US2608531A - Electrolytic preparation of manganese dioxide - Google Patents
Electrolytic preparation of manganese dioxide Download PDFInfo
- Publication number
- US2608531A US2608531A US125085A US12508549A US2608531A US 2608531 A US2608531 A US 2608531A US 125085 A US125085 A US 125085A US 12508549 A US12508549 A US 12508549A US 2608531 A US2608531 A US 2608531A
- Authority
- US
- United States
- Prior art keywords
- anode
- manganese dioxide
- electrolytic
- titanium
- anodes
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 230000001427 coherent effect Effects 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- 230000002999 depolarising effect Effects 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- UOCLRXFKRLRMKV-UHFFFAOYSA-N trolnitrate phosphate Chemical compound OP(O)(O)=O.OP(O)(O)=O.[O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O UOCLRXFKRLRMKV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
- Y10T428/292—In coating or impregnation
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- This invention relates to the electrolyticpreparationof manganese dioxide. It relates "particularly to improved anodestobe used in the production of manganese dioxide by electrolysis of solutions containing manganese sulphate and sulphuricacid. 1
- Titaniumchips preparedfin the manner described and having a sieves'ize up to '35mesh-are compacted under 5 a suitable pressure and in -a suitable 'diefor the production of the-anodesoi my-inventionm
- the pressure used for "the production of theseanodes has a definite relation ship -to the behavior of the electrolytic process in which they are-used.
- I have, shown the relationship between pressureused to compact the titaniumchips and the current efficiency for several diiferent' current densities.
- Titanium chips made in other ways can .be
- anode consists essentially of particles of hydrogen-containing titanium, having a size not greater than mesh, compressed into a coherent body at a pressure of from 10 to tons per square inch.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Description
Aug. 26, 1952 ox 2,608,531
ELECTROLYTIC PREPARATION OF MANGANESE DIOXIDE Filed Nov. 2, 1949 2 Sl-lEETS-SHEET 1 Re/afion f Currenf Efficiency To Pressure 02 Compac Tiny 0f T/fan/um Anode-s Am s/s fz 20 I00 /Z0 I40 I60 Vo/zaye-Carrenf Dena/f Re/af/bnsh/p For T/J Anodes INVENTOR Aug. 26, 1952 ox 2,608,531
ELECTROLYTIC PREPARATION OF MANGANESE DIOXIDE /0 a0. 5o a0 Patented Aug. 26, 1952 ELECTROLYTIC PREnAItA'rIonoFU MANGANESE DIOXIDE Abraham L. Fox, Washington, D. assignor 'to 9:":3
ReginaldS. Dean, Washington, D. C; v
' This invention relates to the electrolyticpreparationof manganese dioxide. It relates "particularly to improved anodestobe used in the production of manganese dioxide by electrolysis of solutions containing manganese sulphate and sulphuricacid. 1
It is well known in the art to produceelectrolytic manganese dioxidehaving valuable propertiesas a depolarizer forprimary cells and for other purposes by the electrolysis of solutions containing'about 50 grams per liter of manganese 'assulphate and 25 grams per liter of sulphuric acid. This electrolysis has been carried oncommercially using graphite anodes and either graphite ordead cathodes; This combination has been-open to ajconsiderable number of practical objections. 'Inor'der to obta'in current efficiency above 7 0% it'hasf been necessary to carry 'onthe electrolysis within a fairly limitedirange of acidity. "maintain'the temperature around 90 C. and to use a low current density, namely, fromlO to 20 amperes "pjersquare foot. The close control of these conditions'has been rendered necessarynot only by the efiect; ,of the mentionedjv'a'riables upon the quality fof the product but'be'cause' the graphite anodes deteriorate rapidly when'fhigher acidity or higher current densities are used. Other materials for anodes have been suggested, such as platinum andyarious alloys of lead and othe'rmetals. These anodes, however, 'haveall be'en unsatisfactory either because of costlorthe quality of "the product produced. It is the aim of "the present invention to provide an anode for the production of electrolytic manganese whichpermits a wider choicebf the other "variables, such as solution temperature, acidity and current density, without a deterioration of thequality of the manganese dioxide produced to any such extent as has been heretofore known in the art. t l I have found that'anodes may be formed principally'of titanium in accordance with my copending application, Serial No'. 109,061, filed August 6, 1949, whichgive excellent results. It is not satisfactory, however, to usefmass'iye titanium of either the ductile or castv'ariety. All such solid forms of titanium which I have tried are not satisfactory as anodesforthe deposition Toffmanganese dioxide. The voltage required for deposition on such anodes is prohibitively high and the current efficiency poor; I have found, however, that if the anode be fabricated from titanium'chips, entirely satisfactory results may be obtained.
