SEA WATER ELECTROLYSIS SYSTEMS AND METHODS

专利摘要:
"seawater electrolysis system and method".is a seawater electrolysis device that is provided with an electrode (30) that includes an anode (a) that is made of titanium coated with a coating containing iridium oxide, a cathode (k), an electrolysis vessel main body (20) that houses the anode (a) and cathode (k), and a power supply unit (40) that passes a current between anode (a) and cathode (k) in such a way that an electric current density at the surface of anode (a) and cathode (k) is 20 a/dm2 or more, where the water electrolysis device of the sea electrolyzes the sea water in the main body of electrolysis vessel (20).
公开号:BR112013010763B1
申请号:R112013010763-4
申请日:2011-11-17
公开日:2022-01-11
发明作者:Hiroshi Mizutani；Hiroyuki TAKANAMI；Tatsuya Matsumura；Kenji Nakamura；Takashi Ike
申请人:Mitsubishi Heavy Industries Environmental & Chemical Engineering Co., Ltd；
IPC主号:

专利说明:

Field of Invention
[001] The present invention relates to a seawater electrolysis system having a seawater electrolysis device for generating hypochlorous acid by performing seawater electrolysis and also relates to a seawater electrolysis method. sea. Fundamentals of the Invention
[002] Thermal power plants, nuclear power plants, seawater desalination plants, chemical plants and others that use a large amount of seawater include parts in contact with seawater. Conventionally, deposition (adhesion) and proliferation of seaweeds and shells in these parts, for example, seawater inlets, piping, condensers and various types of coolers caused serious problems.
[003] In order to solve the problems described above, a seawater electrolysis device was proposed that performs the electrolysis of natural seawater to generate hypochlorous acid and fills the hypochlorous acid thus generated into a seawater inlet. , thus suppressing the deposition of marine growth (reference to Patent Document 1, for example).
[004] The seawater electrolysis device has such a structure in which anodes and cathodes, as electrodes, are arranged inside a cabinet-shaped electrolysis vessel main body to distribute seawater inside the vessel main body. of electrolysis. As seawater contains chloride ions and hydroxide ions, the electric current passing between the anodes and the cathodes produces chlorine at the anodes and sodium hydroxide at the cathodes. Then, the chlorine reacts with the sodium hydroxide to generate hypochlorous acid which is effective in suppressing the adhesion of marine growth.
[005] In general, an electrode, particularly an anode, that is disposed within an electrolysis vessel of the seawater electrolysis device is constructed using a titanium base plate that is coated with a platinum-dominant composite metal. (a platinum dominant coating material) (reference to Patent Document 2, for example).
[006] Although not yet practically available as a seawater electrolysis device, such a suggestion has been made that an iridium oxide-dominant composite metal, i.e., an iridium oxide-dominant coating material, be used as a material. coating for an anode for electrolysis (reference to Patent Document 3, for example).
[007] There is also known a seawater electrolysis device in which concentrated water that has a high salinity concentration is discharged from seawater concentrating equipment, such as a seawater desalination plant. , is used as treated water. Such a seawater electrolysis device is one in which the concentration of hypochlorous acid contained in the electrolyzed water produced by performing concentrated water electrolysis is increased to decrease electricity consumption, thus improving the efficiency of the seawater electrolysis device and also decrease the size of the seawater electrolysis device (reference to Patent Document 4, for example). [Prior Art Documents]
[008] [Patent Documents]
[009] [Patent Document 1] Japanese Patent No. 3389082
[010] [Patent Document 2] Japanese Unexamined Published Patent Application No. 2001-262388
[011] [Patent Document 3] Japanese Published Unexamined Patent Application No. H8-85894
[012] [Patent Document 4] Japanese Unexamined Published Patent Application No. H9-294986 Summary of the Invention Problem to be solved by invention
[013] In an electrode coated with a platinum-dominant coating material, due to influences from the oxygen generated in the vicinity of an anode and plates (calcium, magnesium, or similar) deposited in the vicinity of a cathode during electrolysis, the early erosion of the electrode takes place. Therefore, it is necessary to wash and replace the electrode frequently, resulting in increased maintenance costs.
[014] Furthermore, there is a tendency for chlorine to be generated more efficiently with an increase in the electric current density at the electrode surface. This tendency is also found in a case where concentrated seawater is introduced into the seawater electrolysis device to generate hypochlorous acid.
[015] However, the amount of oxygen generated in the vicinity of the anode and of plates deposited in the vicinity of the cathode is also increased with an increase in electrical current density, resulting in rapid electrode wear. As a result, in the electrode coated with a platinum-dominant coating material, it is impossible to increase the electric current density at the electrode surface. Thus, it was considered the technical common sense that the maximum value of electric current density is kept at approximately 15 A/dm2, for example.
[016] As described above, as it is necessary to keep the electrical current density low during electrolysis, the generation of hypochlorous acid from seawater in a sufficient amount requires the arrangement of many electrodes, resulting in increases in manufacturing costs. and an increase in device size.
[017] The present invention was produced in view of the problems described above, whose objective is to provide a seawater electrolysis device, a seawater electrolysis system and a seawater electrolysis method capable of improving durability. of electrodes and also to suppress the reduction of the effectiveness in the generation of chlorine. Solution to the problem
[018] The inventors have conducted research on an electrode for a seawater electrolysis device and have concluded that when an electric current is passed through an anode coated with an iridium oxide coating material at an electric current density that exceeds 15 A/dm2, it is effective in improving electrode resistance and also in suppressing reduced efficiency in generating chlorine in contrast to the technical common sense of conventional electrodes coated with a plant-dominant coating material.
[019] In other words, the seawater electrolysis device is provided with an electrode that includes an anode made of titanium which is coated with a coating material containing iridium oxide and a cathode, an electrolysis vessel main body housing the anode and cathode, and a power supply unit that passes an electrical current between the anode and the cathode in such a way that an electrical current density at the surface of the anode and that of the cathode is 20 A/dm2 or more .
[020] In the seawater electrolysis method of the present invention, seawater is distributed within the main body of the electrolysis vessel, an electric current is passed between the anode and the cathode in such a way that an electric current density on the surface of the anode and that of the cathode is 20 A/dm2 or more to electrolyze seawater inside the main body of electrolysis vessel.
[021] In the present invention, the electric current density at the electrode surface is 20 A/dm2 or more which is greater than a conventional electric current density of 15 A/dm2. So, hydrogen gas is generated at the cathode during electrolysis in a larger amount than a conventional case. An electrode washing effect is exerted due to the large amount of hydrogen gas, thus making it possible to prevent the deposition of manganese plates on the anode and the deposition of calcium, magnesium or similar plates on the cathode. Although the amount of oxygen generated in the vicinity of the anode increases, an iridium oxide is sufficiently resistant to oxygen, thus making it possible to prevent the electrode from eroding by oxygen.
[022] In the present invention, the electric current density at the anode surface and that of the cathode between which electric current is passed through the power supply unit can be included in a range of 20 A/dm2 or more and 40 A /dm2 or less. The electrical current density can preferably be included in a range of 20 A/dm2 or more and 30 A/dm2 or less.
[023] When the electric current density is excessively large, for example in excess of 40 A/dm2, the amount of plaque deposited on the anode and cathode exceeds the amount at which the hydrogen wash effect is effective. In contrast, in the present invention, an upper limit value of the electrical current density is set at 40 A/dm 2 and preferably at 30 A/dm 2 . So, it is possible to effectively develop the washing effect by hydrogen and also effectively prevent plaque deposition on anode and cathode.
[024] The seawater electrolysis device according to the present invention can be further (additionally) provided with one or more electrolysis vessel main bodies, one or a plurality of connecting pipes, each connecting an outlet port of seawater from one of the electrolysis vessel main bodies and a seawater inlet port from the other of the electrolysis vessel main bodies, and one or a plurality of degassing units for removing a gas within each of the pipelines of connection.
[025] With an increase in electrical current density, a liquid-to-gas ratio decreases due to hydrogen generated at the cathode, thus resulting in a reduction in the effectiveness in generating chlorine. In contrast, when gas, in particular hydrogen gas, is removed by the degassing unit installed in the connecting piping, it is possible to maintain the interior of the electrolysis vessel at a predetermined liquid-gas ratio or reduce and also prevent reduction. of effectiveness.
[026] The seawater electrolysis system according to the present invention is provided with the seawater electrolysis device according to the present invention described above and a concentration unit to raise the concentration of ions of chloride contained in seawater to be introduced into the main body of electrolysis vessel.
[027] The seawater electrolysis method, according to the present invention, increases the concentration of chloride ions contained in seawater that is subjected to electrolysis, distributes seawater with increased concentration of chloride ions chloride inside the electrolysis vessel main body, and generates an electric current between the anode and the cathode to electrolyze the seawater inside the electrolysis vessel main body.
[028] In the present invention, the concentrated water which has the increased concentration of chloride ions and electrical conductivity is introduced into the seawater electrolysis device. Furthermore, as an anode coating material contains an iridium oxide, it is possible to set the electric current density at the electrode surface to a high value, thus increasing the concentration of hypochlorous acid contained in the electrolyzed water produced. That is, by generating hypochlorous acid in an increased amount per unit area of the electrode, the electrode can be reduced in area to decrease the size of the device.
[029] In the present invention, the electric current density at the anode and cathode surface between which an electric current is passed through the power supply unit can be included in a range of 20 A/dm2 or more and 60 A /dm2 or less. The electrical current density can preferably be included in a range of 20 A/dm2 or more and 50 A/dm2 or less.
