EP1789608B1 - Electrolysis device for the production of alkali metal - Google Patents

Electrolysis device for the production of alkali metal 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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EP05784834A
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German (de)
French (fr)
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EP1789608A2 (en
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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Description

Die vorliegende Erfindung betrifft eine Elektrolysevorrichtung zur Herstellung von Alkalimetall aus einer flüssigen Alkalimetall-Schwermetalllegierung.The present invention relates to an electrolyzer for producing alkali metal from a liquid alkali metal heavy metal alloy.

Im Zusammenhang mit der vorliegenden Erfindung sind unter einen Alkalimetall insbesondere Natrium, Kalium oder Lithium zu verstehen.In the context of the present invention, an alkali metal is to be understood as meaning in particular sodium, potassium or lithium.

Natrium ist ein wichtiges anorganisches Grundprodukt, das u.a. zur Herstellung von Natrium-Verbindungen wie zum Beispiel Natriumperoxid, Natriumhydrid, Natriumboranat und Natriumamid, zur Titangewinnung durch Metallothermie, sowie zu Reduktionszwecken in der organischen chemischen Industrie, zur Reinigung von Kohlenwasserstoffen und Altöl, zu Kondensationen, zur Alkoxidherstellung, als Polymerisationskatalysator und in der präparativen organischen Chemie eingesetzt wird. Die Natriumgewinnung erfolgt heute hauptsächlich nach dem Downs-Verfahren durch Schmelzflusselektrolyse eines ternären Gemisches aus NaCl, CaCl2 und BaCl2.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 findet u.a. Verwendung in der Kerntechnik zur Herstellung von Tritium, als Legierungszusatz zu Aluminium, Blei oder Magnesium, bei organischen Synthesen, zur Synthese komplexer Metallhydride, zur Herstellung metallorganischer Verbindungen, für Kondensationen, Dehydrohalogenierungen, zur Herstellung ternärer Amine oder quarnären Ammoniumsalzen, in der Mineralölindustrie als Katalysator und zur Entschwefelung, zur Polymerisation von Isopren zu cis-Polymeren, in der Keramikindustrie zur Regelung des Ausdehnungskoeffizienten, Senkung der Schmelztemperatur und dergleichen, zur Herstellung von Schmiermitteln, als Desoxidations- und Reinigungsmittel bei der Metallurgie von Eisen, Nickel, Kupfer und deren Legierungen. Lithium wird im Stand der Technik im industriellen Maßstab ebenfalls nach dem Downs-Prozess durch Elektrolyse von wasserfreien Alkalichloridschmelzen hergestellt, wobei die Schmelzpunkte der Salzschmelzen durch Zusätze von Alkalichloriden herabgesetzt werden.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.

Bei beiden Metallen, Natrium und Lithium, ist die Standzeit der bekannten Elektrolysezellen auf 2 bis 3 Jahre begrenzt. Eine Unterbrechung der Stromversorgung oder das Abstellen der Zelle führt in der Regel zur Zerstörung der Zelle. Das nach dem Downs-Prozess gewonnene Natrium hat, bedingt durch die Schmelzzusätze, den Nachteil, dass es primär mit Kalzium verunreinigt ist, dessen Restgehalt durch nachträgliche Reinigungsschritte zwar vermindert, aber niemals völlig entfernt werden kann. Bei dem nach dem Downs-Prozess gewonnenen Lithium besteht ein wesentlicher Nachteil darin, dass die wässrigen Lithiumchloridsolen, die bei der chemischen Umsetzung von Lithium anfallen, vor dem Einsatz in der Elektrolyse erst zum wasserfreien Lithiumchlorid aufgearbeitet werden müssen.For both metals, sodium and lithium, 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. In 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.

Kalium ist ebenfalls ein wichtiges anorganisches Grundprodukt, das beispielsweise für die Herstellung von Kaliumalkoholaten, Kaliumamiden und von Kaliumlegierungen verwendet wird. Heute wird es technisch vor allem durch Reduktion von Kaliumchlorid durch Natrium in einer Reaktivdestillation hergestellt. Nachteilig ist, dass das Verfahren bei hohen Temperaturen arbeitet. Außerdem enthält das entstehende Kalium ca. 1% Natrium als Verunreinigung und muss daher noch durch eine weitere Rektifikation aufgereinigt werden. Der größte Nachteil ist, dass das eingesetzte Natrium teuer ist. Dies liegt auch daran, dass Natrium technisch nach dem Downs-Prozess durch Elektrolyse von geschmolzenem Kochsalz gewonnen wird, wobei ein hoher Energieaufwand nötig ist.Potassium is also an important inorganic base product used, for example, in the production of potassium alkoxides, potassium amides and potassium alloys. Today it is technically produced mainly by reduction of potassium chloride by sodium in a reactive distillation. The disadvantage is that the process operates at high temperatures. In addition, 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.

Alkalimetallamalgame fallen bei der Chloralkalielektrolyse nach dem Amalgamverfahren als Zwischenstufe in großen Mengen an und werden in der Regel mit Wasser zu Alkalimetalllaugen umgesetzt und dann im geschlossenen Kreislauf in die Chloralkalielektrolyse zurückgeführt.Alkalimetallamalgame fall in the chloralkali electrolysis by the amalgam process as an intermediate in large quantities and are usually reacted with water to form alkali metal and then recycled in a closed circuit in the Chloralkalielektrolyse.

GB 1,155,927 beschreibt ein Verfahren, nach welchem unter Einsatz eines festen Natriumionenleiters mit Amalgam als Anode und Natrium als Kathode auf elektrochemischem Wege Natriummetall aus Natriumamalgam gewonnen werden kann. Die Ausführung des in GB 1,155,927 beschriebenen Verfahrens führt aber nicht zu den dort beschriebenen Ergebnissen hinsichtlich Natriumumsatz, Produktreinheit und Stromdichte. Ferner verhält sich das beschriebene System im Verlauf weniger Tage instabil, wenn der beanspruchte Temperaturbereich eingehalten wird. 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 However, the method described does not lead to the results described there in terms of sodium conversion, product purity and current density. Furthermore, the system described behaves unstable in the course of a few days, if the claimed temperature range is maintained.

EP 1 114 883 A1 beschreibt ein gegenüber dem in Dokument GB 1,155,927 beschriebenen Verfahren verbessertes Verfahren zur Herstellung eines Alkalimetalls ausgehend von Alkalimetallamalgam. Die Herstellung erfolgt bei diesem Verfahren durch Elektrolyse mit einer Alkaliamalgam enthaltenden Anode, einem Alkalimetallionen-leitenden Festelektrolyt und flüssigem Alkalimetall als Kathode, wobei das Alkaliamalgam als Anode bewegt wird. Die Elektrolyse wird dabei in einer Elektrolysezelle durchgeführt, die einen einseitig geschlossenen rohrförmigen Festelektrolyten umfasst, der in ein konzentrisches Edelstahlrohr derart eingebaut ist, dass ein Ringspalt entsteht. Dieses Verfahren, durchgeführt in dieser Elektrolysezelle, hat gegenüber dem oben erläuterten Stand der Technik, insbesondere gegenüber der Alkalimetall-Herstellung nach dem Downs-Prozess, folgende Vorteile:

