CA1084865A - Method for recovering manganese metal from ferro- manganese - Google Patents
Method for recovering manganese metal from ferro- manganeseInfo
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- CA1084865A CA1084865A CA253,458A CA253458A CA1084865A CA 1084865 A CA1084865 A CA 1084865A CA 253458 A CA253458 A CA 253458A CA 1084865 A CA1084865 A CA 1084865A
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- manganese
- ferromanganese
- chloride
- liquid phase
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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
- 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
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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)
- Manufacture And Refinement Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to a method of producing man-ganese metal from ferromanganese by electrolysis in a molten chloride bath. Iron chloride, such as ferrous and/or ferric chloride in a molten form, is contacted with ferromanganese so as to form a liquid phase containing manganese chloride and a solid phase containing an iron precipitate. The liquid phase is then enriched with manganese chloride and feed of iron chloride and electrolyzed in an electrolysis cell. The manganese metal will settle on the cathode of the cell. The method obviates the necessity of having to purify the elec-trolyte continuously as in known methods.
This invention relates to a method of producing man-ganese metal from ferromanganese by electrolysis in a molten chloride bath. Iron chloride, such as ferrous and/or ferric chloride in a molten form, is contacted with ferromanganese so as to form a liquid phase containing manganese chloride and a solid phase containing an iron precipitate. The liquid phase is then enriched with manganese chloride and feed of iron chloride and electrolyzed in an electrolysis cell. The manganese metal will settle on the cathode of the cell. The method obviates the necessity of having to purify the elec-trolyte continuously as in known methods.
Description
1084~65 This invention relates to the recovery of manganese metal from ferr ~anganese.
From the U. S. Patent 3,024,116, French Patent 1,463,101 and Belgian Patent 688,998, as well as from the scientific and technical literature defined among others by the following disclosures: A,R, SUCHKOV and N, MICHINA-Zh, Prikl, Khim. 39(1966) 2157-2162, V,YU. MINDIN and R.I.
AGLADZE Elektrokhim Margantsa 4 (1969) 250-63, L. B. BOLDINA, A,R, SUCHKOV and L,A, PARAMONOVA - Sb. Tr. Tsent. Nauch Issled.
Inst. Chem. Met 70 (1969)111-8), it is known to produce manganese by refining electrolysis in a molten salt bath, the anode being soluble and formed by more or less carburized ferromanganese.
This method has however the drawback that the electrolyte is progressively loaded with impurities in such a way that even if the first amount of metal settling on the cathode is of good quality, this will not be true for the later metal deposit unless the electrolyte is regularly renewed or at least unless said electrolyte is subjected to a very frequent purifying, which operation is however never mentioned in the patents or scientific and technical literature mentioned above.
An essential object of the invention is to provide a method allowing to obviate this drawback.
For this purpose, the method according to the invention first comprises contacting the ferromanganese and iron chloride such as ferrous and/or ferric chloride, in molten chlorides, causing the formation of a liquid phase containing manganese chloride and a solid phase containing ~084~6S
an iron precipitate, and then electrolyzing the liquid phase enriched with manganese chloride and purified from iron chloride, in an electrolysis cell allowing to settle on the cathode thereof, manganese metal, Advantageously the method according to the invention comprises a first contacting of ferromanganese and iron chloride followed by separating the liquid phase and solid phase obtained, and contacting said liquid phase with a second amount of ferromanganese allowing to purify said phase from the iron chloride and possibly from metals nobler than manganese, and thereafter electrolyzing the:~
thus purified liquid phase so as to settle manganese on the cathode.
In a particular embodiment, the purified liquid phase is fed to the cathode compartment of the electro- :
lysis cell to form therein the electrolyte, and at least that solid phase resulting from the first contacting of ferromanganese and iron chloride is fed to the anode compart- .
ment while avoiding any passage of said solid phase towards the cathode compartment, the electrolyte containing regenera-ted iron chloride formed in the anode compartment being recovered from said compartment to be used again as iron chloride source, in the first contacting of ferromanganese and iron chloride.
