method is effective, but the gas production rate of electrolysis is too low and the coverage area is too small, which is the main reason why the subsequent research cannot be broken.
In addition, humans have been aware of the attachment of marine organisms to the hull more than 2,000 years ago, which not only poses a hazard to the overall safety structure, but also increases the navigational resistance of the ship. Therefore, it has traditionally used mechanical anti-fouling means to regularly carry out the bottom and the ship. The attachment of the attached organism on the shell can effectively remove the adhesion of the microbial membrane to the marine organism, but it needs to be docked regularly, and it takes time and the economy is not ideal. In the 20th century, toxic antifouling coatings were widely used to release organisms that constitute microbial membranes by releasing toxic substances (biocide) to prevent microbial colonization, adhesion and growth in seawater. According to the data, about 70% of the merchant ships in the world at the beginning of the 21st century used tributyltin (TBT) toxic antifouling coatings, saving about $2.4 billion in fuel and related costs each year. However, the toxicity of TBT to the marine environment, marine life and human health is very obvious. Therefore, since January 1, 2008, the International Maritime Organization (IMO) has completely banned the use of ships worldwide to alleviate the marine environment. hurt.
However, the newly developed environmentally friendly coatings are very expensive, about 2-3 times that of conventional TBT antifouling paints. Therefore, antifouling technology or heterogeneous coatings different from antifouling coatings are still expected by many researchers. For example: Japan's Mitsubishi Heavy Industries conductive paint, China's 2007 invention patent I283162 "system and method for inhibiting marine organisms using conductive rubber coating" or 2002 invention patent 514680 "method and system for preventing sea organisms adhesion", all using anode Electrolysis of sea water Produces chlorine to poison microbial membrane-covered organisms to prevent microbial colonization, adhesion and growth in seawater, and consumes only about 0.1 W/m ² of energy. Free chlorine is a strong oxidant, which can stun or kill bacteria, spores and young people in the sea to achieve the effect of preventing bio-adhesion, but the hydrogen ion of the cathodic electrolysis causes hydrogen embrittlement of the steel hull or metal member ( Hydrogen embrittlement).
In another example, T. Nakayama of Japan (US Patent No. 6,197,168B1 and European Union Patent No. EP 0985639A1) uses a titanium nitride (TiN) film to alternately apply direct current of 1.0 V and -0.6 V (slightly lower than the voltage of electrolyzed chlorine gas). After 209 days of on-site seawater test results, it can effectively inhibit the attachment of marine organisms. The mechanism of inhibition is based on the micro-current and hydroxyl radicals (‧OH), which can destroy the microorganisms that sea creatures depend on, thus effectively inhibiting microorganisms. Membrane parasitic, common polluted sea creatures such as barnacles, tube worms and sea lice can not be attached and formed on the outer surface of the immersion water, but subsequent studies have found that titanium will be reduced and detached from the titanium nitride electrode, resulting in this The application of technology is subject to high manufacturing costs and low durability.
In fact, T. Nakayama's titanium nitride electrocatalyst-catalyzed hydroxyl radicals are derived from a small amount of titanium dioxide (TiO ₂ ) in titanium substrates, since TiO ₂ is a well-known photocatalyst oxide capable of catalytically catalyzing hydrogen and oxygen. Free radicals; while titanium nitride is a well-known nitride, not a well-known good catalyst oxide, so pure titanium nitride only has a small amount of electrical catalyst to catalyze the hydrogen radicals.
It can be seen from the above that since the material used for the anode is not a good electric catalyst, the gas generation efficiency is poor at the time of electrolysis, and the surface of the ship's shell cannot be effectively covered, and if a large amount of gas is generated, it is large. Increase energy consumption without cost. Titanium dioxide is a well-known photocatalyst oxide which can be used as an anode material. Although there is a chance to solve the above problems, the high titanium dioxide resistance is not an excellent electrocatalyst oxide, so the effect is still not good, especially in the catalytic catalytic hydrogen. In the case of oxygen free radicals, the power consumption is high and it is not enough to prevent the hull from being attached by sea creatures.

