US3471383A - Continuous anode for electrolytic cells - Google Patents

Continuous anode for electrolytic cells Download PDF

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Publication number
US3471383A
US3471383A US430684A US3471383DA US3471383A US 3471383 A US3471383 A US 3471383A US 430684 A US430684 A US 430684A US 3471383D A US3471383D A US 3471383DA US 3471383 A US3471383 A US 3471383A
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United States
Prior art keywords
cell
web
graphite
mercury
anode
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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
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US430684A
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English (en)
Inventor
Herman H Tiedemann
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GAF Corp
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GAF Corp
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Publication date
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    • 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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/033—Liquid electrodes
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/30—Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof
    • C25B9/303—Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof comprising horizontal-type liquid electrode
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells

Definitions

  • the present invention relates to an improved continuous anode for electrolytic cells. It involves use of elongated flexible web material which is particularly suitable for use as anodic material in electrolytic chlorine caustic cells, but it has uses also in other types of electrolytic cells.
  • a particular object of the present invention is to make it possible to eliminate the conventional anode block replacement described above.
  • the present invention involves as a particular feature the use of a graphite cloth web as an anode.
  • This Web is a long strip of fabric well loaded with the carbonaceous material.
  • contactors are provided in the apparatus for the efficient distribution of electric current through the graphite web or cloth.
  • the arrangement is such that the wear or attrition of the carbonaceous substance of the graphite or graphite-loaded cloth is quite uniform.
  • the cloth or web is moved by suitable simple mechanism, and preferably continuously, or at regular short intervals, so as to take care of the depletion of the graphite substance and keep the cell opearting in a uniform manner.
  • the arrangement of the present invention preferably is such that a long web of cloth or fabric anode either fabricated largely of graphite, or impregnated with graphite to a suitable degree, is fed into the cell at one end and out the other end at such a rate that it is substantially completely consumed. In some cases the web may be fed through the cell and back near the point of entrance before it leaves the cell.
  • the arrangement preferably is such that the voltage rise to compensate for changes in conductivity is minimal.
  • the spent carbon bearing web or anode preferably be continuously reeled out of the cell for discard, although as noted above the movement may be discontinuous provided it is made at frequent intervals.
  • the continuous anode web may be passed through either a horizontal cell or a vertical cell, both types being well known. In general, the same principles are involved in both situations.
  • FIGURE 1 is a diagrammatic view of a typical prior art cell in vertical section showing the conventional graphite anodes in the form of blocks suspended into the cell.
  • FIGURE 2 shows the concept of the present invention as applied to a continuous flexible web anode in a horizontal cell. This view is generally like that of FIG- URE 1, the same basic cell arrangement being involved but the stationary block anodes are replaced with a continuous flexible web of suitable conductive carbon bearing or graphitic cloth.
  • FIGURE 3 shows a vertical type cell in which the principles of the invention are involved, this being a vertical sectional view.
  • FIGURE 4 illustrates a variation in the system of FIGURE 2.
  • FIGURE 1 shows a basic layout for a typical mercury type chlorinecaustic cell.
  • Anodes 13, of which four are shown, are suspended from the ceiling of the cell in such a manner that they can be lowered, i.e., their height may be adjusted. Suspending means are not shown except that each block has an upwardly extending column passing through the ceiling 15 of the cell.
  • Electric current is supplied from a source 19, distributed through several conductors 21 to the several anodes.
  • Cathode contactor points or members 25 are shown resting on the floor 27 of the cell, these being electrically connected through suitable conductors 29 to the negative side of the current supply 31.
  • the latter flows through an inlet 35 into the cell and moves to the left along the fioor of the cell in a horizontal layer 33 to outlet 37. From the latter, the mercury which by now is an amalgam with sodium is taken to the denuder for mercury recovery. The recovered mercury is then recycled through inlet 35.
  • the same system obviously is applicable to treatment of other salts, especially other alkali metal halides besides sodium chloride.
