EP0219367B1 - Organische Elektrolysezelle mit Verbrauchselektrode - Google Patents

Organische Elektrolysezelle mit Verbrauchselektrode Download PDF

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EP0219367B1
EP0219367B1 EP86401895A EP86401895A EP0219367B1 EP 0219367 B1 EP0219367 B1 EP 0219367B1 EP 86401895 A EP86401895 A EP 86401895A EP 86401895 A EP86401895 A EP 86401895A EP 0219367 B1 EP0219367 B1 EP 0219367B1
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Prior art keywords
electrode
electrolysis cell
organic
electrosynthesis
group
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French (fr)
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EP0219367A1 (de
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Jacques Chaussard
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Societe Nationale des Poudres et Explosifs
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Societe Nationale des Poudres et Explosifs
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • 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
    • C25B9/30—Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof

Definitions

  • the present invention relates to an electrolysis cell for electrosynthesis, in an organic medium, of organic or organometallic compounds, comprising two electrodes, one and only one of which is consumed during electrosynthesis by the electrochemical reaction of which it is the seat.
  • South African patent No. 6806413 describes the synthesis of tetraethyl lead in an electrolysis cell comprising a consumable anode in the form of a metallic strip which passes between two cathodes in the form of discs.
  • This system has a number of drawbacks.
  • the thickness of the anode must in particular be small so that the interelectrode space remains constant; the speed of advance of the anode must therefore be rapid, and, to avoid rupture of the ribbon, the device requires a relatively complicated mechanical system.
  • FR-1 412 239 describes an electrolysis cell designed to operate in an aqueous medium and comprising 2 compartments, cathodic and anodic, separated by a diaphragm.
  • the wedge-shaped anode is made of graphite.
  • SU-1,046,022 describes an anode device for obtaining metal powders by electrolysis of aqueous solutions using consumable anodes, comprising an anode chamber in the form of a triangular prism and soluble anode elements, in the form of plates arranged horizontally.
  • the wall of the chamber oriented towards the cathode is in the form of a grid composed of insulated fins and inclined with respect to the horizontal plane.
  • German patent 2107305 describes for example such a device.
  • Electrolysis cells comprising a consumable anode have already been described for the electrosynthesis of oxalic acid from carbon dioxide, on the one hand with aluminum in Chim. lnd. (Milan) 55. (1973) 156 and on the other hand with zinc in J. Appl. Electrochem. 11 (1981) 743, for the electrocarboxylation of ethylene (Tetrahedron Lett. 1973,3025) and for that of thioethers (Patent of the Democratic Republic of Germany No. 203537).
  • central electrode acts as a consumable anode (metal bar for example); in others, it acts as a cathode (graphite for example).
  • cathode graphite for example
  • the present invention aims to provide an electrolysis cell allowing simple continuous industrial use, having the advantages of the above-mentioned industrial cells, namely in particular maintaining a constant gap between the electrodes, without having the disadvantages.
  • the inclination, at a point of a surface, with respect to the vertical is conventionally considered to be the angle formed by the plane of tangency to the surface at this point and by the vertical passing through this point.
  • the cell according to the invention has many advantages. First of all, it allows a constant and preferably small gap (less than 5 mm) to be maintained between the two electrodes during the entire duration of the electrolysis, which is very important in an organic conductive medium, in order to avoid excessive power consumption and overheating by Joule effect.
  • One of the two electrodes being progressively consumed during the electrochemical reaction a means is necessary necessarily allowing the distance between the two electrodes to be kept constant, which is obtained in the context of this invention, thanks to the particular design and geometry of the cell. It is also necessary to be able to easily replace the consumable electrode as soon as it is completely consumed, or better, for continuous processes, as it is consumed, without stopping and disturbing the electrolysis.
  • the cell according to the invention allows very easy replacement of the consumable electrode, without stopping the electrolysis, by superposition of one (or more) another block on the solid metal block (s) constituting the consumable electrode, which is a considerable advantage when implementing continuous processes. In addition, the entire electrode is consumed, without falling or loss.
  • the cell according to the invention also allows the use of massive consumable electrodes, therefore not very bulky for a given mass, and of various shapes. This fact is economically very interesting.
