EP0428171B1 - Cellule d'électrolyse pour la production de composés peroxo et perhalogénés - Google Patents

Cellule d'électrolyse pour la production de composés peroxo et perhalogénés Download PDF

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Publication number
EP0428171B1
EP0428171B1 EP90121897A EP90121897A EP0428171B1 EP 0428171 B1 EP0428171 B1 EP 0428171B1 EP 90121897 A EP90121897 A EP 90121897A EP 90121897 A EP90121897 A EP 90121897A EP 0428171 B1 EP0428171 B1 EP 0428171B1
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electrolysis cell
cell according
cathode
anode
platinum
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EP0428171A1 (fr
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Michael Dr. Gnann
Erwin Dr. Rossberger
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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
    • C25B9/70—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 electrolytic cell for the anodic production of peroxo compounds, e.g. of peroxodisulfates, peroxomonosulfates, peroxodiphosphates, and the corresponding acids; and of perhalogenates and their acids, in particular perchlorates or perchloric acid.
  • peroxo compounds e.g. of peroxodisulfates, peroxomonosulfates, peroxodiphosphates, and the corresponding acids
  • perhalogenates and their acids in particular perchlorates or perchloric acid.
  • Membrane electrolysis cells mostly of the filter press type, have been gaining technical importance in the industrial production of chlorine and sodium hydroxide for several years.
  • the numerous cell constructions described in the magazine and patent literature are not suitable for the production of, for example, peroxodisulfates or peroxodisulfuric acid, because the anode material used in the chlor-alkali electrolysis cells, mostly based on titanium support / mixed oxide made from Group VIII metals and titanium, is technically used to form peroxodisulfate not suitable because its current efficiency and its stability are too low.
  • the current yield can be increased to technically interesting values when using iridium-containing mixed oxides, but only if fluoride-containing anolyte additives are used, which, however, soon destroy the coating and thus render the anode unusable (cf.Fukuda et al., Electrochimica Acta 24 (1979) , 363-365).
  • Electrolysis cells which are constructed using partially contacted composite electrodes are known (cf. J. Balej and H. Vogt, "Electrochemical Reactors", Progress Process Engineering 22 (1984), 371-389).
  • the electrolytic cells for the production of peroxodisulfuric acid require a separator which separates the cathode compartment from the anodically formed peroxodisulfate, so that its reduction on the cathode surface is reduced or prevented.
  • Various constructions use platinum foil strips as anodes, which are fixed to tantalum sheet by roll seam welding (i.e. only locally).
  • platinum wire is used, which is either fixed on flat titanium wire meshes by spot welding or wound spirally around a silver wire coated with tantalum and attached to it by, for example, spot welding.
  • an anodic current density of 5 kA / m2 based on the platinum surface, cannot be exceeded, since otherwise the current load on the contact points between the support and platinum will be too high, which would then lead to their destruction by heating and corrosion.
  • Cells for the production of salts of peroxodisulfuric acid have a similar structure. However, constructions without a separator or diaphragm can also be used here if the peroxodisulfate is precipitated as a salt during the electrolysis and the electrolyte flows through the cell sufficiently quickly.
  • Tantalum or titanium anodes coated with platinum foils are also used for the production of perhalates, in particular for the production of perchloric acid and its salts. In terms of service life and yields, these offer advantages over graphite anodes coated with lead dioxide.
  • Platinate-coated titanium has so far been technically used for production not proven by perchlorates. For reasons similar to the anodes used to date for the production of peroxodisulfates, the anodic current densities of 5 kA / m 2 cannot be exceeded even in the production of perchloric acid or perchlorates.
  • the invention relates to an electrolysis cell of the filter press type consisting of alternately arranged, provided with electrolyte feed cathodes and anodes, which is characterized in that the cathodes and anodes consist of cuboid hollow bodies, between which there are frame-shaped seals, and which are liquid-tight and insulated from one another via these seals are connected to a cell package, the cathode hollow bodies are permeable to liquid and gas, the anode hollow bodies have openings for the transport of the anolyte in and out above and below the platinum support, and the effective anode surface through the platinum metal layer consisting of a valve metal support and a platinum support thereon, which are available is formed by hot isostatic pressing (HIP) of a platinum foil on a valve metal carrier.
  • HIP hot isostatic pressing
  • the platinum foil preferably has a thickness of 20 to 100 ⁇ m, and in particular 50 ⁇ m.
