US3560355A - Method and device for operating mercury-process electrolytic cells - Google Patents

Method and device for operating mercury-process electrolytic cells Download PDF

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Publication number
US3560355A
US3560355A US718438A US3560355DA US3560355A US 3560355 A US3560355 A US 3560355A US 718438 A US718438 A US 718438A US 3560355D A US3560355D A US 3560355DA US 3560355 A US3560355 A US 3560355A
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United States
Prior art keywords
mercury
brine
cell
inlet
electrolytic cell
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Expired - Lifetime
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US718438A
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English (en)
Inventor
Hiroshi Shibata
Teruo Imai
Shigeji Kumaki
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Kureha Corp
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Kureha Corp
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Priority claimed from JP2456067A external-priority patent/JPS5220960B1/ja
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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
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/36—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in mercury cathode 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • 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
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/36—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in mercury cathode cells
    • C25B1/42—Decomposition of amalgams
    • 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 refined brine recirculated to a mercury-cathode cell is introduced into the cell in the form of a falling laminarflow curtain along almost the entire inner surface of an inlet transverse wall of the cell above the recovered mercury inlet, the laminar-flow curtain of brine thereby reaching and thoroughly washing the entering mercury to prevent any alkaline wash water flowing above the mercury from reaching the graphite anode.
  • This laminar-flow curtain is formed by a long and narrow brine inlet provided in and extending horizontally across almost the full width of the transverse Wall at a position sufficiently high above the surface level of the electrolyte in the cell.
  • This invention relates generally to the field of mercury-process electrolysis of brine and more particularly to new improvements in mercury-process electrolytic cells and in the operation thereof.
  • the mercury which has left the denuding tower still contains some alkali in a residual state. Accordingly, water is added to this mercury either before it enters the mercury pump or after it has been delivered by the pump thereby to wash the mercury, which is then separated from the wash water and recirculated to the electrolytic cell.
  • the alkaline wash water which has accompanied the mercury and entered the electrolytic cell undergoes almost no mixing with the electrolyte, and most of this wash water flows as a laminar flow below the electrolyte and is conducted, together with the mercury, to the lower part of the graphite anode. Consequently, the part of the anode in the vicinity of the mercury inlet of the electrolytic cell is particularly subjected to severe local erosion, whereby the anode is consumed in an uneven manner (as indicated in FIG. 1(a) described hereinafter).
  • a brine supply method and device whereby the supply brine is supplied in the form of a falling laminar-flow curtain descending along substantially the entire inner surface of a transverse wall directly above a mercury inlet for introducing recovered mercury into the cell, the supply brine curtain thereby reaching the mercury thus introduced thereby to wash the entire upper surface of this mercury and the region thereabove.
  • FIGS. 1(a) and 1(b) are side elevational views showing states of erosion of anodes used in mercury-process electrolytic cells (the original states of the anodes prior to use being indicated by intermittent lines), FIG. 1(a) showing an anode used in a conventional electrolytic cell, and FIG. 1(b) showing an anode used in an electrolytic cell according to the invention;
  • FIG. 2 is a side elevational view, in vertical section, showing the essential structure of one example of a known electrolytic cell provided with a top box;
  • FIG. 3 is a side elevational view, in vertical section, showing the essential structure of one example of an electrolytic cell embodying the invention, the plane of the section being parallel to the mercury flow path;
  • FIG. 4 is an elevational view, in section taken along the plane indicated by line IV-IV in FIG. 3;
  • FIG. 5 is a partial elevational view, in section similar to FIG. 4, showing another example of a preferred embodiment of the invention.
  • brine 7 enters a top box 3 partitioned from the electrolytic chamber 1 by an inverted weir or baflie through a brine inlet 6 consisting of one or more pipes.
  • mercury 8 enters the bottom of the electrolytic cell below the top box 3 through a mercury inlet passageway 4 and under and past a mercury bafile 5. The brine 7 and the mercury 8 together pass under and past the brine bafile 2 and enter the electrolytic chamber 1.
  • alkaline wash water 9 enters the mercury inlet passageway 4 together with the mercury 8 and some of this wash water 9 accompanies the mercury into the top box 3, most of this wash water flowing in a laminar flow between the mercury and the brine. Consequently, in the case where the flow path in the top box 3 is short, the neutralisation of the alkaline wash water is incomplete, and a portion of this wash water in an unneutralised state flows into the region below the anode 10 to cause the aforementioned anode erosion.
