WO2024009599A1 - Réservoir d'électrolyse - Google Patents

Réservoir d'électrolyse Download PDF

Info

Publication number
WO2024009599A1
WO2024009599A1 PCT/JP2023/017232 JP2023017232W WO2024009599A1 WO 2024009599 A1 WO2024009599 A1 WO 2024009599A1 JP 2023017232 W JP2023017232 W JP 2023017232W WO 2024009599 A1 WO2024009599 A1 WO 2024009599A1
Authority
WO
WIPO (PCT)
Prior art keywords
cathode
anode
opening
frame
side fluid
Prior art date
Application number
PCT/JP2023/017232
Other languages
English (en)
Japanese (ja)
Inventor
秀成 石丸
裕史 井上
Original Assignee
株式会社トクヤマ
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.)
Filing date
Publication date
Application filed by 株式会社トクヤマ filed Critical 株式会社トクヤマ
Publication of WO2024009599A1 publication Critical patent/WO2024009599A1/fr

Links

Images

Classifications

    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/09—Nitrogen containing compounds
    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • the present invention relates to an electrolytic cell, and more specifically, although not limited thereto, an electrolytic cell that can be suitably used to produce a quaternary ammonium hydroxide aqueous solution using a quaternary ammonium salt aqueous solution as a raw material. Regarding.
  • Patent Documents 1 to 4 listed below disclose manufacturing methods for producing a quaternary ammonium hydroxide aqueous solution using a quaternary ammonium salt aqueous solution as a raw material.
  • an electrolytic cell is used that includes a cathode frame, a cathode plate fixed to the inner surface of the cathode frame, an anode frame and an anode plate fixed to the inner surface of the anode frame. be done.
  • At least one cation exchange membrane is disposed between the cathode plate and the anode plate, a cathode chamber is defined between the cathode frame and the cation exchange membrane, and a cathode chamber is defined between the anode frame and the cation exchange membrane.
  • An anode chamber is defined between the exchange membrane and the exchange membrane.
  • An anode side fluid discharge path is provided for discharging the anode side fluid from the supply path and the anode chamber.
  • the cathode frame has a plurality of upper passages extending from a plurality of upper openings arranged at intervals in the width direction and a plurality of lower openings extending from a plurality of lower openings arranged at intervals in the width direction.
  • a plurality of extending lower channels are disposed, one of the upper channel and the lower channel forming the cathode side fluid discharge channel, and the other of the upper channel and the lower channel forming the cathode side fluid discharge channel. This constitutes a cathode side fluid supply path.
  • the anode frame has a plurality of upper channels extending from a plurality of upper openings arranged at intervals in the width direction and a plurality of channels extending from a plurality of lower openings arranged at intervals in the width direction.
  • One of the upper and lower flow channels constitutes the anode side fluid discharge channel, and the other of the upper and lower flow channels constitutes the anode side fluid discharge channel. Configure a fluid supply path.
  • the cathode side fluid that is, the quaternary ammonium hydroxide aqueous solution is circulated through the cathode side fluid supply path, the cathode chamber, and the cathode side fluid discharge path
  • the anode side fluid that is, the anode side fluid is circulated through the anode side fluid supply path, the anode chamber, and the anode side fluid discharge path.
  • the quaternary ammonium salt aqueous solution is circulated.
  • the effective flow cross-sectional area of the cathode-side fluid supply path and the effective flow cross-sectional area of the cathode-side fluid discharge path are set to be substantially the same, and the anode-side fluid
  • the effective flow cross-sectional area of the supply path and the effective flow cross-sectional area of the anode side fluid discharge path are set to be substantially the same.
  • an electrolytic cell of the form proposed by the present inventors in Japanese Patent Application No. 2022-33651 that is, the upper end of the cathode plate is formed with at least one upper through-opening that matches the upper opening of the cathode frame).
  • the lower end of the cathode plate is formed with at least one lower through-opening aligned with the lower opening of the cathode frame
  • the upper end of the anode plate is formed with at least one lower through opening aligned with the upper opening of the anode frame.
  • at least one upper through opening is formed in the anode plate
  • at least one lower through opening is formed in the lower end of the anode plate that aligns with the lower opening in the anode frame;
  • the maximum The effective channel area is set to the minimum necessary to achieve the highest electric field efficiency.
  • the present invention has been made in view of the above facts, and its main technical problem is to provide a new and improved electrolytic cell that avoids an increase in electrolytic voltage and ensures stable operation of the electrolytic cell. be.
  • the inventors have made the effective channel cross-sectional area CD of the cathode-side fluid discharge channel larger than the effective channel cross-sectional area CS of the cathode-side fluid supply channel.
  • the above main technical problem can be achieved by making the effective flow cross-sectional area AD of the anode-side fluid discharge path larger than the effective flow cross-sectional area AS of the anode-side fluid supply path.
  • an anode side fluid supply path for supplying an anode side fluid to an anode chamber defined between the anode frame and the ion exchange membrane, and an anode side fluid for discharging the anode side fluid from the anode chamber.