In view of the deficiencies of the prior art, the creators of the present invention believe that there should be a catalyst oxide having a better effect, which can be provided in the water immersion part of the vehicle (the water immersion part refers to a portion below the water line, and the vehicle is as Ship hull, oil rig, wind turbine platform, or wharf facility, etc., the following is a description of the carrier as the hull.) The surface is used as an anode, and the cathode layer is provided on the surface of the hull. After providing electric energy, it forms a circuit together with seawater, and has better electrolysis efficiency. It can electrolyze a large amount of oxygen and hydrogen, or chlorine gas and hydrogen gas to completely cover the surface of the ship's shell to form a hydrophobic layer. The effect of bubble reduction and cabin noise suppression, and the production of hydroxyl radicals with strong oxidizing power, can effectively prevent the antifouling function of marine organisms from attaching, and will not affect the marine ecology.
Accordingly, the creator of the present invention provides a layered structure which can be provided on the surface of the water immersion portion of the carrier as an anode, and can be sprayed on the surface of the hull by means of arc spraying to form an anode electric contact. The layered structure of the medium is combined with the surface of the hull provided with a foil-doped oxide, a foil-titanium alloy or a graphite-doped oxide to form a cathode surface, and then supplied with electric energy through a DC power supply to form an electrocatalyst with seawater. System (electrocatalysis).
Wherein, the anode electrical catalyst layer structure comprises an electric catalyst layer, and the material is selected from one of the group consisting of cerium doped oxide, manganese mixed oxide, or cerium mixed oxide. The antimony doped oxide is preferably doped with seawater resistant corrosion resistant oxides, such as antimony doped titanium tin oxide, antimony doped antimony tin oxide, antimony doped niobium tin oxide. Or yttrium doped titanium nickel oxide or the like. The cerium mixed oxide is preferably a mixed seawater resistant oxide such as titanium oxide or titanium tin oxide.
Therefore, the present invention creates an electrocatalytic function of tempering the layered structure by ruthenium, bismuth, or mixed manganese, and suppresses the material cost price thereof, and is disposed through the surface of the hull. In combination with the foregoing cathode layer and power supply, it can have the function of electrolyzing oxygen and hydrogen, or chlorine gas and hydrogen gas, and has better electrolysis effect than the prior art. The electrocatalyst can also catalyze free radicals with strong oxidizing power to inhibit sea creature fouling without any conventional rust and antifouling paint coating, and can switch the electrolysis gas or antifouling by adjusting the DC voltage value. The damage function, through the change of the current value to adjust the gassing volume, in response to the functional requirements of different work tasks on the surface of the hull.

(B). . . Ship

(C). . . Block

(D). . . Block

(1). . . Vehicle immersion department

(11). . . hull

(111). . . Submarine gate

(2). . . Layered structure

(twenty one). . . Electrocatalyst layer

(twenty two). . . Insulation

(twenty three). . . Titanium layer

The first drawing is a schematic view of the surface of the hull of the invention. The second drawing is a sectional view of the layered structure on the surface of the hull.