[030] When the electric current density is excessively large, for example in excess of 60 A/dm2, plaques are generated at the anode and cathode in such an amount that it exceeds the amount when the hydrogen wash effect is effective. In contrast, in the present invention, an upper limit value of the electrical current density is set at 60 A/dm 2 and preferably at 50 A/dm 2 . Thus, it is possible to effectively exert the hydrogen washing effect and also effectively prevent plaque deposition on the anode and cathode.
[031] The seawater electrolysis system of the present invention can be additionally provided with a hydrogen separation unit that separates hydrogen gas generated at the cathode from seawater after electrolysis. It is thus possible to more effectively exert the washing effect by the hydrogen gas and also effectively prevents the deposition of plaque on the anode and cathode.
[032] In the seawater electrolysis device according to the present invention, a tantalum oxide can be added to the coating material.
[033] Tantalum which is highly resistant to oxygen is added to the coating material, thus making it possible to improve the resistance to oxygen generated at the anode and more effectively prevent abnormal electrode erosion.
[034] In the seawater electrolysis device according to the present invention, it is acceptable for the electrode to include a plurality of double pole electrode plates in which a part thereof in a seawater distribution direction is given as the anode. and another part of these is given as the cathode, several groups of electrodes in which the double pole electrode plates are arranged with a gap in the distribution direction are arranged parallel to each other, and the double pole electrode plates in each of the Adjacently parallel electrode groups are arranged in such a way that the anode is opposite the cathode.
[035] As described above, the double pole electrode plates, each of which has the anode and cathode, are arranged in a concentrated manner, thus making it possible to downsize the device itself.
[036] Furthermore, as each of the double pole electrode plates is arranged along the direction of seawater distribution, there is no chance that the seawater distribution will be impeded. It is then possible to maintain a high flow velocity of seawater and also effectively prevent the deposition of plates on an electrode by seawater.
[037] Also, as the anode is opposite the cathode in each of the electrode groups that are adjacently parallel to each other, an electric current is passed between the anode and the cathode, thus making it possible to effectively electrolyze the seawater that is distributed. between the electrodes.
[038] In the seawater electrolysis device according to the present invention, a gap between the double pole electrode plates adjacent to each other in the distribution direction in each of the electrode groups can be eight times or more than a gap between electrode groups that are adjacently parallel to each other.
[039] When the gap between the double pole electrode plates adjacent to each other in the distribution direction is small, an electric current is generated which is distributed between the double pole electrode plates, i.e. a leakage current that contributes less for electrolysis. Leakage current becomes more apparent with an increase in electrical current density at the surface of an electrode. In contrast, as described above, by maintaining an appropriate gap between adjacent dual pole electrode plates in the distribution direction, leakage current generation can be suppressed to prevent a reduction in the effectiveness of seawater electrolysis.
[040] In the present invention, the seawater electrolysis device can be provided with a circulating flow path that mixes the seawater after electrolysis flowing from an outlet port of the electrolysis vessel main body with seawater before flowing into the electrolysis vessel main body from an inlet port.
[041] There are concerns that plates may deposit on the surface of an electrode with an increase in electrical current density. However, when seawater after electrolysis is mixed through the circulating flow path with seawater before electrolysis, it is possible to prevent plaque deposition on the electrode surface since seeding crystallization effects can be obtained. by plate compositions contained in seawater that has passed through the electrolysis vessel of the seawater electrolysis device. Effect of the Invention
[042] According to the present invention, it is possible to improve the resistance of an electrode and also suppress the reduction in the effectiveness in generating chlorine by preventing the deposition of plaques on the electrode. Brief Description of Drawings
[043] FIG. 1 is a diagram showing a first embodiment of a seawater electrolysis system in accordance with the present invention.
[044] FIG. 2 is a longitudinal cross-sectional view showing a seawater electrolysis device of the first embodiment.
[045] FIG. 3 is an enlarged view showing major parts of the seawater electrolysis device.
[046] FIG. 4 is a graph explaining a constant current control curve of a constant current control circuit in a power supply unit.
[047] FIG. 5 is a schematic view showing a second embodiment of a seawater electrolysis system in accordance with the present invention.
[048] FIG. 6 is a schematic view showing a modified example of the second embodiment.
[049] FIG. 7 is a schematic view showing a third embodiment of a seawater electrolysis system in accordance with the present invention.
[050] FIG. 8 is a schematic view showing a description of a hydrogen separator in the third embodiment.
[051] FIG. 9 is a graph showing the results of a test determining effectiveness in generating chlorine.
[052] FIG. 10 is a graph showing the results of a test determining electrode erosion. Detailed Description of the Invention
[053] Next, an explanation will be made of the first embodiment of the present invention with respect to FIG. 1 through FIG. 4.
[054] A 100A seawater electrolysis system of the first embodiment is such a system in which seawater is obtained from an inlet channel 1 through which seawater is distributed, the seawater electrolysis is carried out using a seawater electrolysis device 10 and then the seawater thus treated is filled into the inlet channel 1.
[055] The seawater electrolysis system 100A is, as shown in FIG. 1, supplied with the seawater electrolysis device 10, a storage tank 50, an inlet part 60, and a fill part 70. The seawater W that has been subjected to electrolysis by the electrolysis device of seawater 10 is stored in the storage tank 50. The inlet part 60 introduces the seawater W into the seawater electrolysis device 10 from the inlet channel 1. Then the filling part 70 fills the seawater W in storage tank 50 to inlet channel 1.
[056] As shown in FIG. 2, the seawater electrolysis device 10 includes an electrolysis vessel main body 20, an electrode support box 26, terminal blocks 28, 29, and a plurality of electrodes 30.
[057] The electrolysis vessel main body 20 is provided with a substantially tubular outer shell 21, the ends of which are open. An upstream cover portion 22 is installed at one end of the outer casing 21 to block the opening at one end. Also installed at the other end of the outer shell 21 is a downstream cover portion 24 to block the opening at the other end. The electrolysis vessel main body 20 is fixed for predetermined pressure resistance by the outer shell 21, the upstream lid part 22 and the downstream lid part 24.
[058] Furthermore, the upstream lid part 22 is provided with an inlet port 23 communicatively connecting through the inside and outside of the electrolysis vessel main body 20, and the downstream lid part 24 is provided with an outlet port 25 communicatively connecting through the interior and exterior of the electrolysis vessel main body 20. That is, into the electrolysis vessel main body 20, seawater W is introduced from the inlet port 23 from the upstream cover part 22 and distributed in one direction inside the outer casing 21 from the inlet port 23 to the outlet port 25. Then, seawater W flows from the outlet port 25 out of the main body of electrolysis vessel 20. Next, the side of the inlet port 23 within the electrolysis vessel main body 20 is called upstream, while the side of the outlet port 25 is called downstream.
[059] The electrode support box 26 is a tubular member made of an electrically insulating material such as plastic and housed within the main body of electrolysis vessel 20 so as to extend in the seawater distribution direction W. The electrode support box 26 is attached to the upstream cover portion 22 and to the downstream cover portion 24 by means of a plurality of fasteners 27. Furthermore, a plurality of support bars 26a for supporting the electrodes 30 are provided. installed inside the electrode holder box 26.
[060] The terminal blocks 28, 29 have functions to supply an electrical current to the electrodes 30 supported inside the electrode support box 26 from the outside of the electrolysis vessel main body 20, and they are arranged in pairs on both sides of electrode holder box 26.
[061] The electrode 30 is formed in the form of a plate, and a plurality of electrodes 30 are fixed and supported in arrangement on the support bar 26a in the electrode holder box 26. In the present embodiment, three are used as the electrodes 30 types of plates, i.e. a double pole electrode plate 31, an anode plate 32 and a cathode plate 33.
[062] The double pole electrode plate 31 is structured in such a way that a titanium base plate as an electrode plate is made up of two parts, one of which is given as an anode A and the other is given as a cathode. K. That is, a half on one side of the double pole electrode plate 31 is constituted as anode A coated with an iridium oxide-containing coating material (Iridium oxide dominant coating material), while a half on the other side of electrode plate 31 is constituted as the cathode K uncoated with the dominant iridium oxide coating material.
[063] Furthermore, anode plate 32 is structured in such a way that the dominant iridium oxide coating material is coated over the entire titanium base plate, and anode plate 32 as a whole acts as anode A during electrolysis. On the other hand, a titanium base plate which is not coated is adopted as the cathode plate 33, and the cathode plate 33 as a whole acts as the cathode K during electrolysis.
[064] The amount of iridium oxide by mass ratio in the dominant iridium oxide coating material is set at 50% or more, and preferably set in a range of 60% to 70%. In this way, it is possible to obtain favorable coating effects of the iridium oxide.
[065] Furthermore, it is preferred that tantalum be added to the iridium oxide dominant coating material. It is most preferred that the iridium oxide-dominant coating material does not contain platinum.
[066] Here, an explanation will be made of the arrangement of three different types of electrodes 30 within the electrode holder box 26. The double pole electrode plate 31, anode plate 32 and cathode plate 33 are respectively attached and supported on support bars 26a within the electrode support box 26.
[067] Of the electrodes described above 30, as shown in FIG. 2 and in FIG. 3, the plurality of double pole electrode plates 31 are arranged in such a way that they extend along the seawater distribution direction W, while each anode A faces the seawater inlet side and each cathode K is facing the sea water outlet side. Furthermore, the double pole electrode plates 31 are arranged in series with a gap in the distribution direction, thus constituting a group of electrodes M. Next, the various groups of electrodes M are installed so as to be parallel to each other with a range, that is, they are installed in a plural number parallel to each other.
