US3535214A - Process and cell for the production of manganese of low carbon content by means of a fused electrolytic bath - Google Patents

Process and cell for the production of manganese of low carbon content by means of a fused electrolytic bath Download PDF

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US3535214A
US3535214A US564301A US3535214DA US3535214A US 3535214 A US3535214 A US 3535214A US 564301 A US564301 A US 564301A US 3535214D A US3535214D A US 3535214DA US 3535214 A US3535214 A US 3535214A
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manganese
cell
electrolyte
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electrolysis
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Rene F P Winand
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Universite Libre de Bruxelles ULB
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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
    • C25C3/30—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
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/36—Alloys obtained by cathodic reduction of all their ions
    • 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

Definitions

  • Manganese is produced by electrolysis of a fused salt bath based upon a system such as MnO-SiO -CaO, MnO-Si-(b-MgO, MnOCaOMgO,
  • CM CM
  • CaO-l-MgO to Si0 it is desirable that the ratio by weight of CM) or CaO-l-MgO to Si0 be not less than 0.75.
  • the present invention relates to a process for the production of manganese of low carbon content by means of a fused electrolytic bath.
  • the object of the present invention comprises essentially to overcome the said disadvantages and to provide Patented Oct. 20, 1970 a process for the production of metallic manganese by means of a fused electrolytic bath, on an industrial scale, the starting material being an electrolyte of well specified composition so as to produce an industrially pure manganese at a very interesting cost price.
  • the process according to the invention comprises the use of an electrolytic bath selected among the group comprising the ternary systems and MnOMgOAl O as well as the complex systems based on compounds of said ternary systems.
  • the process comprises adjusting the quantity of lime with reference to the quantity of silica in the electrolytic bath in a ratio by weight which shall not be less than .75.
  • the process comprises adjusting the total of the quantity of lime and magnesia with reference to the total of the quantity of silica and alumina in the electrolytic bath in a ratio by weight which shall not be less than .75.
  • the process according to the invention may advantageously be also used to prepare a manganese based alloy.
  • At least one metal having an aflinity for oxygen less than, equal to, or slightly in excess of that of manganese is introduced in the electrolytic bath so that said metal or metals are deposited at the cathode alongside of the manganese, so as to alloy itself with the latter.
  • the affinity of said metal for oxygen is in excess of that of manganese, it will be sufficient to maintain a cathodic current density sufliciently high or to exhaust the bath partially of manganese in order to achieve this.
  • the melting temperature of the added metal is lower than the temperature of the electrolyte and of the melted cathodic metal, it is possible to introduce it directly in metallic form in the electrolysis cell.
  • the invention also relates to an electrolysis cell which may, in particular, he used for working the said process.
  • Said cell comprises a container above which is mounted at least one carbon anode and the bottom thereof is provided with a cavity wherein terminates one lead of cathodic current, said cavity being intended to contain metal, such as manganese, to be extracted, providing the cathode, an electrolyte being located above the latter and comprising said metal in the shape of an oxide compound, characterized in that the lead of cathodic current is effected by means of a refrigerated conductor so that it shall be coated with a protective layer of said solidified metal, a liquid layer of the said metal floating on top of the solidified metal.
  • FIG. 1 is an elevational view, partially broken away, of a first form of embodiment of the object of the invention.
  • FIG. 2 is an elevational view, partially broken away, of a second form of embodiment of the object of the invention.
  • FIG. 3 is an elevational view, partially broken away, of a third form of embodiment of the object of the invention.
  • FIG. 4 is an elevational view, partially broken away, of a fourth form of embodiment of the object of the invention.
  • FIG. 5 is an elevational view, partially broken away, of a fifth form of embodiment of the object of the invention.
  • FIG. 6 shows a section in the liquidus of the system plotted over the quantity of MnO.
  • FIG. 7 shows a section in the liquidus of the system plotted over the MnO content.
  • FIG. 8 is a diagrammatic view illustrating the process according to the invention.
  • FIG. 1 shows a laboratory cell used to demonstrate that it is possible to produce by the electrolysis of certain electrolyte compositions manganese with a very low carbon concentration.
