EP1789608B1 - Dispositif d'electrolyse destine a la fabrication de metal alcalin - Google Patents

Dispositif d'electrolyse destine a la fabrication de metal alcalin Download PDF

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Publication number
EP1789608B1
EP1789608B1 EP05784834A EP05784834A EP1789608B1 EP 1789608 B1 EP1789608 B1 EP 1789608B1 EP 05784834 A EP05784834 A EP 05784834A EP 05784834 A EP05784834 A EP 05784834A EP 1789608 B1 EP1789608 B1 EP 1789608B1
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EP
European Patent Office
Prior art keywords
alkali metal
alloy
electrolysis
tube
tubes
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German (de)
English (en)
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EP1789608A2 (fr
Inventor
Günther Huber
Michael Lutz
Michael Wille
Holger Friedrich
Josef Guth
Uwe Behling
Axel Franke
Elisabeth Gunkel
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode

Definitions

  • the present invention relates to an electrolyzer for producing alkali metal from a liquid alkali metal heavy metal alloy.
  • an alkali metal is to be understood as meaning in particular sodium, potassium or lithium.
  • Sodium is an important inorganic base product which can be used, inter alia, for the preparation of sodium compounds such as sodium peroxide, sodium hydride, sodium borohydride and sodium amide for the extraction of titanium by metallothermy, as well as for reduction purposes in the organic chemical industry, for the purification of hydrocarbons and used oil, for condensations, for alkoxide production, as a polymerization catalyst and in preparative organic chemistry.
  • the sodium extraction is carried out today mainly by the downs method by melt electrolysis of a ternary mixture of NaCl, CaCl 2 and BaCl 2 .
  • Lithium finds inter alia. Use in nuclear technology for the production of tritium, as an alloying addition to aluminum, lead or magnesium, in organic syntheses, for the synthesis of complex metal hydrides, for the preparation of organometallic compounds, for condensations, dehydrohalogenations, for the production of ternary amines or quaternary ammonium salts, in the mineral oil industry as a catalyst and for desulfurization, for the polymerization of isoprene to cis polymers, in the ceramic industry for controlling the expansion coefficient, lowering the melting temperature and the like, for the production of lubricants, as deoxidizing and cleaning agents in the metallurgy of iron, nickel, copper and their alloys.
  • Lithium is also produced in the prior art on an industrial scale by the Downs process by electrolysis of anhydrous alkali metal chloride melts, wherein the melting points of the molten salts are reduced by additions of alkali chlorides.
  • the service life of the known electrolysis cells is limited to 2 to 3 years. An interruption of the power supply or the shutdown of the cell usually leads to the destruction of the cell.
  • the sodium obtained by the Downs process due to the melt additives, has the disadvantage that it is primarily contaminated with calcium, the residual content of which is reduced by subsequent purification steps, but never completely removed.
  • the lithium obtained by the downs process a significant disadvantage is that the aqueous lithium chloride used in the chemical reaction of Lithium incurred, must be worked up before use in the electrolysis only to anhydrous lithium chloride.
  • Potassium is also an important inorganic base product used, for example, in the production of potassium alkoxides, potassium amides and potassium alloys.
  • the disadvantage is that the process operates at high temperatures.
  • the resulting potassium contains about 1% sodium as an impurity and must therefore be purified by another rectification.
  • the biggest disadvantage is that the sodium used is expensive. This is also due to the fact that sodium is obtained technically by electrolysis of molten common salt after the Downs process, which requires a great deal of energy.
  • GB 1,155,927 describes a process by which sodium metal can be obtained from sodium amalgam electrochemically using a solid sodium ion conductor with amalgam as the anode and sodium as the cathode.
  • the execution of in GB 1,155,927 does not lead to the results described there in terms of sodium conversion, product purity and current density.
  • the system described behaves unstable in the course of a few days, if the claimed temperature range is maintained.
  • the object of the present invention was to provide an electrolysis apparatus based on the method described in US Pat EP 1 114 883 A1 described method and the device disclosed therein and allows production of alkali metals on an industrial scale.
  • the electrolysis device according to the invention has the advantage that it is modular. At least two tubes arranged one above the other are connected to form an electrolysis unit through which a volumetric flow of alkali-metal-heavy metal alloy flows from the first to the last tube.
