EP0808920B1 - Procédé de réduction électrochimique de composés organiques - Google Patents

Procédé de réduction électrochimique de composés organiques Download PDF

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Publication number
EP0808920B1
EP0808920B1 EP97108224A EP97108224A EP0808920B1 EP 0808920 B1 EP0808920 B1 EP 0808920B1 EP 97108224 A EP97108224 A EP 97108224A EP 97108224 A EP97108224 A EP 97108224A EP 0808920 B1 EP0808920 B1 EP 0808920B1
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acid
und
groups
bis
compounds
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German (de)
English (en)
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EP0808920A1 (fr
Inventor
Günther Huber
Andreas Dr. Weiper-Idelmann
Andreas Dr. Kramer
Rolf Dr. Golombek
Markus Dr. Frede
Luise Dr. Spiske
Karl Heinz Schehlmann
Volker Steuer
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BASF SE
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BASF SE
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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
    • 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
    • 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

Definitions

  • the present invention relates to a method for electrochemical Reduction of organic compounds.
  • a disadvantage of these established manufacturing processes is that the electrodes after inactivation of the catalytically active layer often from the Electrolysis apparatus removed and fed to an external regeneration must be, so that short catalyst life is an economical Exclude use of the electrochemical synthesis system.
  • Another The disadvantage is the complex production of the catalytically active Layer as such and the difficulty in achieving sufficient Connection to the carrier electrode.
  • the development effort for a classic electrode coating process is economically justified often only for larger technical processes, such as chlor-alkali electrolysis or the cathodic dimerization of acrylonitrile.
  • the use of commercial heterogeneous catalysts are often prohibited because one thermal change in thermal coating processes or a Coverage of the active areas during cold gluing processes is not excluded can be.
  • a catalytically active electrode that consists of a filter layer with a flow through it Suspension of finely dispersed catalyst material on a porous body is carried out according to EP-B 0 479 052 in one process used to separate metal ions from process and waste water.
  • the invention lies in the The task is based on a method for reducing organic compounds to provide, which on the one hand provides high space-time yields, a high Selectivity with multiply reducible compounds enables the Avoid formation of hydrogen during the reduction and in industrial Scale is applicable.
  • This object is achieved by means of a method for electrochemical reduction of an organic compound by contact bring the organic compound with a cathode, the cathode a carrier made of a conductive material and one on top of it through Pre-formed, electrically conductive, cathodically polarized layer includes.
  • the catalytically active electrode due to the pressure drop across the Pre-formed, electrically conductive, cathodically polarized Layer stabilized.
  • the catalytically active electrode can be used for regeneration suspended again by reversing the flow and, for example, by filtration or suction. This makes the reduction more organic Connections carried out on a system that is suitable for a to form and disassemble catalytically active electrode in the process, whereby only interventions that are necessary in the operational practice of a chemical operation, such as switching pumps and Actuators.
  • cathodically polarized layer electrically conductive materials are used as a carrier for the electrically conductive.
  • materials such as stainless steel, steel, nickel, nickel alloys, tantalum, platinum-plated Tantalum, titanium, platinized titanium, graphite, electrode carbon and the like To name materials and their mixtures.
  • the supports are in the form of permeable porous material, i.e. the carrier has pores.
  • These can be in the form of commercially available filter fabrics be woven from metal wires or carbon fibers.
  • Filter fabric according to the type of linen weave, twill weave, twill weave, the lace weave and the satin weave.
  • the pore size of the support is generally 5 to 300 ⁇ m, preferably 50 to 200 ⁇ m.
  • Carrier preferably at least about 30%, more preferably at least about 20% and especially about 50% free space, the free The maximum area is approximately 70%.
  • cathodic Polarized layer can use all electrically conductive materials as long as it is possible, by floating on the carrier defined above to form a layer.
  • the cathodically polarized layer preferably contains a metal conductive metal oxide or carbon-like material such as e.g. Coal, in particular Activated carbon, carbon black or graphite, or a mixture of two or more of it.
  • a metal conductive metal oxide or carbon-like material such as e.g. Coal, in particular Activated carbon, carbon black or graphite, or a mixture of two or more of it.
  • All classic hydrogenation metals are preferred as metals the metals of subgroups I, II and VIII of the periodic table, especially Co, Ni, Fe, Ru, Rh, Re, Pd, Pt, Os, Ir, Ag, Cu, Zn, Pb and Cd.
