CA1069315A - Method for preparing manganese chloride and manganese by igneous electrolysis of the manganese chloride obtained - Google Patents
Method for preparing manganese chloride and manganese by igneous electrolysis of the manganese chloride obtainedInfo
- Publication number
- CA1069315A CA1069315A CA253,489A CA253489A CA1069315A CA 1069315 A CA1069315 A CA 1069315A CA 253489 A CA253489 A CA 253489A CA 1069315 A CA1069315 A CA 1069315A
- Authority
- CA
- Canada
- Prior art keywords
- manganese
- chloride
- compound
- oxidized
- reaction
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910021380 Manganese Chloride Inorganic materials 0.000 title claims abstract description 24
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 title claims abstract description 24
- 235000002867 manganese chloride Nutrition 0.000 title claims abstract description 24
- 239000011565 manganese chloride Substances 0.000 title claims abstract description 24
- 229940099607 manganese chloride Drugs 0.000 title claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 23
- 229910052748 manganese Inorganic materials 0.000 title claims description 23
- 239000011572 manganese Substances 0.000 title claims description 23
- 238000005868 electrolysis reaction Methods 0.000 title claims description 13
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 26
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 20
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000001110 calcium chloride Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005272 metallurgy Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 235000002908 manganese Nutrition 0.000 description 15
- 235000011148 calcium chloride Nutrition 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 235000011147 magnesium chloride Nutrition 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 241000982035 Sparattosyce Species 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 244000137282 Agathosma betulina Species 0.000 description 1
- 235000013388 Agathosma crenulata Nutrition 0.000 description 1
- 235000009269 Barosma crenulata Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000209117 Castanea crenata Species 0.000 description 1
- 235000003801 Castanea crenata Nutrition 0.000 description 1
- 101001126084 Homo sapiens Piwi-like protein 2 Proteins 0.000 description 1
- 102100029365 Piwi-like protein 2 Human genes 0.000 description 1
- GYMWQLRSSDFGEQ-ADRAWKNSSA-N [(3e,8r,9s,10r,13s,14s,17r)-13-ethyl-17-ethynyl-3-hydroxyimino-1,2,6,7,8,9,10,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-yl] acetate;(8r,9s,13s,14s,17r)-17-ethynyl-13-methyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-diol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.O/N=C/1CC[C@@H]2[C@H]3CC[C@](CC)([C@](CC4)(OC(C)=O)C#C)[C@@H]4[C@@H]3CCC2=C\1 GYMWQLRSSDFGEQ-ADRAWKNSSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229940062650 buchu Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/06—Halides; Oxyhalides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Silicon Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to a method for preparing manganese chloride from at least one oxidized manganese com-pound. The oxidized manganese compound is lixiviated with any one of calcium chloride, magnesium chloride or alkaline and alkaline-earth chlorides. The reaction between the oxidized compound and the chloride produces the manganese chloride in a liquid form. The method provides a high productivity yet obviates the problems of corrosion in the equipment and the requirement of condensing gases as in known methods.
This invention relates to a method for preparing manganese chloride from at least one oxidized manganese com-pound. The oxidized manganese compound is lixiviated with any one of calcium chloride, magnesium chloride or alkaline and alkaline-earth chlorides. The reaction between the oxidized compound and the chloride produces the manganese chloride in a liquid form. The method provides a high productivity yet obviates the problems of corrosion in the equipment and the requirement of condensing gases as in known methods.
Description
10~ 15 This invcntion has for object a method ~or preparing manganese chloride from at least one oxidized manganese compound.
This method is particularly useful for elabo-rating metal manganese with more than 95% maganese by igneous electrolysis.
