EP0687312B1 - Agencement d'electrode pour processus electrolytiques formant des gaz dans des cellules a membrane ou a diaphragme - Google Patents

Agencement d'electrode pour processus electrolytiques formant des gaz dans des cellules a membrane ou a diaphragme Download PDF

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Publication number
EP0687312B1
EP0687312B1 EP94906164A EP94906164A EP0687312B1 EP 0687312 B1 EP0687312 B1 EP 0687312B1 EP 94906164 A EP94906164 A EP 94906164A EP 94906164 A EP94906164 A EP 94906164A EP 0687312 B1 EP0687312 B1 EP 0687312B1
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EP
European Patent Office
Prior art keywords
electrode
membrane
gas
electrode arrangement
arrangement according
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
Application number
EP94906164A
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German (de)
English (en)
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EP0687312A1 (fr
Inventor
Robert Scannell
Bernd Busse
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.)
De Nora Deutschland GmbH
Original Assignee
Heraeus Elektrochemie GmbH
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Publication of EP0687312A1 publication Critical patent/EP0687312A1/fr
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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
    • 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
    • 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

Definitions

  • the invention relates to an electrode arrangement for gas-forming electrolytic processes, in particular processes in membrane cells, consisting of a flat electrode structure with at least two electrically conductive and mechanically firmly connected electrode elements, between each of which a gap is provided for gas discharge, the electrode elements along the column bearing surfaces for an ion exchange membrane or a diaphragm and edge regions adjacent to the gap are designed as a gas discharge device and their use.
  • a membrane electrolysis cell of the filter press type with pairs of planar electrodes is known, the electrodes each containing at least one open active part and a membrane being arranged between the pairs of electrodes; a seal is arranged between the electrode edge and the membrane edge; the perforated central part of the electrodes has a grid-like structure, the grid rods of the electrodes assigned in pairs being offset from one another by a maximum of half a rod width and the grid rods of an electrode being arranged such that their distance from one another is smaller than the projection of their width; the grids have a convex curvature at least on the active side, the thickness of the seal between the electrode edge and the membrane edge being equal to or less than the height of the portion of the grid rod projecting beyond the electrode edge. It turns out to be problematic that with one Such an arrangement with depletion and gas bubbles in the area of the storage surface must be expected, which has an unfavorable effect on the membrane and the electrode coating.
  • the electrolytic cell is intended for the electrolysis of an aqueous halide-containing electrolyte, such as brine, in order to produce an aqueous alkali metal hydroxide solution and halogen and hydrogen.
  • an aqueous halide-containing electrolyte such as brine
  • an electrode arrangement for gas-forming electrolysers in particular membrane electrolysers, with a vertically arranged plate electrode, a counter electrode and a membrane between the two electrodes is known; the plate electrode is divided into horizontal strips, the entire active electrode surface of which is arranged parallel and at the shortest distance from the counterelectrode, but a gap is provided between the membrane and the electrode for discharging the gas formed during the electrochemical reaction;
  • the horizontal strips in the area of their upper edge are each provided with an angled gas discharge element, on which the rising gas expands and is partly guided behind the electrode.
  • the electrode gap between the membrane and the two electrodes which is always required for gas discharge, proves to be problematic, such a relatively large electrode spacing also resulting in an increase in the cell voltage.
  • an electrode arrangement for gas-forming electrolyzers in particular for monopolar membrane electrolyzers with vertically arranged plate electrodes and counter electrodes and a membrane between plate electrode and counter electrode is known;
  • electrically conductive and electrically connected surface structures are known as pre-electrodes, which run in parallel planes to the plate electrodes.
  • the fabric serving as an electrode is in the form of perforated sheets, expanded metals, wire mesh or wire mesh, the distance between the fabrics being between 1 and 5 mm; the plate electrodes are continuously divided horizontally into several separate units in order to improve the current distribution in the membrane and to reduce the voltage drop on the surfaces facing the membrane.
  • EP-OS 0 150 018 discloses a process for the electrolysis of liquid electrolytes by means of perforated electrodes in electrolysis cells divided by ion exchange membrane, a gas space being formed laterally to the main flow direction of the electrolyte due to gas bubble formation. By bursting at the phase boundary, the resulting gas bubbles give off their gas content to the gas space adjacent to the main flow direction, which is formed in the case of plate-shaped electrodes by the rear space behind the electrode.
