EP2576869B1 - Elektrode für elektrolysezellen - Google Patents

Elektrode für elektrolysezellen Download PDF

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Publication number
EP2576869B1
EP2576869B1 EP11738600.3A EP11738600A EP2576869B1 EP 2576869 B1 EP2576869 B1 EP 2576869B1 EP 11738600 A EP11738600 A EP 11738600A EP 2576869 B1 EP2576869 B1 EP 2576869B1
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EP
European Patent Office
Prior art keywords
holes
flat
lamellar elements
electrode
membrane
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.)
Active
Application number
EP11738600.3A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2576869C0 (de
EP2576869A1 (de
Inventor
Karl-Heinz Dulle
Frank Funck
Dirk Hoormann
Stefan Oelmann
Peter Woltering
Carsten Schmitt
Philipp Hofmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Thyssenkrupp Nucera Italy Srl
Original Assignee
Thyssenkrupp Nucera Italy Srl
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Publication of EP2576869A1 publication Critical patent/EP2576869A1/de
Application granted granted Critical
Publication of EP2576869B1 publication Critical patent/EP2576869B1/de
Publication of EP2576869C0 publication Critical patent/EP2576869C0/de
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • 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
    • 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
    • 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

Definitions

  • the invention relates to an electrode and a method for gas-generating electrochemical processes, which, in the installed state, is arranged parallel to an ion exchange membrane, consisting of a plurality of horizontal lamellar elements which, in the manner of a flat C-profile, consist of a flat belly part and one or more flank parts, and between the flat belly part and the other flank part(s) one or more arbitrarily shaped transition regions are arranged, wherein the lamellar elements have a plurality of through openings.
  • US2009/050472A1 describes an electrolysis cell having a gas diffusion electrode having two major surfaces, the first major surface of the gas diffusion electrode facing the membrane and in contact with a planar porous element through which an electrode current is to flow, and the second major surface of the gas diffusion electrode in contact with a current distributor having a plurality of elastic conductive projections for pressing the gas diffusion electrode against the planar porous element.
  • US 4 822 460 A describes an electrolytic cell having means defining a space adapted to accommodate a portion of the membrane surface of the cell during operation of the cell. By maintaining the pressure in one electrode compartment higher than the other, the membrane portion is forced toward and into the membrane-receiving space so that any wrinkles formed on the membrane are removed.
  • an electrolysis electrode of an electrolysis cell for gas-generating electrochemical processes which is arranged parallel to an ion exchange membrane when installed, consisting of a large number of horizontal lamellar elements, which in turn are structured and three-dimensionally shaped and are in direct contact with the membrane with a partial surface, the lamellar elements having grooves and holes, and the majority of the holes being arranged in grooves, and the hole surfaces lying entirely or partially in the grooves or protruding into them.
  • the disadvantage is that the groove arrangement creates a surface that has structural elevations and depressions, which leads to disadvantageous gas stagnation and, as a result, to an uneven current density distribution across the ion exchange membrane.
  • the present invention has set itself the task of solving this problem. This is to be achieved by providing an electrode that no longer has the aforementioned disadvantages and a method for operating the electrode according to the invention, a reduction in the cell voltage and an associated reduction in electrical energy requirements is to be achieved.
  • the problem is solved by using an electrode in an electrolysis cell for gas-generating electrochemical processes.
  • the electrode comprises a plurality of horizontal lamellar elements which consist of a flat belly part and one or more flank parts in the manner of a flat C-profile, and one or more transition regions of any shape are arranged between the flat belly part and the other flank part(s), wherein the lamellar elements have a plurality of through openings and a flat surface without structural elevations and depressions, and wherein the flat belly part has a plurality of through openings arranged in rows, which are arranged diagonally to one another.
  • the present invention differs from a continuous perforated sheet, as used for example in EN 69600860 T2 , in the DE 243256 A1 , and the DE 2630883 A1 is proposed in that the electrode is composed of a large number of lamellar elements that are formed three-dimensionally by deliberately stretching them through cold forming. This bending increases the stability of the electrode and improves the flatness of the surface in contact with the membrane.
  • a composition of individual elements is, as cited at the beginning, state of the art.
  • the diagonal arrangement of the openings makes optimal use of the area of the belly section to accommodate the greatest possible number of openings and thus reduce gas stagnation even further.
