US2148404A - Production of alkali metals - Google Patents

Production of alkali metals Download PDF

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Publication number
US2148404A
US2148404A US68275A US6827536A US2148404A US 2148404 A US2148404 A US 2148404A US 68275 A US68275 A US 68275A US 6827536 A US6827536 A US 6827536A US 2148404 A US2148404 A US 2148404A
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US
United States
Prior art keywords
sodium
alkali metal
amalgam
cell
electrolyte
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
Application number
US68275A
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English (en)
Inventor
Harvey N Gilbert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US68275A priority Critical patent/US2148404A/en
Application granted granted Critical
Publication of US2148404A publication Critical patent/US2148404A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
    • C25C1/04—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals in mercury cathode cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/36—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in mercury cathode cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/033—Liquid electrodes
    • 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
    • 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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts

Definitions

  • This invention relates to the electrolysis of alkali metal compounds to produce alkali metals and other valuable products and more particularly to electrolysis processes which utilize liquid 5 metal electrodes.
  • a number of methods have been proposed for producing metallic sodium or sodium compounds by the use of a two-cell system employing a'liquid metal electrode whereby a fused sodium salt is first electrolyzed with a liquid metal cathode to form the sodium alloy and this liquid sodium alloy then-is used'as anode in a cell employing a fused sodium compound as electrolyte, e. g., caus- 'tic soda, whereby metallic sodium is released at the cathode.
  • This method of producing sodium has not enjoyedany substantial commercial use and so far as I am aware is not commercially,
  • a significant disadvantage of this two-cell system of producing sodium has been the excessively high temperatures. These high temperatures, e. g., 350 :0. 5 or higher makit impractical to employ mercury as liquid electrode because of the high vapor pressure of'mercury at such elevated temperatures. Further disadvantages of the high temperatures are that thworking life of the equip- 40 ment is seriously shortened because of the tendency of rapid corrosion at high temperatures, relatively massive and expensive equipment is required, and there is considerable loss of energy in the form of radiated heat.
  • An object of the present invention is to pro- 10 vide a. practicable method whereby an aqueous solution of an alkali metal compound may be electrolyzed witha liquid metal cathode to produce a liquid alkali metal alloy and that alloy be utilized as anode in an electrolytic operation to 15 produce alkali metal, e. g., metallic sodium.
  • an,aqueous solution of sodium chloride is electrolyzed in a cell having a flowing stream of mercury or sodium amalgam as cathode.
  • chlorine is liberated at the anode and means are provided for removing the gaseous chlorine as formed.
  • Sodium liberated at the cathode unites with the mercury to form amalgam, so .that'the liquid cathode flowing from the cell is richer in sodium than the mercury or amalgam entering the cell.
  • the concentration of sodium in the amalgam leaving the cold cell may vary widely; aconcentration of around 0.1 to 0.2% by weight is suitable.
  • the liquid amalgam leaving the cell is led to a second cell in which the amalgam is utilized as anode.
  • the amalgam flows constantly through the second cell.
  • the second cell employs as electrolyte the fused, eutectic mixture of sodium hydroxide and sodium iodide which contains about 55% by weight of sodium hydroxide and 45% by weight of sodium iodide and has a melting point of about 225 C. The temperature of this fused electrolyte is maintained at about 240-250" C.