  • Another advantage is the fact that, taking into account the geometry of the cell and in particular the inclination of the non-consumable electrode, the space requirement on the ground is very reduced, which allows a saving of space which is economically very appreciable.
  • the consumable electrode is the anode (anodic oxidation) as for the examples which follow but sometimes the consumable electrode is the cathode as is the case for the electrosynthesis of tetramethyl lead in acetonitrile medium from methyl bromide with lead cathode according to HE. Ulery JECS 116, 1201, 1969:
  • the consumable electrode consists of at least one solid metal block.
  • the metal is chosen from the group consisting of magnesium, aluminum, zinc and their alloys, namely any alloy containing at least one of the three aforementioned metals.
  • Many other metals are also suitable, such as copper, nickel, and lead.
  • the choice of metal depends inter alia on the compound which one wants to synthesize.
  • the consumable electrode is for example constituted by the corresponding metal or an alloy based on this metal.
  • magnesium is preferred.
  • a metal chosen from the group formed by magnesium, zinc, aluminum and their alloys.
  • the solid metal blocks can be, for example, ingots whose cross section is square, or rectangular, or trapezoidal, or circular, or in any other form. They can optionally be machined before use so that their geometry is adapted to that of the non-consumable electrode. Preferably, but without this having an imperative character, such machining is carried out to facilitate the start of electrolysis.
  • the consumable electrode consists of solid metal blocks stacked, each layer of the stack comprising only one block.
  • at least one layer of the stack comprises several blocks arranged side by side.
  • the consumable electrode is applied under the effect of its own weight, by gravity, against the other non-consumable electrode.
  • the consumable electrode is applied against the other electrode under the sole effect of its own weight.
  • the consumable electrode is applied against the other electrode under the effect, in addition to its own weight, of that of an inert charge resting on the consumable electrode.
  • the inert charge is electrically conductive and also serves to ensure the electrical supply of the consumable electrode.
  • the consumable electrode is applied against the other electrode under the effect, in addition to its own weight, of the force produced by a compressed spring between the upper part of the consumable electrode and a wall of the cell.
  • the non-consumable electrode is made of a conductive material.
  • a conductive material such as iron, aluminum and nickel, alloys such as stainless steel, metal oxides such as Pb0 2 and Ni0 2 , graphite.
  • metals such as iron, aluminum and nickel, alloys such as stainless steel, metal oxides such as Pb0 2 and Ni0 2 , graphite.
  • it is made of a metal chosen from the group consisting of nickel and stainless steel.
  • the distance between the active surfaces of the two electrodes is less than 5 mm. This distance is conventionally measured on a common perpendicular, between the two parallel surfaces;
  • the two electrodes are separated by an electrical insulating material allowing the electrolysis solution to pass and whose shape and dimensions allow the active surfaces of the 2 electrodes to remain parallel during electrosynthesis.
  • this electrical insulating material must have sufficient mechanical strength to support the consumable electrode which rests on this material.
  • the electrical insulating material is a plastic material in the form of a grid whose thickness is less than 5 mm and whose mesh consists of two networks of parallel wires, these two networks being superimposed, crossed, fixed one on the other at the contact points of the wires, the thickness of the wires of each network being the same.
  • the two networks are fixed to each other by welding and the wires of the two networks have the same thickness.
  • the distance between the wires of each network is between a few millimeters and a few centimeters.
  • the wires in each network may not be parallel; their thickness may not be constant provided that after assembling the networks, the mesh has a constant maximum thickness at several points, less than about 5 mm.
  • the cross section of the wires can be arbitrary, for example square, rectangular, circular, elliptical, trapezoidal.
  • the plastic material can be, for example, polypropylene, polyethylene or polytetrafluoroethylene.
  • Such plastic gratings have on the one hand a high vacuum rate, which allows easy circulation of the electrolysis solution between the two electrodes and on the other hand a relatively small contact surface with the electrodes, which avoids an excessive reduction in their active surface.
  • a fabric As other materials separating the two electrodes, it is possible to use, within the framework of the present invention, a fabric, a canvas or a porous material of constant thickness such as for example a ceramic or a felt.
