EP0359631A1 - Elektrolysezelle und Elektrolyseanlage für deren Inbetriebnahme - Google Patents

Elektrolysezelle und Elektrolyseanlage für deren Inbetriebnahme Download PDF

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Publication number
EP0359631A1
EP0359631A1 EP89402435A EP89402435A EP0359631A1 EP 0359631 A1 EP0359631 A1 EP 0359631A1 EP 89402435 A EP89402435 A EP 89402435A EP 89402435 A EP89402435 A EP 89402435A EP 0359631 A1 EP0359631 A1 EP 0359631A1
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Prior art keywords
electrolysis
electrolysis cell
emulsion
anode
cerium
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Application number
EP89402435A
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English (en)
French (fr)
Inventor
Dominique Horbez
Alain Storck
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/021—Process control or regulation of heating or cooling
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B9/01—Electrolytic cells 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof

Definitions

  • the present invention relates to an electrolysis cell intended in particular for the implementation of a process coupling both an electrolysis of a chemical species in solution and simultaneous extraction of the chemical species produced, in an organic phase.
  • the invention relates more particularly to a cell intended for the electrochemical oxidation of cerium 3+ into cerium 4+ and simultaneous extraction of cerium 4+ in the organic phase.
  • FR-A 2 570 087 an electrolysis cell for electrochemically oxidizing cerium 3+ to cerium 4+.
  • Said cell comprises two anode compartments, a cathode compartment located between the two aforementioned anode compartments, and two cationic membranes separating each of the two anode compartments from the cathode compartment.
  • FR-A 2 570 087 there is also described a method of electrolytic oxidation of a chemical species involving the aforementioned cell, characterized in that said solution is treated in the first anode compartment of an electrolysis cell comprising a first anode compartment and a cathode compartment separated by a first cationic membrane, the solution from the first anode compartment is then treated in a second anode compartment of the above-mentioned electrolysis cell and separated from the above-mentioned cathode compartment by a second cationic membrane, recovers the solution from the second anode compartment which constitutes the production, an electrolyte is circulated in the aforementioned cathode compartment.
  • This type of apparatus makes it possible to obtain "Faraday” yields and a high transformation rate of cerium 3+.
  • a first objective of the invention is to provide an electrolysis cell which makes it possible inter alia to implement a process involving the electrolysis of a chemical species in the aqueous phase and the extraction of the species produced in the emulsified organic phase in said aqueous phase.
  • Another objective of the invention is to propose an electrolysis cell which does not use heavy technology.
  • Another objective of the invention is to provide an electrolyte cell which can be used on an industrial scale and which can operate both continuously or discontinuously.
  • a final objective of the invention is to have an electrolysis cell having a great flexibility of adaptation as a function of the electrochemical operation to be carried out.
  • the electrolysis cell of the invention is characterized in that it consists of an enclosure in which are placed face to face two base electrodes electrically isolated from each other, the base cathode consisting of a solid plate of a conductive material and the base anode being a volume anode consisting of a plate full of a conductive material on which are placed one or more grids of expanded metal and that in said cell is placed at each end of that here, on either side of the electrodes, a plate of insulating material pierced with orifices.
  • a preferred variant of the invention consists in interposing between the two base electrodes, one or more electrode modules consisting, on the one hand, of a plate full of a conductive material working on a cathode face and on the 'other anode face and, on the other hand, one or more expanded metal grids placed on the anode face; the electrode module (s) being inserted so that the anode side of the plate faces the base cathode and optionally faces the cathode side of another module; the electrode module (s) being electrically isolated from the base electrodes and possibly from each other.
  • the electrolysis cell of the invention shown in FIG. 1 consists of an enclosure (1) having an externally parallelepeledic shape (preferably cubic or rectangular) made of insulating material, for example glass, conventional plastic material such as polyvinylidene difluoride, polyvinyl chloride, polypropylene, polymers of the methyl methacrylate type (PLEXIGLAS®).