It has'jlikewise been necessary to 'i claims. (c1. 204--83) 'I'prefertouse titanium 'chipswhich are made by the mechanical disintegration, such as cutting with a lathe tool of the product formed by the reaction of molten magnesium ontitaniumtetrachloride. The chips-made from such a reduction product are conveniently purifiedfrom-magnesium and magnesium chloride by leaching" with dilute hYdI'OOhIOIiCaOid. Such chips contain a certain amount of hydrogen which appears to be actually advantageous to the production of anodes for the practice of my invention.
Titaniumchips preparedfin the manner described and having a sieves'ize up to '35mesh-are compacted under 5 a suitable pressure and in -a suitable 'diefor the production of the-anodesoi my-inventionmThe pressure used for "the production of theseanodes has a definite relation ship -to the behavior of the electrolytic process in which they are-used. In Figured, I have, shown the relationship between pressureused to compact the titaniumchips and the current efficiency for several diiferent' current densities. In every case illustrated in-this figure the cell was operated at 90 Cw ItZwill'be seen'that,- in general, the lower the pressure used tocompact the chips into the anodeand, therefore, the more porous the anode, the better will be the current efiiciency at any particular current density. The low. limit for the pressureused to compact the chips into the anodeis, of course, determined by the. necessary mechanical strength of the anode and its tendency to disintegrate during the electrolysis. I haveifound that pressuresaszlow as 10 tons per square". inch givean anode with satisfactory properties in this respect. pressures may be .used with some sacrificeiin anode strength and life.: 1 1. l
.Lower The results given arefor the preferredform of titanium for my invention, "namely,- the chips made from the reduction product of titanium tetrachloride with magnesium, which chips have been subsequently leached with acid. Increased mechanical strength can be obtained in anodes formed in this way by sintering invacuum'ortin an inert atmosphere. Such increasein strength, however is accompanied by a decrease; in the valueof such anodes for my inventionl as. an example, I heat an anode made by compacting the titanium chips at20 tons per-square inchrto 800C. for one hour in vacuum.,.The resulting anode gives approximately the same result in the electrolytic cell as would be obtained had the chips been compressed at 50 or tons per square inch. 1
Titanium chips made in other ways can .be
used for the practice of my invention and titabody at a pressure of from to 50 tons per square inch.
4. Process as defined in claim 1, in which the anode consists essentially of particles of hydrogen-containing titanium, having a size not greater than mesh, compressed into a coherent body at a pressure of from 10 to tons per square inch.
5. Process as defined in claim 1, in which the anode is partially coated with a film of graphite.
6. Process as defined in claim 1, in which the electrolysis is carried out at a temperature between atmospheric and 100 C.
7. The method of claim 1, iurther characterized by the electrolysis being carried out at a current density of from 30 to amperes per square foot.
ABRAHAM L. FOX
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Name Date Clemens Aug. 5, 1947 OTHER REFERENCES Transactions of the Electrochemical Society, vol. '76 (1939), pages 401 to 425.
United States Department of Interior, Bureau of Mines, Bulletin 463, published 1946, pages 66 and 67.
