US3282820A - Current supply system for electrolytic cells - Google Patents

Current supply system for electrolytic cells Download PDF

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Publication number
US3282820A
US3282820A US203929A US20392962A US3282820A US 3282820 A US3282820 A US 3282820A US 203929 A US203929 A US 203929A US 20392962 A US20392962 A US 20392962A US 3282820 A US3282820 A US 3282820A
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United States
Prior art keywords
receptacle
cover
cell
metal
anodes
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Expired - Lifetime
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US203929A
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English (en)
Inventor
Szechtman Joshua
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Chlormetals Inc
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Chlormetals Inc
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Priority to US203929A priority Critical patent/US3282820A/en
Priority to GB23671/63A priority patent/GB1013122A/en
Priority to FI1236/63A priority patent/FI42706B/fi
Priority to DK291763AA priority patent/DK112050B/da
Application granted granted Critical
Publication of US3282820A publication Critical patent/US3282820A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts

Definitions

  • This invention relates to electrolytic cells of the type employed for the decomposition of salts, :such as alkali metal chlorides and alkaline earth metal chlorides, and is more particularly concerned with a current-conducting construction for such cells which is effective to cooperate with the cell to connect the cell in a current circuit, e.g. to connect the anodes with a source of electrolysis current and to lead the current from the cell cathode.
  • salts such as alkali metal chlorides and alkaline earth metal chlorides
  • Electrolytic cells of the horizontal type are known for the electrolysis of salts such as alkali metal salts and alkaline earth metal salts.
  • salts such as alkali metal salts and alkaline earth metal salts.
  • my co-pending application Serial No. 699,979, filed December 2, 1957, now Patent No. 3,104,213, issued September 17, 1963 I have described a cell which is suitable for high-temperature electrolysis of molten salts, using a molten lead cathode.
  • electrolysis current is supplied to the anodes through the cell cover and the current flows from the sole of the cell upon which the lead cathode is supported.
  • the operation of an electrolytic cell at elevated temperatures naturally involves thermal expansion and contraction of the cell, and a problem arises with regard to the connection of the cell to the electrolysis current conductors.
  • Flexible conductors generally in the form of multiple strands, can be used. However, when very large currents are involved, such flexible conductors do not give the optimum results that can be achieved with rigid conductors. Rigid conductors, however, have not heretofore been used in a manner which effectively solves the problems created by the above-mentioned thermal expansion and contraction.
  • an object of the present invention to provide a construction for an electrolytic cell which permits the electrically-conductive connection of rigid conductors to the cell in a manner which will compensate for any expansion and contraction of the cell itself.
  • the invention is concerned with an electrolytic cell having a cover which is formed firom a material which will conduct electricity, more specifically graphite, and with a sole or bot-tom formed from an electrically-conductive metal, e.g. iron, and formed with a conductive extension.
  • the anodes are electrically connected to the cover without passing through it as described, for example, in my said co-pending application Serial No. 699,979.
  • the anodes may be supported from the cover by means of stems which are connected to the cover by direct attachement to its lower side or the anodes may be directly connected to the cover, or the lower surface of the graphite cover may itself serve as the anode.
  • the anode stems are in electrically-conducting relationship with the cover and with the anodes so that when electrolytic current is fed to the cover, it passes directly through the anode stems to the anodes.
  • the cell sole and the sole extension are in direct electrically conductive relationship so that electrolytic current flows from the sole through the extension.
  • the cover or at least part of it, is enclosed by a covered container adapted to containing a body of an electrically-conductive metal which is molten at the operating temperature of the cell, the container including a cover which is relatively movable in relation to the container walls, and the rigid conductor means extend into the container for immersion in the body of metal contained therein.
  • the rigid conductor is advantageously connected to the container cover, i.e. the part of the container which is not directly connected to the cell itself.
  • the portion of the cell sole defined by the sole extension is at least partly enclosed by a second covered container adapted to contain a body of an electrically-conductive metal which is molten at the operating temperature of the cell, the container including a cover which is relatively movable in relation to the container walls, and the rigid conductor means is positioned for electrically conductive relationship; with the body of electrically-conductive metal.
  • the container cover is connected to the sole extension, and the rigid conductor means extends into the container for immersion in the body of metal contained therein.
  • the molten metal provides the principal conductive path between the rigid conductor means and the cell and thus absorbs any movement between the cell and the rigid conductor means so that an effective connection is achieved at all times, regardless of the extent of thermal expansion and contraction of the cell.
  • FIG. 1 is a longitudinal cross-sectional view of an electrolytic cell construction embodying features of the present invention, as seen generally along the line l1 of FIG. 2;