  • This cell comprises essentially an induction coil 1 of 18 turns cooled by a water circulation and supplied in a medium frequency (8,000 Hz.) by an alternator not shown in the figure, the interior sidewall of the cell being provided by an inner graphite casing 2 intended to contain the electrolyte, a crucible support 3, made from copper sheet cooled by a water circulation, a graphite crucible 4 protecting against attack by the molten electrolyte an alumina crucible 5, with a bored bottom intended to receive the manganese 13 providing the cathode, asbestos sheets 6 insulating the different parts of the cell the ones from the others, a wall and a bottom of carbon free refractory material 7, for example made from tamped magnesia, a cell support 8 made from refractory bricks, a graphite anode 9, a cath
  • FIG. 2 shows another laboratory cell used for the run of tests having for their object to determine the conditions under which it is possible to produce manganese having a low silicon content while exhausting the electrolyte as much as possible.
  • Said cell comprises same as that shown in FIG. 1 an induction coil 1, a graphite casing 2, a crucible support 3 made from copper sheet cooled by water flowing in the pipes 15, asbestos sheets 6, a wall and a hearth made from refractory material 7, such as carbon free tamped magnesia, a support 8 made from refractory bricks, a graphite anode 9, a cathodic current lead 10 made from tungsten, a thermocouple 11 made from PtRh 18 and two other thermocouples 12 made from chromel-alumel.
  • the essential difference between the cells shown in FIG. 1 and in FIG. 2 is the fact that the crucible 5 of the cell shown in FIG. 1 is replaced by a cylindrical recess 5 provided in the hearth of the cell.
  • the electrolyte 14 is placed in the graphite casing 2, on the magnesia hearth 7, in contacting relationship with the cathodic manganese 13 and with the anode 9.
  • FIG. 3 shows a third form of embodiment of a laboratory cell, which was also used in the run of the orientation tests and which differs essentially from the cells shown in the FIGS 1 and 2 on account of the fact that it does not comprise a graphite casing permitting to provide a supplementary heating on account of the medium frequency induction in said casing.
  • Said cell comprises essentially a coil 1, wherein fiows cooling water and which surrounds a wall 6 made from copper sheet, an interior wall 7 of carbon free magnesia based refractory concrete, at crucible support 3 made from copper sheet, a cell support 8 carried out in refractory bricks, a cathodic current lead comprising a copper tube 10 and cooled internally by a Water flow admitted through a pipe 16 and leaving by a pipe 17 of said tube 10, a mild or stainless steel component 18 being screwed on the top end of the pipe 10.
  • This cell also comprises liquid manganese 13 providing the cathode, an anode 9, electrolyte 14 in contacting relationship with said anode and said cathode as well as a lid 19 provided with bores 20 and protected in its bottom portion by an asbestos screen 21.
  • Said lid 19 is used to maintain, inside the cell, a reducing atmosphere in order to prevent a repeated oxidation of the manganese monoxide of the charge, while the bores 20 are used for the progressive charging of said cell.
  • FIG. 4 shows an electrolysis cell which was used to carry out large scale laboratory tests. In principle, it corresponds fairly well to the cell shown in FIG. 3. It comprises an outer casing 6 made from ordinary steel sheet carried on a tripod 8, a wall and a bottom made from refractory bricks 7, a carbon free magnesia concrete refractory lining 7', provided inside the wall and the bottom 7, a cathodic current lead comprising a copper tube 10 internally cooled by a circulation of water supplied through a pipe 16 and withdrawn through a pipe 17, a mild or stainless steel component 18 being screwed in the top end of the copper tube 10, a bath of liquid manganese 13 providing the cathode, a graphite anode 9, a stainless steel thermal screen 22 provided with bores 20 for the progressive charging of the cell, three angles 23 mounted radially and carrying, on the one hand, the screen 22 and, on the other hand, a tubular sleeve 24 guiding the anode 9, removable steel lids 19 protected on their inside faces by a
  • Said cell also comprises an electrolyte 14 in contacting relationship with cathodic manganese 13 placed in the bottom of the cell.
  • an electrolyte 14 in contacting relationship with cathodic manganese 13 placed in the bottom of the cell.
  • it is possible to maintain a layer of solid electrolyte 14' in contacting relationship with the lining 7'. It is, however, suificient to increase the power slightly in order to melt the electrolyte charge completely.
  • a tap hole 25 is provided for the metal 13 and another hole 26, provided above the first tap hole 25 is provided to remove exhausted electrolyte.