In a particular embodiment of the invention, said liquid phase loaded with manganese chloride and freed of iron chloride, is fed as electrolyte to the cathode compartment of the electrolysis cell, while ferro-manganese is fed to the anode compartment while preventing solid particles formed of ferromanganese and precipitated 1C~84865 iron from passing into the cathode compartment, the electro-j lyte containing manganese chloride and iron chloride formed in the anode compartment being recovered from the electro-lysis cell in said compartment and being subjected to purification by adding a fresh amount of ferromanganese thus forming a solid phase containing precipitated iron and a liquid phase that may be fed again as electrolyte into the cathode compartment.
Other details and features of the invention will stand out from the description given below by way of non limitative example and with reference to the accompanying drawings, in which:
Figure 1 is a block-diagram of the method according to a first embodiment of the invention.
Figure 2 is a block-diagram of the method according to a second embodiment of the invention, Figure 3 is a block-diagram of the method according to a third embodiment of the invention.
In the various figures the same reference numerals pertain to similar elements.
Generally the method for recovering manganese metal from ferromanganese by electrolysis in a molten salt bath according to the invention comprises at least one stage during which ferromanganese and iron chloride such as ferrous and/or ferric chloride, are contacted in molten chlorides, notably alkali and/or alkaline-earth metal chlorides, so as to obtain an electrolyte loaded with manganese chloride and substantially free from iron chloride, so as to be suitable for recovering manganese by igneous electrolysis during another stage where said electrolyte is then fed to an 1~486S
electrolysis cell for settling manganese metal on the cathode.
According to the invention, it has indeed been noticed that the contacting of ferromanganese and iron chloride in molten salts generates thermodynamic and kinetic conditions which are very suitable industrially for forming an iron precipitate and manganese chloride according to the following chemical reaction:
( )Fe e > Mn + Fe 3 [Mn~Fe + 2Fe+++ ~ 3Mn + 2Fé
In that case where the method for recovering manganese according to the invention would comprise but the one step of contacting ferromanganese and iron chloride, said step could be considered as a purifying step for a molten salt bath loaded with manganese chloride and iron chloride by means of which, due to the addition of an excess ferromanganese, the iron chloride is removed according to one of the above reactions.
With this purification, it is possible to remove metals nobler than manganese which could possibly be present in the molten salt bath.
Figure 1 relates to a block-diagram for a first embodiment of the method according to the invention that comprises two successive steps of contacting erro-manganese and iron chloride.
In more details, this particular embodiment of the method compriseschlorinating during a first step I, in a selective way, the manganese contained in ferromanganese by means of ferrous and/or ferric chloride in a molten bath of alkali and/or alkaline-earth metals which are so ~)84865 selected as to obtain a melting point lower than 700C and preferably lower than 600C, subjecting during a second step II, said molten salt bath containing the manganese as manganous chloride to a purifying operation by means of a second selective chlorinating of the manganese contained in an excess ferromanganese notably so as to remove any excess ferrous and/or ferric chloride and metals nobler than the manganese possibly present in the bath, subjecting said purified bath during a third step III, to an electrolysis by means of which manganese is settled on the cathode and chlorine is released at the anode, re-melting during a fourth step IV, that manganese settled on the cathode to obtain same as a single mass, and finally during a fifth step V, con-tacting thechlorine released at the anode with the iron pre-cipitated in the metal form during the first step and possibly the second step of chlorinating so as to regenerate the ferrous and/or ferric chloride.
Arrow 1 shows the feeding of crushed ferro-manganese in step I of the method.
Arrow 2 shows the passage of the mixture of molten chlorides containing the manganese chloride and the excess ferrous and/or ferric chloride t~ the purifying step II during which an excess crushed fe~romanganese shown by arrow 3, is added.
From this purifying step the thus-purified molten chlorides pass as shown by arrow 4 to an electrolysis cell of step III where the manganese settles on the cathode and goes to Step IV as shown by arrow 5, the chlorine released at the anode as well as the manganese-poor electro-lyte being contacted in step V with spent ferromanganese and 10~486S
precipitated iron from step I as shown in sequence by arrows 6, 7 and 8, so as to regenerate the iron chloride.
The spent electrolyte taken along with the cathode manganese deposit towards melting step IV is recovered as shown by arrow 9, in recovery step V.
The spent electrolyte which is loaded with ferric and/or ferrous chloride from recovery step V is then directed again to chorinating step I as shown by arrow 10.
