EP1179612B1 - Verfahren zur elektrochemischen Reduktion organischer Verbindungen. - Google Patents
Verfahren zur elektrochemischen Reduktion organischer Verbindungen. Download PDFInfo
- Publication number
- EP1179612B1 EP1179612B1 EP01117681A EP01117681A EP1179612B1 EP 1179612 B1 EP1179612 B1 EP 1179612B1 EP 01117681 A EP01117681 A EP 01117681A EP 01117681 A EP01117681 A EP 01117681A EP 1179612 B1 EP1179612 B1 EP 1179612B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lead
- cystine
- cathode
- solution
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
Definitions
- the present invention relates to a method for electrochemical reduction of organic compounds.
- Electrode is often used as the cathode, which is characterized by a high overvoltage against hydrogen distinguished.
- lead cathodes are Reduction of aldehydes, ketones, carboxylic acids and carboxylic esters to alcohols, the reduction of heterocycles and Dehalogenations (overview: M.M. Baizer in Organic Electrochemistry, Marcel Dekker, New York 1991, p. 362 ff., I. Nishiguchi et al., Electroorg. Synth. 1991, p. 331). Numerous processes are also carried out on an industrial scale using lead cathodes (overview: "Industrial Electrochemistry” by Pletcher and Walsh, Chapman and Hall, London 1989, pp. 313-319).
- lead-plated carrier cathodes for example made of copper or titanium (M.M. Baizer in Organic Electrochemistry, Marcel Verlag Dekker, New York 1991, p.274).
- Corresponding coating processes are expensive and complicated, however. in this connection you have to rely on flat geometries so that the Coating receives good adhesion to the carrier.
- lead surfaces are easily deactivated be (EP 0 931 856), whereby the current efficiency and the Area-time benefits decrease. Corrosion is also described by lead electrodes. To regenerate the The electrolytic cell must have a complete cathode surface be dismantled. The resulting high downtime severely restrict economic usability.
- the patent DE 1 024 518 shows that Tin cathodes at a current density of 500 A / sqm cystine too Cysteine can be reduced with 100% electricity yield. own Experiments show that by increasing the current densities up to 2000 A / sqm of tin the electricity yields drop below 30%, because under these conditions the evolution of hydrogen starts much earlier. In addition, the electricity yield increases follows-up attempts continue.
- US-A-2,925,371 discloses a cathode for electrochemical Reduction of organic compounds from an electrical conductive carrier, for example made of stainless steel, with a foam-like coating made of electrochemically deposited lead consists.
- the object of the present invention is to provide a process aimed at reducing organic Industrial scale connections.
- the object is achieved by a method according to claim 1.
- the lead layer of the cathode used has a loose structure with a density which is greatly reduced compared to solid lead in the range between 0.001 and 2 g / cm 3 , preferably between 0.01 and 1 g / cm 3 .
- the increase in surface area documented by the reduced density has an advantageous effect on the area-time performance of chemical processes.
- the cathode carrier consists of an electrically conductive Material, preferably made of a metal other than an alkali or Alkaline earth metal or a metal alloy or graphite.
- the electrically conductive carrier particularly preferably consists of a metal or a metal alloy selected from the Group copper, nickel, tin, zinc, titanium, iron, steel, Stainless steel, cadmium and lead.
- Elements can also be selected as alloy components from the group tungsten, chrome, cobalt, molybdenum, manganese, Bismuth, aluminum, mercury, zirconium, vanadium, silicon, Boron, niobium, tantalum, antimony, phosphorus and carbon, to be available.
- metal also includes metal alloys, as stated above.
- Such a carrier can be combined with one or more others of the metals mentioned may be coated.
- coating are all methods known to the person skilled in the art, e.g. Electroplate or sputtering.
- the shape of the electrically conductive carrier is not critical. she is preferably selected from the large number of known or available electrode geometries, e.g. Plate, net, foam, Washer, tube, sieve plate, rod etc. selected.
- the lead layer deposited on the electrically conductive carrier is distinguished by a reduced density compared to solid lead in the range from 0.001 to 2 g / cm 3 , preferably between 0.01 and 1 g / cm 3 .
- the production of a cathode used according to the invention is characterized in that in a known per se Electrolysis cell on an electrically conductive support, which as Is switched cathode, from a lead salt-containing aqueous Catholyte solution using electrochemical deposition Lead layer is deposited with reduced density.