  • the cathode in this second cell may be made of iron or steel or other suitable conductive material. The electrolysis in the second cell results in constant removal of sodium from the flowing amalgam anode and the liberation of molten sodium metal at the cathode.
  • the molten sodium having a lower specific gravity than that of the electrolyte, rises towards the surface and suitable collecting means are provided above the cathode for entrapping the rising sodium and conducting it out to a closed receiver so that it is kept out of contact from the air. From time to time the collected sodium may be removed from the receiver.
  • halide to be mixed with the hydroxide and the proportions thereof will be determined chiefly by the temperature at which it is desired to operate the electrolytic cell.
  • an electrolyte which has a melting point not greater than about 300 C. I prefer to employ an electrolyte which has a melting point not greater than about 300 C. with such ,an electrolyte-the cell may be operated at temperatures slightly above 300 C., e. g. up to 310 6., at which temperatures the vapor pressure of -mercury is around one-third of an atmosphere and hence the loss in mercury due to vaporizatlon at ordinary pressures is small. .11 the melting point of the electrolyte is not over 250 C. the
  • f'eell may be operated at temperatures sufliciently "low that the vapor pressure of the mercury is not over about one tenth of an atmosphere, under which conditions there is little or no loss of mercury due .to vaporization.
  • vari- -ous fused mixtures containing an alkali metal fer to usesubstantially eutectic mixtures of these substances.
  • Eutectic mixture Melting point C.) NaOH ('79 molar %)+NaBr 260 KOH (72 molar%)+KI 250' KQH (65 molar %)+KBr 300 LiOH (45.5 molar %)+LiI 180 LiOH (45 molar +LiBr 2'75 LiOH (63 molar %)+LiCl 290
  • my invention relates to the electrolysis of alow-melting mixture of alkali metal hydroxide and alkali metal halide, utilizing a liquid alkali metal alloy as anode, so as to liberate alkali metal at the cathode.
  • the mixture of alkali metal hydroxide and halide may be an eutectic mixture or some mixture approximating or approaching the eutectic, i. e., a mixture having a melting point lower than that of its lowest melting component.
  • the invention is not restricted to using alkali metal amalgam as the anode, since other low melting alloys of alkali metals are utilized for this purpose. Examples of such are "Woods metal" and other similar alloys of bismuth, lead, tin and/or cadmium. It is preferable, however, in most cases to use an amalgam electrode.
  • the cell in a bath containing iodide, there is no formation of either iodate or per iodine. Hence the cell may be operated practically indefinitely without changing or replacing the electrolyte or readjusting the composition thereof.
  • I claim: 1. A process for the recovery of an alkali metal from an alloy of said metal having a melting point not higher than about C. comprising employing said alloy in the liquid state as anode in an electrolytic cell which contains as electrolyte a fused mixture of alkali metal hydroxide and alkali metal halide having a melting point below 300 C.
  • a process for the recovery of an alkali metal from an alkali metal amalgam comprising'employing said amalgam as anode in an electrolytic cell which contains asvelectrolyte a fused mixture of alkali metal hydroxide and alkali metal halide, said mixture having a melting point below 3 00 C.
  • a process for the recovery of an alkali metal from an alkali metal amalgam comprising employing said amalgam as anode in an electrolytic cell which contains as electrolyte a fused, substantially eutectic mixture 01. an alkali metal hydroxide and an alkali metal halide.
  • a process for the recovery of sodium from sodium amalgam comprising employing said amalgam as anode in an electrolytic, cell which contains as electrolyte a fused eutectic mixture of sodium hydroxide and sodium iodide,