The arrow 11 shows the discharge from puri-fying step II, of the partly manganese-poor ferromanganese which is however loaded with impurities.
Figure 2 ~hows as a block-diagram a second:
embodiment which differs from the first embodiment by a combination of steps III and V. Such combination occurs in the electrolysis cell proper. Indeed according to the inven-tion, the purified electrolyte from step II is fed to cathode compartment C of the electrolysis cell as shown by arrow 4, while the spent ferromanganese and the precipitated iron from step I, that is to say the solid phase formed during said first step, are fed to anode compartment A without any passage of said solid phase to cathode compartment C. The manganese-poor electrolyte which is loaded again with ferrous and/or ferric chloride and extracted at the electrolysis cell anode, is cycled back as shown by arrow 10 to step I.
This embodiment has the advantage relative to the embodiment as shown in Figure 1 of avoiding the problems entailed in the removal of chlorine gas from the electrolysis in step III. Indeed in the embodiment shown in Figure 2, the chlorine is used during the electrolysis proper to regenerate the iron chloride.
.
:
1~)848~5 Said iron chloride is formed in the anode compartment by reacting the iron from step I either with the chorine gas formed at the anode, or in situ by anodic dissolving.
On the other hand the electrolyte is caused to flow inside the electrolysis cell from cathode compart-ment A as shown by arrow 12 so as to avoid ferrous and/or ferric chloride contacting the cathode, Figure 3 relates to a third embodiment of the method according to the invention which differs from both preceding embodiments by the steps I and V being combined inside the electrolysis cell with step III.
Thus according to the invention the liquid phase that contains molten chlorides loaded with manganese choride and freed of iron chloride in step II, is fed to cathode compartment C of the electrolysis cell while ferromanganese is fed as shown by arrow 1, to anode compart-ment A while preventing solid particles formed by ferro-manganese and precipitated iron from passing into the cathode ~0 compartment, The electrolyte that contains manganese chloride and iron chloride formed in the anode compartment is dis-charged therefrom as shown by arrow 2 and it is subjected to the purifying step II by adding a fresh amount of ferro-manganese shown by arrow 3, to extract the iron chloride by forming a solid phase containing the precipitated iron and a liquid phase that comprises the phase which can be fed again as shown by arrow 4, to the cathode compartment. Said solid phase containing the impurities is separated from the liquid phase as shown by arrow 11.
The flow of electrolyte to the cell is . ~,os~t3G5 from the cathode compartment to the anode compartment as shown by arrow 12 so as to take the anolyte out of the cell without same contacting the cathode. Any danger of polluting the cathode deposit with the ferromanganese impurities is thus excluded~
The anolyte is then purified during step II
by selective chorinating of the manganese contained in an excess ferromanganese. .
The ferromanganese used in the method accord-ing to the invention is crushed before subjecting same tothe chlorinating and it may contain from 0.1 to 8% carbon, The practical example below further explains the invention:
Example Standard carbided ferromanganese, that is ferromanganese containing about 78% manganese and from 6 to 8% carbon is so crushed as to have grains with a diameter smaller than 5 mm, This crushed ferromanganese is selec*
tively chlorinated at 600C during 1 hour in the presence of a molten electrolyte containing initially 20% by weight of ferrous chloride, 30% by weight of NaCl and 50% by weight of CaC12.
The metallurgy efficiency for the manganese extraction was 95%.
The electrolyte obtained after decanting was subjected at a temperature of 600C for 10 minutes to a purifying operation with an excess standard carbided ferromanganese which had been crushed in the same way as described above.
The electrolyte thus purified has been 1~8g~865 subjected to the electrolysis.
The cathode manganese deposit produced, after melting, a manganese ingot with more than 99.9% contained manganese, the cathode current efficiency being higher than 90%.
It must be understood that the invention is in no way limited to the above embodiments and that many changes can be made therein without departing from the scope of the invention as defined by the appended claims,
From the U. S. Patent 3,024,116, French Patent 1,463,101 and Belgian Patent 688,998, as well as from the scientific and technical literature defined among others by the following disclosures: A,R, SUCHKOV and N, MICHINA-Zh, Prikl, Khim. 39(1966) 2157-2162, V,YU. MINDIN and R.I.