[068] The groups of M electrodes that are adjacently parallel to each other are arranged so as to deviate only by half the distance of each relative double pole electrode plate 31 in the distribution direction. Thus, the double pole electrode plates 31 in each of the electrode groups M, which are adjacently parallel to each other, are in a state where an anode A is opposite a cathode K. Furthermore, in the present embodiment, as shown in FIG. 3, it is preferred that a gap d1 between the double pole electrode plates 31 which are adjacent in the distribution direction in each of the electrode groups M be set to be 8 times or more a gap between the electrode groups M which are adjacently parallel to each other, i.e. a gap d2 between the double pole electrode plates 31 which are adjacently parallel to each other.
[069] On the other hand, the plurality of anode plates 32 are arranged parallel to each other along the seawater distribution direction W on the downstream side of the double pole electrode plates 31, and the plurality of cathode plates 33 are arranged parallel to each other along the seawater distribution direction W on the upstream side of the double pole electrode plates 31.
[070] A downstream end of each of the anode plates 32 is connected to the downstream terminal block 29 of the pair of terminal blocks 28, 29, while an upstream end of each of the anode plates 32 is opposite to the cathode K of each of the double pole electrode plates 31 in a direction orthogonal to the distribution direction. In other words, the upstream end of the anode plate 32 and the cathode K of the double pole electrode plate 31 are alternately arranged so that they overlap when viewed in the direction orthogonal to the distribution direction. Furthermore, the upstream end of the cathode plate 33 is connected to the terminal block 28 of the pair of terminal blocks 28, 29. In addition, the downstream end of each of the cathode plates 33 is opposite the anode A of each of the double pole electrode plates 31 in the direction orthogonal to the distribution direction. In other words, the downstream end of each cathode plate 33 and the anode A of the double pole electrode plate 31 are alternately arranged so that they overlap when viewed from the direction orthogonal to the distribution direction.
[071] The power supply unit 40 is a device for supplying an electrical current to be used during the electrolysis of seawater W and provided with a direct current power supply 41 and a constant current control circuit 42. The direct current power supply 41 is a power supply for emitting continuous electrical energy. In addition, the alternating electrical energy output from an alternating current power supply, for example, can be rectified into direct current and then output.
[072] Constant current control circuit 42 is a circuit for outputting a direct current supplied from the direct current power supply 41 as a constant current. Regardless of a change in electrical resistance across the current-passing sections, the constant current control circuit 42 is capable of delivering a predetermined constant current to the current-passing section. That is, when direct electrical power is input from the direct current power supply 41, as shown in FIG. 4, the constant current control circuit 42 controls a voltage value of the direct electrical power in a range of deflection width ΔV, whereby a desired electrical current value in the constant current control curve is output as a constant current.
[073] In the above-described constant current control circuit 42, anodes A are connected to downstream terminal block 29 and cathodes K are connected to upstream terminal block 28 via conductors on wires 43, 44. Thereby, a constant current generated in constant current control circuit 42 is passed through electrodes 30 via terminal blocks 28, 29.
[074] In that case, in the power supply unit 40 of the present embodiment, the constant current control circuit 42 generates a constant current in such a way that the electric current density on the surface of the electrode 30 is included in a range of 20 A/dm2 to 40 A/dm2 and preferably in a range of 20 A/dm2 to 30 A/dm2. That is, constant current is generated depending on the surface area of electrode 30 within the electrolysis vessel main body 20, and constant current is supplied to electrode 30, whereby the electric current density at the surface of electrode 30 is included. in a range of 20 A/dm2 to 40 A/dm2 and preferably in a range of 20 A/dm2 to 30 A/dm2.
[075] In an electrode coated with a conventional platinum-dominant composite metal (platinum-dominant coating material), the amount of oxygen and accelerated eroding plates from the electrode increases, with an increase in electrical current density. Then, a maximum value of the electric current density is set to approximately 15 A/dm2. In contrast, in the present embodiment, the electrolysis is performed at an electrical current density greater than the conventional electrical current density. That is, electrolysis is performed at an electrical current density in a range from 20 A/dm2 to 40 A/dm2, and preferably from 20 A/dm2 to 30 A/dm2.
[076] Storage tank 50 is a tank that temporarily stores seawater W flowing from the outlet port 25 of the main body of electrolysis vessel 20 in the seawater electrolysis device described above 10. sea W is introduced into the tank via an intermediate flow path 51 connected to the outlet port 25 of the electrolysis vessel main body 20.
[077] Inlet port 60 includes an inlet flow path 61, a first pump 62, a first flow meter 64 and a first on/off control valve 63.
[078] The inlet flow path 61 is a flow path which is connected at one end of which to the inlet channel 1 and at the other end to the inlet port 23 of the electrolysis vessel main body 20 in the electrolysis device. of sea water 10.
[079] The first pump 62 is installed midway along the inlet flow path 61. The first pump 62 pumps up seawater W into the inlet channel 1 at a constant outlet, whereby mar W is introduced at gateway 23.
[080] The first flow meter 64 is installed downstream of the inlet flow path 61, detecting a flow rate Q1 of seawater W passing through the inlet flow path 61.
[081] Furthermore, the first open/close control valve 63 is a valve that is installed upstream of the first flow meter 64 in the inlet flow path 61 and controlled to open and close based on the flow rate Q1 of the seawater W detected by the first flowmeter 64. By this constitution, the flow rate of seawater W that is distributed through the flow path is adjusted depending on an area ratio of a seawater distribution region from the inlet flow path 61 to that of the electrolysis vessel main body 20. Thus, it is possible to adjust the flow rate of seawater W which is distributed within the electrolysis vessel main body 20 at an arbitrary rate.
[082] In the seawater electrolysis device 10 of the present embodiment, it is preferred that the first open/close control valve 63 is controlled in such a way that the flow velocity of seawater W which is distributed within the body of electrolysis vessel 20 is at least 0.7 m/s (meters/second) or more.
[083] It is acceptable that the flow velocity of seawater W within the electrolysis vessel main body 20 is adjusted not only by controlling the opening/closing of the first open/close control valve 63, but also adjusted, for example, controlling the output of the first pump 62.
[084] The fill portion 70 includes a fill flow path 71, a second pump 72, a second on/off control valve 73, and a second flow meter 74.
[085] The fill flow path 71 is a flow path that is connected at one end of this to the storage tank 50 and connected at the other end to the inlet channel 1.
[086] The second pump 72 is installed midway along the fill flow path 71. The second pump 72 pumps up seawater W into the storage tank 50 at a constant outlet, through which the water of sea W is introduced into the inlet channel 1.
[087] The second flowmeter 74 is installed downstream of the infill flowpath 71, detecting a flow rate Q2 of seawater W passing through the infill flowpath 71.
[088] The second open/close control valve 73 is a valve that is installed upstream of the second flow meter 74 in the fill flow path 71 and controlled to open and close based on the flow rate Q2 of the water from the sea W detected by the second flow meter 74. By this constitution, the flow rate of sea water W to be filled in inlet channel 1 is adjusted. It is acceptable that not only the second open/close control valve 73 is controlled for open/close to adjust an amount of seawater W filled into the inlet channel 1, but also, for example, the second pump 72 is controlled to the outlet to adjust the amount of seawater W filled into the inlet channel 1.
[089] Next, an explanation will be given for the operation of the seawater electrolysis device 10 of the present embodiment and a method for performing the seawater electrolysis W using the seawater electrolysis device 10.
[090] The seawater W which is distributed through the inlet channel 1 is partially introduced by the inlet part 60 into the electrolysis vessel main body 20 from the inlet port 23 of the electrolysis vessel main body 20 of the seawater electrolysis device 10. That is, the seawater W inside the inlet channel 1 is pumped up to the inlet flow path 61 by the first pump 62, through which the seawater W is introduced into the electrolysis vessel main body 20 via the inlet flow path 61. By this constitution, the electrodes 30 inside the electrolysis vessel main body 20 are immersed in the seawater W. At this time, the first discharge valve opening/closing control 63 is opened and closed depending on a flow rate detected by the first flow meter 64. Thereby, the seawater W which is distributed inside the electrolysis vessel main body 20 in the distribution direction it's help so as to have a desired flow rate.
[091] As described above, the seawater W that is distributed within the electrolysis vessel main body 20 is subjected to electrolysis by the electrodes 30. That is, a desired constant current is generated in the constant current control circuit 42 with based on direct electrical power from the direct current power supply 41 in the power supply unit 40, and constant current is supplied to the terminal blocks 28, 29 via the wire leads 43, 44. terminal blocks 28, 29 is distributed in series within the electrolysis vessel main body 20 sequentially through anode plates 32, double pole electrode plates 31 and cathode plates 33.
[092] More specifically, when an electrical current that is delivered to anode plate 32 from constant current control circuit 42 reaches a cathode K of a double pole electrode plate 31 via seawater W , the electric current is distributed inside the double-pole electrode plate 31 and thereby reaches the anode A of the double-pole electrode plate 31. Then, the electric current that is distributed through the seawater W arrives at the cathode K from another double pole electrode plate 31 opposite the above anode A. As described above, electrical current is distributed from the anode plate 32 to the plurality of double pole electrode plates 31 sequentially and finally distributed to the electrode plate 31 in sequence. cathode 33. At this time, the electric current density on the surface of each of the electrodes 30 is controlled by the constant current control circuit 42 in a range of 20 A/dm2 to 40 A/dm2 and preferably in a range of 20 A/dm2 to 30 A/dm2.
[093] The electric current passing through seawater W, as described above, has constant electric current density at the surface of electrode 30 by operating a constant current control circuit 42 independent of a change in the electrical resistance of the water. that is, the seawater W that is distributed inside the electrolysis vessel main body 20 changes in value of electrical resistance from moment to moment. However, as shown in FIG. 4, constant current control circuit 42 controls the voltage at a predetermined deflection width ΔV, whereby the electric current density at the surface of electrode 30 is kept constant.
[094] As described above, an electric current is passed through seawater W between electrodes 30 to electrolyze it.
[095] That is, at anode A, as shown in the following Formula (1), chlorine ions in seawater W lose electrons and to cause oxidation, thus resulting in the generation of chlorine. formula 1