  • the effective passage cross-sectional area CD of the cathode-side fluid discharge passage is larger than the effective passage cross-sectional area CS of the cathode-side fluid supply passage, and the effective passage cross-sectional area AD of the anode-side fluid discharge passage is larger than the effective passage cross-sectional area CS of the cathode-side fluid supply passage.
  • An electrolytic cell is provided.
  • the cathode frame is provided with at least one upper channel extending from an upper opening located at an upper end of the inner surface and at least one lower channel extending from a lower opening located at a lower end of the inner surface. has been established,
  • the anode frame has at least one upper channel extending from an upper opening located at an upper end of the inner surface and at least one lower channel extending from a lower opening located at a lower end of the inner surface.
  • the cathode plate extends continuously from above the upper opening of the cathode frame to below the lower opening of the cathode frame,
  • the upper end of the cathode plate is formed with at least one upper through opening aligned with the upper opening of the cathode frame, and the lower end of the cathode plate is formed with at least one upper through opening aligned with the upper opening of the cathode frame.
  • At least one lower through opening is formed in alignment;
  • the anode plate extends continuously from above the upper opening of the anode frame to below the lower opening of the anode frame, The upper end of the anode plate is formed with at least one upper through opening aligned with the upper opening of the anode frame, and the lower end of the anode plate is formed with at least one upper through opening aligned with the upper opening of the anode frame.
  • At least one lower through opening is formed in alignment;
  • the upper through-opening of the cathode plate and the upper passage of the cathode frame constitute one of the cathode-side fluid discharge passage and the cathode-side fluid supply passage;
  • the lower flow path of the cathode frame constitutes the other of the cathode fluid discharge path and the cathode fluid supply path,
  • the upper through-opening of the anode plate and the upper passage of the anode frame constitute one of the anode-side fluid discharge passage and the anode-side fluid supply passage;
  • the lower flow path of the anode frame constitutes the other of the anode side fluid discharge path and the anode side fluid supply path.
  • the cathode frame has a plurality of upper passages extending from a plurality of upper openings spaced apart in the width direction at an upper end of the inner surface, and a plurality of upper channels spaced apart in the width direction at a lower end of the inner surface.
  • a plurality of lower flow passages extending from a plurality of lower openings arranged at intervals are arranged,
  • the anode frame includes a plurality of upper channels extending from a plurality of upper openings arranged at intervals in the width direction at an upper end of the inner surface, and a plurality of upper channels extending at intervals in the width direction at a lower end of the inner surface.
  • a plurality of lower flow passages extending from the plurality of lower openings are arranged,
  • a plurality of upper through-openings are formed at the upper end of the cathode plate, each of which aligns with each of the upper openings of the cathode frame, and a lower end of the cathode plate is formed with a plurality of upper through openings that are aligned with each of the plurality of upper openings of the cathode frame.
  • a plurality of lower through openings are formed that respectively align with each of the plurality of lower openings
  • a plurality of upper through openings are formed at the upper end of the anode plate, each of which aligns with each of the upper openings of the anode frame, and a lower end of the anode plate is formed with a plurality of upper through openings that are aligned with each of the upper openings of the anode frame.
  • a plurality of lower through openings are formed that respectively align with each of the plurality of lower openings, The number of the upper through-opening of the cathode plate and the upper flow path of the cathode frame or the lower through-opening of the cathode plate and the lower flow path of the cathode frame that constitute the cathode side fluid discharge path.
  • the upper opening and the lower opening of the cathode frame and the upper through-opening and the lower through-opening of the cathode plate have a circular cross-sectional shape
  • the upper opening and the lower opening of the anode frame and the upper through-opening and the lower through-opening of the anode plate have a circular cross-sectional shape
  • the cathode plate and the anode plate are rectangular plates.
  • At least one cation exchange membrane is disposed between the cathode plate and the anode plate in an electrolytic cell as described above, and such electrolytic cell is used to produce a quaternary ammonium salt.
  • a quaternary ammonium hydroxide aqueous solution is produced using an aqueous solution as a raw material.
  • the effective passage cross-sectional area CD of the cathode side fluid discharge passage is larger than the effective passage cross-sectional area CS of the cathode side fluid supply passage, and the effective passage cross-sectional area AD of the anode side fluid discharge passage is Since it is larger than the effective passage cross-sectional area AS of the anode side fluid supply passage, as will be clearly understood from the examples described later, an increase in electrolytic voltage is avoided and stable operation of the electrolytic cell is ensured.
  • FIG. 1 is a simplified cross-sectional view showing a preferred embodiment of an electrolytic cell constructed according to the present invention.
  • 2 is a simplified cross-sectional view taken along line II-II in FIG. 1, showing a cathode frame and a cathode plate in the electrolytic cell shown in FIG. 1.
  • FIG. FIG. 2 is a partially enlarged cross-sectional view showing an upper opening of the cathode frame, an upper through-hole formed in the cathode plate, and an upper communication opening formed in the gasket in the electrolytic cell shown in FIG. 1;