AGLADZE Elektrokhim Margantsa 4 (1969) 250-63, L. B. BOLDINA, A,R, SUCHKOV and L,A, PARAMONOVA - Sb. Tr. Tsent. Nauch Issled.
Inst. Chem. Met 70 (1969)111-8), it is known to produce manganese by refining electrolysis in a molten salt bath, the anode being soluble and formed by more or less carburized ferromanganese.
This method has however the drawback that the electrolyte is progressively loaded with impurities in such a way that even if the first amount of metal settling on the cathode is of good quality, this will not be true for the later metal deposit unless the electrolyte is regularly renewed or at least unless said electrolyte is subjected to a very frequent purifying, which operation is however never mentioned in the patents or scientific and technical literature mentioned above.
An essential object of the invention is to provide a method allowing to obviate this drawback.
For this purpose, the method according to the invention first comprises contacting the ferromanganese and iron chloride such as ferrous and/or ferric chloride, in molten chlorides, causing the formation of a liquid phase containing manganese chloride and a solid phase containing ~084~6S
an iron precipitate, and then electrolyzing the liquid phase enriched with manganese chloride and purified from iron chloride, in an electrolysis cell allowing to settle on the cathode thereof, manganese metal, Advantageously the method according to the invention comprises a first contacting of ferromanganese and iron chloride followed by separating the liquid phase and solid phase obtained, and contacting said liquid phase with a second amount of ferromanganese allowing to purify said phase from the iron chloride and possibly from metals nobler than manganese, and thereafter electrolyzing the:~
thus purified liquid phase so as to settle manganese on the cathode.
In a particular embodiment, the purified liquid phase is fed to the cathode compartment of the electro- :
lysis cell to form therein the electrolyte, and at least that solid phase resulting from the first contacting of ferromanganese and iron chloride is fed to the anode compart- .
ment while avoiding any passage of said solid phase towards the cathode compartment, the electrolyte containing regenera-ted iron chloride formed in the anode compartment being recovered from said compartment to be used again as iron chloride source, in the first contacting of ferromanganese and iron chloride.
In a particular embodiment of the invention, said liquid phase loaded with manganese chloride and freed of iron chloride, is fed as electrolyte to the cathode compartment of the electrolysis cell, while ferro-manganese is fed to the anode compartment while preventing solid particles formed of ferromanganese and precipitated 1C~84865 iron from passing into the cathode compartment, the electro-j lyte containing manganese chloride and iron chloride formed in the anode compartment being recovered from the electro-lysis cell in said compartment and being subjected to purification by adding a fresh amount of ferromanganese thus forming a solid phase containing precipitated iron and a liquid phase that may be fed again as electrolyte into the cathode compartment.
Other details and features of the invention will stand out from the description given below by way of non limitative example and with reference to the accompanying drawings, in which:
Figure 1 is a block-diagram of the method according to a first embodiment of the invention.
Figure 2 is a block-diagram of the method according to a second embodiment of the invention, Figure 3 is a block-diagram of the method according to a third embodiment of the invention.
In the various figures the same reference numerals pertain to similar elements.
Generally the method for recovering manganese metal from ferromanganese by electrolysis in a molten salt bath according to the invention comprises at least one stage during which ferromanganese and iron chloride such as ferrous and/or ferric chloride, are contacted in molten chlorides, notably alkali and/or alkaline-earth metal chlorides, so as to obtain an electrolyte loaded with manganese chloride and substantially free from iron chloride, so as to be suitable for recovering manganese by igneous electrolysis during another stage where said electrolyte is then fed to an 1~486S
electrolysis cell for settling manganese metal on the cathode.
According to the invention, it has indeed been noticed that the contacting of ferromanganese and iron chloride in molten salts generates thermodynamic and kinetic conditions which are very suitable industrially for forming an iron precipitate and manganese chloride according to the following chemical reaction:
( )Fe e > Mn + Fe 3 [Mn~Fe + 2Fe+++ ~ 3Mn + 2Fé
In that case where the method for recovering manganese according to the invention would comprise but the one step of contacting ferromanganese and iron chloride, said step could be considered as a purifying step for a molten salt bath loaded with manganese chloride and iron chloride by means of which, due to the addition of an excess ferromanganese, the iron chloride is removed according to one of the above reactions.