[096] On the other hand, at cathode K, as shown in the following formula (2), electrons are imparted to water in seawater W to cause a reduction, thus resulting in the generation of hydroxide ions and hydrogen gas. Formula 2

[097] Furthermore, as shown in the following formula (3), hydroxide ions generated at cathode K react with sodium ions in seawater W to generate sodium hydroxide.Formula 3

[098] Also, as shown in formula (4), sodium hydroxide reacts with chlorine to generate hypochlorous acid, sodium chloride, and water.Formula 4

[099] As described above, electrolysis of seawater W generates hypochlorous acid which is effective in suppressing marine growth adhesion.
[0100] Next, the seawater W, which has been subjected to electrolysis, flows from the outlet port 25 of the main body of electrolysis container 20, passes through the intermediate flow path 51 and is temporarily stored in the storage tank. storage 50. Then, the seawater W in the storage tank 50 is filled into the inlet channel 1 via the filling part 70. That is, the seawater W containing hypochlorous acid in the storage tank 50 is filled into the storage channel 50. inlet 1 via the fill flow path 71 by activating the second pump 72. At this time, the second open/close control valve 73 is opened and closed depending on a flow rate detected by the second flow meter 74 , thus adjusting an amount of the hypochlorous acid-containing seawater W W that flows into the inlet channel 1.
[0101] In this case, in general, manganese plates resulting from manganese ions contained in seawater W are deposited on anode A coated with a coating material with dominant iridium oxide during electrolysis. As anode A undergoes accelerated erosion due to the deposition of manganese plates and also the catalytic activities on the surface of electrode 30 are reduced, there is a disadvantage in reducing the effectiveness of chlorine generation. Furthermore, resulting plates of magnesium and calcium contained in seawater W are deposited on cathode K to accelerate erosion of electrode 30.
[0102] In contrast, according to the above embodiment, the electrical current density at the surface of electrode 30 is set at 20 A/dm2 or more, which is greater than a conventional electrical current density of 15 A/dm2. Thus, hydrogen gas is generated in association with electrolysis at the cathode K in a greater amount than a conventional case. The washing effect at electrode 30 can be developed due to the greater amount of hydrogen gas generated, thus making it possible to prevent the deposition of manganese plaques on anode A and the deposition of plaques such as calcium and magnesium on cathode K.
[0103] Furthermore, the amount of oxygen generated in the vicinity of an anode A is also increased with an increase in the electric current density at the surface of electrode 30. However, as iridium oxide is sufficiently resistant to oxygen, it is possible to prevent the erosion caused by oxygen of an anode A coated with the coating material containing iridium oxide.
[0104] When the electric current density at the surface of electrode 30 is excessively large, for example in excess of 40 A/dm2, the plates deposit on anode A and cathode K in such an amount that it exceeds the amount where the effect of hydrogen washing is effective. In contrast, in the present embodiment, the upper limit of the electrical current density is set at 40 A/dm2. Thus, it is possible to effectively develop the hydrogen washing effect and effectively prevent plaque deposition on anode A and cathode K. Furthermore, when the upper limit of electric current density is set to 30 A/dm2, it is possible to effectively develop the washing effect due to hydrogen and also effectively prevent plaque deposition.
[0105] As described above, in the present embodiment, the iridium oxide is contained in the coating material of anode A and the electric current density at the surface of electrode 30 is set in a range of 20 A/dm2 to 40 A/dm2 and preferably in a range of 20 A/dm2 to 30 A/dm2. Then, it is possible to effectively develop the washing effect by hydrogen gas. Thus, it is also possible to improve the resistance of the electrode 30 and suppress the reduction in the efficiency in the generation of chlorine, preventing the deposition of plaques on the electrode 30.
[0106] In addition to the improved maintenance of the seawater electrolysis device 10, the number of electrodes 30 can be reduced to decrease the size of the device due to greater effectiveness in generating chlorine.
[0107] Furthermore, when tantalum oxide is added to the dominant iridium oxide coating material coating anode A, tantalum exhibits great resistance to oxygen. As a result, it is possible to more effectively prevent abnormal erosion of electrode 30 due to oxygen generated in the vicinity of anode A.
[0108] It is noted that no platinum is contained in the coating material with dominant iridium oxide, thus making it possible to reduce the cost.
[0109] Still in the present embodiment, the double pole electrode plates 31 are arranged in series to constitute a group of M electrodes, and the various groups of M electrodes are arranged parallel to each other, whereby many double pole electrode plates 31 are arranged in a concentrated manner. It is then possible to downsize the device, while ensuring a large amount of total chlorine generation.
[0110] In addition, as the double pole electrode plates 31 are individually arranged along the seawater distribution direction W, there is no chance that the distribution of seawater W will be impeded. It is then possible to maintain the seawater W at a high flow velocity and also effectively develop the effect of preventing plaque deposition on electrode 30.
[0111] Then the anode A is opposite the cathode K between the groups of electrodes M which are adjacently parallel to each other. Then, an electric current is passed between anode A and cathode K, thus making it possible to effectively electrolyze seawater W that is distributed between electrodes 30.
[0112] When a gap is small between the double pole electrode plates 31 adjacent to each other in the seawater distribution direction W, an electric current is developed which is distributed between the double pole electrode plates 31, i.e. , a leakage current that contributes less to electrolysis. The leakage current becomes clearer with increasing electrical current density at the surface of electrode 30, thus resulting in a reduction in the efficiency of electrolysis in seawater.
[0113] In contrast, in the present embodiment, a gap d1 between adjacent double pole electrode plates 31 in the distribution direction in each of the electrode groups M is eight times or more than a gap d2 between the electrode groups M that are adjacently parallel to each other. That is, a gap between the double pole electrode plates 31 adjacent to each other in the distribution direction is properly maintained, thus making it possible to suppress the occurrence of leakage current and prevent the reduction in seawater electrolysis efficiency.
[0114] Next, an explanation will be made for a seawater electrolysis system 100B of the second embodiment according to the present invention with respect to FIG. 5. In the second embodiment, constituents similar to the first embodiment are given the same reference numbers, and a detailed explanation of these is omitted here.
[0115] As shown in FIG. 5, the seawater electrolysis system 100B of the second embodiment is provided with a circulation part 80 between the inlet flow path 61 of an inlet part 60 and the fill flow path 71 of a fill part 70 The circulation part 80 mixes seawater W within a fill flow path 71 with seawater in an inlet flow path 61. The circulation part 80 includes a flow flow path 81, a third flow meter 84, and a third on/off control valve 83.
[0116] The circulation flow path 81 is a flow path that is connected at one end to the infill flow path 71 and connected at the other end to the inlet flow path 61. In the present embodiment, one end of the flow path is circulating flow 81 is connected between a second pump 72 and a second on/off control valve 73 in the fill flow path. The other end of the circulating flow path 81 is connected between a first pump 62 and a first on/off control valve 63 in the inlet flow path 61.
[0117] The third flow meter 84 is installed midway along the circulating flow path 81, detecting a flow rate Q3 of seawater W passing through the circulating flow path 81.
[0118] Furthermore, the third open/close control valve 83 is a valve that is installed downstream of the third flow meter 84 in the circulation flow path 81, and controlled to open and close based on the flow rate Q3 of seawater W detected by the third flowmeter 84. Thus, it is possible to control, whenever necessary, the flow rate of seawater W circulating from the fill flowpath 71 via a circulating flowpath 81 to input flow path 61.
[0119] In the above described seawater electrolysis system 100B, when seawater W stored in a storage tank 50 after electrolysis is introduced by the second pump 72 into the fill flow path 71, the seawater W is separated into seawater W which is distributed through the fill flow path 71 and seawater W which is distributed through the circulating flow path 81 in a branch part of the fill flow path 71 to which one end of the circulation flow path 81 is connected.
[0120] Seawater W that has passed through the circulating flow path 81 is introduced into the inlet flow path 61 at the other end of the circulating flow path 81. That is, the seawater W, after electrolysis , which has passed through the circulating flow path 81, flows together with seawater W, prior to electrolysis, which has passed through the inlet flow path 61 and is introduced back into the electrolysis vessel main body 20. At this time, the third open/close control valve 83 is opened and closed depending on a flow rate detected by the third flow meter 84, thus making it possible to adjust the flow rate of seawater W, after electrolysis, which flows along with the seawater W flowing through the inlet flow path 61.
[0121] As described above, the seawater W, after electrolysis, that flowed from the outlet port 25 of the electrolysis vessel main body 20 is distributed through the circulation flow path 81 and thereby flows back to the electrolysis vessel main body 20 from the inlet port 23 thereof.
[0122] In this case, plate compositions such as manganese, magnesium and calcium deposited during electrolysis are found in seawater W after electrolysis. Seawater W is again introduced into the electrolysis vessel main body 20, thus making it possible to prevent plaque deposition on the surface of electrode 30 due to seeding crystallization effects of the plaque compositions. That is, the plate compositions act as seed crystals and the newly generated plates are deposited on the seed crystals, thus making it possible to prevent the precipitation of plates on the surface of the electrode 30. It is then possible to improve the resistance of the electrode 30 and also to suppress the reduction of the efficiency in the generation of chlorine.
[0123] An explanation has been given so far in detail of the embodiments of the present invention. The present invention should not, however, be restricted, and may be modified in a number of ways including some design change without abandoning the technical idea of the same.
[0124] For example, in the seawater electrolysis system 100B, it is preferred that the seawater W that is filled from the fill part 70 in the inlet channel 1 is set to approximately 2500 ppm in terms of the concentration of hypochlorous acid.