  • FIG. 2 is a transverse sectional view of the cell shown in FIG. 1, taken generally along the line 22 of FIG. 1;
  • FIG. 3 is a transevrse sectional view of a conductor assembly as seen generally along the line 33 of FIG. 1.
  • the cell body 12 of the cell 10 is suitably formed from metal, e.g. iron, and is supported upon an insulating support 14, indicated in the drawing as refractory blocks or bricks, but it will be understood that any other convenient insulating base may be employed.
  • the cell 10 defines a-sole sursuriace 15 upon which the liquid cathode 16, e.g. molten lead, is adapted to rest and to flow from left to right.
  • the elongated cell body 12 is formed with an elongated channel of which the sole 15 is the bottom and which provides the electrolysis chamber 17.
  • the sole 15 may be horizontal or it may slope slightly toward the right. The slope of the sole may vary but a slope of 1 or less is preferred.
  • the cell is adapted to operate at elevated temperatures for the electrolysis of molten salts, e.g. temperatures of 810 to 850 C. which are suitable for the electrolysis of molten sodium chloride, any convenient means for heating the cell body and maintaining it at an elevated temperature may be employed.
  • Closing the cell is a cover 30 which extends completely across the cell body 12 and also extends from one end of the cell body to the other.
  • This cover is formed from an electrically-conductive material and, most suitably, it is formed from gnaphite.
  • the cover 30 directly supports the anodes 50 and such support is suitably effected by means of anode stems 52.
  • the stems 52 are received in slots 53 and 54 formed in the cover 30 and in the anode blocks 50, respectively, so that these parts are removably interconnected, or the stems may be removably connected only with the cover, or only with the anodes, or all parts may be integnally interconnected. Indeed, all of the above-mentioned parts may be formed as a single unified body so that, in efiect, the lower surface of the cover serves as the anode. Further, while the cover 30 is shown as an integral body extending over the entire cell, it is advantageously formed from a plurality of sections extending across the cell body 12, the sec-.
  • a continuous refractory lining 60 is provided along the entire interior walls of the electrolysis chamber 17 of the cell, the lining 60 serving as an electrical insulator and also as a protector of the walls against chemical attack by the chemical contents within the chamber. Since the cover must be electrically insulated from the body of the cell, because it is a conductor of electrolysis current, an insulating sheet 61 completely overlies the top edges of the walls of the cellbody 12.
  • the exterior of the cell body is suitably provided with :a tight heat-insulating covering 63.
  • the weight of the cover upon the cell body together with the insulating sheet 61 is generally sufficient, but if a tighter relationship is desired, a plurality of spaced-apart clamps (not shown), can be used to secure the cover to the cell body. Such clamps must, of course, be insulated from the cell body in order to prevent electrical contact between cover 30 and cell body 12.
  • the exterior insulating cover effects not only heat-insulation but electrical-insulation as well.
  • An outlet channel '70 is suitably provided in cover 30 to permit venting of the electrolysis chamber of gases evolved above the level of the electrolyte.
  • molten alkali metal chloride or alkaline earth metal chlorine are introduced at the left-hand end of the cell body, the molten lead suitably being introduced through a conduit 80 and the electrolyte being introduced through a conduit 82,
  • the conduit 82 extends upwardly into the electrolysis chamber 17 and discharges through a self-regulating float valve, indicated diagrammatically at 84, of the type described in FIG. 5 of my copending application Serial No. 699,979.
  • a transverse wall 88 extending between the side walls of the cell body and engaged by the cover 30 to define the downstream end of the electrolysis chamber proper and to define an end compartment 89.
  • the cell bottom slopes downwardly in the vicinity of the transverse wall in order to form a well 90 into which the wall can extend to form a liquid seal against passage of the lighter electrolyte into the end compartment as long as the liquid level of the cathode is maintained.
  • the end compartment 89 is formed with an outlet opening 92.
  • a tall cylindrical sleeve 94 is provided with apertures 95 and with a nose 96 normally disposed in outlet opening 92 at the top of a sleeve 93, the cathode level being maintained by the apertures 95 through which the alloy formed in the cell is discharged.
  • the upper end of the sleeve 94 extends into a recess in cover 30 and it may be lifted, e.g. by electromagnetic means, to permit emptying of the cathode from the cell, as described in my co-pending application Serial No. 699,979. Suitable electrical insulation (not shown) prevents contact between sleeve 94 and cover 30.
  • Adjustment of the anodecath-o-de gap may be effected in any convenient manner but it is most suitably effected in the manner described in my co-pending application Serial No. 89,943, filed February 17, 1961, now abandoned, wherein the sleeve 93 is threadedly engaged with the insulating tube 97 and the level' of the apertures is adjusted by rotating sleeve 93.
  • rigid current conductors are connected to the anodes and the cathode of the cell in a manner which eliminates any problem of thermal expansion or contraction of the cell, or any part of it, by providing a construction in which the conductors are adapted to be immersed in a molten current-conducting metal.
  • the top of .the cell cover 30 is enclosed by a receptacle 100 defined by side walls 102 and end walls 104, with the cell cover itself serving as the bottom for the receptacle.
  • the bottom ends of the side walls and end walls are formed with an inwardly-dirmted flange 106 which is received within a peripheral recess 108 formed in the lower portion of the cell cover 30.