  • FIG. 5 shows an electrolysis cell which could be used on an industrial scale. It comprises an outer casing 6 made from ordinary steel sheet carried on a support 8 carried out, for example, in the shape of concrete pillars, walls and a bottom made from refractory bricks 7, a carbon free magnesia concrete inside lining 7, cathodic current leads comprising copper tubes 10 at the top of each of which is provided a mild or stainless steel component 18 screwed on the top ends of said tubes 10, the latter being cooled internally by a water circulation, a bath of liquid manganese 13 providing the cathode, a plurality of anodes 9 made from, for example Stiderberg quality, carbon, a vault 19 made from silica provided with bores 20 connected to pipes, not shown in the figure, in order to exhaust the gases released at the anode, bores 20 connected to feed hoppers, also not shown in the figure, and lastly bores 20 closed by a door in order to permit watching the run of the cell and the descent of the charge.
  • the electrolyte 14 is contained in the cell and is in contacting relationship with the cathodic manganese 13 and the anodes 9.
  • a tap hole 25 enables the removal of the metal built up on the cathode while another hole 26 is used to remove exhausted electrolyte.
  • the anodes 9 pass through the vault 19, the leak tightness is provided by means of an appropriate device 29.
  • the vault 19 maintains a reducing atmosphere inside the furnace in order to prevent the repeated oxidization of the manganese monoxide. However, in certain cases where a slight repeated oxidization of the manganese monoxide is permissible, said vault need not be provided.
  • FIG. 1 100 gr. of electrolytic manganese were provided prior to the electrolysis, in the alumina crucible 5, in order to provide an adequate cathodic surface after melting. 2 kgs. of a mixture containing 45% MnO, 37.5% SiO and 17.5% CaO by weight were then introduced in the cell. The melting of the charge was carried out by medium frequency heating. 30 minutes after stabilization at about 1,400 C. of the temperature recorded by the thermocouple 11, the anode was introduced in the electrolyte 14 formed by said mixture and the electrolysis current was cut in. This test was carried out with current intensities between 80 and 150 amps. and electricity quantities from 50 through 200 amps-hr.
  • the test considered was carried out for three different systems of anodic operation. In the are system, the voltage at the cell terminals was between the limits of 35 and 60 v. for 100 amps. The carbon content achieved in this case was far below 0.01%. In the anode effect system, i.e., when the latter is dipped but not wetted by the electrolyte, the voltage at the cell terminals was about 20 v. for 100 amps. The carbon content being .07% on the average. Lastly, in the case of the test carried out with the anode dipped and wetted by the electrolyte, the voltage at the terminals was close on 10 v. for 100 amps. and the carbon content was between the limits of 0.04 and 0.09%.
  • the MnO content was brought down to 46% and the ratio by Weight of the total of the quantity of lime and magnesia with reference to the total of the quantity of silica and alumina was adjusted to a value of .85.
  • the total quantity of the charge used was 2 kgs.
  • the average voltage at the cell terminals was about 8.3 v.
  • the cathodic current efiiciency based on the valence 2 for manganese, was about 70% which corresponds to a rate of exhaustion of the electrolyte of 92%.
  • the silicon content of the metal produced was 2%.
  • the carbon content was, however, very high (2.8%) on account of the fact that the cathodic metal had come into contacting relationship with the graphite casing 2.
  • THIRD TEST The cell used for this test is shown in FIG. 3.
  • the high carbon content originates from the frequent short circuits between the carbon anode and the cathodic manganese during the melting period of the electrolyte.
  • the aluminum and calcium content this must be ascribed to the excessive cathodic current density.
  • a modification of this test comprised lowering the anode 9 in the electrolyte 14 so as to escape the anode eifect.
  • a voltage of 19 v. for 700 amps. was noted for a distance of 3.5 cm. between anode and cathode.
  • the cathodic current etficiency was about 70%.
  • a loss of manganese with reference to the total quantity introduced in the cell was due on the one hand to the volatilisation in the arc of a part of the metal initially provided on the cell hearth and, on the other hand, to the fact that part of the electrolyte remained solid in contacting relationship with the side walls of the cell and therefore did not participate in the electrolysis.
  • the noted current efficiency was therefore under evaluated for the same reasons.
  • the current intensity used for this test corresponded to an average current density of about 350 amps./dm.
  • the average carbon content of the final metal produced was less than .06%.
  • the electrolyte was maintained at a temperature within the limits of 1,380 and 1,500 C., a regular check of the iron content of the electrolyte being carried out by means of X-ray fluorescence analysis.