[0125] In that case, the total amount of hypochlorous acid thus generated is substantially proportional to the total amount of electrical current supplied from the power supply unit 40 to the electrodes 30. Then, the amount of electrical current supplied to the electrodes 30 can be recorded to calculate the total amount of hypochlorous acid thus generated. Furthermore, the concentration of hypochlorous acid in the seawater W that is filled into the inlet channel 1 can be calculated by dividing the total amount of hypochlorous acid thus generated by a flow rate Q2 of the seawater W that is filled into the channel inlet 1. Then, the second open/close control valve 73 is controlled depending on the total amount of hypochlorous acid to determine the flow rate Q2 of seawater W that is filled in inlet channel 1. It is thus It is possible to easily adjust the concentration of hypochlorous acid in seawater W to 2500 ppm.
[0126] Furthermore, as a modified example shown in FIG. 6, it is acceptable for the seawater electrolysis device 10 to be provided with a plurality of main bodies of electrolysis vessels 20 and for connecting piping 85 to be installed to connect the outlet port 25 to the inlet port 23 of each one of the main bodies of electrolysis vessels 20 and a degassing valve 86 as a degassing unit to remove the gas within the connecting pipeline 85. The degassing valve 86 is a valve which can be controlled to open and close. When the pressure within the electrolysis vessel main body 20 increases to a predetermined high pressure, the degassing valve 86 is opened to release the gas into the seawater W.
[0127] A liquid-to-gas ratio decreases due to hydrogen generated at the cathode K with an increase in electrical current density, thus resulting in a reduced effectiveness in chlorine generation. However, in particular, the hydrogen gas is removed by the degassing valve 86 installed in the connection pipe 85, whereby it is possible to suppress the liquid-gas ratio inside the electrolysis vessel main body 20 to a predetermined level and prevent the reduction. in effectiveness.
[0128] In the above embodiment, an explanation has been made of electrode 30 with respect to an example using a dual pole electrode plate 31. However, it is acceptable that, for example, an anode plate 32 and a cathode plate 33 are arranged opposite each other without using the double pole electrode plate 31 and an electric current is passed through seawater W between the anode plate 32 and the cathode plate 33. It is also acceptable that the anode plate 32 and the cathode plate 33 are alternately arranged whereby electric current is passed through the seawater W between the anode plate 32 and the cathode plate 33 which are adjacent and opposite each other.
[0129] Furthermore, in the above embodiment, the double pole electrode plate 31 is arranged in such a way that an anode A is turned towards the seawater inlet side and the cathode K is turned towards the water outlet side. from the sea. However, the double pole electrode plate 31 can be arranged in such a way that the anode A is facing the seawater outlet side and the cathode K is facing the seawater inlet side.
[0130] Next, an explanation will be made of a seawater electrolysis system 100C of the third embodiment according to the present invention with respect to FIG. 7 and to FIG. 8. In the third embodiment as well, constituents similar to the first embodiment will be given the same reference numbers, with a detailed explanation omitted here.
[0131] As shown in FIG. 7, the seawater electrolysis system 100C of the third embodiment is provided with a seawater electrolysis device 10, an inlet part 60, a hydrogen separator 90, a storage tank 50, a filling 70 and a circulating part 80. The inlet part 60 introduces seawater W into the seawater electrolysis device 10 from an inlet channel 1. The hydrogen separator 90 separates the hydrogen into electrolyzed water E discharged from the seawater electrolysis device 10. The storage tank 50 stores the electrolyzed water E that has been subjected to electrolysis by the seawater electrolysis device 10. The filling part 70 fills the electrolyzed water E from the tank 50 in the inlet channel 1. The circulating part 80 circulates the electrolyzed water E in the seawater electrolysis device 10. The seawater desalination device 65 is installed in the inlet part 60.
[0132] In that case, in the power supply unit 40 of the present embodiment, a constant current is generated by the constant current control circuit 42 such that an electric current density on the surface of an electrode 30 is in a range of 20 A/dm2 to 60 A/dm2 and preferably in a range of 20 A/dm2 to 50 A/dm2. That is, constant current is generated depending on the surface area of electrode 30 within the electrolysis vessel main body 20 and supplied to electrode 30. Thus, the electrical current density at the surface of electrode 30 is in a range of 20 A /dm2 to 60 A/dm2 and preferably in a range of 20 A/dm2 to 50 A/dm2.
[0133] In an electrode coated with a conventional platinum-dominant composite metal (platinum-dominant coating material), the amount of oxygen and plaque that accelerate electrode erosion is also increased with an increase in electrical current density. Then, a maximum value of the electric current density was set approximately 15 A/dm2. In contrast, in the present embodiment, electrolysis is performed over a range of electric current density from 20 A/dm2 to 60 A/dm2, and preferably in a range from 20 A/dm2 to 50 A/dm2 that is greater than a conventional case.
[0134] The inlet portion 60 includes an inlet flow path 61, a first pump 62, a seawater desalination device 65, a first flow meter 64 and a first open/close control valve 63.
[0135] The seawater desalination device 65 is a device for separating seawater into pure water (desalinated water) and concentrated water C using a reverse osmosis membrane (RO membrane). The pure water separated by the seawater desalination device 65 is fed via a pure water line 66 into a pure water tank (not shown), while the concentrated water C is introduced into the seawater electrolysis device 10 via the first open/close control valve 63 of the inlet flow path 61.
[0136] In the seawater electrolysis device 10 of the present embodiment, it is preferred that the first open/close control valve 63 is controlled so that the concentrated water C that is distributed inside the main body of electrolysis vessel 20 have a flow velocity of at least 0.7 m/s or more.
[0137] It is acceptable that not only the first open/close control valve 63 is controlled to open and close to adjust the flow rate of concentrated water C within the electrolysis vessel main body 20, but also that, for example, the first pump 62 is output-controlled to adjust the flow rate of the concentrated water C within the electrolysis vessel main body 20.
[0138] The hydrogen separator 90 is a device for separating the hydrogen gas contained in the electrolyzed water E flowing from the outlet port 25 of the main body of electrolysis vessel 20 in the seawater electrolysis device 10. As shown in FIG. 8, the hydrogen separator 90 is provided with a water receiving tank 92 having an exhaust pipe 91 in an upper part thereof, an inlet pipe 93 which is connected to the outlet port 25 of the electrolysis vessel main body 20 through the intermediate flow path 8 to direct electrolyzed water in a gaseous phase part 92a ascending into the water receiving tank 92, a sprinkler nozzle 94 installed midway along the introduction pipe 93 and an agitator 95 installed in a descending liquid phase portion 92b within the water receiving tank 92.
[0139] The sprinkler nozzle 94 ejects the electrolyzed water E which has been introduced into the introduction pipe 93 in the gaseous phase part 92a ascending into the water receiving tank 92. The agitator 95 is constituted with a screw 96 and a motor 97 which rotates the screw 96, thereby stirring a liquid pooled in the liquid phase part 92b of the water receiving tank 92. In addition, a discharge port 98 is installed in a lower part of the water receiving tank 92 through which the electrolyzed water is discharged.
[0140] Storage tank 50 is a tank that temporarily stores electrolyzed water E that is discharged from discharge port 98 of hydrogen separator 90.
[0141] The circulation part 80 is a part that circulates electrolyzed water E flowing through the fill flow path 71 into the inlet flow path 61 of the inlet part 60. The circulation part 80 includes a flow path of circulation 81, a third flow meter 82 and a third on/off control valve 83.
[0142] The circulating flow path 81 is a flow path which is connected at one end thereof to the infill flow path 71 and connected at the other end to the inlet flow path 61. In the present embodiment, one end of the path flow control 81 is connected between the second pump 72 and the second on/off control valve 73 in the fill flow path 71. The other end of the circulation flow path 81 is connected between the first flow control valve 71. opening/closing 63 and the first flow meter 64 in the inlet flow path 61.
[0143] The third flow meter 82 is installed halfway along the circulating flow path 81, detecting a flow rate Q3 of the electrolyzed water E passing through the circulating flow path 81.
[0144] In addition, the third on/off control valve 83 is a valve that is installed downstream of the third flow meter 82 in the circulation flow path 81 and controlled to open and close based on the flow rate Q3 of the electrolyzed water E detected by the third flowmeter 82. Through this constitution it is possible to control the flow rate of the electrolyzed water E which is circulated to the inlet flow path 61 from the fill flow path 71 via the flow path circulation 81 at arbitrary rate.
[0145] Next, an explanation will be given of the operation of the 100C seawater electrolysis system of the present embodiment and a method for performing the seawater electrolysis W using the 100C seawater electrolysis system .
[0146] The seawater W that is distributed through the inlet channel 1 is partially introduced into the seawater desalination device 65 by the inlet part 60. That is, the seawater W inside the inlet channel 1 is pumped into the inlet flow path 61 by the first pump 62, whereby the seawater W is introduced into the seawater desalination device 65 via the inlet flow path 61. Thus, the seawater W is separated into pure water and concentrated water C.
[0147] Desalination device 65 allows seawater W to pass through membrane RO by applying pressure to seawater W, thus concentrating the salt content of seawater W to filter pure water. Thus, the concentration of chlorine ions in seawater W is increased, for example, up to a range from 20,000 mg/L to 30,000 to 40,000 mg/L, resulting in the production of concentrated water C. Pure water is fed through from a pure water line 66 to a pure water tank (not shown) which stores the pure water, while the concentrated water C is introduced via the inlet flow path 61 into the electrolysis vessel main body 20.
[0148] In this way, the electrodes 30 inside the electrolysis vessel main body 20 are immersed in the concentrated water C. At this time, the first open/close control valve 63 is opened and closed depending on a flow rate detected by the first flow meter 64, whereby the concentrated water C which is dispensed in the distribution direction within the electrolysis vessel main body 20 is adjusted so as to provide a value of a desired flow rate.