  • the perforated electrodes can consist of expanded metal or sheet metal strips, among other things.
  • EP-OS 0 150 018 A problem with the arrangements known from EP-OS 0 150 018 is the relatively complex construction of electrodes with gas flow-guiding elements, which are composed of individual sheet metal strips.
  • the object of the invention is to develop an electrode arrangement with an open structure, possibly with a grid-like structure, in which rapid gas bubble discharge with increased electrolyte exchange in the region between the electrode and membrane is to be achieved with a high degree of efficiency; moreover, the electrode arrangement should be easy to manufacture, its long-term stability should be increased and the catalytically active surface should be enlarged.
  • the simple manufacture of the electrode arrangement has proven to be particularly advantageous; Furthermore, the different usability can be regarded as advantageous, for example, as being supported directly on the membrane and as a cathode at a distance from the membrane.
  • FIG. 1a shows a plan view of the surface of the electrode arrangement, while FIG. 1b shows a cut-out section A from FIG. 1a; Figure 1c shows a cross section in the profile of the electrode arrangement.
  • Figure 2 shows a perspective view of a partially broken electrode arrangement
  • Figure 3 shows the use of the electrode arrangement according to the invention in a membrane electrolysis cell schematically in a fragmentary partial representation.
  • the electrode arrangement 1 made from a flat electrode sheet has a multiplicity of lamellar electrode elements 2 which are each separated from one another by a gap 3; the upper edges 4 of the electrode elements 2 are angled along a schematically represented line 5 on the side facing away from the membrane, in order to allow the gas bubbles formed in the region of the electrodes to be drawn off rapidly.
  • the schematically illustrated essentially diamond-shaped openings 8 of the expanded metal can be seen from FIG. This means that the electrochemically active electrode area increases to an area of 1.15 cm 2 compared to a closed area of, for example, 1 cm 2 by expanded metal openings.
  • Expanded metal with a web width in the range from 1.5 to 4 mm is advantageously used.
  • the long dimension of the opening (LWD) is in the range of 2 to 4.5 mm
  • the short dimension of the opening (SWD) is in the range of 1.2 to 3 mm.
  • the angle between the upper edges 4 and the plane of the electrode arrangement 1 is approximately 30 °.
  • a bevel angle in the range of 20-35 ° has proven to be advantageous.
  • Particularly suitable materials for the electrode arrangement are titanium sheet with a noble metal and non-noble metal activation or nickel sheet with a noble metal activation.
  • the electrode arrangement has proven particularly useful when used as an anode and cathode in a membrane cell for chlor-alkali electrolysis or for hydrogen oxygen generation.
  • the edge strips 6 and 7 consist of either expanded metal or continuous sheet metal.
  • the membrane lies directly on the area designated by reference number 10, while the rear area, which extends into the electrolyte space, is open for the purpose of gas discharge.
  • spacer elements are provided between the end face 10 of the electrode arrangement 1 and the ion exchange membrane, not shown, which consist of an electrolyte-resistant material, but are also not shown here.
  • FIG. 3 shows a schematic cross-sectional representation of a single membrane cell unit, only the ion exchange membrane with cathode and anode being shown in cross-section, and the representation of the associated one Peripherals such as clamping elements, power supply, gas discharge have been omitted for a better overview.
  • the anodically connected electrode 1 rests with its end face 10 directly on the surface of the diaphragm 11 shown schematically, the requirement for rapid gas discharge being clearly recognizable due to the openings 8 shown here only schematically in the region of the electrode elements .
  • a corresponding process also takes place on the opposite side of the membrane 11 by means of the cathodically connected electrode 1 '; however, it should be noted here that the cathodic electrode is arranged at a distance from the membrane for the purpose of mass exchange and stability of the membrane, for example is supported by spacer elements 13 with respect to the ion exchange membrane 11 in order to achieve a distance in the range of 1 to 3 mm; however, it is also possible to form a distance between the membrane and the cathodic electrode by means of the pressure difference.
  • gas bubbles are discharged in a vertical direction from the catholyte 14, a gas collection device (not shown here) likewise being provided.
  • the fragmentary cell vessel containing anolyte and catholyte is designated by reference number 15.
  • the membrane cell arrangement is particularly suitable for electrolysis cells for chlorine production, but it can also be used for hydrogen / oxygen production.