  • Ni, Co, Ag and Fe are preferably used as Raney-Ni, Raney-Co, Raney-Ag and Raney-Fe, which may be caused by foreign metals like Mo, Cr, Au, Mn, Hg, Sn or other elements of the periodic table, in particular S, Se, Te, Ge, Ga, P, Pb, As, Bi and Sb can be doped, used.
  • the metals used according to the invention are preferably finely divided and / or activated form.
  • conductive metal oxides e.g. Magnetite become.
  • the cathodically polarized layer can also by itself Alluvial formation of the carbonaceous material defined above can be formed.
  • the cathode can be constructed in situ by the above metals and conductive oxides each on carbonaceous Materials, especially activated carbon, are washed onto the support.
  • the present invention also relates to a method of the here in The type in question, the cathodically polarized layer being a metal or a conductive metal oxide or a mixture of two or more of which, each applied to activated carbon, contains.
  • the above metals can be in the form of nanoclusters, their manufacture e.g. is described in DE-A-44 08 512, on surfaces, such as. Metals and carbonaceous materials, to the carrier be washed ashore.
  • the cathodically polarized layer can be an electrically conductive one
  • Metal oxides or nanoclusters on the support improves or the surface the cathode enlarged, with electrically conductive oxides such as magnetite and Coal, especially activated carbon, carbon black, carbon fiber and graphite are.
  • a Cathode used which is obtained by first electrically conductive auxiliary material is washed onto the carrier and then this auxiliary material in situ by reduction of salts of metals of the I., II. And / or VIII. Subgroup on the coated electrode with these Metals is doped.
  • salts of the above Metals are preferred Metal halides, phosphates, sulfates, chlorides, carbonates, nitrates and the metal salts of organic acids, preferably formates, acetates, propionates and benzoates, particularly preferably acetates.
  • the cathode used according to the invention is constructed in situ by that the above Metals or metal oxides directly or after application of the electrically conductive auxiliary material washed onto the carrier become.
  • the average particle size of the particles forming the layer defined above and the thickness of the layer is always chosen so that an optimal Relationship between filter pressure loss and hydraulic throughput guaranteed and an optimal mass transfer is possible.
  • the average particle size about 1 to about 400 microns, preferably about 30 to about 150 microns
  • the thickness of the layer is generally about 0.05 mm to about 20 mm, preferably about 0.1 to about 5 mm.
  • the pore size of the support in general the pore size of the support the average diameter of the layer forming particles, so that two or more particles during the Forming the layer on the carrier across the spaces Form bridges, which has the advantage that due to the formation of the layer the carrier no significant flow obstruction for the to be reduced solution containing organic compound is formed.
  • the pore size of the support is about two to about four times as large like the average particle size of the particles forming the layer.
  • Pore sizes are used that are smaller than the average particle size of the particles forming the layer, but then very precisely the flow obstruction emanating from the layer being formed pay attention.
  • the cathode used according to the invention in situ by floating the components forming the layer on the electrically conductive carrier formed, the forming the layer Particle-containing solution flows through the carrier until the entire Solids content of this solution is washed up or held.
  • the current densities within the process according to the invention are generally about 100 to about 10,000 A / m 2 , preferably about 1,000 to about 4,000 A / m 2 .
  • the throughput of the solution containing the organic compounds to be reduced is generally about 1 to about 4,000 m 3 / (m 2 xh), preferably about 50 to about 1,000 m 3 / (m 2 xh).
  • a system pressure of generally approximately 1 ⁇ 10 4 Pa (absolute) to approximately 4 ⁇ 10 6 Pa, preferably approximately 4 ⁇ 10 4 Pa to approximately 1 ⁇ 10 6 Pa the pressure loss in the layer is approximately 1 at the flow rates used according to the invention x 10 4 Pa to about 2 x 10 5 Pa, preferably about 2.5 x 10 4 Pa to about 7.5 x 10 4 Pa.
  • the process according to the invention is generally carried out at temperatures between approximately -10 ° C to the boiling point of the solvent or Solvent mixture carried out, but temperatures between about 20 ° C and about 50 ° C, especially near room temperature, are preferred.
  • the method according to the invention can be dependent on the one to be reduced Compound in acid, i.e. at a pH below 7, preferably is -2 to 5, more preferably 0 to 3, in neutral, i.e. at pH about 7, and in basic, i.e. at a pH, the over 7, preferably 9 to 14 and especially 12 to 14 medium is carried out.