  • the number of tubes can be increased arbitrarily. Likewise, the number of electrolysis units used in parallel can be arbitrarily increased.
  • the electrolysis device according to the invention is intended for continuous operation. The flow of the liquid alkali metal heavy metal alloy is preferably driven by a pump located outside the electrolyzer.
  • the essentially horizontally arranged tubes, together with the solid electrolyte tubes inserted into them, form the reaction modules in which the electrolysis takes place.
  • the inventive design of the electrolysis device ensures that the alkali metal heavy metal alloy is guided so that the transport of the alkali metal dissolved in the heavy metal is ensured to the surface of the alkali metal ion conductive solid electrolyte for high current densities of an industrial production.
  • the electrolysis device according to the invention by the appropriate choice of material for the construction of the electrolysis device according to the invention a long life can be achieved, as is usual for devices of industrial chemistry.
  • the electrolysis can be interrupted at any time in the device according to the invention without damaging the device.
  • the device according to the invention is supplied with a liquid alkali metal heavy metal alloy, in particular an alkali metal amalgam with sodium, potassium or lithium as alkali metal.
  • a liquid alkali metal heavy metal alloy in particular an alkali metal amalgam with sodium, potassium or lithium as alkali metal.
  • Other possible heavy metals as part of the liquid alkali metal heavy metal alloy are gallium or lead or alloys of gallium, lead and mercury.
  • the sodium concentration of this solution In order to maintain sodium amalgam in liquid form, the sodium concentration of this solution must be less than 1% by weight, preferably 0.2 to 0.5% by weight. In order to maintain potassium amalgam in liquid form, the potassium concentration of the solution is less than 1.5% by weight, preferably 0.3 to 0.6% by weight. In order to keep lithium amalgam in liquid form, the lithium concentration of the solution is less than 0.19% by weight, preferably 0.02 to 0.06% by weight.
  • Stainless steel or graphite is preferably used as the material for the essentially horizontally arranged, interconnected tubes.
  • ceramic materials such as NASICON ® are used in the manufacture of sodium into consideration, the composition of which in the EP-A 0 553 400 is specified.
  • Sodium ion-conducting glasses are also suitable as well as zeolites and feldspars. In the production of potassium is also a variety of materials in question. Both the use of ceramics and the use of glasses are possible. For example, the following materials can be considered: KBiO 3 , gallium oxide-titanium dioxide-potassium oxide systems, alumina-titania-potassium oxide systems and KASICON ® glasses.
  • Callum ⁇ "-alumina, cate- ⁇ -alumina and potassium- ⁇ / ⁇ " -alumina, respectively, can be prepared from sodium ⁇ "-alumina, sodium ⁇ -alumina and sodium ⁇ / ⁇ " -alumina by cation exchange, respectively. In the production of lithium is also a variety of materials in question.
  • Li 4-x Si 1-x P x O 4 Li-beta "-Al 2 O 3, Li-beta-Al 2 O 3, lithium analogs of NASICON ® ceramics, lithium ion conductors with perovskite structure, and sulfidic glasses as lithium ion conductors.
  • the solid electrolyte tubes are closed on one side and preferably thin-walled, but pressure-resistant and designed with a circular cross-section.
  • the superposed, interconnected tubes have a length between 0.5 m and 2 m, preferably between 0.9 m and 1.1 m.
  • the inner diameter of the tubes is between 35 mm and 130 mm, preferably between 65 mm and 75 mm.
  • the tube thickness (wall thickness) is between 1 mm and 30 mm, preferably between 2.5 mm and 3.6 mm when using commercially available welded tubes, and preferably between 15 and 20 mm when the tube is made by casting.
  • the solid electrolyte tubes have an outer diameter between 30 mm and 100 mm, preferably between 55 mm and 65 mm.
  • the wall thickness of the solid electrolyte tubes is between 0.9 mm and 2.5 mm, preferably between 1.2 mm and 1.8 mm.
  • They have a length of between 20 cm and 75 cm, preferably between 45 cm and 55 cm.