  • FIG. 3 is a simplified cross-sectional view similar to FIG. 2 showing a cathode frame and a cathode plate in a modified example of an electrolytic cell constructed according to the present invention.
  • the illustrated electrolytic cell constructed according to the present invention includes a cathode frame 4 (FIG. 1), an anode frame 6 (FIG. 1), a cathode side upper wall member 8, an anode Side upper wall member 10, cathode side lower wall member 12, anode side lower wall member 14, cathode side front wall member 16 (FIG. 2), anode side front wall member (not shown), cathode side rear wall member 18 ( 2) and an anode side rear wall member (not shown), the housing 2 has a hollow rectangular parallelepiped shape.
  • the cathode frame 4, the anode frame 6, the cathode front wall member 16, the anode front wall member, the cathode rear wall member 18, and the anode rear wall member extend substantially vertically, and the cathode upper wall member 8 , the anode side upper wall member 10, the cathode side lower wall member 12, and the anode side lower wall member 14 extend substantially horizontally.
  • the base end surface (the right end surface in FIG. 1) of the cathode side upper wall member 8 is connected to the inner surface upper end edge of the cathode frame 4 by a suitable connecting means such as a fastening screw or an adhesive, and
  • the cathode side front wall member 16 is connected to the front surface of the cathode frame 4, the anode side front wall member is connected to the front surface of the anode frame 6 by appropriate connecting means, and the cathode side rear wall member 18 is connected to the rear surface of the cathode frame 4.
  • anode side rear wall member is connected to the rear surface of the anode frame 6 by suitable connection means.
  • the upper wall members 8 and 10, the lower wall members 12 and 14, the front wall member 16, and the rear wall member 18 on the cathode side and the anode side are connected to the cathode frame 4 or the anode frame 6 as described above.
  • these wall members may be integrally formed in advance and connected to the cathode frame 4 or the anode frame 6.
  • the wall portion can also be formed integrally with the cathode frame 4 or the anode frame 6.
  • a sealing member is interposed between the cathode frame 4 or the anode frame 6. It can also be fixed.
  • an extension portion can also be used by extending a gasket 38 described later from a size corresponding to the cathode plate 32 or the anode plate 56 to a size corresponding to the cathode frame 4 or the anode frame 6.
  • cathode frame 4 and the anode-side rear wall member may be in the form of a solid block or a plate, except for the openings and channels described below, and may be made of olefin resins such as polypropylene and polyethylene, vinyl chloride resins, and fluorocarbon resins. It can be formed from an appropriate synthetic resin such as.
  • Cathode frame 4 anode frame 6, cathode upper wall member 8, anode upper wall member 10, cathode lower wall member 12, anode lower wall member 14, cathode front wall member 16, anode front wall member
  • a suitable sealing member (not shown), such as a gasket, may be interposed between the interconnection portions of the cathode-side rear wall member 18 and the anode-side rear wall member.
  • the upper end of the inner surface (the left side in FIG. 1) of the cathode frame 4 has a width direction (direction perpendicular to the plane of the paper in FIG.
  • a plurality of (six in the illustrated case) upper openings 20 are formed at equal intervals in the left-right direction
  • the cathode frame 4 has a plurality of (six in the illustrated case) upper channels 22 (one of which is shown in FIGS. 1 and 3) extending substantially horizontally through the cathode frame 4 from each of the upper openings 20.
  • the upper opening 20 and the lower opening 24 may be circular, and the cross-sectional shape of the upper flow path 22 and the cross-sectional shape of the lower flow path 26 may be circular, matching the circular shapes of the upper opening 20 and the lower opening 24.
  • the upstream flow path 22 and the downstream flow path 26 are connected by an outer flow path (not shown) disposed outside the housing 2, and an outer flow path 31 (part of which is shown in FIG. 2). (shown) is also equipped with a circulation pump, a product storage tank, and multiple valve members for flow control (the outer flow path and the above-mentioned components arranged therein are As these are well known to those skilled in the art, detailed explanations thereof are omitted here).
  • a cathode plate 32 is fixed to the inner surface of the cathode frame 4.
  • the cathode plate 32 extends continuously from above the upper opening 20 formed in the cathode frame 4 to below the lower opening 24 formed in the cathode frame 4. There is.
  • the cathode plate 32 is composed of a rectangular plate made of a suitable conductive metal such as nickel, and its upper end surface is in contact with or close to the inner surface (i.e., lower surface) of the cathode side upper wall member 8, and The end surface is in contact with or close to the inner surface (i.e., the upper surface) of the cathode side lower wall member 12, the front surface thereof is in contact with or close to the inner surface (i.e., the rear surface) of the front wall member 16, and the rear surface is in contact with or close to the inner surface (i.e., the rear surface) of the cathode side lower wall member 12. It is in contact with or close to the inner surface (i.e., front surface) of 18.
  • the fixation of the cathode plate 32 to the cathode frame 4 can be conveniently carried out, for example, by screwing fastening screws (not shown) into the cathode frame 4 through the cathode plate 32 at the four corners of the cathode plate 32.
  • a plurality of (six in the illustrated case) upper through openings 34 are formed at the upper end of the cathode plate 32 at equal intervals in the width direction (perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIG. 2).
