EP0183096B1 - Membrane unit for electrolytic cell - Google Patents
Membrane unit for electrolytic cell Download PDFInfo
- Publication number
- EP0183096B1 EP0183096B1 EP85114059A EP85114059A EP0183096B1 EP 0183096 B1 EP0183096 B1 EP 0183096B1 EP 85114059 A EP85114059 A EP 85114059A EP 85114059 A EP85114059 A EP 85114059A EP 0183096 B1 EP0183096 B1 EP 0183096B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- electrolytic cell
- gasket
- membrane unit
- unit
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 239000012528 membrane Substances 0.000 title claims description 75
- 239000000463 material Substances 0.000 claims description 20
- 239000012779 reinforcing material Substances 0.000 claims description 17
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 239000003014 ion exchange membrane Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims 2
- 238000005341 cation exchange Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920003935 Flemion® Polymers 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 229920002681 hypalon Polymers 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000012858 resilient material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
-
- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- 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
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
Definitions
- This invention relates to membranes for use in electrolytic cells and, more particularly, to a membrane unit which will resist tearing upon application of a compressive force to a gasket bearing surface of the membrane.
- membranes for use in electrolytic cells there are many well-known membranes for use in electrolytic cells.
- typical membranes include the perfluorinated carboxylic or sulfonic cation exchange membranes such as the Nafion® membranes manufactured by E. I. duPont de Nemours and Company or the Flemion® membranes manufactured by Asahi Glass Company, Ltd.
- These membranes are typically available in sheet form and employed in filter press-type or flat plate-type electrolytic cells having monopolar or bipolar electrodes. Examples of bipolar, filter press-type cells are described in U.S. Patent Nos. 4,111,779 and 4,108,742.
- the bipolar, filter press-type electrolytic cell is composed of several bipolar unit cells arranged in series.
- One bipolar unit cell has an anode and cathode compartment separated by a partition wall.
- the anode and cathode are attached to opposite sides of the partition wall.
- the membrane is usually interposed between two adjacent unit cells to separate the anode compartment from the cathode compartment.
- a plurality of anode and cathode frames are installed in a parallel fashion and a longitudinal compressive clamping means is applied to the anode and cathode frames with the membrane interposed between the frames to form the electrolytic cell in toto.
- a gasket between the membrane and the anode or cathode frame to provide the electrolytic cell with fluid-tight, i.e., a liquid- and gas-tight seal to prevent leakage of electrolyte between anode and cathode compartments or to the atmosphere. It is important to have a complete liquid- and gas-tight seal in electrolytic cells because these cells typically operate under corrosive environments.
- one side of the gasket is in contact with the lateral face of an electrode frame and the other side of the gasket is in contact with one side of the membrane's peripheral surface.
- Typical gasket materials include resilient material such as rubber or an elastomer.
- Commercial bipolar membrane electrolyzers generally use ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) as gasket material between the membrane and electrode frames. These materials tend to deform and expand outwardly as pressure is applied to the frames via the frame members. As the gaskets deform outwardly, certain membranes which are in contact with the gaskets tend to stretch when they are pulled under the pressure of the outwardly deforming gaskets. This stretching of the membrane beneath the gaskets employed on adjacent electrode frames can cause the membranes to break or tear when attempting to compress the frames into a fluid-tight cell.
- resilient gaskets require a high compressive force to effect a seal which increases the risk of breaking or tearing the membrane.
- GB-A-2 013 242 describes a method and an apparatus for installing a membrane to a finger type electrolytic cell; it refers to installing and securing the membrane by mechanical means. From FR-A-2 146 602 it is known to use membranes provided with frame-like peripheral portions.
- the present invention refers to an ion exchange membrane unit according to claim 1. Preferred embodiments of this membrane unit are subject matter of claims 2 to 5. The present invention also resides in an electrolytic cell according to claim 6 comprising the membrane unit, and in a method of sealing an electrolytic cell according to claim 7.
- Figure 1 is a perspective view of a membrane unit of the present invention showing a membrane having a plurality of openings and a reinforcing material along the periphery of the sheet.
- Figure 2 is a cross-sectional view taken long line 5-5 of Figure 1.
- Figure 3 is a sectional view showing a portion of an electrolytic cell series assembly including the membrane unit of Figure 1.
- a rectangular sheet 11 made of a membrane material is shown with a layer of a reinforcing material 12 attached to a peripheral portion of the membrane on opposite planar surfaces thereof.
- Figure 2 more clearly illustrates the reinforcing material 12 as a strip being heat sealed to both sides of the membrane 11 through the opening 13, and only along a gasket-bearing surface of the membrane.
- Gasket-bearing surface is defined as that portion of the periphery of the membrane sheet which is subject to compression forces in order to effect a seal at the periphery of an electrode frame of an electrolyzer.
- the reinforcing material 12 has a picture-frame shape. It is to be understood, however, that the membrane unit or structure of this invention is not limited to a rectangular sheet but can be circular or of some other desired shape.
