US3607684A - Manufacture of alkali metals - Google Patents

Manufacture of alkali metals Download PDF

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Publication number
US3607684A
US3607684A US711600A US3607684DA US3607684A US 3607684 A US3607684 A US 3607684A US 711600 A US711600 A US 711600A US 3607684D A US3607684D A US 3607684DA US 3607684 A US3607684 A US 3607684A
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United States
Prior art keywords
alkali metal
anode
cathode
diaphragm
sodium
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 - Lifetime
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US711600A
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English (en)
Inventor
Anselm Thomas Kuhn
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Publication date
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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
    • 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

Definitions

  • the diaphragm is polycrystalline ceramic material which has ions of the alkali metal or ions capable of being replaced by the alkali metal.
  • the diaphragm is permeable only to monovalent cations and therefore will pass only the cations ofthe alkali metal which is being manufactured.
  • Halogen can be recovered as the anode product or a halogenated hydrocarbon can be recovered as the anode product by introducing a hydrocarbon or partially halogenated hydrocarbon into the anode compartment.
  • the present invention relates to the manufacture of alkali metals. More particularly it relates to an improved electrolytic process for the manufacture of alkali metals, especially metallic sodium, and to a novel apparatus for carrying out the improved process.
  • the present invention provides a process which avoids all these difficulties and allows the electrolytic production of alkali metal, most usefully sodium, potassium or lithium, in a highly pure state without further treatment and with relatively low energy consumption.
  • an alkali metal which comprises passing an electrolyzing current from an anode in contact with a fused metal halide salt comprising ions of the alkali metal and not other monovalent cations, consecutively through the fused salt and through a diaphragm which is a polycrystalline ceramic material permeable only to monovalent cations, to a cathode in the form of the liquid alkali metal and removing alkali metal liberated on the cathode side of the diaphragm.
  • Suitable polycrystalline ceramic materials for use as the diaphragm are inorganic materials having a crystal lattice structure which contains a large number of defects and containing ions of the alkali metal which it is desired to produce by electrolysis or other monovalent cations capable of replacement by ions of the desired metal. The number of defects must not, however, be so large as to render the material an electronic conductor.
  • One very suitable material is that known as beta-alumina. This has the approximate composition Na 0,llAl and the sodium ions in the crystal lattice can exchange with alkali metal ions, for instance sodium, potassium or lithium ions, introduced from outside.
  • Other suitable materials are certain aluminates, alumino-silicates and titanates.
  • the invention also includes within its scope an electrolytic cell for the manufacture of an alkali metal which comprises an anode chamber and a cathode chamber separated by a dividing wall, at least part of the area of the dividing wall consisting of a polycrystalline ceramic material permeable only to monovalent cations and any part of the remaining wall being an electrical insulator, the anode chamber being adapted to contain a body of fused metal halide electrolyte in contact with the wall of polycrystalline ceramic material and containing an anode for contacting the fused electrolyte, a liquid alkali metal cathode contacting the wall of polycrystalline ceramic material within the cathode chamber, inlet means for feeding electrolyte to the anode chamber, exit means for removing an anode product from the anode chamber and exit means for removing liquid alkali metal from the cathode chamber.
  • An electrolytic cell according to the invention may be arranged with a ceramic diaphragm in the form of a flat sheet or alternatively in the form of a closed surface such as a cylindrical wall with one or more anodes inside or outside the cylinder and the liquid alkali metal cathode on the opposite side of the cylindrical wall.
  • a ceramic diaphragm in the form of a flat sheet or alternatively in the form of a closed surface such as a cylindrical wall with one or more anodes inside or outside the cylinder and the liquid alkali metal cathode on the opposite side of the cylindrical wall.
  • the diaphragm is permeable only to monovalent cations, the alkali metal is liberated in a high state of purity, for example greater than 99.9 percent, so that a wider range of diluent salts can be used containing cations not permissible in prior art cells and there can be no danger of recombination with halogen liberated on the anode side.
  • electrolyte components of lower purity than heretofore can be employed if desired since the impurities are arrested by the diaphragm. Maintenance of a mixed electrolyte composition is also easier since any diluent salts employed are not lost during electrolysis.
  • the cell can be worked at high temperature to employ only a halide of the desired alkali metal, for instance sodium chloride, as the molten electrolyte.
  • a halide of the desired alkali metal for instance sodium chloride
  • very low-melting mixtures of sodium chloride and aluminum chloride containing up to 60 moles AlCl may be employed.