  • the present invention contemplates overcoming this problem by supplying the brine to the electrolytic cell in a manner such that the brine is in a falling laminar-flow curtain along the entire surface of a transverse wall at the mercury inlet section of the electrolytic cell thereby to cause continuous washing and neutralising of the surface of the mercury entering the cell by the resulting vertical flow of the brine thus supplied.
  • the form of the downward flow of the supply brine herein specified by the term Falling laminar-flow curtain can be obtained, in general, by causing the brine newly supplied into the electrolyte brine remaining in the electrolytic cell to descend over the entire surface of the transverse wall in a laminar-flow separate from but within the remaining electrolyte brine.
  • the existence of this separate laminar flow can be detected, for example, by adding a dye to the supply brine to colour the same and observing that the liquid thus coloured flows in a descending curtain in a thin film along the transverse Wall, which flow reaches the mercury surface to accomplish continuous washing of this mercury surface.
  • An electrolytic cell most suitable for obtaining such a descending laminar flow along a transverse wall is a cell, for example with a structure such that the supply brine flows into the electrolytic cell through a long and narrow gap which is at a level above the surface of the stagnant electrolyte at the transverse wall of the metcury inlet and is provided across the entire horizontal length of the transverse wall.
  • mercury 12 and wash water 13 which have arrived through a mercury passageway 11 are separated at an inverted weir or baflle provided at the lower part of a transverse wall 14 of the electrolytic cell, where only the mercury is separated out and, flowing under the baflle 15 and into the electrolytic chamber 16, flows downstream (to the right as viewed in FIG. 3) along and above the bottom 17 of the electrolytic chamber.
  • acidic supply brine 20 is supplied from a passageway 18 in the form of a trough disposed on the outer side of the upper part of the transverse wall 14, through a gap 19, provided in the upper part, preferably at the top as shown in the drawings, of the transverse wall, and into the electrolytic chamber 16. Since the surface 21 of the electrolyte within the electrolytic chamber is lower than the overflow lip of the gap 19, the supply brine first falls along the entire inner surface of the transverse wall 14. The kinetic energy of this falling brine is such that, although this brine curtain enters the electrolyte within the electrolytic cell, most of this brine flows along the surface of the transverse wall without mixing with the electrolyte and directly reaches the mercury surface.
  • the supply brine be only fresh brine supplied newly to the electrolytic cell, it being possible to supply brine in the same manner also in the case where a portion of dilute brine which has been used once in the electrolytic cell is mixed With fresh supply brine, and the resulting brine mixture is supplied to the electrolytic cell.
  • brine inlet gap 19 may be in the form of a discontinuous gap consisting of a plurality of intermittent divisional gaps as in the example illustrated in FIG. 5.
  • the brine inlet was provided in a side surface of the electrolytic cell along the mercury flow path at a position near the mercury inlet.
  • the anode in the vicinity of the mercury inlet was consumed unevenly as indicated in FIG. 1(a) when operated at a current of a/dm. for approximately three months, whereby the initial thickness of 150 mm. was reduced to a thickness of from 70 to 90 mm. at the upstream part of the anode.
  • the method of operating said cell which comprises supplying said brine as a falling laminar-flow curtain descending along substantially the entire inner surface of said trarisverse wall and reaching the mercury thus introduced thereby to wash the entire upper surface of said mercury and the region thereabove.
  • a mercury-process brine electrolytic cell having a transverse inlet wall and adapted to contain an amount of electrolyte which fills the cell to a normal surface level
  • the improvement which comprises a supply brine flow inlet at the top and extending horizontally across substantially the full width of said transverse wall, said supply brine flow inlet being discontinuous, and comprising a horizontal in-line row of a plurality of divided parts.
  • brine supply means comprising, in combination, a brine flow inlet at the top of and extending horizontally across substantially the full width of said transverse wall at a position substantially higher than said normal electrolyte surface level and a brine supply passageway disposed at the top of the transverse wall and on the side of the transverse wall opposite the interior of the cell and opening into said brine flow inlet, said supply brine flow inlet being discontinuous, and comprising a horizontal in-line row of a plurality of divided parts.
  • a substantially vertical transverse inlet wall extending across the width of the cell at the inlet end of said cell, said inlet wall having a mercury inlet opening into the cell at the bottom of the wall and extending horizontally across substantially the full width of the cell, said inlet wall further having a brine flow inlet in the upper portion of the wall substantially above said normal electrolyte surface level and a brine supply passageway disposed at the upper portion of said inlet wall and opening into said brine flow inlet, said brine flow inlet extending horizontally across substantially the full width of said cell and being sufficiently far above said normal electrolyte surface level that when the cell is filled to said normal surface level with brine and a falling laminar-flow curtain of brine is flowed through said inlet and down along substantially the entire inner surface of said transverse wall, it will flow down through the brine to the mercury in