  • the alkali metal heavy metal alloy passes through the alloy inlet into the first annular gap surrounding the solid electrolyte tubes.
  • the electrolysis is operated by applying an electric voltage between the outside of the solid electrolytic tube closed on one side composed of an alkali metal ion-conductive solid electrolyte and the inside so that the alkali metal heavy metal alloy flowing outside in the first annular gap in the longitudinal direction forms the positive pole the alkali metal formed forms the negative pole.
  • the voltage difference causes an electrolysis current, which causes alkali metal to be oxidized at the alkali metal-heavy metal alloy-ion conductor interface, then transported through the ionic conductor as the alkali metal ion, and then reduced back to metal at the ionic conductor-alkali metal interface in the solid electrolyte tube.
  • the alkali metal heavy metal alloy stream is continuously depleted in terms of its alkali metal content in proportion to the flowing electrolysis stream.
  • the thus transferred to the inside of the solid electrolyte tube alkali metal can be removed continuously from there via the alkali metal.
  • the electrolysis is carried out at a temperature in the range of 260 to 400 ° C.
  • the temperature should be below the boiling point of mercury, preferably at 310 ° C to 325 ° C if the alkali metal is sodium, and 265 ° C to 280 ° C if the alkali metal is potassium, and 300 ° C to 320 ° C if the alkali metal is lithium.
  • the alkali metal heavy metal alloy is already preheated to 200 ° C to 320 ° C, preferably preheated to 250 ° C to 280 ° C fed to the electrolysis apparatus according to the invention.
  • a heat exchanger in particular a countercurrent heat exchanger, be assigned to the electrolysis device, so that the depleted in relation to the alkali metal, leaving the last tube of the electrolyzer hot alkali metal heavy metal alloy heats the alloy inlet of the first tube.
  • Preheating of the alkali metal heavy metal alloy is also possible with the help of wound around the inlet heating wires.
  • the opening of the solid electrolyte tube is directed outward.
  • the closure device is designed with respect to the seals that the filled with alkali metal heavy metal alloy space in the substantially horizontal tubes to both the environment, as well as the interior of the solid electrolyte tube is sealed leak-free. Furthermore, the closure device also meets the requirement to seal the interior of the solid electrolyte tube against the environment.
  • the closure device is preferably at least partially releasably connected to the tube, so that the solid electrolyte tubes can be replaced easily in case of repair.
  • the electrolysis device preferably comprises 2 to 100 tubes, more preferably 5 to 25 tubes per electrolysis unit. It contains n electrolysis units arranged in parallel with n preferably between 1 and 100, more preferably between 5 and 20.
  • the electrolysis apparatus comprises an alloy distributor for supplying at least one electrolysis unit with the alkali metal heavy metal alloy, wherein the alloy distributor is connected to an electrolysis unit via an outlet connection in each case.
  • the alkali metal heavy metal alloy level in the alloy manifold is preferably kept constant.
  • the alloy manifold is constantly half filled with liquid alkali metal heavy metal alloy.
  • n outlet nozzles each of which opens into an electrolysis unit designed as a series-connected pipe system. The alkali metal heavy metal alloy volume flow entering the alloy manifold is thus divided into n parallel individual volume flows.
  • the alloy feed and the alloy run are arranged on the tubes so that the alkali metal heavy metal alloy is passed as a meandering current through the electrolysis unit.
  • the alkali metal heavy metal alloy runs through an electrolysis unit comprising a pipe system of substantially horizontally arranged pipes, wherein it flows from a pipe via its disposed on one side alloy flow in the next lower pipe on its arranged on the same side alloy inlet, then flows through it horizontally in order to leave it again down over the arranged on the other side alloying flow and flow to the next substantially horizontal pipe.
  • the electrolyzer includes an alloy collector for receiving the alkali metal heavy metal alloy passed through the electrolysis unit, which alloy collector may be connected to the alloy manifold for at least partial recycling of the alkali metal heavy metal alloy.
  • the recycled, with respect to the alkali metal Depleted alkali metal heavy metal alloy is mixed in the alloy manifold with alkali metal-enriched alkali metal heavy metal alloy.
  • alloy dispenser is constantly and exclusively supplied with enriched alkali metal heavy metal alloy and the alkali metal heavy metal alloy depleted in the electrolysis unit is collected in the alloy collector and not recycled.