  • the required working temperature may be maintained by surrounding the cell with a hot-air jacket if the resistance-heating effect of the electrolyzing current is insufficient.
  • electric heaters submerged in the salt or even submerged combustion gas heaters may be employed.
  • halogen for instance chlorine
  • these cells can be operated at relatively low temperatures without any danger of alkali metal coming into contact with the anode product, it can readily be arranged to carry out electro-organic reactions, for instance a hydrocarbon halogenation reaction or the further halogenation of a partially-halogenated hydrocarbon, in the anode compartments if desired.
  • electro-organic reactions for instance a hydrocarbon halogenation reaction or the further halogenation of a partially-halogenated hydrocarbon
  • FIG. 1 and FIG. 2 of the drawings show schematically, and not to scale, sectional elevations of two embodiments of apparatus according to the invention.
  • FIG. 3 shows a plan view of a ceramic diaphragm suitable for use in the cell of FIG. 1.
  • the drawings will be discussed with reference to the production of sodium and chlorine, although as stated hereinbefore the apparatus may be adapted for the production of other alkali metals and other halogens or halogenated organic compounds.
  • a rectangular anode compartment 1 is bounded by sidewalls 2 and the cell cover 3, for example of nickel or bricklined steel, together with a bottom wall 4 forming a diaphragm between the anode compartment and the cathode compartment 5.
  • the diaphragm is preferably constructed as a window-frame arrangement as shown in MG. 3 wherein sheets of beta-alumina 6 are hold in steel frames as indicated at 7.
  • An upper and lower frame are spaced apart by the beta-alumina sheets so as to preserve electrical isolation between the opposite faces of the diaphragm.
  • Cathode compartment 17 is an empty jacket provided with inlet and output pipes 18 and 19 for circulating a heating medium for instance hot air, through the jacket.
  • Cathode compartment is filled with liquid sodium, which is withdrawn from the cell during elecrolysis by way of pipe 20, which passes through electrically insulating means 21 in walls 14 and I5, and pipe 22, which will normally be connected to a receiver for liquid sodium (not shown).
  • Standpipe 23 and end-caps 24, 25, 26 are provided for ease of filling the cathode compartment with sodium before start-up.
  • the negative current lead is shown at 27 passing through electrically-insulating means 28 in the outer casing to contact the body of sodium metal in the cathode compartment.
  • the negative connection may, if desired be made alternatively to the sodium-filled pipes 20 or 23.
  • This design of cell has a further advantage over prior art sodium cells in that the anodes may be made adjustable in the vertical direction so that they may be moved towards the diaphragm to compensate for anode wear, thereby maintaining a low electrical resistance in the current path through the fused electrolyte.
  • the cell shown in FIG. 2 is made cylindrical in plan to take advantage of the enhanced strength of a cylindrical-shaped ceramic diaphragm.
  • the cylindrical diaphragm of beta-alumina 29 is connected to a stand-pipe 30 ofcast iron or nickel to act as the negative current connector, and sodium fills this stand-pipe so as to form a good electrical conductor leading to the liquid sodium cathode in the cathode compartment proper.
  • the base of anode compartment 1 is electrically isolated from the cathode compartment by an insulating floor 31.
  • the anodes 32 (only two shown) are graphite rods arranged in a ring around ceramic diaphragm 29. 33 is the outlet for chlorine produced at the anodes.
  • the anode and cathode leads are electrically isolated from each other at the cell cover either by making this of concrete or asbestos board or by passing one or more of the connections through insulating means in the cover.
  • the jackets around the cell are as in FIG. 1 apart from having a cylindrical shape.
  • FIG. 24 A laboratory-scale elecrolytic cell was constructed in accordance with the schematic representation shown in the accompanying drawing, FIG. 24.
  • An outer glass container 34 was used to form within it an anode chamber 35.
  • a ceramic tube 36 was cemented to the rim of a beta-alumina crucible 37 to form a cathode chamber 38 within the anode chamber.
  • the top of the anode chamber was covered by a glass lid 39 having an upstanding central column 40 spaced around the ceramic tube 36 and closed at the upper end by a gastight seal 4l.
  • a weighted amount of sodium was placed in the crucible 37 as indicated at 42 to form the cell cathode and a steel tube 43 was passed through the seal 41 so as to have its lower end immersed in the sodium and act as the current lead from the sodium cathode.
  • a quantity of electrolyte consisting of equimolar pro ortions of sodium chloride and aluminum chloride was p accd ll'l the anode chamber as indicated at 44 and an anode 45 was passed through sealing means 46 in the glass cover so that its lower end was immersed in the electrolyte. 47 is a thermocouple for measuring the electrolyte temperature. The cell was placed in an oven maintained at 295 C. :5" C.
  • a process for the manufacture of an alkali metal which comprises passing an electroyzing current from 1. an anode in contact with a fused metal halide salt comprising ions of the alkali metal and no other monovalent cations,
  • fused metal halide salt is a mixture of the chlorides of sodium and aluminum.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US711600A 1967-03-31 1968-03-08 Manufacture of alkali metals Expired - Lifetime US3607684A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB14782/67A GB1200103A (en) 1967-03-31 1967-03-31 Manufacture of alkali metals

