US2503337A - Electrolytic cells of the liquid electrode type - Google Patents

Electrolytic cells of the liquid electrode type Download PDF

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Publication number
US2503337A
US2503337A US696694A US69669446A US2503337A US 2503337 A US2503337 A US 2503337A US 696694 A US696694 A US 696694A US 69669446 A US69669446 A US 69669446A US 2503337 A US2503337 A US 2503337A
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United States
Prior art keywords
cell
electrode
cover
mercury
channel
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Expired - Lifetime
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US696694A
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English (en)
Inventor
Hirsh Benjamin Woolf
Carter Charles
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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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
    • 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
    • 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

Definitions

  • This invention relates to improvements in electrolytic cells having a liquid electrode, and more particularly to improvements in cells of this type for the electrolysis of aqueous solutions of alkali metal chlorides, using a flowingmercury cathode.
  • the anodes are usually formed of graphite plates or blocks which are so fixed on carbon rods passing through the cover of the cell that their undersurfaces are arranged substantially parallel to, and but a short distance above, the mercury cathode.
  • the cover is joined to the cell in a gas-tight manner, e. g., it may be fixed to the trough by bolting it to the sides using a suitable jointing material, to render the seal gas-tight, or if it is sufficiently heavy the cover may make its own joint by pressing on suitable plastic luting material between it and the sides.
  • the cover is also provided with outlet pipes through which chlorine evolved at the anode is drawn off.
  • mercury'and an alkali metal chloride solution are causecl'to flow through the cell at rates which depend on the working conditions; the linear flow of'the alkali metal chloride solution inthe cell is comparatively slow, in general it is less than 2 cms. per second and usually between 0.25 and 1cm. per second.
  • the level of the solution in the cell is adjusted so that it does not reach to the lid,
  • a principal object of this invention is the provision of electrolytic cells of the liquid electrode type which are specially welladapted to the electrolysis of aqueous solutions, wherein high velocity flow of the electrolyte in the inter-elemtrode space is involved.
  • a further object is the provision of cells of the subject type which are well adapted to electrolysis of aqueous solutions under super-atmospheric pressure.
  • Another object is the provision of such cells,'in which flow of electrolyteis permitted only in the inter-electrode space between the solid anode and the flowing cathode.
  • a still further object is the provision of cells which make possible the electrolysis of aqueous alkali metal chloride solutions to form chlorine at a minimum operating voltage and with very high efficiency.
  • a cell of the liquid electrode type in which the solid electrodes in the upper part of the cell are so arranged that substantially the whole of the cross-section of the cell above the inter-electrode gap is inaccessible to longitudinal flow of electrolyte. Additionally these cells include means external of the cell for adjusting the height of the interelectrode space and means for sealing the cell from the surrounding atmosphere.
  • the present invention consists in an electrolytic cell comprising two portions, i. e.,
  • a base which provides an elongated plane mercury electrode carrying surface and a cover which carries an assembly of solid electrode material having the lower surface but a short distance above and substantially parallel to the upper surface of the mercury electrode and arranged to permit the withdrawal of fluid from the inter-electrode i surrounding the mercury carrying surface and adapted to contain mercury and the upper portion comprises a cover into which the solid electrode assembly is fitted and which is provided with a rigid skirt depending below the solid electrode assembly and adapted to fit loosely in the channel in the trough-shaped vessel when the cover is in position.
  • the channel is provided with a resilient deformable packing adapted to contact both the skirt and a wall of the channel and thus assist the formation of an improved seal;
  • the packing is of sponge rubber, or is an endless inflated rubber tube.
  • the invention is especially adapted for use in a. cell of the type having a flowing mercury cathode, the channel forming part of the seal being then around the perimeter of the bottom of the cell over which the mercury cathode flows, this mercury helping to form the seal.
  • the solid electrode of such a cell may be suspended from the cover of the cell.
  • the appropriate electrical connections and means for introducing and removing the electrolyte, mercury, and the products of electrolysis are also provided.
  • the skirt and the cover are of ebonite, concrete, or other insulating material resistant to chlorine, or they may be of metal, e. g., steel, coated with such protective insulating material.
  • the trough-shaped body being maintained out of contact with the electrolyte, may be constructed from a suitable metal, such as steel.
  • the skirt extends down into the channel, and between the inner wall of the channel and the skirt an endless band of sponge rubber or an endless inflated rubber tube is fitted which presses against both the channel wall and the skirt.
  • mercury and electrolyte are caused to flow through the trough-shaped vessel and the current is switched on.
  • the mercury cathode will not only flow over the plane bottom of the vessel but will also fill the space in the channel not occupied by the rubber tube or the skirt, thus reinforcing the seal to prevent escape of chlorine, and protecting the rubber packing against corrosion. Nevertheless, adjustments can be made in the position of the cover, and thus, of the anode attached to it, and it will be possible to make these adjustments without interrupting the electrolysis.
  • the resilient deformable packing in the channel By providing the resilient deformable packing in the channel, the diversion of the mercury flow from the plane surface to the channel can be reduced to small proportions. It will be apparent that this latter desirable condition can more readily be realised if the thickness of the sides of the cover is only slightly less then the width of the channel.
  • Figure 1 is a vertical section along the line l-I of Figure 3, showing a specific form of our electrolytic cells.
  • Figure 2 is a vertical section of another form of our cells which incorporates different means for removal of chlorine formed in the electrolysis than the structure illustrated in Figure 1.