- Any cell known to the person skilled in the art is an electrolytic cell suitable.
- a selection of frequently used cells can be found in textbooks, e.g. B. in "Industrial Electrochemistry” by Pletcher and Walsh, Chapman and Hall, London 1989, pp. 141-166.
- Suitable as lead salts for the lead salt-containing aqueous solution all lead salts, the lead in the second level included, e.g. Lead (II) carbonate, lead (II) chloride, Lead (II) fluoride, lead (II) acetate, lead (II) formate, Lead (II) oxalate, lead (II) nitrate and their basic salts, Lead (II) sulfate and lead (II) oxide.
- Lead (II) carbonate e.g. Lead (II) carbonate, lead (II) chloride, Lead (II) fluoride, lead (II) acetate, lead (II) formate, Lead (II) oxalate, lead (II) nitrate and their basic salts, Lead (II) sulfate and lead (II) oxide.
- Mineral acids preferably hydrochloric acid, sulfuric acid and Phosphoric acid in a concentration between 0.5 M and 12 M, in the case of hydrochloric acid up to 8.5 M (concentrated hydrochloric acid)
- organic acids e.g. Acetic acid, formic acid, citric acid, lactic acid or the salts thereof with ammonium, tetraalkylammonium, sodium or the salts thereof with ammonium, tetraalkylammonium, sodium or Potassium ions, or complexing agents for divalent lead ions, for example EDTA or NTA in amounts of 1 to 3 Equivalents based on the amount of lead present.
- the solution containing lead salt can additionally contain inorganic salts as conductive salts.
- inorganic salts as conductive salts. Examples of this are all alkali, alkaline earth metal and ammonium salts, e.g. B. Sodium chloride, sodium sulfate, ammonium chloride, Lithium perchlorate.
- the aqueous solution containing lead salt can also be used water-miscible cosolvents such as ethanol, methanol, i-propanol, n-propanol, acetonitrile, ethylene glycol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Tetrahydrofuran, 1,4-dioxane, methyl acetate, Ethyl acetate, formic acid, dimethylformamide, Sulfolane, ethylene carbonate, N, N'-dimethylpropyleneurea, N, N'-dimethylethylene urea, N-methylpyrrolidone, Tetramethylurea and hexamethylphosphoric triamide in Concentrations of 0.1 to 80 wt.%, Preferably 1 to 50 wt. % contain.
- water-miscible cosolvents such as ethanol, methanol, i-propanol, n-propanol, acet
- the lead ion concentration is in the lead salt containing aqueous solution preferably between 1 ppm and 20 g / l, especially preferably between 10 ppm and 10 g / l.
- the pH of the electrolysis solution is preferably between 1 and 6, particularly preferably between 1 and 3.
- the deposition of the lead layer is preferably achieved by applying a cathode potential between -0.1 V and the value at which hydrogen evolution starts at the cathode.
- Current densities of 0.1 A / m 2 to 4000 A / m 2 , preferably 10 to 3000 A / m 2, are set here.
- the temperature is when performing the procedure critical. It can be freely selected in a wide range. A lower temperature limit is due to the freezing point Given catholyte solution, an upper limit due to the stability the electrolytic cell. In the case of membrane cells, this is especially the thermal stability of the membrane. In this In this case, the temperature is limited to a maximum of 60 ° C.
- the formation of the lead layer can be done before or at the same time with the reduction of an organic compound.
- the method according to the invention can be analogous to the known ones electrochemical process for the reduction of such compounds performed using the cathode according to the invention become. (Overview: M.M. Baizer in Organic Electrochemistry, Verlag Marcel Dekker, New York 1991, pp. 362 ff.)
- the compound to be reduced is preferably an organic sulfur compound, e.g. B. a disulfide compound, a sulfinic acid, sulfoxide or a thioether, or an organic carbonyl compound, for example an aldehyde or ketone.
- Particularly preferred disulfide compounds are cystine, N-alkanoyl-cystine, homocystine and N-alkanoyl homocystine.
- the concentration of the compound to be reduced is 0.01 M to 10 M, preferably 0.1 to 5 M.
- the solvent used is preferably an aqueous solution of mineral acid, for example hydrochloric acid, sulfuric acid or phosphoric acid, or of sodium or potassium hydroxide, sodium or potassium carbonate or acetate, ammonia , Ammonium chloride or ammonium acetate used in concentrations between 0.1 M and 12 M.
