EP1285103B1 - Cellule electrolytique polyvalente bipolaire destinee a des charges electriques elevees - Google Patents

Cellule electrolytique polyvalente bipolaire destinee a des charges electriques elevees Download PDF

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Publication number
EP1285103B1
EP1285103B1 EP01960214A EP01960214A EP1285103B1 EP 1285103 B1 EP1285103 B1 EP 1285103B1 EP 01960214 A EP01960214 A EP 01960214A EP 01960214 A EP01960214 A EP 01960214A EP 1285103 B1 EP1285103 B1 EP 1285103B1
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EP
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Prior art keywords
electrode
bipolar
electrolyte
sheets
electrolysis cell
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Expired - Lifetime
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EP01960214A
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German (de)
English (en)
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EP1285103A1 (fr
Inventor
Michael Gnann
Wolfgang Thiele
Gerd Heinze
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United Initiators GmbH and Co KG
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United Initiators GmbH and Co KG
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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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • 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

  • the invention relates to a bipolar switched multipurpose electrolysis cell in a high design for preferably high current loads between 1 and 10 kA / m 2 per bipolar single cell. It can be used with appropriate adaptation of the materials for the electrodes and the other cell assemblies to the relevant substance system both in environmental technology for the electrochemical degradation of inorganic and organic pollutants and in the chemical and pharmaceutical industries for the production of inorganic and organic products.
  • a special application is the production of peroxodisulfates and perchlorates.
  • Bipolar electrolysis cells in Filterpressenbauart consisting of a tenter, the two electrode edge plates with power supply and any number of bipolar electrode plates and peripheral equipment for the supply and removal of the electrolyte solutions and the cooling or tempering, are known in numerous embodiments and for a variety of applications , They can be carried out undivided or divided by means of ion exchange membranes or microporous diaphragms into two- or multi-chamber cells.
  • the required electrode or electrolyte chambers can be formed as separate assemblies or integrated into the electrode edge plates or in the bipolar electrode plates.
  • the great advantage of the bipolar electrolysis cells is that the power supply only needs to be brought to the outside of the two edge plates, while the current transport in the bipolar single cells only from the one side of the electrode plate on the other side mostly internal.
  • a simple bipolar electrode plate consist in the anode and cathode side of the same electrode material.
  • anodes and cathodes made of different materials, preferably consisting of metal sheets. These can then be connected to each other directly or indirectly via contact body electrically conductive.
  • bipolar dual purpose electrolysis cell which is necessary herein to achieve the gas lift effect for electrolyte recirculation, as part of a versatile and applicable gas lift electrolysis and reaction system is in the DE 44 38 124 described.
  • This is an electrolysis cell construction optimized for the use of buoyancy by the developed gases with a total height of 1.5 to 2.5 m.
  • the bipolar electrode plates consist of electrode base bodies made of impregnated graphite or of plastics with incorporated inlets and outlets for the electrolyte solutions and the cooling medium as well as electrodes and electrolyte spaces applied on both sides or in the case of the graphite base bodies.
  • the two electrodes are electrically conductively connected to one another via these, in the case of the plastic base body by introduced contact elements.
  • Such contact elements are arranged within the sealed by electrolyte frame made of elastic material sealing surfaces. The contact is made by the contact pressure during assembly.
  • bipolar electrolysis cells with plastic base bodies have so far been able to prevail only for low to moderate current loads of 100 to 1000 A and for low operating temperatures.
  • the electrodes used can not normally be used as easy-to-manufacture and thus also easily replaceable in the sense of a multi-purpose cell metal-electrode sheets.
  • welded constructions for the two half-cells of a bipolar unit which often consist of different electrode materials or material composites, are usually unavoidable.
  • the equipment required for this purpose is relatively large.
  • the assembly is much more complicated than that of the cell structures in which this contact can be made automatically when clamping together.
  • the transition to other electrode materials usually requires a modified construction adapted to the material properties.
  • An electrolysis cell for high current loads in monopolar execution is in DE 39 38 160 described.
  • the monopolar design has the fundamental disadvantage that a large number of single cells must be connected in series in order to come into a favorable voltage range for the current transformation (for example 200 V).