It is known in the present art, as described in the following disclosures:A.H. SULLY - Manganese -Butterworths - London (1955~, Ullmans Encyklopadie der Technischen Chemie- Band 12 - Urban und Schwartzenberg -M~nchen - (1960), DURRER/VOLKERT - Mettalurgie der Ferrole-gierungen-Springer Verlag Berlin ~1972), to elaborate the metal manganese by silicothermic or aluminothermic reduction of oxidized manganese compounds, by electrolysis in aqueous sulfuric solution (R.S. DEAN-Electrolytic Manganese and its Alloys - The Ronald Press Company - New-York - 1952) or in aqueous hydrochloric solution (J.H. JACOBS and P.E. CHURCHWARD
Trans. Electrochem. Soc. 94 (1948) 108-121), by electrolysis of oxidized manganese compounds dissolved in calcium fluoride (U.S. Pat. 3,018,233) or by electrolysis of molten oxide mixtures (Belgian Pat. 683,660~. Many works show moreover that it is easy to obtain manganese at the cathode of an electrolysis cell operating with molten chloride baths in which the manganese is present as manganous chloride MnC12 ~U.S. Pat. 2,752,299 ; 2,752,303 ; 2,877,110 ; 3,024,106 ;
Brit. Pat. 880,017).
It thus became clear that the manganous chloride could form an attractive raw material for the preparation of metal manganese by electrolysis as long as it is possible to obtain an electrolyte containing manganous chloride under ~ .
- 1 - ~
t~
attractive cost conditions.
For instance to elaborate manganous chloride, many writers have studied the chlorinating of oxidized manganese compounds by chlorine gas and by hydrochloric acid gas:U.S. Pat. 2,752,299 ; Brit.Pat. 880,017 ; G.Pat. 1,106,622 ;
Y. OKAHARA and I. IWASAKI - Trans. AIME 247 (1970)73-80 ;B.T.
MAC MILLAN and T. L. TURNER - U. S. Bureau of Mines R.I. 5082 (1954) and 5281 (1954) ; A.A. COCHRAN and W. L. FALKE - J. of Metals-(1967) 28-32 - U.S. Bureau of Mines R.I. 6859 (1967);
H. HOHN, B. JANGG, L. PUTZ and E. SCHMILD, Progress in Mineral Dressing - Ed. Almgvistand Wiskell (Sweden) (1958)683-703 -Y. G. BUCHU - KURI and M. I . MEHEDLISHVILI Soobshch. Akad. Nauk.
Gruz . S . S . R. 57 ( 2) ~1970) 349-352~ .
Such a chlorinating reaction leads either to volatilizing the manganous chloride which is thereafter condensed, or to the forming of a chlorinated mass obtained with said reaction and containing said manganous chloride, which manganous chloride can be separated by aqueous lixiviating.
In the latter case, the manganous chloride is crystallized by ~vaporating the water from the aqueous solution and thereafter it is dehydrate by heating.
Said elaborating methods have however many drawbacks which are notably associated with the treatment instal-lations being corroded by the chlorine or hydrochloric acid, w~ th~ problems for condensing chloride gases or with the diffi-culty for dehydrating the manganous chloride without conta-minating same with oxides or hydroxides.
Still another method lies in performing the volatilizing chlorinating of manganese from oxidized manganese compounds by making use of calcium chloride as chlorinating 3~5 agent, as described by M~C MILI~N and ~rul~ER (U.S. Bureau of Mines R.I. 5082 (1954) and 5281 (1954) above), and A.
BOYADZHIEV (Minne Delo Met. (Sofia) 18 (7) (1963) 29-33).
A technical and economical study of this latter method shows that even if it is easier to perform than chlorinating with chlorine gas or hydrochloric acid gas due to the better behaving of the installations relative to corrosion, it is however required to use a very high flow rate of carrier gas to insure a high enough productivity on an industrial scale, and the condensing of MnC12 vapour even if it is possible causes technological problems which are difficult to solve to ob~ain satisfactory condensing through-puts.
The object of the invention is to provide a new method for preparing manganese chloride from oxidized manga-nese compounds, particularly the preparation of an electro-lyte for the igneous electrolysis used to produce manganese chloride, method with which it is possible to obviate the drawbacks of the above-described known methods.
For this purpose according to the invention, the oxidized mansanese compound is lixiviated with at least one chloride selected in the group formed by the calcium chloride anf the magnesium chloride~ so as to obtain by the reaction of the oxidized compound with said chloride, the manganese chloride in the liquid form.