- the electrochemical reduction of cystine and homocystine is preferably carried out in aqueous hydrochloric acid, sulfuric acid, sodium or potassium hydroxide solution or in an ammoniacal solution.
- the concentration of the cystine can be between 0.1 M and the saturation concentration. Saturated cystine or homocystine solutions are particularly preferred.
- the reduction of N-acetylcystine is preferably carried out at pH values between 5 and 13.
- the electrolysis is carried out at temperatures between 0 ° C and 70 ° C, preferably at temperatures between 10 ° C and 50 ° C.
- Current densities are 0.1 A / m2 to 20,000 A / m2, preferably 10-5000 A / m2.
- cysteine hydrochloride from cystine in a hydrochloric acid electrolysis solution the unusually high current density of 2000 A / qm with a Area-time performance of 7.3 kg of cysteine hydrochloride hydrate per hour and sqm of membrane area (see G1.1 in scheme 1). This area-time performance is up to at least 5 Days of operation constant. In the electrolysis solution is at a detection limit of 0.5 ppm no lead was detectable.
- Another advantage of the method according to the invention is that easy regeneration of the cathode.
- the regeneration is possible without disassembling the cell.
- the lead layer is thereby in one embodiment by rinsing the catholyte space with Water or mechanically removed with the catholyte.
- the lead layer becomes partial or completely dissolved.
- Aqueous solutions are suitable for this of mineral acids or organic acids in concentrations between 0.1 and 10 M except for sulfuric acid. Examples of this are hydrochloric acid, phosphoric acid or acetic acid. Possibly can the aqueous acid solution complexing agent Increase in solubility of the resulting lead salt in quantities between 0.5 and 5 equivalents based on that to be resolved Amount of lead can be added.
- Complexing agent for lead (II) ions are e.g. EDTA, NTA and citric acid. The temperatures are here within the working area of electrochemical Cell.
- Example 1 Production of a cathode used according to the invention
- Cell used A cell divided by means of a membrane made of Nafion 324 (electrode or membrane area 0.01 m 2 ) with electrodes arranged plane-parallel and consisting of a copper cathode, an oxygen-developing DSA anode (DeNora GmbH, anolyte: 20 percent sulfuric acid). The electrode-membrane distance was 1.8 cm. Catholyte and anolyte solutions were pumped through the cell from reservoirs (batch recycle operation).
- Example 2 Production of a cathode used according to the invention
- Example 2 Analogously to Example 1, the electrolytic deposition of the lead on the copper cathode was carried out from a solution of 2.00 g of basic lead carbonate in a solution of 360 g of cystine and 367 g of conc. HCl in 1314 g water at 6.9 A. Response time: 15 h. Residual content of lead in solution ⁇ 0.5 ppm. Conversion of cystine to cysteine hydrochloride: 99.7% (measured with HPLC and rotation value ⁇ ).
- ElectroMPCell ElectroMPCell AB, T ⁇ by, Sweden
- DSA anode an oxygen-developing DSA anode
- Nafion 324 cation exchange membrane as described in Example 2, a loose Lead layer deposited (pumping rate 1-2 l / h).
- 360 g of cystine were converted to cysteine hydrochloride analogously to Example 4.
- the reaction was complete after a reaction time of 7.0 hours. (Degree of conversion> 99.7%, determined by HPLC). Calculated area-time performance 7.52 kg cysteine hydrochloride monohydrate per m2 membrane area and per hour.
- Example 2 Analogously to Example 1, 750 mg of dissolved lead white was used loose lead deposited on a lead cathode. 1.00 kg As in Example 3, cystine became cysteine hydrochloride reduced. Total reaction time: 21.8 hours. Calculated area-time performance: 6.71 kg cysteine hydrochloride monohydrate per square meter Membrane area and per hour.
- Example 8 Reduction of cystine to cysteine hydrochloride, comparative example to example 3
- an electrolysis apparatus consisting of an electrolysis cell with disc-shaped electrodes (anode: DSA titanium expanded metal, cathode: lead sieve plate with loosely separated lead, electrodes used on both sides and each suspended with the help of concentrically welded rods, diameter 7.5 cm) and the As in the periphery constructed in Example 1, a solution of 1.523 g of L-cysteine sulfinic acid monohydrate in 600 ml of 2N hydrochloric acid was reacted at 10 A and a reaction temperature of 15 ° C. for 4.5 hours. The reaction solution contains 60% cystine (S, S) dioxide, 20% cystine sulfinic acid and 20% cystine ( 1 H-NMR spectroscopic examination).