  • the renewal of the electrolysis solution between the electrodes can, for example, be ensured by mechanical agitation or by forced circulation using a pump, for example.
  • the active surface of the consumable electrode opposite the active surface of the other electrode dissolves.
  • the consumable electrode therefore descends gradually, by gravity, under the simple effect of its own weight.
  • the dissolution being stronger at the locations closest to the non-consumable electrode, the consumable electrode tends to conform as best as possible to the shape of the non-consumable electrode, which limits the risks of irregular dissolution.
  • the electrolysis cell shown in Figures 1 and 2 comprises a tank whose bottom wall is formed by the cathode 12, which is not consumable.
  • the active surface of the non-consumable electrode 12 is conical, the tip of the cone being directed downwards. This active surface has at all points a constant inclination of 15 degrees relative to the direction 19 which is that of the axis of the cone. For the cell shown in Figures 1 and 2 this axis is vertical.
  • the upper wall 21 of the tank is cylindrical and extends the cone so that the cylinder and the cone have the same axis, the diameter of the cylinder being the same as that of the base circle of the cone.
  • the walls 20 and 21 are made of an electrical insulating material or internally covered with an electrical insulator 11, for example a paint or any other electrically insulating coating.
  • the anode 14 consists of a stack of cylindrical solid metal ingots whose diameter is slightly less than that of the cylindrical wall 21 of the tank. It is applied under the sole effect of its own weight against the cathode 12 which, alone, ensures the maintenance of the anode 14.
  • the anode 14 and the cathode 12 are separated by a plastic material 15 in the form of a mesh such as that shown in FIG. 3.
  • the mesh consists of two networks of parallel wires A 1 B 1 C 1 ... N 1 of part and A 2 8 2 C Z ... N 2 on the other hand.
  • the wires of these two networks are cylindrical, with a diameter of 1 mm. The distance between the wires is 1 cm.
  • the two networks are superimposed, crossed at right angles and welded to the contact points of the wires.
  • the electrolysis solution 16 circulates from bottom to top in the cell. Pipes 18 allow the arrival and the exit of this solution 16, in the direction of the arrows 17.
  • the inlet pipe extends the tip of the cathode 12 along the axis of the cell.
  • the electrodes 12 and 14 are supplied with electric current by a DC voltage source, not shown in FIGS. 1 and 2.
  • the active surface of the non-consumable electrode 12 When the axis of the cell is rotated by an alpha angle around the tip of the cone, the active surface of the non-consumable electrode 12 always has at all its points a constant inclination of 15 degrees relative to the direction D represented by the axis of the cell and any straight line of direction D passing through any point of the consumable anode 14 crosses the active surface of the non-consumable cathode 12.
  • First of all alpha must be less than 45 degrees in the context of the present invention.
  • the inclination of the active surface of the non-consumable electrode 12 is between (15 + alpha) and 115-alphal.
  • the inclination relative to the vertical must be less than 45 degrees, that is to say for this particular embodiment, that alpha must be less than 30 degrees. Otherwise, there may be significant anomalies in the functioning of the cell.
  • the upper wall 20 of the electrolysis cell according to the invention is removable or has a part removable so as to allow the introduction of massive metal blocks.
  • FIG. 4 A complete installation allowing the continuous electrolysis of a solution is schematically represented in FIG. 4.
  • It consists of a closed circuit comprising a jacketed reactor 51 allowing the loading and recovery of the products, an electrolysis cell 52 and a pump 53 allowing the circulation of the electrolysis solution in the circuit.
  • the lower part of the reactor 51 is connected to the lower part (inlet) of the cell 52 and the outlet of the cell 52 is connected to the upper part of the reactor 51.
  • the jacketed reactor 51 is cooled by a circulation of water, symbolized by the arrows 54.
  • the cell 52 shown diagrammatically in FIG. 4 is that shown in FIGS. 1 and 2.
  • the present invention also relates to the use of the new electrolysis cells described above, provided with an anode consumable in a metal chosen from the group formed by magnesium, zinc, aluminum and their alloys for electrosynthesis. in an organic solvent medium of organic compounds chosen from the group consisting of carboxylic acids, alcohols, ketones and aldehydes by electrochemical reduction of organic halides.
