US2356515A - Methods for producing manganese in metal state and pure manganese dioxide, if desired, from manganese ores - Google Patents
Methods for producing manganese in metal state and pure manganese dioxide, if desired, from manganese ores Download PDFInfo
- Publication number
- US2356515A US2356515A US411430A US41143041A US2356515A US 2356515 A US2356515 A US 2356515A US 411430 A US411430 A US 411430A US 41143041 A US41143041 A US 41143041A US 2356515 A US2356515 A US 2356515A
- Authority
- US
- United States
- Prior art keywords
- manganese
- solution
- pure
- dioxide
- producing
- 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 - Lifetime
Links
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title description 16
- 229910052748 manganese Inorganic materials 0.000 title description 15
- 239000011572 manganese Substances 0.000 title description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title description 14
- 238000000034 method Methods 0.000 title description 12
- 229910052751 metal Inorganic materials 0.000 title description 4
- 239000002184 metal Substances 0.000 title description 4
- 239000000243 solution Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 229940124024 weight reducing agent Drugs 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910017358 Fe2(SO4) Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical compound [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
Definitions
- This invention has ior its object a producing-metallic manganese and'if'desired pure manganese dioxide, from manganese ores.
- the manganese ore is converted into manganese sulphate by solution in sulphuric acid or, at least in part, by the anolyte recovered from a final electrolysis step in the process, and by operating in presence of a reducing agent which converts the manganese dioxide, being by itself only slightly responsive to'attack by diluted acids, into manganese monoxide which on the contrary is easily attacked.
- a mixed solution of manganese sul- -phate and of'sulphate of the element used as reducing agent is thus obtained; said solution is subsequently neutralised for the precipitation of the .reducingagent from the solution and the latter is subsequently carried again into the process.
- the electrolysis is carried out with advantage in such a manner as to obtain and keep the anolyte and catholyte separate for their re-use in the process.
- Pyrolusite is dissolved by means of sulphuric acid in the presence of ferrous sulphate which acts as a reducing agent; the manganese oxides are'thus reduced into manganese monoxide and are dissolved by sulphuric acid thus producing a lusite having a 50% content of M1102, 70 kg. of iron are used said iron being recovered in the process,.and 600 kg. of diluted (20%) sulphuric acid,.this acid also being recovered.
- the electrolysis step is carried out with the aid of porous separating partitions in conditions proper to obtain the catholyte separately.
- the neutralisation step may be improved by having the residual ferrous salts, if any, converted into i'erricstate by a Previous addition ofmanganese dioxide obtained in theelectrolysis step.
- the ferric hydrate which precipitates as an effect of the neutralisation may be regenerated into ferrous sulphate which is subsequently carried'again in the process in the ore solution step; for this purpose the ferric hydrate is dissolved in sulphuric-acid in the presence of sulphur dioxide or of an alkali sulphide or, in accordance with a feature of this invention, in the anolyte recovered from the electrolysis stepand consisting of an acid solution of manganese sulphate and-of. ammonium sulphate.
- the solution thus obtained consisting of pure manganese sulphate, is treated by an electrolysis step in which manganese in metal state is obtained at the cathode, a portion of said mang'anese being usedif desired for the purification of the solution as above stated; by a proper control of the electrolysis step it is also. possible to obtain pure manganese dioxide on the anode, which may be used in oxidising steps preceding the neutralisation step.
- Theelectrolysis is effected with advantage by means of cells having porous partitions to secure the separation of the anolyte and catholyte from each other; in these circumstances the acid anolyte is obtained separately for further use either in the attack of the ore or'for regenerating the ferric hydrate which has been precipitated as an 'efiect of the neutralisation step, said ferric hydrate being regenerated into ferrous sulphate by treatment with said anolyte in presence of a reducing agent; on the other hand the recovered catholyte may be used again in the process for neutralizing the acid solution of manganese sulphate, ferric sulphate and ammonium sulphate.
Description
' solution of MnSOr and Fe2(SO4) Say for the purpose of treating 100 kg. of pyro- Patented Aug. 22, 1944- METHODS FOR PRODUCING MANGAN IN METAL STATE AND PURE MANGANESE DI- OXIDE, IF DESIRED,
ORES
FROM. MANGANESE Pietro Guareschi', Genoa, Italy; vested in the Alien Property Custodian .No Drawing. AppIicationJSeptember 18,- 1941, Serial No. 411,430. .In Italy October 8, 1940 This invention has ior its object a producing-metallic manganese and'if'desired pure manganese dioxide, from manganese ores.
In the method of this invention the manganese ore is converted into manganese sulphate by solution in sulphuric acid or, at least in part, by the anolyte recovered from a final electrolysis step in the process, and by operating in presence of a reducing agent which converts the manganese dioxide, being by itself only slightly responsive to'attack by diluted acids, into manganese monoxide which on the contrary is easily attacked. A mixed solution of manganese sul- -phate and of'sulphate of the element used as reducing agent is thus obtained; said solution is subsequently neutralised for the precipitation of the .reducingagent from the solution and the latter is subsequently carried again into the process.
Finally the solution of manganese sulphate is electrolysed and thus metallic manganese and,
-if desired, pure manganese .dioxide is obtained;
the electrolysis is carried out with advantage in such a manner as to obtain and keep the anolyte and catholyte separate for their re-use in the process.