[0149] Then, the concentrated water C which is distributed inside the electrolysis vessel main body 20 is subjected to electrolysis by the electrode 30. That is, a desired constant current is generated in the constant current control circuit 42 based on on constant electrical power from the direct current power supply 41 in the power supply unit 40, and the constant current is supplied via wire leads 43, 44 to terminal blocks 28, 29. An electrical current supplied via the terminal blocks 28, 29 is distributed in series sequentially through an anode plate 32, a double pole electrode plate 31 and a cathode plate 33 within the electrolysis vessel main body 20.
[0150] More specifically, the electrical current distributed from the constant current control circuit 42 to the anode plate 32 arrives at the cathode K of the double pole electrode plate 31 via concentrated water C. The electrical current is distributed inside the double pole electrode plate 31 and thus arrives at an anode A of the double pole electrode plate 31. Then the electric current passing through the concentrated water arrives at the anode K of another double pole electrode plate 31 opposite anode A. As described above, electrical current is distributed from anode plate 32 sequentially through the plurality of double pole anode plates 31 and finally distributed to cathode plate 33. A density of electrical current of the electrical current at that time on the surface of each of the electrodes 30 is controlled by the constant current control circuit 42 so as to be in a range of 20 A/dm2 to 60 A/dm2 and preferably in a range of 20 A/dm2 to 50 A/dm2.
[0151] As described above, the electric current passing through concentrated water C has constant electric current density at the surface of each of the electrodes 30 due to the operation of the constant current control circuit 32, independent of a change in electrical resistance of concentrated water C. That is, concentrated water C that is distributed within the main body of electrolysis vessel 20 undergoes a change in value of electrical resistance from moment to moment. As shown in FIG. 4 , constant current control circuit 42 controls the voltage to provide a predetermined deflection width ΔV whereby the electrical current density at the surface of electrode 30 is kept constant.
[0152] As described above, an electric current is distributed within the concentrated water C between the electrodes 30, by which the concentrated water C is subjected to electrolysis.
[0153] That is, at anode A, as shown in Formula (1) of the first embodiment, chlorine ions in concentrated water C lose electrons and cause oxidation, thus generating chlorine.
[0154] On the other hand, at cathode K, as shown in Formula (2) of the first embodiment, electrons are imparted to water in concentrated water C to cause a reduction, thus resulting in the generation of hydroxide ions and hydrogen gas.
[0155] Furthermore, as shown in Formula (3) of the first embodiment, the hydroxide ions generated at cathode K react with sodium ions in concentrated water to generate sodium hydroxide.
[0156] Furthermore, as shown in Formula (4) of the first embodiment, sodium hydroxide reacts with chlorine to generate hypochlorous acid, sodium chloride and water.
[0157] As described above, based on electrolysis of concentrated water C, hypochlorous acid is generated which is effective in suppressing marine growth deposition.
[0158] As the concentration of chlorine ions in concentrated water C is increased to a value in the range of 30,000 mg/L to 40,000 mg/L, the concentration of hypochlorous acid is preferably set in a range of 2,500 ppm to 5,000 ppm.
[0159] Then the concentrated water C that has been subjected to electrolysis flows from the outlet port 25 of the main body of electrolysis vessel 20 as electrolyzed water E, together with hydrogen gas, passing through the intermediate flow path 8 and flowing in a 90 hydrogen separator.
[0160] A gas-liquid mixing fluid composed of hydrogen gas and electrolyzed water E is introduced into an introduction line 93 of the hydrogen separator 90 and ejected through a spray nozzle 94 into a gas phase part 92a of the hydrogen separator 90. water receiving tank 92. Thus, hydrogen gas mixed with electrolyzed water E as bubbles is subjected to deaeration and emitted from the exhaust pipe 91.
[0161] On the other hand, the electrolyzed water E is stored in the liquid phase part 92b of the water receiving tank 92. The electrolyzed water stored E is stirred by a stirrer 95. That is, the electrolyzed water E is forcibly stirred by a spiral flow caused by a screw 96 rotated by a motor 97. Thus, the plates deposited in association with electrolysis are prevented from flocculating at the bottom of the receiving tank 92. The electrolyzed water E which has been temporarily stored in the receiving tank of water 92 is discharged from the discharge port 98 installed at the bottom of the water receiving tank 92 and introduced into the storage tank 50.
[0162] When the electrolyzed water E that has been temporarily stored in the storage tank 50 is introduced by the second pump 72 into the fill flow path 71, the electrolyzed water E is branched into electrolyzed water E which is distributed through the flow path of E. fill 71 and electrolyzed water E which is distributed through the circulating flow path 81 into a branching part of the infill flow path 71 to which one end of the circulating flow path 81 is connected.
[0163] The electrolyzed water E that is distributed through the fill flow path 71 is filled in the inlet channel 1. That is, the electrolyzed water E that contains hypochlorous acid in the storage tank 50 is filled in the inlet channel 1 by midway through the fill flow path 71 by activating the second pump 72. At this time, the second open/close control valve 73 is opened and closed depending on the flow rate detected by the second flow meter 74, thereby adjusting the flow rate. flow rate of electrolyzed water E that is filled into inlet channel 1 and contains hypochlorous acid.
[0164] In this case, the total amount of hypochlorous acid generated is substantially proportional to the total amount of electrical current supplied from the power supply unit 40 to the electrodes 30. Then, the amount of electrical current supplied to the electrodes 30 is recorded for calculate the total amount of hypochlorous acid generated. Furthermore, the concentration of hypochlorous acid in electrolyzed water E that is filled into inlet channel 1 can be calculated by dividing the total amount of hypochlorous acid generated by a flow rate Q2 of seawater W that is filled into inlet channel 1. Then, the second on/off control valve 73 is controlled depending on the total amount of hypochlorous acid to determine the flow rate Q2 of the electrolyzed water E that is filled into inlet channel 1. It is then possible to adjust the concentration of hypochlorous acid in electrolyzed water E.
[0165] On the other hand, the electrolyzed water E that is distributed through the circulating flow path 81 is introduced into the inlet flow path 61 at the other end of the circulating flow path 81. That is, the electrolyzed water E that passed through the circulating flow path 81 flows together with the seawater W passing through the inlet flow path 61 and is again introduced into the electrolysis vessel main body 20. At this time, the third open/open control valve closure 83 is opened and closed depending on the flow rate detected by the third flow meter 82, thus making it possible to adjust the flow rate of the electrolyzed water E flowing together with the seawater W which is distributed through the inlet flow path 61 .
[0166] As described above, the electrolyzed water E that flowed from the outlet port 25 of the electrolysis vessel main body 20 is distributed through the circulation flow path 81, thus flowing again in the electrolysis vessel main body 20 from the gateway 23.
[0167] According to the above embodiment, concentrated water C with increased chlorine ion concentration and electrical conductivity is introduced into the seawater electrolysis device 10. Furthermore, as an anode coating material A contains an oxide of iridium, it is possible to set the electrical current density at the surface of electrode 30 in a range of 20 A/dm2 to 60 A/dm2 and preferably in a range of 20 A/dm2 to 50 A/dm2. Thus, it is possible to increase the concentration of hypochlorous acid contained in the generated electrolyzed water E. That is, hypochlorous acid is produced in an increased amount per unit area of the electrode, thus making it possible to decrease the electrode area and decrease the size of the device. .
[0168] Seawater in the vicinity of a river mouth or within a bay has a lower concentration of chlorine ions than normal seawater and also lower electrical conductivity. So, there may be a problem in the stability of the operation due to abnormal electrode erosion. Meanwhile, concentrated water C is subjected to treatment by seawater electrolysis device 10 to increase chlorine ion concentration and electrical conductivity. Thus, it is possible to stabilize the performance of the treatment.
[0169] Furthermore, the augmented hydrogen gas is subjected to a degassing process by the hydrogen separator 90. Then, there is no chance that the hydrogen gas will damage the second pump 72 and the piping which is subsequent to the storage tank 50 .
[0170] Further, as the circulation part 80 is installed, the plate compositions such as manganese, magnesium and calcium generated during electrolysis are introduced into the main body of electrolysis vessel 20 together with electrolyzed water E. Then, the electrolyzed water E containing plate compositions is again introduced into the main body of electrolysis vessel 20, thus making it possible to prevent the deposition of plates on the surface of electrode 30 by crystallization effects by seeding the plate compositions. That is, the plaque compositions act as seed crystals and the newly generated plaques are deposited on the seed crystals. Thus, it is possible to prevent the precipitation of plaques on the surface of the electrode 30. It is thus possible to improve the durability of the electrode 30 and also to suppress the reduction in the efficiency in the generation of chlorine.
[0171] When the electric current density at the surface of electrode 30 is excessively large, for example in excess of 60 A/dm2, plates are generated at an anode A and at a cathode K in such an amount that it exceeds an amount when the hydrogen washing effect is effective. In contrast, in the present embodiment, as an upper limit of the electric current density is set at 60 A/dm2, it is possible to effectively exert the washing effect due to hydrogen and effectively prevent plaque deposition on anode A and cathode. K. Furthermore, when an upper limit of electric current density is set to 50 A/dm2, it is possible to effectively develop the hydrogen wash effect and effectively prevent plaque deposition.
[0172] As described above, in the present embodiment, an anode coating material A contains an iridium oxide and the electric current density at the surface of electrode 30 is set in a range of 20 A/dm2 to 60 A/dm2 and preferably in a range of 20 A/dm2 to 50 A/dm2. Thus, it is possible to effectively obtain the washing effect due to hydrogen gas. Thus, it is possible to improve the resistance of the electrode 30 and suppress the reduction in the efficiency in the generation of chlorine by preventing the deposition of plaques on the electrode 30.
