US3396095A - Method and apparatus for the continuous regulation of the distance between the electrodes of electrolytic cells with liquid mecury cathodes - Google Patents

Method and apparatus for the continuous regulation of the distance between the electrodes of electrolytic cells with liquid mecury cathodes Download PDF

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Publication number
US3396095A
US3396095A US418990A US41899064A US3396095A US 3396095 A US3396095 A US 3396095A US 418990 A US418990 A US 418990A US 41899064 A US41899064 A US 41899064A US 3396095 A US3396095 A US 3396095A
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Prior art keywords
anode
mercury
cathode
electrolysis
distance
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Expired - Lifetime
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US418990A
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English (en)
Inventor
Jacques Van Diest
Menier Jean
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Solvay SA
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Solvay SA
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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
    • C25B15/00—Operating or servicing cells
    • C25B15/04—Regulation of the inter-electrode distance

Definitions

  • the objects of the invention are to improve the control of the distance between the anode and the liquid mercury cathode of electrolytic mercury cells.
  • An object of the invention is to provide for a setting of the distance between the electrodes while the electrolysis of the cell is continued and electrolysis by the electrode being adjusted is discontinued.
  • Another object of the invention is to provide for a manual setting of the electrode distances to achieve optimum electrolysis of a solution.
  • the prior art anode regulation devices had limitations resulting from the nature of the electrolysis process. Dur ing the electrolysis of brine solutions in electrolytic cells having a mercury cathode the graphite anodes are consumed and the increased distance between the electrode results in a loss of the energy necessary for electrolysis. Due to increased distance between the electrodes it is necessary to regulate from time to time the distance between the anode and the cathode.
  • the present invention is a definite improvement of the prior art where the distance between the electrodes is regulated independently of the charge on the cell.
  • the result is that the reference point from which the adjustment is made is always the same no matter what the charge on the cell may be.
  • Another new and unexpected result is that the reference point is practically independent of the degree of erosion of the anode.
  • FIG. 1 shows a plot of the voltage change in the present invention as the anode is advanced toward the mercury cathode.
  • FIG. 2 is a schematic representation of the cross-section of a series of Solvay mercury electrolytic cells connected in series with the improvements of the present invention added thereto.
  • the procedure of the present invention is carried out by first opening switch 7 connecting the bottom of the preceding cell 12 with the anodes 25 and 25.
  • Anode 25' represents the anode to be regulated. Since anode 25 and cathode 23 are no longer under a voltage and instrument 29 representing a voltmeter, ammeter or galvanometer can then be connected between the anode 25 and the cathode 23.
  • the apparatus 31 represents the automatic regulation device of U.S. Patent No. 3,052,618 which automatically advances the anode until the voltage suddenly drops and then retracts the anode to a position where the distance between the anode and cathode produces a maximum production of the cell.
  • FIG. 1 illustrates the voltage variation on galvanometric relay 29 as anode 25' advances toward mercury cathode 23. As the graphite anode contacts the mercury cathode the voltage falls off to zero.
  • the present invention may be carried out by manually disengaging switch 7 and connecting in series anode 25', the galvanometric relay 29, the capacitor 30 and mercury cathode 23.
  • the galvanometric relay 29 registers a voltage variation.
  • the galvanometric relay 29 registers a fall-off of voltage to zero as the anode contacts the cathode.
  • the control apparatus 31 may be actuated automatically by galvanometric relay 29 to ad vance the anode 25 until it comes in contact with the cathode 23 and then to retract the anode 25' to the optimum electrode position.
  • FIG. 2 In a normal electrolysis operation the cells of FIG. 2 are connected in series. Direct current flows from 34 to copper conductors 6 to the anodes 5 and 5'. Brine solution 4 in cell 1 is electrolyzed by the passage of current from anode plates 8 and 8' to the mercury cathode 3. The current is conducted through the bottom of the mercury cell 2 to copper conductors 6 to the succeeding cell through switch 7. Anodes 15 and 15' and plates 18 and 18' conduct the current through cell 11 and electrolysis brine solution 14 by passage of current to mercury cathode 13. The bottom of the cell 12 conducts the current through a copper connector 6 to switch 7' which is shown in an open position. During the electrolysis operation switch 7 will be connected as shown in the solid lines of switch 7. The current flows through anodes 25 and 25 and anode plates 28 and 28 in cell 21 through the brine solution 24 to mercury cathode 23. The bottom 3 of the cell 22 conducts the current through copper connector 6 to terminal 33.
