WO2022044850A1 - 電解装置 - Google Patents

電解装置 Download PDF

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Publication number
WO2022044850A1
WO2022044850A1 PCT/JP2021/029808 JP2021029808W WO2022044850A1 WO 2022044850 A1 WO2022044850 A1 WO 2022044850A1 JP 2021029808 W JP2021029808 W JP 2021029808W WO 2022044850 A1 WO2022044850 A1 WO 2022044850A1
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WIPO (PCT)
Prior art keywords
spacer
electrode
axis direction
plate
central axis
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Application number
PCT/JP2021/029808
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English (en)
French (fr)
Japanese (ja)
Inventor
宏幸 高波
Original Assignee
三菱重工環境・化学エンジニアリング株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 三菱重工環境・化学エンジニアリング株式会社 filed Critical 三菱重工環境・化学エンジニアリング株式会社
Priority to KR1020237007170A priority Critical patent/KR102559708B1/ko
Priority to MX2023001968A priority patent/MX2023001968A/es
Priority to CN202180052325.2A priority patent/CN116096943B/zh
Publication of WO2022044850A1 publication Critical patent/WO2022044850A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/63—Holders for electrodes; Positioning of the electrodes

Definitions

  • the present invention relates to an electrolytic device that electrolyzes a liquid to be treated such as seawater, salt water, water, or a liquid for organic synthesis.
  • a device that electrolyzes (hereinafter referred to as “electrolysis") various liquids (solutions to be treated) such as seawater, salt water, water, and solutions for organic synthesis is called an electrolytic device.
  • the electrolyzer includes an electrolytic cell that electrolyzes the liquid to be treated, an introduction port that introduces the liquid to be treated into the electrolytic cell, and an discharge port that discharges the liquid to be treated after electrolysis from the electrolytic cell.
  • the electrolyzers are a vertical electrolyzer arranged upright in the vertical direction (hereinafter referred to as “vertical electrolyzer”) and a horizontal electrolyzer arranged horizontally laid down or tilted (hereinafter referred to as “horizontal electrolyzer”). It is roughly divided into “devices”).
  • a plurality of electrode plates for electrolyzing the liquid to be treated are housed in the electrolytic cell.
  • measures have been taken to prevent deposits such as scales from accumulating in the electrolytic cell.
  • the accumulation of deposits such as scale is prevented by utilizing the gas lift effect.
  • a rectifying plate is arranged in another tank connected to the electrolytic cell in which the electrode plate is housed, and the flow velocity near the wall surface of the electrolytic cell is increased to deposit the deposits. Is being prevented.
  • the electrolytic cell is installed at an angle so that the liquid to be treated flowing inside the electrolytic cell becomes an ascending flow to prevent the deposit of the deposit. ..
  • the introduction port and the discharge port are perpendicular to the length direction of the electrolytic cell (in the case of the vertical electrolyzer, the height direction), that is, on the side surface of the electrolytic cell.
  • the flow velocity of the liquid to be treated becomes slow near the wall surface of the electrolytic cell facing the introduction port or the discharge port, so that deposits such as scales are formed near the wall surface. Easy to deposit. Therefore, by providing the rectifying plate as in Patent Document 2 in the vertical electrolyzer of Patent Document 1, it is possible to improve the effect of preventing the deposition of the deposits as in the horizontal electrolyzer of Patent Document 3. ..
  • Patent Document 2 since the rectifying plate is arranged in a tank different from the electrolytic cell in which the electrode plate is housed, the size of the electrolytic cell becomes large. In order to avoid the increase in size, it is conceivable to arrange a straightening vane inside the electrolytic cell. However, since the plurality of electrode plates are housed in the electrolytic cell as electrode modules closely arranged with each other, if the rectifying plates are arranged apart from the electrode modules, the electrolytic cell must be made larger than before. After all, it is unavoidable to increase the size of the electrolytic cell.
  • the present invention has been devised in view of the above-mentioned problems, and in a vertical electrolyzer or a horizontal electrolyzer in which an introduction port and a discharge port are arranged on the side surface of a cylindrical electrolytic cell, deposits such as scales are attached. It is an object of the present invention to provide an electrolytic apparatus capable of suppressing the accumulation of an electrolytic cell and reducing the size.
  • the electrolyzer of the present invention is formed in a cylindrical shape, and has an outer cylinder in which an inlet and an outlet for a liquid to be treated are separated from each other in the central axis direction and arranged on the side surfaces thereof, and a laminate orthogonal to the central axis direction. Connected to a metal and plate-shaped primary polarity base at equal intervals in the direction, it extends in the central axis direction inside the outer cylinder, and one of the inlet and the outlet is opened. A plurality of first electrode plates of the first polarity arranged in the vicinity of the outer cylinder are connected to a metal and plate-shaped second polarity base at equal intervals in the stacking direction, and inside the outer cylinder in the central axis direction.
  • the plurality of second electrode plates of the second polarity and the plurality of second electrode plates of the second polarity arranged in the vicinity of the other opening of the introduction port and the discharge port. It has a plurality of insulating first electrode side spacers arranged.
  • the one opening is located on the radial outer side of the outer cylinder in the direction orthogonal to the central axis direction and the stacking direction from the gap in the stacking direction formed between the plurality of first electrode plates, and the other.
