EP0219367A1 - Organische Elektrolysezelle mit Verbrauchselektrode - Google Patents

Organische Elektrolysezelle mit Verbrauchselektrode Download PDF

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Publication number
EP0219367A1
EP0219367A1 EP86401895A EP86401895A EP0219367A1 EP 0219367 A1 EP0219367 A1 EP 0219367A1 EP 86401895 A EP86401895 A EP 86401895A EP 86401895 A EP86401895 A EP 86401895A EP 0219367 A1 EP0219367 A1 EP 0219367A1
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Prior art keywords
electrolysis cell
consumable electrode
electrode
consumable
organic
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French (fr)
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EP0219367B1 (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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing 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.
  • US Patents 3,573,178 and US 3,141,841 describe the synthesis of tetraethyl lead in an electrolysis cell comprising an anode constituted by lead beads separated from the cylindrical cathode by a porous insulating wall. Balls are added during electrolysis to replace those which are consumed.
  • this device does not work well for very reducing metals such as magnesium, aluminum, zinc, titanium, which are covered with an insulating oxide layer which considerably increases the contact resistance between grains.
  • the presentation in granules of these metals is sometimes expensive.
  • metallic sludge and dust often form, which disrupts operation.
  • 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 breaking the ribbon, the device requires a relatively complicated mechanical system.
  • 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. Ind. (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 a direction D is conventionally considered as being the angle formed by the plane of tangency to the surface at this point and by the line having the direction D passing through this point .
  • a direction can be materialized by an infinity of parallel lines.
  • the direction D with respect to which the surface of the non-consumable electrode has a constant inclination is the vertical direction.
  • the angle formed by these two directions is zero.
  • any point of the consumable electrode is meant a point as well located on its surface as inside the (or) block, solid metal constituting this electrode.
  • 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.
  • 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, given the geometry of the cell and in particular the inclination of the non-consumable electrode, the footprint on the ground is very small, which allows an economically significant gain in space.
  • 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 geometry of the non-consumable electrode is such that it alone maintains the consumable electrode, that is to say that no other wall of the cell performs this function. This is the case, for example, when the active surface of the non-consumable electrode is conical or dihedral.
  • the consumable electrode can also be maintained, according to another variant, both by the non-consumable electrode and by an inert wall of the cell. This is the case, for example, when the active surface of the non-consumable electrode is in the form of a flat surface forming a dihedral with an inert wall of the cell. This variant is also described later ( Figure 5).
  • 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 Nio 2 , graphite.
  • metals such as iron, aluminum and nickel, alloys such as stainless steel, metal oxides such as Pb0 2 and Nio 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 of each network may not be parallel their thickness may not be constant provided that after assembly of 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 becomes s out.
  • 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 FIGS. 1 and 2 comprises a tank, one of the walls of which is constituted by cathode 2, which is not consumable.
  • the active surface of the non-consumable electrode 2 consists of two rectangular surfaces, of the same dimensions, arranged in the form of a dihedron whose edge 3, horizontal, constitutes the lowest part of the tank.
  • This active surface has at all points a constant inclination of 17 degrees relative to direction 9, which is the vertical direction and which can for example be materialized by the vertical of the section plane along I I-II passing through the edge 3.
  • the other walls of the tank are on the one hand vertical walls passing through the edges of the cathode 2 other than the aforementioned edge 3 and on the other hand a horizontal wall 10 closing the tank at its upper part. All these walls, other than those constituting the cathode 2, are made of an electrical insulating material or internally covered with an electrical insulator 1, for example a paint or any other electrically insulating coating.
  • the anode 4 consists of a stack of solid metal ingots of trapezoidal section. Each layer of the stack comprises only one ingot. The dimensions (length and width) of the ingots are slightly smaller than those of the tank.
  • the anode 4 is applied under the sole effect of its own weight against the cathode 2 which, alone, ensures the maintenance of the anode 4.
  • the anode 4 and the cathode 2 are separated by a plastic material 5 in the form of a grid.
  • Figure 6 shows a perspective view.
  • the mesh consists of two networks of parallel wires A ⁇ B 1 C 1 ... N 1 on the one hand and A 2 B 2 C 2 ... N 2 on the other.
  • 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 6 circulates from bottom to top in the cell read the. Pipes 8 allow the arrival and the exit of this solution 16, in the direction of the arrows 7.
  • the electrodes 2 and 4 are supplied with electric current by a DC voltage source, not shown in FIGS. 1 and 2.