  • alkali metal is removed according to the invention via the alkali metal.
  • the alkali metal effluent is connected via a discharge with an alkali metal collector into which the discharge from its top opens.
  • the alkali metal collector is preferably in the form of a collecting trough with a lid.
  • the introduction of the alkali metal into the alkali metal collector from its top has the advantage that the alkali metal can not flow back from the alkali metal collector via the discharge into the electrolysis unit, for example in the case of a broken solid electrolyte tube. Backflow could result in the destruction of the entire electrolysis unit, as the recycle alkali metal would come into contact with alkali metal heavy metal alloy and an exothermic backreaction would occur.
  • the liquid alkali metal passes through heated pipes in storage tanks.
  • the alkali metal collector is located higher than the alloy manifold and / or the alkali metal collector contains an inert gas having an increased pressure relative to the environment. This has the advantage that, for example, in the case of a broken solid electrolyte tube, no alkali metal heavy metal alloy can get to the alkali metal contained in the alkali metal collector.
  • the inert gas preferably has an overpressure between 0.2 bar and 10 bar, more preferably 1 bar.
  • the alkali metal is transported by the pressure of the emerging in the interior of the solid electrolyte tube alkali metal against the inert gas pressure and / or against the resulting due to the height difference between the alkali metal source and the alkali metal collector forces in the alkali metal collector.
  • each tube and each solid electrolyte tube has a separate electrical connection. This ensures that when the interruption of an electrical connection, the electrolysis device is not completely put out of action, but only locally a pipe or a solid electrolyte tube.
  • each of the closure devices preferably contains an alkali metal drain and an electrical connection for the cathode.
  • the electrical power supply of the cathode can be carried out, for example, via the alkali metal drain designed as an electrically conductive discharge tube.
  • the electrical connection for the cathode of a multiplicity of solid electrolyte tubes contained in an electrolysis unit preferably extends via an elastic, electrically conductive band which contacts a negative bridge.
  • the negative bridge is an electrically conductive component which is connected to the negative pole of a voltage source. It is connected to the electrical connection of the cathode in the interior of each of the plurality of solid electrolyte tubes via an elastic, electrically conductive band.
  • the band is elastic to compensate for different thermal expansion properties of the negative bridge and the electrical connection. Furthermore, the band can be designed as a fuse, which is destroyed in the case of too high current through the heat generated.
  • Each electrically conductive band may further comprise an individual electrical resistance designed to apply the same voltage to each tube.
  • the alkali metal collector is electrically insulated from the interior of the respective solid electrolyte tube. This is achieved, for example, in that the respective pipe lead through which the discharge opens into the top of the alkali metal collector is made electrically insulated, so that between the individual alkali metal sources, all of which are connected via their discharge to the alkali metal collector, and between the respective Alkali metal source and the alkali metal collector is an electrical potential separation. This is possible only because the alkali metal drips from the top into the alkali metal collector (filled, for example, with nitrogen) and does not form a continuous liquid thread. In case of breakage of a solid electrolyte tube, such as. a short circuit of the affected leads avoided.
  • the electrical terminal for the anode passes over the tube which contacts a positive bridge.
  • the positive bridge is an electrically conductive component which is connected to the positive pole of a voltage source. It may for example be designed as a flat bar with a plurality of balcony-like projections, wherein in each case a tube rests on a projection and supported by this on the one hand and on the other hand is electrically contacted. In the case of the plus bridge, this is preferably a massive steel construction that can take on this dual function. However, the plus bridge may also be an additional non-supporting aluminum rail which is connected to the pipes via elastic, electrically conductive bands.
  • a displacement body is arranged in the interior of each of the solid electrolyte tubes so that there is a second annular gap for receiving the liquid alkali metal between the outside of the displacement body and the inside of the solid electrolyte tube.
  • a displacement body can serve a solid metal body.
  • This metal body has the further advantage that it can be used as a cathode when the electrolysis is started with a solid electrolyte tube not yet filled with alkali metal.
  • As a displacement body but can also serve a closed hollow body. This hollow body has the advantage that it can be more easily inserted into the solid electrolyte tube due to its lower weight, without damaging them.