  • the opening is located on the radial outer side of the outer cylinder in the direction orthogonal to the central axis direction and the stacking direction from the gap in the stacking direction formed between the plurality of second electrode plates, and the plurality of first electrodes are located.
  • the one-electrode side spacer has an inclined surface inclined from the central axis direction, and the liquid to be treated is directed from the one opening toward the central axis direction or from the central axis direction toward the one opening.
  • the first electrode side spacer is arranged at the ends of two adjacent first electrode plates and substantially creates a gap between the two first electrode plates at the ends. It is provided with a first spacer that closes all of them and sandwiches and fixes a second polarity electrode plate located between the two first electrode plates.
  • the electrolytic device of the present invention in addition to the original function of the spacer on the first electrode side as an insulating spacer that prevents adjacent first electrode plates from coming into contact with each other, rectification that induces the flow of the liquid to be treated. It also functions as a board. Therefore, the size of the electrolytic device can be reduced, and the accumulation of deposits such as scale can be suppressed.
  • FIG. 1 is a cross-sectional view taken along the line AA of FIG. It is a perspective view which shows a part of the electrolytic apparatus of FIG. 1 by disassembling. It is a schematic diagram for demonstrating the structure of the electrode module of the electrolytic apparatus of FIG. It is sectional drawing for demonstrating a spacer. 6 (a) is an XZ plan view of the first spacer, and FIG. 6 (b) is a view of the first spacer arranged between two adjacent anode plates or cathode plates as viewed from the Z direction. FIG.
  • (C) and (d) are views of the first spacers provided at both ends of the plurality of laminated anode plates as viewed from the Z direction. It is a figure which shows by disassembling the second spacer. It is a schematic diagram for demonstrating the structure of the electrode module of the electrolytic apparatus (monopolar type) which concerns on a modification.
  • a cylindrical outer cylinder is used for the electrolytic cell.
  • An introduction port for introducing the liquid to be treated into the inside of the outer cylinder and a discharge port for discharging the electrolyzed liquid to be treated from the inside of the outer cylinder are arranged on the side surface of the outer cylinder.
  • the introduction port and the discharge port are arranged apart from each other in the direction of the central axis of the outer cylinder (hereinafter referred to as "central axis direction" or "length direction of the electrolytic cell”), and the central axis. It is arranged in a direction substantially perpendicular to the direction (that is, the side surface of the outer cylinder).
  • the electrolyzer of the embodiment and the modified example may be a vertical type in which the central axis of the outer cylinder is substantially in the vertical direction, or may be a horizontal type in which the central axis of the outer cylinder is substantially in the horizontal direction. good.
  • the term "substantially vertical direction” as used herein includes not only the vertical direction but also a direction inclined by 45 degrees or more from the horizontal direction.
  • the "substantially horizontal direction” includes not only the horizontal direction but also a direction inclined by less than 45 degrees from the horizontal direction.
  • it is desirable that the liquid to be treated flowing inside the electrolytic cell is designed to be an upward flow.
  • FIGS. 1 to 7 the electrolyzer of the embodiment will be described below with reference to FIGS. 1 to 7.
  • a bipolar horizontal electrolyzer is shown as an example.
  • the electrolytic apparatus of the modified example will be described with reference to FIG.
  • a monopolar horizontal electrolyzer is shown as an example.
  • an orthogonal coordinate system with an X-axis, a Y-axis, and a Z-axis will be appropriately described.
  • FIGS. 1 to 5 since the drawings are simplified as appropriate, there are minor differences such as the number of electrode plates (anode plate, cathode plate, bipolar electrode plate) being different in each of the drawings. However, it is a figure for demonstrating the same electrolytic apparatus.
  • the electrolyzer 1 of the present embodiment is a bipolar horizontal electrolyzer arranged so that the central axis of the outer cylinder 2 of the electrolytic cell formed in a cylindrical shape coincides with the X axis.
  • the X-axis may be arranged in the horizontal direction (direction perpendicular to the vertical direction), but is tilted by a predetermined angle (for example, about 5 degrees) from the horizontal direction so that the discharge port 4 described later is above the introduction port 3. It is desirable to be arranged.
  • the side surface 2a of the outer cylinder 2 is provided with two openings separated from each other in the X-axis direction.
  • the opening on the left side in the figure is a discharge port 4 for discharging the liquid to be treated from the outer cylinder 2, and the opening on the right side in the figure is an introduction port for introducing the liquid to be treated into the outer cylinder 2.
  • the broken line arrow in FIG. 2 indicates the flow of the liquid to be treated.
  • the introduction port 3 and the discharge port 4 are arranged 180 degrees apart from each other in the circumferential direction of the outer cylinder 2.
  • the introduction port 3 opens toward the minus ( ⁇ ) direction of the Z axis
  • the discharge port 4 opens toward the plus (+) direction of the Z axis.
  • the Z axis is perpendicular to the central axis (X axis) of the outer cylinder 2.
  • the electrolytic cell is configured to include an outer cylinder 2 and flanges 15N and 15P described later that seal both ends of the outer cylinder 2.