  • an electrolysis cell is used provided with an anode consumable in a metal chosen from the group formed by magnesium and its alloys for the electrosynthesis of carboxylic acids by electrochemical reduction of organic halides in the presence of carbon dioxide.
  • aromatic chains mention may, for example, be made of substituted or unsubstituted phenyl, thiophene, furan and pyridine rings.
  • the carboxyl group can as well be linked to an aliphatic carbon as to a carbon of an aromatic ring.
  • the use of a magnesium anode provides the best results. In particular, tests have been carried out with an anode either of aluminum or of zinc, all other conditions identical elsewhere. The yields are then lower than those obtained with the magnesium anode.
  • the organic solvents used are the low protein solvents usually used in organic electrochemistry, such as hexamethylphosphorotriamide (HMPT) letetrahydrofuran (THF), N-methylpyrolidone (NMP), dimethylformamide (DMF).
  • the organic solvent conventionally contains an indifferent electrolyte such as tetrabutylammonium tetrafluoroborate (BF 4 NBu 4 ) or lithium perchlorate.
  • an indifferent electrolyte such as tetrabutylammonium tetrafluoroborate (BF 4 NBu 4 ) or lithium perchlorate.
  • the yields obtained in the carboxylate formed are high, very often greater than 99%.
  • the yields of isolated carboxylic acid vary from 70 to 90% of the yield of carboxylate formed.
  • an electrolysis cell is used provided with an anode consumable in a metal chosen from the group formed by magnesium, zinc, aluminum and their alloys for the electrosynthesis of alcohols, by electrochemical reduction. of organic halides having an atom or a functional group stabilizing carbanions attached to the carbon carrying the halogen, in the presence of carbonyl derivatives.
  • the latter can be aldehydes as well as ketones; the yields are high and the implementation relatively simple.
  • the organic halides have at least one atom or a functional group stabilizing carbanions, attached to the carbon carrying the halogen, that is to say located in the alpha position relative to the halogen.
  • atoms and functional groups which stabilize carbanions are well known to those skilled in the art. Mention may be made, for example, of halogens, ester, ketone, allyl, benzene, alkoxy or nitrile groups.
  • benzyl chloride By way of illustration and without limitation, mention may be made, for example, of benzyl chloride, benzyl bromide, allyl chloride, 3-chloro 2 methyl propene, 3-chloro 1 butene, 1-chloro 1-methyl ethyl acetate, carbon tetrachloride, dichlorophenylmethane, 1-phenyl 3-chloro propene and 1-methyl 3-chloropropene.
  • R, and R 2 together with the carbon atom to which they are attached, form a ring, saturated or unsaturated, substituted or unsubstituted, optionally comprising one or more heteroatoms such as nitrogen, oxygen , phosphorus or sulfur.
  • heteroatoms such as nitrogen, oxygen , phosphorus or sulfur.
  • the alcohols obtained according to the process which is the subject of the present invention correspond to the general formula wherein R, R, and R 2 have the above meaning.
  • organic solvents and the indifferent electrolytes used are the same as those mentioned above for the synthesis of carboxylic acids.
  • DMF is used as solvent and the electrolysis is carried out at a temperature between -20 ° C. and + 30 ° C.
  • an electrolysis cell is used provided with an anode consumable in a metal chosen from the group formed by magnesium, zinc, aluminum and their alloys for the electrosynthesis of ketones and aldehydes by electrochemical reduction of organic halides in the presence of organic acid anhydrides.
  • a metal chosen from the group formed by magnesium, zinc, aluminum and their alloys for the electrosynthesis of ketones and aldehydes by electrochemical reduction of organic halides in the presence of organic acid anhydrides.
  • the implementation is simple and the mass and faradaic yields high.
  • R 3 has an aliphatic chain substituted with at least one aromatic group, for example in benzyl chloride, benzyl bromide, 1-phenyl 1-chloro ethane and 1-phenyl 1-chloro propane.
  • R 3 can carry non-electro-reducible functions or more difficult to reduce than the R 3 -X bond, under the experimental conditions of electrosynthesis.
  • non-electroreducible functions are, for example, the cyano, ether, sulfide or ester functions.