  • a plurality (three in the illustrated case) of lower through-openings 36 are provided at the lower end of the cathode plate 32 at equal intervals in the width direction (direction perpendicular to the plane of the paper in FIG.
  • each of the upper through openings 34 formed in the cathode plate 32 is positioned in alignment with each of the upper openings 20 formed at the upper end of the cathode frame 4.
  • each of the upper through-openings 34 is the same shape (and thus circular) and the same size as each of the upper openings 20 described above.
  • it is important that each of the lower through-openings 36 formed in the cathode plate 32 is positioned in alignment with each of the lower openings 24 formed in the lower end of the cathode frame 4. It is.
  • each of the lower through-openings 36 is the same shape (and thus circular) and the same size as each of the lower openings 24 described above.
  • upper through opening 34 (and upper opening 20) is located proximate the upper end of cathode plate 32
  • lower through opening 36 (and lower opening 24) is located proximate the lower end of cathode plate 32. .
  • a gasket 38 be interposed between the cathode frame 4 and the cathode plate 32.
  • the gasket 38 allows the cathode plate 32 to be stably fixed to the cathode frame 4, and also prevents corrosion caused by liquid penetration into the interface between the cathode frame 4 and the cathode plate 32.
  • the gasket 38 may be a rectangular plate having substantially the same dimensions as the cathode plate 32 (as described above, the gasket 38 may be sized to correspond to the cathode frame 4), and may be made of a suitable elastomer, such as silicone rubber or ethylene propylene.
  • a gasket 38 is interposed between the cathode frame 4 and the cathode plate 32, a fastening screw (not shown) is inserted into the cathode frame 4 through the gasket 38 together with the cathode plate 32 at the four corners of the cathode plate 32. Can be screwed on.
  • a fastening screw (not shown) is inserted into the cathode frame 4 through the gasket 38 together with the cathode plate 32 at the four corners of the cathode plate 32. Can be screwed on.
  • a plurality of holes (six in the illustrated case) that communicate with each of the upper through openings 34 formed in the cathode plate 32 and each of the upper openings 20 formed in the cathode frame 4.
  • An upper communication opening 40 is formed at the lower end of the gasket 38 to connect each of the lower through openings 36 formed in the cathode plate 32 and each of the lower openings 24 formed in the cathode frame 4.
  • a plurality (three in the illustrated case) of lower communication openings 42 are formed in communication with each other.As will be more clearly understood by referring to FIG.
  • the side communication opening 42 is larger than the upper side through-opening 34 and the upper side opening 20 and the lower side through-hole 36 and the lower side opening 24.
  • the upper side communication opening 40 and the lower side communication opening 42 formed in the gasket 38 are If the through-opening 34 and the upper opening 20 and the lower through-opening 36 and the lower opening 24 are of substantially the same dimensions, the gasket 38 will expand somewhat to open the upper communicating opening as the electrolytic cell continues to operate. 40 and the lower communication opening 42 are reduced and displaced, and as a result, the communication between the upper through opening 34 and the upper opening 20 and the communication between the lower through opening 36 and the lower opening 24 become insufficient or damaged.
  • the upper communication opening 40 and the lower communication opening 42 have a circular shape having a diameter that is larger by a predetermined length than the diameters of the upper through-hole 34 and the upper opening 20 and the lower through-opening 36 and the lower opening 24.
  • Each of the upper communication opening 40 and the lower communication opening 42 does not necessarily have to be concentric with each of the upper through-hole 34 and the upper opening 20 and the lower through-opening 36 and the lower opening 24, and may be eccentric.
  • the diameters of the upper communication opening 40 and the lower communication opening 42 and the eccentricity relative to the upper through opening 34 and the upper opening 20 and the lower through opening 36 and the lower opening 24 are determined by the expansion of the gasket 38 due to continuous operation of the electrolytic cell.
  • the preferred size of the upper communication opening 40 and lower communication opening 42 is the size of the upper through-hole 34 and upper opening 20 and the lower through-opening 36 and lower opening 24 +30 mm or less, preferably +20 mm or less, more preferably +10 mm or less.
  • the material used for the gasket 38 should preferably have a coefficient of linear expansion of 3 ⁇ 10 ⁇ 4 (1/°C) or less, more preferably 1.5 ⁇ 10 ⁇ 4 (1/°C) or less, and most preferably 1/°C or less. ⁇ 10 ⁇ 4 (1/°C) or less.
  • the anode frame 6 is substantially identical to the cathode frame 4 described above. More specifically, the cathode frame 4 and the anode frame 6 have plane symmetry between them with a virtual plane extending perpendicularly to the plane of the paper in FIG. 1 as a plane of symmetry. Therefore, the anode frame 6 is provided with an upper opening 44, an upper channel 46, a lower opening 48, and a lower channel 50. In order to avoid duplication of explanation, detailed explanations of the upper opening 44, the upper channel 46, the lower opening 48, and the lower channel 50 will be omitted.
  • the upper flow path 46 and the lower flow path 50 are connected by an outer flow path (not shown) provided outside the housing 2, and the outer flow path includes a circulation pump and a raw material storage tank. and a plurality of valve members etc. for flow control are also arranged (the outer flow path and the above-mentioned components arranged therein are well known to those skilled in the art, so detailed descriptions thereof will not be provided). (Description is omitted in this specification).