Publications (1)

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US3607684A true US3607684A (en) 1971-09-21

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Family Applications (1)

Application Number Title Priority Date Filing Date
US711600A Expired - Lifetime US3607684A (en) 1967-03-31 1968-03-08 Manufacture of alkali metals

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US (1) US3607684A (en:Method)
BE (1) BE713021A (en:Method)
DE (1) DE1758022A1 (en:Method)
FI (1) FI48758C (en:Method)
FR (1) FR1560064A (en:Method)
GB (1) GB1200103A (en:Method)
IL (1) IL29659A (en:Method)
NL (1) NL6804483A (en:Method)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089770A (en) * 1977-07-11 1978-05-16 E. I. Du Pont De Nemours And Company Electrolytic cell
US4786391A (en) * 1986-11-13 1988-11-22 Siemens Aktiengesellschaft Arrangement for holding a glass member
US4804448A (en) * 1987-06-24 1989-02-14 Eltron Research, Inc. Apparatus for simultaneous generation of alkali metal species and oxygen gas
US4846943A (en) * 1986-06-06 1989-07-11 Lilliwyte Societe Anonyme Manufacture of an alkali metal aluminum halide compound and alkali metal
US4882017A (en) * 1988-06-20 1989-11-21 Aluminum Company Of America Method and apparatus for making light metal-alkali metal master alloy using alkali metal-containing scrap
US4956066A (en) * 1988-02-01 1990-09-11 Froning Edilbert A K Device for carrying out field supported ion exchange in plane-parallel plates
US5904821A (en) * 1997-07-25 1999-05-18 E. I. Du Pont De Nemours And Company Fused chloride salt electrolysis cell
US6402910B1 (en) * 1995-09-08 2002-06-11 Basf Aktiengesellschaft Electrolytic cell
WO2003078696A1 (en) * 2002-03-15 2003-09-25 Millennium Cell, Inc. Hydrogen-assisted electrolysis processes
US20060102491A1 (en) * 2004-11-10 2006-05-18 Kelly Michael T Processes for separating metals from metal salts
CN113279015A (zh) * 2021-05-21 2021-08-20 中南大学 一种基于固态电解质的双室熔盐电解槽制备高纯锂的方法
US20230119799A1 (en) * 2021-01-21 2023-04-20 Li-Metal Corp. Electrowinning cell for the production of lithium and method of using same
US20230175156A1 (en) * 2020-05-01 2023-06-08 Elysis Limited Partnership System and process for starting up an electrolytic cell
US20230349061A1 (en) * 2021-01-21 2023-11-02 Li-Metal Corp. Process for production of refined lithium metal
US11976375B1 (en) * 2022-11-11 2024-05-07 Li-Metal Corp. Fracture resistant mounting for ceramic piping
US12188140B2 (en) 2021-01-21 2025-01-07 Arcadium Lithium Intermediate Irl Limited Electrorefining apparatus and process for refining lithium metal