  • R s represents a group OR s
  • the corresponding anhydrides are then mixed anhydrides of carboxylic acids and carbonic acid. In the other cases, they are anhydrous carboxylic acids.
  • R 4 and R 5 can carry non-electro-reducible functions, or more difficult to reduce than the bond R 3 ⁇ X, under the experimental conditions of electrosynthesis, and none of the functions carried by R 3 or R 4 does must be more electrophilic than the anhydride function itself.
  • R 4 and R 5 represent a linear or branched alkyl chain.
  • R 4 and R s are identical.
  • R 4 and R s are identical and represent an alkyl chain, linear or branched, as is the case for example for acetic anhydride.
  • organic solvents and the indifferent electrolytes used are the same as those mentioned above for the synthesis of carboxylic acids.
  • DMF is used as solvent.
  • the direction D is to preferably the vertical direction.
  • the cathode 12 made of stainless steel, is a cone with a height of 100 mm and a base diameter of 53 mm.
  • the other walls of the tank are made of stainless steel and are internally covered with an inert electrical insulating coating 11.
  • the anode 14 consists of a stack of cylindrical aluminum blocks with a diameter of 50 mm and a height of 100 mm.
  • the plastic material 15 in the form of a mesh is polypropylene. This mesh is just placed on the active surface of the cathode 12, the shape of which it matches, before the introduction of the anode 14.
  • the lower aluminum block was machined so that it is approximately in the form of a cone with a height of 100 mm and a base diameter of 50 mm, which is easily achieved from of a cylindrical block having these dimensions.
  • the machined block which introduces the shape of the cathode is introduced, then several other blocks are stacked on this lower block up to the top of the cell.
  • the dimethylbenzylcarbinol formed is isolated, and identified according to the usual methods, well known to those skilled in the art.
  • the alcohol formed was isolated after hydrolysis of the solution using an aqueous solution of ammonium chloride and extraction with ether. After evaporation of the ether, the crude alcohol was purified by distillation. The pure alcohol thus isolated (purity verified by CPG) is identified by its NMR and IR spectra.
  • the yield of distilled dimethylbenzylcarbinol obtained is 60% (purity greater than 95%).
  • the intensity of the current is fixed at the start at 2.5 A since the optimal operating conditions are then already met, the anode being in the optimal position relative to the cathode.
  • Example 1 The same test is carried out as that of Example 1 but without machining the lower block before the first electrolysis. The same result is obtained but the operating equilibrium is much longer to reach.

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  • Organic Chemistry (AREA)
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  • Electrochemistry (AREA)
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Claims (12)

1. Elektrolysezelle für die Elektrosynthese von organischen oder metallorganischen Verbindungen in organischem Medium mit zwei Elektroden (12 und 14), von denen nur eine (14) im Lauf der Elektrosynthese durch die elektrochemische Reaktion, deren Platz sie ist, verbraucht wird, dadurch gekennzeichnet,
- daß die verbrauchbare Elektrode (14) aus wenigstens einem massiven Metallblock besteht und sich unter der Wirkung ihres Eigengewichts gegen die andere Elektrode (12) anlegt, von der sie durch ein elektrisch isolierendes Material (15) getrennt ist, das die Elektrolyselösung (16) durchfließen läßt und dessen Form und Abmessungen den aktiven Oberflächen der beiden Elektroden (12 und 14) ermöglichen, im Lauf der Elektrosynthese parallel zu bleiben,
- und daß die aktive Oberfläche der nicht verbrauchbaren Elektrode (12) konisch ist und eine Neigung unter 45° bezüglich der Vertikalen aufweist.
2. Elektrolysezelle nach dem Anspruch 1, dadurch gekennzeichnet, daß die verbrauchbare Elektrode (14) aus gestapelten massiven Metallblöcken besteht, wobei jede Schicht des Stapels nur einen einzigen Block aufweist.
3. Elektrolysezelle nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die nicht verbrauchbare Elektrode (12) aus einem Metall ist, das aus der aus Nickel und nichtoxidierendem Stahl bestehenden Gruppe gewählt ist.
4. Elektrolysezelle nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß der Abstand zwischen den aktiven Oberflächen der beiden Elektroden (12 und 14) unter 5 mm ist.
