DE1783137C3 - Electrolytic process for the extraction of an alkali metal from a molten salt of this metal - Google Patents
Electrolytic process for the extraction of an alkali metal from a molten salt of this metalInfo
- Publication number
- DE1783137C3 DE1783137C3 DE1783137A DE1783137A DE1783137C3 DE 1783137 C3 DE1783137 C3 DE 1783137C3 DE 1783137 A DE1783137 A DE 1783137A DE 1783137 A DE1783137 A DE 1783137A DE 1783137 C3 DE1783137 C3 DE 1783137C3
- Authority
- DE
- Germany
- Prior art keywords
- metal
- molten salt
- solid electrolyte
- sodium
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
-
- 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
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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
- C25C7/04—Diaphragms; Spacing elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/20—Cells with non-aqueous electrolyte with solid electrolyte working at high temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Metallurgy (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrolytic Production Of Metals (AREA)
- Conductive Materials (AREA)
Description
Die Erfindung betrifft ein elektrolytisches Verfahren zur Gewinnung eines Alkalimetalls aus einer Salzschmelze dieses Metalls.The invention relates to an electrolytic method for obtaining an alkali metal from a Molten salt of this metal.
Seit langem ist das Downs-Verfahren zur elektrolytischen Herstellung von Alkalimetallen aus ihren Salzschmelzen bekannt, wobei mittlerweile zahlreiche Modifizierungen dieses Verfahrens vorgenommen wurden. Grundlegend wird hierbei zur Trennung von Kathoden- und Anodenraum ein Diaphragma ingewandt, d. h. eine halbdurchlässige Membrane, die lediglich eine mechanische Filterfunktion ausübt. Zahlreiche Materialien wurden bereits auf ihre Eignung für derartige Diaphragmen untersucht, darunter auch Tonerde und Natriumaluminat.The Downs process has long been used for the electrolytic production of alkali metals from their Molten salts known, with numerous modifications of this process being made in the meantime became. Basically, a diaphragm is used to separate the cathode and anode compartment, d. H. a semi-permeable membrane that only has a mechanical filter function. Numerous Materials have already been examined for their suitability for such diaphragms, including Clay and sodium aluminate.
Es wurde demgegenüber nun ein echtes neues elektrolytisches Verfahren gefunden, bei dem die Abscheidung des Metalls durch chemische Reaktion Innerhalb des Kristallgitters einer als fester Elektrolyt wirkenden Trennwand zwischen der Anodenzone lind Kathodenzone erfolgt. Die Metallabscheidung erfolgt also nicht mitteln der Kathode, sondern mittels dieses als Trennwand dienenden festen Elektrolyts durch chemische Reaktion.In contrast, a real new electrolytic process has now been found in which the Deposition of the metal by chemical reaction Within the crystal lattice as a solid electrolyte acting partition between the anode zone and cathode zone takes place. The metal deposition does not take place by means of the cathode, but by means of this solid electrolyte serving as a partition by chemical reaction.
Erfindungsgegenstand ist ein elektrolytisches Verfahren zur Gewinnung eines Alkalimetalls aus einer Salzschmelze, dieses Metalls, das dadurch gekennzeichnet ist, daß die anodisch geschaltete Salzschmelze von dem Kathodenraum durch einen festen Elektrolyten kristalliner Struktur, die im wesentlichen aus den Ionen des Aluminiums und Sauerstoffs in Kristallgitterbindung und den Kationen des Metalls, die im Kristallgitter unter dem Einfluß des elektrischen Feldes beweglich sind, besteht, getrennt wird, der undurchlässig für das Metall, die Salzschmelze und deren Anionen und selektiv leitend für die Kationen des Metalls »st. so daß lediglich diese Kationen durch den festen Elektrolyten zu dessen Kathodenseite wandern, wo sie zu Metall reduziert Wevimifisweise wird bei der elektrolytischen Gewinnung von Natrium ein fester Elektrolyt aus Natrium-/J-aluminiumoxid verwendet.The subject of the invention is an electrolytic process for the production of an alkali metal from a molten salt, this metal, which is characterized in that the anodically connected molten salt is removed from the cathode compartment by a solid electrolyte of a crystalline structure, which essentially consists of the ions of aluminum and oxygen in a crystal lattice bond and the Cations of the metal, which are mobile in the crystal lattice under the influence of the electric field, is separated, which is impermeable to the metal, the molten salt and its anions and selectively conductive to the cations of the metal »st. so that only these cations migrate through the solid electrolyte to the cathode side where they metal reduces We vimifisweise is alumina-J used in the electrolytic recovery of sodium, a solid electrolyte of sodium /.
Günstieerweise wird das Metall im Kathodenraum auf einer niedrigeren Temperatur und unter einem niedrigeren Druck gehalten als die Salzschmelze im Anoden raum.Conveniently, the metal is in the cathode compartment kept at a lower temperature and pressure than the molten salt in the Anode space.
