US3630862A - Process for regenerating electrolytic solutions obtained in the electrolytic production of manganese dioxide - Google Patents

Process for regenerating electrolytic solutions obtained in the electrolytic production of manganese dioxide Download PDF

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Publication number
US3630862A
US3630862A US11513A US3630862DA US3630862A US 3630862 A US3630862 A US 3630862A US 11513 A US11513 A US 11513A US 3630862D A US3630862D A US 3630862DA US 3630862 A US3630862 A US 3630862A
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electrolytic
electrolyte
manganese
solution
calcium
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US11513A
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English (en)
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Eberhard Preisler
Kurt Grapentin
Ernst Harmsen
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Knapsack AG
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Knapsack AG
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/21Manganese oxides

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  • Aqueous electrolytic solutions containing manganese sulfate, calcium sulfate and sulfuric acid, obtained in the electrolytic production of manganese (1V)-oxide at elevated temperatures in electrolytic cells are regenerated.
  • the electrolytic solution is withdrawn from the electrolytic cell, cooled down to temperatures at least 5 centigrade degrees lower than the electrolysis temperature, precipitated matter is isolated therefrom after a period of at least 15 minutes, and the solution is recycled to the electrolytic cell.
  • the present invention relates to a process for regenerating aqueous electrolytic solutions containing manganese sulfate, calcium sulfate and sulfuric acid, obtained in the electrolytic production of manganese IV)-oxide at elevated temperatures.
  • Manganese dioxide is normally precipitated electrolytivally from a sulfuric acid manganese sulfate solution, at temperatures of between 80 and 98 C.
  • cell electrolyte a sulfuric acid manganese sulfate solution
  • an electrolyte portion to be withdrawn therefrom and to be neutralized by means of commercial manganese (III) -oxide prepared from crude manganese ore.
  • the resulting solution which is termed regenerated electrolyte hereinafter, is recycled to the cell electrolyte.
  • manganese ore is often found to contain rather considerable proportions of calcium compounds. These may appear in commercial manganese (ID-oxide produced therefrom, in the form of carbonates, sulfates, oxides or even silicates, for example.
  • ID-oxide produced therefrom, in the form of carbonates, sulfates, oxides or even silicates, for example.
  • cell electrolyte for ore-extraction, the above compounds are decomposed by the sulfuric acid contained in the electrolyte with the resultant formation of an equivalent proportion of calcium sulfate.
  • regenerated electrolyte solutions saturated or supersaturated with calcium sulfate are obtained.
  • the cell electrolyte and regenerated electrolyte are, however, strongly concentrated electrolytic solutions containing manganese sulfate together with magnesium sul fate and potassium sulfate, depending on the source of origin of the starting material, for example up to 0.5 mol/ liter magnesium sulfate in those cases in which African crude manganese dioxide is the starting material.
  • the cell electrolyte contains sulfuric acid in a rather high concentration of between about 0.2 and 1.0 mol/liter. In view of this, the salts and sulfuric acid aforesaid were tested as to their influence upon the temperature responsive solubility of CaSO -2H O.
  • FIG. 3 The strong influence of sulfuric acid on the temperature responsiveness of the solubility of CaSO -2H O is illustrated in FIG. 3 of the accompanying diagrams. As shown therein, the presence of H 50 in a concentration of merely 0.1 mol produces at C. a solubility approximately percent higher than that at 20 C.
  • the process of the present invention for regenerating an aqueous electrolytic solution containing manganese sulfate, calcium sulfate and sulfuric acid, obtained in the electrolytic production of manganese (IV)-oxide at elevated temperatures in an electrolytic cell comprises more particularly withdrawing the electrolyte solution from the electrolytic cell, cooling the solution down to temperatures at least 5 centigrade degrees, preferably 14 to 40 centigrade degrees lower than the electrolysis temperature, isolating precipitated matter therefrom after a period of at least 15 minutes, preferably 1 to 3 hours, and recycling the said solution to the electrolytic cell.
  • a preferred feature of the present invention comprises subjecting the electrolytic solutions, prior to cooling them, to treatment with manganese (II)-oxide or manganese (ID-carbonate to effect partial or complete neutralization of the sulfuric acid therein and, in the case of partial neutralization, neutralizing residual sulfuric acid by means of calcium oxide, calcium hydroxide or calcium carbonate.
  • manganese (II)-oxide or manganese (ID-carbonate) to effect partial or complete neutralization of the sulfuric acid therein and, in the case of partial neutralization, neutralizing residual sulfuric acid by means of calcium oxide, calcium hydroxide or calcium carbonate.
  • a further preferred feature of the present invention comprises neutralizing the electrolytic solution, freeing it from undissolved solid matter and then cooling it with agitation.
  • a still further preferred feature of the present invention provides for the quantities of water evaporated during the electrolysis and regeneration of the electrolyte to be replaced with corresponding quantities of fresh water, the water being added to the electrolytic solution following isolation of precipitated matter and prior to recycling the said solution to the electrolytic cell.
  • Room temperature is the lower temperature limit down to which the electrolytic solution should conveniently be cooled. Needless to say it is also possible for the solution to be cooled down to temperatures lower than room temperature, but this would imply the use of efficient cooling means and render the process a commercially less attractive procedure.
  • the solubility curves shown in FIG. 5 of the accompanying diagrams illustrate the basic idea underlying the process of the present invention.
  • the saturation solubility of the cell electrolyte is a function of its temperature (point A)
  • the suspension is found to at least cool down to a temperature at which the same saturation concentration is reached (point B).
  • the regenerated electrolyte is filtered to free it from undissolved or precipitated matter and recycled then to the cell electrolyte cycle.
  • FIG. 5 shows the solubility curves for CaSO -2H O for the electrolyte described in Example 1 hereinafter. As shown therein, the curve of the cell electrolyte is situated below the curve for the regenerated electrolyte. Thus, it is possible by inoculation with CaSO -2H O crystals at a given working temperature to always produce a regenerated electrolyte supersaturated with respect to the cell electrolyte. In other words, a cell electrolyte supersaturated with calcium sulfate would be obtained if the two electrolytes were mixed together.
  • EXAMPLE 1 The starting material was a cell electrolyte. It contained 110 grams MnSO 70 grams H grams MgSO and 3.5 kg. K 50 per liter and had a temperature of 95 C. The electrolyte was mixed in an agitator vessel with reduced manganese dioxide until the free sulfuric acid was found to have been substantially neutralized. It was immaterial whether the last residues of the free acid were neutralized with reduced crude manganese dioxide or with a further basic material, for example calcium carbonate, calcium hydroxide or sodium carbonate or a similar compound. The neutralized electrolyte was cooled with agitation, within 3 hours, down to a temperature of C., and filtered. The resulting regenerated electrolyte was recycled to the cell electrolyte cycle. CaSO -2H O could not be found to be precipitated therein.
  • EXAMPLE 2 The starting material was a cell electrolyte. It contained 100 grams MnSO 50 grams H 50 and 20 grams MgSO per liter and had a temperature of C.
  • the cell electrolyte was treated in the manner set forth in Example 1 using reduced crude manganese dioxide or, e.g. natural rhodochrosite (MnCO and the resulting suspension was conveyed from the agitator vessel to a settling tank, in which it was cooled down to about 40 C. and allowed to stand for some hours. Following filtration, the regenerated electrolyte was ready for use.
  • MnCO reduced crude manganese dioxide or, e.g. natural rhodochrosite
  • a process for regenerating an aqueous electrolytic solution containing manganese sulfate, calcium sulfate and sulfuric acid, obtained in the electrolytic production of manganese (IV)-oxide at elevated temperatures in an electrolytic cell which comprises withdrawing the electrolytic solution from the electrolytic cell, cooling the said solution down to temperatures at least 5 centigrade degrees lower than the electrolysis temperature, isolating precipitated matter therefrom after a period of at least 15 minutes, and recycling the said solution to the electrolytic cell.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US11513A 1969-02-20 1970-02-16 Process for regenerating electrolytic solutions obtained in the electrolytic production of manganese dioxide Expired - Lifetime US3630862A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1908416A DE1908416C3 (de) 1969-02-20 1969-02-20 Verfahren zum Regenerieren von wäßrigen mangansulfate calciumsulfat- und schwefelsäurehaltigen Elektrolytlösungen, die bei der elektrolytischen Gewinnung von Mangan(IV)-oxid anfallen