  • the electrolytic device 1 is made of metal to a plurality of anode plates 12P electrically connected to a metal anode current-carrying plate 11P via a metal first base 13P, and to a metal cathode current-carrying plate 11N. It has a plurality of cathode plates 12N electrically connected via a second base 13N. Both the anode plate 12P and the cathode plate 12N are rectangular in the XZ plane, extend in the X-axis direction inside the outer cylinder 2, and are equidistant in the Y-axis direction orthogonal to both the X-axis and the Z-axis. Each is laminated (parallel).
  • the anode plate 12P is arranged in the vicinity of one opening (here, the discharge port 4) of the introduction port 3 and the discharge port 4, and the cathode plate 12N is the other opening of the introduction port 3 and the discharge port 4. (Here, it is arranged in the vicinity of the introduction port 3).
  • the anode energizing plate 11P bent and formed in an L shape, the first base 13P rectangular in the YZ plane to which the anode energizing plate 11P is fixed, and the plurality of anode plates 12P fixed to the first base 13P.
  • the anode energization block 10P is configured by the above.
  • an L-shaped bent cathode energizing plate 11N, a rectangular second base 13N in the YZ plane to which the cathode energizing plate 11N is fixed, and a plurality of cathode plates 12N fixed to the second base 13N are used.
  • Cathode energization block 10N is configured.
  • welding bolts 53 for fixing the flanges 15N and 15P that seal both ends of the outer cylinder 2 are installed in advance at the four corners of each.
  • the anode energization block 10P and the cathode energization block 10N are attached to both ends of the outer cylinder 2, respectively.
  • the anode energization block 10P is arranged at the end on the discharge port 4 side
  • the cathode energization block 10N is arranged at the end on the introduction port 3 side.
  • an electrode module 5 and an electrode support frame 50 for supporting the electrode module 5 are arranged inside the outer cylinder 2.
  • the electrode module 5 includes an anode plate 12P connected to the first base 13P and a cathode plate 12N connected to the second base 13N, and a plurality of rectangular electrode plates 40 are laminated. It is formed in the shape of a square column.
  • the anode energizing plate 11P and the cathode energizing plate 11N are omitted from the electrode module 5, and each configuration is simplified for easy understanding.
  • the spacers 20 and 30 described later are shown in the Y-axis direction. The length of is expressed larger than it actually is. Further, as described above, FIGS.
  • 1, 3, and 4 are simplified views, and there are minor differences such as a difference in the number of electrode plates in each figure, but all of them are the same electrolytic device 1. It is a figure for demonstrating.
  • the number of electrode plates arranged in the electrode module 5 is set to several tens to several hundreds depending on the design.
  • the anodic portion is shown by a light dot pattern
  • the cathodic portion is shown by a dark dot pattern.
  • the electrode plate 40 is a bipolar type electrode plate. That is, both the anodic anode portion 40P and the cathodic cathode portion 40N are formed on one electrode plate 40.
  • a monopolar type electrode plate in which only the anodic property or the cathodic property appears on one electrode plate is used.
  • the anodic parts and the cathodic parts are alternately arranged to face each other in the direction of stacking (Y-axis direction). As shown in FIG.
  • the electrode module 5 when electrolyzing the liquid to be processed by the electrolyzer 1, the electrode module 5 is electrically connected to the power supply device 6 via the anode energizing plate 11P and the cathode energizing plate 11N.
  • the positive potential (positive potential) of the power supply device 6 is applied to the anode energizing plate 11P
  • the negative potential (negative potential) is applied to the cathode energizing plate 11N, so that each electrode plate of the electrode module 5 ( A predetermined polarity of anodic or cathodic appears in 12P, 12N, 40).
  • the anode plate 12P is anodic
  • the cathode plate 12N is cathodic.
  • half of the electrode plate 40 is an anodic anode portion 40P, and the other half is a cathodic cathode portion 40N.
  • the electrode support frame 50 has a pair of first support frames 51 that sandwich the electrode module 5 in the stacking direction (Y-axis direction), and a direction perpendicular to both the X-axis and the stacking direction (that is,). , Z-axis direction), and has a pair of second support frames 52 that are fixed to the first support frame 51 by sandwiching the pair of first support frames 51.
  • the pair of first support frames 51 are fixed to each other with the anode plate 12P, the cathode plate 12N, and the electrode plate 40 sandwiched by a plurality of bolts 43 (broken line in FIG. 4) extending in the stacking direction (Y-axis direction). Will be done.
  • the pair of second support frames 52 abut on the end faces (XY planes) of the first support frame 51 and are fixed to the first support frame 51 by screws 44 (see FIG. 5).
  • the electrode support frame 50 supports the electrode module 5 by pressing the square pillar-shaped electrode module 5 from all sides, and prevents the electrode module 5 from being deformed.
  • Each first support frame 51 is integrally formed with a rectangular first plate portion 51a corresponding to the length of the electrode module 5 in the X-axis direction and the first plate portion 51a, and is arranged at predetermined intervals in the X-axis direction. It is provided with a plurality of first flange portions 51b.
  • the second support frame 52 is integrally formed with the rectangular second plate portion 52a corresponding to the length of the electrode module 5 in the X-axis direction and the second plate portion 52a, and is arranged at predetermined intervals in the X-axis direction.
  • a plurality of second flange portions 52b are provided.
  • the first flange portion 51b and the second flange portion 52b are combined, and the inner diameter of the outer cylinder 2 is abbreviated.
  • a circular flange portion 50b having the same or slightly smaller outer diameter is formed.