  • Die Zelle erlaubt einen Prozess mit einem um 40% geringeren Energiebedarf, die Vorstufe dabei eingeschlossen, bedingt durch die höhere Stromausbeute aufgrund der verhinderten Rückreaktion und durch die geringe Zellspannung.
  • Die Zelle hat keine prozessbedingte Limitierung der Lebensdauer.
  • Es ist Teillast oder gar die Unterbrechung der Produktion möglich.
  • Es werden nur flüssige Stoffe eingesetzt und erzeugt, die leicht zu dosieren sind.
  • Die Salze werden in der Vorstufe des beschriebenen Prozesses als wässrige Solen eingesetzt.
  • Der Apparat läuft voll automatisch.
  • Es werden hochreine Alkalimetalle erzeugt.
  • Es sind keine zusätzlichen Reinigungsschritte mehr erforderlich.
EP 1 114 883 A1 describes one opposite to the one in the document GB 1,155,927 method described improved method for producing an alkali metal starting from alkali metal amalgam. The preparation is carried out in this method by electrolysis with an alkali metal amalgam-containing anode, an alkali metal ion-conductive solid electrolyte and liquid alkali metal as a cathode, wherein the alkali metal amalgam is moved as an anode. The electrolysis is carried out in an electrolytic cell comprising a tubular solid electrolyte closed on one side, which is installed in a concentric stainless steel tube such that an annular gap is formed. This method, carried out in this electrolysis cell, has the following advantages over the prior art explained above, in particular as compared to the alkali metal preparation according to the Downs process:
  • The cell allows a process with a 40% lower energy consumption, the precursor included, due to the higher current efficiency due to the prevented back reaction and the low cell voltage.
  • The cell has no process-related limitation of the lifetime.
  • Partial load or even interruption of production is possible.
  • Only liquid substances are used and produced that are easy to dose.
  • The salts are used in the preliminary stage of the process described as aqueous sols.
  • The device runs fully automatically.
  • It produces high purity alkali metals.
  • There are no additional cleaning steps required.

Aufgabe der vorliegenden Erfindung war es, eine Elektrolysevorrichtung bereitzustellen, die auf dem in der EP 1 114 883 A1 beschriebenen Verfahren und der darin offenbarten Vorrichtung basiert und eine Herstellung von Alkalimetallen im industriellen Maßstab ermöglicht.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.

Diese Aufgabe wird erfindungsgemäß gelöst durch eine Elektrolysevorrichtung zur Herstellung von Alkalimetall aus einer flüssigen Alkalimetall-Schwermetalllegierung, gekennzeichnet durch

  • mindestens zwei übereinander im Wesentlichen horizontal angeordnete, durch Verbindungsstutzen miteinander verbundene Rohre, die eine Elektrolyseeinheit bilden,
  • zwei in jedem der Rohre angeordnete, an einem Ende geschlossene, an dem anderen Ende eine Öffnung aufweisende Festelektrolytröhren, die Alkalimetallionen leiten, wobei die Festelektrolytröhren in dem Rohr konzentrisch angeordnet und mit der Öffnung je einem Ende des Rohrs zugewandt sind, so dass sich ein erster Ringspalt zur Führung der eine Anode bildenden flüssigen Alkalimetall-Schwermetalllegierung zwischen der Innenseite des Rohrs und der Außenseite der Festelektrolytröhren befindet,
  • einen Legierungszulauf und einen Legierungsablauf für die flüssige Alkalimetall-Schwermetalllegierung in jedem der Rohre, die zueinander horizontal beabstandet von oben beziehungsweise von unten in den ersten Ringspalt eines Rohres münden,
  • einen gegenüber dem Legierungszulauf, dem ersten Ringspalt und dem Legierungsablauf abgedichteten Innenraum in jeder der Festelektrolytröhren zur Aufnahme von dem als Kathode nutzbaren flüssigen Alkalimetall; der mit einem Alkalimetallablauf verbunden ist und
  • je zwei Verschlussvorrichtungen, die an den zwei Enden jedes Rohres angeordnet sind.
This object is achieved by an electrolyzer for the production of alkali metal from a liquid alkali metal heavy metal alloy, characterized by
  • at least two tubes arranged one above the other substantially horizontally and interconnected by connecting sockets, which form an electrolysis unit,
  • two solid electrolyte tubes arranged in each of the tubes, closed at one end and having an opening at the other end, conducting alkali metal ions, the solid electrolyte tubes being concentrically disposed within the tube and facing each end of the tube with the opening such that a first one Annular gap for guiding the anodes forming liquid alkali metal heavy metal alloy between the inside of the tube and the outside of the solid electrolyte tubes,
  • an alloy inlet and an alloy outlet for the liquid alkali metal heavy metal alloy in each of the tubes, which open to each other horizontally spaced from above or from below into the first annular gap of a pipe,
  • an inner space sealed to the alloy inlet, the first annular gap and the alloy outlet in each of the solid electrolyte tubes for receiving the liquid alkali metal usable as a cathode; which is connected to an alkali metal effluent and
  • two closure devices each, which are arranged at the two ends of each tube.

Die erfindungsgemäße Elektrolysevorrichtung hat den Vorteil, dass sie modular aufgebaut ist. Es sind mindestens zwei übereinander angeordnete Rohre zu einer Elektrolyseeinheit verbunden, die durch einen Volumenstrom aus Alkalimetall-Schwermetalllegierung vom ersten bis zum letzten Rohr durchströmt wird. Die Anzahl der Rohre kann dabei beliebig erhöht werden. Ebenso kann die Anzahl der parallel eingesetzten Elektrolyseeinheiten beliebig vergrößert werden. Die erfindungsgemäße Elektrolysevorrichtung ist für den kontinuierlichen Betrieb vorgesehen. Die Strömung der flüssigen Alkalimetall-Schwermetalllegierung wird vorzugsweise durch eine außerhalb der Elektrolysevorrichtung liegende Pumpe angetrieben. Die im Wesentlichen waagerecht angeordneten Rohre bilden zusammen mit den in sie eingeschobenen Festelektrolytröhren die Reaktionsmodule, in denen die Elektrolyse stattfindet. Durch den erfindungsgemäßen Aufbau der Elektrolysevorrichtung wird sichergestellt, dass die Alkalimetall-Schwermetalllegierung so geführt wird, dass der Transport des in dem Schwermetall gelösten Alkalimetalls an die Oberfläche des Alkalimetallionen leitenden Festelektrolyten für hohe Stromdichten einer industriellen Produktion gewährleistet ist.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.

Ferner kann durch die geeignete Werkstoffauswahl für die Konstruktion der erfindungsgemäßen Elektrolysevorrichtung eine lange Standzeit erreicht werden, wie es für Vorrichtungen der industriellen Chemie üblich ist. Die Elektrolyse kann bei der erfindungsgemäßen Vorrichtung jederzeit unterbrochen werden, ohne die Vorrichtung zu schädigen.Furthermore, 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.

Der erfindungsgemäßen Vorrichtung wird eine flüssige Alkalimetall-Schwermetalllegierung zugeführt, insbesondere ein Alkalimetallamalgam mit Natrium, Kalium oder Lithium als Alkalimetall. Weitere mögliche Schwermetalle als Bestandteil der flüssigen Alkalimetall-Schwermetalllegierung sind Gallium oder Blei oder Legierungen aus Gallium, Blei und Quecksilber.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. 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.

