US3450524A - Process for the preparation of pure manganese - Google Patents

Process for the preparation of pure manganese Download PDF

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Publication number
US3450524A
US3450524A US590586A US3450524DA US3450524A US 3450524 A US3450524 A US 3450524A US 590586 A US590586 A US 590586A US 3450524D A US3450524D A US 3450524DA US 3450524 A US3450524 A US 3450524A
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United States
Prior art keywords
manganese
cathode
bath
electrolytic
preparation
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Expired - Lifetime
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US590586A
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English (en)
Inventor
Claude Pascaud
Louis Graff
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Ugine Kuhlmann SA
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Ugine Kuhlmann SA
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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
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • 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
    • C25C3/30—Electrolytic production, recovery or refining of metals by electrolysis of melts of manganese
    • 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
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • 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

Definitions

  • the inventive process comprises the electrolytic refining of a soluble anode formed of manganese alloy in a molten bath containing manganese chloride and at least one element from the group consisting of alkaline and alkaline-earth chlorides, removing the cathode from the bath at the end of the operation, and extracting the pure manganese from the salt and metal magma collected on the cathode.
  • manganese alloys may be utilized; however, it is particularly advantageous to use terromanganese. It is possible to utilize a previously refined rferroma-nganese and, also, the ferromanganese carbides wherein practically all the manganese is combined as M-n C.
  • the cathode is removed at the end of the electrolytic operation and cooled under an inert atmosphere to prevent the reaction between the pure manganese deposited and the air components.
  • the present process eliminates the need tor an inert atmosphere :by carrying out the electrolysis at a temperature not above 600 C., whereby the composition :salt bath gives an adequate melting temperature, and permits the direct removal and cooling of the cathode in free air. At such a temperature the manganese does not noticeably react with the air components. Thus, there is no need for a special apparatus tor keeping the atmosphere inert while the cathode is removed and cooled.
  • the electrolytic process is preferably carried out with the baths having a melting temperature below 530 C. so that the difference between the working .temperature which advantageously does not exceed 600 C.-and the melting temperature of the bath should be sufiicient to allow a good dripping of the cathode when removed from the electrolytic cell.
  • the baths of the following general composition have a melting temperature below 600 C.:
  • the manganese collected on the cathode may be separated by melting the solidified salts when the cathode mass is removed from the bath.
  • the pure manganese deposited on the cathode is separated by remelting the salt and extracted metal magma, where the remelting comprises two phases: the cathode is placed into an inert atmosphere furnace first heated slightly above the melting point of the salt bath, so as 'to melt the salts of the magma and not the manganese, a portion of this molten bath is eventually extracted, then the temperature is raised above the melting point of the manganese (for instance to 1290 C.) so as to melt the manganese which is surmounted with a protective layer of molten salts, and said manganese is cast into an ingotm-old under this protective layer.
  • the iollowing example is a complete illustration of the invention process.
  • the particular apparatus utilized is represented in the drawing. It comprises:
  • An anodic set 5 comprising a number of cylindric baskets 6, made of perforated sheet, provided with a perforated bottom, and containing the impure metal to be refined.
  • Such an arrangement is preferable to one annular basket, because it facilitates the progressive exchange of baskets when the mass of anodic metal is exhausted of manganese and also because it .aids the electric bath to circulate more readily through the charge.
  • These baskets are mechanically and electrically connected to .a flange 7, and electrically insulated from the other parts of the apparatus, and connected to the positive terminal of the direct current generator.
  • a lid 8 resting on flange 7 with interposition of an elastomer gasket 10 ensuring a seal and electric insulation.
  • a quickly re- 3 movable clamping device 9 cleats the lid on flange 7 integral to the cell.
  • a cathode 18 on which the refined manganese is deposited is connected electrically to the negative terminal of the direct current generator and mechanically to a body 12 electrically insulated from the lid.
  • a quickly removable junction 13 insures both mechanical joinder and excellent electrical contact.
  • cathode 18 has a disc 17 to gather the manganese crystals that would accidently be separated from the cathodic deposit.
  • the cathode may be of various shapes, for example, it may be a cylindric solid, hollow rod, ribbed section, or
  • Cooling circuits 14 are provided to maintain the elastomer gaskets at a temperature below their decomposition temperature, and the external parts at a temperature not dangerous for handling. Other devices may be annexed to the apparatus, such as sighting scuttles, temperature taps at various points, safety valves, and measuring and regulation instruments.
  • a removable intermediary bottom 15 formed of a perforated sheet doubled with a close meshed grid of 0.5 to 1 mm. and having a few-centimeter-high edge is provided to collect the crystals that are separated from the cathode, as well as the sludges which are normally formed after a long working-time of the cell and which result, among other causes, from the mechanical breaking of the anodic charge. Said bottom may be removed, after the lid and the baskets have been taken ofi, by means of rods 16.
  • the electrolytic current utilized has an intensity of 1-100 a./dm. at 0.01 to 3 volts.
  • the apparatus insofar as the electrolytic direct current is insuflicient to keep the bath at its working temperature, external electric resistances or liquid or solid fuel burners may be utilized; it is also possible to heat the bath by means of a number of auxiliary metallic electrodes extending into the bath, utilizing a low alternating voltage current, while taking care that both electrolytic and auxiliary heating electric circuits have no common points. If the latter way of heating is adopted, the cell may be formed from a shell of thin sheet, highly insulated outside, and coated inside with a casing of ceramic material formed from alumina or silico-alumina compounds or any other material resistent to the action of the electrolytic bath.
  • the direct current generator it is preferable to electrically set a number of cells in series, the anode of the first one being connected to the positive terminal of the generator and its cathode to the anode of the second, the cathode of the second to the anode of the third, and so on to the last cell, the cathode of which is connected to the negative terminal of the generator.
  • the intensity increased progressively from 200 a. to 250 a.
  • the whole amount of electricity utilized was 5,350 amperes-hours.
  • the cathode deposit, weighing 7,130 g. after dripping, was removed without any particular precaution. Without waiting for its complete cooling, it was introduced into the alumina crucible of an induction furnace in which the atmosphere was argon. The temperature being brought to 650 C., the salt retained by the manganese crystals melted and collected at the bottom of the crucible. The major part of said salt was drawn 01? and recovered to be later recycled in the electrolytic cell. The temperature of the furnace was then brought to 1,290 C. (melting point of Mn 1,260 C.). The liquid manganese surmounted with a liquid layer was cast in an ingot-mold.
  • the ingot thus obtained had the following composition:
  • the electrolytic process for the preparation of pure manganese comprising:
  • the electrolytic process of claim 3 characterized by said molten salts consisting of 20% MnCl 30% NaCl and 50% OaCl 5.
  • the electrolytic process of claim 3 characterized by said molten salts consisting of 12% MnCl 22% NaCl, 61% CaCl and 5% KCl.