  • anode plate 56 is fixed to the inner surface of the anode frame 6.
  • the anode plate 56 is substantially identical to the cathode plate 32 described above, except that it is formed from any suitable conductive metal for an anode, such as titanium with an indium oxide plated surface. be.
  • the cathode plate 32 and the anode plate 56 have plane symmetry between them with an imaginary plane extending perpendicularly to the plane of the paper in FIG. 1 as a plane of symmetry. Therefore, the anode plate 56 has a rectangular shape that extends continuously from above the upper opening 44 formed in the anode frame 6 to below the lower opening 48 formed in the anode frame 6. be.
  • the anode plate 56 is formed with an upper through opening 58 and a lower through opening 60 that are aligned with the upper opening 44 and the lower opening 48 formed in the anode frame 6, respectively. To avoid duplication of explanation, detailed explanation of the anode plate 56 will be omitted.
  • a gasket 62 is also interposed between the anode frame 6 and the anode plate 56.
  • This gasket 62 is also substantially the same as the gasket 38 interposed between the cathode frame 4 and the cathode plate 32. More specifically, the gasket 38 and the gasket 62 have plane symmetry between them with an imaginary plane extending perpendicularly to the plane of the paper in FIG. 1 as a plane of symmetry. Therefore, the gasket 62 includes an upper communication opening 64 that communicates between the upper opening 44 formed in the anode frame 6 and the upper through-hole 58 formed in the anode plate 56, as well as the lower communication opening 64 formed in the anode frame 6.
  • a lower communication opening 66 is formed that communicates the side opening 48 and the lower through-hole 60 formed in the anode plate 56 . To avoid duplication of explanation, detailed explanations of the gasket 62, the upper communication opening 64, and the lower communication opening 66 will be omitted.
  • a cation exchange membrane 68 is disposed between the cathode plate 32 and the anode plate 56.
  • the cation exchange membrane 68 which itself may have a well-known form, has a rectangular plate shape, and its upper edge is held between the cathode side upper wall member 8 and the anode side upper wall member 10, and its lower edge is on the cathode side. It is held between the lower wall member 12 and the anode side lower wall member 14, and the front side edges of the cathode frame 4 and the anode frame 6 are held between the cathode side front wall member 16 and the anode side front wall member.
  • cathode frame 4 and the anode frame 6 are held between the cathode side rear wall member 18 and the anode side rear wall member.
  • Cation exchange membrane 68, cathode side upper wall member 8, anode side upper wall member 10, cathode side lower wall member 12, anode side lower wall member 14, cathode side front wall member 16, anode side front wall member, and cathode side rear A suitable sealing member (not shown) can be interposed between the wall member 18 and each of the anode side rear wall members.
  • a cathode chamber or product chamber 70 is defined between the cathode plate 32 and the cation exchange membrane 68, and an anode chamber or raw material chamber 72 is defined between the anode plate 56 and the cation exchange membrane 68.
  • a diluted quaternary ammonium hydroxide aqueous solution (or pure water) is circulated through the product chamber 70, and more specifically, the lower flow path 26 and the upper flow path 22 formed in the cathode frame 4. It flows into the product chamber 70 through one of the two and flows out from the product chamber 70 through the other.
  • the quaternary ammonium salt aqueous solution is circulated through the raw material chamber 72, and more specifically, it flows into the raw material chamber 72 through one of the lower channel 50 and the upper channel 46 formed in the anode frame 6, and flows out through the other. be done.
  • An electrolytic voltage is applied between the cathode plate 32 and the anode plate 56. In this way, the concentration of the quaternary ammonium hydroxide aqueous solution circulating in the product chamber 70 is gradually increased. Since such electrolysis is well known to those skilled in the art, a detailed explanation thereof will be omitted herein.
  • the cathode plate 32 and the anode plate 56 extend through the upper openings 20 and 44 formed in the cathode frame 4 and anode frame 6, respectively.
  • the upper through-hole 34 extends continuously from above to below the lower openings 24 and 48, and is aligned with the upper openings 20 and 44 and the lower openings 24 and 48 in the cathode plate 32 and the anode plate 56, respectively.
  • the cathode plate 32 and the anode plate 56 extend over substantially the entire inner surface of the cathode frame 4 and the anode frame 6, respectively, and therefore the electrolytic cell
  • the relative current-carrying areas of the cathode plate 32 and the anode plate 56 are large relative to the size of the anode plate , and thus electrolysis is performed with improved electrolysis efficiency.
  • the effective flow cross-sectional area CD of the cathode-side fluid discharge passage is larger than the effective flow cross-sectional area CS of the cathode-side fluid supply passage, and similarly, the effective flow cross-sectional area CD of the cathode-side fluid discharge passage is larger than the effective flow cross-sectional area CS of the cathode-side fluid supply passage. It is important that the passage cross-sectional area AD is larger than the effective passage cross-sectional area AS of the anode side fluid supply passage.
  • the phrase "effective flow path cross-sectional area" means the smallest cross-sectional area in the flow path.