  • the thickness of the valve metal carrier (valve metal sheet) is preferably chosen so that that it can be easily processed into electrodes and can be stably installed in appropriate cell constructions; the thickness is preferably 1 to 6 mm, in particular 2 to 4 mm, and primarily 3 mm.
  • the welding of the composite sheets produced by hot isostatic pressing can be carried out using suitable, known welding techniques, e.g. by TIG welding or laser technology.
  • suitable, known welding techniques e.g. by TIG welding or laser technology.
  • the welding zone must be absolutely free of platinum, otherwise alloys are created that are not corrosion-resistant.
  • the platinum foil has a thickness of 20 to 100 ⁇ m.
  • the valve metal is titanium, niobium or tantalum.
  • the valve metal carrier has a thickness of 1 to 6 mm.
  • Separators are located between the hollow cathode bodies (1) and the hollow anode bodies (2), by means of which the catholyte spaces are separated from the anolyte spaces.
  • the separator consists of a fluorinated cation exchange membrane containing sulfonic acid groups. It lies on the openwork, liquid and gas permeable cathode surface and is attached at a distance of 0.5 to 5 mm to the platinum anode surface.
  • the active cathode parts (12) of the hollow cathode body (1) are perforated. They are roughened and / or provided with a coating which reduces the cathode polarization.
  • the openings above and below the platinum support for the supply and removal of the anolyte are slit-shaped openings or are formed by a large number of adjacent bores. The width of the slot-shaped openings or the diameter of the bores increases from the electrolyte feed or discharge (52, 62) to the opposite side.
  • the anode hollow bodies are equipped with inlets and outlets for a coolant (71, 72) and consist of three chambers, from which the upper and lower serve the electrolyte guide and the middle of the rear cooling of the active anode surfaces.
  • the sealing material for the frame-shaped seals (3) is a vinylidene fluoride-hexafluoropropylene copolymer.
  • Another object of the invention is the use of an electrolytic cell according to the invention for the electrolytic production of peroxo and perhalogenate compounds.
  • the electrolytic cell according to the invention is formed from rectangular, rectangular hollow bodies for cathodes and anodes, which are isolated from one another by frame-shaped seals and are connected to one another in a liquid-tight manner, e.g. are screwed.
  • the anode hollow body has an opening for the supply and removal of the anolyte, preferably a slot-shaped opening or a number of holes, above and below the rectangular platinum support.
  • Separators are preferably located between the anode and cathode bodies; the separators are expediently clamped between the frame-shaped seals.
  • a separator made of a fluorinated cation exchange membrane (KIA membrane) containing sulfonic acid groups is preferably used to produce the peroxo compounds, e.g. a cation exchange membrane of the type NAFION® 423 (semipermeable membranes based on poly (perfluoroalkylene) sulfonic acid).
  • the separator preferably lies on the perforated, liquid and gas permeable cathode surface; the distance of the separator from the smooth, flat platinum anode surface (platinum layer of the composite anode) is preferably 0.5 to 5 mm.
  • the active cathode parts in the cathode hollow bodies preferably consist of a sheet provided with openings, e.g. Expanded metal, perforated sheet or blind plates.
  • the composite anodes are used in the cells according to the invention with a smooth, uninterrupted platinum surface, that is to say not as, for example, expanded metal.
  • the electrolysis cell is preferably operated with a hydrostatic overpressure in the anode compartment of more than 0.02 bar (2000 Pa) compared to the cathode compartment. This is sufficient to press the cation exchange membrane against the cathode made of perforated material and thus to ensure the necessary distance between the anode surface and the KIA membrane. In order to keep the cell voltage low, this distance should preferably not exceed 5 mm, and in particular 3 mm.
  • anodic product current yields of 92 to 96% can be achieved with the arrangement according to the invention; the amount of gaseous oxygen anodically formed as a by-product is therefore so small that even with a 0.5 mm distance between Anode and separator no disturbing gas bubble effect occurs.
  • Flow speeds of> 0.3 m / sec should preferably be maintained. Since the cathode material is perforated and is preferably made of expanded metal, the electrolytically generated hydrogen can easily escape "to the rear".
  • the surface of the cathode is removed by mechanical and / or chemical measures, e.g. by sandblasting and / or etching in acids, provided with a finely structured roughening; the resulting increase in surface area results in a reduction in the cathode polarization (hydrogen overvoltage), corresponding to a reduction in the effective cathodic current density, as a result of which the cell voltage is reduced to the same extent.