  • insulating material for example glass, conventional plastic material such as polyvinylidene difluoride, polyvinyl chloride, polypropylene, polymers of the methyl methacrylate type (PLEXIGLAS®).
  • said enclosure has a removable wall in order to facilitate the handling of the electrodes and the maintenance of the apparatus.
  • an inlet (2) and an outlet (3) for the fluid there are provided an inlet (2) and an outlet (3) for the fluid.
  • the fluid supplied at the bottom of the cell is discharged at the top of the latter.
  • a flared shape 10 as illustrated in FIG. 2: the walls narrowing between the cell body and the entry or exit of fluids.
  • One advantage of the electrolysis cell of the present invention is that it can have either a monopolar configuration or a bipolar configuration.
  • anode (4) and a cathode (5) which are connected to a current supply. They consist of a plate full of conductive material.
  • one or more grids (6) of expanded metal are added which increase the anodic surface and which, moreover, have a turbulence promoting effect which promotes the transfer of anodic material.
  • the grids are made of mesh, the largest opening of which can be placed parallel or perpendicular to the flow of the fluid.
  • the number of grids can vary between 1 and 5 and is preferably between 2 and 4.
  • the ratio between the anodic and cathodic surface can vary within wide limits from 1.0 to 10 but preferably it is chosen between 4.0 and 7.0.
  • a preferred embodiment of the electrolysis cell of the invention is the bipolar configuration which makes it possible to obtain specific surface areas of electrodes even higher.
  • bipolar configuration there are two basic electrodes (4), (6) and (5) and at least one electrode module (7). Only the base electrodes are connected to a current supply.
  • the base cathode (5) consists of a solid plate, therefore of small surface, which favors the transfer of material.
  • the anode consists of a solid plate (4) and one or more grids of expanded metal (6).
  • One or more electrode modules are interposed between the anode and the base cathode.
  • a set of electrodes consisting of a solid plate (8) one of the faces of which functions as an anode and the other face of which operates as cathode.
  • On the anode face of said plate (8) one or more expanded metal grids (9) are placed.
  • the electrode module (s) are stacked so that the anode side faces the cathode side of another module or the base cathode (5).
  • the electrolysis cell of the invention has great flexibility of use, in particular for covering a wide range of electrode surfaces, owing to the fact that it is possible to act both on the number of grids of expanded metal and on the number of modules implemented.
  • the missing modules should be replaced by solid plates (11) made of insulating material (plastic) in order to fill the dead volume. Said plates are placed outside the anode and / or the base cathode.
  • the electrodes As regards the characteristics of the electrodes, their chemical nature will be specified. They are made of a conductive material resistant to chemical and electrochemical oxidation.
  • the base anode (4), the base cathode (5) and the solid plate (8) playing both the cathode and anode roles can be more particularly made of graphite, titanium, titanium coated with '' a precious metal, for example platinum, palladium, irridium.
  • a solid metal plate is used.
  • the geometric shape of the solid electrodes it depends on the shape of the enclosure.
  • the expanded metal grid (s) may also be made of titanium, optionally coated with a precious metal. It will not depart from the scope of the invention to use the expanded metal in the form of a canvas.
  • the electrodes are electrically isolated from each other.
  • the electrodes can be separated by a spacer (12) made of insulating materials.
  • plastics As insulating materials, the following plastics may be mentioned by way of examples: - polyvinyl chloride, - polyvinylidene difluoride - polypropylene, - polymethyl methacrylate (PLEXIGLAS®).
  • the spacer which is interposed between the base electrodes and any modules is preferably in the form of a frame which consists of an insulating plate having the dimensions of the cathode, hollowed out in its center and the width of said frame is minimized but sufficient to ensure mechanical stability of the electrode assembly.
  • the thickness of the spacer delimits the distance between the electrodes. It is desirable that it be as small as possible in order to reduce the dead volumes in the cell. Generally, the distance between the two electrodes varies between 1 mm and 5 mm and, preferably, is chosen around 2 mm.
  • Another characteristic of the electrolysis cell of the invention is the presence of a plate (13) of insulating material pierced with orifices, located at each end of the cell and placed on either side of the electrodes.
