EP0428171A1 - 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

Info

Publication number
EP0428171A1
EP0428171A1 EP90121897A EP90121897A EP0428171A1 EP 0428171 A1 EP0428171 A1 EP 0428171A1 EP 90121897 A EP90121897 A EP 90121897A EP 90121897 A EP90121897 A EP 90121897A EP 0428171 A1 EP0428171 A1 EP 0428171A1
Authority
EP
European Patent Office
Prior art keywords
electrolytic cell
cell according
anode
cathode
platinum
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.)
Granted
Application number
EP90121897A
Other languages
German (de)
English (en)
Other versions
EP0428171B1 (fr
Inventor
Michael Dr. Gnann
Erwin Dr. Rossberger
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.)
United Initiators GmbH and Co KG
Original Assignee
United Initiators GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6393684&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0428171(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by United Initiators GmbH and Co KG filed Critical United Initiators GmbH and Co KG
Publication of EP0428171A1 publication Critical patent/EP0428171A1/fr
Application granted granted Critical
Publication of EP0428171B1 publication Critical patent/EP0428171B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • C25B9/17—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
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

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) , 363365).
  • 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 guaderiform 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 form a cell package, the cathode hollow bodies are permeable to liquid and gas, the anode hollow bodies have openings above and below the platinum support for the supply and removal of the anolyte, 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 insulated 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 electrolytic 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 rectangular hollow bodies for cathodes 1 and anodes 2, seals 3, which are arranged between the alternating anodes and cathodes are pressed in liquid-tight by means of threaded rods 4 and isolate the electrodes of opposite polarity from one another.
  • 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 NAFION® 423 cation exchange membranes (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, guaderiform hollow anode body comprises two opposite anode base surfaces from 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, guaderiform hollow cathode 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 can be designed, for example, as expanded metal, perforated sheet metal or as blind plates. In the event of In a cell without a separator, 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 interior 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 upper and lower edges, 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 according to the prior art for the production of peroxo compounds in cells (with separators) 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. 1m 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 composed 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 used without cation exchange shear membrane used under the following conditions: Electrolyte: 2.1M H2SO4, 1.4M K2SO4, 0.3M 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 according to the invention are also suitable for the production of HClO4 according to the process of DE-PS 10 31 288.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP90121897A 1989-11-16 1990-11-15 Cellule d'électrolyse pour la production de composés peroxo et perhalogénés Expired - Lifetime EP0428171B1 (fr)

Applications Claiming Priority (2)

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

Publications (2)

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

Family

ID=6393684

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90121897A Expired - Lifetime EP0428171B1 (fr) 1989-11-16 1990-11-15 Cellule d'électrolyse pour la production de composés peroxo et perhalogénés

Country Status (7)

Country Link
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6503386B2 (en) 2000-04-20 2003-01-07 Degussa Ag Process for the production of alkali metal- and ammonium peroxodisulfate
US9540740B2 (en) 2012-07-13 2017-01-10 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use thereof
US9556527B2 (en) 2011-07-14 2017-01-31 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use of the same