  • the cathode side fluid discharge path CD includes six upper through openings 34 in which the cathode plate 32 is formed, an upper communication opening 40, an upper opening 20, an upper flow path 22 following the upper through opening 34, and a part of the outer passage 31, and the cross-sectional area of the upper communication opening 34, the upper opening 20, the upper passage 22, and a part of the outer passage 31 is the same as the cross-sectional area of the upper through-opening 34, or is smaller than that. Therefore, the effective flow cross-sectional area CD of the cathode-side fluid discharge path is defined by the total cross-sectional area of the six upper through-openings 34.
  • the effective channel cross-sectional area CS of the cathode side fluid supply channel includes three lower through openings 36 formed in the cathode plate 32, a lower communication opening 42 following the lower through opening 36, and a lower opening 24.
  • the lower passage 26 and a part of the outer passage 31 and the cross-sectional area of the lower communication opening 42, the lower opening 24, the lower passage 26, and a part of the outer passage 31 is defined by the lower passage 26 and a part of the outer passage 31. It is equal to or larger than the cross-sectional area of the through-opening 36, and therefore, the effective flow cross-sectional area CD of the cathode side fluid discharge path is defined by the total cross-sectional area of the three lower through-openings 36.
  • the cross-sectional area of a portion of the outer flow path 31 is larger than the cross-sectional area of the upper through-opening 34 to the lower through-opening 36.
  • the cross-sectional area of a portion of the outer flow path 31 is preferably 1.0 times or more, more preferably 1.5 times or more, the cross-sectional area of the upper through-opening 34 to the lower through-opening 36.
  • the cross-sectional area of a portion of the outer flow path 31 with respect to the upper through-opening 34 to the lower through-opening 36 is appropriately determined in consideration of the effective flow path cross-sectional area and the amount of fluid supplied.
  • the effective channel cross-sectional area CD of the cathode-side fluid discharge channel is twice the effective channel cross-sectional area CS of the cathode-side fluid supply channel.
  • the cross-sectional area of the upper through-opening 34 and the lower through-opening 36 formed in the cathode plate 32 be set to the minimum necessary in order to achieve maximum electric field efficiency.
  • the inventors of the present invention found that gas is generated due to electrolytic action in the cathode chamber or product chamber 70, and that gas is generated in the cathode side fluid discharge path on the cathode side. In addition to the fluid, the gas produced is also flowed.
  • the effective channel cross-sectional area CD of the cathode-side fluid discharge channel is set to be the same as the effective channel cross-sectional area CS of the cathode-side fluid supply channel, the flow velocity will be lower in the cathode-side fluid discharge channel than in the cathode-side fluid supply channel. This increases backpressure, which tends to increase the electrolysis voltage and impede stable operation of the electrolyzer.
  • the effective flow cross-sectional area CD of the cathode-side fluid discharge path is set larger than the effective flow cross-sectional area CS of the cathode-side fluid supply path.
  • the number of upper through openings 34 (six) is larger than the number of lower through openings 36 (three), and the cathode side fluid discharge path is
  • the effective passage cross-sectional area CD is made larger than the effective passage cross-sectional area CS of the cathode side fluid supply passage, if desired, the number of upper through openings 34 and the number of lower through openings 36 may be made the same.
  • the cross-sectional area of each of the upper through-openings 34 is set larger than the cross-sectional area of each of the lower through-openings 36, so that the effective flow cross-sectional area CD of the cathode-side fluid discharge path is equal to the effective flow path of the cathode-side fluid supply path. It can also be made larger than the cross-sectional area CS.
  • three upper through-openings 34 are formed at equal intervals in the width direction (left-right direction in FIG.
  • each of the upper through-openings 34 is set to be twice the cross-sectional area of each of the lower through-openings 36.
  • a plurality of upper through openings 34 and lower through openings 36 are formed in the cathode plate 32 at equal intervals in the width direction, but if desired, the cathode plate 32 has a plurality of widths. It is also possible to form one upper through-opening and one lower through-opening that extend elongated in the direction, and the cross-sectional area of the upper through-opening 34 to be larger than the cross-sectional area of the lower through-opening 36.
  • the cathode plate 32 is continuous from above the upper opening 20 formed in the cathode frame 4 to below the lower opening 24 formed in the cathode frame 4.
  • the upper end of the cathode plate 32 has a plurality of upper through-openings spaced at equal intervals in the width direction (direction perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIGS. 2 and 4).
  • 34 is formed, and a plurality of lower through-openings 36 are formed at the lower end of the cathode plate 32 at equal intervals in the width direction (direction perpendicular to the plane of the paper in FIG. 1, horizontal direction in FIGS. 2 and 4).
  • the cathode plate 32 may be extended from below the upper opening 20 formed in the cathode frame 4 to above the lower opening 24 formed in the cathode frame 4.
  • the cathode plate 32 does not have an upper through opening 34 and a lower through opening 36, and the upstream end of the cathode fluid discharge path is defined by the upper opening 20 formed in the cathode frame 4.
  • the downstream side of the cathode side fluid supply path can also be defined by a lower opening 24 formed in the cathode frame 4.