  • the strong brine of the salt being electrolyzed is supplied through inlet line 41, shown at the right of the cell. It flows along the cell from right to left as electrolysis takes place. Gaseous chlorine is evolved from the top of the cell through outlet 43 and the spent brine passes out through outlet 45. The sodium of course is converted primarily to NaOH.
  • the conventional graphite anodes 11 are rapidly consumed.
  • the number of anodes may vary considerably. Four only are shown in FIGURE 1, but in a commercial cell the number usually is much greater.
  • FIGURE 2 the arrangement of the present invention for a horizontal cell is shown in FIGURE 2.
  • the body of the cell is much the same as that of FIGURE 1, mercury being supplied through inlet 35a and the mercury-sodium amalgam passing out through outlet 37a.
  • Electric current is supplied from the positive source 19a and negative source 31a.
  • Anode points 25a are the same as in FIGURE 1 in general arrangement.
  • Outlet 75 is designed to prevent substantial chlorine gas leakage. It is rewound on take-up roller 77. It may be discarded or in many cases it can be impregnated with carbon for reuse.
  • the mercury layer 83 in FIGURE 2 is essentially the same as layer 33 in FIGURE 1. In both cases the anodes must be kept above and out of contact with the mercury layer.
  • FIGURE 3 there is shown a vertical type cell having walls 101 and 103 which enclose the brine being electrolyzed.
  • the strong brine enters through inlet 105 and the weak spent brine emerges through outlet 107.
  • a continuous mercury film which serves as the cathode, is obtained by spilling the denuded mercury entering at the top through inlet 111 down over a vertical cathodic grid.
  • the latter is indicated diagrammatically at 113.
  • the mercury is converted to the sodium amalgam.
  • the amalgam is pumped off through outlet 113 to the denuder system which is conventional and forms no part of the present invention.
  • the continuous anodic web of graphite cloth is supplied from a reel 115.
  • the web 119 passes downwardly around a pair of guide rollers 121 and 123. From the latter the web passes upwardly through the vessel and thence through outlet 125 and around guide roller 127 to a take-up reel 129. The spent web is rewound on the latter and can be discarded or subsequently carbonized or graphited anew to serve as a new anode.
  • the mechanical features involved in reeling the cloth through the vertical cell are simpler than those in the horizontal cell.
  • Current is supplied to the web through suitable electric contactors such as the rollers 127 and 121 and 123.
  • suitable electric contactors such as the rollers 127 and 121 and 123.
  • the connections are not shown but would be obvious to those skilled in the art.
  • supplemental contact rollers may be positioned along the path of the graphite web, along the incoming downward traveling stretch if desired and particularly along the rising stretch.
  • Sufficiently conductive contacts must be supplied to give effective electrolytic current to the cell.
  • FIGURE 4 it will be understood that the web is essentially the same as web 65 in FIGURE 2, and its arrangement and functioning are similar.
  • additional support rollers 167 are provided in the bath. These must be kept above the mercury level to avoid shorting out the cell, and therefore they are preferably small rollers. Moreover, they may be raised or lowered, as indicated in the dotted lines, to cause the web to make better electrical contact, that is, to wrap more effectively around the guide rollers 161, which correspond in other respects to roller 61 of FIGURE 2. This arrangement affords better electrical contact between the web and the main guide rollers.
  • the rollers 167 may be raised until their lower surfaces are essentially in line with the lower surfaces of guide rollers 161, as well as rollers 171 and 173. The latter correspond to the rollers 71 and 73 of FIGURE 2. This arrangement may be desirable or necessary in some cases to avoid shorting the cell by the rollers being too close to the mercury layer.
  • Graphite cloth is a relatively new product and is preferred for the purposes of the present invention. It is possible, however, to use other carbonaceous webs or carbonloaded webs of various fabrics for accomplishing the same general purposes.
  • the web material must be one which will not distintegrate in the bath. It will be app r eciated that the present invention eliminates many problems connected with the prior art practices.
  • the web itself have a good content of conductive graphite. It is also essential, of course, that it be kept out of contact with the mercury layer, but properly spaced therefrom so as to obtain maximum operating efiiciency at optimum voltage and current values.
  • said mercury cathode is a continuous mercury film which is obtained by spilling denuded mercury, entering at the top of said electrolytic cell, over a vertical cathodic grid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatment Of Fiber Materials (AREA)
US430684A 1965-02-05 1965-02-05 Continuous anode for electrolytic cells Expired - Lifetime US3471383A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US43068465A 1965-02-05 1965-02-05