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108743A (en) * 1977-05-02 1978-08-22 Ford Motor Company Method and apparatus for separating a metal from a salt thereof
ES248117Y (es) * 1980-01-10 1981-01-16 Tijeras,con afilalapices moldeado, para escolares
DE3340294C2 (de) * 1983-11-08 1985-09-19 Degussa Ag, 6000 Frankfurt Vorrichtung und Verfahren zur Schmelzflußelektrolyse von Alkalimetallhalogeniden

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089770A (en) * 1977-07-11 1978-05-16 E. I. Du Pont De Nemours And Company Electrolytic cell
FR2397473A1 (fr) * 1977-07-11 1979-02-09 Du Pont Cellule d'electrolyse
US4846943A (en) * 1986-06-06 1989-07-11 Lilliwyte Societe Anonyme Manufacture of an alkali metal aluminum halide compound and alkali metal
US4786391A (en) * 1986-11-13 1988-11-22 Siemens Aktiengesellschaft Arrangement for holding a glass member
US4804448A (en) * 1987-06-24 1989-02-14 Eltron Research, Inc. Apparatus for simultaneous generation of alkali metal species and oxygen gas
US4956066A (en) * 1988-02-01 1990-09-11 Froning Edilbert A K Device for carrying out field supported ion exchange in plane-parallel plates
US4882017A (en) * 1988-06-20 1989-11-21 Aluminum Company Of America Method and apparatus for making light metal-alkali metal master alloy using alkali metal-containing scrap
US6402910B1 (en) * 1995-09-08 2002-06-11 Basf Aktiengesellschaft Electrolytic cell
US5904821A (en) * 1997-07-25 1999-05-18 E. I. Du Pont De Nemours And Company Fused chloride salt electrolysis cell
US20060169593A1 (en) * 2002-03-15 2006-08-03 Jianguo Xu Hydrogen-assisted electrolysis processes
US20040011662A1 (en) * 2002-03-15 2004-01-22 Millennium Cell, Inc. Hydrogen-assisted electrolysis processes
WO2003078696A1 (en) * 2002-03-15 2003-09-25 Millennium Cell, Inc. Hydrogen-assisted electrolysis processes
US7108777B2 (en) * 2002-03-15 2006-09-19 Millennium Cell, Inc. Hydrogen-assisted electrolysis processes
US20060102491A1 (en) * 2004-11-10 2006-05-18 Kelly Michael T Processes for separating metals from metal salts
US20230175156A1 (en) * 2020-05-01 2023-06-08 Elysis Limited Partnership System and process for starting up an electrolytic cell
US20230119799A1 (en) * 2021-01-21 2023-04-20 Li-Metal Corp. Electrowinning cell for the production of lithium and method of using same
US20230349061A1 (en) * 2021-01-21 2023-11-02 Li-Metal Corp. Process for production of refined lithium metal
US12173420B2 (en) 2021-01-21 2024-12-24 Li-Metal Corp. Electrowinning cell for the production of lithium and method of using same
US12180602B2 (en) * 2021-01-21 2024-12-31 Arcadium Lithium Intermediate Irl Limited Process for production of refined lithium metal
US12180603B2 (en) 2021-01-21 2024-12-31 Arcadium Lithium Intermediate Irl Limited Process for production of refined lithium metal
US12188140B2 (en) 2021-01-21 2025-01-07 Arcadium Lithium Intermediate Irl Limited Electrorefining apparatus and process for refining lithium metal
US12188141B2 (en) * 2021-01-21 2025-01-07 Arcadium Lithium Intermediate Irl Limited Electrowinning cell for the production of lithium and method of using same
CN113279015A (zh) * 2021-05-21 2021-08-20 中南大学 一种基于固态电解质的双室熔盐电解槽制备高纯锂的方法
US11976375B1 (en) * 2022-11-11 2024-05-07 Li-Metal Corp. Fracture resistant mounting for ceramic piping
US20240158940A1 (en) * 2022-11-11 2024-05-16 Li-Metal Corp. Fracture resistant mounting for ceramic piping

Also Published As

Publication number Publication date
BE713021A (en:Method) 1968-09-30
NL6804483A (en:Method) 1968-10-01
DE1758022A1 (de) 1973-08-16
IL29659A (en) 1971-07-28
FI48758B (en:Method) 1974-09-02
FI48758C (fi) 1974-12-10
FR1560064A (en:Method) 1969-03-14
GB1200103A (en) 1970-07-29

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