  • the upper second support frame 52 is provided with an opening 52c at a position corresponding to the discharge port 4, and is provided below.
  • the second support frame 52 is provided with an opening 52d at a position corresponding to the introduction port 3.
  • the openings 52c and 52d are formed only in one of the second support frames 52 of the pair of second support frames 52, depending on the positions of the introduction port 3 and the discharge port 4 arranged in the outer cylinder 2. In some cases. For example, when the introduction port 3 and the discharge port 4 are arranged at the same position when viewed in the circumferential direction of the outer cylinder 2, only one of the second support frames 52 of the pair of the second support frames 52 has the opening 52c and the opening 52c.
  • the opening 52d is formed.
  • the electrode module 5 including the anode energization block 10P and the cathode energization block 10N is firmly bound by the electrode support frame 50 and then inserted into the outer cylinder 2.
  • An annular gasket 16 having an inner diameter substantially the same as that of the outer cylinder 2 is arranged on one end surface of the outer cylinder 2.
  • a rectangular gasket 17 having substantially the same outer shape as the first base 13P, having a rectangular opening formed in the center, and having through holes 18 formed in the vicinity of the four corners of the opening is arranged.
  • a flange 15P having a rectangular opening 15a having substantially the same shape as the opening of the gasket 17 is arranged in the center. Through holes 15b are provided in the vicinity of the four corners of the opening 15a of the flange 15P.
  • the positions of the four through holes 18 formed in the gasket 17 and the positions of the four through holes 15b formed in the flange 15P correspond to the positions of the four welding bolts 53 provided in the first base 13P, respectively. ing. Therefore, first, the four through holes 18 of the gasket 17 are inserted into each of the four welding bolts 53 of the first base 13P, and then the four through holes 15b of the flange 15P are inserted into each of the four welding bolts 53. Are inserted respectively. Then, a nut (not shown) is fitted into the welding bolt 53, and the first base 13P and the flange 15P are hermetically fixed by sandwiching the gasket 17. Next, the flange 15P and the outer cylinder 2 sandwich the gasket 16 and are airtightly fixed by bolts and nuts (not shown).
  • an anode terminal box 14P covering the anode energizing plate 11P is fixed to the flange 15P in order to protect the anode energizing plate 11P.
  • the first base 13P and the second base 13N have the same shape, and the flange 15P and the flange 15N have the same shape. Therefore, similarly, on the other end surface of the outer cylinder 2, the second base 13N and the flange 15N, and the flange 15N and the outer cylinder 2 are hermetically fixed by sandwiching a gasket (corresponding to gaskets 16 and 17) (not shown). To. Further, in order to protect the cathode energizing plate 11N, the cathode terminal box 14N covering the cathode energizing plate 11N is fixed to the flange 15N.
  • the electrolytic device 1 has, as the anode-side spacer 20, the anode-side first spacer 21 arranged between all of the two adjacent anode plates 12P among the plurality of anode plates 12P, and among the plurality of anode plates 12P.
  • An anode-side first spacers 21A and 21B are provided between the anode plates 12P located at both ends and the first plate portion 51a closest to the anode plates 12P, respectively.
  • the electrolytic device 1 is integrated as the anode side spacer 20 by sandwiching and fitting the through holes from both sides through the through holes formed inside the anode plate 12P (for example, the central portion).
  • the anode side second spacer 22 is provided.
  • the anode-side first spacers 21, 21A, and 21B are arranged at the ends of the anode plate 12P on the first base 13P side, respectively, and are located between the two anode plates 12P at this end, or the anode plates at this end. Substantially all the gaps in the Y-axis direction and the Z-axis direction between the 12P and the first plate portion 51a are closed.
  • the anode-side second spacer 22 substantially has a gap in the Y-axis direction between the anode plate 12P to which the anode-side second spacer 22 is fixed and the two electrode plates 40 adjacent to the anode plate 12P. Block everything. However, as will be described later, in the XZ plane, the dimension of the anode side second spacer 22 is smaller than the dimension of the anode plate 12P, so that the anode plate 12P to which the anode side second spacer 22 is fixed and the two electrode plates 40 adjacent to the anode plate 12P are fixed.
  • the gap between the anode side and the second spacer 22 When the gap between the anode side and the second spacer 22 is viewed from the X-axis direction, the gap (near both ends of the anode side second spacer 22 in the Z-axis direction) is not closed and is to be processed.
  • the liquid can flow.
  • the electrolytic device 1 is arranged as the cathode side spacer 30 at the end of the two adjacent cathode plates 12N on the second base 13N side, and Y between all of the two cathode plates 12N at this end.
  • the cathode-side second spacer 32 closes substantially all the gaps in the Y-axis direction between the electrode plate 40 to which the cathode-side second spacer 32 is fixed and the two cathode plates 12N adjacent to the electrode plate 40. ..
  • the dimension of the cathode side second spacer 32 is smaller than the dimension of the electrode plate 40, so that the electrode plate 40 to which the cathode side second spacer 32 is fixed and the two cathode plates 12N adjacent to the electrode plate 40 are fixed.
  • the gap between the cathode side and the second spacer 32 When the gap between the cathode side and the second spacer 32 is viewed from the X-axis direction, the gap between the cathode side second spacer 32 and the portion without the cathode side second spacer 32 (near both ends of the cathode side second spacer 32 in the Z axis direction) is not closed and is processed.