  • the reaction at normal pressure and at room temperature is particularly preferred carried out.
  • the type of used Cell type, the shape and arrangement of the electrodes are not decisive Influence, so that in principle all cell types common in electrochemistry can be used.
  • Electrode materials can generally be perforated materials such as Nets, expanded metal sheets, lamellas, profile webs, grids and smooth sheets use. With the plane-parallel electrode arrangement, this is done in Shape of flat surfaces, in the embodiment with candle-shaped electrodes in the form of a cylindrical arrangement.
  • anode material or its coating depends on Anolyte solvent. So are preferred in organic systems Graphite electrodes used, while in aqueous systems preferably Materials or coatings with low oxygen overvoltage be used.
  • acidic anolytes are titanium or Tantalum carrier with electrically conductive intermediate layers, on which electrically conductive mixed oxides of IV. to VI. Subgroup to be applied are doped with metals or metal oxides of the platinum group.
  • iron or nickel anodes are preferred Commitment.
  • protic solvents i.e. Solvent
  • Solvent which contain or release protons and / or hydrogen bonds
  • can train e.g. Water, alcohols, amines, Carboxylic acids etc., if necessary. in a mixture with aprotic polar solvents, such as. THF to use in the inventive method.
  • aprotic polar solvents such as. THF
  • Alcohols e.g. Methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol or tert-butanol
  • ethers e.g. Diethyl ether, 1,2-dimethoxyethane, Furan, tetrahydrofuran and dimethylformamide are used.
  • water is preferred, optionally as a mixture with one or more of the above.
  • Alcohols, ethers and DMF are used, with a mixture of water Methanol, THF or D
  • the corresponding alcohols can also be used Acids or amines can be used.
  • Fatty acids are preferably used as carboxylic acids.
  • carboxylic acids The following should be mentioned: Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, isovaleric acid.
  • Fatty alcohols are understood to mean the following alcohols: 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 10-undecen-1-ol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1- Hexadecanol, 1-heptadecanol, 1-octadecanol.
  • the reduction according to the invention is carried out in the presence of a Auxiliary electrolytes made.
  • the addition of the same serves for adjustment the conductivity of the electrolysis solution and / or to control the selectivity the reaction.
  • the content of the electrolyte is usually one Concentration from about 0.1 to about 10, preferably about 1 up to about 5% by weight, based in each case on the reaction mixture.
  • Auxiliary electrolyte come protonic acids, such as organic acids, whereby Methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid can be called and mineral acids, e.g. Sulfuric acid and phosphoric acid, into consideration.
  • Neutral salts can also be used as auxiliary electrolytes be used.
  • Metal cations of lithium come as cations, Sodium, potassium, but also tetraalkylammonium cations, e.g. Tetramethylammonium, Tetraethylammonium, tetrabutylammonium and dibutyldimethylammonium in question.
  • tetraalkylammonium cations e.g. Tetramethylammonium, Tetraethylammonium, tetrabutylammonium and dibutyldimethylammonium in question.
  • anions fluoride, tetrafluoroborate, Sulfonates, e.g. Methanesulfonate, benzenesulfonate, toluenesulfonate, Sulfates, e.g. Sulfate, methyl sulfate, ethyl sulfate, phosphates such as e.g.
  • Basic compounds such as e.g. Alkali or alkaline earth metal hydroxides, carbonates, bicarbonates and alcoholates can be used, where the alcoholate anions are methylate, ethylate, butylate and isopropylate are preferably used.
  • the invention can Process not only using a homogeneous solution of the organic compound to be reduced in a suitable solvent be carried out, but also consisting of a two-phase system from a phase containing at least one organic solvent such as defined above and the organic compound to be reduced, and one second, water-containing phase.
  • the electrochemical reduction according to the invention can either be continuous or be carried out discontinuously.
  • the cathode is first produced in situ by placing on the Support a catalytically active layer is formed by floating.
  • the carrier is left as long as a suspension of the finely divided Metal and / or the conductive metal oxide and / or the nanocluster and / or the carbonaceous material, that is, the material that is washed up should be flowed through until essentially the entire amount of material contained in the suspension on the carrier. If this the case can be visually recognized, for example, that the to At the beginning of the precoat, cloudy suspension becomes clear.
  • the Carrier through a suspension of the material forming the intermediate layer flows through until essentially the entire amount used located on the carrier. Subsequently, mm floating of the cathodically Proceed polarized layer forming material as described above.