  • the effective flow cross-sectional area of the cathode side fluid discharge passage is defined by the total cross-sectional area of the upper openings 20, and the effective flow passage cross-sectional area of the cathode-side fluid supply passage is defined by the total cross-sectional area of the lower openings 24.
  • the effective flow passage cross-sectional area AD of the anode side fluid discharge passage and the effective flow passage cross-sectional area CS of the cathode side fluid supply passage has been specifically explained, the effective flow passage cross-sectional area AD of the anode side fluid discharge passage and the anode
  • the relationship between the effective passage cross-sectional area AS of the side fluid supply passage is also exactly the same, and in order to avoid duplication of explanation, the effective passage cross-sectional area AD of the anode side fluid discharge passage and the effective passage cross-sectional area of the anode side fluid supply passage are A specific explanation of the relationship with the cross-sectional area AS will be omitted.
  • Examples 1 to 3 and comparative example 1 An electrolytic cell having the configuration as shown in FIGS. 1 to 3 or 4 is prepared and operated in a constant current control mode, and the average value of the cell voltage (voltage between the anode plate and the cathode plate) during the operation time is was detected.
  • the effective channel cross-sectional area CD of the cathode-side fluid discharge channel is larger than the effective channel cross-sectional area CS of the cathode-side fluid supply channel
  • the effective channel cross-sectional area of the anode-side fluid discharge channel is AD was larger than the effective channel cross-sectional area AS of the anode side fluid supply channel.
  • the effective channel cross-sectional area CD of the cathode-side fluid discharge channel and the effective channel cross-sectional area CS of the cathode-side fluid supply channel are the same, and similarly, the effective channel cross-sectional area CD of the cathode-side fluid discharge channel is the same.
  • the cross-sectional area AD and the effective channel cross-sectional area AS of the anode side fluid supply channel were the same.
  • the average value of cell voltage was as shown in Table 1.
  • the details and operating conditions of the electrolytic cell components are as follows. Operating time: 30 days Cathode: Nickel plate (thickness 2mm, surface dimensions 1m x 1m) Anode: Titanium plate with indium oxide plated on the surface (thickness 2mm, surface dimensions 1m x 1m) Cation exchange membrane: Chemours Company ) Replacement membrane (thickness 1mm) sold under the product name “N324” Gasket: EPDM (the diameters of the upper and lower communication openings are 2 mm larger than the corresponding diameters of the upper and lower through-holes, respectively) Raw material (anode side fluid): Methylammonium chloride aqueous solution Product (cathode side fluid): Methylammonium hydroxide aqueous solution Current: 1000A (10A/dm 2 ) Operating temperature: 70°C Temperature when assembling electrolytic cell: 20°C Raw material (anode side fluid) flow rate: 20L/min Product (cathode side fluid) flow rate: 20
  • one cation exchange membrane 68 is disposed between cathode plate 32 and anode plate 56, but a plurality of cation exchange membranes 68 are disposed between cathode plate 32 and anode plate 56.
  • the present invention can also be applied to electrolytic cells in which membranes (cation exchange membranes and anion exchange membranes) are provided.
  • Electrolytic cell housing 4 Cathode frame 6: Anode frame 8: Cathode side upper wall member 10: Anode side upper wall member 12: Cathode side lower wall member 14: Anode side lower wall member 16: Cathode side front wall Member 18: Cathode side rear wall member 20: Upper opening 22: Upper channel 24: Lower opening 26: Lower channel 31: Outside channel 32: Cathode plate 34: Upper through opening 36: Lower through opening 38: Gasket 40: Upper communication opening 42: Lower communication opening 44: Upper opening 46: Upper channel 48: Lower opening 50: Lower channel 56: Anode plate 58: Upper through opening 60: Lower through opening 62: Gasket 64: Upper communication opening 66: Lower communication opening 68: Cation exchange membrane 70: Product chamber (cathode chamber) 72: Raw material room (anode room)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Le réservoir d'électrolyse selon l'invention, dans lequel une augmentation de la tension d'électrolyse est empêchée et un fonctionnement stable du réservoir d'électrolyse est assuré, comprend : un corps de cadre de cathode ayant une plaque de cathode fixée à une surface interne de celui-ci ; un corps de cadre d'anode ayant une plaque d'anode fixée à une surface interne de celui-ci ; une membrane échangeuse d'ions disposée entre le corps de cadre de cathode et le corps de cadre d'anode ; un canal d'alimentation en fluide côté cathode pour fournir un fluide côté cathode à une chambre de cathode établie entre le corps de cadre de cathode et la membrane échangeuse d'ions ; et un canal d'évacuation de fluide côté cathode pour évacuer le fluide côté cathode de la chambre de cathode ; un canal d'alimentation en fluide côté anode pour fournir un fluide côté anode à une chambre d'anode établie entre le corps de cadre d'anode et la membrane échangeuse d'ions ; et un canal d'évacuation de fluide côté anode pour évacuer le fluide côté anode de la chambre d'anode. La surface de section transversale de canal efficace CD du canal d'évacuation de fluide côté cathode est supérieure à la surface de section transversale de canal efficace CS du canal d'alimentation en fluide côté cathode. La surface de section transversale de canal efficace AD du canal d'évacuation de fluide côté anode est plus grande que la surface de section transversale de canal efficace AS du canal d'alimentation en fluide côté anode.
PCT/JP2023/017232 2022-07-08 2023-05-08 Réservoir d'électrolyse WO2024009599A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022110449A JP2024008512A (ja) 2022-07-08 2022-07-08 電解槽
JP2022-110449 2022-07-08