  • the electrolyte-side and power-side connection leads to high costs in the design.
  • the desired versatile multi-purpose electrolysis cell for high current loads can therefore hardly be realized on this basis.
  • the invention is therefore based on the problem to provide a constructed according to the filter press principle bipolar Mehr thoroughlyelektrolyseelektrolyseelektrolysezelle with plastic body in which a good and reliable contact of the metal electrode plates is guaranteed even at high current loads, bypassing the disadvantages of the known technical solutions.
  • the cathode and anode plates of a bipolar element with the respective contact rails are screwed on one or both sides expediently by means of countersunk screws.
  • this gland is only for better handling and is responsible only to a small extent for the flow of current, which is optimized only by the press contact.
  • the metal electrode plates are in the case of anode plates of valve metals preferably made of titanium, which in the electrochemically active region in a known manner with active layers of precious metals, noble metal oxides, mixed oxides of precious metals and other metals and other metal oxides such. B. lead dioxide, are occupied.
  • active layers and other valve metals such as tantalum, niobium or zirconium into consideration. But also leaded, nickeled, copper-plated steel or nickel-based alloys are suitable for special applications.
  • the anode sheets have a noble metal support of solid platinum and are obtainable by hot isostatic pressing of platinum foil and titanium sheet.
  • the cathode material used is preferably stainless steel, nickel, titanium, steel and lead.
  • cathodes made of high-alloy stainless steels of material no. 1.4539 are preferably used, whose active electrode surface is in the form of expanded metal and which rest directly on the perforated cathode frame part serving as a support.
  • contact rails are preferably used those made of copper, which can be tin-plated or silvered on the contact surfaces or coated with precious metals.
  • the current contact surfaces of the electrodes are preferably provided with well-conductive coatings, such as e.g. Electroplated platinum, gold, silver or copper layers.
  • the contact bars and the electrode contacts are preferably gold-plated or platinum-plated, and the current is transmitted through the press contact produced by clamping the electrode stack.
  • the following advantages also result for electrodes without gas evolution:
  • the current transport from the contact surfaces through the metal electrode sheets is favored, since at the same effective electrode area, same thickness of the electrode sheets and the same current load relevant for the current transport cross section increases with the height of the electrode plates and at the same time the path length for the current transport with increasing height is lower , Under these boundary conditions, the electrical resistance and thus the voltage drop in the electrode sheets decreases with the square of the cell height.
  • substantially thinner or less electrically conductive electrode plates or significantly higher current loads can therefore be used in the narrow and high electrode plates to be used according to the invention. This is particularly important for broken electrode sheets, in which yes, a reduction in the cross section for the current transport must be taken into account, of great importance. Also, in the case of mounting the cell stack in the case of thin sheet metal electrodes, any waviness of the sheet after the pressing is compensated, and thus a parallelism of the electrode is achieved.
  • Copper pipes soldered onto the contact rails on the outside of the contacts allow the contacts to be opened by means of cooling water, even at high current loads be kept below room temperature. In this way, heating of the cell frame, the sealing system and the current contacts and the associated problems such as deformations and overheating are completely avoided.
  • the parallelism of the electrodes to each other is the prerequisite for high current yields and uniform electrode corrosion.
  • the height of the cell plays a role in the cooling of the highly loaded contact rails.
  • the contacts especially at higher electrolyte temperatures in a bipolar cell constructed according to the invention, assume a significantly lower temperature than in the electrolysis cells with inner contact elements, in which under comparable conditions at the contact elements significantly higher temperatures are measured than in the cell interior.
  • Another already mentioned very essential Advantage of the distance between the cell frame and contact bar is that so that a drainage of a possibly exiting to a small extent electrolyte can take place. If electrolyte penetrates into the contact gap, salt forms and the contact deteriorates within a very short time.
  • the leaking coolant is lowered in the level below the height of the inlet.
  • a very small electrode spacing of 2 to 4 mm and thus a low electrolyte resistance and a high flow velocity can be achieved.
  • FIGS. 1a to 3c 3 show, by way of example and schematically, three embodiments of a divided bipolar multipurpose electrolysis cell in sectional views through the electrochemically active regions, the upper figures representing side views and the lower figures representing plan views.