  • This depolarization effect can be enhanced by coating the effective cathode surfaces with metals and / or oxides from group VIII of the Periodic Table of the Elements, this coating then advantageously being produced with a surface-rich microstructure.
  • the cathode material is preferably stainless steel.
  • the openings in the anode hollow bodies above and below the preferably rectangular platinum support for the supply and removal of the anolyte are preferably slit-shaped openings or are formed by a large number of bores lying side by side.
  • the width of the slit-shaped openings or the diameter of the bores is preferably from the electrolyte supply or discharge seen from the opposite side larger.
  • the anode hollow bodies are preferably designed such that the back of the active anode surfaces are cooled can, they are provided with inlets and outlets for a coolant, especially for cooling water.
  • the anode hollow bodies are designed in such a way that they consist of three chambers, the upper and lower of which serve to guide the electrolyte and the middle to cool the rear of the active anode surfaces.
  • FIGS 1 and 2 show schematically the structure of an electrolysis cell according to the invention:
  • the electrolytic cell essentially consists of two end cathodes 18 of identical construction (mirror image symmetrical), a plurality of rectangular hollow bodies for cathodes 1 and anodes 2, seals 3 which are pressed between the alternating anodes and cathodes by means of threaded rods 4 in a liquid-tight manner and the electrodes of opposite polarity isolate from each other.
  • separators are present which separate the differently composed electrolytes of the cathode and anode compartments from one another; separators are preferably used for separators known for chlor-alkali electrolysis, in particular cation exchange membranes of the type NAFION® 423 (semipermeable membranes based on poly (perfluoroalkylene) sulfonic acid) ).
  • the separators lie between the seal 3 and the frame of the cathode 1 in such a way that electrolyte leakage ("wicking" of the cation exchange membrane to the outside) is reliably prevented by a protruding edge of the seal.
  • Each of the rectangular, rectangular cathode or anode hollow bodies has pipe sockets 51, 61, 52, 62 for the supply 51, 52 or discharge 61, 62 of catholyte or anolyte (respectively in diametrical position 51/61 or 52/62) .
  • These pipe sockets, which are arranged alternately with the polarity are flexibly connected to the inlet 91, 92 or outlet manifolds 101, 102 of the cell packet.
  • the anode hollow bodies also have pipe sockets for the supply and discharge 72 of cooling water.
  • the cooling of the anode hollow bodies enables electrolysis operation with current densities of up to 15 kA / m2 and more, because it reliably prevents the heating of the anode surface caused by ohmic voltage losses and thus guarantees a high product yield with low oxygen development.
  • This anode cooling also has a particularly favorable effect in the synthesis of peroxodisulfuric acid and perchloric acid, where particularly low temperatures are to be maintained.
  • the hollow anode bodies On both sides or on one side, the hollow anode bodies have 2 connection lugs for the power supply (positive polarity), which is carried out by means of flexible copper elbows from copper power supply rails.
  • the cathode hollow bodies 1 are connected to the negative pole of the rectifier; the power connection takes place above and / or below the cathodes.
  • FIGS. 3 to 5 show embodiments for the structure of the anode hollow body 2 described in FIGS. 1 and 2 in cross section (FIG. 3), in plan view (FIG. 4) and in section of plane AB of FIG. 4 (FIG. 5).
  • the flat, cuboid anode hollow body comprises two opposite anode base surfaces made of the actual anode parts 22 covered with platinum foil, side boundaries 21 and diametrically arranged coolant connections 71, 72.
  • the pipe connections are positioned diametrically opposite on the anode hollow body.
  • the electrolyte supply parts of the anode are welded to the anode hollow body in such a way that a slot or a series of bores for the inflow and outflow of the anolyte are provided between the anode part 22 and the end plate 8.
  • the anode support body is formed from so-called valve metals, preferably titanium.
  • the welding of the composite sheets produced by hot isostatic pressing e.g. a platinum foil of 50 ⁇ m thickness on a 3 mm thick titanium sheet
  • suitable welding techniques e.g. TIG welding or laser technology.
  • the welding zone must be absolutely free of platinum, otherwise alloys are created that are not corrosion-resistant.
  • the inside of the anode part 22/21/22/21 can contain elements to increase the Reynolds number, e.g. Flow baffles included (not shown).
  • the electrolyte supply parts of the anode body can be provided with internals for leveling the flow.