  • the flank sections can also be provided with continuous openings as an option.
  • the through openings are arranged in the contact area of the respective lamellar element with the ion exchange membrane when the electrode is installed in an electrolysis cell.
  • This arrangement serves the purpose of supplying the ion exchange membrane with electrolyte during operation of the electrolysis cell and of ensuring gas discharge.
  • the through openings are formed as punched holes. These openings can have any geometric shape, although openings with a round cross-section are preferred.
  • the lamella elements in the case of round through-openings have a sheet thickness that is smaller than the hole diameter, or the lamella elements in the case of non-round through-openings have a sheet thickness that is smaller than the hydraulic cross-section.
  • the one or the further flank parts are inclined away from the membrane at an angle of at least 10 degrees when installed in an electrolysis cell.
  • the transition regions are advantageously shaped as a rounded edge.
  • the distance between the individual horizontally arranged lamella elements in a C-profile is 0 to 5 mm, preferably 0 to 2 mm and particularly preferably 0 mm.
  • the process is optimized, since approximately 6 to 10% of the membrane surface is recovered and is available for the actual electrolysis process.
  • the electrolysis process that is the subject of the present invention is characterized by the use of a flat electrode as described above. Electrolyzers in single-cell design or in filter press design are advantageously used for the production of the halogen gases.
  • Fig.1 Shows a lamella element 1 in the form of a flat C-profile.
  • the flanks 2 and 3 bent backwards are kept very short in relation to the flat belly part 8, which is designed to be much wider.
  • Between the flanks 2 and 3 and the belly part 8 are the transition areas 4a and 4b.
  • the lamella element 1 has holes 5 arranged in rows in the flat belly area 8, whereby these rows of holes are arranged parallel to one another and the openings from one row of holes to the next are arranged diagonally to one another. This means that the available area of the belly part 8 can be used most effectively for electrolysis. It is advantageous to find another row of holes in the Transition areas 4a or 4b, or further additional rows of holes are provided in the flanks 2 and 3 themselves.
  • a significant advantage of this design is that the belly part 8, when installed, is arranged plane-parallel to the membrane 7, in which the electrochemical reaction can take place.
  • the membrane 7 is supplied with lye or brine via the holes 5.
  • the cell voltage of an electrolysis cell was determined using an electrode that was constructed from a C-profile-like design of the lamella elements of the present invention.
  • the cell voltage of an electrolysis cell was determined using an electrode that was constructed from a C-profile-like design of the DE 102005006555 A1 disclosed invention, which differs in that the holes provided are arranged in grooves and the surface of the slat elements thus has structural elevations and depressions.
  • the holes in the flat belly part are not arranged diagonally to one another. Both C-profiles used therefore differed in their design only in their surface properties.
  • Both C-profiles used in the test had 11 ⁇ 62 holes, which in the case of the design according to the invention were arranged in rows of holes that were arranged diagonally to one another.
  • the hole diameter was 1.5 mm and the height of the C-profile was 23 mm.
  • the advantageous effect of the grooves is emphasized, which is based on the fact that the area with the highest current density, namely the contact area, is ideally supplied with reactant via the grooves provided by fluid flowing in from below and, on the other hand, the product gas that is formed and is much more voluminous is guided upwards via the grooves or via the holes to the back of the electrolysis electrode.
  • the person skilled in the art would initially have no desire to make a structural change to the lamellar elements.
  • the comparative test carried out here achieved a significant voltage reduction of approximately 60 mV (standardized to 90°C, 32 wt.% NaOH and 6 kA/m 2 ) when the groove structure of the lamellar elements was dispensed with and the openings were arranged diagonally to each other. This is attributed to gas stagnation within the grooves, which in the EN 10 2005 006 555 A1 was not taken into account.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP11738600.3A 2010-05-28 2011-05-23 Elektrode für elektrolysezellen Active EP2576869B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010021833A DE102010021833A1 (de) 2010-05-28 2010-05-28 Elektrode für Elektrolysezelle
PCT/EP2011/002552 WO2011147557A1 (de) 2010-05-28 2011-05-23 Elektrode für elektrolysezellen

Publications (3)

Publication Number Publication Date
EP2576869A1 EP2576869A1 (de) 2013-04-10
EP2576869B1 true EP2576869B1 (de) 2024-08-14
EP2576869C0 EP2576869C0 (de) 2024-08-14

Family

ID=44474965

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11738600.3A Active EP2576869B1 (de) 2010-05-28 2011-05-23 Elektrode für elektrolysezellen