  • the bipolar Mehr thoroughlyektektolytzelle like these in their first embodiment according to Fig. 1a and 1b is shown, and carries the reference numeral 10, is part of an electrolysis device, not shown.
  • the bipolar Mehr thoroughlyektektolysezelle 10 consists of an electrode base body 12 made of plastic, on both sides of the metal electrode sheets or electrode plates are mounted, in this embodiment the one electrode plate 14 solid, and the other electrode plate 16 is broken in the electrochemically active region.
  • the electrode main body 12 has a double-T shape in cross section in both the vertical and horizontal directions, whereby channels 18, 20 are formed between the electrode main body 12 and the respective electrode plates 14, 16.
  • an electrolyte sealing frame 22 made of elastic material is additionally attached, which forms a further channel 24 on the outside of the solid electrode sheet 14 as viewed from the electrode base body 12.
  • the channel 24 formed by the solid electrode plate 14 and the electrolyte sealing frame 22 and the channel 20 formed between the electrode base body 12 and the perforated electrode plate 16, which is referred to below as the electrode back space serve to receive the electrolyte solutions for the electrolysis.
  • the channel 18 formed between the electrode base body 12 and the solid electrode plate 14 serves to receive cooling liquid for cooling the solid electrode sheet 14 and possibly the electrode base body 12 and is referred to in the following as a cooling space.
  • the electrode base body 12 supply and discharge lines for the electrolyte solutions are incorporated, wherein the leads 26 and 28 are arranged in a lower central region of the electrode base body 12 and the associated leads 30 and 32 are arranged in an upper central region thereof.
  • the inlets and outlets are connected via respective inlet ports 34, 36 and outlet ports 38, 40 to the electrolyte passages 24 and 20 through which the electrolytic solutions for electrolysis are passed, with the inlet and outlet ports 34 and 38 for the solid electrode sheet 14 trained channel 24 pass through the massive electrode sheet 14.
  • Cooling space 18 is provided, into which or through which a coolant, in this case cooling water, via in a lower or upper central region of the electrode body 1 2 arranged supply lines 42 and leads 44 and corresponding connection channels 46 and 48 can be passed or pumped.
  • a coolant in this case cooling water
  • the perforated metal electrode sheet requires no additional cooling, since it is sufficiently cooled by the electrolyte solution and rests only in marginal areas on the body, whereby a heat accumulation is avoided.
  • ion exchange membrane 50 On the perforated metal electrode plate 16 is an ion exchange membrane 50 which is attached by suitable means to the perforated electrode plate 1 6.
  • contact rails 52 contact the laterally elongated metal electrode sheets 14 and 16 and are formed between the respective contact rails and the edge of the main body 12 gaps 54, which are bounded laterally by the metal electrode sheets.
  • a further embodiment is shown.
  • a multipurpose electrolytic cell designated 110 is shown, wherein components corresponding to those of the first embodiment according to Fig. 1a and 1b correspond, with the same reference numerals, each augmented by the number 100, are provided. It will be discussed below only the differences, so that reference is otherwise made to the description of the first embodiment.
  • cooling chambers 118 are provided between the main body 112 and the electrode sheets, in order to cool the solid electrode sheets 114.
  • the cooling chambers 118 are in turn supplied via supply lines 142 and discharges 144 and corresponding connecting channels 146 and 148 with cooling liquid.
  • Fig. 3a and 3b is another, designated 210 non-inventive contemporary multi-purpose electrolysis cell, wherein components, those according to the first embodiment according to Fig. 1a and 1b correspond, with the same reference numerals, each augmented by the number 200, are provided. It will only deal with the differences in the following.
  • a solid 14 and a perforated electrode plate 16 is used in the first embodiment
  • two perforated electrode plates 216 are used, wherein for their electrical insulation in addition to one of the electrode sheets, a thin sealing frame 256 is mounted on which the ion exchange membrane 250 is attached via suitable means.
  • the ion exchange membrane 250 can also be arranged directly on an electrode sheet, in which case a thin sealing frame is attached to the membrane or to the free electrode sheet. Due to the exclusive use of perforated electrode plates, cooling chambers are not required in this embodiment.
  • Fig. 4 the current transport is illustrated by a cell of three inventively constructed bipolar electrode plates and the two edge electrode plates with double-sided power supply and up to the lateral contact rails widened plastic base bodies.
  • the design variant was based on Fig. 1a with a perforated and a solid metal electrode plate per bipolar electrode plate.
  • the names of the numbered components are the same as in Fig. 1 ,
  • the invention is not on the in the FIGS. 1 and 4 limited shown constructive embodiments.