  • FIGS. 6 and 7 show embodiments for the construction of a cathode hollow body according to FIG. 1 in section (FIG. 6) and in plan view (FIG. 7).
  • the flat, rectangular cathode hollow body 1 consists of the electrochemically active cathode parts 12, which are welded to the lateral edges with U-profiles 13 and 14, the cathode parts 12 being able to be designed, for example, as expanded metal, perforated sheet metal or as blind plates.
  • the cathode can also be equipped with metal sheets (instead of expanded metal), the cathode then being constructed like the anode and thus can also be cooled.
  • the electrolyte supply and discharge pipes 61 are located below and above the cathode parts 12. The pipe connections are positioned diametrically opposite on the hollow cathode body.
  • Both cathode parts are welded to one another along the lines a-b-c-d, as a result of which the hollow cathode body, which is closed to the outside, is formed. It can contain internals (not shown) to equalize the electrolyte flow and the current distribution.
  • Stainless steel is preferably used as the material for the cathode body.
  • stainless steel from WSt has been used to produce the peroxo or perhalogenate compounds. No. 1.4539 proven.
  • the stainless steel parts are welded using suitable, known welding techniques. After the welding process, the cathode body is brought into a completely flat state at its edges 17, which are contacted with the frame seal and possibly with the separator, if necessary by mechanical finishing.
  • the cathode plates 12 are generally roughened; it can take place on the finished cathode body, for example (after covering the sealing edges 17) by means of sandblasting and / or by means of a pickling paste.
  • the cathode plates can be processed according to methods known per se, for example with Raney nickel (for example by flame or plasma spraying), or thermally with mixed oxides composed of Ti, Ta and / or Zr on the one hand and Pt, Ru and / or on the other hand Ir, coat. If necessary (e.g. with Raney pads), extractable parts (such as aluminum or magnesium) are removed in alkaline or acidic solutions.
  • the "end cathodes" 18 of the electrolytic cell consist of hollow bodies closed on one side; the side facing the inside of the cell either consists of a "perforated”, that is to say liquid and gas permeable, or of a smooth metal sheet which leaves slots or bores at the top and bottom, while the opposite side consists of a solid metal plate 19 and forms the cell wall (see Fig. 1).
  • the electrolytic cell consists of n anodes and n + 1 cathodes.
  • a (double) anode built in accordance with the invention with two 0.06 m2 of platinum surface takes up 0.6 kA of current per anode at the current densities of 5 kA / m2 previously used in technology.
  • the electrolytic cell according to the invention can be operated with 1 kA as a permanent load and with 1.8 kA peak load.
  • the current densities customary in the prior art for the production of peroxo compounds in cells (with separators) divided can be considerably exceeded in the electrolysis cell according to the invention.
  • An appropriately equipped electrolysis system can therefore absorb peak electricity (e.g. night electricity) from electricity providers relatively quickly and flexibly; on the other hand, it can be operated down to 2 kA / m2 without loss of load.
  • the electrolysis cell according to the invention only requires no space (space requirement). For example, for a 8.33 kA / m2 electrolysis cell for the production of ammonium peroxodisulfate (APS) for 7 kA nominal current consumption - corresponding to a production of approx. 28 kg / h APS - only one parking space of 0.7 x 0.7 m2 with a height of approx. 1 m is required. The cells usual up to now require a multiple of this space.
  • APS ammonium peroxodisulfate
  • Suitable seals are, for example, seals made of Viton® (a heat and chemical-resistant, vulcanizable fluoroelastomer based on vinylidene fluoride-hexafluoropropylene copolymers); With these seals, the compression on the outside is limited by round or rectangular parts made of materials that are resistant to the electrolyte (eg ceramics, polyvinylidene fluoride, IT seals). In this way, a defined distance between the cell segments and a defined seal compression can be set.
  • Viton® a heat and chemical-resistant, vulcanizable fluoroelastomer based on vinylidene fluoride-hexafluoropropylene copolymers
  • the electrolytic cells according to the invention can also be operated without separators, e.g. for the production of potassium or sodium peroxodisulfate with simultaneous precipitation of the salts and for the production of sodium perchlorate (with the addition of sodium dichromate as cathodic top layer former).