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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)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
US68275A 1936-03-11 1936-03-11 Production of alkali metals Expired - Lifetime US2148404A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US68275A US2148404A (en) 1936-03-11 1936-03-11 Production of alkali metals

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68274A US2234967A (en) 1936-03-11 1936-03-11 Production of alkali metals
US68275A US2148404A (en) 1936-03-11 1936-03-11 Production of alkali metals

Publications (1)

Publication Number Publication Date
US2148404A true US2148404A (en) 1939-02-21

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US68275A Expired - Lifetime US2148404A (en) 1936-03-11 1936-03-11 Production of alkali metals
US68274A Expired - Lifetime US2234967A (en) 1936-03-11 1936-03-11 Production of alkali metals

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US (2) US2148404A (forum.php)
BE (1) BE420511A (forum.php)
DE (2) DE891027C (forum.php)
FR (1) FR818993A (forum.php)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2660514A (en) * 1949-04-08 1953-11-24 Frederick A Rohrman Removal of nitrogen from mixtures of combustible gases
US2867568A (en) * 1955-09-01 1959-01-06 Horizons Inc Electrolytic production of hydrides
US3472745A (en) * 1967-03-08 1969-10-14 North American Rockwell Fusible alkali-metal salt electrolyte
US4156635A (en) * 1978-03-29 1979-05-29 The United States Of America As Represented By The United States Department Of Energy Electrolytic method for the production of lithium using a lithium-amalgam electrode
US20040011662A1 (en) * 2002-03-15 2004-01-22 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

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2733202A (en) * 1956-01-31 Electrolytic cells
US2542523A (en) * 1941-08-27 1951-02-20 Ici Ltd Electrolysis of aqueous salt solutions in liquid cathode cells
DE871063C (de) * 1942-12-13 1953-03-19 Lech Chemie Gersthofen Verfahren zur Gewinnung von Alkalimetallen
US2773824A (en) * 1944-09-14 1956-12-11 Robert Q Boyer Electrolytic cells
US2598228A (en) * 1945-02-03 1952-05-27 Wyandotte Chemicals Corp Electrolytic apparatus
US2539743A (en) * 1946-01-03 1951-01-30 Reynolds Metals Co Electrolytic refining of impure aluminum
US2812304A (en) * 1946-01-09 1957-11-05 John A Wheeler Means for cooling reactors
US2840520A (en) * 1954-07-26 1958-06-24 Wurbs Alfred Production of amalgams
DE1009172B (de) * 1954-10-07 1957-05-29 Habil Ludwig Kandler Dipl Phys Verfahren zur elektrischen Nutzung der Zersetzungsenergie von Amalgamen
US3311504A (en) * 1960-05-02 1967-03-28 Leesona Corp Fuel cell
US3085968A (en) * 1960-08-16 1963-04-16 Olin Mathieson Cathode sealing means for electrolytic cell
US3265490A (en) * 1963-04-09 1966-08-09 Tekkosha Co Production of alkali metals from alkali amalgam
US3427237A (en) * 1967-05-01 1969-02-11 Thomas M Morris Electrolysis method and electrolytic cell
GB1226036A (forum.php) * 1967-10-14 1971-03-24
WO2014025904A2 (en) * 2012-08-07 2014-02-13 Langley Justin Method for the integration of carbochlorination into a staged reforming operation as an alternative to direct residue oxidation for the recovery of valuable metals

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE73304C (de) * C. TH. J. VAUTIN in London, England Quecksilber-Kathode für elektrolytische Zellen
DE158574C (forum.php) *
GB190317640A (en) * 1903-08-14 1904-08-13 Edgar Arthur Ashcroft Improvements in or relating to the Production of Alkali Metals.
DE410180C (de) * 1920-12-13 1925-03-02 Gualtiero Poma Verfahren zur Reduktion organischer oder anorganischer Stoffe durch Natriumamalgam
DE630145C (de) * 1934-06-02 1936-05-22 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von anorganischen und organischen Salzen der Alkali- oder Erdalkalimetalle

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2660514A (en) * 1949-04-08 1953-11-24 Frederick A Rohrman Removal of nitrogen from mixtures of combustible gases
US2867568A (en) * 1955-09-01 1959-01-06 Horizons Inc Electrolytic production of hydrides
US3472745A (en) * 1967-03-08 1969-10-14 North American Rockwell Fusible alkali-metal salt electrolyte
US4156635A (en) * 1978-03-29 1979-05-29 The United States Of America As Represented By The United States Department Of Energy Electrolytic method for the production of lithium using a lithium-amalgam electrode
US20040011662A1 (en) * 2002-03-15 2004-01-22 Millennium Cell, Inc. Hydrogen-assisted electrolysis processes
US20060169593A1 (en) * 2002-03-15 2006-08-03 Jianguo Xu 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

Also Published As

Publication number Publication date
US2234967A (en) 1941-03-18
DE898815C (de) 1953-12-03
DE891027C (de) 1953-09-24
BE420511A (forum.php) 1937-04-30
FR818993A (fr) 1937-10-07

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