Auf Grund der erfindungsgemaß angewandten festen Elektrolyten als Halbzellentrennwand ergibt sich eine kationische Verbindung zwischen den anodischen und den kathodischen Reaktionszonen der Einrichtung, wobei der feste Elektrolyt praktisch undurchlässig gegenüber sämtlichen in den Vornchtunoen angewandten flüssigen Reaktionsteilnehmern 1St, wenn diese Reaktionspartner in elementarer oder anodische' Form oder in Verbindungsform vorliegen, während beim bekannten Diaphragma zwingend zumindest eine dieser Formen zunächst durch das Filter diffundieren muß und erst anschließend zur Reakt;on Hangt. Durch die Erfindung wird auch das schwierige Problem der PolarisierungsüberspannungDue to the inventively applied solid electrolyte as a half-cell dividing wall there is a cationic communication between the anodic and cathodic reaction zones of the device, wherein the solid electrolyte is practically impervious to all applied in the Vornchtunoen liquid reactants t 1S, if this reactant in elemental or anodic 'Form or be present in connection form, while in the known diaphragm at least one of these forms must first diffuse through the filter and only then to react ; on depends. The invention also eliminates the difficult problem of polarization overvoltage
vermieden. , ... .«,.·■ r-avoided. , .... «,. · ■ r-
Der feste Elektrolyt bringt erhebliche Vorteile. Er besitzt einen kristallinen Aufbau, der durch Sintern von gepulverten Oxiden aus Aluminium und Sauerstoff gebildet wird, welche die gleiche Zusammensetzung oder eine ähnliche Zusammensetzung wie /,-Aluminiumoxid besitzen.The solid electrolyte has considerable advantages. It has a crystalline structure that is produced by sintering is formed by powdered oxides of aluminum and oxygen, which have the same composition or have a composition similar to /, - aluminum oxide.
/i-Aluminiumoxid oder Natrium-yi-alumtniurnoxid wird gewöhnlich durch die Formel Na2O 11 Al2O5 wiedergegeben und läßt sich als eine Reihe von Schichten aus Α'.,Ο., vorstellen, die voneinander im Abstand durch Säulen aus linearen Al-O-Bindungsketten «ehalten werden, wobei Natriumionen Plätze zwische"n den vorstehend aufgeführten Schichten und den Säulen einnehmen. Dieses Material wird in weitem Umfang bei der Herstellung von feuerfesten Steinen zur Auskleidung von öfen verwendet, die der Korrosion durch eine basische Schmelze und'oder Schlacke ausgesetzt sind, während erfindungsgemäß diese Bimetalloxide mit dem kristallinen Gitter vom /i-Aiuminiumoxidtyp wirksame feste Reagenzien für die Zerlegung von geschmolzenen Alkalimetallsalzen sind./ i-aluminum oxide or sodium yi-aluminum oxide is usually represented by the formula Na 2 O 11 Al 2 O 5 and can be thought of as a series of layers of Α '., Ο., spaced from one another by columns of linear Al-O bond chains are obtained, with sodium ions occupying places between the layers listed above and the pillars. This material is widely used in the manufacture of refractory bricks for lining furnaces which are susceptible to corrosion by a basic melt and or slag, while in the present invention, these bimetal oxides having the crystalline lattice of the / i-aluminum oxide type are effective solid reagents for the decomposition of molten alkali metal salts.
Bei der Verwendung des Bimetalloxides in einer Zelle zur Trennung eines geschmolzenen Metalls von einem Metallsalz hiervon kann das wandernde Metallion aus Natrium oder einem anderen Alkalimetall herstammen.When using the bimetal oxide in a cell to separate a molten metal of a metal salt thereof, the migrating metal ion can be sodium or another alkali metal come from.
Bei der nachfolgend beschriebenen Zelle ergibt die Bimetalloxidtrennwand eine wirksame Sperrschicht gegenüber einem nichtionischen Massentransport der Reaktionsteilnehmer, an Ionen von flüssigen Elektrolytreaktionspartnern und gegenüber Elektronenströmung. In der Zeichnung ist schematisch eine typische Ausführungsform dargestellt, wobei die Zelltrennwand gemäß der Erfindung verwendet wird.In the cell described below, the bimetal oxide partition provides an effective barrier against a non-ionic mass transport of the reactants, of ions of liquid electrolyte reaction partners and opposite electron flow. In the drawing is a typical one schematically Embodiment shown, wherein the cell partition according to the invention is used.
In der Figur ist die Verwendung eines ionisch leitenden Bimetalloxides als Trennschicht, d.h. als fester Elektrolyt in einer Zelle mit einer Anode in einem flüssigen Reaktionsteilnehmer und einer Kathode in Berührung mit einem flüssigen Reaktionsteilnehmer als Elektrolyt gezeigt.In the figure is the use of an ionically conductive bimetal oxide as a separating layer, i.e. as a more solid one Electrolyte in a cell with an anode in a liquid reactant and a cathode shown in contact with a liquid reactant as an electrolyte.