- a solution was found in the electrolysis apparatus according to Example 10 of 130.0 g of 2,4-dicarboxy-2-methyl-thiazolidine in one Mixture of 526 ml of water and 144 g of hydrochloric acid at 9.5 A and Temperatures of 16-20 ° C implemented. After a reaction time of 5 hours 66% N- (1-carboxyethyl) cysteine, 19% lactic acid and 15 % Cysteine received. The reaction solution was evaporated and the solid from 0.5 M hydrochloric acid with exclusion of oxygen recrystallized. N- (1-carboxyethyl) cysteine is obtained in the form of colorless crystals.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
Besonders bevorzugte Disulfidverbindungen sind Cystin, N-Alkanoyl-cystin, Homocystin und N-Alkanoylhomocystin.
Die Konzentration der zu reduzierenden Verbindung beträgt 0.01 M bis 10 M, bevorzugt 0.1 bis 5 M. Als Solvens wird vorzugsweise eine wässrige Lösung von Mineralsäure, z.B. Salzsäure, Schwefelsäure oder Phosphorsäure, oder von Natriumoder Kaliumhydroxid, Natrium- oder Kaliumcarbonat oder - acetat, Ammoniak, Ammoniumchlorid oder Ammoniumacetat in Konzentrationen zwischen 0.1 M und 12 M verwendet.
Die elektrochemische Reduktion des Cystins und Homocystins wird bevorzugt in wässriger Salzsäure, Schwefelsäure, Natriumoder Kaliumhydroxidlösung oder in ammoniakalischer Lösung durchgeführt. Die Konzentration des Cystins kann zwischen 0.1 M und der Sättigungskonzentration liegen. Besonders bevorzugt sind gesättigte Cystin- bzw. Homocystinlösungen.
Die Reduktion von N-Acetylcystin wird bevorzugt bei pH-Werten zwischen 5 und 13 durchgeführt.
Die Elektrolysen werden bei Temperaturen zwischen 0°C und 70°C durchgeführt, bevorzugt bei Temperaturen zwischen 10°C und 50°C.
Stromdichten betragen 0.1 A/qm bis 20000 A/qm, bevorzugt 10-5000 A/qm.
Der Elektroden-Membranabstand betrug 1,8 cm. Katholyt- und Anolytlösung wurden aus Reservoirs durch die Zelle gepumpt (batch-recycle-Betrieb).
Reaktionszeit: 15 h.
Restgehalt an Blei in Lösung < 0,5 ppm.
Umsatz von Cystin zu Cysteinhydrochlorid: 99,7 % (gemessen mit HPLC und Drehwert α).
Errechnete Flächen-Zeit-Leistung 7,41 kg Cysteinhydrochlorid-monohydrat pro qm Membranfläche und pro Std.
Errechnete Flächen-Zeit-Leistung 7,52 kg Cysteinhydrochlorid-monohydrat pro qm Membranfläche und pro Std.
Die Katholytlösung wurde aus Zelle und Vorratsbehälter abgelassen und durch eine Lösung von 1,00 kg Cystin, 1019 g konz. HCl und 3651 g Wasser ersetzt. Diese wurde bei einer Stromstärke von 20 A und einem Durchfluß von 11 l/h umgesetzt. Nach einer Reaktionszeit von 15,2 Std. waren 90 % Cystin umgesetzt. Nach 24 h enthielt die Lösung noch 2,7 % Cystin.
Claims (3)
- Verfahren zur elektrochemischen Reduktion einer organischen Schwefelverbindung oder einer organischen Carbonylverbindung, dadurch gekennzeichnet, daß eine Kathode aus einem elektrisch leitenden Träger mit einem Überzug aus elektrochemisch abgeschiedenem Blei mit einer Dichte zwischen 0,001 und 2 g/cm3 verwendet wird.
- Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Schwefelverbindung eine Disulfidverbindung ist.
- Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß die Disulfidverbindung ausgewählt ist aus der Gruppe Cystin, N-Alkanoyl-cystin, Homocystin und N-Alkanoylhomocystin.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10039171A DE10039171A1 (de) | 2000-08-10 | 2000-08-10 | Kathode für Elektrolysezellen |
DE10039171 | 2000-08-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1179612A1 EP1179612A1 (de) | 2002-02-13 |
EP1179612B1 true EP1179612B1 (de) | 2004-02-11 |
Family
ID=7652052
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01117681A Expired - Lifetime EP1179612B1 (de) | 2000-08-10 | 2001-07-26 | Verfahren zur elektrochemischen Reduktion organischer Verbindungen. |
Country Status (5)
Country | Link |
---|---|
US (1) | US6669828B2 (de) |
EP (1) | EP1179612B1 (de) |
JP (1) | JP3392125B2 (de) |
DE (2) | DE10039171A1 (de) |
ES (1) | ES2213657T3 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1473357A1 (de) * | 2003-04-29 | 2004-11-03 | The Procter & Gamble Company | Flüssigkeitsspender zur Reinigung von Toilettenbecken |
DE102004006562B4 (de) * | 2004-02-06 | 2008-03-27 | Dsl Dresden Material Innovation Gmbh | Verfahren zum Beschichten von Bleigitterbändern, daraus hergestellte Bleigitter und deren Verwendung |
US7655611B2 (en) * | 2004-12-14 | 2010-02-02 | The University Of Houston System | Structural family on non-ionic carbohydrate based surfactants (NICBS) and a novel process for their synthesis |
JP2007182623A (ja) * | 2005-12-08 | 2007-07-19 | Mitsui Mining & Smelting Co Ltd | 金属薄体の製造方法 |
US9512012B2 (en) * | 2007-12-08 | 2016-12-06 | Comsats Institute Of Information Technology | Sonoelectrolysis for metal removal |
CN102191513B (zh) * | 2011-04-28 | 2012-08-22 | 北京化工大学 | 一种不溶性钛基催化电极的制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2422468A (en) * | 1942-07-04 | 1947-06-17 | Standard Oil Dev Co | Electrolytic production of pinacols |
US2485258A (en) * | 1944-01-03 | 1949-10-18 | Standard Oil Dev Co | Electrodepositing lead on copper from a nitrate bath |
DE1024518B (de) * | 1955-11-29 | 1958-02-20 | Aschaffenburger Zellstoffwerke | Verfahren zur Herstellung von Cysteinhydrochlorid |
US2925371A (en) * | 1956-06-01 | 1960-02-16 | Carwin Company | Electrolytic cell |
CA1232227A (en) * | 1982-02-18 | 1988-02-02 | Christopher Vance | Manufacturing electrode by immersing substrate in aluminium halide and other metal solution and electroplating |
DE4319951A1 (de) * | 1993-06-16 | 1994-12-22 | Basf Ag | Elektrode, bestehend aus einem Eisen-haltigen Kern und einem Blei-haltigen Überzug |
US5626738A (en) * | 1995-11-17 | 1997-05-06 | American Health Foundation | Methods for the separation and detection of nitrosothiols |
ES2108654B1 (es) * | 1996-05-07 | 1998-07-01 | Univ Alicante | Procedimiento para la sintesis electroquimica de n-acetilcisteina a partir de cistina. |
DE19620861A1 (de) * | 1996-05-23 | 1997-11-27 | Basf Ag | Verfahren zur elektrochemischen Reduktion organischer Verbindungen |
-
2000
- 2000-08-10 DE DE10039171A patent/DE10039171A1/de not_active Withdrawn
-
2001
- 2001-07-26 EP EP01117681A patent/EP1179612B1/de not_active Expired - Lifetime
- 2001-07-26 DE DE50101464T patent/DE50101464D1/de not_active Expired - Lifetime
- 2001-07-26 ES ES01117681T patent/ES2213657T3/es not_active Expired - Lifetime
- 2001-08-09 JP JP2001242325A patent/JP3392125B2/ja not_active Expired - Fee Related
- 2001-08-10 US US09/927,227 patent/US6669828B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US6669828B2 (en) | 2003-12-30 |
JP2002105686A (ja) | 2002-04-10 |
JP3392125B2 (ja) | 2003-03-31 |
EP1179612A1 (de) | 2002-02-13 |
ES2213657T3 (es) | 2004-09-01 |
US20020027083A1 (en) | 2002-03-07 |
DE50101464D1 (de) | 2004-03-18 |
DE10039171A1 (de) | 2002-02-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0627020B1 (de) | Elektrochemisches verfahren zur herstellung von glyoxylsäure | |
DE3704915A1 (de) | Elektrochemisches verfahren zum austausch von halogenatomen in einer organischen verbindung | |
EP1179612B1 (de) | Verfahren zur elektrochemischen Reduktion organischer Verbindungen. | |