5. Elektrolysezelle nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sich die verbrauchbare Elektrode (14) an die andere Elektrode (12) außer unter der Wirkung ihres Eigengewichts unter der einer inerten Last anlegt, die auf der verbrauchbaren Elektrode (14) ruht.
6. Elektrolysezelle nach dem Anspruch 5, dadurch gekennzeichnet, daß die inerte Last elektrisch leitend ist und dazu dient, die elektrische Stromzuführung zur verbrauchbaren Elektrode (14) zu sichern.
7. Elektrolysezelle nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sich die verbrauchbare Elektrode (14) gegen die andere Elektrode (12) nur unter der Wirkung ihres Eigengewichts anlegt.
8. Elektrolysezelle nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das elektrisch isolierende Material (15) ein Kunststoff in Netzwerkform ist, dessen Dicke unter 5 mm ist und dessen Netzwerk aus zwei Netzen von parallelen Fäden zusammengesetzt ist, wobei diese beiden Netze übereinandergelegt, gekreuzt und untereinander an Kontaktpunkten der Fäden befestigt sind, wobei die Dicke der Fäden jedes Netzes die gleiche ist.
9. Verwendung einer mit einer verbrauchbaren Anode aus einem aus der von Magnesium, Zink, Aluminium und deren Legierungen gebildeten Gruppe gewählten Metall versehenen Elektrolysezelle nach irgendeinem der vorstehenden Ansprüche für die Elektrosynthese von organischen Verbindungen, die aus der von den Carbonsäuren, den Alkoholen, den Ketonen und den Aldehyden gebildeten Gruppe gewählt sind, in organischem Medium durch elektrochemische Reduktion organischer Halogenide.
10. Verwendung nach dem Anspruch 9, einer mit einer verbrauchbaren Anode aus einem aus der von Magnesium und seinen Legierungen gebildeten Gruppe gewählten Metall versehenen Elektrolysezelle für die Elektrosynthese von Carbonsäuren durch elektrochemische Reduktion organischer Halogenide in Gegenwart von Kohlendioxidgas.
11. Verwendung, nach dem Anspruch 9, einer mit einer verbrauchbaren Anode aus einem aus der von Magnesium, Aluminium, Zink und deren Legierungen gebildeten Gruppe gewählten Metall versehenen Elektrolysezelle für die Elektrosynthese von Alkoholen durch elektrochemische Reduktion organischer Halogenide mit einem Atom oder einer Funktionsgruppe als Stabilisator von Carbonionen, das bzw. die am Halogenträgerkohlenstoff fixiert ist, in Gegenwart von carbonylierten Abkömmlingen.
12. Verwendung, nach Anspruch 9, einer mit einer verbrauchbaren Anode aus einem aus der vom Magnesium, Aluminium Zink und deren Legierungen gebildeten Gruppe gewählten Metall versehenen Elektrolysezelle für die Elektrosynthese von Ketonen oder Aldehyden durch elektrochemische Reduktion organischer Halogenide in Gegenwart von Anhydriden organischer Säuren.