Advantageously the oxidized manganese compound is lixiviated with a molten salt bath that contains besides one compound selected in the group formed by the calcium chloride and the magnesium chloride, alkaline and alkaline-earth chlorides other than the ones mentioned above.
Other details and ~eatures of the invention will stand out from the description given below by way of non limitative example, of some embodiments vf the invention.
The method according to the invention lies essetially in the lixiviating of the oxidized manganese compounds with calcium dichloride, magnesium dichloride or mixtuxes of alkaline or alkaline-earth chlorides that contain at least one of both said c~lorides so as to elabo-rate directly manganous chloride in liquid form, in solution in a molten salt bath. Thus the problem associated with the volatilizing and condensing of the manganous chloride as in the known art, is avoided.
It has been noticed according to the invention that it is easily possible to separate by decanting and filtering, the solid residue obtained by reacting calcium chloride and/or magnesium chloride with oxidized manganese compounds from the molten chloride bath formed so as to obtain directly an electrolyte which after puryfying, for example by a pre-electrolysis under low voltage or by a treatment with crushed ferro-manganese as described in ano ther patent in the name o~ the Inventor, could be subjected to electrolysis for elaborating metal manganese.
Advantageously in the method according to the invention, the chlorine contained in the calcium chloride or magnesium chloride used for lixiviating and released at the electrolysis cell anode can be recovered and commercia-lized. This is a remarkable advantage relative to the known methods for chlorinating with chlorine gas or hydrochloric acid gas.
The exidized manganese compounds to be r~acted ~0~1315 with the calcium chloride anc~or mac3nesium chloride are manganous oxide, manganese carbonate, hlgher oxicles such as Mn304, Mn203 or MnO2, hydrated, carbonated, siliceous or oxidized manganese ores, or else metallurgy residues such as slag from Martin furnace, electric steel furnace or ferro-manganese or silicomanganese-elaborating furnace, that is any material containing manganese combined with oxygen.
In a particularly advantageous embodiment, use is made as oxidized manganese compound, of a compound in which the manganese is bivalent; under such conditions, said oxidized compound is comprised of manganese carbonate, it is not required to decompose same before performing thereon the chlorinating; the decomposition may indeed occur together with the chlorinating.
On the other hand, if the manganese present in the oxidized compound to be treated has a valence higher than two, it might beadvantageous but not indispensable to perform a previous reduction of the oxidized manganese compound down to valence two for example by means of carb~n monoxide, hydrogen or carbon, or to perform the chlorinating in a reducing atmosphere in the presence of a solid reducing agent such as carbon.
In a preferred embodiment of the invention, silica, alumina or a mixture of both said materials is added to the oxidized manganese compound to be chlorinated, so as to form silicates, aluminates or silico-a]uminates together with the calcium or magnesium oxides produced by the chlo-rinating reaction. Under such conditions, the temperature to he reached for the lixiviation may be lower by a hundred Celsius degrees relative to that temperature which would ~0~:3~5 be required in the absence of sllica or alumina to obtain the same manganous chloride concentration in the molten salt bath.
It is clear that the silica or alumina could also be part of the oxidized manganese compound to be chlori-nated, which would be the case for slag or ore for example.
- Moreover in some cases to lower the melting point of the ~lectrolyte, to lower the vapour pressure or to influence the thermodynamic action of one component in the molten salt bath before or after the chlorinating reaction, it might be useful to add to the molten salts, small amounts of other haloids or oxides.
A practical example of a particular embodiment of the method according to the invention will be ~iven hereinafter.
Example.
Loads each comprising one mole MnO or MnC03 have been heated in the presence of one mole CAC12 and one half mole SiO2 under cover from air during one half hour at various temperatures. After decanting, it did appear that the overfleoting liquid phase comprising MnC12 and CaC12 had molar ratios MnC12/CaC12 from 0.2 to 0.8 when the reaction temperature is raised from 800 to 1000Co The tests have shown that the reaction is very fast and that the balance appears to be reached. Moreover, the solid residue is easi-ly de~anted and the hot filtering does not cause any problem.