  • An electrolytic cell according to the invention is made up of 7 anodes which are coated on both sides with 0.06 m2 (0.255 x 0.235) platinum foil of 50 ⁇ m thickness on a 3 mm thick Ti sheet by hot isostatic pressing (HIP), and 8 cathode bodies, the active ones Cathode surfaces consist of expanded metal with a mesh size of 12.7 x 6 mm, web width 2 mm. It is equipped with a KIA membrane NAFION® 423 with a thickness of 330 ⁇ m (support fabric PTFE), which rests on the cathode and is set to a distance of 2.5 mm from the anode surface using an IT-supported VITON® seal.
  • HIP hot isostatic pressing
  • the cathode surfaces were treated by sandblasting and chemical pickling in dilute sulfuric acid (1: 1) in such a way that the surface roughness was medium (gray color).
  • the anolyte consists of 0.2 M H2SO4, 2.6 M (NH4) 2SO4, 0.9 M (NH4) 2S2O8 and an addition of ammonium thiocyanate (4.5 g / kg produced (NH4) 2S2O8 at 40 ° C).
  • a solution of 1 M H2SO4 and 3.5 M (NH4) 2SO4 is used as the catholyte.
  • ammonium peroxodisulfate is generated with a current efficiency of 92 to 96%; with a residence time of the anolyte in the electrode gap of 0.35 sec. adjusted with the help of a circulation pump.
  • 1.120 kg of product (dried, chemically pure) are obtained by crystallization, centrifugation, washing and drying.
  • the voltage of the electrolytic cell remained in the range of 6.4 to 6.6 volts. This results in an energy requirement of 1.6 kWh / kg of product.
  • the electrolytic cell according to Example 1 is advantageously without a cation exchange membrane used under the following conditions: Electrolyte: 2.1 M H2SO4, 1.4 M K2SO4, 0.3 M K2S2O8; 1.5 g NaSCN / kg K2S2O8 produced; Current density: 9 kA / m2, corresponding to 7.56 kA Cell current; Temperature: 25 ° C. At a cell voltage of 5.9 volts, potassium peroxodisulfate is precipitated from the electrolyte (suspension electrolyte) with a current efficiency of 75% and removed from the electrolyte by means of customary separation and cleaning steps. Energy requirement: 1.56 kwh / kg.
  • Example 3 In an electrolysis cell according to Example 3, a solution of 3.0 M H2SO4, 2.8 M Na2SO4 and 0.2 M Na2S2O8 with the addition of 12 g NaSCN per kg of Na2S2O8 produced at 8 kA / m2 is electrolyzed. Temperature: 25 ° C. The residence time of the electrolyte in the electrode gap does not exceed 0.4 s. If the electrolyte composition is kept constant, sodium peroxodisulfate (NPS) precipitates from the suspension electrolyte with a current efficiency of 62%. With a voltage of 6.2 volts, the energy requirement is 2.25 kWh / kg.
  • NPS sodium peroxodisulfate
  • the cells of the invention are also suitable for the production of HClO4 according to the process of DE-PS 10 31 288.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (15)

  1. Cellule d'électrolyse de type filtre-presse pour la préparation de composés peroxo et perhalogénate formée de cathodes et d'anodes disposées de façon alternée et munies d'amenées de l'électrolyte, caractérisée en ce que les cathodes (1) et les anodes (2) sont constituées de corps creux parallélépipédiques entre lesquels se trouvent des garnitures en forme de cadre, et qui sont reliés par l'intermédiaire de ces garnitures, de façon étanche aux liquides et isolément les uns des autres, pour former un empilage de cellules, les corps creux cathodiques (1) sont perméables aux liquides et aux gaz, les corps creux anodiques (2) possèdent au-dessus et au-dessous du placage de platine des ouvertures pour l'entrée et la sortie de l'anolyte, et la surface active des anodes est formée par la couche métallique de platine d'une anode composée constituée d'un support en métal pour soupape et d'un placage en platine qui le recouvre, pouvant être obtenue par compression isostatique à chaud d'une feuille de platine sur un support en métal de transition.
  2. Cellule d'électrolyse selon la revendication 1, caractérisée en ce que la feuille de platine a une épaisseur de 20 à 100 µm.
  3. Cellule d'électrolyse selon l'une des revendications 1 ou 2, caractérisée en ce que le métal pour soupape est le tantale, le niobium ou le titane.
  4. Cellule d'électrolyse selon l'une des revendications 1 ou 2, caractérisée en ce que le support en métal pour soupape a une épaisseur de 1 à 6 mm.