  • As a displacement body can serve a one-sided closed, exactly to the shape of the interior of the solid electrolyte tube adapted thin-walled sheet metal tube, which is inserted into the solid electrolyte tube, so that forms a very narrow second annular gap. In the thin-walled sheet metal tube, another body can be used for reinforcement.
  • the displacement body designed as a sheet metal tube has the advantage that the amount of alkali metal that is mixed in the failure of the solid electrolyte tube with alkali metal heavy metal alloy, is very low.
  • a heated with thermal air, thermally insulated heating chamber surrounds the tubes with the closure devices.
  • the electrolyzer is thereby brought to the temperature required in the electrolysis, that it is installed in the circulating heated, against the environment thermally insulated heating chamber.
  • the heating can be done by electrical means or with oil or gas burners.
  • heating is only necessary when starting the electrolysis or in phases in which the electrolysis is interrupted.
  • a cooling of the electrolysis device according to the invention can be done by the heating chamber ambient air supplied and hot exhaust air is removed.
  • the invention further relates to the use of the electrolysis apparatus according to the invention for the production of sodium, potassium or lithium from a liquid alkali metal amalgam.
  • Figure 1 shows schematically an electrolysis device according to the invention with a plurality of electrolysis units.
  • the electrolysis apparatus comprises a multiplicity of pipes 1, which are arranged one above the other substantially horizontally and are interconnected, which form an electrolysis unit 2.
  • the tubes 1 within an electrolysis unit 2 are connected to each other via connecting pieces 3.
  • the tubes 1 different electrolysis units 2 have no connection with each other.
  • At the ends of each tube 1 closure devices 4 are arranged, which are each connected to a connecting piece 3.
  • An alloy distributor 5 is filled up to approximately half with liquid alkali metal heavy metal alloy 6 and supplies the n electrolysis units 2 via an outlet nozzle 7 with the alkali metal heavy metal alloy 6.
  • the outlet nozzle 7 discharges into a Alloy inlet 8 of a tube 1, which is located near one end of the tube 1.
  • the tube 1 in the first annulus, not shown
  • the alkali metal heavy metal alloy 6 is thus guided as a meandering current through the electrolysis unit 2.
  • an alloy collector 10 receives the alkaline metal heavy metal depleted by the electrolysis with respect to the alkali metal, which is either returned to the electrolyzer or discharged into a storage vessel.
  • the alkali metal resulting from the electrolysis is withdrawn at each end of the tube 1 by an alkali metal effluent (not shown).
  • FIG. 2 shows a further schematic illustration of an electrolysis device according to the invention.
  • each tube 1 there are three superimposed tubes 1 an electrolysis unit 2 shown.
  • each tube 1 are two closed at one end, at the other end an opening 11 having solid electrolyte tubes 12 are present.
  • the solid electrolyte tubes 12 are arranged concentrically in the tube 1 and with the opening 11 each one end of the tube 1 faces.
  • a first annular gap 13 Between the inside of the tube 1 and the outside of the solid electrolyte tubes 12 is a first annular gap 13 for guiding the anodes forming liquid alkali metal heavy metal alloy 6, which passes from the alloy manifold 5 via the outlet port 7 and the alloy inlet 8 in the uppermost tube 1 and through the annular gap 13 along the solid electrolyte tubes 12 to the alloy outlet 9, which opens into a connecting piece 3, flows.
  • Each shutter 4 serves as a support for a solid electrolyte tube 12 which is detachable, so that a defective solid electrolyte tube 12 can be easily exchanged.
  • the inner space 14 of the solid electrolyte tube 12 is sealed against the alkali metal heavy metal alloy leading parts of the electrolysis unit 2, in particular with respect to the alloy inlet 8, the first annular gap 13 and the alloy outlet 9 of the tube 1, in which the solid electrolyte tube 12 is located.
  • the interior space 14 serves to absorb liquid alkali metal formed there during the electrolysis, which can be used as the cathode of the electrolysis device.
  • the interior space 14 is connected to an alkali metal outlet 15, which via a discharge line 16 directs the alkali metal 22 to an alkali metal collector 17 positioned above the alloy distributor 5.