As reducing agent a solution'of a soluble iron salt in ferrous state is used with advantage since -most of impurities presentinthe ore and consisting usually mainly of iron, arsenic,antimony,
-etc. precipitate with said salt at the time of the neutralisation step. r
An embodiment of theamethod of this invention is hereinafter described by way of example assuming that pyrolusite is treated and that iron is used as reducing agent.
Pyrolusite is dissolved by means of sulphuric acid in the presence of ferrous sulphate which acts as a reducing agent; the manganese oxides are'thus reduced into manganese monoxide and are dissolved by sulphuric acid thus producing a lusite having a 50% content of M1102, 70 kg. of iron are used said iron being recovered in the process,.and 600 kg. of diluted (20%) sulphuric acid,.this acid also being recovered.
The removal of impurities of the class of cop- I per, zinc, cadmium, etc., from the. solution is, ef-
fected by precipitating saidmetals by pure electrolytic manganese in powder state, said manganese being taken from the manganese obtained by electrolysis in the final step of the process. 4 Subsequently iron is precipitated by neutralising the solution; said neutralisation may be ef- 1 Claim. (01. 204-105) method for.
fected as usually by means of calcium carbonate or ammonia gas or in solution in presence of ammonium salts, or preferably, in accordance with this invention, by taking advanfageof the catholyte recovered from the subsequent electrolysis stepand consisting of an alkaline solution of ammonium salts with manganese sulphate;
.forsuch apurpose the electrolysis step is carried out with the aid of porous separating partitions in conditions proper to obtain the catholyte separately.
The neutralisation step may be improved by having the residual ferrous salts, if any, converted into i'erricstate by a Previous addition ofmanganese dioxide obtained in theelectrolysis step.
The ferric hydrate which precipitates as an effect of the neutralisation may be regenerated into ferrous sulphate which is subsequently carried'again in the process in the ore solution step; for this purpose the ferric hydrate is dissolved in sulphuric-acid in the presence of sulphur dioxide or of an alkali sulphide or, in accordance with a feature of this invention, in the anolyte recovered from the electrolysis stepand consisting of an acid solution of manganese sulphate and-of. ammonium sulphate.
The solution thus obtained, consisting of pure manganese sulphate, is treated by an electrolysis step in which manganese in metal state is obtained at the cathode, a portion of said mang'anese being usedif desired for the purification of the solution as above stated; by a proper control of the electrolysis step it is also. possible to obtain pure manganese dioxide on the anode, which may be used in oxidising steps preceding the neutralisation step.
Theelectrolysis is effected with advantage by means of cells having porous partitions to secure the separation of the anolyte and catholyte from each other; in these circumstances the acid anolyte is obtained separately for further use either in the attack of the ore or'for regenerating the ferric hydrate which has been precipitated as an 'efiect of the neutralisation step, said ferric hydrate being regenerated into ferrous sulphate by treatment with said anolyte in presence of a reducing agent; on the other hand the recovered catholyte may be used again in the process for neutralizing the acid solution of manganese sulphate, ferric sulphate and ammonium sulphate.
What I claim as myinvention and desire to secure by United States Letters Patent is-:
The cyclic process of producing metallic manganese from impure manganese dioxide ores,
which'consists in treating the ore with sulphuric anolyte and acid in the presence of ferrous sulphate; adding metallic manganese to the resulting solution to precipitate metal impurities less electro-positlve' than manganese, adding manganese dioxide to convert the iron to the ferric state, neutralizing the solution by the addition of an alkali to precipitate ferric iron, filtering out the latter, electrolyzing the filtrate in a diaphragm-type cell to deposit metallic manganese at the cathode and generate the solution and returning it to the ore dissolving step.
PIETRO GUARESCHI.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2356515X | 1940-10-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2356515A true US2356515A (en) | 1944-08-22 |
Family
ID=11435440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US411430A Expired - Lifetime US2356515A (en) | 1940-10-08 | 1941-09-18 | Methods for producing manganese in metal state and pure manganese dioxide, if desired, from manganese ores |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2356515A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2417259A (en) * | 1942-04-15 | 1947-03-11 | American Manganese Corp | Electrolytic process for preparing manganese and manganese dioxide simultaneously |
| US2542888A (en) * | 1944-09-14 | 1951-02-20 | Ever Ready Co | Electrochemical processes of producing manganese from aqueous manganese salt solution |
| US2546547A (en) * | 1945-02-26 | 1951-03-27 | Crimora Res And Dev Corp | Electrodeposition of manganese |
| US2741590A (en) * | 1953-02-19 | 1956-04-10 | Kunin Robert | Electrolytic recovery of manganese |
| US2798038A (en) * | 1953-12-02 | 1957-07-02 | Reginald S Dean | Electrodepositing manganese |
-
1941
- 1941-09-18 US US411430A patent/US2356515A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2417259A (en) * | 1942-04-15 | 1947-03-11 | American Manganese Corp | Electrolytic process for preparing manganese and manganese dioxide simultaneously |
| US2542888A (en) * | 1944-09-14 | 1951-02-20 | Ever Ready Co | Electrochemical processes of producing manganese from aqueous manganese salt solution |
| US2546547A (en) * | 1945-02-26 | 1951-03-27 | Crimora Res And Dev Corp | Electrodeposition of manganese |
| US2741590A (en) * | 1953-02-19 | 1956-04-10 | Kunin Robert | Electrolytic recovery of manganese |
| US2798038A (en) * | 1953-12-02 | 1957-07-02 | Reginald S Dean | Electrodepositing manganese |
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