Number
Claims (1)
1. PROCESS OF PREPARING ELECTROLYTIC MANGANESE DIOXIDE HAVING GOOD DEPOLARIZING PROPERTIES IN A DRY CELL WHICH COMPRISES PASSING A UNIDIRECTIONAL CURRENT THROUGH AN ELECTROLYTE CONSISTING ESSENTIALLY OF WATER, MANGANESE SULPHATE AND SULPHURIC ACID FROM A METALLIC CONDUCTING CATHODE TO A POROUS ANODE CONSISTING ESSENTIALLY OF TITANIUM PARTICLES COMPACTED INTO A COHERENT BUT INCOMPLETELY CONSOLIDATED POROUS MASS HAVING A LARGE SURFACE AREA WHEREBY TO FORM A DEPOSIT OF ELECTROLYTIC MNO2 ON THE ANODE, AND SEPARATING THE DEPOSITED MNO2 FROM THE ANODE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US125085A US2608531A (en) | 1949-11-02 | 1949-11-02 | Electrolytic preparation of manganese dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US125085A US2608531A (en) | 1949-11-02 | 1949-11-02 | Electrolytic preparation of manganese dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2608531A true US2608531A (en) | 1952-08-26 |
Family
ID=22418114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US125085A Expired - Lifetime US2608531A (en) | 1949-11-02 | 1949-11-02 | Electrolytic preparation of manganese dioxide |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2608531A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2798038A (en) * | 1953-12-02 | 1957-07-02 | Reginald S Dean | Electrodepositing manganese |
| DE1217345B (en) * | 1957-04-09 | 1966-05-26 | Amalgamated Curacao Patents Co | Process for the production of an anode for the electrolysis of electrolytes containing chlorine ions |
| US3436323A (en) * | 1966-07-25 | 1969-04-01 | Furukawa Electric Co Ltd | Electrolytic method for preparing manganese dioxide |
| DE1592395A1 (en) * | 1966-07-29 | 1970-12-17 | Furukawa Electric Co Ltd | Manufacturing method of electrolytic manganese peroxide |
| DE3521827A1 (en) * | 1985-06-19 | 1987-01-02 | Hoechst Ag | ANODE SYSTEM FOR THE ELECTROLYTIC PRODUCTION OF BROWN STONE |
| US4997492A (en) * | 1990-06-08 | 1991-03-05 | Nippon Mining Co., Ltd. | Method of producing anode materials for electrolytic uses |
| US5061358A (en) * | 1990-06-08 | 1991-10-29 | Nippon Mining Co., Ltd. | Insoluble anodes for producing manganese dioxide consisting essentially of a titanium-nickel alloy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2424958A (en) * | 1943-08-31 | 1947-08-05 | Dorr Co | Process of electrodepositing a manganese dioxide compound |
-
1949
- 1949-11-02 US US125085A patent/US2608531A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2424958A (en) * | 1943-08-31 | 1947-08-05 | Dorr Co | Process of electrodepositing a manganese dioxide compound |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2798038A (en) * | 1953-12-02 | 1957-07-02 | Reginald S Dean | Electrodepositing manganese |
| DE1217345B (en) * | 1957-04-09 | 1966-05-26 | Amalgamated Curacao Patents Co | Process for the production of an anode for the electrolysis of electrolytes containing chlorine ions |
| US3436323A (en) * | 1966-07-25 | 1969-04-01 | Furukawa Electric Co Ltd | Electrolytic method for preparing manganese dioxide |
| DE1592395A1 (en) * | 1966-07-29 | 1970-12-17 | Furukawa Electric Co Ltd | Manufacturing method of electrolytic manganese peroxide |
| DE3521827A1 (en) * | 1985-06-19 | 1987-01-02 | Hoechst Ag | ANODE SYSTEM FOR THE ELECTROLYTIC PRODUCTION OF BROWN STONE |
| US4997492A (en) * | 1990-06-08 | 1991-03-05 | Nippon Mining Co., Ltd. | Method of producing anode materials for electrolytic uses |
| US5061358A (en) * | 1990-06-08 | 1991-10-29 | Nippon Mining Co., Ltd. | Insoluble anodes for producing manganese dioxide consisting essentially of a titanium-nickel alloy |
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