- the membrane 11 is made of a material having ion exchange properties. Such membrane is substantially impervious to the hydrodynamic flow of the electrolyte and the passage of gas products produced during electrolysis. Suitable are cation exchange membranes such as those composed of fluorocarbon polymers having a plurality of pendant sulfonic acid groups or carboxylic acid groups or mixtures of sulfonic and carboxylic acid groups.
- sulfonic acid groups and “carboxylic acid groups” are meant to include salts of sulfonic acid or salts of carboxylic acid which are suitably converted to or from the acid group by processes such as hydrolysis.
- carboxylic acid type cation exchange membrane is commercially available from Asahi Glass Company under the trademark Flemion®.
- a suitable membrane having cation exchange properties is a perfluorosulfonic acid membrane sold commercially by E. I. duPont de Nemours and Company under the trademark Nafion®.
- the reinforcing material 12 can be made of any material suitable for strengthening the gasket bearing surface area of the membrane 11.
- the reinforcing material 12 can be of the same or different material as the membrane.
- Preferably the reinforcing material 12 should have a heavier scrim than that of the membrane material.
- Both the membrane and the reinforcing material should be made of a corrosion-resistant, non-contaminating material which is stable upon contact with electrolyte media present in an electrolytic cell.
- Suitable materials which can be employed in accordance with this invention include, but are not limited to, the following: fluorine-containing polymers such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP) and perfluoroalkoxy resin (PFA); polysulfide polymers, polyvinyl chloride, fluoroelastomers such as Viton®, a trademark of E. I. duPont de Nemours and Company, and chlorosulfonated polyethylenes such as Hypalon®, a trademark of E. I. duPont de Nemours and Company.
- fluorine-containing polymers such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP) and perfluoroalkoxy resin (PFA); polysulfide polymers, polyvinyl chloride, fluoroelastomers such as Viton®, a trademark of E. I. duPont de Nem
- the membrane 11 contains perforations or openings 13 along its periphery or gasket-bearing surface.
- the reinforcing material 12 is secured to the gasket bearing surface and covers the openings 13 on both sides of the membrane 11.
- the membrane having such openings 13 allows the reinforcing material 12 on one side of the membrane to form a bond through the membrane to the reinforcing material 12 on the opposite side through the openings 13. This is particularly useful when bonding a reinforcing material which is difficult to attach to the membrane material.
- a membrane unit generally designated by reference number 10, comprising a membrane 11 and a reinforcing material 12 attached to both sides of the membrane 11 through the openings 13, is interposed between two electrode frame units 14.
- a gasket 18 may be interposed between the membrane unit 10 and an electrode frame 14. It is also within the scope of the invention to interpose a gasket 18 on both sides of the membrane unit 10 and two adjacent electrode frames 14. Any gasket used in an electrolytic cell of the filter press type may be used.
- the gasket should be made of a corrosion resistant material, should have a high volume resistivity and good sealability after it has been compressed.
- Suitable materials for the gasket 14 may be, for example, EPDM, a chlorinated polyethylene (CPE), a polytetrafluoroethylene such as Teflon®, manufactured by E. I. duPont de Nemours and Company, and reinforced asbestos.
- An anode 15 and a cathode 16 are electrically connected with connectors 17 through the electrode frame 14.
- the electrolysis assembly above is typical of bipolar electrolytic cells of the filter press type such as described in U.S. Patent Nos. 4,111,779 and 4,108,742. Any cell of the filter press type may be used in the present invention.
- the membrane unit 10 and a gasket 18 are interposed between two adjacent electrode frames 14 and a compressive force is applied to the cell assembly.
- the compressive force may be applied by any means known to those skilled in the art, for example, by clamping the frames together or by using a hydraulic ram.
- a hydraulic ram is used to squeeze the electrode frames, gaskets and membranes together.