  • the alkali metal collector 17 is preferably filled with an inert gas under pressure.
  • the alkali metal collector 17 is in the embodiment of the present invention shown in Figure 2 as a collecting channel 18 with a Lid 19 designed, the derivative 16 opens from the top through the lid 19 in the alkali metal collector 17.
  • the alkali metal heavy metal alloy 6 does not get into the alkali metal collector 17. Therefore, the failure of the electrolysis apparatus according to the invention is tolerated without the electrolysis must be interrupted and without causing consequential damage or loss of quality in the alkali metal produced. With the undamaged solid electrolyte tubes 12, the electrolysis can be continued.
  • FIG. 3 shows an embodiment of an electrolysis unit with its electrical connections.
  • the electrolysis unit 2 is again formed by a plurality of tubes 1.
  • Each tube 1 and each solid electrolyte tube 12 (not shown) has a separate electrical connection.
  • Each closure device 4 contains an alkali metal outlet 15 and an electrical connection for the cathode.
  • the electrical connection for the cathode in all solid electrolyte tubes 12 on one side of the tubes 1 by means of a lying on negative electrical potential first negative bridge 20, which is connected via one elastic electrically conductive band 21 to each one designed as a metal tube alkali metal outlet 15.
  • the electrically conductive band is indicated in Figure 3 only for a tube 1, but also designed for all other tubes.
  • a second negative bridge 23 is connected to the cathodes on the other side of the tubes 1.
  • the alkali metal leading part of the closure device 4 is electrically isolated from the leading part of the alkali metal-heavy metal alloy.
  • the positive bridge 24 is used in addition to the electrical contact for the production of the individual tubes 1 (see Figure 4) and is attached by means of a suspension 25 to a supporting frame.
  • FIG. 4 shows an embodiment of the present invention with multiple plus bridges for multiple electrolysis units.
  • the tubes 1 of the five illustrated electrolysis units 2 each lie on a projection 26 of a positive bridge 24 and are thus supported on the one hand and on the other hand electrically contacted.
  • the plus bridge 24 with the projections 26 is preferably a solid steel construction.
  • FIG. 5 shows a detail of two tubes arranged one above the other.
  • the first annular gap 13 can be seen, which surrounds the solid electrolyte tube 12.
  • the interior of the solid electrolyte tube 12 is almost completely filled by a displacement body 27, so that only a second annular gap 28 between the outside of the displacement body 27 and the inside of the solid electrolyte tube 12 remains free for the resulting alkali metal.
  • the alkali metal is forced by the newly formed alkali metal in serving as alkali metal drain hole 29 29 of the closure device 4.
  • the alkali metal heavy metal alloy 6 flows through the first annular gap 13 of the upper tube via a sieve 31 and an annular space 30 in the connecting piece 3 and from there into the lower tube.
  • This geometric design in which the connecting pieces 3 open into an annular space 30, which is separated from the respective first annular gap 13 by a circumferential sieve 31, is advantageous for the distribution of the alkali metal-heavy metal alloy flow over the cross section of the first annular gap serving as a reaction zone 13. Furthermore, this arrangement prevents disturbing solid particles from entering the reaction zone and leading to blockages there.
  • the production of the electrolysis unit shown in detail in Figure 5 is carried out by welding of turned parts to the welds 32 shown. But it is also the one-piece production of these parts by metal casting possible.