Um Natriumamalgam in flüssiger Form zu halten, muss die Natriumkonzentration dieser Lösung Werte von weniger als 1 Gew.-%, bevorzugt 0,2 bis 0,5 Gew.-% aufweisen. Um Kaliumamalgam in flüssiger Form zu halten, liegt die Kaliumkonzentration der Lösung bei weniger als 1,5 Gew.-%, vorzugsweise 0,3 bis 0,6 Gew.-%. Um Lithiumamalgam in flüssiger Form zu halten, liegt die Lithiumkonzentration der Lösung bei weniger als 0,19 Gew.-%, vorzugsweise 0,02 bis 0,06 Gew.-%.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.

Als Material für die im Wesentlichen horizontal angeordneten, miteinander verbundenen Rohre wird vorzugsweise Edelstahl oder Graphit gewählt. Als Material für die Festelektrolytröhren kommen bei der Natriumherstellung keramische Materialien wie NASICON® in Betracht, deren Zusammensetzung in der EP-A 0 553 400 angegeben ist. Auch Natriumionen-leitende Gläser sind geeignet sowie Zeolithe und Feldspate. Bei der Herstellung von Kalium kommt ebenfalls eine Vielzahl von Materialien in Frage. Sowohl die Verwendung von Keramiken als auch die Verwendung von Gläsern sind möglich. Beispielsweise kommen folgende Materialien in Betracht: KBiO3, Galliumoxid-Titandioxid-Kaliumoxid-Systeme, Aluminiumoxid-Titandioxid-Kaliumoxid-Systeme und KASICON®-Gläser. Bevorzugt sind jedoch Natrium-β"-Aluminiumoxid, Natrium-β-Aluminiumoxid und Natrium-β/β"-Aluminiumoxid beziehungsweise Kalium-β"-Aluminiumoxid, Katium-β-Aluminiumoxid und Kalium-β/β"-Aluminiumoxid. Kallum-β"-Aluminiumoxid, Katium-β-Aluminiumoxid beziehungsweise Kalium-β/β"-Aluminiumoxid können ausgehend von Natrium-β"-aluminiumoxid, Natrium-β-Aluminiumoxid beziehungsweise Natrium-β/β"-Aluminiumoxid durch Kationenaustausch hergestellt werden. Bei der Herstellung von Lithium kommt ebenfalls eine Vielzahl von Materialien in Frage. Beispielsweise kommen folgende Materialien in Betracht: Li4-xSi1-xPxO4, Li-beta"-Al2O3, Li-beta-Al2O3, Lithiumanaloga von NASICON®-Keramiken, Lithiumionenleiter mit Perowskitstruktur und sulfidische Gläser als Lithiumionenleiter.Stainless steel or graphite is preferably used as the material for the essentially horizontally arranged, interconnected tubes. As the material for the solid electrolyte 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. However, preferred are sodium β "-alumina, sodium β-alumina and sodium β / β" -alumina or potassium β "-alumina, catium-β-alumina and potassium β / β" -alumina. Callum β "-alumina, cate-β-alumina and potassium-β / β" -alumina, respectively, can be prepared from sodium β "-alumina, sodium β-alumina and sodium β / β" -alumina by cation exchange, respectively. In the production of lithium is also a variety of materials in question. For example, the following materials are considered: 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.

Die Festelektrolytröhren sind einseitig geschlossen und vorzugsweise dünnwandig, aber druckfest und mit einem kreisförmigen Querschnitt gestaltet.The solid electrolyte tubes are closed on one side and preferably thin-walled, but pressure-resistant and designed with a circular cross-section.

Die übereinander angeordneten, miteinander verbundenen Rohre weisen eine Länge zwischen 0,5 m und 2 m, bevorzugt zwischen 0,9 m und 1,1 m auf. Der Innendurchmesser der Rohre beträgt zwischen 35 mm und 130 mm, bevorzugt zwischen 65 mm und 75 mm. Die Rohrdicke (Wandstärke) liegt zwischen 1 mm und 30 mm, bevorzugt zwischen 2,5 mm und 3,6 mm, wenn handelsübliche, geschweißte Rohre verwendet werden und bevorzugt zwischen 15 und 20 mm, wenn das Rohr durch Gießen hergestellt wurde.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.

Die Festelektrolytröhren weisen einen Außendurchmesser zwischen 30 mm und 100 mm auf, bevorzugt zwischen 55 mm und 65 mm. Die Wandstärke der Festelektrolytröhren beträgt zwischen 0,9 mm und 2,5 mm, bevorzugt zwischen 1,2 mm und 1,8 mm.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.

Sie weisen eine Länge von zwischen 20 cm und 75 cm, bevorzugt zwischen 45 cm und 55 cm auf.They have a length of between 20 cm and 75 cm, preferably between 45 cm and 55 cm.

Damit ergibt sich eine Spaltbreite des ersten Ringspaltes zwischen 2,5 mm und 15 mm, bevorzugt zwischen 4,5 mm und 5,5 mm.This results in a gap width of the first annular gap between 2.5 mm and 15 mm, preferably between 4.5 mm and 5.5 mm.

Die Alkalimetall-Schwermetalllegierung gelangt über den Legierungszulauf in den die Festelektrolytröhren umgebenden ersten Ringspalt. Die Elektrolyse wird dadurch betrieben, dass zwischen der Außenseite der einseitig geschlossenen Festelektrolytröhre, die aus einem Alkalimetallionen-leitenden Festelektrolyten besteht, und der Innenseite eine elektrische Spannung angelegt wird, so dass die außen in dem ersten Ringspalt in Längsrichtung strömende Alkalimetall-Schwermetalllegierung den Pluspol und das innen gebildete Alkalimetall den Minuspol bildet. Die Spannungsdifferenz bewirkt einen Elektrolysestrom, der dazu führt, dass an der Grenzfläche zwischen Alkalimetall-Schwermetalllegierung und Ionenleiter Alkalimetall oxidiert, dann als Alkalimetallion durch den Ionenleiter transportiert wird und dann an der Grenzfläche zwischen lonenleiter und Alkalimetall im Innenraum der Festelektrolytröhre wieder zu Metall reduziert wird. Bei der Elektrolyse wird also der Alkalimetall-Schwermetalllegierungsstrom hinsichtlich seines Alkalimetallgehaltes proportional zum fließenden Elektrolysestrom kontinuierlich abgereichert. Das so auf die Innenseite der Festelektrolytröhre überführte Alkalimetall kann von dort über den Alkalimetallablauf kontinuierlich abgeführt werden. Die Elektrolyse wird bei einer Temperatur im Bereich von 260 bis 400°C durchgeführt. Für die Elektrolyse eines Alkalimetallamalgams sollte die Temperatur unterhalb der Siedetemperatur von Quecksilber liegen, bevorzugt bei 310°C bis 325°C, falls das Alkalimetall Natrium ist, und bei 265°C bis 280°C, falls das Alkalimetall Kalium ist, und bei 300°C bis 320°C falls das Alkalimetall Lithium ist.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. In the case of electrolysis, therefore, 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. For the electrolysis of an alkali metal amalgam, 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.