  • the current intensity was maintained at 1,100 amps. for 10 v. the distance between the anode and the cathode being kept between 6 and 8 cm. These conditions were maintained for 4 hours, until the iron content of the electrolyte had dropped below .2%.
  • the anode was removed from the bath and the cell was left to cool. About 24 hours after the stoppage of the cell, the ironfree electrolyte still containing about 40% MnO as well as 8.9 kgs. of metal was withdrawn.
  • the analysis of this metal with reference to the metal actually produced by the electrolysis yielded approximately the following composition:
  • the cathodic liquid manganese is carried on a solid layer formed by one or more refractory oxides which do not react with the manganese.
  • the electric cathodic contact between the liquid manganese and the feed of cathodic current is effected by means of a conductor, which is cooled so as to become coated with a layer of solidified manganese. The reasons for this is to prevent any contamination of the manganese produced at the cathode by the metal or metals comprising the cathodic current feed.
  • the electrolyte may comprise three or a plurality of the following compounds: MnO, CaO, SiO A1 and MgO.
  • MnO manganese
  • CaO calcium oxide
  • SiO A1 magnesium oxide
  • MgO magnesium oxide
  • a mixture of oxides comprising 30% of CaO, 20% of MgO and 50% 'SiO by weight may dissolve up to 60% of MnO by weight while maintaining all the time a melting temperature below 1,450 C., as shown in FIG. 6.
  • a substantial lowering of the melting temperature is noted when 4% by weight of alumina is added to said mixture.
  • Mixtures of this kind when subjected to electrolysis, have revealed themselves even more interesting than the MnO-CaO-SiO mixtures.
  • FIG. 7 shows the melting temperatures of this mixture plotted over the MnO content. It should be noted that the melting temperature does not exceed 1,450 C. in so far as the quantity of MnO remains below 40%. It is possible to subject said mixture to the electrolysis at about 1,550 through l,600 C., with a voltage at the cell terminals of less than 10 v. for an average current density of 250 amps. per dm. and a distance between the anode and the cathode of 5 cms. In that case a metal of very high purity as regards the silicon content is produced.
  • composition of electrolyte which appear to offer greatest interest for the performance in practice of the process according to the invention are the following:
  • the anode used in the electrolysis cell for working the process according to the invention may be of amorphous carbon, of graphite or more currently of 'Soderberg type.
  • the metal produced by electrolysis is essentially characterized by a very low carbon content (less than .l%) and a low silicon content (less than 2%).
  • the content of other impurities is conditioned by the purity of the electrolyte.
  • all of the iron contained in the electrolyte passes into the manganese deposited at the cathode.
  • any other element having an affinity for oxygen lower than, equal to or slightly in excess of that of manganese i.e., for example, chromium, cobalt, copper, nickel, silicon and aluminium.
  • the silicon content of the metal produced at the cathode is essentially conditioned by the index of basicity of the electrolyte and of the degree of final exhaustion of the latter.
  • said index is maintained at a value equal to or higher than unity and the electrolysis is stopped at the time when about 15% MnO remain in the electrolyte, it is possible to achieve silicon contents of less than 1%. Under those conditions, and in so far as the electrolyte does not contain impurities more reducible than MnO, it is possible to produce a manganese of about 99% or more.
  • said ores may be subjected beforehand to a treatment of partial reduction or decarbonation, so that said manganese shall be present in the electrolyte as monoxide. It may also be necessary to add to said ore or mixture of ores the oxides needed in order that the overall composition of the electrolyte shall approximate the ideal composition mentioned hereinbefore.
  • the ore used at the start shall meet, after reduction beforehand, the following average analysis:
  • the remainder being alkaline oxides and alkaline earths and titanium oxide.
  • FIG. 8 is a diagrammatic illustration of said different operations.
  • the arrow 31 represents the addition of 2,190 kgs. of decarbonated ore with 63% MnO.
  • the arrow 32 represents the addition of 71 kgs. of lime, the arrow 33 represents the withdrawal of 1,000 kgs. of ferromanganese with 94% manganese, less than .1% of carbon and less than 2% silicon.
  • the arrow 34 represents the removal of 323 kgs. of oxygen combined with the carbon of the anode.
  • the arrow 35 represents the removal of 939 kgs. of electrolyte exhausted down to 15 MnO.
  • the arrow 36 represents a recycling of 1,142 kgs. of electrolyte exhausted down to 15% MnO.
  • the metallurgical efiiciency of said operation would be 90%.