  • the carrier provided with an intermediate layer with a solution or a suspension of a metal salt of a metal with which the carrier layer to be doped, to flow through, and by applying a suitable Voltage to the cell is present in this solution or suspension To reduce metal cations in situ at the cathode.
  • the reducing organic compound fed into the system After completion of the production of the cathode, the reducing organic compound fed into the system and introduced a previously precisely defined amount of electricity into the system. Thanks to the precise control of the amount of electricity supplied, it is within limits of the method according to the invention possible, also partially reduced compounds isolate.
  • the layer can be built up again as described above and then new educt can be added and implemented.
  • steps implementation (reduction), renewal of the catalyst and renewed implementation (reduction) also carried out alternately by first floating the cathode as described above is produced in situ, then the organic to be reduced Connection supplied and this is implemented after the completion of the implementation the flow direction within the electrolytic cell is changed and the spent catalyst, e.g. by filtering, is then removed the cathode in turn with fresh the cathodically polarized layer educational material is built up and then further reduced.
  • the process is the electrolysis unit, consisting of at least one Cathode with a common catholyte circuit, stationary as homogeneous continuous reactor operated. That means that after one time Flooding the catalyst with a defined concentration level of starting materials and products. For this, the reaction solution is constantly pumped in a circuit via the electrochemically active cathode and the circuit continuously fed educt, from this circuit constantly Product is removed so that the reactor content is constant over time remains.
  • At least two electrolysis units are connected in series, whereby the starting material is fed to the first unit and the product to the last unit is removed. This way of driving ensures that in the first electrolysis unit (s) with significantly cheaper concentration profiles is worked as in the last unit (s). So on average across all electrolysis units compared to a reaction procedure, in which the electrolysis units are operated in parallel, higher space-time yields reached.
  • organic compounds are in the process according to the invention all organic compounds with reducible groups as starting materials applicable. It can be used as products, depending on the total amount of charge added, both partially reduced compounds as completely reduced compounds can also be obtained. For example starting from an alkyne, the corresponding alkene as well are obtained as the corresponding fully hydrogenated or reduced Alkane.
  • Organic compounds which have at least one are preferably reduced of the following reducible groups or bonds: C-C double bonds, C-C triple bonds, aromatic C-C linkages, Carbonyl groups, thiocarbonyl groups, carboxyl groups, ester groups, C-N triple bonds, C-N double bonds, aromatic C-N bonds, Nitro groups, nitroso groups, C-halogen single bonds, with further preferably an organic compound is selected from one selected Group containing: nitriles, dinitriles, nitro, dinitro compounds, saturated and unsaturated ketones, aminocarboxylic acids.
  • the above definition includes all organic compounds which have at least one CC double bond, such as, for example, unsaturated carboxylic acids, aromatic compounds which are substituted by one or more alkenyl groups, and compounds of the general formula (A) wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen, an alkyl group, an aryl group, an aralkyl group, an alkylaryl group, an alkoxyalkyl group, an alkoxy group or an acyl group.
  • the above definition includes all organic compounds which have at least one CC triple bond, such as, for example, the compounds of the general formula (B), R 1 - ⁇ - R 2 where R 1 and R 2 are as defined above.
  • the above definition includes all organic compounds which have at least one heterocyclic ring, such as 5-, 6- or higher-membered, unsaturated heterocycles which contain 1 to 3 nitrogen atoms and / or an oxygen or sulfur atom, for example compounds of the general formula (D. ) where Y, X 1 and R 1 are as defined above.
  • the above definition includes all organic compounds which have at least one carbon-heteroatom double bond, such as aldehydes, ketones and the corresponding thio compounds and imines, which can be represented by the following general formula (E) where X, R 1 and R 2 are as defined above and also aliphatic or aromatic, saturated or unsaturated carboxylic acid derivatives, which then have the structure R 1 COOR 2 , where R 1 and R 2 are again as defined above.
  • the above definition includes all organic compounds which have at least one CN triple bond, such as dinitriles and mononitriles, the latter being represented by the following general formula (F) R 1 - C ⁇ N where R 1 is as defined above.
  • a filter plate was covered with a 50 ⁇ m twill weave made of stainless steel material no. 1.4571 installed as cathode.
  • the filtrate can be removed from a cavity under the filter fabric via a separate filtrate line.
  • a titanium anode coated with Ta / Ir mixed oxide was used as the anode Development of oxygen used.