The elaboratea MnC12-CaC12mLxture~éæ suitable f~ a direct electrolysis which gave solid, powdery and dendritic manganese deposits. After melting said deposits, it was pos-sible to obtain massive manganese metal with a puritybetter than 99.9% manganese.
It is o be noticed that the usable temperature ~0~,315 range is very large, said temperature being limited on the one hand but by the melting temperature of the chloride mixture used for lixiviating and on the other hand but by the boiling point of the manganous chloride that lies at 1230~C when it has a unit thermodynamic activity and a higher temperature when this thermodynamlc activity is lower than a unit value. However due to kinetic reaction conditions on the one hand and to spare the energy required on the other hand, it has been noticed that temperatures lying between 300 and 1200C and preferably between 500 and llOO~C
allow to obtain valid industrial resu~ts.
The calcium chloride used can be a~y-product of the Solvay method for elaborating sodium carbonate or it can originate from more complex salts extracted from underground rock-salt mines or salt-pans, or even rom brine from sea-water unsalting installations after evaporating and dehydrating.
It must be understood that the invention is in no way limited to the above embodiments and that many changes can be brought therein without departing from the scope of the invention as defined by the appended claims.
This method is particularly useful for elabo-rating metal manganese with more than 95% maganese by igneous electrolysis.
It is known in the present art, as described in the following disclosures:A.H. SULLY - Manganese -Butterworths - London (1955~, Ullmans Encyklopadie der Technischen Chemie- Band 12 - Urban und Schwartzenberg -M~nchen - (1960), DURRER/VOLKERT - Mettalurgie der Ferrole-gierungen-Springer Verlag Berlin ~1972), to elaborate the metal manganese by silicothermic or aluminothermic reduction of oxidized manganese compounds, by electrolysis in aqueous sulfuric solution (R.S. DEAN-Electrolytic Manganese and its Alloys - The Ronald Press Company - New-York - 1952) or in aqueous hydrochloric solution (J.H. JACOBS and P.E. CHURCHWARD
Trans. Electrochem. Soc. 94 (1948) 108-121), by electrolysis of oxidized manganese compounds dissolved in calcium fluoride (U.S. Pat. 3,018,233) or by electrolysis of molten oxide mixtures (Belgian Pat. 683,660~. Many works show moreover that it is easy to obtain manganese at the cathode of an electrolysis cell operating with molten chloride baths in which the manganese is present as manganous chloride MnC12 ~U.S. Pat. 2,752,299 ; 2,752,303 ; 2,877,110 ; 3,024,106 ;
Brit. Pat. 880,017).
It thus became clear that the manganous chloride could form an attractive raw material for the preparation of metal manganese by electrolysis as long as it is possible to obtain an electrolyte containing manganous chloride under ~ .
- 1 - ~
t~
attractive cost conditions.
For instance to elaborate manganous chloride, many writers have studied the chlorinating of oxidized manganese compounds by chlorine gas and by hydrochloric acid gas:U.S. Pat. 2,752,299 ; Brit.Pat. 880,017 ; G.Pat. 1,106,622 ;
Y. OKAHARA and I. IWASAKI - Trans. AIME 247 (1970)73-80 ;B.T.
MAC MILLAN and T. L. TURNER - U. S. Bureau of Mines R.I. 5082 (1954) and 5281 (1954) ; A.A. COCHRAN and W. L. FALKE - J. of Metals-(1967) 28-32 - U.S. Bureau of Mines R.I. 6859 (1967);
H. HOHN, B. JANGG, L. PUTZ and E. SCHMILD, Progress in Mineral Dressing - Ed. Almgvistand Wiskell (Sweden) (1958)683-703 -Y. G. BUCHU - KURI and M. I . MEHEDLISHVILI Soobshch. Akad. Nauk.
Gruz . S . S . R. 57 ( 2) ~1970) 349-352~ .
Such a chlorinating reaction leads either to volatilizing the manganous chloride which is thereafter condensed, or to the forming of a chlorinated mass obtained with said reaction and containing said manganous chloride, which manganous chloride can be separated by aqueous lixiviating.
In the latter case, the manganous chloride is crystallized by ~vaporating the water from the aqueous solution and thereafter it is dehydrate by heating.