Vorzugsweise wird die Alkalimetall-Schwermetalllegierung bereits auf 200°C bis 320°C, bevorzugt auf 250°C bis 280°C vorgeheizt der erfindungsgemäßen Elektrolysevorrichtung zugeführt. Dazu kann der Elektrolysevorrichtung ein Wärmetauscher, insbesondere ein Gegenstrom-Wärmetauscher, zugeordnet sein, so dass die in Bezug auf das Alkalimetall abgereicherte, das letzte Rohr der Elektrolysevorrichtung verlassende heiße Alkalimetall-Schwermetalllegierung den Legierungszulauf des ersten Rohres beheizt. Ein Vorheizen der Alkalimetall-Schwermetalllegierung ist aber auch mit Hilfe von um den Zulauf gewickelten Heizdrähten möglich.Preferably, 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. For this purpose, 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.

An den beiden Stirnseiten der im Wesentlichen waagerecht angeordneten Rohre befindet sich je eine Verschlussvorrichtung, die geeignet ist, jeweils eine einseitig geschlossene Festelektrolytröhre, bestehend aus einem Alkalimetallionen-leitenden Festelektrolyten, aufzunehmen. Die Öffnung der Festelektrolytröhre ist nach außen gerichtet. Die Verschlussvorrichtung ist hinsichtlich der Abdichtungen so ausgeführt, dass der mit Alkalimetall-Schwermetalllegierung gefüllte Raum in den im Wesentlichen waagerechten Rohren sowohl zur Umgebung, als auch zum Innenraum der Festelektrolytröhre leckagefrei abgedichtet ist. Ferner erfüllt die Verschlussvorrichtung auch die Forderung, den Innenraum der Festelektrolytröhre gegen die Umgebung abzudichten. Die Verschlussvorrichtung ist vorzugsweise zumindest teilweise lösbar mit dem Rohr verbunden, so dass die Festelektrolytröhren im Reparaturfall problemlos ausgetauscht werden können.On the two end faces of the substantially horizontally arranged tubes is ever a closure device which is suitable, each one closed on one side solid electrolyte tube consisting of an alkali metal ion-conducting solid electrolyte record. 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.

Die erfindungsgemäße Elektrolysevorrichtung umfasst vorzugsweise 2 bis 100 Rohre, besonders bevorzugt 5 bis 25 Rohre pro Elektrolyseeinheit. Sie enthält n parallel angeordnete Elektrolyseeinheiten mit n bevorzugt zwischen 1 und 100, besonders bevorzugt zwischen 5 und 20.The electrolysis device according to the invention 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.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die Elektrolysevorrichtung einen Legierungsverteiler zum Versorgen mindestens einer Elektrolyseeinheit mit der Alkalimetall-Schwermetalllegierung, wobei der Legierungsverteiler über je einen Auslassstutzen mit einer Elektrolyseeinheit verbunden ist. Der Alkalimetall-Schwermetalllegierungsstand in dem Legierungsverteiler wird vorzugsweise konstant gehalten. Der Legierungsverteiler ist zum Beispiel ständig zur Hälfte mit flüssiger Alkalimetall-Schwermetalllegierung gefüllt. Im Boden des Legierungsverteilers befinden sich n Auslassstutzen, die jeweils in eine als hintereinander geschaltetes Rohrsystem gestaltete Elektrolyseeinheit münden. Der dem Legierungsverteiler zulaufende Alkalimetall-Schwermetalllegierungsvolumenstrom wird folglich auf n parallele einzelne Volumenströme aufgeteilt.In a preferred embodiment of the present invention, 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. For example, the alloy manifold is constantly half filled with liquid alkali metal heavy metal alloy. In the bottom of the alloy distributor there are 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.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind der Legierungszulauf und der Legierungsablauf an den Rohren so angeordnet, dass die Alkalimetall-Schwermetalllegierung als mäanderförmiger Strom durch die Elektrolyseeinheit geführt wird. Die Alkalimetall-Schwermetalllegierung läuft dabei durch eine Elektrolyseeinheit umfassend ein Rohrsystem aus im Wesentlichen waagerecht angeordneten Rohren, wobei sie von einem Rohr über dessen an einer Seite angeordneten Legierungsablauf in das nächst tiefere Rohr über dessen auf der selben Seite angeordneten Legierungszulauf fließt, dieses dann waagerecht durchströmt, um es wiederum über den an der anderen Seite angeordneten Legierungsablauf nach unten zu verlassen und dem nächsten im Wesentlichen waagerechten Rohr zuzufließen.In a preferred embodiment of the present invention, 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.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung enthält die Elektrolysevorrichtung einen Legierungssammler zur Aufnahme der durch die Elektrolyseeinheit geströmten Alkalimetall-Schwermetalllegierung, wobei der Legierungssammler zur zumindest teilweisen Rückführung der Alkalimetall-Schwermetalllegierung mit dem Legierungsverteiler verbunden sein kann. Die zurückgeführte, bezüglich des Alkalimetalls abgereicherte Alkalimetall-Schwermetalllegierung wird im Legierungsverteiler mit bezüglich des Alkalimetalls angereicherter Alkalimetall-Schwermetalllegierung vermischt.In a preferred embodiment of the present invention, 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.

In einer anderen Ausführungsform der vorliegenden Erfindung wird Legierungsverteiler ständig und ausschließlich mit angereicherter Alkallmetall-Schwermetalllegierung versorgt und die in der Elektrolyseeinheit abgereicherte Alkalimetall-Schwermetalllegierung wird im Legierungssammler gesammelt und nicht wieder rückgeführt.In another embodiment of the present invention, 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.

Das im Innenraum der Festelektrolytröhren entstandene Alkalimetall wird erfindungsgemäß über den Alkalimetallablauf abgeführt. Vorzugsweise ist der Alkalimetallablauf über eine Ableitung mit einem Alkalimetallsammler verbunden, in den die Ableitung von seiner Oberseite aus mündet. Der Alkalimetallsammler hat vorzugsweise die Form einer Sammelrinne mit einem Deckel. Die Einführung des Alkalimetalls in den Alkalimetallsammler von seiner Oberseite aus hat den Vorteil, dass das Alkalimetall nicht aus dem Alkalimetallsammler über die Ableitung in die Elektrolyseeinheit zurückfließen kann, beispielsweise im Falle einer zerbrochenen Festelektrolytröhre. Ein Zurückfließen könnte in der Zerstörung der gesamten Elektrolyseeinheit resultieren, da das zurückfließende Alkalimetall mit Alkalimetall-Schwermetalllegierung in Kontakt kommen und eine exotherme Rückreaktion ablaufen würde.The resulting in the interior of the solid electrolyte tubes alkali metal is removed according to the invention via the alkali metal. Preferably, 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.

Aus dem Alkalimetallsammler läuft das flüssige Alkalimetall über beheizte Rohrleitungen in Lagertanks. In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist der Alkalimetallsammler höher als der Legierungsverteiler angeordnet und/oder der Alkalimetallsammler enthält ein Inertgas mit einem gegenüber der Umgebung erhöhten Druck. Dies hat den Vorteil, dass zum Beispiel im Falle einer zerbrochenen Festelektrolytröhre keine Alkalimetall-Schwermetalllegierung zu dem in dem Alkalimetallsammler enthaltenen Alkalimetall gelangen kann. Das Inertgas weist vorzugsweise einen Überdruck zwischen 0,2 bar und 10 bar auf, besonders bevorzugt 1 bar. Das Alkalimetall wird durch den Druck des im Innenraum der Festelektrolytröhre neu entstehenden Alkalimetalls gegen den Inertgasdruck und/oder gegen die aufgrund des Höhenunterschieds zwischen der Alkalimetallquelle und dem Alkalimetallsammler entstehenden Kräfte in den Alkalimetallsammler transportiert.From the alkali metal collector, the liquid alkali metal passes through heated pipes in storage tanks. In a preferred embodiment of the present invention, 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.

Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung weist jedes Rohr und jede Festelektrolytröhre einen separaten elektrischen Anschluss auf. Dadurch wird erreicht, dass bei der Unterbrechung eines elektrischen Anschlusses die Elektrolysevorrichtung nicht vollständig außer Betrieb gesetzt wird, sondern nur lokal ein Rohr oder eine Festelektrolytröhre.According to a preferred embodiment of the present invention, 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.

Vorzugsweise enthält bei der erfindungsgemäßen Elektrolysevorrichtung jede der Verschlussvorrichtungen einen Alkalimetallablauf und einen elektrischen Anschluss für die Kathode. Die elektrische Stromversorgung der Kathode kann beispielsweise über den als elektrisch leitfähiges Ableitungsrohr ausgeführten Alkalimetallablauf erfolgen.In the electrolysis apparatus according to the invention, 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.

Der elektrische Anschluss für die Kathode von einer Vielzahl der in einer Elektrolyseeinheit enthaltenen Festelektrolytröhren verläuft vorzugsweise über je ein elastisches elektrisch leitfähiges Band, das eine Minusbrücke kontaktiert. Die Minusbrücke ist ein elektrisch leitfähiges Bauteil, das an den Minuspol einer Spannungsquelle angeschlossen ist. Sie ist jeweils über ein elastisches elektrisch leitfähiges Band mit dem elektrischen Anschluss der Kathode im Innenraum jeder der Vielzahl von Festelektrolytröhren verbunden. Das Band ist elastisch, um verschiedene Wärmedehnungseigenschaften der Minusbrücke und des elektrischen Anschlusses auszugleichen. Ferner kann das Band als Schmelzsicherung ausgebildet sein, die im Falle einer zu hohen Stromstärke durch die entstehende Wärme zerstört wird.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.

Jedes elektrisch leitfähige Band kann ferner einen individuellen elektrischen Widerstand aufweisen, der so ausgelegt ist, dass an jedem Rohr die gleiche Spannung anliegt.Each electrically conductive band may further comprise an individual electrical resistance designed to apply the same voltage to each tube.

Der Alkalimetallsammler ist gegenüber dem Innenraum der jeweiligen Festelektrolytröhre elektrisch isoliert. Dies wird zum Beispiel dadurch erreicht, dass die jeweilige Rohrdurchführung, durch die die Ableitung in die Oberseite des Alkalimetallsammlers mündet, elektrisch isoliert ausgeführt ist, so dass zwischen den einzelnen Alkalimetallquellen, die alle über ihre Ableitung mit dem Alkalimetallsammler verbunden sind, und zwischen der jeweiligen Alkalimetallquelle und dem Alkalimetallsammler eine elektrische Potentialtrennung besteht. Dies ist nur möglich, da das Alkalimetall von oben in den (z.B. mit Stickstoff gefüllten) Alkalimetallsammler eintropft und keinen durchgehenden Flüssigkeitsfaden bildet. Im Falle eines Bruches einer Festelektrolytröhre wird so u.a. ein Kurzschluss der betroffenen Ableitungen vermieden.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.

In einer bevorzugten Erfindung der vorliegenden Erfindung verläuft der elektrische Anschluss für die Anode über das Rohr, das eine Plusbrücke kontaktiert. Die Plusbrücke ist ein elektrisch leitfähiges Bauteil, das an den Pluspol einer Spannungsquelle angeschlossen ist. Sie kann beispielsweise als Flachstange mit einer Vielzahl von balkonartigen Vorsprüngen gestaltet sein, wobei jeweils ein Rohr auf einem Vorsprung aufliegt und durch diesen einerseits getragen und andererseits elektrisch kontaktiert wird. Bei der Plusbrücke handelt es sich in diesem Fall vorzugsweise um eine massive Stahlkonstruktion, die diese Doppelfunktion übernehmen kann. Die Plusbrücke kann jedoch auch eine zusätzliche nicht tragende Aluminiumschiene sein, die über elastische, elektrisch leitfähige Bänder mit den Rohren verbunden ist.In a preferred embodiment of the present invention, 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.

In einer bevorzugten Ausführungsform der erfindungsgemäßen Elektrolysevorrichtung ist im Innenraum jeder der Festelektrolytröhren ein Verdrängungskörper so angeordnet, dass sich ein zweiter Ringspalt zur Aufnahme des flüssigen Alkalimetalls zwischen der Außenseite des Verdrängungskörpers und der Innenseite der Festelektrolytröhre befindet. Durch den Verdrängungskörper wird das Volumen im Innenraum der Festelektrolytröhre, das durch Alkalimetall ausgefüllt werden kann, verringert. Dies hat den Vorteil, dass zu jedem Zeitpunkt nur eine geringe Menge von Alkalimetall in der Festelektrolytröhre enthalten ist, so dass bei einem plötzlichen Versagen der Festelektrolytröhre nur diese geringe Menge mit der die Festelektrolytröhre umgebenden Alkalimetall-Schwermetalllegierung in Kontakt kommen kann. Damit wird das Energiepotential der Rückreaktion möglichst gering gehalten. Als Verdrängungskörper kann ein massiver Metallkörper dienen. Dieser Metallkörper hat den weiteren Vorteil, dass er als Kathode eingesetzt werden kann, wenn die Elektrolyse mit einer noch nicht mit Alkalimetall gefüllten Festelektrolytröhre gestartet wird. Als Verdrängungskörper kann aber auch ein geschlossener Hohlkörper dienen. Dieser Hohlkörper hat den Vorteil, dass er aufgrund seines geringeren Gewichts einfacher in die Festelektrolytröhre eingeschoben werden kann, ohne diese zu beschädigen. Ferner kann als Verdrängungskörper ein einseitig geschlossenes, genau an die Form des Innenraums der Festelektrolytröhre angepasstes dünnwandiges Blechrohr dienen, das in die Festelektrolytröhre eingeführt wird, so dass sich ein sehr schmaler zweiter Ringspalt ausbildet. In das dünnwandige Blechrohr kann ein weiterer Körper zur Verstärkung eingesetzt werden. Der als Blechrohr ausgeführte Verdrängungskörper hat den Vorteil, dass die Menge an Alkalimetall, die beim Versagen der Festelektrolytröhre mit Alkalimetall-Schwermetalllegierung gemischt wird, sehr gering ist.In a preferred embodiment of the electrolysis device according to the invention, 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. By the displacement body, the volume in the interior of the solid electrolyte tube, which can be filled by alkali metal, reduced. This has the advantage that only a small amount of alkali metal is contained in the solid electrolyte tube at any time, so that in a sudden failure of the solid electrolyte tube, only this small amount can come into contact with the alkaline metal heavy metal alloy surrounding the solid electrolyte tube. This keeps the energy potential of the reverse reaction as low as possible. As 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. Further, 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.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung umgibt eine mit Umluft beheizte, thermisch gedämmte Heizkammer die Rohre mit den Verschlussvorrichtungen. Die Elektrolysevorrichtung wird dadurch auf die bei der Elektrolyse erforderliche Temperatur gebracht, dass sie in die mit Umluft beheizte, gegen die Umgebung thermisch gedämmte Heizkammer eingebaut ist. Die Beheizung kann auf elektrischem Wege oder mit Öl- oder Gasbrennern erfolgen. Gegebenenfalls ist eine Beheizung nur beim Anfahren der Elektrolyse oder in Phasen, in welchen die Elektrolyse unterbrochen ist, notwendig. Eine Kühlung der erfindungsgemäßen Elektrolysevorrichtung kann erfolgen, indem der Heizkammer Umgebungsluft zugeführt und heiße Abluft entnommen wird.In a preferred embodiment of the present invention, 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. Optionally, 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.