  • the direction 9 becomes a direction D making an alpha angle with the vertical direction
  • the active surface of the non-consumable electrode 2 always has all its points a constant inclination of 17 degrees relative to this direction D and any straight line of direction D passing through any point of the consumable anode 4 crosses the active surface of the non-consumable cathode 2.
  • 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 electrode 2 is (17 + alpha) to one of the rectangular surfaces and areas 117 - alpha) to each other, is 117 + or - alpha!.
  • this inclination 1 1 7 + or - alpha relative to the vertical must be less than 45 degrees, that is to say for this particular embodiment, that alpha must be less than 28 degrees. Otherwise, there may be significant anomalies in the operation of the cell, in particular in the movement of the consumable electrode.
  • the electrolysis cell shown in Figures 3 and 4 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 3 and 4 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 grid such as that shown in FIG. 6 and previously described.
  • 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. 3 and 4.
  • 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 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 cathode 12 which is not consumable.
  • 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 - alpha ,.
  • 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 electrolysis cell shown in FIG. 5 comprises a cell, one of the walls of which is constituted by the cathode 32, which is not consumable.
  • the active surface of the cathode 32 is a rectangular surface, one of the sides 33 of which is horizontal and constitutes the lowest part of the tank. This active surface has at all points a constant inclination of 20 degrees relative to the direction 39 which is the vertical direction which can for example be materialized by the vertical of the cutting plane passing through the side 33.
  • the other walls of the tank are on the one hand vertical walls passing through the 4 sides of the rectangular cathode 32 and on the other hand a horizontal wall 40 closing the tank at its upper part. All these walls, other than that constituting the cathode 32 are made of an electrically insulating material or internally covered with an electrical insulator 31, for example a paint or any other electrically insulating coating.
  • Anode 34 consists of a stack of metal ingots massive rectangular section. Each layer of the stack comprises only one ingot.
  • the dimensions (length and width) of the ingots are slightly smaller than those of the tank.
  • the anode 34 is applied under the sole effect of its own weight against the cathode 32 and against the wall 42 of the tank which passes through the side 33 and which forms a dihedral with the cathode 32.
  • the anode 34 and the cathode 32 are separated by a plastic material 35 in the form of a grid such as that shown in FIG. 6 and previously described.
  • the electrolysis solution 36 circulates from bottom to top in the cell. Pipes 38 allow the arrival and exit of this solution 36, in the direction of the arrows 37.
  • the electrodes 32 and 34 are supplied with electric current by a DC voltage source, not shown in FIG. 5.
  • the direction 39 becomes a direction D making an alpha angle with the vertical direction 39.
  • the active surface of the cathode 32 always has of course at all points a constant inclination of 20 degrees relative to this direction D.
  • the cell can be rotated either by an alpha angle less than 25 degrees clockwise while looking at Figure 5, or by an alpha angle less than 45 degrees in reverse.
  • the upper walls 10, 20 and 40 of the electrolysis cells according to the invention are removable or have a removable part so as to allow the introduction of solid metal blocks.
  • FIG. 7 A complete installation allowing the continuous electrolysis of a solution is schematically represented in FIG. 7. It consists of a closed circuit comprising a reactor 51 with double jacket allowing the loading and the 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. 7 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-protic solvents usually used in organic electrochemistry, such as hexamethylphosphorotriamide (HMPT) tetrahydrofuran (THF), N-methylpyrolidone (NMP), dimethylformamide (DMF).
  • the organic solvent conventionally contains an indifferent electrolyte such as tetrabutylammonium tetrafluoroborate (BF4NB U4 ) or lithium perchlorate.
  • an indifferent electrolyte such as tetrabutylammonium tetrafluoroborate (BF4NB U4 ) 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 provided with an anode consumable from 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 halogen, in the presence 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.
  • the alcohols obtained according to the process which is the subject of the present invention correspond to the general formula in which R, R 1 and R 2 have the abovementioned meaning.
  • R, R 1 and R 2 have the abovementioned meaning.
  • the carbonyl derivatives are ketones, that is to say when R 1 and R 2 are different from hydrogen, tertiary alcohols are obtained.
  • 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 of 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 represents an aliphatic chain substituted by 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 5 represents an OR 6 group
  • 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 R 3 -X bond, 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.
  • R4 and R5 represent a linear or branched alkyl chain.
  • R 4 and R 5 are identical.
  • R 4 and R 5 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 made of stainless steel, has an active surface of 20 dm 2 .
  • the other walls of the tank are also made of stainless steel but are internally covered with an electrically insulating paint.