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  • 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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Measurement Of Radiation (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne un agencement d'électrode pour des processus électrolytiques formant des gaz dans des cellules à membrane, qui présente une lame plane contenant des éléments lamellaires (2) d'électrode, les éléments d'électrode adjacents étant séparés les uns des autres par une fente (3). Afin que les gaz puissent mieux se dégager de la zone électrode-membrane, les éléments lamellaires d'électrode sont munis d'une structure en métal déployé dont les ouvertures facilitent le passage des gaz. Les éléments d'électrode comportent des arêtes supérieures (4) coudées qui permettent un dégagement vertical des gaz. L'agencement d'électrode s'utilise principalement sous forme d'électrode connectée de manière anodique, en appui direct sur la membrane échangeuse d'ions, mais il peut également s'utiliser sous forme de cathode, placée à distance de la membrane.

Claims (10)

  1. Dispositif d'électrodes pour des procédés électrolytiques formant du gaz, en particulier des procédés dans des cellules à membranes, constitué d'une structure d'électrodes planes avec au moins deux éléments d'électrodes électroconducteurs et reliés ensemble solidement mécaniquement, entre lesquels est prévu à chaque fois une fente pour l'évacuation de gaz, les éléments d'électrodes présentant le long de la fente des surfaces de support pour une membrane échangeuse d'ions ou un diaphragme et des domaines d'arêtes adjacents à la fente étant formés comme dispositif d'évacuation de gaz, caractérisé en ce qu'au moins les surfaces de support des éléments d'électrodes (2) présentent des domaines perméables au liquide et au gaz.
  2. Dispositif d'électrodes selon la revendication 1, caractérisé en ce que les surfaces de support des éléments d'électrodes (2) se trouvent dans un plan.
  3. Dispositif d'électrodes selon la revendication 1 ou 2, caractérisé en ce que les éléments d'électrodes (2) présentent dans leur domaine de surface total des domaines perméables au liquide et au gaz.
  4. Dispositif d'électrodes selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'élément d'électrode (2) est formé de métal déployé.
  5. Dispositif d'électrodes selon la revendication 4, caractérisé en ce que le rapport de la surface électrocatalytiquement active à la surface géométrique de l'élément d'électrode (2) se trouve dans le domaine de 0,9:1 à 2,0:1.
  6. Dispositif d'électrodes selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les éléments d'électrodes sont reliés ensemble par l'intermédiaire d'au moins deux bandes de bords externes opposées (6, 7), les éléments d'électrodes (2) et les bandes de bords externes (6, 7) étant constitués d'une tôle pour électrode plane continue.
  7. Dispositif d'électrodes selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'élément d'électrode est constitué de métal poreux ou microporeux.
  8. Dispositif d'électrodes selon la revendication 7, caractérisé en ce que l'élément d'électrode est constitué de titane fritté ou de nickel fritté.
  9. Dispositif d'électrodes selon la revendication 7 ou 8, caractérisé en ce que la dilatation maximale des pores se trouve dans le domaine de la dilatation maximale des bulles de gaz.
  10. Utilisation du dispositif d'électrodes selon l'une quelconque des revendications 1 à 9 comme anode ou cathode d'une cellule à membrane.
EP94906164A 1993-03-05 1994-01-28 Agencement d'electrode pour processus electrolytiques formant des gaz dans des cellules a membrane ou a diaphragme Expired - Lifetime EP0687312B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4306889A DE4306889C1 (de) 1993-03-05 1993-03-05 Elektrodenanordnung für gasbildende elektrolytische Prozesse in Membran-Zellen und deren Verwendung
DE4306889 1993-03-05
PCT/EP1994/000240 WO1994020649A1 (fr) 1993-03-05 1994-01-28 Agencement d'electrode pour processus electrolytiques formant des gaz dans des cellules a membrane, et son utilisation

Publications (2)

Publication Number Publication Date
EP0687312A1 EP0687312A1 (fr) 1995-12-20
EP0687312B1 true EP0687312B1 (fr) 1997-01-08

Family

ID=6482002

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94906164A Expired - Lifetime EP0687312B1 (fr) 1993-03-05 1994-01-28 Agencement d'electrode pour processus electrolytiques formant des gaz dans des cellules a membrane ou a diaphragme

Country Status (17)