Die Erfindung hat ferner die Verwendung der erfindungsgemäßen Elektrolysevorrichtung zur Herstellung von Natrium, Kalium oder Lithium aus einem flüssigen Alkalimetall-Amalgam zum Gegenstand.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.

Zeichnungdrawing

Anhand der Zeichnung wird die Erfindung nachstehend näher erläutert.Reference to the drawings, the invention will be explained in more detail below.

Es zeigt:

Figur 1
eine schematische Darstellung einer erfindungsgemäßen Elektrolysevorrichtung mit einer Vielzahl von Elektrolyseeinheiten, die eine Vielzahl von Rohren umfassen,
Figur 2
eine schematische Darstellung einer erfindungsgemäßen Elektrolysevorrichtung mit einem oberhalb des Legierungsverteilers angeordneten Alkalimetallsammlers,
Figur 3
eine Ausführungsform einer Elektrolyseeinheit in einer erfindungsgemäßen Elektrolysevorrichtung mit ihren elektrischen Anschlüssen,
Figur 4
eine Ausführungsform mit Plusbrücken für eine erfindungsgemäße Elektrolysevorrichtung und
Figur 5
einen Ausschnitt aus zwei übereinander angeordneten Rohren mit Verdrängungskörpern in den Festelektrolytröhren.
It shows:
FIG. 1
a schematic representation of an electrolysis device according to the invention with a plurality of electrolysis units comprising a plurality of tubes,
FIG. 2
a schematic representation of an electrolysis device according to the invention with an above the alloy distributor arranged alkali metal collector,
FIG. 3
An embodiment of an electrolysis unit in an electrolysis device according to the invention with its electrical connections,
FIG. 4
an embodiment with plus bridges for an electrolysis device according to the invention and
FIG. 5
a section of two tubes arranged one above the other with displacement bodies in the solid electrolyte tubes.

Besondere AusführungsformenSpecial embodiments

Figur 1 zeigt schematisch eine erfindungsgemäße Elektrolysevorrichtung mit einer Vielzahl von Elektrolyseeinheiten.Figure 1 shows schematically an electrolysis device according to the invention with a plurality of electrolysis units.

Die Elektrolysevorrichtung umfasst eine Vielzahl von übereinander im Wesentlichen horizontal angeordneten, miteinander verbundenen Rohren 1, die eine Elektrolyseeinheit 2 bilden. Die dargestellte Vorrichtung enthält eine Vielzahl von Elektrolyseeinheiten 2, die parallel zueinander angeordnet sind und mit n = 1, 2, .....n durchnummeriert sind. Die Rohre 1 innerhalb einer Elektrolyseeinheit 2 sind über Verbindungsstutzen 3 miteinander verbunden. Die Rohre 1 verschiedener Elektrolyseeinheiten 2 weisen keine Verbindung untereinander auf. An den Enden jedes Rohres 1 sind Verschlussvorrichtungen 4 angeordnet, die mit je einem Verbindungsstutzen 3 verbunden sind. Ein Legierungsverteiler 5 ist bis ca. zur Hälfte mit flüssiger Alkalimetall-Schwermetalllegierung 6 gefüllt und versorgt die n Elektrolyseeinheiten 2 über je einen Auslassstutzen 7 mit der Alkalimetall-Schwermetalllegierung 6. Der Auslassstutzen 7 mündet dabei in einen Legierungszulauf 8 eines Rohres 1, der in der Nähe eines Endes des Rohres 1 liegt. In dem Rohr 1 (in dem nicht dargestellten ersten Ringraum) strömt die Alkalimetall-Schwermetalllegierung 6 bis in die Nähe des anderen Endes des Rohres 1, wo sich der Legierungsablauf 9 dieses Rohres 1 befindet. Durch den Legierungsablauf 9, einen Verbindungsstutzen 3 und einen Legierungszulauf 8 des nächst tieferen Rohres 1 gelangt die Alkalimetall-Schwermetalllegierung 6 in dieses nächste tiefer liegende Rohr 1, um in Längsrichtung wiederum dieses zu durchströmen. Die Alkalimetall-Schwermetalllegierung 6 wird also als mäanderförmiger Strom durch die Elektrolyseeinheit 2 geführt. Aus dem letzten Rohr 1 jeder der n Elektrolyseeinheiten 2 nimmt ein Legierungssammler 10 die durch die Elektrolyse bezüglich des Alkalimetalls abgereicherte Alkalimetall-Schwermetalllegierung auf, die entweder in die Elektrolysevorrichtung zurückgeführt oder in einen Lagerbehälter abgeführt wird. Das bei der Elektrolyse entstandene Alkalimetall wird durch einen (nicht dargestellten) Alkalimetallablauf an jedem Ende des Rohres 1 abgezogen.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 device shown contains a plurality of electrolysis units 2, which are arranged parallel to one another and are numbered n = 1, 2, ..... n. 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. In the tube 1 (in the first annulus, not shown) flows the alkali metal heavy metal alloy 6 to near the other end of the tube 1, where the alloying 9 of this tube 1 is located. Through the alloy outlet 9, a connecting piece 3 and an alloy inlet 8 of the next lower tube 1, the alkali metal heavy metal alloy 6 enters this next lower-lying tube 1, in order to flow through it in the longitudinal direction. The alkali metal heavy metal alloy 6 is thus guided as a meandering current through the electrolysis unit 2. From the last tube 1 of each of the n electrolysis units 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).

Figur 2 zeigt eine weitere schematische Darstellung einer erfindungsgemäßen Elektrolysevorrichtung.FIG. 2 shows a further schematic illustration of an electrolysis device according to the invention.