  • the recess 108 is filled with removable graphite blocks 110 which are joined to the remainder of the cover and serve to clamp the flange 106 in fluid-tight relationship.
  • the blocks 110 are secured in place by any convenient means, and most suitably by graphite bolts 112 which pass through the blocks from their lower surfaces, which rest upon the insulating sheet 61, and then pass through suitable apertures in the flange 106 and are threadedly engaged in the upper portion of the cell cover.
  • the gas outlet 70 suitably extends from the main cover body into the adjacent block.
  • a cover 115 Overlying the top edges of the side and end walls of the receptacle 100 is a cover 115.
  • relative mobility with concurrent fluid-tightness between the walls of the receptacle and the cover 115 is provided by the peripheral sealing and sliding construction shown at the upper ends of FIG. 1.
  • This construction has been exaggerated in size in order to show the relative relationships more clearly.
  • the upper ends of the walls 102 and 104 are formed with a continuous trough having a bottom wall 122, secured, as by welding, to the walls 102 and 104, and a side wall 124 having a peripheral flange 126.
  • the cover 115 is dimensioned to extend outwardly over the trough, and its end portions are retroverted as indicated at to define a slot in which the flange 126 is received.
  • a sliding seal member 132 overlies the flange 126 and supports the cover.
  • This seal member may be of any suitable type and formed of a material resistant to the elevated temperatures and to the materials with which it may come in contact, but most advantageously it is formed from a soft copper enveloped within mica.
  • the retroverted portion 130 is crimped over the flange 126 and the seal so that a close sliding fit is provided and, if desired, the connection can be made even tighter by applying clamps (not shown) to bear in the directions indicated by the arrows in FIG. 1.
  • the relatively movable but sealing construction described above is completed by the provision of a continuous dam 135 depending from the cover 115 and positioned to be received in the trough 120, with the trough being filled with a hydraulic sealing fluid 138, which is suitably molten lead.
  • the receptacle 100 is adapted to be filled with a current-conducting fluid 139, and this is most suitably molten sodium.
  • the above-described seal prevents the escape of sodium vapors into the atmosphere and the seal member 132 prevents the escape of vapors from the trough 120.
  • FIG. 1 A typical, particularly suitable, rigid conductor assembly is illustrated in FIG. 1 and is also seen in FIG. 2.
  • This conductor assembly which is indicated generally at 140, is formed from a plurality of rigid L- shaped copper strips 142 nested together and secured at their sides by connecting strips 144.
  • the vertical legs a of the strips 142 extend downwardly through the cover in space-d apart relationship and are then bent at .right angles to define the horizontal legs b which extend through the receptacle substantially parallel to the cell cover.
  • the side connecting strips 144 hold the assembly together and maintain the or otherwise rigidly secured to the cover 115.
  • One of the advantages of the conductor assembly construction illustrated is that the bottom ends of the vertical spaces between the conductor strips seen in FIG. 3 can be closed off, and these spaces filled with a cooling fluid, suitable aperatures in the conductors being provided to permit circulation. It is a further advantage of the conducting construction illustrated that the body of sodium 139 overlying the cover serves to seal the large top surface of the cover and thus to prevent ingress of air should the cell be operated under vacuum.
  • the construction of the invention insures ample supply of current to the cell, whatever the current requirements may be, from rigid conductors without concern for thermal expansion or contraction.
  • the sole or negative side of the cell is also suitably connected to rigid conductors in a manner which insures adequate current flow and complete freedom from any conflict with the thermal expansion or contraction of the cell.
  • a receptacle 150 defined by a bottom 152 and side and end walls 154 extends under the cell body 12 and is provided with a cover 156.
  • the cover 156 is associated with the walls of receptacle 150 in a fluid-tight yet relatively movable manner by a seal construction, indicated generally at 158, which is suitably exactly like that described above comprising elements 120-138.
  • the interior of the receptacle 150 is adapted to receive a body 160 of a current-conducting fluid, such as molten sodium, and the rigid current conductor assembly 162 which is immersed in the fluid 160, and which extends upwardly through the bottom 152 of the receptacle 150, suitably has the same construction as the current conductor unit 140 described above and, as in the case of the positive side of the cell, a plurality of assemblies 162 may be employed. Since space requirements may limit the width of the assemblies 162, it may be necessary to have more assemblies 162 than a-ssemblies 140, e.g. twice as many.
  • the extension 170 passes through the cover 156 and is rigidly secured to it, e.g. by brazing.
  • each cell were provided with a construction of the type described above for feeding the anodes of the cells, these constructions would be effective to compensate not only for expansions and contractions between the parts of the cell and the rigid conductors supplying current to the anodes, but also relative expansion and contraction between the two succeeding cells.
  • a conductor-connecting construction in accordance with the invention is provided both for the anodes and for the cathode of each cell in the series.
  • the conductor strips of the conductor assemblies 140 are connected with the conductor strips of the conductor assemblies 162 of a preceding cell, and similarly the assemblies 162 of the cell illustrated are connected to the assemblies 140 of a succeeding cell.