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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)
US590586A 1965-11-03 1966-10-31 Process for the preparation of pure manganese Expired - Lifetime US3450524A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR36996A FR1463101A (fr) 1965-11-03 1965-11-03 Procédé de fabrication de manganèse pur

Publications (1)

Publication Number Publication Date
US3450524A true US3450524A (en) 1969-06-17

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ID=8591669

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Application Number Title Priority Date Filing Date
US590586A Expired - Lifetime US3450524A (en) 1965-11-03 1966-10-31 Process for the preparation of pure manganese

Country Status (11)

Country Link
US (1) US3450524A (no)
AT (1) AT264857B (no)
BE (1) BE688998A (no)
CH (1) CH478247A (no)
ES (1) ES332567A1 (no)
FR (1) FR1463101A (no)
GB (1) GB1166106A (no)
LU (1) LU52289A1 (no)
NL (1) NL6615525A (no)
NO (1) NO120449B (no)
SE (1) SE332083B (no)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711386A (en) * 1969-12-04 1973-01-16 Us Interior Recovery of metals by electrodeposition
US4069114A (en) * 1975-05-27 1978-01-17 Universite Libre De Bruxelles Method for recovering manganese metal from ferromanganese
US4869790A (en) * 1986-10-14 1989-09-26 The British Petroleum Company P.L.C. Metal separation process
CN111364058A (zh) * 2020-03-25 2020-07-03 中南大学 一种用于制备金属锰的电解装置

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1064586B (it) * 1975-07-11 1985-02-18 Univ Bruxelles Cella elettrolitica per il trattamento di materiali olverulenti o spezzettati e procedimento di utilizzazione di tale cella
CN102816962A (zh) * 2011-06-08 2012-12-12 伍宏斌 一种低硅高纯金属锰及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US704393A (en) * 1901-02-27 1902-07-08 Albert Simon Manufacture of iron, manganese, and alloys of these metals by aid of electricity.
US1861625A (en) * 1929-03-30 1932-06-07 Westinghouse Lamp Co Method of producing rare metals by electrolysis
US2398589A (en) * 1939-01-11 1946-04-16 Molybdenum Corp Method of making manganese
CA602888A (en) * 1960-08-02 S. Cooper Hugh Recovery of manganese from metallurgical slags, dusts and ores
US3018233A (en) * 1960-02-09 1962-01-23 Manganese Chemicals Corp Producing manganese by fused salt electrolysis, and apparatus therefor
US3028233A (en) * 1960-05-31 1962-04-03 Walter M Weil Recovery of manganese from metallurgical slags, dusts, and ores

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA602888A (en) * 1960-08-02 S. Cooper Hugh Recovery of manganese from metallurgical slags, dusts and ores
US704393A (en) * 1901-02-27 1902-07-08 Albert Simon Manufacture of iron, manganese, and alloys of these metals by aid of electricity.
US1861625A (en) * 1929-03-30 1932-06-07 Westinghouse Lamp Co Method of producing rare metals by electrolysis
US2398589A (en) * 1939-01-11 1946-04-16 Molybdenum Corp Method of making manganese
US3018233A (en) * 1960-02-09 1962-01-23 Manganese Chemicals Corp Producing manganese by fused salt electrolysis, and apparatus therefor
US3028233A (en) * 1960-05-31 1962-04-03 Walter M Weil Recovery of manganese from metallurgical slags, dusts, and ores

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711386A (en) * 1969-12-04 1973-01-16 Us Interior Recovery of metals by electrodeposition
US4069114A (en) * 1975-05-27 1978-01-17 Universite Libre De Bruxelles Method for recovering manganese metal from ferromanganese
US4869790A (en) * 1986-10-14 1989-09-26 The British Petroleum Company P.L.C. Metal separation process
CN111364058A (zh) * 2020-03-25 2020-07-03 中南大学 一种用于制备金属锰的电解装置

Also Published As

Publication number Publication date
NL6615525A (no) 1967-05-05
AT264857B (de) 1968-09-25
ES332567A1 (es) 1967-11-01
GB1166106A (en) 1969-10-08
SE332083B (no) 1971-01-25
DE1533460B2 (de) 1972-06-22
NO120449B (no) 1970-10-19
FR1463101A (fr) 1966-06-03
LU52289A1 (no) 1967-01-03
CH478247A (fr) 1969-09-15
DE1533460A1 (de) 1969-12-18
BE688998A (no) 1967-03-31

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