With this purification, it is possible to remove metals nobler than manganese which could possibly be present in the molten salt bath.
Figure 1 relates to a block-diagram for a first embodiment of the method according to the invention that comprises two successive steps of contacting erro-manganese and iron chloride.
In more details, this particular embodiment of the method compriseschlorinating during a first step I, in a selective way, the manganese contained in ferromanganese by means of ferrous and/or ferric chloride in a molten bath of alkali and/or alkaline-earth metals which are so ~)84865 selected as to obtain a melting point lower than 700C and preferably lower than 600C, subjecting during a second step II, said molten salt bath containing the manganese as manganous chloride to a purifying operation by means of a second selective chlorinating of the manganese contained in an excess ferromanganese notably so as to remove any excess ferrous and/or ferric chloride and metals nobler than the manganese possibly present in the bath, subjecting said purified bath during a third step III, to an electrolysis by means of which manganese is settled on the cathode and chlorine is released at the anode, re-melting during a fourth step IV, that manganese settled on the cathode to obtain same as a single mass, and finally during a fifth step V, con-tacting thechlorine released at the anode with the iron pre-cipitated in the metal form during the first step and possibly the second step of chlorinating so as to regenerate the ferrous and/or ferric chloride.
Arrow 1 shows the feeding of crushed ferro-manganese in step I of the method.
Arrow 2 shows the passage of the mixture of molten chlorides containing the manganese chloride and the excess ferrous and/or ferric chloride t~ the purifying step II during which an excess crushed fe~romanganese shown by arrow 3, is added.
From this purifying step the thus-purified molten chlorides pass as shown by arrow 4 to an electrolysis cell of step III where the manganese settles on the cathode and goes to Step IV as shown by arrow 5, the chlorine released at the anode as well as the manganese-poor electro-lyte being contacted in step V with spent ferromanganese and 10~486S
precipitated iron from step I as shown in sequence by arrows 6, 7 and 8, so as to regenerate the iron chloride.
The spent electrolyte taken along with the cathode manganese deposit towards melting step IV is recovered as shown by arrow 9, in recovery step V.
The spent electrolyte which is loaded with ferric and/or ferrous chloride from recovery step V is then directed again to chorinating step I as shown by arrow 10.
The arrow 11 shows the discharge from puri-fying step II, of the partly manganese-poor ferromanganese which is however loaded with impurities.
Figure 2 ~hows as a block-diagram a second:
embodiment which differs from the first embodiment by a combination of steps III and V. Such combination occurs in the electrolysis cell proper. Indeed according to the inven-tion, the purified electrolyte from step II is fed to cathode compartment C of the electrolysis cell as shown by arrow 4, while the spent ferromanganese and the precipitated iron from step I, that is to say the solid phase formed during said first step, are fed to anode compartment A without any passage of said solid phase to cathode compartment C. The manganese-poor electrolyte which is loaded again with ferrous and/or ferric chloride and extracted at the electrolysis cell anode, is cycled back as shown by arrow 10 to step I.
This embodiment has the advantage relative to the embodiment as shown in Figure 1 of avoiding the problems entailed in the removal of chlorine gas from the electrolysis in step III. Indeed in the embodiment shown in Figure 2, the chlorine is used during the electrolysis proper to regenerate the iron chloride.
.
:
1~)848~5 Said iron chloride is formed in the anode compartment by reacting the iron from step I either with the chorine gas formed at the anode, or in situ by anodic dissolving.
On the other hand the electrolyte is caused to flow inside the electrolysis cell from cathode compart-ment A as shown by arrow 12 so as to avoid ferrous and/or ferric chloride contacting the cathode, Figure 3 relates to a third embodiment of the method according to the invention which differs from both preceding embodiments by the steps I and V being combined inside the electrolysis cell with step III.
Thus according to the invention the liquid phase that contains molten chlorides loaded with manganese choride and freed of iron chloride in step II, is fed to cathode compartment C of the electrolysis cell while ferromanganese is fed as shown by arrow 1, to anode compart-ment A while preventing solid particles formed by ferro-manganese and precipitated iron from passing into the cathode ~0 compartment, The electrolyte that contains manganese chloride and iron chloride formed in the anode compartment is dis-charged therefrom as shown by arrow 2 and it is subjected to the purifying step II by adding a fresh amount of ferro-manganese shown by arrow 3, to extract the iron chloride by forming a solid phase containing the precipitated iron and a liquid phase that comprises the phase which can be fed again as shown by arrow 4, to the cathode compartment. Said solid phase containing the impurities is separated from the liquid phase as shown by arrow 11.