  • Said plate can be produced, for example, from the aforementioned plastics. Its shape matches that of the enclosure.
  • orifices having a diameter which can vary, for example, between 0.5 mm and 5.0 mm and of preparation between 1.0 and 2.0 mm.
  • a preferred variant of the invention illustrated in FIG. 2 consists in filling the space defined in the upper and lower part of the cell, by introducing obstacles to the circulation of the fluid such as for example grids or balls (14). made of insulating material. At the level of the arrival of the fluid (2), this avoids an excessive jet effect and the flow is uniform.
  • the arrival of the fluid takes place at the anode due to the presence of the spacer between anode and cathode.
  • the fluid circulates in a longitudinal direction.
  • the electric current it flows in a transverse direction.
  • the electrolysis cell which is the subject of the present invention therefore has the following advantages: - high capacity electrolyser (due to high specific electrode areas). -
  • the fluid feeds are made at the level of the anodes so as to favor the transfer of material there and also to avoid the coalescence of the emulsion in the meshes of the expanded metal. - Dead volumes are minimized so as to avoid coalescence and settling of the emulsion.
  • the electrolysis cell of the invention can be integrated into an electrolysis assembly making it possible to implement a method coupling both an electrolysis operation and an extraction operation.
  • an electrochemical oxidation process of cerium 3+ to cerium 4+ in emulsion which consists in simultaneously carrying out the electrochemical oxidation of cerium 3+ in cerium 4+ in the aqueous phase and the extraction of cerium 4+ 4+ formed in an organic phase extracting cerium 4 + emulsified in the aqueous phase which makes it possible to obtain, after separation of the phases, an organic phase loaded with cerium 4 +.
  • the aqueous phase consists of the cerium 3+ salt solution. Mention may be made, as salts, of cerium sulfate or nitrate III. Its maximum concentration depends on the solubility of the salt and can vary for example according to the solubility between 0.1 and 1.5 moles / liter. The minimum bound is not critical, but a lower concentration results in a lower current density.
  • a mineral acid preferably sulfuric or nitric acid, is added in an amount such that the normality of the aqueous phase varies between 0.5 and 5 N and preferably between 1 and 2 N.
  • the aqueous phase defined above is brought into contact with an organic phase containing a water-insoluble cerium extracting agent 4+.
  • the extraction agent used in the process of the invention must be able to selectively extract the cerium 4+.
  • a cationic extraction agent and more particularly an organophosphorus acid can be used.
  • R3 represents R2 or hydrogen and R1 and R2 are aliphatic, cycloaliphatic and / or aromatic hydrocarbon radicals.
  • Said radicals can contain from 1 to 18 carbon atoms and at least one of them comprises at least 4 carbon atoms.
  • mono- or dialkylphosphoric mono- or dialkylphosphonic, alkylphenylphosphonic, mono- or dialkylphosphinic acids.
  • the organic phase contains, where appropriate, an organic diluent inert with respect to the extracting agents in order to improve the hydrodynamic properties of the organic phase.
  • organic diluents Many organic solvents or their mixtures can be used as diluents. However, in the present case, a diluent must be chosen which cannot be oxidized by cerium 4+.
  • an aliphatic hydrocarbon such as, for example, hexane, heptane, dodecane, petroleum fractions of the kerosene or isoparaffin type.
  • the proportion of extracting agent in the organic phase is not critical and can vary within wide limits. However, it is generally advantageous for it to be as high as possible. Thus, in the case of cationic extractants, a concentration of extractant of 0.5 to 2.0 moles per liter of organic phase leads to advantageous hydrodynamic separation conditions.
  • the aqueous phase and the organic phase are brought into contact by emulsifying the organic phase in the aqueous phase.
  • the proportion of the organic phase relative to the aqueous phase can vary within wide limits.
  • the organic phase can represent from 5 to 66% of the volume of the two phases and, preferably, from 33 to 66%, and more preferably 50%.
  • the organic phase is emulsified in the aqueous phase by stirring.