[0173] So, in addition to maintenance enhancements to the seawater electrolysis device 10, the number of electrodes 30 can be decreased to decrease the size of the device due to greater efficiency in chlorine generation.
[0174] In the above embodiment, an explanation has been made of electrode 30 with respect to an example using a dual pole electrode plate 31. However, it is acceptable that, for example, an anode plate 32 and a cathode plate 33 are arranged opposite each other without using the double pole electrode plate 31 and for an electric current to pass through seawater W between the anode plate 32 and the cathode plate 33. It is also acceptable that the anode plate 32 and the cathode plate 33 are alternately arranged whereby electric current passes through the seawater W between the anode plate 32 and the cathode plate 33 which are adjacent and opposite to each other. Furthermore, in the above embodiment, a double pole electrode plate 31 is arranged in such a way that an anode A is facing the seawater inlet side and a cathode K is facing the seawater outlet side. However, the double pole electrode plate 31 can be arranged in such a way that anode A faces the seawater outlet side and cathode K faces the seawater inlet side.
[0175] Furthermore, in the present embodiment, it is adopted that the seawater desalination device 65 using an RO membrane as a device for concentrating seawater W generates concentrated water C. However, the device for generating Concentrated water C is not restricted to the above device and, for example, a method of concentrating sea water W using a distillation method can be adopted.
[0176] Further, a method for separating hydrogen gas from electrolyzed water mixed with hydrogen gas E is not restricted to the method of the present embodiment in which the hydrogen separator 90 with the spray nozzle 94 is used, but may include a method in which a gas-liquid separator using a centrifugal machine, for example, is used as long as a gas-liquid mixing fluid can be separated into a gas and a liquid.
[0177] It is also accepted that hydrogen is separated not by separately installing the hydrogen separator 90 as a gas-liquid separator, but by adding the storage tank 50, for example, a gas-liquid separation function to dilute hydrogen gas by supplying air to a liquid phase.
[0178] In addition, electrolyzed water E can all be supplied to inlet channel 1, without circulating part 80 installed, if plaque deposition on the surface of electrode 30 is not a problem. Example
[0179] Next, an explanation will be made of an example. (Test to determine the effectiveness in the generation of chlorine)
[0180] A test was conducted to study a relationship between an electric current density at the surface of an electrode and the effectiveness of chlorine generation during the electrolysis of seawater W and concentrated water C.
[0181] An anode plate and a cathode plate were provided, each of which was a plate with an electrode area of 50 x 50 mm and arranged opposite each other with a gap of 5 mm. As anode plate, used as a titanium base plate coated with a coating material containing an iridium oxide (IrO2) in 50% or more by mass ratio. In addition, a titanium base plate free of a coating material was used as the cathode plate. The concentration of chlorine ions in the seawater W was 20,000 mg/L and the concentration of chlorine ions in the concentrated water W was 30,000 to 40,000 mg/L.
[0182] The anode plate and the cathode plate were immersed in the seawater W and the concentrated water C. The seawater W and the concentrated water C were distributed at a flow rate of 250 mL/min and a current Electricity was passed between the anode plate and the cathode plate for electrolysis. Then, a determination was made for the effectiveness of chlorine generation at each electric current density.
[0183] Efficiency in chlorine generation means a ratio of the amount of chlorine that is actually generated to the amount of chlorine that can theoretically be generated based on the electrical current density of distributed electric current.
[0184] FIG. 9 shows the result of determining the effectiveness in generating chlorine.
[0185] As shown in FIG. 9, when the electric current density is less than 20 A/dm2, both seawater W and concentrated water C have increased chlorine generation effectiveness with an increase in electric current density.
[0186] W without concentration seawater is effective in generating constant chlorine, when the electric current density is in a range of 20 A/dm2 to 30 A/dm2 and gradually decreases the effectiveness in chlorine generation when the density electrical current exceeds 30 A/dm2. Furthermore, when the electric current density is 20 A/dm2 or 30 A/dm2, the chlorine generation efficiency is the highest value obtained, that is, 96%.
[0187] It was concluded that when the electric current density is 15 A/dm2, which is obtained as technical common sense for an electrode coated with a platinum-containing coating material, the effectiveness in chlorine generation is 93%.
[0188] From this fact, it is now understood that even for seawater W, in an electrode coated with a coating material containing iridium oxide, the electric current density is set to be in the range of 20 A/ dm2 to 30 A/dm2, thus making it possible to obtain a high efficiency in the generation of chlorine. The high efficiency in chlorine generation is considered to be caused by the increase in the amount of hydrogen gas generated resulting in the effect of washing the plates deposited on an anode plate and on a cathode plate by the hydrogen gas.
[0189] An amount of chlorine that can theoretically be generated increases with an increase in electrical current density. So, even when the chlorine generation efficiency shows the same value, more chlorine is generated when the electric current density is higher.
[0190] Thus, when the electric current density is set at 40 A/dm2, the efficiency in chlorine generation is 93%, which is equivalent to the electric current density of 15 A/dm2. However, an amount of chlorine generated is greater at an electrical current density of 40 A/dm2 than at an electrical current density of 15 A/dm2. So, it is effective to set the electric current density to 40 A/dm2 in view of the amount of chlorine generated. On the other hand, when the electric current density exceeds 40 A/dm2, it is outside a range where the washing effect can be effectively developed due to hydrogen gas. In addition, the efficiency of chlorine generation is reduced compared to an electrical current density of 15 A/dm2. So, an upper limit of the electric current density is preferably set at 40 A/dm2. Thus, it was concluded that a greater amount of chlorine generated can be ensured, while the efficiency in chlorine generation is also kept high.
[0191] When the electric current density is in the range of 20 A/dm2 to 50 A/dm2, concentrated water C is effective in generating constant chlorine. When the electrical current density is set to 60 A/dm2, concentrated water C maintains a high efficiency in chlorine generation, ie 96%.
[0192] As is clear from the description above, concentrated water C is able to obtain a greater effectiveness in the generation of chlorine by configuring the electric current density as being in a range of 20 A/dm2 to 60 A/dm2 . It was concluded that the electric current density can be made high compared to seawater W without being concentrated.
[0193] As described above, the test of the determination of effectiveness in the generation of chlorine revealed that concentrated water C is introduced into the seawater electrolysis device 10, the electric current density at the electrode surface during electrolysis is set in the range from 20 A/dm2 to 60 A/dm2 and preferably in a range from 20 A/dm2 to 50 A/dm2, thus making it possible to obtain high efficiency in the generation of chlorine.
[0194] The electrode gradually erodes when electrolysis is performed for an extended period of time. Thus, the curve indicating the result in the determination in FIG. 9 is considered more inclined. In addition, it is assumed that the most effective electric current density is set in the above range, in particular, after electrode erosion. (Electrolysis life test results)
[0195] A test was conducted to study a relationship between an electrical current density during seawater electrolysis W and an amount of catalyst retention.
[0196] As with the chlorine generation effectiveness determination test, an anode plate and a cathode plate were provided, each of which was a plate with an electrode area of 50 x 50 mm and arranged opposite each other. , with a gap of 5 mm. Two types of electrode plates were prepared as the anode plate, i.e. a titanium base plate coated with a coating material containing iridium oxide (IrO2) at 50% or more by mass ratio and a base plate of titanium coated with a platinum (Pt) containing coating material. A titanium base plate free of a coating material was used as the cathode plate.
[0197] The anode plate and the cathode plate were respectively immersed in seawater W, and the same was distributed at a flow rate of 250 mL/min. Additionally, an electric current passed between the anode plate and the cathode plate for electrolysis. Then, determination was made for an amount of catalyst retention at each electric current density with time.
[0198] Catalyst retention amount means an amount of electrode catalyst retained after electrolysis. The amount of catalyst retention decreases with time, whereby the electrode erodes accordingly. FIG. 10 shows the result of determining the amount of catalyst retention.
[0199] As shown in FIG. 10, it was found that when the titanium base plate coated with platinum-containing (Pt/Ti) coating material is used as the anode plate, the amount of catalyst retention gradually decreases over time, and in particular , the amount of catalyst retention apparently decreases with an increase in electric current density.
[0200] On the other hand, when the titanium base plate coated with the coating material containing iridium oxide (IrO2) is used as the anode plate, the amount of catalyst retention does not decrease with time.
[0201] Thus, it was concluded that the anode plate coated with the iridium oxide-containing coating material has higher electrode resistance than the anode plate coated with the platinum-containing coating material. Industrial Applicability
[0202] The present invention relates to a seawater electrolysis system which is provided with a seawater electrolysis device for generating hypochlorous acid when performing seawater electrolysis and also relates to a method for electrolysis of sea water.
[0203] According to the present invention, it is possible to improve the resistance of an electrode and suppress the reduction in the effectiveness in the generation of chlorine by preventing the deposition of plaques on the electrode. Description of Reference Numbers A: anode K: cathode M: electrode group W: sea water C: concentrated water 10: sea water electrolysis device 20: electrolysis vessel main body 30: electrode 31: electrode plate double pole 32: anode plate 33: cathode plate 40: power supply unit 60: inlet part 65: seawater desalination device (concentrating device) 70: fill part 80: circulation part 81 : circulation flow path 90: hydrogen separator (hydrogen separation device) 100A, 100B, 100C: seawater electrolysis system