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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)
  • Hybrid Cells (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Claims (10)

  1. Cellule électrolytique polyvalente bipolaire pour des charges électriques élevées, se composant d'un cadre de serrage, de deux plaques extérieures d'électrode avec des tôles d'électrode métalliques et une arrivée de courant ainsi que de plaques d'électrode bipolaires, ces dernières se composant de:
    chacune un corps de base d'électrode (12) en matière plastique, avec des espaces arrière d'électrode (20) et/ou des espaces de refroidissement (18) usinés sur un côté ou sur les deux côtés, des conduits d'arrivée et de départ usinés pour les solutions électrolytiques (26, 28, 30, 32) et le fluide de refroidissement (42, 44),
    de tôles d'électrode métalliques (14, 16) installées sur les deux côtés sur le corps de base (12), qui sont massives et/ou perforées dans la région électrochimiquement active,
    de cadres d'étanchéité (22) pour l'électrolyte, en matière plastique élastique, posés sur les tôles d'électrode métalliques massives (14),
    de membranes échangeuses d'ions (50) appliquées sur les tôles d'électrode métalliques perforées (16) et/ou les cadres d'étanchéité pour l'électrolyte (22) pour la séparation des espaces des électrodes,
    caractérisée en ce que les plaques d'électrode présentent un rapport hauteur:largeur de 30:1 à 1,5:1, les tôles d'électrode métalliques (14, 16), dans lesquelles la tôle d'électrode (14) est massive et l'autre tôle d'électrode (16) est perforée dans la région électrochimiquement active, et les cadres d'étanchéité pour l'électrolyte (22) sortent latéralement au-delà du corps de base d'électrode (12) et sont assemblés aussi bien avec des rails de contact perpendiculaires (52) disposés à une distance de 1 à 50 mm des corps de base d'électrode (12) que, également dans la région des cadres d'étanchéité pour l'électrolyte (22), avec les corps de base d'électrode (12) en plaques d'électrodes bipolaires mécaniquement stables, à monter comme des unités autonomes, dans laquelle l'isolation électrique de deux unités bipolaires voisines l'une par rapport à l'autre est assurée par les cadres d'étanchéité pour l'électrolyte (22), avec étanchéité simultanée des espaces d'électrolyte, lors du serrage des plaques d'électrode au moyen du cadre de serrage par la pression de serrage, dans laquelle les rails de contact (52) sont en contact avec les tôles d'électrode métalliques prolongées latéralement (14) et (16) et des fentes (54) sont formées entre les rails de contact respectifs et le bord du corps de base d'électrode (12), qui limitent latéralement les tôles d'électrode métalliques.
  2. Cellule électrolytique polyvalente bipolaire selon la revendication 1, caractérisée en ce que les tôles d'anode sont constituées de métaux de soupape, de référence de titane, avec des couches actives en métaux nobles.