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5221452A (en) * 1990-02-15 1993-06-22 Asahi Glass Company Ltd. Monopolar ion exchange membrane electrolytic cell assembly
US5254233A (en) * 1990-02-15 1993-10-19 Asahi Glass Company Ltd. Monopolar ion exchange membrane electrolytic cell assembly
CN1042659C (zh) * 1994-03-23 1999-03-24 王国诚 垂直供电棒单极压滤机式电解槽
DE4419683C2 (de) * 1994-06-06 2000-05-04 Eilenburger Elektrolyse & Umwelttechnik Gmbh Bipolare Filterpressenzelle für anodische Oxidationen an Platin
JP3555197B2 (ja) * 1994-09-30 2004-08-18 旭硝子株式会社 複極型イオン交換膜電解槽
DE4438110A1 (de) * 1994-10-26 1996-05-02 Eilenburger Elektrolyse & Umwelttechnik Gmbh Verfahren zum anodischen, oxidativen Abbau von organischen Schadstoffen in Prozeßlösungen und Abwässern
US7824532B2 (en) * 1995-04-26 2010-11-02 Life Technologies Corporation Apparatus and method for electrophoresis
DE19530218A1 (de) * 1995-08-17 1997-02-20 Eilenburger Elektrolyse & Umwelttechnik Gmbh Verfahren zur kombinierten elektrochemischen Herstellung von Natriumperoxodisulfat und Natronlauge
US5643437A (en) * 1995-11-03 1997-07-01 Huron Tech Canada, Inc. Co-generation of ammonium persulfate anodically and alkaline hydrogen peroxide cathodically with cathode products ratio control
US6200440B1 (en) 1995-11-03 2001-03-13 Huron Tech Corp Electrolysis cell and electrodes
US6027620A (en) * 1995-11-03 2000-02-22 Huron Tech Corp Filter press electrolyzer
DE19624024A1 (de) * 1996-06-17 1997-12-18 Verein Fuer Kernverfahrenstech Verfahren zur Herstellung von Halogenen, Oxoverbindungen der Halogene sowie zur Herstellung von Peroxyverbindungen durch Elektrolyse
DE19962672A1 (de) * 1999-12-23 2001-06-28 Eilenburger Elektrolyse & Umwelttechnik Gmbh Verfahren und Vorrichtung zur Herstellung oder Regenerierung von Peroxodisulfaten
DE10022592B4 (de) * 2000-05-09 2010-03-04 Peroxid-Chemie Gmbh & Co. Kg Bipolare Mehrzweckelektrolysezelle für hohe Strombelastungen
NL1019070C2 (nl) * 2001-10-01 2003-04-02 Gerrit Albert Zilvold Inrichting voor het uitvoeren van een elektrolyse van een halogenideverbinding.
JP4209848B2 (ja) * 2003-03-27 2009-01-14 ジルフォルド，ヘンドリック，マルティン ハロゲン化化合物に電気分解を実施するための装置
RU2311495C2 (ru) * 2003-03-27 2007-11-27 Хендрик Мартин ЗИЛВОЛД Аппарат для осуществления процесса электролиза галогенидного соединения
GB2427373A (en) * 2005-03-05 2006-12-27 Catal Internat Ltd A reactor
US7374645B2 (en) * 2006-05-25 2008-05-20 Clenox, L.L.C. Electrolysis cell assembly
US20080116144A1 (en) 2006-10-10 2008-05-22 Spicer Randolph, Llc Methods and compositions for reducing chlorine demand, decreasing disinfection by-products and controlling deposits in drinking water distribution systems
US20100283169A1 (en) * 2009-05-06 2010-11-11 Emmons Stuart A Electrolytic cell diaphragm/membrane
JP5387250B2 (ja) * 2009-09-09 2014-01-15 株式会社Ｉｈｉ 過塩素酸塩の製造方法及び製造装置
JP2011256431A (ja) * 2010-06-09 2011-12-22 Ihi Corp 過塩素酸塩の製造装置
TW201406998A (zh) 2012-07-13 2014-02-16 United Initiators Gmbh & Co Kg 無分隔電解槽及其用途
US20140209466A1 (en) 2013-01-31 2014-07-31 Wyatt Technology Corporation Corrosion resistant electrodes for electrophoretic mobility measurements and method for their fabrication
JP6189655B2 (ja) * 2013-06-14 2017-08-30 Ｋｙｂ株式会社 アノードの製造方法
JP6193005B2 (ja) 2013-06-14 2017-09-06 Ｋｙｂ株式会社 保持装置及びそれを備えた高速めっき装置
JP6189656B2 (ja) 2013-06-14 2017-08-30 Ｋｙｂ株式会社 給電部材及びそれを備えた高速めっき装置
US8617403B1 (en) 2013-06-25 2013-12-31 Blue Earth Labs, Llc Methods and stabilized compositions for reducing deposits in water systems
NL2014542B1 (nl) 2015-03-27 2017-01-06 Van Den Heuvel Watertechnologie B V Werkwijze en inrichting voor het behandelen van een effluentstroom afkomstig van een of meer elektrolysecellen.
CN107557809A (zh) * 2017-08-10 2018-01-09 云南龙蕴科技环保股份有限公司 一种新型框式电解槽

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB512966A (en) * 1937-05-21 1939-09-29 Oesterr Chem Werke Improvements in or relating to process for the electrolytic production of persulphuric acid and persalts and apparatus for carrying out the process
FR2307887A1 (fr) * 1975-04-15 1976-11-12 Asahi Glass Co Ltd Cuve electrolytique du type filtre presse
US4217199A (en) * 1979-07-10 1980-08-12 Ppg Industries, Inc. Electrolytic cell
EP0350895A1 (fr) * 1988-07-13 1990-01-17 Peroxid-Chemie GmbH Electrode composite métal valve/platine