Publications (1)

Publication Number Publication Date
WO2024009599A1 true WO2024009599A1 (fr) 2024-01-11

Family

ID=89453054

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/017232 WO2024009599A1 (fr) 2022-07-08 2023-05-08 Réservoir d'électrolyse

Country Status (3)

Country Link
JP (1) JP2024008512A (fr)
TW (1) TW202403106A (fr)
WO (1) WO2024009599A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5497581A (en) * 1978-01-03 1979-08-01 Gen Electric Electricity collector and fluid distribution separator board for chloride electrolytic cell using ion transfer hindrance membrane
JPS59137969U (ja) * 1983-03-02 1984-09-14 鐘淵化学工業株式会社 電解槽
JPS60125386A (ja) * 1983-12-09 1985-07-04 Tanabe Seiyaku Co Ltd フイルタ−プレス型電解槽
JP2004285427A (ja) * 2003-03-24 2004-10-14 Mitsui Chemicals Inc ガス拡散電極を備えたイオン交換膜電解槽
WO2009004937A1 (fr) * 2007-07-05 2009-01-08 Tokuyama Corporation Procédé de production d'hydroxyde d'ammonium quaternaire
US20140262759A1 (en) * 2013-03-15 2014-09-18 Tennant Company Electrolytic cell having a transition duct outlet

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5497581A (en) * 1978-01-03 1979-08-01 Gen Electric Electricity collector and fluid distribution separator board for chloride electrolytic cell using ion transfer hindrance membrane
JPS59137969U (ja) * 1983-03-02 1984-09-14 鐘淵化学工業株式会社 電解槽
JPS60125386A (ja) * 1983-12-09 1985-07-04 Tanabe Seiyaku Co Ltd フイルタ−プレス型電解槽
JP2004285427A (ja) * 2003-03-24 2004-10-14 Mitsui Chemicals Inc ガス拡散電極を備えたイオン交換膜電解槽
WO2009004937A1 (fr) * 2007-07-05 2009-01-08 Tokuyama Corporation Procédé de production d'hydroxyde d'ammonium quaternaire
US20140262759A1 (en) * 2013-03-15 2014-09-18 Tennant Company Electrolytic cell having a transition duct outlet

Also Published As

Publication number Publication date
JP2024008512A (ja) 2024-01-19
TW202403106A (zh) 2024-01-16

Similar Documents

Publication Publication Date Title
KR890003860B1 (ko) 멀티 셀 전해조
NO159538B (no) Elektrodekonstruksjon og elektrolysecelle.
CA3134418A1 (fr) Dispositif a double flux de gaz dote d'une fonctionnalite de refroidissement
US7785453B2 (en) Electrode for electrolytic cell
WO2024009599A1 (fr) Réservoir d'électrolyse
JPS60218490A (ja) 電極および電解槽
EP0120628B2 (fr) Cellule électrolytique
CN115989343A (zh) 用于单极电化学装置的组合式电流载体、循环腔和框架
JP2024027150A (ja) 生成装置
JPH08502788A (ja) 電解槽デザインおよびそのための電極
WO2023167134A1 (fr) Réservoir d'électrolyse
US20210123149A1 (en) Fluid electrolysis apparatus
US4729822A (en) Electrolytic cell
KR102411386B1 (ko) 션트전류 해소를 위한 전해 셀프레임
JPH10309581A (ja) イオン水生成装置の電解槽
CN109735865B (zh) 电解制氢氧配组装置及其制备方法
KR200285556Y1 (ko) 전해조
CA1220444A (fr) Pile electrolytique a debit en vortex amont du compartiment d'anode
CN118591661A (en) Electrolytic cell
US4329218A (en) Vertical cathode pocket assembly for membrane-type electrolytic cell
JPH10158875A (ja) 複極式フィルタープレス型電解槽
US5372692A (en) Bipolar electrolytic cell
JP2024008512A5 (fr)
WO2023104266A1 (fr) Électrolyseur doté d'un empilement de modules à quatre couches soudés
JPS599632B2 (ja) 電解槽

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23835140

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)