Said elaborating methods have however many drawbacks which are notably associated with the treatment instal-lations being corroded by the chlorine or hydrochloric acid, w~ th~ problems for condensing chloride gases or with the diffi-culty for dehydrating the manganous chloride without conta-minating same with oxides or hydroxides.
Still another method lies in performing the volatilizing chlorinating of manganese from oxidized manganese compounds by making use of calcium chloride as chlorinating 3~5 agent, as described by M~C MILI~N and ~rul~ER (U.S. Bureau of Mines R.I. 5082 (1954) and 5281 (1954) above), and A.
BOYADZHIEV (Minne Delo Met. (Sofia) 18 (7) (1963) 29-33).
A technical and economical study of this latter method shows that even if it is easier to perform than chlorinating with chlorine gas or hydrochloric acid gas due to the better behaving of the installations relative to corrosion, it is however required to use a very high flow rate of carrier gas to insure a high enough productivity on an industrial scale, and the condensing of MnC12 vapour even if it is possible causes technological problems which are difficult to solve to ob~ain satisfactory condensing through-puts.
The object of the invention is to provide a new method for preparing manganese chloride from oxidized manga-nese compounds, particularly the preparation of an electro-lyte for the igneous electrolysis used to produce manganese chloride, method with which it is possible to obviate the drawbacks of the above-described known methods.
For this purpose according to the invention, the oxidized mansanese compound is lixiviated with at least one chloride selected in the group formed by the calcium chloride anf the magnesium chloride~ so as to obtain by the reaction of the oxidized compound with said chloride, the manganese chloride in the liquid form.
Advantageously the oxidized manganese compound is lixiviated with a molten salt bath that contains besides one compound selected in the group formed by the calcium chloride and the magnesium chloride, alkaline and alkaline-earth chlorides other than the ones mentioned above.
Other details and ~eatures of the invention will stand out from the description given below by way of non limitative example, of some embodiments vf the invention.
The method according to the invention lies essetially in the lixiviating of the oxidized manganese compounds with calcium dichloride, magnesium dichloride or mixtuxes of alkaline or alkaline-earth chlorides that contain at least one of both said c~lorides so as to elabo-rate directly manganous chloride in liquid form, in solution in a molten salt bath. Thus the problem associated with the volatilizing and condensing of the manganous chloride as in the known art, is avoided.
It has been noticed according to the invention that it is easily possible to separate by decanting and filtering, the solid residue obtained by reacting calcium chloride and/or magnesium chloride with oxidized manganese compounds from the molten chloride bath formed so as to obtain directly an electrolyte which after puryfying, for example by a pre-electrolysis under low voltage or by a treatment with crushed ferro-manganese as described in ano ther patent in the name o~ the Inventor, could be subjected to electrolysis for elaborating metal manganese.
Advantageously in the method according to the invention, the chlorine contained in the calcium chloride or magnesium chloride used for lixiviating and released at the electrolysis cell anode can be recovered and commercia-lized. This is a remarkable advantage relative to the known methods for chlorinating with chlorine gas or hydrochloric acid gas.
The exidized manganese compounds to be r~acted ~0~1315 with the calcium chloride anc~or mac3nesium chloride are manganous oxide, manganese carbonate, hlgher oxicles such as Mn304, Mn203 or MnO2, hydrated, carbonated, siliceous or oxidized manganese ores, or else metallurgy residues such as slag from Martin furnace, electric steel furnace or ferro-manganese or silicomanganese-elaborating furnace, that is any material containing manganese combined with oxygen.
In a particularly advantageous embodiment, use is made as oxidized manganese compound, of a compound in which the manganese is bivalent; under such conditions, said oxidized compound is comprised of manganese carbonate, it is not required to decompose same before performing thereon the chlorinating; the decomposition may indeed occur together with the chlorinating.
On the other hand, if the manganese present in the oxidized compound to be treated has a valence higher than two, it might beadvantageous but not indispensable to perform a previous reduction of the oxidized manganese compound down to valence two for example by means of carb~n monoxide, hydrogen or carbon, or to perform the chlorinating in a reducing atmosphere in the presence of a solid reducing agent such as carbon.