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US3471383A true US3471383A (en) 1969-10-07

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US (1) US3471383A (de)
DE (3) DE1571738C2 (de)
FR (1) FR1467401A (de)
GB (1) GB1136142A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637468A (en) * 1968-04-29 1972-01-25 Dalic Sa Electrodes for electrolytic processes
US4360417A (en) * 1980-07-03 1982-11-23 Celanese Corporation Dimensionally stable high surface area anode comprising graphitic carbon fibers
US20150114926A1 (en) * 2011-07-29 2015-04-30 Pacesetter, Inc. Anode foils for electrolytic capacitors and methods for making same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB189624803A (en) * 1896-11-05 1897-03-13 Franz Alois Brausil An Improved Apparatus for Ornamenting Strips or Frames of Wood and the like Material.
US1750831A (en) * 1927-03-05 1930-03-18 Cairns Dev Company Art of making metal fabrics
US2323042A (en) * 1939-05-30 1943-06-29 Honsberg Werner Process for the electrolytic decomposition of metal compounds
US2933438A (en) * 1958-12-19 1960-04-19 Leslie E Lancy Electro processing and apparatus therefor
US2953507A (en) * 1952-10-09 1960-09-20 Schwarzkopf Dev Co Method for electrolytic thickness reduction of metal wires
US3244612A (en) * 1961-11-29 1966-04-05 George W Murphy Demineralization electrodes and fabrication techniques therefor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE410004C (de) * 1924-03-30 1925-02-21 Carl Gaiser Elektrisches Dauer- und Trockenelement, insbesondere fuer elektrische Taschenlampen,Handlampen und fuer beliebige andere Zwecke
DE453764C (de) * 1926-10-06 1927-12-19 Carl Gaiser Graphitelektroden in Band- oder Blattform
DE923842C (de) * 1952-02-26 1955-02-21 Huels Chemische Werke Ag Verfahren zur Durchfuehrung elektrolytischer Prozesse
BE639017A (de) * 1962-10-22

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB189624803A (en) * 1896-11-05 1897-03-13 Franz Alois Brausil An Improved Apparatus for Ornamenting Strips or Frames of Wood and the like Material.
US1750831A (en) * 1927-03-05 1930-03-18 Cairns Dev Company Art of making metal fabrics
US2323042A (en) * 1939-05-30 1943-06-29 Honsberg Werner Process for the electrolytic decomposition of metal compounds
US2953507A (en) * 1952-10-09 1960-09-20 Schwarzkopf Dev Co Method for electrolytic thickness reduction of metal wires
US2933438A (en) * 1958-12-19 1960-04-19 Leslie E Lancy Electro processing and apparatus therefor
US3244612A (en) * 1961-11-29 1966-04-05 George W Murphy Demineralization electrodes and fabrication techniques therefor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637468A (en) * 1968-04-29 1972-01-25 Dalic Sa Electrodes for electrolytic processes
US4360417A (en) * 1980-07-03 1982-11-23 Celanese Corporation Dimensionally stable high surface area anode comprising graphitic carbon fibers
US20150114926A1 (en) * 2011-07-29 2015-04-30 Pacesetter, Inc. Anode foils for electrolytic capacitors and methods for making same
US9412525B2 (en) * 2011-07-29 2016-08-09 Pacesetter, Inc. Anode foils for electrolytic capacitors and methods for making same

Also Published As

Publication number Publication date
DE1935530U (de) 1966-03-31
FR1467401A (fr) 1967-01-27
DE1571738B1 (de) 1972-06-08
DE1571738C2 (de) 1973-01-04
GB1136142A (en) 1968-12-11

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