  3. Cellule électrolytique polyvalente bipolaire selon la revendication 1 ou 2, caractérisée en ce que les tôles d'anode présentent un dépôt de métal noble en platine massif, réalisable par pressage isostatique à chaud d'une feuille de platine et une tôle de titane.
  4. Cellule électrolytique polyvalente bipolaire selon la revendication 1, 2 ou 3, caractérisée en ce que le matériau des tôles de cathode est le nickel, le titane, l'acier, l'acier allié ou le plomb.
  5. Cellule électrolytique polyvalente bipolaire selon la revendication 4, caractérisée en ce que les tôles de cathode se composent d'aciers fortement alliés, par exemple des aciers portant le numéro de matériau 1.4539, dont les faces d'électrode actives sont en métal déployé, et qui reposent à l'arrière directement sur la partie de cadre de cathode perforée servant d'appui.
  6. Cellule électrolytique polyvalente bipolaire selon l'une quelconque des revendications précédentes, caractérisée en ce que les faces de contact électrique des électrodes sont munies de revêtements bons conducteurs, en platine, or, argent, ou en couches de cuivre.
  7. Cellule électrolytique polyvalente bipolaire selon l'une quelconque des revendications précédentes, caractérisée en ce que les rails de contact sont composés de cuivre, qui est étamé, préalablement argenté ou revêtu d'un métal noble.
  8. Cellule électrolytique polyvalente bipolaire selon l'une quelconque des revendications précédentes, caractérisée en ce que les rails de contact et les contacts d'électrode sont dorés ou platinés et la transmission du courant est effectuée par le contact à pression engendré par le serrage du paquet d'électrodes.
  9. Cellule électrolytique polyvalente bipolaire selon l'une quelconque des revendications précédentes, caractérisée en ce qu'il existe entre des corps de base d'électrode et des rails de contacts placés perpendiculairement un entrefer de plusieurs millimètres, qui permet un drainage en cas de légères fuites d'électrolyte et empêche une attaque insidieuse des contacts électriques.
  10. Cellule électrolytique polyvalente bipolaire selon l'une quelconque des revendications précédentes, caractérisée en ce que les plaques d'électrode présentent une hauteur de 1,5 à 3 m et un rapport hauteur:largeur de 10:1 à 1,5:1.
EP01960214A 2000-05-09 2001-05-09 Cellule electrolytique polyvalente bipolaire destinee a des charges electriques elevees Expired - Lifetime EP1285103B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10022592 2000-05-09
DE10022592A DE10022592B4 (de) 2000-05-09 2000-05-09 Bipolare Mehrzweckelektrolysezelle für hohe Strombelastungen
PCT/EP2001/005344 WO2001086026A1 (fr) 2000-05-09 2001-05-09 Cellule electrolytique polyvalente bipolaire destinee a des charges electriques elevees