  • the liquid can flow.
  • the above-mentioned "closes substantially all the gaps” means that the gap between two adjacent electrode plates or the gap between the electrode plates and the electrode support frame 50 is completely closed, and the gap is very small. It is a concept that also includes closing the space in a state where it remains. Since "substantially all the gaps are closed", any spacer can smoothly guide the liquid to be treated.
  • the anode-side spacer 20 may be arranged in contact with two adjacent anode plates 12P, and the cathode-side spacer 30 may be arranged in contact with two adjacent cathode plates 12N.
  • the anode-side spacer 20 and the cathode-side spacer 30 are made of a highly insulating material (for example, rubber or plastic resin).
  • the plurality of anode-side spacers 20 have an inclined surface inclined with respect to the central axis (X-axis) of the outer cylinder 2, and may be directed toward the X-axis from one opening (for example, the introduction port 3) or.
  • the flow of the liquid to be treated is guided from the X-axis direction toward one opening (for example, the discharge port 4). That is, the anode-side spacer 20 has a function as a straightening vane in addition to the original function of preventing two adjacent anode plates 12P from contacting each other and electrically short-circuiting.
  • the anode-side spacer 20 guides the flow of the liquid to be treated from the X-axis direction toward the discharge port 4, as shown by the broken line arrow in FIG.
  • the discharge port 4 is located radially outward from the gap formed between the plurality of anode plates 12P. In FIG. 2, the discharge port 4 is located before the flow direction of the liquid to be treated is changed by approximately 90 degrees by the anode-side spacer 20.
  • the plurality of cathode-side spacers 30 have an inclined surface inclined with respect to the central axis (X-axis) of the outer cylinder 2 from the X-axis direction toward the other opening (for example, the discharge port 4) or.
  • the flow of the liquid to be treated is guided from the other opening (for example, the introduction port 3) toward the X-axis direction. That is, the cathode side spacer 30 also has a function as a rectifying plate in addition to the original function of preventing two adjacent cathode plates 12N from contacting each other and electrically short-circuiting.
  • the cathode side spacer 30 guides the flow of the liquid to be treated from the introduction port 3 in the X-axis direction as shown by the broken line arrow in FIG.
  • the introduction port 3 is located radially outward from the gap formed between the plurality of cathode plates 12N.
  • the flow direction of the liquid to be treated introduced from the introduction port 3 is changed by approximately 90 degrees by the cathode side spacer 30.
  • the introduction port 3 and the discharge port 4 are provided so as to be offset by 180 degrees in the circumferential direction of the outer cylinder 2, the inclined surface of the cathode side spacer 30 and the inclined surface of the anode side spacer 20 are centered. It is tilted at an angle of about 45 degrees with respect to the axis (X axis).
  • the shapes of the anode-side first spacers 21, 21A, 21B of the anode-side spacer 20 and the cathode-side first spacer 31 of the cathode-side spacer 30 will be described in detail. Although they are arranged differently from each other as shown in FIGS. 2 and 4, they all have the same shape as shown in the view of the XZ plane of FIG. 6A when viewed from the Y-axis direction. As shown in FIG. 6A, the anode-side first spacers 21, 21A, 21B and the cathode-side first spacer 31 are in the Z-axis direction of the anode plate 12P or the cathode plate 12N when viewed from the Y-axis direction.
  • the inclined surface 231 corresponding to the hypotenuse of the substantially right triangle portion is one of the inclined surfaces of the anode side spacer 20 and the cathode side spacer 30.
  • the inclined surface 231 is a linear inclined surface here, it may be an arc-shaped inclined surface recessed toward the rectangular portion in order to induce the flow of the liquid to be treated more smoothly.
  • a plurality of through holes separated in the Z-axis direction are formed in the rectangular portions of the anode-side first spacers 21, 21A, 21B, and the cathode-side first spacer 31 of the cathode-side spacer 30.
  • 232 is formed.
  • two through holes 232 are formed in these spacers.
  • Through holes are formed in the anode plate 12P and the cathode plate 12N at positions corresponding to the through holes 232 of these spacers. Then, these spacers are fixed to the pair of first plate portions 51a together with the corresponding electrode plates by the through bolts (not shown) having a diameter of several mm corresponding to the through holes 232.
  • a concave notch 233 penetrating in the Z-axis direction is provided at the center of the substantially right triangle portion of the anode-side first spacer 21 and the cathode-side first spacer 31 in the Y-axis direction. It is formed.
  • the notch 233 of the anode-side first spacer 21 is fixed by sandwiching the cathode portion 40N of the electrode plate 40 arranged between the two adjacent anode plates 12P.
  • the notch 233 of the cathode side first spacer 31 is fixed by sandwiching the anode portion 40P of the electrode plate 40 arranged between the two adjacent cathode plates 12N.
  • a stepped portion 234 recessed in the Y-axis direction is formed at the upper right end portion of the anode-side first spacer 21A in the XY plane.
  • One of the electrode plates 40 located at both ends of the electrode module 5 in the stacking direction, for example, the cathode portion 40N of the electrode plate 40 located at the uppermost position in FIG. 4 is recessed in the stepped portion 234 of the anode-side first spacer 21A. Be placed. Then, the cathode portion 40N of the electrode plate 40 is sandwiched and fixed between the stepped portion 234 of the anode-side first spacer 21A and the first plate portion 51a. Further, as shown in FIG.