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US3630862A true US3630862A (en) 1971-12-28

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US11513A Expired - Lifetime US3630862A (en) 1969-02-20 1970-02-16 Process for regenerating electrolytic solutions obtained in the electrolytic production of manganese dioxide

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US (1) US3630862A (cs)
JP (1) JPS5518661B1 (cs)
BE (1) BE746290A (cs)
CS (1) CS166253B2 (cs)
DE (1) DE1908416C3 (cs)
FR (1) FR2037112B1 (cs)
GB (1) GB1292218A (cs)
NL (1) NL166730C (cs)
NO (1) NO126313B (cs)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01158293A (ja) * 1987-12-15 1989-06-21 Tlv Co Ltd スチームトラップの弁口構造

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1874827A (en) * 1931-05-12 1932-08-30 Burgess Battery Co Production of manganese dioxide
US2119560A (en) * 1936-09-10 1938-06-07 Stephen M Shelton Electrolytic process for the extraction of metallic manganese
FR1448939A (fr) * 1965-06-28 1966-08-12 E J Lavino & Co Procédé de préparation d'une solution de sulfate de manganèse à partir de ferromanganèse et d'un minerai essentiellement constitué par du bioxyde de manganèse

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Publication number Publication date
NO126313B (cs) 1973-01-22
DE1908416A1 (de) 1970-09-10
GB1292218A (en) 1972-10-11
CS166253B2 (cs) 1976-02-27
FR2037112A1 (cs) 1970-12-31
DE1908416C3 (de) 1974-06-12
NL7002456A (cs) 1970-08-24
FR2037112B1 (cs) 1974-08-09
BE746290A (fr) 1970-08-20
JPS5518661B1 (cs) 1980-05-20
NL166730B (nl) 1981-04-15
DE1908416B2 (de) 1973-11-08
NL166730C (nl) 1981-09-15

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