Publications (2)

Publication Number Publication Date
EP1285103A1 EP1285103A1 (fr) 2003-02-26
EP1285103B1 true EP1285103B1 (fr) 2013-01-02

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EP01960214A Expired - Lifetime EP1285103B1 (fr) 2000-05-09 2001-05-09 Cellule electrolytique polyvalente bipolaire destinee a des charges electriques elevees

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US (1) US7018516B2 (fr)
EP (1) EP1285103B1 (fr)
JP (1) JP4808898B2 (fr)
CN (1) CN1197999C (fr)
AU (1) AU2001281770A1 (fr)
BR (1) BR0110700A (fr)
CA (1) CA2407875C (fr)
DE (1) DE10022592B4 (fr)
ES (1) ES2398742T3 (fr)
NO (1) NO20025397L (fr)
RU (1) RU2002132878A (fr)
TW (1) TW526289B (fr)
WO (1) WO2001086026A1 (fr)
ZA (1) ZA200208519B (fr)

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DE10108452C2 (de) * 2001-02-22 2003-02-20 Karl Lohrberg Elektrolyseeinrichtung
US20050031936A1 (en) * 2003-05-16 2005-02-10 Joos Nathaniel Ian Symmetrical flow field plates
SE526127C2 (sv) * 2003-11-14 2005-07-12 Nilar Int Ab En packning, ett bipolärt batteri och en metod för tillverkning av ett bipolärt batteri med en sådan packning
US7722745B2 (en) * 2004-07-27 2010-05-25 Von Detten Volker Device for plating contacts in hermetic connector assemblies
US20080198531A1 (en) * 2007-02-15 2008-08-21 Lih-Ren Shiue Capacitive deionization system for water treatment
DE102010024299A1 (de) * 2010-06-18 2011-12-22 Uhde Gmbh Einzelelementelektrolysezelle zur Herstellung von Peroxodisulfat
DE102010063254A1 (de) * 2010-12-16 2012-06-21 FuMA-Tech Gesellschaft für funktionelle Membranen und Anlagentechnologie mbH Membran-Elektroden-Anordnung mit zwei Deckschichten
GR20130100562A (el) * 2013-10-03 2015-05-18 Θεοδωρος Ευσταθιου Καραβασιλης Κυτταρο ηλεκτρολυσης με κασετες ηλεκτροδιων
EP3397795B1 (fr) * 2015-12-30 2023-06-07 Innovative Hydrogen Solutions, Inc. Cellule électrolytique pour moteur à combustion interne
JP2024102507A (ja) * 2023-01-19 2024-07-31 トヨタ自動車株式会社 水電解スタック及び水電解システム
GB2642040A (en) * 2024-06-19 2025-12-31 Enapter S R L Electrochemical stack

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US2477139A (en) * 1944-04-04 1949-07-26 Western Electric Co Conducting bearing
DE3420483A1 (de) * 1984-06-01 1985-12-05 Hoechst Ag, 6230 Frankfurt Bipolarer elektrolyseapparat mit gasdiffusionskathode
DE3938160A1 (de) * 1989-11-16 1991-05-23 Peroxid Chemie Gmbh Elektrolysezelle zur herstellung von peroxo- und perhalogenatverbindungen
IT1244722B (it) * 1991-02-11 1994-08-08 S E S P I S R L Apparecchiatura per elettrolisi ed elettrodialisi
DE4211555C1 (de) * 1992-04-06 1993-12-02 Eilenburger Chemie Werk Gmbh Bipolare Filterpressenzelle zur Herstellung von Peroxodisulfaten
DE4438124A1 (de) * 1994-10-27 1996-05-02 Eilenburger Elektrolyse & Umwelttechnik Gmbh Gas-Lift-Elektrolyse- und Reaktionssysteme zur Herstellung von Produkten und zur Anwendung in der Umwelttechnik
JPH0995791A (ja) * 1995-10-04 1997-04-08 Sasakura Eng Co Ltd 固体高分子電解質水電解装置及びその電極構造

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Publication number Publication date
CN1197999C (zh) 2005-04-20
ES2398742T3 (es) 2013-03-21
HK1055767A1 (en) 2004-01-21
AU2001281770A1 (en) 2001-11-20
CA2407875A1 (fr) 2002-10-29
DE10022592B4 (de) 2010-03-04
NO20025397D0 (no) 2002-11-11
CA2407875C (fr) 2009-12-29
JP4808898B2 (ja) 2011-11-02
EP1285103A1 (fr) 2003-02-26
DE10022592A1 (de) 2001-11-15
ZA200208519B (en) 2003-11-07
BR0110700A (pt) 2003-03-18
NO20025397L (no) 2002-11-11
WO2001086026A1 (fr) 2001-11-15
CN1427900A (zh) 2003-07-02
TW526289B (en) 2003-04-01
US7018516B2 (en) 2006-03-28
US20030150717A1 (en) 2003-08-14
JP2003534452A (ja) 2003-11-18
RU2002132878A (ru) 2004-04-10
WO2001086026A8 (fr) 2002-02-21

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