  5. Cellules d'électrolyse selon l'une des revendications précédentes, caractérisée en ce que, entre les corps creux cathodiques (1) et les corps creux anodiques (2), se trouvent des séparateurs qui séparent les compartiments cathodiques des compartiments anodiques.
  6. Cellule d'électrolyse selon l'une des revendications précédentes, caractérisée en ce que le séparateur est constitué par une membrane échangeuse de cations fluorée contenant des groupes acide sulfonique.
  7. Cellule d'électrolyse selon l'une des revendications précédentes, caractérisée en ce que le séparateur s'appuie sur la surface ajourée, perméable aux liquides et aux gaz, de la cathode.
  8. Cellule d'électrolyse selon l'une des revendications 5 à 7, caractérisée en ce que le séparateur est disposé à une distance de 0,5 à 5 mm de la surface de l'anode de platine.
  9. Cellule d'électrolyse selon l'une des revendications précédentes, caractérisée en ce que les parties cathodiques actives (12) du corps creux cathodique (1) ont une structure ajourée.
  10. Cellule d'électrolyse selon l'une des revendications précédentes, caractérisée en ce que les parties cathodiques actives (12) sont décapées et/ou munies d'un revêtement qui abaisse la polarisation de la cathode.
  11. Cellule d'électrolyse selon l'une des revendications précédentes, caractérisée en ce que les ouvertures pour l'entrée et la sortie de l'électrolyte situées au-dessus et au-dessous du placage en platine sont des ouvertures en forme de fentes ou sont formées par de multiples orifices juxtaposés.
  12. Cellule d'électrolyse selon la revendication 11, caractérisée en ce que la largeur des ouvertures en forme de fentes ou le diamètre des orifices s'agrandit du côté de l'amenée de l'électrolyte (52) par rapport au côté opposé.
  13. Cellule d'électrolyse selon l'une des revendications précédentes, caractérisée en ce que les corps creux anodiques sont équipés de conduites d'amenée et de sortie d'un réfrigérant (71, 72) et en ce qu'ils sont constitués de trois chambres, la chambre supérieure et la chambre inférieure servant à la conduite de l'électrolyte et celle du milieu au refroidissement par l'arrière de la surface active de l'anode.
  14. Cellule d'électrolyse selon l'une des revendications précédentes, caractérisée en ce que le matériau d'étanchéité pour les garnitures en forme de cadre (3) est un copolymère de fluorure de vinylidène-hexafluoropropylène.
  15. Utilisation d'une cellule d'électrolyse selon l'une des revendications 1 à 14 pour la préparation de composés peroxo et perhalogénate.
EP90121897A 1989-11-16 1990-11-15 Cellule d'électrolyse pour la production de composés peroxo et perhalogénés Expired - Lifetime EP0428171B1 (fr)

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Application Number Priority Date Filing Date Title
DE3938160A DE3938160A1 (de) 1989-11-16 1989-11-16 Elektrolysezelle zur herstellung von peroxo- und perhalogenatverbindungen
DE3938160 1989-11-16

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EP0428171A1 EP0428171A1 (fr) 1991-05-22
EP0428171B1 true EP0428171B1 (fr) 1993-09-29

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US (1) US5082543A (fr)
EP (1) EP0428171B1 (fr)
JP (1) JPH03173789A (fr)
DE (2) DE3938160A1 (fr)
ES (1) ES2059959T3 (fr)
RU (1) RU2025544C1 (fr)
TR (1) TR25047A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2546389A1 (fr) 2011-07-14 2013-01-16 United Initiators GmbH & Co. KG Procédé de fabrication de peroxodisulfate alcalin ou d'ammonium dans une pièce d'électrolyse non divisée
WO2014009536A1 (fr) 2012-07-13 2014-01-16 United Initiators Gmbh & Co. Kg Cellule électrolytique dépourvue de séparateur et son utilisation

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US5221452A (en) * 1990-02-15 1993-06-22 Asahi Glass Company Ltd. Monopolar ion exchange membrane electrolytic cell assembly
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RU2025544C1 (ru) 1994-12-30
DE59002925D1 (de) 1993-11-04
EP0428171A1 (fr) 1991-05-22
JPH03173789A (ja) 1991-07-29
ES2059959T3 (es) 1994-11-16
DE3938160A1 (de) 1991-05-23
TR25047A (tr) 1992-09-01
US5082543A (en) 1992-01-21

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