The construction, features and embodiments of the present invention will be described with the aid of the drawings, and the reviewers will have a better understanding of the present invention.
Please refer to the first figure and the second figure. The invention relates to a water immersion part (1) (such as, but not limited to, a ship's hull, oil rig, wind power generator). Platform, or terminal facilities, etc., and the submerged part is the part below the waterline. The following description uses the vehicle immersion part (1) as the hull (11), and the electrocatalyst seawater is the preferred embodiment. Description) The surface is a layered structure (2) as an anode, such as but not limited to a cathode layer disposed on the surface of the hull (11) and disposed on the surface of the hull (11) (preferably There is a distance from the anode, such as but not limited to being disposed in the block (D) or the sea floor door (111), and the material thereof is preferably selected from one of the following groups: foil doped oxide, foil titanium Alloys, or graphite oxides, and power supplies form a circuit with seawater.
Thereby, when the power supply is powered, the overall electrolysis efficiency is improved by the electric layer (21) in the layered structure (2), and the functions of oxygen and hydrogen, or chlorine and hydrogen are electrically deposited. , a hydrophobic surface can be formed to reduce seawater resistance, and since the bubble of the hydrophobic surface is similar to a spring with mass, it can resonate with the relative audio of the noise emitted by the cabin to suppress noise. According to research, different sizes The bubble suppressing ability is also different, and the inner diameter of 1 mm to 100 mm can suppress the noise of 30 Hz to 3000 Hz by 10 dB to 40 dB, so the hydrophobic surface has the effect of suppressing cabin noise, and also because of the electric catalyst layer (21). And the electrocatalyst catalyzes a hydroxyl radical having a strong oxidizing power to inhibit the surface of the hull (11) from being attached to the sea creature without applying conventional rust and antifouling paint, and The output voltage value of the power supply is changed to switch the electrolysis gas or the electrocatalyst function, or the output current value is changed to change the gas production volume of the electrolysis gas to meet various needs.
Further, the electrocatalyst layer (21) may be selected from one of the group consisting of cerium doped oxide, manganese mixed oxide, titanium oxynitride, or cerium mixed oxide. The doping described below means that the cerium accounts for 15 wt.% or less of the electric catalyst layer (21), and the mixing means that manganese or cerium accounts for more than 15 wt.% of the electric catalyst layer (21).
When the electrocatalyst layer (21) is an antimony doped oxide, the layered structure (2) is suitable for electrocatalyst gassing and surface antifouling, and preferably occupies the electric catalyst layer ( 21) 5wt.% ~ 15wt.%, wherein when the doping amount of germanium is high, the layered structure (2) is preferably used for gassing out of the electric catalyst, and the voltage value provided by the power supply is about When 1.1V ~ 1.25V, the electric catalyst can be used to analyze hydrogen and oxygen. When the voltage supplied by the power supply is about 1.30V ~ 1.50V, the electric catalyst can be used to separate chlorine and hydrogen. Moreover, when the doping amount of cerium is low, the layered structure (2) is preferably used for catalyzing free radicals of the electrocatalyst to prevent sea creature fouling, and at this time, the potential provided by the power supply is compared In terms of the reference voltage, it is preferably about 0.6V to 0.9V vs. SCE.
Further, in the above-mentioned cerium-doped oxide, the oxide is preferably a seawater-resistant oxide, and the seawater-resistant oxide is preferably selected from one of the group consisting of titanium tin oxide, titanium antimony oxide. , titanium antimony tin oxide, or titanium nickel oxide.
When the electrocatalyst layer (21) is a manganese mixed oxide, the layered structure (2) preferably provides an electrocatalyst to catalyze free radicals to prevent the function of marine biofouling, and manganese preferably accounts for 30 wt.% of the electrocatalyst layer (21). In the manganese mixed oxide, the oxide is preferably a seawater resistant oxide, and the seawater resistant oxide is preferably selected from one of the group consisting of titanium oxide or titanium oxynitride.
Then, when the electrocatalyst layer (21) is a cerium mixed oxide, the layered structure (2) preferably provides an electric catalyst to catalyze free radicals to prevent biofouling, and preferably 25 wt.% ~ 40 wt.% of the electrocatalyst layer (21). In the mixed oxide of the cerium, the oxide is preferably a seawater resistant oxide, and the seawater resistant oxide is preferably selected from the group consisting of titanium oxide or titanium tin oxide.
When the hull (11) has oxidative corrosion, the inner side of the electric catalyst layer (21) is preferably inner side of the hull (11) toward the hull (11). a system is provided of a thickness of 5μm ~ 30μm insulating layer (22), and the material of the insulating layer (22) is preferably selected from the group in one of the following: nitrogen dioxide _{(TiO 2-x N x,} x <0.2) Or chrome oxide for better insulation. If the purpose of the layered structure (2) is for electrowinning gas production, a titanium layer (23) is preferably provided between the insulating layer (22) and the electric catalyst layer (21) to improve gas production. Efficiency.
In addition, the creation of the present invention may also have the following embodiments depending on the purpose of use:
When the layered structure (2) is mainly used for electrolysis of hydrogen and oxygen, or chlorine and hydrogen, the titanium oxide (TiO _2-x N _x , x) of 5 μm ~ 30 μm is applied before the hull (11). <0.2) as the insulating layer (22), followed by coating a titanium layer (23) coated with a thickness of about 100 μm to 300 μm, and finally coating a 10 μm to 100 μm yttrium-doped titanium tin oxide ((Ru-SnTi) O ₂ ), thereby forming a layered structure (2) of titanium oxynitride, titanium layer (23), and yttrium-doped titanium tin oxide from the inside to the outside, thereby improving the overall electrolysis effect.
If the layered structure (2) is mainly used for catalytically catalyzing free radicals, then 5 μm ~ 30 μm of titanium oxynitride (TiO _2-x N _x , x) is first applied to the surface of the hull (11). <0.2) As the insulating layer (22), a titanium-manganese mixed oxide ((MnTi)O ₂ ) of 10 μm to 100 μm is further applied, thereby forming titanium oxynitride and titanium manganese from the inside to the outside. The layered structure (2) of the mixed oxide enhances the effect of the overall electrocatalyst catalyzing free radicals. In addition, the invention can also be implemented by applying 5 μm ~ 30 μm of titanium oxynitride (TiO _2-x N _x , x < 0.2) as the insulating layer (22) before the hull (11), and then Coating a layered structure (2) of 10μm ~ 100μm titanium oxynitride (TiN _x O _y , 1.6<x<1.8, 0.1<y<0.3) is also significant for improving the overall catalytic free radicals of electrocatalysts. effect.
It can be seen from the above that the layered structure (2) created by the present invention is used as an anode, and can be degassed by an electric catalyst to form a hydrophobic layer on the surface of the hull (11), and has microbubble drag reduction and suppression of the engine room. The effect of noise can improve the ship's (B) function of reducing navigation resistance and noise suppression. It can also be catalyzed by electrocatalyst to make the anode produce a strong oxidizing ability of hydroxyl radicals to prevent sea creatures from adhering to the surface of the hull (11) without applying any coating that prevents rust or prevents marine organisms from adhering. And provide great results for environmental protection.
In summary, the creation of the present invention is indeed in line with the industrial applicability, and is not found in the publication or public use before the application, nor is it known to the public, and has non-obvious knowledge, conforms to the patentable requirements, and is patented according to law. Application.
However, the above-mentioned statements are a preferred embodiment of the invention in the creation of the invention, and all the changes in the scope of the patent application according to the invention are within the scope of the claim.