In a preferred embodiment of the invention, silica, alumina or a mixture of both said materials is added to the oxidized manganese compound to be chlorinated, so as to form silicates, aluminates or silico-a]uminates together with the calcium or magnesium oxides produced by the chlo-rinating reaction. Under such conditions, the temperature to he reached for the lixiviation may be lower by a hundred Celsius degrees relative to that temperature which would ~0~:3~5 be required in the absence of sllica or alumina to obtain the same manganous chloride concentration in the molten salt bath.
It is clear that the silica or alumina could also be part of the oxidized manganese compound to be chlori-nated, which would be the case for slag or ore for example.
- Moreover in some cases to lower the melting point of the ~lectrolyte, to lower the vapour pressure or to influence the thermodynamic action of one component in the molten salt bath before or after the chlorinating reaction, it might be useful to add to the molten salts, small amounts of other haloids or oxides.
A practical example of a particular embodiment of the method according to the invention will be ~iven hereinafter.
Example.
Loads each comprising one mole MnO or MnC03 have been heated in the presence of one mole CAC12 and one half mole SiO2 under cover from air during one half hour at various temperatures. After decanting, it did appear that the overfleoting liquid phase comprising MnC12 and CaC12 had molar ratios MnC12/CaC12 from 0.2 to 0.8 when the reaction temperature is raised from 800 to 1000Co The tests have shown that the reaction is very fast and that the balance appears to be reached. Moreover, the solid residue is easi-ly de~anted and the hot filtering does not cause any problem.
The elaboratea MnC12-CaC12mLxture~éæ suitable f~ a direct electrolysis which gave solid, powdery and dendritic manganese deposits. After melting said deposits, it was pos-sible to obtain massive manganese metal with a puritybetter than 99.9% manganese.
It is o be noticed that the usable temperature ~0~,315 range is very large, said temperature being limited on the one hand but by the melting temperature of the chloride mixture used for lixiviating and on the other hand but by the boiling point of the manganous chloride that lies at 1230~C when it has a unit thermodynamic activity and a higher temperature when this thermodynamlc activity is lower than a unit value. However due to kinetic reaction conditions on the one hand and to spare the energy required on the other hand, it has been noticed that temperatures lying between 300 and 1200C and preferably between 500 and llOO~C
allow to obtain valid industrial resu~ts.
The calcium chloride used can be a~y-product of the Solvay method for elaborating sodium carbonate or it can originate from more complex salts extracted from underground rock-salt mines or salt-pans, or even rom brine from sea-water unsalting installations after evaporating and dehydrating.
It must be understood that the invention is in no way limited to the above embodiments and that many changes can be brought therein without departing from the scope of the invention as defined by the appended claims.
Claims (12)
1. Method for preparing manganese chloride from at least one oxidized manganese compound, in which the oxidized manganese compound is lixiviated with at least one chloride selected in the group formed by the calcium chloride and the magnesium chloride, so as to obtain, by the reaction of the oxidized compound with said chloride, the manganese chloride in the liquid form.
2. Method as defined in claim 1, in which the oxidized manganese compound is lixiviated at a temperature lying between 300 and 1200°C.
3. Method as defined in claim 2, in which the oxidized manganese compound is lixiviated at a temperature lying between 500 and 1100°C.
4. Method as defined in claim 1, in which the oxidized manganese compound is lixiviated with a molten salt bath that contains besides one compound selected in the group formed by the calcium chloride and the magnesium chloride, alkaline and alkaline-earth chlorides other than the ones mentioned above.
5. Method as defined in claim 4, in which after the reaction of the oxidized manganese compound with the calcium chloride or magnesium chloride, a decanting is performed followed by a hot filtering so as to separate the reaction solid residue.
6. Method as defined in claim 1, in which after the reaction of the oxidized manganese compound with the calcium chloride and/or magnesium chloride, the metals nobler than manganese are removed from the molten salt bath.
7. Method as defined in claim 1, in which the liquid manganese chloride is subjected to an igneous electro-lysis so as to settle the manganese on the cathode.