EP0308838B1 (de) | Verfahren zur Herstellung von fluorierten Acrylsäuren und ihren Derivaten | |
DE4217338C2 (de) | Elektrochemisches Verfahren zur Reduktion von Oxalsäure zu Glyoxylsäure | |
DE2710802C3 (de) | Verfahren zur Herstellung von Elektroden für Elektrolysezellen | |
DE3323047A1 (de) | Verfahren zur herstellung von phenaethylaminen | |
EP0911428B1 (de) | Verfahren zur Herstellung von Wismutverbindungen | |
DE2213528A1 (de) | Verfahren zur Beseitigung verbrauchter Überzüge von metallischen Elektroden | |
EP0293856B1 (de) | Verfahren zur Herstellung fluorierter Vinylether | |
DE1558765B2 (de) | Gleichzeitige elektrolytische herstellung von zinn und mangandioxid | |
EP1913178A1 (de) | Verfahren zur herstellung von 1,1,4,4-tetraalkoxy-but-2-enderivaten | |
DE4217336C2 (de) | Elektrochemisches Verfahren zur Herstellung von Glyoxylsäure | |
DE3811472A1 (de) | Verfahren zur aufarbeitung von metallchloridloesungen | |
DE4205423C1 (de) | Elektrochemisches Verfahren zur Herstellung von Glyoxylsäure | |
CH682661A5 (de) | Verfahren zur Reduktion aromatischer Nitroverbindungen mit Hilfe dreiwertiger Titanverbindungen. | |
DE2730329C2 (de) | Verfahren zur kontinuierlichen elektrolytischen Wiedergewinnung von Zink durch Elektrolyse | |
DE1558765C (de) | Gleichzeitige elektrolytische Her Stellung von Zinn und Mangandioxid | |
CH331606A (de) | Verfahren zur elektrolytischen Abscheidung von reinem Indium | |
DE2854487A1 (de) | Verfahren zur herstellung von oxalsaeure aus kohlendioxid und vorrichtung zu dessen durchfuehrung | |
DE102009001168A1 (de) | Verfahren zur Herstellung von Hypophosphiten und Phosphiten | |
DE1906292C3 (de) | Verfahren zur elektrolytischen Behandlung von alpha, beta- monoolefinischen Nitriten | |
DE2929357A1 (de) | Verfahren zur gleichzeitigen herstellung von stickstoffmonoxid und alkalihydroxid | |
DE3405059A1 (de) | Katalytische anode mit bleibasis, verfahren zu deren herstellung und ihre verwendung | |
DE2734162A1 (de) | Elektrochemisches verfahren zur herstellung von mangandioxid |
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 |
|
17P | Request for examination filed |
Effective date: 20010726 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE ES FR IT LI Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
AKX | Designation fees paid |
Free format text: CH DE ES FR IT LI |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RTI1 | Title (correction) |
Free format text: PROCESS FOR THE ELECTROCHEMICAL REDUCTION OF ORGANIC COMPOUNDS. |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE ES FR IT LI |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
REF | Corresponds to: |
Ref document number: 50101464 Country of ref document: DE Date of ref document: 20040318 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2213657 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20041112 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PUE Owner name: WACKER CHEMIE AG Free format text: CONSORTIUM FUER ELEKTROCHEMISCHE INDUSTRIE GMBH#ZIELSTATTSTRASSE 20#81379 MUENCHEN (DE) -TRANSFER TO- WACKER CHEMIE AG#HANNS-SEIDEL-PLATZ 4#81737 MUENCHEN (DE) |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20110725 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20120726 Year of fee payment: 12 Ref country code: FR Payment date: 20120806 Year of fee payment: 12 Ref country code: ES Payment date: 20120726 Year of fee payment: 12 Ref country code: DE Payment date: 20120720 Year of fee payment: 12 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50101464 Country of ref document: DE Effective date: 20140201 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20140331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130731 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140201 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130731 |
|
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: 20130731 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130726 |
|
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: 20130727 |