  • the inventors believe that the anode which is disconnected by the opening of the switch 7 acts like a chlorine electrode because of a certain amount of chlorine gas adsorbed on the graphite anode.
  • This chlorine electrode accounts for the voltage between the anode and the cathode when electrolysis is discontinued under this anode.
  • the voltmeter is connected between the adjustable anode 25 and the liquid mercury cathode 23 to measure the voltage between the anode and cathode and to determine the exact moment when the graphite anode comes in contact with the layer of mercury. When the contact takes place, the voltage suddenly drops.
  • a galvanometric relay and a capacitor can be connected in series with the anode to be adjusted and its corresponding mercury cathode so that when the switch 7' is opened and the anode is lowered to the mercury cathode, the capacitor will be charged. At the moment when the graphite anode comes into contact with the mercury cathode, the capacitor discharges suddenly.
  • This method is specially advantageous because it permits the distance between the electrodes to be regulated before the cell is in operation, i.e. it is not under any voltage and there is no sodium in the mercury. It is therefore possible to connect an auxiliary source of current and a resistor between the anode to be adjusted and the mercury cathode in such a manner as to charge the capacitor.
  • the improvement of the present invention facilitates automatic regulation.
  • the necessary impulse to actuate an automatic anode advancing and positioning mechanism is achieved by the sudden variation of voltage and/or current.
  • the relay pointer will swing in a definite direction and will come into contact with a point which is electrically connected with an auxiliary circuit serving to lower the anode, and then return immediately to its original position at the moment when the anode comes into contact with the mercury cathode.
  • the capacitor will discharge and the cessation of electric current will cause the pointer to swing in the opposite direction to that previously observed when the capacitor relay circuit was connected.
  • the pointer will now come into contact with a point connected electrically with an auxiliary circuit for withdrawing the anode to the point where the yield of the cell will be a maximum.
  • the improved control of the present invention makes it possible to obtain a reference position that is reproducible independently of the charge of the cell and of the degree of erosion of the electrodes.
  • a further advantage of the present invention is that all the anodes of the cell will be brought to approximately the same optimum distance from the surface of the mercury cathode.
  • an electrolytic mercury cell for the electrolysis of brines having at least one adjustable anode, a mercury cathode and a direct current source connected in series, the improvement comprising:
  • measuring instrument means connected in series with said adjustable anode and said mercury cathode and the advance of said adjustable anode is reversed when said measuring instrument indicates a sudden decrease and said adjustable anode is retracted a predetermined distance from a point of reversal in space, said distance being chosen for pro ducing optimum conditions for maximum electrolysis production.
  • an electrolytic mercury cell for the electrolysis of brines having at least one adjustable anode, a mercury cathode and a direct current source connected in series, the improvement comprising:
  • measuring instrument means connected in series with said adjustable anode and with said mercury cathode said measuring instrument being connected to indicate a sudden decrease upon contact between said adjustable anode and said mercury cathode;
  • circuit means connecting said instrument means with said advancing and retracting means and said instrument means actuates said advancing and retracting means.
  • an electrolytic mercury cell for the electrolysis of brines having at least one adjustable anode, a mercury cathode and a direct current source connected in series, the improvement comprising:
  • (c) means comprising galvanometric means and a capacitor connected in series with said adjustable anode and said mercury cathode and means whereby the advance of said adjustable anode is reversed when said galvanometric means indicates a sudden decrease and said adjustable anode is retracted a predetermined distance upon ceasing its advance, and said distance producing optimum conditions for maximum electrolysis production.
  • an electrolytic mercury cell for the electrolysis of brines having at least one adjustable anode, a mercury cathode and a direct current source connected in series, the improvement comprising:
  • circuit means connecting said galvanometric with said advancing and retracting means whereby said galvanometric means actuates said advancing and retracting means.