  • the anode 4 consists of a stack of massive magnesium ingots. These ingots have the following dimensions: length: 360 mm, upper width: 130 mm, lower width laughing: 120 mm, height: 50 mm.
  • the plastic material 5 in the form of a mesh is polypropylene. This mesh is just placed on the active surface of the cathode 2, the shape of which it follows, before the introduction of the anode 4. The complete installation is such as that shown diagrammatically in FIG. 7.
  • the three lower ingots are machined so as to best match the dihedral shape of the cathode.
  • the other ingots are then stacked thereon to the top of the cell.
  • the voltage quickly stabilizes at around 12 volts, which proves the proper functioning of the cell, namely in particular that the active surfaces of the two electrodes remain well parallel with a constant deviation.
  • the phenylcetic acid formed is isolated, and identified according to the usual methods well known to those skilled in the art.
  • the nickel cathode 2 has an active surface of 1 dm 2 .
  • the other walls of the tank are made of stainless steel and are internally covered with an electrically insulating paint 1.
  • the anode 4 consists of a stack of cubic blocks (50 mm in dimension) made of aluminum.
  • the plastic material 5 and the installation are the same as those of Example 1.
  • the lower aluminum block was machined so that its cross section is trapezoidal and can thus, when the wedge horizontally at the top of the cathode, have from the start of electrolysis, a larger active surface.
  • the other cubes are not machined and are stacked on the first to the top of the cell.
  • the solution thus obtained is circulated in the installation.
  • 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 chloride solution of ammonium 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 thus obtained is 56% (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 2 The same test is carried out as that of Example 2 but without machining the lower block of the anode. The same result is obtained but the operating equilibrium takes longer to reach.
  • 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 and the installation are the same as those of Example 1.
  • the lower aluminum block was machined so that it is approximately in the form of a cone. 100 mm high and 50 mm base diameter, which is easily achieved from a cylindrical block with these dimensions.
  • the block After positioning the plastic material 15 in the form of a grid on the active surface of the cathode, the block is introduced. machined which follows the shape of the cathode, then stacked on this lower block several other blocks to the top of the cell.
  • the operation is then carried out under the same conditions as for example 2.
  • the electrolysis voltage stabilizes very quickly, due to the machining of the first block.
  • the yield of distilled dimethylbenzylcarbinol obtained is 60% (purity greater than 95%).
  • Example 4 The same test is carried out as that of Example 4 but without machining the lower block before the first electrolysis. The same result is obtained but the operating equilibrium is much longer to reach.
  • Example 3 The same test is carried out as that of Example 3, with the only difference that the anode 4 consists of a stack of blocks of length 50 mm, height 50 mm and width 25 mm, each layer of the stack. consisting of 2 blocks placed side by side. Pure dimethylbenzylcarbinol is obtained with a yield of 53%.
  • the nickel cathode 32 has an active surface of 0.5 dm 2 .
  • the other walls of the tank are made of stainless steel and are internally covered with an electrically insulating paint 31.
  • the anode 34 consists of a stack of aluminum blocks of length 50 mm, height 50 mm and width 30 mm.
  • the plastic 35 and the installation are the same as those of Example 1.
  • the 2 lower blocks so that their geometry is combined with that of the dihedral lower part of the cell.
  • the operation is then carried out under the same conditions as those of Example 2.
  • Example 2 The following examples were carried out under the same general conditions as those of Example 1.
  • the halogenated derivatives listed in Table I were used in place of benzyl chloride.
  • Table I also specifies the solvent used and the results obtained.
  • the acids obtained were identified by IR and NMR spectrometries as well as by their melting point for some of them.
  • the yields of isolated acid are expressed in% relative to the starting organic halide.
  • Table II specifies for each example the halogenated derivative and the starting carbonylated derivative, the nature of the solvent of the electrolyte and of the electrodes, the temperature at which the electrolysis is carried out, the molar ratio between the two starting materials, the Faraday number per mole of organic halide, the yield of isolated pure alcohol expressed in% relative to the starting organic halide.
  • the alcohols obtained were identified by spectrometry IR and NMR sorting.
  • the cathode 2 made of nickel, has a surface of 1- dm2.
  • the other walls of the tank are made of stainless steel and are internally covered with an electrically insulating paint.
  • Anode 4 consists of a stack of cubic blocks (50 mm side) made of magnesium.
  • the plastic material 5 and the installation are the same as those of Example 1.
  • the lower magnesium block was machined so that its cross section was trapezoidal.
  • the other cubes are not machined and are stacked on the first to the top of the cell.
  • the electrolysis intensity is 2A and the temperature 25 ° C.
  • the DMF is evaporated and the residue is hydrolyzed with hot diluted HC l.
  • the be: is isolated: .zylmethylketone by extraction with ether with a yield of 39%.
  • the pure benzylmethylketone thus isolated was identified by its IR and NMR spectra and its purity was checked by GC (> 95%).