  • the organic phase being emulsified in the aqueous phase the aqueous solution of the cerous salt is electrolysed under the conditions given below.
  • the electrolysis is preferably carried out at room temperature: most often between 15 ° C and 25 ° C. It is possible to work at a higher temperature, which promotes the kinetics of the electrochemical reaction and the transfer of materials to the electrodes, but the choice of temperature depends on the solubility of the cerous salt.
  • the conditions of the electrolysis operation depend on the discontinuous or continuous mode of operation of the electrolysis cell and will be specified below.
  • an organic phase highly charged with cerium 4+ is recovered which is separated from the aqueous phase by any appropriate means, in particular decantation.
  • the electrolysis cell of the invention is perfectly suited for the implementation of the process defined above.
  • an electrolysis assembly comprising at least the following means: - a mixer intended to form and stabilize the emulsion, - means for conveying the emulsion, - the electrolysis cell previously described, - Means intended to evacuate the gas produced at the cathode.
  • a continuously operating electrolysis unit further includes: - means for supplying the aqueous phase, - means for supplying the organic phase, - Means for withdrawing the emulsion charged in this case produced electrochemically.
  • FIG. 3 is a schematic representation of an installation operating continuously according to a preferred variant of the invention.
  • the installation is supplied from the outside in aqueous phase (15) introduced into a storage tank (16) and in organic phase (17) introduced into a storage tank (18).
  • Two pumps (19) and (20) convey said fluids and food try in (21) and (22) the mixer (23).
  • the emulsion formed is conveyed via a pump (27) to the inlet (2) of the electrolysis cell (1), object of the present invention.
  • the charged emulsion passes through a degasser (28) then a refrigerant (29).
  • a part of the emulsion drawn off at (31) in the lower part of the mixer constitutes the production. It is then sent to a storage tank (33), optionally equipped with a withdrawal valve (34), by means of a pump (32).
  • the mixer (23) is equipped with a central agitation (24) and possibly with a valve (25) for drawing off. It can be envisaged to use a static mixer of the KENICS® or SULZER® type. Preferably, a stirred tank is used.
  • the electrolysis cell (1) has been described in detail and is preferably a bipolar cell.
  • the degasser (28) is intended to remove the gas produced at the cathode. You can use a flat or coil degasser. Preferably, a flat degasser is used and it should preferably be given an elongated shape in order to avoid the formation of dead zones.
  • these are metering pumps.
  • the pump (25) intended to convey the emulsion it is possible to use a centrifugal or volumetric pump.
  • a centrifugal pump is preferably used.
  • the operating conditions of the installation depend on the size of the various devices involved in the installation. By way of illustration, they are specified below for a concrete embodiment of the invention.
  • the electrolysis cell represented by FIGS. 1 and 2 and then used in the examples has the following characteristics.
  • a variable number of electrodes having a square shape are stacked.
  • the electrodes full plates or expanded metal grids are 13 cm side.
  • the cell has a base cathode which is a plate (5) of platinum titanium having a surface of 0.017 m2 and a base anode which is a volume anode consisting of a plate (4) of platinum titanium having an area of 0.017 m2 and a stack of 1 to 4 grids (6) of 2.5 micron platinized expanded titanium, of standard mesh N (10 x 5.8 x 1.1 mm) for which the effective area of electrode is 1.407 m2 per m2 of grid.
  • the basic electrodes there is between the basic electrodes, from 1 to 4 additional electrode modules consisting, on the one hand, of a plate (8) in platinum titanium having a surface of 0.017 m2, working on one side in cathode and on the other side in anode and, on the other hand, from 1 to 4 grids (9) of 2.5 ⁇ m platinum-expanded expanded titanium, of standard mesh, as described above.
  • the electrode module (s) are inserted so that the anode side of the plate faces the base cathode and possibly faces the cathode side of another module.
  • the following table specifies the anodic (A ea ) and cathodic (A ec ) surfaces likely to be obtained as well as the surface ratio A ea / A ec .
  • the surface area ratio A ea / A ec can vary between 2.4 and 6.6.