权利要求:
Claims (14)
[0001]
1. Seawater electrolysis system, CHARACTERIZED in that it comprises: a seawater electrolysis device (10) including an anode (A) which is made of titanium coated with a coating material containing iridium oxide, a cathode (K), an electrolysis vessel main body (20) that houses the anode (A) and cathode (K), and a power supply unit (40) that passes an electrical current between the anode (A) ) and the cathode (K), and a circulation flow path (81) that mixes the seawater, after electrolysis, flowing from an outlet port of the electrolysis vessel main body (20) with the water from the seawater before flowing into the electrolysis vessel main body (20) from an inlet port, wherein the seawater electrolysis device (10) passes an electrical current between the anode (A) and the cathode (K) in such a way that an electric current density on the surface of the anode (A) and that of the cathode (K) is included from 2 0 A/dm2 to 40 A/dm2 to electrolyze seawater inside the electrolysis vessel main body (20).
[0002]
2. Seawater electrolysis system, according to claim 1, CHARACTERIZED by the fact that: the density of electric current on the surface of the anode (A) and that of the cathode (K) between which the current power is passed through the power supply unit (40) is included from 20 A/dm2 to 30 A/dm2.
[0003]
3. Seawater electrolysis system, according to claim 1, CHARACTERIZED by the fact that a tantalum oxide is added to the coating material.
[0004]
4. Seawater electrolysis system, according to claim 1, CHARACTERIZED in that: the electrode (30) includes a plurality of double pole electrode plates (31) in each of which a part of the electrode itself in one direction the seawater distribution is given as the anode (A) and the other part of itself is given as the cathode (K), a plurality of electrode groups (M), in which the pole electrode plates (31) are arranged with a gap in the distribution direction, are arranged so as to be parallel to each other, and the double pole electrode plates (31) in the electrode groups (M) adjacently parallel to each other are arranged in such a way so that the anode (A) is opposite the cathode (K).
[0005]
5. Seawater electrolysis system, according to claim 4, CHARACTERIZED by the fact that: a gap between the double pole electrode plates (31) that are adjacent in the distribution direction in each of the electrode groups (M) is configured to be 8 times or more a gap between groups of electrodes (M) that are adjacently parallel to each other.
[0006]
6. Seawater electrolysis system, according to claim 1, CHARACTERIZED in that it additionally comprises: one or a plurality of electrolysis container main bodies (20), one or a plurality of connection pipes (85 ), each of which connects a seawater outlet port of one of the electrolysis vessel main bodies (20) with a seawater inlet port of the other of the electrolysis vessel main body (20) ), and one or a plurality of degassing units (86) for removing a gas within the connecting pipes (85).
[0007]
7. Seawater electrolysis method using the seawater electrolysis system as defined in any one of claims 1 to 6, the seawater electrolysis method CHARACTERIZING the fact that seawater is introduced into the main body of electrolysis vessel (20), an electric current is passed between the anode (A) and the cathode (K) in such a way that the electric current density on the surface of the anode (A) and that of the cathode (K) is included from 20 A/dm2 to 40 A/dm2 for electrolyzing seawater inside the electrolysis vessel main body (20), and a circulating flow path (81) that mixes seawater, after electrolysis, which is discharged from the electrolysis vessel main body (20) with seawater to be introduced into the electrolysis vessel main body (20).
[0008]
8. Seawater electrolysis system, CHARACTERIZED in that it comprises: a seawater electrolysis device (10) having an anode (A) which is made of titanium coated with a coating material containing iridium oxide, a cathode (K), an electrolysis vessel main body (20) that houses the anode (A) and cathode (K), and a power supply unit (40) that passes an electrical current between the anode (A) ) and the cathode (K), a concentration unit (65) for increasing the concentration of chloride ions contained in seawater to be introduced into the electrolysis vessel main body (20), a circulating flow path (81 ) which mixes seawater, after electrolysis, flowing from an outlet port of the electrolysis vessel main body (20) with seawater before flowing into the electrolysis vessel main body (20) at from the inlet port, where the electric current is passed between the anode (A) and the cathode (K) to to electrolyze seawater inside the electrolysis vessel main body (20), and wherein the density of electric current over the surface of the anode (A) and cathode (K) between which the electric current is passed through the unit power supply unit (40) is included from 20 A/dm2 to 60 A/dm2.
[0009]
9. Seawater electrolysis system, according to claim 8, CHARACTERIZED by the fact that: the density of electric current on the surface of the anode (A) and that of the cathode (K) between which the current power is passed through the power supply unit (40) is included from 20 A/dm2 to 50 A/dm2.
[0010]
10. Seawater electrolysis system, according to claim 8, CHARACTERIZED by the fact that it is provided with hydrogen separation means (90) to separate hydrogen gas generated at the cathode (K) from seawater after the electrolysis.
[0011]
11. Seawater electrolysis system, according to claim 8, CHARACTERIZED by the fact that tantalum oxide is added to the coating material.
[0012]
12. Seawater electrolysis system, according to claim 8, CHARACTERIZED by the fact that: the electrode (30) includes a plurality of double pole electrode plates (31) in which a part of them in one direction distribution of sea water is given as the anode (A) and the other part is given as the cathode (K), a plurality of groups of electrodes (M), in which the double pole electrode plates (31) are arranged with a gap in the distribution direction, are arranged so as to be parallel to each other, and the double pole electrode plates (31) in each of the electrode groups (M) adjacently parallel to each other are arranged in such a way that the anode (A) is opposite the cathode (K).
[0013]
13. Seawater electrolysis system, according to claim 12, CHARACTERIZED by the fact that: a gap between the double pole electrode plates (31) that are adjacent in the distribution direction in each of the electrode groups (M) is configured to be 8 times or more than a gap between groups of electrodes (M) that are adjacently parallel to each other.
[0014]
14. Seawater electrolysis method by using the seawater electrolysis system as defined in any one of claims 8, 9 to 13, CHARACTERIZED by the fact that: the concentration of chloride ions contained in seawater that is subjected to electrolysis is increased, seawater with increased concentration of chloride ions is introduced into the main body of electrolysis vessel (20), electric current is passed between anode (A) and cathode (K) for electrolysis - using the seawater inside the electrolysis vessel main body (20), a circulation flow path (81) mixes the seawater after electrolysis, which is discharged from the electrolysis vessel main body (20) with seawater to be introduced into the main body of electrolysis vessel (20), and wherein the electric current density on the surface of the anode (A) and that of the cathode (K) between which the current power is passed through the power supply unit (40) is included from 20 A/dm2 to 60 A/dm2.

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KR101624095B1|2016-06-07|

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KR20150116914A|2015-10-16|

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WO2012070468A1|2012-05-31|

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KR101585304B1|2016-01-13|

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MY164970A|2018-02-28|

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AU2011333018C1|2014-09-25|

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TW201235512A|2012-09-01|

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CN105239090B|2018-06-05|

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AU2011333018B2|2014-07-03|

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AU2011333018A1|2013-03-14|

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CN103201412B|2016-02-03|

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KR20130079569A|2013-07-10|

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法律状态:
2021-05-18| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2021-05-25| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-11-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-11| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/11/2011, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |

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申请号 | 申请日 | 专利标题

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JP2010-260509|2010-11-22|

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JP2010260509A|JP5752399B2|2010-11-22|2010-11-22|Seawater electrolysis apparatus, seawater electrolysis system and seawater electrolysis method|

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