Country Status (10)

Country Link
US (1) US11162178B2 (https=)
EP (1) EP2576869B1 (https=)
JP (1) JP6353226B2 (https=)
KR (2) KR20170089935A (https=)
CN (1) CN102906310A (https=)
BR (1) BR112012030076B1 (https=)
CA (1) CA2800845C (https=)
DE (1) DE102010021833A1 (https=)
RU (1) RU2576318C2 (https=)
WO (1) WO2011147557A1 (https=)

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB719838A (en) * 1951-07-28 1954-12-08 Bamag Meguin Ag Improvements in or relating to electrodes for electrolytic cells
DE2245926A1 (de) * 1971-09-22 1973-04-19 Oronzio De Nora Impianti Horizontale, planare, bipolare diaphragmenzellen
US4059500A (en) * 1975-04-14 1977-11-22 Georgy Mikirtychevich Kamarian Electrode unit
GB1579427A (en) * 1976-08-04 1980-11-19 Ici Ltd Electrodes for electrolytic cells
US4265719A (en) * 1980-03-26 1981-05-05 The Dow Chemical Company Electrolysis of aqueous solutions of alkali-metal halides employing a flexible polymeric hydraulically-impermeable membrane disposed against a roughened surface cathode
JPS5883466U (ja) * 1981-11-27 1983-06-06 ペルメレツク電極株式会社 イオン交換膜を用いる電解用電極
US4421609A (en) * 1979-07-16 1983-12-20 Compagnie Generale Des Etablissements Michelin Process for producing electrode with current outlets
GB2180556A (en) * 1985-07-29 1987-04-01 Permelec Electrode Ltd Apertured electrode for electrolysis
DE3603254A1 (de) * 1986-02-03 1987-08-06 Ht Hydrotechnik Gmbh Elektrolysezelleneinheit
US4822460A (en) * 1984-11-05 1989-04-18 The Dow Chemical Company Electrolytic cell and method of operation
JPH05140782A (ja) * 1991-11-14 1993-06-08 Permelec Electrode Ltd 電極構造体
US5593555A (en) * 1994-06-01 1997-01-14 Heraeus Electrochemie Bitterfeld Gmbh Electrode structure for a monopolar electrolysis cell operating by the diaphragm or membrane process
US20050236269A1 (en) * 2002-07-12 2005-10-27 Salvatore Peragine Structure for cathodic fingers of chlor-alkali diaphragm cells
US20060163081A1 (en) * 2003-06-24 2006-07-27 Giovanni Meneghini Expandable anode for diaphragm cells
DE102006046807A1 (de) * 2006-09-29 2008-04-03 Uhdenora S.P.A. Elektrolysezelle
US20090050472A1 (en) * 2006-01-16 2009-02-26 Uhdenora S.P.A. Elastic Current Distributor for Percolating Cells
US20090098404A1 (en) * 2007-10-16 2009-04-16 Honda Motor Co., Ltd. System for forming holes in metal sheet

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE243256C (https=)
DE2630883C2 (de) 1976-07-09 1985-02-07 Basf Ag, 6700 Ludwigshafen Verwendung einer nach dem Plasma- oder Flammspritzverfahren auf einem metallischen Träger aufgebrachten porösen anorganische Oxide enthaltenden Schicht als Diaphragma in einer Elektrolysezelle
DE3219704A1 (de) 1982-05-26 1983-12-01 Uhde Gmbh, 4600 Dortmund Membran-elektrolysezelle
DE3401637A1 (de) * 1984-01-19 1985-07-25 Hoechst Ag, 6230 Frankfurt Verfahren zum elektrolysieren von fluessigen elektrolyten
SU1724736A1 (ru) * 1988-06-30 1992-04-07 Предприятие П/Я В-2287 Электрод
IT1263900B (it) * 1993-02-12 1996-09-05 Permelec Spa Nora Migliorata cella di elettrolisi cloro-soda a diaframma poroso e processo relativo
DE4306889C1 (de) * 1993-03-05 1994-08-18 Heraeus Elektrochemie Elektrodenanordnung für gasbildende elektrolytische Prozesse in Membran-Zellen und deren Verwendung
DE4415146C2 (de) 1994-04-29 1997-03-27 Uhde Gmbh Elektrode für Elektrolysezellen mit Ionenaustauscher-Membran
JP3079008B2 (ja) 1995-06-02 2000-08-21 松下電器産業株式会社 ニッケル水素蓄電池
JP2002224674A (ja) * 1996-08-06 2002-08-13 Takio Tec:Kk 基板洗浄用水の製造装置及び製造方法、それらにより製造された基板洗浄用水、並びに該基板洗浄用水を用いた基板の洗浄方法
DE19816334A1 (de) 1998-04-11 1999-10-14 Krupp Uhde Gmbh Elektrolyseapparat zur Herstellung von Halogengasen
EP1033419B1 (en) * 1998-08-25 2006-01-11 Toagosei Co., Ltd. Soda electrolytic cell provided with gas diffusion electrode
DE102005006555A1 (de) 2005-02-11 2006-08-17 Uhdenora S.P.A. Elektrode für Elektrolysezellen