  • a stepped portion 235 recessed in the Y-axis direction is formed at the lower right end portion of the anode-side first spacer 21B in the XY plane.
  • One of the electrode plates 40 located at both ends of the electrode module 5 in the stacking direction, for example, the cathode portion 40N of the electrode plate 40 located at the lowermost position in FIG. 4 is recessed in the stepped portion 235 of the anode-side first spacer 21B. Be placed. Then, the cathode portion 40N of the electrode plate 40 is sandwiched and fixed between the stepped portion 235 of the anode-side first spacer 21B and the first plate portion 51a.
  • the shapes of the anode-side second spacer 22 of the anode-side spacer 20 and the cathode-side second spacer 32 of the cathode-side spacer 30 will be described in detail. Although they are arranged differently from each other as shown in FIGS. 2 and 4, they all have the same shape as shown in the exploded views of FIGS. 7.
  • the length of these second spacers 22 and 32 is shorter than the length of the anode plate 12P or the cathode plate 12N in the Z-axis direction, and it is desirable that the dimensions are about half of the length in the Z-axis direction.
  • the anode-side second spacer 22 is composed of a plate-shaped spacer piece 22A having convex portions 236 at both ends and a plate-shaped spacer piece 22B having concave portions 237 having a diameter of several mm at both ends. As shown in FIG. 7, the recess 237 of the spacer piece 22B protrudes from the plate-shaped portion of the spacer piece 22B. Specifically, the two convex portions 236 of the spacer piece 22A and the two concave portions 237 of the spacer piece 22B are fitted (rivet-fastened) to each other to be integrated into a rectangular shape (or a linear shape). Moreover, a plate-shaped second spacer 22 on the anode side is formed.
  • the cathode-side second spacer 32 is composed of a plate-shaped spacer piece 32A having convex portions 236 at both ends and a plate-shaped spacer piece 32B having concave portions 237 having a diameter of several mm at both ends. As shown in FIG. 7, the recess 237 of the spacer piece 32B protrudes from the plate-shaped portion of the spacer piece 32B. Specifically, the two convex portions 236 of the spacer piece 32A and the two concave portions 237 of the spacer piece 32B are fitted (rivet-fastened) to each other to be integrated into a rectangular shape (or a linear shape). Moreover, a plate-shaped second spacer 32 on the cathode side is formed.
  • the second spacer 22 on the anode side is a spacer piece from one surface of the anode plate 12P in two through holes (not shown, but a small through hole equivalent to the recess 237) formed inside the anode plate 12P.
  • the two concave portions 237 of the 22B are inserted through, and the two convex portions 236 of the spacer piece 22A are fitted into the corresponding concave portions 237 from the other surface of the anode plate 12P, thereby being fixed to the anode plate 12P. As shown in FIG.
  • the center of the anode-side second spacer 22 is the center of the outer cylinder 2 in the Z-axis direction, and the center is at a position equivalent to the center of the opening 52c in the X-axis direction.
  • the white arrow in FIG. 5 shows an example of the flow of the liquid to be treated.
  • the inclined surface inclined from the X-axis direction central axis direction
  • the inclined surface 231 of the spacer 21 and the inclined surface 238 of the second spacer 22 on the anode side effectively guide the flow of the liquid to be treated toward the discharge port 4.
  • the inclined surface 238 has a linear shape here, it may have an arc shape recessed toward the discharge port 4 in order to guide the flow of the liquid to be treated more smoothly. That is, the anode-side second spacer 22 divides the flow of the liquid to be treated to reduce the flow of the liquid to be treated that directly collides with the anode-side first spacer 21, and the anode-side first spacer 21 rectifies the flow.
  • the two spacers, the anode-side first spacer 21 and the anode-side second spacer 22, are arranged in the vicinity of the anode plate 12P, so that the anode-side first spacer 21 It is possible to more effectively suppress the accumulation of deposits such as scale in the vicinity of the anode plate 12P as compared with the case where only the anode plate 12P is arranged.
  • the anode-side spacer 20 may be configured such that the anode-side second spacer 22 is not arranged and only the anode-side first spacer 21 is arranged.
  • the second spacer 32 on the cathode side has two through holes formed inside the electrode plate 40 arranged between two adjacent cathode plates 12N (not shown, but a small through hole equivalent to the recess 237). ), The two concave portions 237 of the spacer piece 32B are inserted from one surface of the electrode plate 40, and the two convex portions 236 of the spacer piece 32A are fitted into the corresponding concave portions 237 from the other surface of the electrode plate 40. By matching, it is fixed to the electrode plate 40. As shown in FIG.
  • the center of the cathode-side second spacer 32 is the center of the outer cylinder 2 in the Z-axis direction, and the center is at a position equivalent to the center of the opening 52d in the X-axis direction. Be placed.
  • an inclined surface inclined from the X-axis direction central axis direction
  • an inclined surface 231 of the cathode side first spacer 31 and an inclined surface 238 of the cathode side second spacer 32 is effectively guided in the X-axis direction.