- the actual compressive force applied will be dictated by the type of material used for the gasket.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66804384A | 1984-11-05 | 1984-11-05 | |
| US668043 | 1984-11-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0183096A1 EP0183096A1 (en) | 1986-06-04 |
| EP0183096B1 true EP0183096B1 (en) | 1991-02-27 |
Family
ID=24680765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85114059A Expired - Lifetime EP0183096B1 (en) | 1984-11-05 | 1985-11-05 | Membrane unit for electrolytic cell |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0183096B1 (zh) |
| JP (1) | JPS61117294A (zh) |
| CN (1) | CN85108122A (zh) |
| AU (1) | AU562125B2 (zh) |
| BR (1) | BR8505502A (zh) |
| CA (1) | CA1287599C (zh) |
| DE (1) | DE3581896D1 (zh) |
| DK (1) | DK501585A (zh) |
| ES (1) | ES296350Y (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4770757A (en) * | 1987-03-03 | 1988-09-13 | E. I. Du Pont De Nemours And Company | Edge reinforcement of membranes for chlor-alkali cells |
| EP0339114A1 (en) * | 1988-04-28 | 1989-11-02 | E.I. Du Pont De Nemours And Company | Edge reinforcement of membranes for chlor-alkali cells |
| US5175795A (en) * | 1988-07-29 | 1992-12-29 | Hitachi, Ltd. | Hybridized frame inference and fuzzy reasoning system and method |
| DE3928934C2 (de) * | 1989-08-31 | 1999-04-29 | Sartorius Gmbh | Textilverstärktes mikroporöses Membranfilter, Verfahren zu seiner Herstellung und seine Verwendung |
| JP3480988B2 (ja) * | 1994-07-01 | 2003-12-22 | ジャパンゴアテックス株式会社 | フッ素系高分子固体電解質膜のためのシール兼補強用膜材及びそれを用いたフッ素系高分子固体電解質膜及びそのメッキ方法 |
| US5945192A (en) * | 1995-06-29 | 1999-08-31 | Japan Gore-Tex, Inc. | Sealing assembly for a solid polymer ion exchange membrane |
| JP4500083B2 (ja) * | 2004-03-29 | 2010-07-14 | 有限会社ルミネ | 画像合成装置及びプログラム |
| AT502170B1 (de) * | 2005-12-23 | 2007-02-15 | Semperit Ag Holding | Formkörper für eine filterpresse |
| CN106830213A (zh) * | 2017-03-27 | 2017-06-13 | 长春云卫科技有限公司 | 酸性氧化电位水电解槽 |
| EP4194588B1 (en) * | 2021-12-08 | 2024-06-26 | thyssenkrupp nucera AG & Co. KGaA | Method for sealing an electrolysis cell and sealed electrolysis cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2146602A5 (en) * | 1971-07-20 | 1973-03-02 | Alsthom | Zinc/air cell - with plastics grid as spacer between anode and microporous membrane |
| EP0066938A2 (en) * | 1981-06-01 | 1982-12-15 | Exxon Research And Engineering Company | Separator-spacer, electrode, and use thereof in electrochemical systems |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1540964A (fr) * | 1966-06-21 | 1968-10-04 | Monsanto Co | Cellule électrolytique et membrane composite |
| JPS53146272A (en) * | 1977-05-27 | 1978-12-20 | Tokuyama Soda Co Ltd | Holder for ion exchange membrane |
| GB2013242B (en) * | 1977-12-26 | 1982-06-16 | Kanegafuchi Chemical Ind | Method and apparatus of installation of membrane to electrolytic cell |
| DE2821983A1 (de) * | 1978-05-19 | 1979-11-22 | Hooker Chemicals Plastics Corp | Dichtelement fuer membranen, insbesondere bei filterpressenartig angeordneten elektrolysezellen |
| JPS5933195B2 (ja) * | 1979-09-04 | 1984-08-14 | 東ソー株式会社 | イオン交換膜の装着方法 |
| US4441977A (en) * | 1980-11-05 | 1984-04-10 | Olin Corporation | Electrolytic cell with sealing means |
| JPS584926U (ja) * | 1981-07-02 | 1983-01-13 | ミサワホ−ム株式会社 | 換気装置 |
-
1985
- 1985-10-31 DK DK501585A patent/DK501585A/da not_active Application Discontinuation
- 1985-11-01 AU AU49293/85A patent/AU562125B2/en not_active Ceased
- 1985-11-01 JP JP60244235A patent/JPS61117294A/ja active Granted
- 1985-11-04 ES ES1985296350U patent/ES296350Y/es not_active Expired
- 1985-11-04 BR BR8505502A patent/BR8505502A/pt unknown
- 1985-11-04 CN CN198585108122A patent/CN85108122A/zh active Pending
- 1985-11-04 CA CA000494496A patent/CA1287599C/en not_active Expired - Fee Related
- 1985-11-05 EP EP85114059A patent/EP0183096B1/en not_active Expired - Lifetime
- 1985-11-05 DE DE8585114059T patent/DE3581896D1/de not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2146602A5 (en) * | 1971-07-20 | 1973-03-02 | Alsthom | Zinc/air cell - with plastics grid as spacer between anode and microporous membrane |
| EP0066938A2 (en) * | 1981-06-01 | 1982-12-15 | Exxon Research And Engineering Company | Separator-spacer, electrode, and use thereof in electrochemical systems |
Also Published As
| Publication number | Publication date |
|---|---|
| ES296350Y (es) | 1988-04-16 |
| DK501585A (da) | 1986-05-06 |
| AU562125B2 (en) | 1987-05-28 |
| DE3581896D1 (de) | 1991-04-04 |
| DK501585D0 (da) | 1985-10-31 |
| JPH0364598B2 (zh) | 1991-10-07 |
| JPS61117294A (ja) | 1986-06-04 |
| ES296350U (es) | 1987-10-16 |
| CN85108122A (zh) | 1986-07-16 |
| AU4929385A (en) | 1986-05-15 |
| BR8505502A (pt) | 1986-08-05 |
| CA1287599C (en) | 1991-08-13 |
| EP0183096A1 (en) | 1986-06-04 |
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