  • the vacuum is filled by a set of full PLEXIGLAS® plates (13 cm x 13 cm).
  • the electrodes are electrically isolated from each other by a spacer (12) which is a plastic frame (P.V.C.) with a thickness of 2 mm.
  • a spacer (12) which is a plastic frame (P.V.C.) with a thickness of 2 mm.
  • a plastic plate P.V.C. pierced with holes of 2 mm in diameter.
  • the ends of the cell have a flared shape (10) as illustrated in FIG. 2.
  • the space defined in the upper and lower part of the cell is filled by a stack of plastic grids (14).
  • the electrolysis cell described above is integrated into a main circuit containing a mixer (23), a pump (27), a degasser (28) and a refrigerant (29).
  • the mixer (23) is equipped with a central agitation (24) and the inlet (30) and the outlet (26) of the emulsion are placed opposite.
  • the pump (27) intended to convey the emulsion at a flow rate specified in the examples is a conventional pump of the centrifugal type.
  • the degasser (28) is a flat degasser having a surface area of 9 dm2.
  • the refrigerant (29) is a double jacket refrigerant, without specific characteristics.
  • the main circuit is coupled to a supply and withdrawal circuit comprising: - a storage tank (16) for the aqueous phase and a metering pump (19), - a storage tank (18) for the organic phase and a metering pump (20), - a metering pump (32) and a storage and settling tank (33) of the emulsion equipped with a withdrawal valve (34).
  • a supply and withdrawal circuit comprising: - a storage tank (16) for the aqueous phase and a metering pump (19), - a storage tank (18) for the organic phase and a metering pump (20), - a metering pump (32) and a storage and settling tank (33) of the emulsion equipped with a withdrawal valve (34).
  • the operation of the electrolysis assembly it varies depending on whether the electrolysis operation is carried out in a continuous or discontinuous mode.
  • the operation for forming the emulsion is identical and carried out with relatively vigorous stirring between 1000 and 1500 revolutions / minute.
  • a sufficient circulation speed is ensured which depends on the configuration of the electrolysis cell. As an indication for the cell described above, it can vary between 0.3 and 1.5 m3 / h depending on whether the configuration is monopolar or bipolar with up to 3 electrode modules.
  • a potential is imposed which depends on the electrochemical operation to be carried out. For example, in the case of the electrochemical oxidation of cerium 3+ to cerium 4+, we place our at the limit of the oxygen release potential. Generally, we place us at less than 50 millivolts of said potential. It depends on the medium and the electrodes. In the case of platinum titanium electrodes, an anode potential of 1.7 to 1.8 volts is defined with respect to the normal hydrogen electrode.
  • the duration of the electrolysis can be continued until obtaining a balance that results in constant tension, intensity and concentration.
  • an operating point is defined which corresponds to a desired conversion rate, which imposes, for a given electrode area, the intensity of the current in the cell and the supply and withdrawal rates.
  • the choice of operating mode depends on the electrochemical operation to be performed and on the desired conversion rate. To obtain high conversion rates, it is preferable to work batchwise. On the other hand, if one wishes lower conversion rates, for example, to achieve the depletion of a solution in a given chemical species, the continuous mode of operation can be preferred because of its adequacy with a mode of production on an industrial scale.
  • the aqueous phase (15) consists of a cerous sulphate solution containing 0.2 mole / liter of cerium 3+ and having a sulfuric acid normality of 1 N. It is introduced into the storage tank (16) and supplied with (21) the mixer (23) at a flow rate of 1.39 liters / hour.
  • the organic phase (17) is composed of di (2-ethylhexyl) phosphoric acid in solution in kerosene at a rate of 1 mole / liter. It is introduced into the storage tank (18) and feeds into (22) the mixer (23) at a flow rate of 1.39 liters / hour.
  • the organic phase is emulsified in the aqueous phase by stirring at 1100 rpm.
  • the content of the emulsion in the organic phase is 50% by volume.
  • the emulsion leaves the mixer (23) at (26) and then circulates at a speed of 880 liters / hour in the main circuit comprising the electrolysis cell (1), the degasser (28) and the refrigerant (29).