Es sind drei übereinander angeordnete Rohre 1 einer Elektrolyseeinheit 2 dargestellt. In jedem Rohr 1 sind zwei an einem Ende geschlossene, an dem anderen Ende eine Öffnung 11 aufweisende Festelektrolytröhren 12 vorhanden. Die Festelektrolytröhren 12 sind in dem Rohr 1 konzentrisch angeordnet und mit der Öffnung 11 je einem Ende des Rohrs 1 zugewandt. Zwischen der Innenseite des Rohrs 1 und der Außenseite der Festelektrolytröhren 12 befindet sich ein erster Ringspalt 13 zur Führung der eine Anode bildenden flüssigen Alkalimetall-Schwermetalllegierung 6, die aus dem Legierungsverteiler 5 über den Auslassstutzen 7 und den Legierungszulauf 8 in das oberste Rohr 1 gelangt und durch den Ringspalt 13 an den Festelektrolytröhren 12 entlang bis zum Legierungsablauf 9, der in einen Verbindungsstutzen 3 mündet, strömt. Jede Verschlussvorrichtung 4 dient als Halterung für eine Festelektrolytröhre 12, die lösbar ist, so dass eine defekte Festelektrolytröhre 12 problemlos ausgetauscht werden kann. Der Innenraum 14 der Festelektrolytröhre 12 ist gegenüber den Alkalimetall-Schwermetalllegierung führenden Teilen der Elektrolyseeinheit 2 abgedichtet, insbesondere gegenüber dem Legierungszulauf 8, dem ersten Ringspalt 13 und dem Legierungsablauf 9 des Rohres 1, in dem sich die Festelektrolytröhre 12 befindet. Der Innenraum 14 dient dazu, während der Elektrolyse dort entstehendes flüssiges Alkalimetall aufzunehmen, das als Kathode der Elektrolysevorrichtung nutzbar ist. Der Innenraum 14 ist mit einem Alkalimetallablauf 15 verbunden, der über eine Ableitung 16 das Alkalimetall 22 zu einem oberhalb des Legierungsverteilers 5 positionierten Alkalimetallsammler 17 leitet. Der Alkalimetallsammler 17 ist vorzugsweise mit einem unter Überdruck stehenden Inertgas gefüllt. Der Alkalimetallsammler 17 ist in der in Figur 2 dargestellten Ausführungsform der vorliegenden Erfindung als Sammelrinne 18 mit einem Deckel 19 gestaltet, wobei die Ableitung 16 von oben durch den Deckel 19 in den Alkalimetallsammler 17 mündet. Beim Ausfall einer der Festelektrolytröhren 12 kann aufgrund dieses Aufbaus nur eine geringe Menge Alkalimetall aus der Ableitung 16 und dem Innenraum 14 mit der Alkalimetall-Schwermetalllegierung in dem Rohr 1 reagieren. Die Alkalimetall-Schwermetalllegierung 6 gelangt nicht in den Alkalimetallsammler 17. Daher wird der Ausfall von der erfindungsgemäßen Elektrolysevorrichtung toleriert, ohne dass die Elektrolyse unterbrochen werden muss und ohne dass es zu Folgeschäden oder Qualitätseinbußen bei dem erzeugten Alkalimetall kommt. Mit dem unbeschädigten Festelektrolytröhren 12 kann die Elektrolyse fortgesetzt werden.There are three superimposed tubes 1 an electrolysis unit 2 shown. In 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. 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. Upon failure of one of the solid electrolyte tubes 12, only a small amount of alkali metal from the drain 16 and the inner space 14 can react with the alkali metal heavy metal alloy in the tube 1 due to this structure. 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.

Figur 3 zeigt eine Ausführungsform einer Elektrolyseeinheit mit ihren elektrischen Anschlüssen.FIG. 3 shows an embodiment of an electrolysis unit with its electrical connections.

Die Elektrolyseeinheit 2 wird wiederum durch eine Vielzahl von Rohren 1 gebildet. Jedes Rohr 1 und jede (nicht dargestellte) Festelektrolytröhre 12 weist einen getrennten elektrischen Anschluss auf. Jede Verschlussvorrichtung 4 enthält außer einem Alkalimetallablauf 15 auch einen elektrischen Anschluss für die Kathode. Der elektrische Anschluss für die Kathode in allen Festelektrolytröhren 12 auf einer Seite der Rohre 1 erfolgt mittels einer auf negativem elektrischen Potential liegenden ersten Minusbrücke 20, die über je ein elastisches elektrisch leitfähiges Band 21 an je einem als Metallröhrchen ausgeführten Alkalimetallablauf 15 angeschlossen ist. Das elektrisch leitfähige Band ist in Figur 3 nur für ein Rohr 1 angedeutet, jedoch für alle anderen Rohre ebenso ausgeführt. Eine zweite Minusbrücke 23 ist mit den Kathoden auf der anderen Seite der Rohre 1 verbunden.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.

Der elektrische Anschluss für die Anode erfolgt über das Rohr 1 selbst, das elektrisch leitfähig ist, indem jedes der Rohre 1 mit seiner Außenseite eine Plusbrücke 24 kontaktiert, die auf einem positiven elektrischen Potential liegt. Der Alkalimetall führende Teil der Verschlussvorrichtung 4 ist dabei von dem Alkalimetall-Schwermetalllegierung führenden Teil elektrisch isoliert. Die Plusbrücke 24 dient außer zur elektrischen Kontaktierung auch zur Herstellung der einzelnen Rohre 1 (siehe Figur 4) und ist mit Hilfe einer Aufhängung 25 an einem tragenden Gestell befestigt.The electrical connection for the anode via the tube 1 itself, which is electrically conductive by each of the tubes 1 contacted with its outside a positive bridge 24, which is at a positive electrical potential. 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.

Figur 4 zeigt eine Ausführungsform der vorliegenden Erfindung mit mehreren Plusbrücken für mehrere Elektrolyseeinheiten.Figure 4 shows an embodiment of the present invention with multiple plus bridges for multiple electrolysis units.

Die Rohre 1 der fünf dargestellten Elektrolyseeinheiten 2 liegen jeweils auf einem Vorsprung 26 einer Plusbrücke 24 auf und werden so einerseits getragen und andererseits elektrisch kontaktiert. Die Plusbrücke 24 mit den Vorsprüngen 26 ist dabei vorzugsweise eine massive Stahlkonstruktion.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.

Figur 5 zeigt einen Ausschnitt aus zwei übereinander angeordneten Rohren.FIG. 5 shows a detail of two tubes arranged one above the other.

Innerhalb eines Rohres 1 ist der erste Ringspalt 13 erkennbar, der die Festelektrolytröhre 12 umgibt. Der Innenraum der Festelektrolytröhre 12 ist fast vollständig von einem Verdrängungskörper 27 ausgefüllt, so dass lediglich ein zweiter Ringspalt 28 zwischen der Außenseite des Verdrängungskörpers 27 und der Innenseite der Festelektrolytröhre 12 für das entstehende Alkalimetall frei bleibt. Das Alkalimetall wird durch das neu entstehende Alkalimetall in eine als Alkalimetallablauf 15 dienende Bohrung 29 der Verschlussvorrichtung 4 gedrückt. Die Alkalimetall-Schwermetalllegierung 6 strömt durch den ersten Ringspalt 13 des oberen Rohres über ein Sieb 31 und einen Ringraum 30 in den Verbindungsstutzen 3 und von dort in das untere Rohr. Diese geometrische Ausführung, in der die Verbindungsstutzen 3 in einen Ringraum 30 münden, der von dem jeweiligen ersten Ringspalt 13 durch ein umlaufendes Sieb 31 abgetrennt ist, ist vorteilhaft für die Verteilung der Alkalimetall-Schwermetalllegierungs-Strömung über den Querschnitt des als Reaktionszone dienenden ersten Ringspaltes 13. Ferner verhindert diese Anordnung, dass störende Festkörperteilchen in die Reaktionszone gelangen und dort zu Blockaden führen. Die Herstellung der in Figur 5 ausschnittsweise dargestellten Elektrolyseeinheit erfolgt durch Verschweißen von Drehteilen an den dargestellten Schweißstellen 32. Es ist aber auch die einstückige Herstellung dieser Teile durch Metaligießen möglich.Within a tube 1, 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.