  • thermal and electrical insulation may be provided whenever desirable, e.g. on the receptacles 115 and 150, and associated parts, and that heating means, e.g. strip heaters, may be applied to the receptacles, conduits, and other parts, where desired, e.g. to maintain the molten metals and other fluids in molten form.
  • heating means e.g. strip heaters
  • Such insulation and heating means have not been shown in the drawings in order to facilitate illustration of the invention.
  • relative dimensions and other relative relationships shown are for illustrative purposes only and can be varied freely.
  • conductor-connecting constructions of this invention may be used with cells other than those of the specific construction to which reference has been made above.
  • construction of this invention may be combined with the flexible outlet construction described and claimed in my concurrently-filed application entitled Outlet System for Electrolytic Cells.
  • means for connecting said sole and said cover in an electric circuit comprising means defining a first receptacle, a body of a metal molten at the temperature of operation of said cell confined in said first receptacle in electrically-conductive contact with said cover, first bus bar means extending into said first receptacle for at lea-st partial immersion in said metal, whereby said first bus :bar means are free from direct contact with said anodes but are in electrically-conductive relationship with said anodes through said metal confined in said first receptacle, first cover means for covering said first receptacle, means for connecting said first cover means to said receptacle in relatively slidable but fluid-tight relationship, means
  • said means comprising means defining a first receptacle, a body of a metal molten at the temperature of operation of said cell confined in said first receptacle in electricallyconductive contact with said cover, first bus bar means extending into said first receptacle for at least partial immersion in said metal, whereby said first :bus bar means are free from direct contact with said anodes but are in electrically-conductive relationship with said anodes through said metal confined in said first receptacle, first cover mean-s for covering said first receptacle, means for connecting said first cover means to said receptacle in relatively slidable but fluid-tight relationship, means defining
  • first bus bar means extending into said first receptacle for at least partial immersion in said metal, whereby said first bus bar means are free from direct contact with said anodes but are in electrically-conductive relationship with said anodes through said metal confined in said first receptacle, first cover means for covering said first receptacle, means for connecting said first cover means to said receptacle in relatively slidable but fluid-tight relationship, means defining a second receptacle, a body of a metal molten at the temperature of operation of said cell confined in said second receptacle in electrically-conductive contact with said sole, second bus bar means extending into said second receptacle for at least partial immersion in said metal, whereby said second bus bar means are free from direct contact with said sole but are in electrically-conductive relationship with said sole through said metal confined in said second receptacle,
  • an electrolytic cell of the horizontal type constructed to operate at elevated tempera tures above the melting point of sodium chloride and having a sole adapted to support a liquid metal cathode, a plurality of anodes, and a cover in electrically-conducting relationship with the anodes of the cell, means for connecting said sole and said cover in an electric circuit, said means comprising means defining a first receptacle, a body of a metal molten at the temperature of operation of said cell confined in said first receptacle in electricallyconductive contact with said cover, first bus bar means extending into said first receptacle for at least partial immersion in said metal, whereby said first bus bar means are free from direct contact with said anodes but are in electrically-conductive relationship with said anodes through said metal confined in said first receptacle, first cover means for covering said first receptacle, means tor connecting said first cover means to said receptacle in relatively slidable but fluid-tight relationship, means defining
  • said means comprising means defining a receptacle, a body of a metal molten at the temperature of operation of said cell confined in said receptacle in electrically-conductive contact With said cover, and bus bar means extending into said receptacle for at least partial immersion in said metal, whereby said bus bar means are free from direct contact wlth said anodes but are in electrically-conductive relationship with said anodes through said metal and said cover when said body of metal is in electrically-conductive contact with said cover,- cover means for covering said receptacle, and means for connecting said cover means to said receptacle in relatively slidable but fluid-tight relationship, said bus bar means defining a receptacle, a body of a metal molten at the temperature of operation of said cell confined in said receptacle in electrically-conductive contact With said cover, and bus bar means extending into said receptacle for at least partial immersion in said metal, whereby said bus bar means are free from direct contact wl
  • said means comprising means defining a receptacle, a body of a metal molten at the temperature of operation of said cell confined in said receptacle in electrically-conductive contact with said cover, and bus bar means extending into said receptacle for at least partial immersion in said metal, whereby said bus bar means are free from directcontact with said anodes but are in electrically-conductive relationship with said anodes through said metal and said cover when said body of metal is in electrically-conductive contact with said cover, cover means for covering said receptacle, and means for connecting said cover means to said receptacle in relatively slidable but fluid-tight relationship, said bus bar means comprising a