Country Link
US (1) US5660698A (fr)
EP (1) EP0687312B1 (fr)
JP (1) JPH08507327A (fr)
AU (1) AU679038B2 (fr)
BG (1) BG99882A (fr)
BR (1) BR9405884A (fr)
CA (1) CA2154692A1 (fr)
CZ (1) CZ284530B6 (fr)
DE (2) DE4306889C1 (fr)
ES (1) ES2097032T3 (fr)
NO (1) NO953111D0 (fr)
PL (1) PL177633B1 (fr)
SA (1) SA94140724B1 (fr)
SK (1) SK108395A3 (fr)
TW (1) TW325927U (fr)
WO (1) WO1994020649A1 (fr)
ZA (1) ZA941191B (fr)

Families Citing this family (18)

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IT1279069B1 (it) * 1995-11-22 1997-12-04 Permelec Spa Nora Migliorato tipo di elettrodo per elettrolizzatori a membrana a scambio ionico
US5849164A (en) * 1996-06-27 1998-12-15 Eltech Systems Corporation Cell with blade electrodes and recirculation chamber
DE19816334A1 (de) * 1998-04-11 1999-10-14 Krupp Uhde Gmbh Elektrolyseapparat zur Herstellung von Halogengasen
ATE263259T1 (de) * 1999-01-08 2004-04-15 Moltech Invent Sa Aluminium-elektrogewinnungszelle mit sauerstoffentwickelnden anoden
US10916674B2 (en) * 2002-05-07 2021-02-09 Nanoptek Corporation Bandgap-shifted semiconductor surface and method for making same, and apparatus for using same
DE10333853A1 (de) * 2003-07-24 2005-02-24 Bayer Materialscience Ag Elektrochemische Zelle
DE102004023161A1 (de) * 2004-05-07 2005-11-24 Eilenburger Elektrolyse- Und Umwelttechnik Gmbh Elektrolysezelle mit Mehrlagen-Streckmetall-Kathoden
US9040012B2 (en) 2009-02-17 2015-05-26 Mcalister Technologies, Llc System and method for renewable resource production, for example, hydrogen production by microbial electrolysis, fermentation, and/or photosynthesis
BRPI1008697A2 (pt) * 2009-02-17 2016-03-08 Mcalister Technologies Llc aparelho e método para captura de gás durante eletrólise
KR101352231B1 (ko) * 2009-02-17 2014-01-15 맥알리스터 테크놀로지즈 엘엘씨 전기분해 중에 핵화를 제어하기 위한 장치 및 방법
US8075750B2 (en) * 2009-02-17 2011-12-13 Mcalister Technologies, Llc Electrolytic cell and method of use thereof
AU2010216050B2 (en) 2009-02-17 2013-07-18 Mcalister Technologies, Llc Electrolytic cell and method of use thereof
DE102010021833A1 (de) * 2010-05-28 2011-12-01 Uhde Gmbh Elektrode für Elektrolysezelle
US20130034489A1 (en) * 2011-02-14 2013-02-07 Gilliam Ryan J Electrochemical hydroxide system and method using fine mesh cathode
US9222178B2 (en) 2013-01-22 2015-12-29 GTA, Inc. Electrolyzer
US8808512B2 (en) 2013-01-22 2014-08-19 GTA, Inc. Electrolyzer apparatus and method of making it
US9127244B2 (en) 2013-03-14 2015-09-08 Mcalister Technologies, Llc Digester assembly for providing renewable resources and associated systems, apparatuses, and methods
JP2016014381A (ja) * 2014-07-03 2016-01-28 ナブテスコ株式会社 車両用空気圧縮装置

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Also Published As

Publication number Publication date
SA94140724B1 (ar) 2005-09-12
DE59401542D1 (de) 1997-02-20
US5660698A (en) 1997-08-26
CZ225695A3 (en) 1996-04-17
PL310407A1 (en) 1995-12-11
WO1994020649A1 (fr) 1994-09-15
CZ284530B6 (cs) 1998-12-16
TW325927U (en) 1998-01-21
ZA941191B (en) 1994-09-20
CA2154692A1 (fr) 1994-09-15
SK108395A3 (en) 1997-05-07
JPH08507327A (ja) 1996-08-06
BG99882A (en) 1996-02-29
DE4306889C1 (de) 1994-08-18
EP0687312A1 (fr) 1995-12-20
PL177633B1 (pl) 1999-12-31
BR9405884A (pt) 1995-12-12
NO953111L (no) 1995-08-08
AU5999694A (en) 1994-09-26
ES2097032T3 (es) 1997-03-16
AU679038B2 (en) 1997-06-19
NO953111D0 (no) 1995-08-08

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