  • the manganese ore mixture contains iron, it is possible to produce a manganese with a low iron content by carrying out beforehand an operation to remove the iron.
  • the ore is subjected to an electrolysis similar to that permitting to achieve a manganese with little impurities, without, however, proceeding as far as to exhaust the manganese from the electrolyte. It is thus possible to produce, on the one hand, an electrolyte containing 35% or more of MnO, for example, but the iron of which has been removed, which is afterwards subjected to an exhaustion electrolysis in another electrolysis cell of the type described hereinbefore and, on the other hand, a ferromanganese of low carbon and silicon content, having a high commercial value compared with heavily carburized manganese pig iron produced by a conventional iron removal method, such as a reducing melt in an electric furnace.
  • a conventional iron removal method such as a reducing melt in an electric furnace.
  • the reduction to MnO will be already completed by keeping the ore, crushed to 28 mesh, for /2 hour at 950 C. in a reducing atmosphere containing 10% CO or other reducing gas; if the ore considered is decarbonated, it is not necessary for it to be crushed, because it will be automatically split by the heat.
  • the reduction to MnO will be already completed by keeping said ore for hour at 800 C. in the presence of a nonoxidising atmosphere.
  • the cells described could possibly be used for the production of other metals than manganese, or the alloys thereof, and the electrolyte could contain minute additions of other oxides or salts than those comprised in the ternary systems cited hereinbefore such as B210, B 0 NaF, CaF and having for their object to reduce the melting temperature thereof or to increase the electric conductivity thereof.

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US564301A 1965-07-16 1966-07-11 Process and cell for the production of manganese of low carbon content by means of a fused electrolytic bath Expired - Lifetime US3535214A (en)

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US4071420A (en) * 1975-12-31 1978-01-31 Aluminum Company Of America Electrolytic production of metal
US4177128A (en) * 1978-12-20 1979-12-04 Ppg Industries, Inc. Cathode element for use in aluminum reduction cell
WO2014194746A1 (zh) * 2013-06-04 2014-12-11 中国科学院过程工程研究所 利用氧化镁为原料电解制备镁合金的方法
US9312522B2 (en) 2012-10-18 2016-04-12 Ambri Inc. Electrochemical energy storage devices
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US9605354B2 (en) 2010-08-06 2017-03-28 Massachusetts Institute Of Technology Electrolytic recycling of compounds
US9735450B2 (en) 2012-10-18 2017-08-15 Ambri Inc. Electrochemical energy storage devices
US9997808B2 (en) 2009-07-20 2018-06-12 Massachusetts Institute Of Technology Liquid metal alloy energy storage device
US20180245851A1 (en) * 2015-09-15 2018-08-30 Outotec (Finland) Oy Method and arrangement for monitoring characteristics of a furnace process in a furnace space and process monitoring unit
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US10205195B2 (en) 2010-09-20 2019-02-12 Massachusetts Institute Of Technology Alkali metal ion battery with bimetallic electrode
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US10396404B2 (en) 2015-02-27 2019-08-27 Massachusetts Institute Of Technology Electrochemical cell with bipolar faradaic membrane
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Cited By (37)

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US4071420A (en) * 1975-12-31 1978-01-31 Aluminum Company Of America Electrolytic production of metal
US4177128A (en) * 1978-12-20 1979-12-04 Ppg Industries, Inc. Cathode element for use in aluminum reduction cell
US9997808B2 (en) 2009-07-20 2018-06-12 Massachusetts Institute Of Technology Liquid metal alloy energy storage device
US9605354B2 (en) 2010-08-06 2017-03-28 Massachusetts Institute Of Technology Electrolytic recycling of compounds
US10205195B2 (en) 2010-09-20 2019-02-12 Massachusetts Institute Of Technology Alkali metal ion battery with bimetallic electrode
US10608212B2 (en) 2012-10-16 2020-03-31 Ambri Inc. Electrochemical energy storage devices and housings
US11211641B2 (en) 2012-10-18 2021-12-28 Ambri Inc. Electrochemical energy storage devices
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AT292324B (de) 1971-08-25
DE1533465A1 (de) 1970-01-08
AT271925B (de) 1969-06-25
BE683660A (it) 1966-12-16
DE1533465B2 (de) 1975-09-18
SE362267B (it) 1973-12-03
FR1505395A (fr) 1967-12-15
GB1158547A (en) 1969-07-16

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