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  • Chemical Kinetics & Catalysis (AREA)
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Claims (14)

  1. Dispositif d'électrolyse pour la préparation d'un métal alcalin à partir d'un alliage liquide métal alcalin-métal lourd (6), caractérisé par :
    - au moins deux tubes (1) reliés les uns aux autres à l'aide de piliers de liaison (3), agencés de manière essentiellement horizontale les uns au-dessus des autres, qui forment une unité d'électrolyse (2),
    - deux tubes d'électrolyte solide (12) agencés dans chacun des tubes (1), fermés à une extrémité, présentant une ouverture (11) à l'autre extrémité, qui conduisent des ions métalliques alcalins, les tubes d'électrolyte solide (12) étant agencés de manière concentrique dans le tube (1) et ayant l'ouverture (11) dirigée vers respectivement une extrémité du tube (1), de sorte qu'une première fente annulaire (13) devant amener l'alliage liquide métal alcalin-métal lourd (6) formant une anode se trouve entre la face intérieure du tube (1) et la face extérieure des tubes d'électrolyte solide (12),
    - une arrivée d'alliage (8) et un écoulement d'alliage (9) pour l'alliage liquide métal alcalin-métal lourd (6) présents dans chacun des tubes (1), et qui débouchent dans la première fente annulaire (13) d'un tube (1) par le haut ou bien par le bas en étant écartés horizontalement l'un de l'autre,
    - un espace intérieur (14), obturé vis-à-vis de l'arrivée d'alliage (8), de la première fente annulaire (13) et de l'écoulement d'alliage (9), présent dans chacun des tubes (12) pour recevoir le métal alcalin liquide pouvant être utilisé en tant que cathode, et qui est relié à un écoulement de métal alcalin (15), et
    - respectivement deux dispositifs d'obturation (4) qui sont agencés aux deux extrémités de chaque tube (1) .
  2. Dispositif d'électrolyse selon la revendication 1, comportant 2 à 100 tubes (1) dans une unité d'électrolyse (2) et
    n unités d'électrolyse (2) agencées de manière parallèle, avec n = 1 à 100.
  3. Dispositif d'électrolyse selon l'une des revendications 1 ou 2, caractérisé par un répartiteur d'alliage (5) pour l'alimentation d'au moins une unité d'électrolyse (2) avec l'alliage métal alcalin-métal lourd (6), le répartiteur d'alliage (5) étant relié avec une unité d'électrolyse (2) par l'intermédiaire de respectivement un pilier d'évacuation (7).
  4. Dispositif d'électrolyse selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'arrivée d'alliage (8) et l'écoulement d'alliage (9) sont agencés sur les tubes (1) de sorte que l'alliage métal alcalin-métal lourd (6) est guidé à travers l'unité d'électrolyse (2) en tant que flux formant des méandres.
  5. Dispositif d'électrolyse selon l'une quelconque des revendications 1 à 4, caractérisé par un collecteur d'alliage (10) pour la réception de l'alliage métal alcalin-métal lourd (6) ayant circulé à travers l'unité d'électrolyse (2), le collecteur d'alliage (10) étant relié avec le répartiteur d'alliage (5) pour une remise en circulation au moins partielle de l'alliage métal alcalin-métal lourd (6).
  6. Dispositif d'électrolyse selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'écoulement de métal alcalin (15) est relié avec un collecteur de métal alcalin (17) par l'intermédiaire d'une dérivation (16), dans lequel la dérivation (16) débouche au niveau de sa face supérieure, le collecteur de métal alcalin (17) est agencé plus haut que le répartiteur d'alliage (5).
  7. Dispositif d'électrolyse selon la revendication 6, caractérisé en ce que le collecteur de métal alcalin (17) contient un gaz inerte ayant une pression augmentée par rapport au milieu ambiant.
  8. Dispositif d'électrolyse selon la revendication 6 ou 7, caractérisé en ce que le collecteur de métal alcalin (17) est isolé électriquement par rapport à l'espace intérieur (14) des tubes d'électrolyte solide (12).
  9. Dispositif d'électrolyse selon l'une quelconque des revendications 1 à 8, caractérisé en ce que chaque tube (1) et tous les tubes d'électrolyte solide (12) présentent un raccordement électrique séparé.
  10. Dispositif d'électrolyse selon l'une quelconque des revendications 1 à 9, caractérisé en ce que chacun des dispositifs d'obturation (4) comporte un écoulement de métal alcalin (15) et un raccordement électrique pour la cathode, le raccordement électrique pour la cathode d'une pluralité de tubes d'électrolyte solide (12) contenus dans une unité d'électrolyse (2) passant par respectivement une lame (21) élastique électriquement conductrice, qui est connectée à un pont négatif (20, 23), chaque lame (21) électriquement conductrice présentant une résistance électrique individuelle conçue de sorte que la même tension soit appliquée à chaque tube (1).
  11. Dispositif d'électrolyse selon la revendication 10, caractérisé en ce que le raccordement électrique pour l'anode passe par le tube (1), qui est connecté à un pont positif (24).