The flow of electrolyte to the cell is . ~,os~t3G5 from the cathode compartment to the anode compartment as shown by arrow 12 so as to take the anolyte out of the cell without same contacting the cathode. Any danger of polluting the cathode deposit with the ferromanganese impurities is thus excluded~
The anolyte is then purified during step II
by selective chorinating of the manganese contained in an excess ferromanganese. .
The ferromanganese used in the method accord-ing to the invention is crushed before subjecting same tothe chlorinating and it may contain from 0.1 to 8% carbon, The practical example below further explains the invention:
Example Standard carbided ferromanganese, that is ferromanganese containing about 78% manganese and from 6 to 8% carbon is so crushed as to have grains with a diameter smaller than 5 mm, This crushed ferromanganese is selec*
tively chlorinated at 600C during 1 hour in the presence of a molten electrolyte containing initially 20% by weight of ferrous chloride, 30% by weight of NaCl and 50% by weight of CaC12.
The metallurgy efficiency for the manganese extraction was 95%.
The electrolyte obtained after decanting was subjected at a temperature of 600C for 10 minutes to a purifying operation with an excess standard carbided ferromanganese which had been crushed in the same way as described above.
The electrolyte thus purified has been 1~8g~865 subjected to the electrolysis.
The cathode manganese deposit produced, after melting, a manganese ingot with more than 99.9% contained manganese, the cathode current efficiency being higher than 90%.
It must be understood that the invention is in no way limited to the above embodiments and that many changes can be made therein without departing from the scope of the invention as defined by the appended claims,
Claims (8)
1. A method for recovering manganese metal from ferro-manganese which comprises:
a) contacting ferromanganese and an iron chloride select-ed from the group consisting of ferrous chloride and ferric chloride in a molten bath of alkali metal and/or alkaline-earth metal chlorides, to provide a liquid phase containing manganese chloride and a solid phase containing iron precipitate and spent ferromanganese;
b) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese;
c) contacting the manganese chloride liquid phase with an additional quantity of ferromanganese to provide a purified liquid phase containing manganese chloride free of iron chlorides and chlorides of metals more noble than manganese;
d) introducing the purified manganese chloride liquid phase into the cathode compartment of an electrolytic cell;
e) introducing the iron precipitate and spent ferroman-ganese into the anode compartment of the cell;
f) conveying electrolyte from the cathode compartment to the anode compartment of the cell while preventing the iron pre-cipitate and spent ferromanganese from passing from the anode compartment to the cathode compartment of the cell;
g) operating the cell to liberate manganese at the cathode and chlorine at the anode, the chlorine reacting with the iron precipitate and spent ferromanganese to produce iron chloride for contact with ferromanganese, in step (a).
a) contacting ferromanganese and an iron chloride select-ed from the group consisting of ferrous chloride and ferric chloride in a molten bath of alkali metal and/or alkaline-earth metal chlorides, to provide a liquid phase containing manganese chloride and a solid phase containing iron precipitate and spent ferromanganese;
b) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese;
c) contacting the manganese chloride liquid phase with an additional quantity of ferromanganese to provide a purified liquid phase containing manganese chloride free of iron chlorides and chlorides of metals more noble than manganese;
d) introducing the purified manganese chloride liquid phase into the cathode compartment of an electrolytic cell;
e) introducing the iron precipitate and spent ferroman-ganese into the anode compartment of the cell;
f) conveying electrolyte from the cathode compartment to the anode compartment of the cell while preventing the iron pre-cipitate and spent ferromanganese from passing from the anode compartment to the cathode compartment of the cell;
g) operating the cell to liberate manganese at the cathode and chlorine at the anode, the chlorine reacting with the iron precipitate and spent ferromanganese to produce iron chloride for contact with ferromanganese, in step (a).