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US718438A 1967-04-19 1968-04-03 Method and device for operating mercury-process electrolytic cells Expired - Lifetime US3560355A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2456067A JPS5220960B1 (enrdf_load_stackoverflow) 1967-04-19 1967-04-19
JP7537167 1967-11-24

Publications (1)

Publication Number Publication Date
US3560355A true US3560355A (en) 1971-02-02

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US718438A Expired - Lifetime US3560355A (en) 1967-04-19 1968-04-03 Method and device for operating mercury-process electrolytic cells

Country Status (11)

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US (1) US3560355A (enrdf_load_stackoverflow)
BE (1) BE713924A (enrdf_load_stackoverflow)
CH (1) CH474451A (enrdf_load_stackoverflow)
DE (1) DE1767243B1 (enrdf_load_stackoverflow)
DK (1) DK121223B (enrdf_load_stackoverflow)
ES (1) ES353084A1 (enrdf_load_stackoverflow)
FR (1) FR1569932A (enrdf_load_stackoverflow)
GB (1) GB1207614A (enrdf_load_stackoverflow)
NL (2) NL6805469A (enrdf_load_stackoverflow)
NO (1) NO120677B (enrdf_load_stackoverflow)
SE (1) SE337010B (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905880A (en) * 1973-05-17 1975-09-16 Ici Ltd Operation of mercury-cathode cells
US4152237A (en) * 1978-08-28 1979-05-01 Olin Corporation Deflected flow inlet system for mercury cells
US4440614A (en) * 1983-11-10 1984-04-03 Olin Corporation Inlet end box brine pipe baffle
US4504366A (en) * 1983-04-26 1985-03-12 Aluminum Company Of America Support member and electrolytic method
US4664760A (en) * 1983-04-26 1987-05-12 Aluminum Company Of America Electrolytic cell and method of electrolysis using supported electrodes
WO2005040457A3 (en) * 2003-10-21 2005-11-03 De Nora Elettrodi Spa Cooling device for end-box of mercury cathode chlor-alkali cells

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905880A (en) * 1973-05-17 1975-09-16 Ici Ltd Operation of mercury-cathode cells
US4152237A (en) * 1978-08-28 1979-05-01 Olin Corporation Deflected flow inlet system for mercury cells
US4504366A (en) * 1983-04-26 1985-03-12 Aluminum Company Of America Support member and electrolytic method
US4664760A (en) * 1983-04-26 1987-05-12 Aluminum Company Of America Electrolytic cell and method of electrolysis using supported electrodes
US4440614A (en) * 1983-11-10 1984-04-03 Olin Corporation Inlet end box brine pipe baffle
WO2005040457A3 (en) * 2003-10-21 2005-11-03 De Nora Elettrodi Spa Cooling device for end-box of mercury cathode chlor-alkali cells
US20070068825A1 (en) * 2003-10-21 2007-03-29 Dario Oldani Cooling device for end-box of mercury cathode chlor-alkali cells

Also Published As

Publication number Publication date
FR1569932A (enrdf_load_stackoverflow) 1969-06-06
ES353084A1 (es) 1970-01-16
CH474451A (fr) 1969-06-30
DK121223B (da) 1971-09-27
NO120677B (enrdf_load_stackoverflow) 1970-11-23
NL134892C (enrdf_load_stackoverflow)
BE713924A (enrdf_load_stackoverflow) 1968-10-21
SE337010B (enrdf_load_stackoverflow) 1971-07-26
GB1207614A (en) 1970-10-07
DE1767243B1 (de) 1971-12-02
NL6805469A (enrdf_load_stackoverflow) 1968-10-21

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