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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 Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US418990A 1964-01-24 1964-12-17 Method and apparatus for the continuous regulation of the distance between the electrodes of electrolytic cells with liquid mecury cathodes Expired - Lifetime US3396095A (en)

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BE642974 1964-01-24

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US3396095A true US3396095A (en) 1968-08-06

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US (1) US3396095A (US08017720-20110913-C00001.png)
BE (1) BE642974A (US08017720-20110913-C00001.png)
DE (1) DE1467243C3 (US08017720-20110913-C00001.png)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3476660A (en) * 1966-03-23 1969-11-04 Ici Ltd Method of sequentially adjusting the anodes in a mercury-cathode cell
US3480528A (en) * 1964-10-19 1969-11-25 Solvay Process for the adjustment of the distance between the electrodes of operating electrolysis cells
US3531392A (en) * 1965-11-11 1970-09-29 Knapsack Ag Arrangement for measuring the current intensity at the single electrodes of electrolytic cells
US3627666A (en) * 1967-11-06 1971-12-14 Pechiney Apparatus for automatically regulating the anode gap in electrolysis cells
US3902983A (en) * 1974-01-07 1975-09-02 Olin Corp Method and apparatus for preventing voltage extremes in an electrolytic cell having automatic adjusting of the anode-cathode spacing
US4069118A (en) * 1975-11-10 1978-01-17 Stauffer Chemical Company Electrolysis control apparatus and method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE554895A (US08017720-20110913-C00001.png) * 1957-02-09
US2328665A (en) * 1939-10-27 1943-09-07 Mathieson Alkali Works Inc Electrolytic cell
US2508523A (en) * 1946-09-11 1950-05-23 Krebs & Co Device for the protection of the cathodes of electrolytic cells
US2834728A (en) * 1953-03-02 1958-05-13 Oronzio De Nora Impianti Method and apparatus for protecting the cathodes of electrolytic cells
US3268427A (en) * 1962-08-30 1966-08-23 Uhde Gmbh Friedrich Electrolysis of alkaline chloride solutions
US3301776A (en) * 1963-04-08 1967-01-31 Metachemical Machines Ltd Apparatus for electrochemical machining of metal

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2328665A (en) * 1939-10-27 1943-09-07 Mathieson Alkali Works Inc Electrolytic cell
US2508523A (en) * 1946-09-11 1950-05-23 Krebs & Co Device for the protection of the cathodes of electrolytic cells
US2834728A (en) * 1953-03-02 1958-05-13 Oronzio De Nora Impianti Method and apparatus for protecting the cathodes of electrolytic cells
BE554895A (US08017720-20110913-C00001.png) * 1957-02-09
US3052618A (en) * 1957-02-09 1962-09-04 Solvay Apparatus for automatic regulation, during working, of the distance between the electrodes of electrolytic cells having a movable mercury cathode
US3268427A (en) * 1962-08-30 1966-08-23 Uhde Gmbh Friedrich Electrolysis of alkaline chloride solutions
US3301776A (en) * 1963-04-08 1967-01-31 Metachemical Machines Ltd Apparatus for electrochemical machining of metal

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3480528A (en) * 1964-10-19 1969-11-25 Solvay Process for the adjustment of the distance between the electrodes of operating electrolysis cells
US3531392A (en) * 1965-11-11 1970-09-29 Knapsack Ag Arrangement for measuring the current intensity at the single electrodes of electrolytic cells
US3476660A (en) * 1966-03-23 1969-11-04 Ici Ltd Method of sequentially adjusting the anodes in a mercury-cathode cell
US3627666A (en) * 1967-11-06 1971-12-14 Pechiney Apparatus for automatically regulating the anode gap in electrolysis cells
US3902983A (en) * 1974-01-07 1975-09-02 Olin Corp Method and apparatus for preventing voltage extremes in an electrolytic cell having automatic adjusting of the anode-cathode spacing
US4069118A (en) * 1975-11-10 1978-01-17 Stauffer Chemical Company Electrolysis control apparatus and method

Also Published As

Publication number Publication date
DE1467243A1 (de) 1969-03-27
DE1467243C3 (de) 1973-11-22
DE1467243B2 (de) 1973-04-19
BE642974A (US08017720-20110913-C00001.png) 1964-07-24

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