8. Method as defined in claim 7, in which the manganese settled on the cathode is subjected to a melting followed by solidifying.
9. Method as defined in claim 1, in which the compound subjected to lixiviating is selected in the group comprised of MnO, Mn304, Mn203, MnO2, manganese carbonate, hydrated, carbonated, siliceous or oxidized manganese ores, metallurgy residues such as slag from Martin furnace, electric steel furnace and ferromanganese or silicomanga-nese-elaborating furnace.
10. Method as defined in claim 9, in which when the oxidized manganese compound contains at least a portion of manganese with a valence higher than two, said lixiviating is made in the presence of a reducing agent such as carbon monoxide, hydrogen or carbon.
11. Method as defined in claim 9, in which when the oxidized manganese compound contains at least a portion of manganese with a valence higher than two, said compound is subjected to a reducing treatment for bringing substantially all of the manganese down to valence two before said lixiviating.
12. Method as defined in claim 1, in which before lixiviating, to the oxidized manganese compound is added at least one compound selected in the group compri-sed of silica and alumina.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE156764A BE829553A (en) | 1975-05-27 | 1975-05-27 | PROCESS FOR PREPARING MANGANESE CHLORIDE AS WELL AS MANGANESE BY ELECTROLYSIS IGNEE OF MANGANESE CHLORIDE OBTAINED |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1069315A true CA1069315A (en) | 1980-01-08 |
Family
ID=3842781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,489A Expired CA1069315A (en) | 1975-05-27 | 1976-05-27 | Method for preparing manganese chloride and manganese by igneous electrolysis of the manganese chloride obtained |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5217392A (en) |
| AT (1) | AT349434B (en) |
| CA (1) | CA1069315A (en) |
| CH (1) | CH601112A5 (en) |
| DE (1) | DE2623436A1 (en) |
| GB (1) | GB1536041A (en) |
| IT (1) | IT1063201B (en) |
| NL (1) | NL7605625A (en) |
| SE (1) | SE409850B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2137716C1 (en) * | 1997-10-23 | 1999-09-20 | Институт органического синтеза Уральского отделения РАН | Method of anhydrous manganese (ii) chloride producing |
| RU2179529C1 (en) * | 2000-07-07 | 2002-02-20 | Институт органического синтеза Уральского отделения Российской академии наук | Method of preparing anhydrous manganese chloride |
| NO317073B1 (en) * | 2001-06-05 | 2004-08-02 | Sintef | Electrolyte and process for the manufacture or refining of silicon |
| RU2372291C2 (en) * | 2004-09-23 | 2009-11-10 | Сёва Дэнко К.К. | Method of producing manganese tetrafluoride |
-
1976
- 1976-05-25 NL NL7605625A patent/NL7605625A/en not_active Application Discontinuation
- 1976-05-25 DE DE19762623436 patent/DE2623436A1/en not_active Withdrawn
- 1976-05-25 IT IT2357876A patent/IT1063201B/en active
- 1976-05-26 SE SE7605989A patent/SE409850B/en unknown
- 1976-05-26 AT AT384476A patent/AT349434B/en not_active IP Right Cessation
- 1976-05-26 CH CH665576A patent/CH601112A5/xx not_active IP Right Cessation
- 1976-05-27 CA CA253,489A patent/CA1069315A/en not_active Expired
- 1976-05-27 GB GB2210476A patent/GB1536041A/en not_active Expired
- 1976-05-27 JP JP6173876A patent/JPS5217392A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2623436A1 (en) | 1976-12-16 |
| IT1063201B (en) | 1985-02-11 |
| ATA384476A (en) | 1978-09-15 |
| JPS5217392A (en) | 1977-02-09 |
| JPS5537491B2 (en) | 1980-09-29 |
| CH601112A5 (en) | 1978-06-30 |
| NL7605625A (en) | 1976-11-30 |
| AT349434B (en) | 1979-04-10 |
| SE7605989L (en) | 1976-11-28 |
| GB1536041A (en) | 1978-12-20 |
| SE409850B (en) | 1979-09-10 |
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