  12. Dispositif d'électrolyse selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'un corps de refoulement (27) est agencé dans l'espace intérieur de chacun des tubes d'électrolyte solide (12) de sorte qu'une deuxième fente annulaire (28) destinée à la réception du métal alcalin liquide se trouve entre la face extérieure du corps de refoulement (27) et la face intérieure des tubes d'électrolyte solide (12).
  13. Dispositif d'électrolyse selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'une chambre de chauffage thermiquement isolée, chauffée par circulation d'air, entoure les tubes (1) avec les dispositifs d'obturation (4).
  14. Utilisation d'un dispositif d'électrolyse selon l'une quelconque des revendications 1 à 13 pour la préparation de sodium, de potassium ou de lithium à partir d'un amalgame liquide de métal alcalin.
EP05784834A 2004-09-14 2005-09-13 Dispositif d'electrolyse destine a la fabrication de metal alcalin Not-in-force EP1789608B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004044404A DE102004044404A1 (de) 2004-09-14 2004-09-14 Elektrolysevorrichtung zur Herstellung von Alkalimetall
PCT/EP2005/009820 WO2006029807A2 (fr) 2004-09-14 2005-09-13 Dispositif d'electrolyse destine a la fabrication de metal alcalin

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EP1789608A2 EP1789608A2 (fr) 2007-05-30
EP1789608B1 true EP1789608B1 (fr) 2008-01-09

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EP (1) EP1789608B1 (fr)
KR (1) KR101274851B1 (fr)
CN (1) CN101018892B (fr)
AR (1) AR053764A1 (fr)
AT (1) ATE383458T1 (fr)
DE (2) DE102004044404A1 (fr)
ES (1) ES2299087T3 (fr)
TW (1) TW200622039A (fr)
WO (1) WO2006029807A2 (fr)

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JP4752932B2 (ja) * 2009-02-25 2011-08-17 株式会社デンソー 送信装置、受信装置、及び送受信装置
US8679668B2 (en) * 2010-06-22 2014-03-25 Basf Se Industrial apparatus for the large-scale storage of electric energy
US9957625B2 (en) 2012-06-11 2018-05-01 Basf Se Electrode unit
TWI545230B (zh) * 2014-09-10 2016-08-11 林信湧 液體電解裝置
US9593031B1 (en) * 2015-08-12 2017-03-14 Jeffrey A. Ogden Chlorine generator
WO2017029333A1 (fr) * 2015-08-18 2017-02-23 Thyssenkrupp Uhde Chlorine Engineers Gmbh Procédé de production d'un tube collecteur de milieux

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GB1155927A (en) 1967-02-20 1969-06-25 Ici Ltd Electrolytic manufacture of alkali metals.
US4089770A (en) * 1977-07-11 1978-05-16 E. I. Du Pont De Nemours And Company Electrolytic cell
DE19859563B4 (de) * 1998-12-22 2008-01-24 Basf Ag Verbessertes Verfahren zur elektrochemischen Herstellung von Alkalimetall aus Alkalimetallamalgam
DE19914221A1 (de) * 1999-03-29 2000-10-05 Basf Ag Verbessertes Verfahren zur elektrochemischen Herstellung von Lithium
DE19926724A1 (de) * 1999-06-11 2000-12-14 Basf Ag Elektrolysezelle zur Herstellung eines Alkalimetalls

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ATE383458T1 (de) 2008-01-15
DE502005002528D1 (de) 2008-02-21
US8114258B2 (en) 2012-02-14
US20080053837A1 (en) 2008-03-06
EP1789608A2 (fr) 2007-05-30
DE102004044404A1 (de) 2006-03-30
WO2006029807A3 (fr) 2006-06-29
KR20070053338A (ko) 2007-05-23
AR053764A1 (es) 2007-05-23
WO2006029807A2 (fr) 2006-03-23
TW200622039A (en) 2006-07-01
KR101274851B1 (ko) 2013-06-13
ES2299087T3 (es) 2008-05-16
CN101018892B (zh) 2010-05-05
CN101018892A (zh) 2007-08-15

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