  • Figure 3 is a top plan view partly in section of a cell of the type shown in Figure 1.
  • the cells consists of a trough-shaped vessel I, having a plane bottom over which can flow mercury indicated at 2, and above it can flow, co-current with the mercury, aqueous electrolyte 3.
  • aqueous electrolyte 3 Around the perimeter of the plane bottom is a channel la.
  • Each cell has a cover 4 carrying a number of solid anode blocks 5, depending from carbon rods 8 which pass through openings to the cover and through which current is supplied to the anodes by means not shown.
  • the joint of the rods with the cover is shown to be sealed by sealing composition 1, but any other suitable method of rendering the joint gas-tight may be used.
  • a skirt 8 Depending from cover 4 is a skirt 8, the lower edge of which dips into the channel la, and an endless inflated rubber tube 9 is disposed between the inner wall of the channel and the skirt.
  • the channel When the cell is in operation, the channel will be filled with mercury, and the assembly of the skirt 8 and tube 9 will form a seal reinforced by the mercury.
  • the rubber tube will thus be protected from the action of the electrolyte, which will con tain dissolved chlorine, by the layer of mercury above it.
  • From each side of cover 4 project laterally a number of lugs In (one on each side being shown), each of which rests on the top of the cell body I.
  • the vessel I is suitably made of steel. but concrete may be used while the cover 4 and skirt 8 may be made of steel covered with ebonite.
  • Appropriate means (not shown) for supplying and withdrawing mercury and electrolyte are also provided at the appropriate ends of the cell, and take the form of orifices in that part of the cell between the
  • Tube 9 is connected with means (not shown) by which the interior of the tube can be evacuated or filled with water under pressure.
  • a seal capable of withstanding high pressures is obtained which seal can be repeatedly made or broken as necessitated by the operation of the cell.
  • cold water is used as the pressuring means for the tube 9 and circulation of the water is maintained,
  • the anode blocks 5 are designed to fill substantially the whole of the cross-section. of the cell above the level oi their undersurface, except that between adjacent blocks there is a gap extendin across the whole cross-section of the cell in which chlorine can rise to one of a number of gas offtakes ll (one of which is shown), one being situated above each gap.
  • Each ofi-take rises to a height above the cell greater than the head of brine immediately beneath it before joining a header (not shown), and thus, together with the gaps immediately beneath it, forms an independent vent by which chlorine can be drawn off from the cell.
  • tube 9 is deflated and the bottom of the vessel 1 is flooded with mercury so as to fill channel Ia and thus cover the tube 9; the lid 4 is then lowered into place with the bolts 12 in a position which gives approximately the correct inter-electrode gap and tube 9 is inflated.
  • the skirt 8 will then bear against tube 9 and thus seal the space inside the cell from the outside atmosphere. Adjustments in the height of the anode can be made as required by movement of the bolts 12; if bolts 12 are raised in lugs I0, the weight of the anode assembly will cause the skirt 8 to deform rubber tube 9 and thus allow the inter-electrode gap to decrease.
  • the inter-electrode gap is too small, it can be raised by lowering bolts 12 in the lugs l and the resilience of tube 9 ensures that the seal will still be maintained. Adjustments can be made in a similar manner during the use of the cell when the anode gap becomes too large as the result of wear.
  • FIG. 2 there is shown the base of the cell l, carrying the flowing inercury cathode 2 above which is the aqueous electrolyte 3.
  • the cell possesses a lid or cover 4 with integral depending skirts 3 extending into channel la in the base i.
  • the solid anode is suspended by tubes M which extend through the lid 4 into the solid anode 5 and terminate at the top I! of a vertical slot running the full width of the anode 5 and extending upwards from the lower surface of the anode through part of its thickness.
  • the hollow tubes I4, supporting the anode furnish communicating passage ways with the inter-electrode space so as to permit removal of chlorine formed in the electrolysis from the inter-electrode space.
  • the cells provided by this invention are adapted for high-speed brine flow and permit brine to be introduced into the cells at superatmospheric pressure.
  • the height above the bottom of the cell to which the passages leading off chlorine, e. g., tubes H in Figures 1 and 3 and tubes M in Figure 2, must extend will be determined by the head of brine at the cell inlet. This head will, in turn, depend on the size of the interelectrode gap and the velocity of the brine. With satisfactory operation with high speed brine conditions, the head of brine corresponds to about 4; inch per foot length of cell. It is convenient to carry all the passages to the same height, although it will be appreciated that the height of the passages at the end by which the brine leaves will not need to be as great as at the other end.
  • An electrolytic cell of the mercury cathode type capable of operating at high electrolyte Velocities, comprising an elongated rectangular trough-like base having a flat bottom section which carries a mercury electrode upon its up per surface, a longitudinal channel in said base along the lengthwise sides of said bottom section, a plate-like cover extending across the cell beyond the edges of the mercury electrode having an integral skirt depending therefrom into said channel, an inflated, resilient tube disposed between a side of the channel wall and said skirt, a solid electrode extending across the inside of the cell within the confines of said cover, said solid electrode being carried by the cover with its undersurface disposed a short distance above the upper surface of the mercury electrode and substantially parallel thereto, conduits for withdrawal of gas from the inter-electrode space extending through said solid electrode and said cover, all free space within the inner confines of said cover above the level of the anode undersuriace, aside from said conduits, being filled with solid material, and means external of the cell for adjusting the inter-electrode space
  • said gap adjusting means comprises an outside threaded section carried in an inside threaded lug extending -from said cell cover.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US696694A 1941-08-27 1946-09-13 Electrolytic cells of the liquid electrode type Expired - Lifetime US2503337A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB10913/41A GB597389A (en) 1941-08-27 1941-08-27 Improvements in or relating to electrolytic cells having liquid electrodes