2. A method for recovering manganese metal from ferro-manganese which comprises:
a) contacting ferromanganese and an iron chloride selected from the group consisting of ferrous chloride and ferric chloride in a molten bath of alkali metal and/or alkaline earth metal chlorides, to provide a liquid phase containing manganese chloride and a solid phase containing iron precipitate and spent ferro-manganese;
b) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese;
c) introducing the manganese chloride liquid phase into the cathode compartment of an electrolytic cell;
d) introducing ferromanganese into the anode compartment of the cell;
e) conveying electrolyte from the cathode compartment to the anode compartment of the cell while preventing ferromanganese from passing from the anode compartment to the cathode compartment of the cell;
f) operating the cell to liberate manganese at the cathode and chlorine at the anode, the chlorine reacting with the ferro-manganese to provide a solid phase containing iron precipitate and spent ferromanganese, and a liquid phase containing manganese chloride, said iron precipitate and spent ferromanganese being prevented from passing from the anode compartment to the cathode compartment of the cell;
g) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese present in the anode compartment of the cell;
h) contacting the manganese chloride liquid phase with an additional quantity of ferromanganese to provide a purified liquid phase containing manganese chloride free of iron chlorides and chlorides more noble than manganese; and, i) introducing the purified manganese chloride liquid phase into the cathode compartment of the cell.
a) contacting ferromanganese and an iron chloride selected from the group consisting of ferrous chloride and ferric chloride in a molten bath of alkali metal and/or alkaline earth metal chlorides, to provide a liquid phase containing manganese chloride and a solid phase containing iron precipitate and spent ferro-manganese;
b) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese;
c) introducing the manganese chloride liquid phase into the cathode compartment of an electrolytic cell;
d) introducing ferromanganese into the anode compartment of the cell;
e) conveying electrolyte from the cathode compartment to the anode compartment of the cell while preventing ferromanganese from passing from the anode compartment to the cathode compartment of the cell;
f) operating the cell to liberate manganese at the cathode and chlorine at the anode, the chlorine reacting with the ferro-manganese to provide a solid phase containing iron precipitate and spent ferromanganese, and a liquid phase containing manganese chloride, said iron precipitate and spent ferromanganese being prevented from passing from the anode compartment to the cathode compartment of the cell;
g) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese present in the anode compartment of the cell;
h) contacting the manganese chloride liquid phase with an additional quantity of ferromanganese to provide a purified liquid phase containing manganese chloride free of iron chlorides and chlorides more noble than manganese; and, i) introducing the purified manganese chloride liquid phase into the cathode compartment of the cell.
3, A method for recovering manganese metal from ferro-manganese which comprises:
a) contacting ferromanganese and an iron chloride selected from the group consisting of ferrous chloride and ferric chloride in a molten bath of alkali metal and/or alkaline earth metal chlorides, to provide a liquid phase containing manganese chloride and a solid phase containing iron precipitate and spent ferromanganese;
b) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese;
c) contacting the manganese chloride liquid phase with an additional quantity of ferromanganese to provide a purified liquid phase containing manganese chloride free of iron chlorides and chlorides of metals more noble than manganese;
d) introducing the purified manganese chloride liquid phase into the cathode compartment of an electrolytic cell;
e) introducing ferromanganese into the anode compartment of the cell;
f) conveying electrolyte from the cathode compartment to the anode compartment of the cell while preventing ferromanganese from passing from the anode compartment to the cathode compartment of the cell;
g) operating the cell to liberate manganese at the cathode and chlorine at the anode, the chlorine reacting with the ferro-manganese to provide a solid phase containing iron precipitate and spent ferromanganese and a liquid phase containing manganese chloride, said iron precipitate and spent ferromanganese being prevented from passing from the anode compartment to the cathode compartment of the cell;
h) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese present in the anode compartment of the cell;
i) contacting the manganese chloride liquid phase with an additional quantity of ferromanganese to provide a purified liquid phase containing manganese chloride free of iron chlorides and chlorides more noble than manganese; and j) introducing the purified manganese chloride liquid phase into the cathode compartment of the cell.