  • the configuration of the cell shown more precisely in FIGS. 1 and 2 is as follows: - base anode (4) and base cathode (5) - 3 electrode modules - anodic stack of 3 grids (6) and (9) - total anodic area: 0.352 m2 - total cathodic surface: 0.068 m2
  • Electrochemical oxidation of cerium 3+ to cerium 4+ is carried out at room temperature.
  • the current intensity is 2.06 A.
  • the organic phase is loaded with cerium 4+.
  • the withdrawal is carried out at a flow rate of 2.78 liters / hour of the emulsion loaded in (31) which is transported to the storage tank (33).
  • Example 1 is reproduced except as regards the composition and the flow rate of the phases, the configuration of the installation remaining identical.
  • the aqueous phase (15) consists of a cerous sulphate solution containing 0.2 mole / liter of cerium 3+ and having a sulfuric acid normality of 2 N. It feeds into (21) the mixer (23) at a rate of 0.93 liter / hour.
  • the organic phase (17) is composed of di (2-ethylhexyl) phosphoric acid in solution in kerosene at the rate of 2 moles / liter. It feeds (22) the mixer (23) at a flow rate of 0.46 liters / hour.
  • the organic phase is emulsified in the aqueous phase by stirring at 1100 rpm.
  • the content of the emulsion in the organic phase is 33%.
  • the emulsion circulates at a speed of 880 liters / hour.
  • Electrolysis is carried out in a manner identical to example 1.
  • the intensity of the current is 1.6 A.
  • the charged emulsion at (31) is drawn off at a flow rate of 1.4 liters / hour.
  • the installation includes only the main circuit shown in Figure 3, namely, the mixer (23), the pump (27), the electrolysis cell (1), the degasser (28) and the refrigerant (29) .
  • the aqueous phase consists of a cerous sulphate solution containing 0.2 mole / liter of cerium 3+ and having a sulfuric acid normality of 1 N. 3000 cm3 of said phase are introduced into the mixer (23).
  • the organic phase is composed of di (2-ethylhexyl) phosphoric acid in solution in kerosene at a rate of 1 mole / liter. 3000 cm3 of said phase are introduced into the mixer (23). In the mixer (23), the organic phase is emulsified in the aqueous phase by stirring at 1100 rpm. The content of the emulsion in the organic phase is 50% by volume.
  • the emulsion leaves the mixer (23) at (26) and then circulates at a speed of 880 liters / hour in the main circuit comprising the electrolysis cell (1).
  • FIGS. 1 and 2 The configuration of the cell shown more precisely in FIGS. 1 and 2 is as follows: - base anode (4) and base cathode (5) - 1 electrode module (7) - anodic stack of 4 grids (6) and (9) - total anodic area: 0.224 m2 - total cathodic surface: 0.034 m2
  • Electrochemical oxidation of cerium 3+ to cerium 4+ is carried out at room temperature, by imposing a potential on the anode of 2.49 volts / ENH.
  • the electrolysis lasts 4 hours.
  • the organic phase is loaded with cerium 4+.
  • Example 3 is reproduced but by modifying the configuration of the electrolysis cell which becomes the following: - base anode (4) and base cathode (5) - 2 electrode modules (7) - anodic stack of 4 grids (6) and (9) - total anodic surface: 0.336 m2 - total cathodic surface: 0.051 m2.
  • Oxidation of cerium 3+ to cerium 4+ is carried out by imposing a potential on the anode of 3.18 volts / ENH.
  • the electrolysis lasts 4 hours 30 minutes.
  • the installation includes only the main circuit shown in Figure 3, namely, the mixer (23), the pump (27), the electrolysis cell (1), the degasser (28) and the refrigerant (29) .
  • the aqueous phase consists of a cerous sulphate solution containing 0.2 mole / liter of cerium 3+ and having a sulfuric acid normality of 1 N. 3000 cm3 of said phase are introduced into the mixer (23).