  • a Nafion 324 cation exchange membrane was used as the separation medium (Commercial product from Du Pont). The shared Cell was placed in a two-circuit electrolysis apparatus with pump circuits built-in.
  • the catholyte was prepared by adding 5 g of vinclozolin [(RS) -3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-oxazoline-2,4-dione] in a mixture consisting of 500 g water, 375 g methanol, 375 g isobutanol and 65 g acetic acid were solved. 1200 g of the catholyte batch were added to the cathode circuit filled.
  • the catholyte preparation is before the reaction chloride-free.
  • ADN adiponitrile
  • HDA hexamethylenediamine
  • the catholyte consisted of a mixture of 693 g of methanol, 330 g of H 2 O, 22 g of NaOH, 55 g of adiponitrile (0.509 mol) and 7.5 g of Raney nickel (BASF H 1 -50).
  • the implementation was carried out as follows: First, the two cell compartments were filled and then the Raney nickel was washed to the above cathode within 10 minutes.
  • the electrolysis was then carried out at a temperature between 30 and 40 ° C. with a current density of 1000 A / m 2 at normal pressure. The electrolysis was stopped after 8.5 F / mol ADN. After the NaOH had been separated off by electrolysis, the product was isolated by distillation. 56 g (95% based on the amount of ADN used) of hexamethylene diamine were obtained.
  • Example 2 Using the same reaction apparatus, the same anolyte and the same catholyte as in Example 2, adiponitrile became 6-aminocapronitrile (ACN) implemented, the manufacture of the cathode and the Electrolysis was carried out in the same manner as in Example 2 however, the electrolysis is terminated after 4 F / mol ADN has been. After separation of the NaOH and subsequent distillation 38.7 g (0.34 mol, 68% based on ADN) aminocapronitrile, 16% hexamethylene diamine and 14% ADN isolated. The selectivities were 79% for Aminocapronitrile and 18.6% for hexamethylenediamine.
  • ACN 6-aminocapronitrile
  • Example 2 The following implementation was carried out using the same device and using the same anolyte as in Example 2 carried out.
  • Example 2 This example was carried out in the same apparatus as Example 2. 1100 g of 1% sulfuric acid were used as the anolyte.
  • the Catholyte consisted of a mixture of 418 g of methanol, 318 g of dist. Water, 297 g of sodium methyl sulfate solution 7.4% in methanol, 55 g Cyclohexanone oxime (0.487 mol) and 8 g copper powder.
  • the implementation was carried out as follows: First, the cell compartments were filled and then the copper powder washes onto the above cathode within 10 minutes. Thereafter, the electrolysis was carried out at a temperature between 30 and 50 ° C with a current density of 1000 A / m 2 under normal pressure. A charge of 12 F / mol based on the oxime used was applied.
  • the catholyte was adjusted to pH with sodium hydroxide solution from 13, the copper powder filtered off, the filtrate concentrated to 639 g and extracted five times with 100 g MTBE each. After drying and removal the crude product of the solvent was distilled. As a reaction product 35.2 g of cyclohexylamine (73% based on the oxime used) be isolated.
  • Example 2 This example was carried out in the same apparatus as Example 2. 1100 g of 1% sulfuric acid were used as the anolyte.
  • the Catholyte consisted of a mixture of 418 g of methanol, 330 g of dist. Water, 297 g sodium methyl sulfate solution, 7.4% in methanol, 55 g 2-butyne-1,4-diol (0.64 mol) and 15 g Raney nickel (BASF H1-50).
  • Example 2 This example was carried out in the same apparatus as Example 2. 1100 g of 1% sulfuric acid were used as the anolyte.
  • the Catholyte consisted of a mixture of 704 g of methanol, 330 g of dist. Water, 11 g sulfuric acid, 55 g nitrobenzene (0.447 mol) and 8 g copper powder.
  • the catholyte was adjusted to pH with sodium hydroxide solution from 13, the copper powder filtered off, the filtrate concentrated to 597 g and extracted five times with 100 g MTBE each. After drying and removal the crude product of the solvent was distilled. As a reaction product 26.2 g of aniline could be isolated.
  • the reaction was carried out at 21 ° C. and a current density of 1000 A / m 2 .
  • the starting material was added in 14 portions.
  • a charge of 6.45 F / mol based on the substrate was applied.
  • the nickel powder was filtered off, the catholyte with Neutralized sulfuric acid and removed the methanol by distillation. To Adjusting the pH to 13 was extracted with MTBE. After drying and removing the solvent, the crude product was distilled. As 37 g of thienylethylamine could be isolated from the reaction product.