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB719838A (en) * 1951-07-28 1954-12-08 Bamag Meguin Ag Improvements in or relating to electrodes for electrolytic cells
DE2245926A1 (de) * 1971-09-22 1973-04-19 Oronzio De Nora Impianti Horizontale, planare, bipolare diaphragmenzellen
US4059500A (en) * 1975-04-14 1977-11-22 Georgy Mikirtychevich Kamarian Electrode unit
GB1579427A (en) * 1976-08-04 1980-11-19 Ici Ltd Electrodes for electrolytic cells
US4421609A (en) * 1979-07-16 1983-12-20 Compagnie Generale Des Etablissements Michelin Process for producing electrode with current outlets
US4265719A (en) * 1980-03-26 1981-05-05 The Dow Chemical Company Electrolysis of aqueous solutions of alkali-metal halides employing a flexible polymeric hydraulically-impermeable membrane disposed against a roughened surface cathode
JPS5883466U (ja) * 1981-11-27 1983-06-06 ペルメレツク電極株式会社 イオン交換膜を用いる電解用電極
US4822460A (en) * 1984-11-05 1989-04-18 The Dow Chemical Company Electrolytic cell and method of operation
GB2180556A (en) * 1985-07-29 1987-04-01 Permelec Electrode Ltd Apertured electrode for electrolysis
DE3603254A1 (de) * 1986-02-03 1987-08-06 Ht Hydrotechnik Gmbh Elektrolysezelleneinheit
JPH05140782A (ja) * 1991-11-14 1993-06-08 Permelec Electrode Ltd 電極構造体
US5593555A (en) * 1994-06-01 1997-01-14 Heraeus Electrochemie Bitterfeld Gmbh Electrode structure for a monopolar electrolysis cell operating by the diaphragm or membrane process
US20050236269A1 (en) * 2002-07-12 2005-10-27 Salvatore Peragine Structure for cathodic fingers of chlor-alkali diaphragm cells
US20060163081A1 (en) * 2003-06-24 2006-07-27 Giovanni Meneghini Expandable anode for diaphragm cells
US20090050472A1 (en) * 2006-01-16 2009-02-26 Uhdenora S.P.A. Elastic Current Distributor for Percolating Cells
DE102006046807A1 (de) * 2006-09-29 2008-04-03 Uhdenora S.P.A. Elektrolysezelle
US20090098404A1 (en) * 2007-10-16 2009-04-16 Honda Motor Co., Ltd. System for forming holes in metal sheet

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PETER SCHMITTINGER: "Chlorine", ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, 1 January 2006 (2006-01-01), pages 71 - 74, XP055006250, Retrieved from the Internet <URL:www.ullmann.com> [retrieved on 20110905], DOI: 10.1002/14356007.a06_399.pub2 *

Also Published As

Publication number Publication date
CA2800845C (en) 2019-04-09
US20130087465A1 (en) 2013-04-11
BR112012030076A2 (pt) 2016-09-20
KR20170089935A (ko) 2017-08-04
RU2012150764A (ru) 2014-07-10
RU2576318C2 (ru) 2016-02-27
BR112012030076B1 (pt) 2020-10-06
CA2800845A1 (en) 2011-12-01
EP2576869C0 (de) 2024-08-14
EP2576869A1 (de) 2013-04-10
KR20130079448A (ko) 2013-07-10
JP2013527324A (ja) 2013-06-27
CN102906310A (zh) 2013-01-30
US11162178B2 (en) 2021-11-02
JP6353226B2 (ja) 2018-07-04
DE102010021833A1 (de) 2011-12-01
WO2011147557A1 (de) 2011-12-01

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