  • the inclined surface 238 has a linear shape here, it may have an arc shape recessed in the minus (-) X-axis direction in order to induce the flow of the liquid to be treated more smoothly. .. That is, the cathode-side second spacer 32 divides the flow of the liquid to be treated to reduce the flow of the liquid to be treated that directly collides with the cathode-side first spacer 31, and the cathode-side first spacer 31 is rectified.
  • the cathode side first spacer 31 and the cathode side second spacer 32 are arranged in the vicinity of the cathode plate 12N, so that the cathode side first spacer 31 It is possible to more effectively suppress the accumulation of deposits such as scale in the vicinity of the cathode plate 12N as compared with the case where only the cathode plate is arranged.
  • the cathode side spacer 30 may be configured such that the cathode side second spacer 32 is not arranged and only the cathode side first spacer 31 is arranged.
  • the electrolytic device 1 has a plurality of spherical or rugby ball-shaped insulating spacers 33 elongated in the Y-axis direction so that the plurality of bipolar electrode plates 40 do not come into contact with each other. May be provided. It is desirable that the dimensions of the spacer 33 in the XZ plane are as small as possible compared to the dimensions of the electrode plate 40 in the XZ plane. As described above, in FIG. 4, the length of the spacer 33 in the Y-axis direction is expressed larger than the actual length for the convenience of showing a simplified diagram for easy understanding.
  • the spacer 33 is a hemispherical or semi-rugby ball-shaped spacer piece having protrusions at both ends, and recesses (anode side) having a diameter of several mm at both ends. It is composed of a hemispherical or semi-rugby ball-shaped spacer piece provided with a second spacer 22 and a second spacer 32 on the cathode side (similar to the second spacer 32 on the cathode side).
  • the spacer 33 is formed in two through holes (not shown, but a small through hole equivalent to the recess) formed inside the electrode plate 40 from one surface of the electrode plate 40 to two of the spacer pieces.
  • the spacer 33 may have a hollow columnar shape that penetrates the bolt 43. In this case, the spacer 33 is sandwiched between the anode portion 40P of the electrode plate 40 and the cathode portion 40N facing the Y-axis direction, and is fastened and fixed by bolts 43.
  • the anode-side spacer 20 and the cathode-side spacer 30 function as an insulating spacer for preventing contact between the laminated electrode plates, and also effectively deposit deposits such as scales. It also has a function as a rectifying plate that suppresses. Therefore, the electrolytic device 1 can be miniaturized and the frequency of maintenance can be reduced, so that long-term operation is possible.
  • the product produced by electrolysis of the electrolytic device 1 differs depending on the type of the liquid to be treated. For example, when the liquid to be treated is seawater or salt water, the product is sodium hypochlorite (hypochlorous acid). Soda).
  • the electrolyzer 1 that can be miniaturized and can be operated for a long period of time is useful as a sodium hypochlorite producing device that is effective for disinfecting the new coronavirus that is prevalent worldwide this year.
  • commercially available sodium hypochlorite is inconvenient because it is diluted with water and used as a disinfectant.
  • sodium hypochlorite at a concentration (0.05%, 500 mg / L) recommended by the Ministry of Health, Labor and Welfare as a safe concentration with little effect on the human body and a medicinal effect is directly produced. can do.
  • the sodium hypochlorite produced by the electrolytic device 1 does not need to be diluted with water, it is sprayed in large quantities on plants and public roads for disinfection of not only the new coronavirus but also other viruses and bacteria. Especially useful if.
  • the principle of producing sodium hypochlorite by the electrolyzer 1 is shown.
  • the liquid to be treated is seawater or salt water.
  • Chlorine (Cl 2 ) generated at the anode (anode plate 12P, anode portion 40P of the electrode plate 40) is sodium hydroxide (NaOH) generated at the cathode (cathode plate 12N, cathode portion 40N of the electrode plate 40) and an electrolytic cell.
  • the reaction is as follows to produce sodium hypochlorite (NaClO). Cl 2 + 2NaOH ⁇ NaClO + NaCl + H 2 O
  • the electrolyzer 1 has, for example, set the current density to 5 A / dm 2 (ampere / sq. Decimeter) and electrolyze for about 12 hours using inexpensive nighttime power to obtain a low concentration of chlorine contained in the liquid to be treated. All ions (100mg / L-2000mg / L) are at the concentration recommended by the Ministry of Health, Labor and Welfare (0.05%, 500mg / L) for the new corona virus countermeasures, and about 1 ton of sodium hypochlorite (100mg / L-2000mg / L). Can be converted to L).
  • the incinerator which is a large space, can be operated during the day on the scheduled day.
  • Sodium hypochlorite disinfectant at the concentration recommended by the Ministry of Health, Labor and Welfare can be sprayed on platforms and public roads.
  • FIG. 8 shows an electrode module 5'when the electrode module 5 of the electrolytic device 1 of the embodiment is a monopolar type.
  • FIG. 8 is a schematic diagram corresponding to FIG.
  • the monopolar electrode module 5'shown in FIG. 8 is largely different in that the electrode plate 40 arranged in the bipolar electrode module 5 shown in FIG. 4 does not exist.
  • the anode portion is shown by a light dot pattern
  • the cathode portion is shown by a dark dot pattern.
  • the same configuration as in FIG. 4 is assigned the same number, and the description including the effect is omitted.