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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)
  • Secondary Cells (AREA)
  • Electrolytic Production Of Metals (AREA)
US203929A 1962-06-20 1962-06-20 Current supply system for electrolytic cells Expired - Lifetime US3282820A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US203929A US3282820A (en) 1962-06-20 1962-06-20 Current supply system for electrolytic cells
GB23671/63A GB1013122A (en) 1962-06-20 1963-06-13 Improvements in or relating to electrolytic cells
FI1236/63A FI42706B (forum.php) 1962-06-20 1963-06-18
DK291763AA DK112050B (da) 1962-06-20 1963-06-19 Elektrolytisk celle.

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US203929A US3282820A (en) 1962-06-20 1962-06-20 Current supply system for electrolytic cells

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US3282820A true US3282820A (en) 1966-11-01

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US (1) US3282820A (forum.php)
DK (1) DK112050B (forum.php)
FI (1) FI42706B (forum.php)
GB (1) GB1013122A (forum.php)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL63281C (forum.php) * 1941-08-27
US742864A (en) * 1898-10-04 1903-11-03 Solvay Process Co Electrolytic process.
US2328665A (en) * 1939-10-27 1943-09-07 Mathieson Alkali Works Inc Electrolytic cell
US2502888A (en) * 1945-09-17 1950-04-04 Ici Ltd Electrolytic cell
US2617762A (en) * 1944-10-23 1952-11-11 Solvay Anode device
US3023393A (en) * 1958-10-22 1962-02-27 Union Carbide Corp Liquid electrical connection for electrolytic cells
US3068165A (en) * 1959-12-01 1962-12-11 Oronzio De Nora Impianti Eiett Mercury cathode electrolytic cell

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US742864A (en) * 1898-10-04 1903-11-03 Solvay Process Co Electrolytic process.
US2328665A (en) * 1939-10-27 1943-09-07 Mathieson Alkali Works Inc Electrolytic cell
NL63281C (forum.php) * 1941-08-27
US2617762A (en) * 1944-10-23 1952-11-11 Solvay Anode device
US2502888A (en) * 1945-09-17 1950-04-04 Ici Ltd Electrolytic cell
US3023393A (en) * 1958-10-22 1962-02-27 Union Carbide Corp Liquid electrical connection for electrolytic cells
US3068165A (en) * 1959-12-01 1962-12-11 Oronzio De Nora Impianti Eiett Mercury cathode electrolytic cell

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GB1013122A (en) 1965-12-15
DK112050B (da) 1968-11-04
FI42706B (forum.php) 1970-06-30

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