(11). . . hull

(2). . . Layered structure

(twenty one). . . Electrocatalyst layer

(twenty two). . . Insulation

(twenty three). . . Titanium layer

Claims (10)

A layered structure for providing a surface of the water immersion portion of the carrier as an anode, comprising an electric catalyst layer disposed on the surface of the water immersion portion of the carrier, the material of the electric catalyst layer being selected from one of the following groups : cerium doped oxide, manganese mixed oxide, titanium oxynitride, or cerium mixed oxide. The layered structure which can be provided on the surface of the water immersion part of the carrier as an anode according to the first aspect of the patent application, wherein the electric catalyst layer is an erbium doped oxide, and the oxide is selected from one of the following groups. : titanium tin oxide, titanium antimony tin oxide, titanium antimony tin oxide, or titanium nickel oxide. As described in claim 2, the layered structure can be provided on the surface of the water immersion portion of the carrier as an anode, wherein 钌 accounts for 5 wt.% to 15 wt.% of the electric catalyst layer. The layered structure which can be provided on the surface of the water immersion part of the carrier as an anode according to the first aspect of the patent application, wherein the electric catalyst layer is a manganese mixed oxide, and the oxide is selected from one of the following groups: Titanium oxide, or titanium oxynitride. The layered structure can be provided on the surface of the water immersion part of the carrier as an anode as described in the fourth aspect of the patent application, wherein manganese accounts for 30 wt.% of the electric catalyst layer. The layered structure which can be provided on the surface of the water immersion part of the carrier as an anode as described in the first aspect of the patent application, wherein the electric catalyst layer is a cerium mixed oxide, and the oxide is selected from one of the following groups: Titanium oxide, or titanium tin oxide. The layered structure can be provided on the surface of the water immersion portion of the carrier as an anode as described in claim 6 of the patent application, wherein titanium accounts for 25 wt.% to 40 wt.% of the electric catalyst layer. The layered structure which can be disposed on the surface of the water immersion portion of the carrier as an anode, wherein the inner side of the surface of the water immersion portion of the carrier is defined as an inner side, and an inner side of the electric catalyst layer is provided with an insulation. Floor. The layered structure which can be disposed on the surface of the water immersion portion of the carrier as an anode, wherein the thickness of the insulating layer is 5 μm to 30 μm, and the material of the insulating layer is selected from the following groups. One: titanium oxynitride, or chromium oxide. The layered structure can be provided on the surface of the water immersion portion of the carrier as an anode according to the eighth aspect of the patent application, wherein a titanium layer is further disposed between the electric catalyst layer and the insulating layer.