a) contacting ferromanganese and an iron chloride selected from the group consisting of ferrous chloride and ferric chloride in a molten bath of alkali metal and/or alkaline earth metal chlorides, to provide a liquid phase containing manganese chloride and a solid phase containing iron precipitate and spent ferromanganese;
b) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese;
c) contacting the manganese chloride liquid phase with an additional quantity of ferromanganese to provide a purified liquid phase containing manganese chloride free of iron chlorides and chlorides of metals more noble than manganese;
d) introducing the purified manganese chloride liquid phase into the cathode compartment of an electrolytic cell;
e) introducing ferromanganese into the anode compartment of the cell;
f) conveying electrolyte from the cathode compartment to the anode compartment of the cell while preventing ferromanganese from passing from the anode compartment to the cathode compartment of the cell;
g) operating the cell to liberate manganese at the cathode and chlorine at the anode, the chlorine reacting with the ferro-manganese to provide a solid phase containing iron precipitate and spent ferromanganese and a liquid phase containing manganese chloride, said iron precipitate and spent ferromanganese being prevented from passing from the anode compartment to the cathode compartment of the cell;
h) separating the manganese chloride liquid phase from the iron precipitate and spent ferromanganese present in the anode compartment of the cell;
i) contacting the manganese chloride liquid phase with an additional quantity of ferromanganese to provide a purified liquid phase containing manganese chloride free of iron chlorides and chlorides more noble than manganese; and j) introducing the purified manganese chloride liquid phase into the cathode compartment of the cell.
4. The method of claim 1 in which the recovered manganese is melted and separated from any solid cathode material which may be admixed therewith.
5. The method of claim 1 in which the ferromanganese is crushed prior to step (a).
6. The method of claim 1 in which the ferromanganese is a carbided ferromanganese containing from about 0.1% to about 8%
carbon.
carbon.
7. The method of claim 1 in which the molten metal chloride is an alkali metal chloride, an alkaline earth metal chloride, or combination thereof, having a melting point below about 700°C.
8. The method of claim 7 in which said molten chloride or combination of chlorides has a melting point below about 600°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BEPV0/156.765 | 1975-05-27 | ||
| BE156765A BE829554A (en) | 1975-05-27 | 1975-05-27 | MANGANESE METAL PREPARATION PROCESS FROM FERROMANGANESE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084865A true CA1084865A (en) | 1980-09-02 |
Family
ID=3842782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,458A Expired CA1084865A (en) | 1975-05-27 | 1976-05-27 | Method for recovering manganese metal from ferro- manganese |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5217309A (en) |
| AT (1) | AT362155B (en) |
| CA (1) | CA1084865A (en) |
| CH (1) | CH602942A5 (en) |
| DE (1) | DE2622898A1 (en) |
| GB (1) | GB1536211A (en) |
| IT (1) | IT1123605B (en) |
| NL (1) | NL7605624A (en) |
| SE (1) | SE409731B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60138434U (en) * | 1984-02-20 | 1985-09-13 | 株式会社井上ジャパックス研究所 | toothbrush device |
| GB2201969B (en) * | 1986-11-25 | 1990-09-19 | Nat Res Dev | Separating a ferro alloy |
-
1976
- 1976-05-21 DE DE19762622898 patent/DE2622898A1/en not_active Withdrawn
- 1976-05-25 AT AT381476A patent/AT362155B/en not_active IP Right Cessation
- 1976-05-25 NL NL7605624A patent/NL7605624A/en not_active Application Discontinuation
- 1976-05-26 CH CH665676A patent/CH602942A5/xx not_active IP Right Cessation
- 1976-05-26 SE SE7605990A patent/SE409731B/en unknown
- 1976-05-26 IT IT23680/76A patent/IT1123605B/en active
- 1976-05-27 CA CA253,458A patent/CA1084865A/en not_active Expired
- 1976-05-27 JP JP51061739A patent/JPS5217309A/en active Granted
- 1976-05-27 GB GB22105/76A patent/GB1536211A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1536211A (en) | 1978-12-20 |
| IT1123605B (en) | 1986-04-30 |
| DE2622898A1 (en) | 1976-12-09 |
| JPS555593B2 (en) | 1980-02-07 |
| ATA381476A (en) | 1980-09-15 |
| CH602942A5 (en) | 1978-08-15 |
| NL7605624A (en) | 1976-11-30 |
| AT362155B (en) | 1981-04-27 |
| SE7605990L (en) | 1976-11-28 |
| SE409731B (en) | 1979-09-03 |
| JPS5217309A (en) | 1977-02-09 |
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