Publications (1)

Publication Number Publication Date
US2503337A true US2503337A (en) 1950-04-11

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Family Applications (1)

Application Number Title Priority Date Filing Date
US696694A Expired - Lifetime US2503337A (en) 1941-08-27 1946-09-13 Electrolytic cells of the liquid electrode type

Country Status (7)

Country Link
US (1) US2503337A (de)
BE (1) BE467972A (de)
CH (1) CH256841A (de)
DE (1) DE810274C (de)
ES (1) ES175082A1 (de)
FR (1) FR933691A (de)
GB (1) GB597389A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599363A (en) * 1948-06-04 1952-06-03 Ici Ltd Electrolytic cell
US2704743A (en) * 1950-11-29 1955-03-22 Solvay Mercury cathode electrolysis apparatus
US2786810A (en) * 1952-09-09 1957-03-26 Dominion Tar & Chemical Co Anodes and cover of electrolytic cells
US2820755A (en) * 1953-11-04 1958-01-21 Amroc Inc Wall structures for electrolytic cells
US3318792A (en) * 1957-12-17 1967-05-09 Ici Ltd Mercury cathode cell with noble metaltitanium anode as cover means
US5395503A (en) * 1986-06-20 1995-03-07 Molecular Devices Corporation Zero volume electrochemical cell

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014002031A1 (de) * 2014-02-13 2015-08-13 Günter Linzmaier Anlage zur Feinmetallisierung

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE173520C (de) *
GB316694A (de) *
GB191226504A (en) * 1912-11-18 1913-11-13 George Philip Malcolm Lee Method of and Means for Cleaning Electro-plating and Finishing Surfaces, more particularly Surfaces in situ.
US1346849A (en) * 1918-07-29 1920-07-20 Robert M Shaw Electrolytic cell
US1575627A (en) * 1924-12-10 1926-03-09 Farbenfab Vorm Bayer F & Co Electrode for use in the electrolytic evolution of gases
US2104678A (en) * 1935-10-01 1938-01-04 Oxford Paper Co Electrolytic cell

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE173520C (de) *
GB316694A (de) *
GB191226504A (en) * 1912-11-18 1913-11-13 George Philip Malcolm Lee Method of and Means for Cleaning Electro-plating and Finishing Surfaces, more particularly Surfaces in situ.
US1346849A (en) * 1918-07-29 1920-07-20 Robert M Shaw Electrolytic cell
US1575627A (en) * 1924-12-10 1926-03-09 Farbenfab Vorm Bayer F & Co Electrode for use in the electrolytic evolution of gases
US2104678A (en) * 1935-10-01 1938-01-04 Oxford Paper Co Electrolytic cell

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599363A (en) * 1948-06-04 1952-06-03 Ici Ltd Electrolytic cell
US2704743A (en) * 1950-11-29 1955-03-22 Solvay Mercury cathode electrolysis apparatus
US2786810A (en) * 1952-09-09 1957-03-26 Dominion Tar & Chemical Co Anodes and cover of electrolytic cells
US2820755A (en) * 1953-11-04 1958-01-21 Amroc Inc Wall structures for electrolytic cells
US3318792A (en) * 1957-12-17 1967-05-09 Ici Ltd Mercury cathode cell with noble metaltitanium anode as cover means
US5395503A (en) * 1986-06-20 1995-03-07 Molecular Devices Corporation Zero volume electrochemical cell

Also Published As

Publication number Publication date
GB597389A (en) 1948-01-26
BE467972A (de)
FR933691A (fr) 1948-04-28
CH256841A (de) 1948-09-15
ES175082A1 (es) 1947-03-16
DE810274C (de) 1951-08-09

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