  • the anode plate 12P is arranged between two adjacent cathode plates 12N among the plurality of cathode plates 12N. Therefore, the notch 233 of the cathode side first spacer 31 is fixed by sandwiching the anode plate 12P. Further, the notch 233 of the first spacer 21 on the anode side is fixed by sandwiching the cathode plate 12N. Further, in the monopolar type electrode module 5', since the electrode plate 40 of the bipolar type electrode module 5 does not exist, the cathode side second spacer 32 is an anode plate 12P arranged between two adjacent cathode plates 12N.
  • the two recesses 237 of the spacer piece 32B are inserted from one surface of the anode plate 12P into the two through holes (not shown, but a minute through hole equivalent to the recess 237) formed inside the anode plate 12P.
  • the two convex portions 236 of the spacer piece 32A are fixed to the anode plate 12P by fitting the two convex portions 236 of the spacer piece 32A into the corresponding concave portions 237 from the other surface of the anode plate 12P. That is, the anode-side second spacer 22 and the cathode-side second spacer 32 are fixed to the anode plate 12P.
  • the spacer 33 may be arranged in the electrode module 5'.
  • the spacer 33 is fixed to the anode plate 12P. Specifically, in the two through holes (not shown) formed inside the anode plate 12P (for example, the central portion), two recesses of one spacer piece of the spacer 33 from one surface of the anode plate 12P. Is inserted and the two convex portions of the other spacer piece of the spacer 33 are fitted into the corresponding concave portions from the other surface of the anode plate 12P, thereby being fixed to the anode plate 12P.
  • the cathode side spacer 30 and the anode side spacer 20 are provided in the vicinity of the introduction port 3 and the discharge port 4, respectively.
  • only one of the anode side spacer 20 and the cathode side spacer 30 may be arranged in only one of the introduction port 3 and the discharge port 4.
  • only the anode side spacer 20 may be arranged to rectify the flow of the liquid to be treated in the vicinity of the discharge port 4, or only the cathode side spacer 30 may be arranged.
  • the flow of the liquid to be treated may be rectified in the vicinity of the introduction port 3.
  • the cathode energization block 10N is provided in the vicinity of the introduction port 3, and the anode energization block 10P is provided in the vicinity of the discharge port 4, but the anode energization block is provided in the vicinity of the introduction port 3.
  • 10P may be provided, and a cathode energizing block 10N may be provided in the vicinity of the discharge port 4.
  • the positive potential (positive potential) of the power supply device 6 is applied to the anode energizing plate 11P
  • the negative potential (minus potential) is applied to the cathode energizing plate 11N.
  • the anode-side spacer 20 guides the flow of the liquid to be treated from one opening (introduction port 3) toward the central axis direction (X-axis direction), and the cathode-side spacer 30 is the central axis.
  • the flow of the liquid to be treated is guided from the direction (X-axis direction) toward the other opening (discharge port 4).
  • the first polarity electrode plate means either an anodic anode plate or a cathodic cathode plate.
  • the second electrode plate having the second polarity means an electrode plate having the opposite polarity to the first electrode plate having the first polarity. Therefore, when the first electrode plate of the first polarity is an anodic anode plate, the second electrode plate of the second polarity is a cathodic cathode plate, and the first polarity base is an embodiment or a modification.
  • the first base and the second polar base mean the second base in the embodiment or the modified example, and the first electrode side spacer and the second electrode side spacer mean the anode side spacer and the cathode side spacer in the embodiment or the modified example, respectively.
  • the first electrode plate of the first polarity is a cathode plate
  • the second electrode plate of the second polarity is an anode plate
  • the first polarity base is the second base.
  • the second polar base means the first base
  • the first electrode side spacer and the second electrode side spacer mean the cathode side spacer and the anode side spacer in the embodiment or the modified example, respectively.
  • Electrolytic device 2 Outer cylinder 2a Side surface 3 Inlet port 4 Discharge port 5, 5'Electrode module 6 Power supply device 10P Anode energization block 10N Catabol energization block 11P Anode energization plate 11N Cathode energization plate 12P Anode plate 12N Cathode plate 13P First base 13N 2nd base 14P anode terminal box 14N cathode terminal box 15a opening 15b through hole 15N, 15P flange 16 gasket 17 gasket 18 through hole 20 anode side spacer 21, 21A, 21B anode side first spacer 22 anode side second spacer 22A spacer piece 22B spacer piece 30 cathode side spacer 31 cathode side first spacer 32 cathode side second spacer 32A spacer piece 32B spacer piece 33 spherical spacer 40 electrode plate 40P anode part (anodic part) 40N Cathodic part (cathodic part) 43 bolts 44 screws (

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  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
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  • Inorganic Chemistry (AREA)
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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
PCT/JP2021/029808 2020-08-25 2021-08-13 電解装置 WO2022044850A1 (ja)

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JP6845975B1 (ja) * 2021-01-14 2021-03-24 三菱重工環境・化学エンジニアリング株式会社 電解システム

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JP6845975B1 (ja) * 2021-01-14 2021-03-24 三菱重工環境・化学エンジニアリング株式会社 電解システム

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MX2023001968A (es) 2023-02-23
KR102559708B1 (ko) 2023-07-25
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KR20230037679A (ko) 2023-03-16
TW202212636A (zh) 2022-04-01

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