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  • 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)
EP86401895A 1985-09-05 1986-08-29 Organische Elektrolysezelle mit Verbrauchselektrode Expired - Lifetime EP0219367B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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

Publications (2)

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EP0219367A1 true EP0219367A1 (de) 1987-04-22
EP0219367B1 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)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283796A1 (de) * 1987-03-18 1988-09-28 Giuseppe Silvestri Einrichtung zum Umbau von elektrolytischen Zellen des Filterpressentyps in Zellen mit kontinuierlich erneuerbaren Aktivanoden
FR2639364A1 (fr) * 1988-11-23 1990-05-25 Poudres & Explosifs Ste Nale Procede d'electrosynthese d'aldehydes
EP0697473A1 (de) 1994-08-18 1996-02-21 Hoechst Aktiengesellschaft Elektrolysezelle mit Verzehranoden

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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
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
EP1953142A1 (de) 1993-06-25 2008-08-06 Aventis Inc. Neuartige Zwischenprodukte zur Herstellung antihistaminischer 4-Diphenylmethyl-/Diphenylmethoxy-Piperidinderivate
US6673933B2 (en) 1998-07-02 2004-01-06 Aventis Pharmaceutical Inc. Antihistaminic piperidine derivatives and intermediates for the preparation thereof
US6683094B2 (en) 1998-07-02 2004-01-27 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
CN103209930B (zh) * 2010-10-22 2014-08-20 金兑奎 金属离子杀菌装置
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

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283796A1 (de) * 1987-03-18 1988-09-28 Giuseppe Silvestri Einrichtung zum Umbau von elektrolytischen Zellen des Filterpressentyps in Zellen mit kontinuierlich erneuerbaren Aktivanoden
FR2639364A1 (fr) * 1988-11-23 1990-05-25 Poudres & Explosifs Ste Nale Procede d'electrosynthese d'aldehydes
EP0370866A1 (de) * 1988-11-23 1990-05-30 Societe Nationale Des Poudres Et Explosifs Verfahren zur Elektrosynthese von Aldehyden
EP0697473A1 (de) 1994-08-18 1996-02-21 Hoechst Aktiengesellschaft Elektrolysezelle mit Verzehranoden

Also Published As

Publication number Publication date
FR2586710A1 (fr) 1987-03-06
ATE54472T1 (de) 1990-07-15
US4686018A (en) 1987-08-11
EP0219367B1 (de) 1990-07-11
JPS6256589A (ja) 1987-03-12
JPH07122155B2 (ja) 1995-12-25
FR2586710B1 (fr) 1990-03-30
DE3672556D1 (de) 1990-08-16

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