BezugszeichenlisteLIST OF REFERENCE NUMBERS

11
Rohrpipe
22
Elektrolyseeinheitelectrolysis unit
33
Verbindungsstutzenconnecting pieces
44
Verschlussvorrichtungclosure device
55
Legierungsverteileralloy distributor
66
Alkalimetall-SchwermetalllegierungAlkali metal-heavy metal alloy
77
Auslassstutzenoutlet
88th
Legierungszulaufalloy inlet
99
Legierungsablaufalloy flow
1010
Legierungssammleralloy collector
1111
Öffnungopening
1212
FestelektrolytröhrenSolid electrolyte tubes
1313
erster Ringspaltfirst annular gap
1414
Innenrauminner space
1515
AlkalimetallablaufAlkali metal flow
1616
Ableitungderivation
1717
AlkalimetallsammlerAlkali metal collector
1818
Sammelrinnecollecting channel
1919
Deckelcover
2020
erste Minusbrückefirst negative bridge
2121
Bandtape
2222
Alkalimetallalkali metal
2323
zweite Minusbrückesecond negative bridge
2424
Plusbrückeplus bridge
2525
Aufhängungsuspension
2626
Vorsprunghead Start
2727
Verdrängungskörperdisplacer
2828
zweiter Ringspaltsecond annular gap
2929
Bohrungdrilling
3030
Ringraumannulus
3131
Siebscree
3232
Schweißstellenwelds

Claims (14)

  1. An electrolysis apparatus for preparing alkali metal from a liquid alkali metal-heavy metal alloy (6), which comprises
    - at least two tubes (1) which are arranged essentially horizontally above one another and are connected to one another by a connecting piece (3) and form an electrolysis unit (2),
    - two solid electrolyte tubes (12) arranged in each of the tubes (1), which conduct alkali metal ions and are closed at one end and have an opening (11) at the other end, with the solid electrolyte tubes (12) being arranged concentrically in the tube (1) and in each case having the opening (11) facing one end of the tube (1) so that a first annular gap (13) for conducting the liquid alkali metal-heavy metal alloy (6) which forms one anode is present between the inside of the tube (1) and the outside of the solid electrolyte tubes (12),
    - an alloy inlet (8) and an alloy outlet (9) for the liquid alkali metal-heavy metal alloy (6) in each of the tubes (1) which open at a horizontal distance from one another from the top or from the bottom, respectively, into the first annular gap (13) of one tube (1),
    - an interior space (14) in each of the solid electrolyte tubes (12) for accommodating the liquid alkali metal which can be employed as cathode, which space is sealed from the alloy inlet (8), the first annular gap (13) and the alloy outlet (9) and is connected to an alkali metal outlet (15) and
    - in each case two closure devices (4) which are located at the two ends of each tube (1).
  2. The electrolysis apparatus according to claim 1 comprising from 2 to 100 tubes (1) in an electrolysis unit (2) and n parallel electrolysis units (2), where n = 1 to 100.
  3. The electrolysis apparatus according to either of claims 1 and 2, having an alloy distributor (5) for supplying at least one electrolysis unit (2) with the alkali metal-heavy metal alloy (6), with the alloy distributor (5) being connected in each case via an outlet piece (7) to an electrolysis unit (2).
  4. The electrolysis apparatus according to any of claims 1 to 3, wherein the alloy inlet (8) and the alloy outlet (9) are located on the tubes (1) at such positions that the alkali metal-heavy metal alloy (6) is conducted as a meandering stream through the electrolysis unit (2).
  5. The electrolysis apparatus according to any of claims 1 to 4 having an alloy collector (10) for collecting the alkali metal-heavy metal alloy (6) which has flowed through the electrolysis unit (2), with the alloy collector (10) being connected to the alloy distributor (5) for at least partial recirculation of the alkali metal-heavy metal alloy (6).
  6. The electrolysis apparatus according to any of claims 1 to 5, wherein the alkali metal outlet (15) is connected via a discharge line (16) to an alkali metal collector (17) into which the discharge line (16) opens from the top, the alkali metal collector (17) being located at a higher level than the alloy distributor (5).
  7. The electrolysis apparatus according to claim 6, wherein the alkali metal collector (17) contains an inert gas at a pressure higher than the surroundings.
  8. The electrolysis apparatus according to either of claims 6 and 7, wherein the alkali metal collector (17) is electrically insulated from the interior space (14) of the solid electrolyte tubes (12).
  9. The electrolysis apparatus according to any of claims 1 to 8, wherein each tube (1) and each solid electrolyte tube (12) has a separate electric connection.
  10. The electrolysis apparatus according to any of claims 1 to 9, wherein each of the closure devices (14) has an alkali metal outlet (15) and an electric connection for the cathode, the electric connection for the cathode of a multiplicity of solid electrolyte tubes (12) present in an electrolysis unit (2) being via an elastic electrically conductive strip (21) in each case which contacts a negative bridge (20, 23), each electrically conductive strip (21) having an individual electric resistance which is designed so that the same voltage is applied to each tube (1).
  11. The electrolysis apparatus according to claim 10, wherein the electric connection for the anode runs via the tube (1) which is in contact with a positive bridge (24).
  12. The electrolysis apparatus according to any of claims 1 to 11, wherein a displacement body (27) is arranged in the interior of each of the solid electrolyte tubes (12) so that there is a second annular gap (28) for accommodating liquid alkali metal between the outside of the displacement body (27) and the inside of the solid electrolyte tube (12).
  13. The electrolysis apparatus according to any of claims 1 to 12, wherein a thermally insulated heating chamber which is heated by means of circulating air surrounds the tubes (1) with the closure devices (4).
  14. The use of an electrolysis apparatus according to any of claims 1 to 13 for preparing sodium, potassium or lithium from a liquid alkali metal amalgam.
EP05784834A 2004-09-14 2005-09-13 Electrolysis device for the production of alkali metal Not-in-force EP1789608B1 (en)

Applications Claiming Priority (2)

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DE102004044404A DE102004044404A1 (en) 2004-09-14 2004-09-14 Electrolysis apparatus for the production of alkali metal
PCT/EP2005/009820 WO2006029807A2 (en) 2004-09-14 2005-09-13 Electrolysis device for the production of alkali metal

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EP1789608B1 true EP1789608B1 (en) 2008-01-09

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US8679668B2 (en) * 2010-06-22 2014-03-25 Basf Se Industrial apparatus for the large-scale storage of electric energy
US20130330634A1 (en) 2012-06-11 2013-12-12 Basf Se Electrode unit
TWI545230B (en) * 2014-09-10 2016-08-11 林信湧 Liquid electrolytic device
US9593031B1 (en) * 2015-08-12 2017-03-14 Jeffrey A. Ogden Chlorine generator
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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 (en) 1998-12-22 2008-01-24 Basf Ag Improved process for the electrochemical production of alkali metal from alkali metal amalgam
DE19914221A1 (en) * 1999-03-29 2000-10-05 Basf Ag Improved process for the electrochemical production of lithium
DE19926724A1 (en) * 1999-06-11 2000-12-14 Basf Ag Electrolytic cell for the production of an alkali metal

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

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