EP86401895A 1985-09-05 1986-08-29 Organische Elektrolysezelle mit Verbrauchselektrode Expired - Lifetime EP0219367B1 (de)

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AT86401895T ATE54472T1 (de) 1985-09-05 1986-08-29 Organische elektrolysezelle mit verbrauchselektrode.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8513188A FR2586710B1 (fr) 1985-09-05 1985-09-05 Cellule d'electrolyse organique a electrode consommable
FR8513188 1985-09-05

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EP0219367A1 EP0219367A1 (de) 1987-04-22
EP0219367B1 true EP0219367B1 (de) 1990-07-11

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US (1) US4686018A (de)
EP (1) EP0219367B1 (de)
JP (1) JPH07122155B2 (de)
AT (1) ATE54472T1 (de)
DE (1) DE3672556D1 (de)
FR (1) FR2586710B1 (de)

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Publication number Priority date Publication date Assignee Title
IT1203373B (it) * 1987-03-18 1989-02-15 Silvestri Silvestri Dispositivo per la trasformazione di celle elettrolitiche di tipo filtro pressa in celle ad elettrodi sacrificali rinnovabili in continuo
FR2617197B1 (fr) * 1987-06-25 1991-07-12 Poudres & Explosifs Ste Nale Cellule d'electrolyse a electrodes bipolaires consommables
FR2624884B1 (fr) * 1987-12-18 1990-04-20 Poudres & Explosifs Ste Nale Procede de synthese electrochimique de cetones alpha saturees
US4834858A (en) * 1988-03-23 1989-05-30 Montvale Process Company, Inc. Electrolytic reactor
DE3813017A1 (de) * 1988-04-19 1989-11-02 Wiederaufarbeitung Von Kernbre Vorrichtung zur elektrochemischen behandlung von radioaktiven brennstoffloesungen
FR2639364B1 (fr) * 1988-11-23 1990-12-28 Poudres & Explosifs Ste Nale Procede d'electrosynthese d'aldehydes
FR2646441B1 (fr) * 1989-04-28 1991-07-12 Poudres & Explosifs Ste Nale Procede d'electrosynthese d'un ester beta gamma insature
FR2688519A1 (fr) * 1992-03-12 1993-09-17 Poudres & Explosifs Ste Nale Procede d'electrosynthese de fluorobiphenyles symetriques.
US6147216A (en) * 1993-06-25 2000-11-14 Merrell Pharmaceuticals Inc. Intermediates useful for the preparation of antihistaminic piperidine derivatives
EP2261208A1 (de) 1993-06-25 2010-12-15 Aventisub II Inc. Zwischenprodukte zur Herstellung antihistaminischer 4-Diphenylmethyl-/Diphenylmethoxy- Piperidinderivate
DE4429354A1 (de) 1994-08-18 1996-02-22 Hoechst Ag Elektrolysezelle mit Verzehranoden
US6683094B2 (en) 1998-07-02 2004-01-27 Aventis Pharmaceuticals Inc. Antihistaminic piperidine derivatives and intermediates for the preparation thereof
US6700012B2 (en) 1998-07-02 2004-03-02 Aventis Pharmaceuticals Inc. Antihistaminic piperidine derivatives and intermediates for the preparation thereof
EP1046616A3 (de) * 1999-02-06 2001-03-21 Vallendar, Hubertus Elektrodenanordnung zur galvanischen Behandlung von strömenden Medien
FR2795749B1 (fr) * 1999-07-02 2001-10-05 Electricite De France Reacteur electrochimique a electrode consommable rotative
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
US20130206664A1 (en) * 2010-10-22 2013-08-15 Tae Gyo Kim Metal ion sterilization device
KR101239206B1 (ko) * 2011-05-06 2013-03-05 김태규 금속 이온 살균장치
US8617403B1 (en) 2013-06-25 2013-12-31 Blue Earth Labs, Llc Methods and stabilized compositions for reducing deposits in water systems
DE102016109822A1 (de) * 2016-05-27 2017-11-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Elektrolytischer Reaktor
US10837116B2 (en) * 2017-11-27 2020-11-17 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Electrolytic reactor
CN113278996A (zh) * 2021-04-01 2021-08-20 安徽海康药业有限责任公司 一种2，4，5-三氟苯乙酸的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US982037A (en) * 1909-09-30 1911-01-17 Mcdonald Electrolytic Company Electrolytic cell.
US1278723A (en) * 1914-08-19 1918-09-10 Frank H Nickle Electrolytic cell.
BE606111A (de) * 1960-07-13
FR1412239A (fr) * 1963-10-23 1965-09-24 Chimica Dell Aniene S P A Soc Cellule d'électrolyse à électrodes multiples réglables
SU1046022A1 (ru) * 1982-06-07 1983-10-07 Новочеркасский Ордена Трудового Красного Знамени Политехнический Институт Им.Серго Орджоникидзе Анодное устройство дл получени металлических порошков

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US4686018A (en) 1987-08-11
FR2586710B1 (fr) 1990-03-30
FR2586710A1 (fr) 1987-03-06
DE3672556D1 (de) 1990-08-16
ATE54472T1 (de) 1990-07-15
EP0219367A1 (de) 1987-04-22
JPH07122155B2 (ja) 1995-12-25

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