  • the organic phase is composed of di (2-ethylhexyl) phosphoric acid in solution in kerosene at a rate of 1 mole / liter. 3000 cm3 of said phase are introduced into the mixer (23). In the mixer (23), the organic phase is emulsified in the aqueous phase by stirring at 1100 rpm. The content of the emulsion in the organic phase is 50% by volume.
  • the emulsion leaves the mixer (23) at (26) and then circulates at a speed of 540 liters / hour in the main circuit comprising the electrolysis cell (1).
  • FIGS. 1 and 2 The configuration of the cell shown more precisely in FIGS. 1 and 2 is as follows: - base anode (4) and bae cathode (5) - anodic stack of 2 grids (6) - total anodic area: 0.064 m2 - total cathodic surface: 0.017 m2
  • Electrochemical oxidation of cerium 3+ to cerium 4+ is carried out at room temperature, by imposing a potential on the anode of 1.63 volts / ENH.
  • the electrolysis lasts 14 hours.
  • the organic phase is loaded with cerium 4+.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Secondary Cells (AREA)
EP89402435A 1988-09-14 1989-09-07 Elektrolysezelle und Elektrolyseanlage für deren Inbetriebnahme Withdrawn EP0359631A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8811956 1988-09-14
FR8811956A FR2636348A1 (fr) 1988-09-14 1988-09-14 Nouvelle cellule d'electrolyse et ensemble d'electrolyse pour sa mise en oeuvre

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EP0359631A1 true EP0359631A1 (de) 1990-03-21

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EP (1) EP0359631A1 (de)
JP (1) JPH02115394A (de)
KR (1) KR900004966A (de)
AU (1) AU4122289A (de)
BR (1) BR8904611A (de)
FI (1) FI894334A7 (de)
FR (1) FR2636348A1 (de)
NO (1) NO893644L (de)
ZA (1) ZA896967B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993018208A1 (en) * 1992-03-04 1993-09-16 Hydro-Quebec Indirect cerium mediated electrosynthesis

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705049A (en) * 1992-04-07 1998-01-06 Hydro-Quebec Indirect cerium mediated electrosynthesis
JP4961130B2 (ja) * 2005-10-27 2012-06-27 株式会社 材料・環境研究所 エッチング液の長寿命化方法
KR101507388B1 (ko) * 2008-01-01 2015-03-31 주식회사 뉴파워 프라즈마 태양광 발전 시설을 이용한 전기 분해 설비

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859195A (en) * 1972-09-20 1975-01-07 Du Pont Apparatus for electrochemical processing
FR2363642A1 (fr) * 1976-09-03 1978-03-31 Battelle Memorial Institute Reacteur electrochimique destine a etre incorpore dans une installation pour la production de bioxyde de titane par voie sulfate a partir de l'ilmenite
EP0271298A2 (de) * 1986-12-11 1988-06-15 British Nuclear Fuels PLC Vorrichtung für elektrolytische Reaktion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859195A (en) * 1972-09-20 1975-01-07 Du Pont Apparatus for electrochemical processing
FR2363642A1 (fr) * 1976-09-03 1978-03-31 Battelle Memorial Institute Reacteur electrochimique destine a etre incorpore dans une installation pour la production de bioxyde de titane par voie sulfate a partir de l'ilmenite
EP0271298A2 (de) * 1986-12-11 1988-06-15 British Nuclear Fuels PLC Vorrichtung für elektrolytische Reaktion

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993018208A1 (en) * 1992-03-04 1993-09-16 Hydro-Quebec Indirect cerium mediated electrosynthesis

Also Published As

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FI894334A7 (fi) 1990-03-15
ZA896967B (en) 1990-06-27
JPH02115394A (ja) 1990-04-27
NO893644D0 (no) 1989-09-12
AU4122289A (en) 1990-03-22
KR900004966A (ko) 1990-04-13
NO893644L (no) 1990-03-15
FR2636348A1 (fr) 1990-03-16
FI894334A0 (fi) 1989-09-13
BR8904611A (pt) 1990-04-24

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