Die Platten oder Scheiben eines zur VerwendungThe plates or disks of one for use
gemäß der Erfindung geeigneten polykristallinen Natrium-ß-aluminiumoxids lassen sich 7. B. nach einem der in der deutschen Patentschrift 1 596 077 vorgeschlagenen Verfahren herstellen.According to the invention, suitable polycrystalline sodium β-aluminum oxide can be produced , for example, by one of the processes proposed in German Patent 1,596,077.
Die Natrium-/i-aluniiniumoxid-Platten gemäß der Erfindung wurden zur Herstellung von elementarem Metall von äußerst hoher Reinheit aus einer ionisierbaren Verbindung des zu gewinnenden Metalls verwendet. Bei dieser Verwendung diente das /}-Aluminiumoxid als Trennwand, durch die eine angelegte Spannung und die dabei erhaltene Stromstärke aus dem Ion das elementare Metall erhalten wird.The sodium / i-aluminum oxide plates according to FIG Invention were used to produce elemental metal of extremely high purity from an ionizable one Compound of the metal to be extracted is used. In this use the /} - aluminum oxide served as a partition through which an applied voltage and the amperage obtained from it the elemental metal is preserved from the ion.
Unter Verwendung einer Zelle, wie in der Figur dargestellt, wurde ein eutektisches Gemisch 2 aus geschmolzenem NaNO3-NaNO2 von 245° C in das Rohr 1 der Figur gegeben. Die Natrium-zi-aluminiumoxid-Platte entsprechend der Platte 3 diente als Trennwand. Eine geringe Menge an geschmolzenem Natrium wurde in das Rohr 6 eingebracht und ein Gleichstrom aus einer Gleichstromquelle, der mit der äußeren Leitung verbunden war, durch die Zelle über die Leiter 4 und 5 der Figur geführt. Das angelegte Potential wird so geregelt, daß der Leiter 4 stärker negativ als die offene Kreisspannung der Zelle wird.Using a cell as shown in the figure, a eutectic mixture 2 of molten NaNO 3 -NaNO 2 at 245 ° C. was placed in the tube 1 of the figure. The sodium-zi-aluminum oxide plate corresponding to plate 3 served as a partition. A small amount of molten sodium was placed in the tube 6 and a direct current from a direct current source connected to the external conduit was passed through the cell through the conductors 4 and 5 of the figure. The applied potential is regulated so that the conductor 4 is more negative than the open circuit voltage of the cell.
ίο Natriumionen verlassen das Gemisch, gehen in die /i-Alumiiiiumoxid-Platte und werden in elementares Natrium 7 überführt und abgeführt.ίο Sodium ions leave the mixture, go into the / i-alumina plate and are in elemental Sodium 7 transferred and discharged.
Bei einer bevorzugten Ausführungsform wird AIuminiummetall oder eine geeignete Legierung hiervonIn a preferred embodiment, aluminum becomes aluminum or a suitable alloy thereof
für die Zellbehälter 8 verwendet. In einem derartigen Fall wird ein isolierendes Material zwischen dem Aluminium und den vorstehend beschriebenen Feststoffelektrolyten angewandt.used for the cell container 8. In such a case, an insulating material is used between the Aluminum and the solid electrolyte described above are used.
Hierzu 1 Blatt Zeichnungen1 sheet of drawings
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US507624A US3404035A (en) | 1965-10-22 | 1965-10-22 | Secondary battery employing molten alkali metal reactant |
DE19661596077 DE1596077B2 (en) | 1965-10-22 | 1966-08-27 | GALVANIC ELEMENT CONSISTS OF AN ANODIC REACTION ZONE A CATHODIC REACTION ZONE AND A FIXED ELECTROLYTE ATTACHED IN BETWEEN |
Publications (3)
Publication Number | Publication Date |
---|---|
DE1783137A1 DE1783137A1 (en) | 1972-08-31 |
DE1783137B2 DE1783137B2 (en) | 1974-08-22 |
DE1783137C3 true DE1783137C3 (en) | 1975-04-17 |
Family
ID=25753414
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE1783137A Expired DE1783137C3 (en) | 1965-10-22 | 1966-08-27 | Electrolytic process for the extraction of an alkali metal from a molten salt of this metal |
Country Status (1)
Country | Link |
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DE (1) | DE1783137C3 (en) |
-
1966
- 1966-08-27 DE DE1783137A patent/DE1783137C3/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE1783137B2 (en) | 1974-08-22 |
DE1783137A1 (en) | 1972-08-31 |
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Legal Events
Date | Code | Title | Description |
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C3 | Grant after two publication steps (3rd publication) | ||
E77 | Valid patent as to the heymanns-index 1977 | ||
8339 | Ceased/non-payment of the annual fee |