  • the reaction was carried out at 23 ° C. and a current density of 1000 A / m 2 .
  • a charge of 5.5 F / mol based on the substrate was applied.
  • the nickel powder was filtered off, the filtrate was mixed with 4% sodium hydroxide added and saturated with NaCl. After separation of the Phases were distilled. 45 g of thienylethylamine could be used as the reaction product be isolated.
  • the reaction was carried out at 21 ° C. and a current density of 1000 A / m 2 .
  • a charge of 4 F / mol based on the substrate was applied.
  • the nickel powder was filtered off, the methanol from the Filtrate removed by distillation and the remaining aqueous crude solution with 5x each 100 g MTBE extracted. After drying and removing the solvent the crude product was distilled. 54.5 g Homoveratrylamine can be isolated.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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Claims (8)

  1. Procédé de réduction électrochimique d'un composé organique par mise en contact du composé organique avec une cathode, la cathode comportant un support constitué d'un matériau conducteur de l'électricité, et une couche à polarisation cathodique, conductrice de l'électricité, déposée sur ce dernier par applications successives.
  2. Procédé selon la revendication 1, dans lequel la couche à polarisation cathodique contient un métal, un oxyde métallique conducteur ou un matériau de type charbon, ou des mélanges d'au moins deux d'entre eux.
  3. Procédé selon la revendication 1 ou 2, dans lequel la couche à polarisation cathodique contient un métal du 1er, IIème ou VIIIème groupe secondaire du Tableau Périodique, dans chaque cas sous forme du métal libre ou de l'oxyde métallique conducteur, ou un mélange d'au moins deux d'entre eux.
  4. Procédé selon au moins l'une des revendications 1 à 3, dans lequel la couche à polarisation cathodique contient un métal ou un oxyde métallique conducteur ou un mélange d'au moins deux d'entre eux, dans chaque cas appliqués sur du charbon actif.
  5. Procédé selon au moins l'une des revendications 1 à 3, dans lequel la couche à polarisation cathodique contient du nickel de Raney, du cobalt de Raney, de l'argent de Raney ou du fer de Raney.
  6. Procédé selon au moins l'une des revendications 1 à 5, dans lequel le support constitué d'un matériau conducteur de l'électricité comporte des pores.
  7. Procédé selon au moins l'une des revendications 1 à 6, dans lequel on réduit un composé organique qui comporte au moins l'un des groupes ou liaisons réductibles suivants :
    doubles liaisons C-C, triples liaisons C-C, liaisons aromatiques C-C, groupes carbonyle, groupes thiocarbonyle, groupes carboxyle, groupes ester, triples liaisons C-N, doubles liaisons C-N, liaisons aromatiques C-N, groupes nitro, groupes nitroso, simple liaison C-halogène.
  8. Procédé selon au moins l'une des revendications 1 à 7, dans lequel on réduit un composé organique choisi dans un groupe comprenant les nitriles, les dinitriles, les composés nitrés et dinitrés, les cétones saturées et insaturées, les acides aminocarboxyliques.
EP97108224A 1996-05-23 1997-05-21 Procédé de réduction électrochimique de composés organiques Expired - Lifetime EP0808920B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19620861 1996-05-23
DE19620861A DE19620861A1 (de) 1996-05-23 1996-05-23 Verfahren zur elektrochemischen Reduktion organischer Verbindungen

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EP0808920A1 EP0808920A1 (fr) 1997-11-26
EP0808920B1 true EP0808920B1 (fr) 2000-04-26

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US (1) US5919349A (fr)
EP (1) EP0808920B1 (fr)
JP (1) JP3856902B2 (fr)
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US10633749B2 (en) * 2014-07-23 2020-04-28 Board Of Trustees Of Michigan State University Electrolyzer reactor and related methods
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WO2020175707A1 (fr) * 2019-02-28 2020-09-03 国立研究開発法人科学技術振興機構 Catalyseur d'électrode et procédé de production d'un composé aminé
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JP3856902B2 (ja) 2006-12-13
EP0808920A1 (fr) 1997-11-26
US5919349A (en) 1999-07-06
DE59701496D1 (de) 2000-05-31
JPH1046381A (ja) 1998-02-17
DE19620861A1 (de) 1997-11-27
ES2146438T3 (es) 2000-08-01

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