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2346945C3 (de) * 1973-09-18 1982-05-19 Peroxid-Chemie GmbH, 8023 Höllriegelskreuth Verfahren zur direkten elektrolytischen Herstellung von Natriumperoxodisulfat
US4626327A (en) * 1985-06-06 1986-12-02 Fmc Corporation Electrolytic process for manufacturing potassium peroxydiphosphate
US4828660A (en) * 1986-10-06 1989-05-09 Athens Corporation Method and apparatus for the continuous on-site chemical reprocessing of ultrapure liquids
US4802959A (en) * 1987-06-16 1989-02-07 Tenneco Canada Inc. Electrosynthesis of persulfate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB512966A (en) * 1937-05-21 1939-09-29 Oesterr Chem Werke Improvements in or relating to process for the electrolytic production of persulphuric acid and persalts and apparatus for carrying out the process
FR2307887A1 (fr) * 1975-04-15 1976-11-12 Asahi Glass Co Ltd Cuve electrolytique du type filtre presse
US4217199A (en) * 1979-07-10 1980-08-12 Ppg Industries, Inc. Electrolytic cell
EP0350895A1 (fr) * 1988-07-13 1990-01-17 Peroxid-Chemie GmbH Electrode composite métal valve/platine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6503386B2 (en) 2000-04-20 2003-01-07 Degussa Ag Process for the production of alkali metal- and ammonium peroxodisulfate
US9556527B2 (en) 2011-07-14 2017-01-31 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use of the same
US9540740B2 (en) 2012-07-13 2017-01-10 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use thereof

Also Published As

Publication number Publication date
DE59002925D1 (de) 1993-11-04
DE3938160A1 (de) 1991-05-23
JPH03173789A (ja) 1991-07-29
US5082543A (en) 1992-01-21
EP0428171B1 (fr) 1993-09-29
TR25047A (tr) 1992-09-01
ES2059959T3 (es) 1994-11-16
RU2025544C1 (ru) 1994-12-30

Similar Documents

Publication Publication Date Title
EP0428171B1 (fr) Cellule d'électrolyse pour la production de composés peroxo et perhalogénés
EP0989206B1 (fr) Cellule d'électrolyse et son utilisation
DE69108018T2 (de) Vorrichtung zur herstellung von chlorsäure und verchlorsäure.
DD209853A5 (de) Elektrolysezelle und dichtung fuer eine elektrolysezelle
DE3420483A1 (de) Bipolarer elektrolyseapparat mit gasdiffusionskathode
DE2827266A1 (de) Verfahren zur elektrolyse in einer membranzelle unter einhaltung eines durch druckbeaufschlagung erzielten gleichmaessigen abstands sowie vorrichtung zur durchfuehrung des verfahrens
EP0350895B1 (fr) Electrode composite métal valve/platine
DE69213362T2 (de) Elektrolyseur und Herstellung davon
DE102007042171A1 (de) Elektrolysezelle mit hoher Stromkapazität zur Herstellung eines Ozon-Sauerstoffgemisches
DE2645121C3 (de) Elektrolysezelle
DE2841148C2 (fr)
DE3228884A1 (de) Vertikal angeordnete plattenelektrode fuer gasbildende elektrolyseure
DE3401812A1 (de) Elektrolysezelle
DE2510396C3 (de) Verfahren zur Elektrolyse wäßriger Natriumchloridlösungen
DE2828621C2 (fr)
DE69818771T2 (de) Diaphragma Chlor-Alkali Elektrolysezelle
DE2821978A1 (de) Anodenelement fuer monopolare, filterpressenartig angeordnete elektrolysezellen
WO1993020261A1 (fr) Cellule bipolaire de type filtre-presse pour fabriquer des sulfates peroxodiques
DE2927024A1 (de) Elektrolytische zelle
DE4419683C2 (de) Bipolare Filterpressenzelle für anodische Oxidationen an Platin
DE10306342B4 (de) Elektrolysevorrichtung
DE68928338T2 (de) Zelle und Verfahren zum Betrieb einer elektrochemischen Zelle vom Typ flüssig-gasförmig
DE2315526C2 (de) Bipolare Zelle
DE2929755A1 (de) Kathodenelement
DE4318533A1 (de) Bipolare Elektrolysezelle

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT

17P Request for examination filed

Effective date: 19910524

17Q First examination report despatched

Effective date: 19930209

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 59002925

Country of ref document: DE

Date of ref document: 19931104

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19931015

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: DEGUSSA AG, FRANKFURT - ZWEIGNIEDERLASSUNG WOLFGAN

Effective date: 19940629

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2059959

Country of ref document: ES

Kind code of ref document: T3

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 19960125

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20081015

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20081121

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20081125

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20081113

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20081125

Year of fee payment: 19

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20091115

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091115

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091116