US3849268A - Method and system for preventing short-circuits in mercury cathode electrolytic cells - Google Patents

Method and system for preventing short-circuits in mercury cathode electrolytic cells Download PDF

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Publication number
US3849268A
US3849268A US00290411A US29041172A US3849268A US 3849268 A US3849268 A US 3849268A US 00290411 A US00290411 A US 00290411A US 29041172 A US29041172 A US 29041172A US 3849268 A US3849268 A US 3849268A
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anode
cathode
distance
voltage
circuit
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English (en)
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N Miyamaoto
K Nakamura
O Nittani
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Adeka Corp
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Asahi Denka Kogyo KK
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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
    • C25B15/06—Detection or inhibition of short circuits in the cell

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  • the anode In the adjusting of the distance between the anode and the cathode, the anode is moved downward towards the cathode at a relatively low speed until the generation of the informational signal while the rate of voltage change is being observed and upon the generation of the informational signal, the anode stops its downward movement and is simultaneously moved upwardly at a relatively high speed, then stopping its upward movement at a point remote by a predetermined distance from the position of the anode where the informational signal is produced, thereby to finally obtain the most logical distance between the anode and the cathode.
  • ABSTRACT 2 Claims 4 Drawing Figures Lgi FI 16 E MULTIVIBRATOR -EMULTIVIBRATOR F I4 I 22 2 35 3 2
  • the present invention relates to a mercury cathode type electrolytic cell used for electrolysis of alkali chlo-- rides, and more particularly to a method of foreseeing a short-circuit between an anode and a cathode of the electrolytic cell before the short-circuit occurs and of adjusting or regulating continuously the distance between the anode
  • the reasons for this are: the fluidizing of the mercury cathode; the rise of the mercury cathode surface attracted by the anode, which approaches the cathode; the microscopically non-uniform distribution of current density due to the deposition of impurities from the electrolyte; the microscopically non-uniform anode surface in composi- 'tion and shape; and the variation of the distance between the anode and the cathode caused by slight variation of the electrolytic conditions and by slight vibrations of the anode or the cathode.
  • the short-circuiting and fusing of the electrodes cause a great loss or damage to electrolytic cell. Therefore, one of the important requirements in the operation of the electrolytic cell is to eliminate completely such short circuits.
  • a conventional method of detecting the short-circuit between the anode and the cathode of an electrolytic cell comprises: observing the voltage of the electric cell or the voltage (or current) between the anode and the cathode and regarding as the shortcireuit the voltage drop in which the voltage'becomes lower than a predetermined value.
  • a partial or local short circuit caused between the anode and the cathode is detected as a reduction in the voltage ofthe electrolytic cell or the voltage between the anode and the cathode.
  • Another object of the present invention is to provide a method of foreseeing or forecasting a short-circuit between an anode and a cathode of a mercury cathode electrolytic cell.
  • a further object ofthe present invention is to provide a method of precisely or definitely and quickly detecting a specific electrical phenomenonca'used immediately before a short-circuit of an anode and a cathode of a mercury cathode electrolytic cell thereby to foresee the short-circuit before it occurs.
  • a still further object of the present invention is to provide a method of logically adjusting or regulating the distance between an anode and a cathode by the utilization of the above-described short-circuitforeseeing method for the operation of a mercury cathode electrolytic cell, thereby to enhance the electric power'efficieney'and safety in'operation of the electrolytic cell.
  • a specific object of the present invention is to provide a method of optimally adjusting or regulating the distance between an anode and a cathode of a mercury cathode electrolytic cell by lowering or moving downward the anode twice toward the cathode thereby to make the distance shorter without risk of a shortcircuit;
  • FIG. 1 is a schematic block diagram showing one embodiment of the present invention which realizes a method of foreseeing a short-circuit between the anode and the cathode (or detecting a specific voltage variation which occurs immediately before the short-circuit) of an electrolytic cell and of adjusting or regulating the distance between the anode and the cathode;
  • FIG. 2 is a voltage-time graph indicating input signals of a threshold-value-responding circuit in ashort-ein cuit-foreseeing section (or, a section detecting a voltage change immediately before a short-circuit between the anode and the cathode);
  • FIG. 3 is a graphical representation indicating the variation of the distance between an anode and a cathode with time in the example illustrated in FIG. 1;
  • FIG. 4 is a similar representation indicating the variation of the distance between an anode and a cathode with time in another embodiment of the present invention.
  • the voltage change per an extremely short period of time that is, the rate of voltage change (or the speed of voltage change) in the above-described specific pulsive or impulsivevoltage variation (voltage drop and restoration) is considerably greater than that in a minute voltage change detected during the period when the short-circuit does not occur between the anode and the cathode.
  • Such a rate of voltage change is maintained for only a considerably short period of time, and the voltage drop is smaller than that caused by the shortcircuit.
  • the voltage between the anode and the cathode is restored back to its original value immediately after the voltage drop.
  • the above-described electrical phenomenon was discovered by the present inventors and has been utilized for providing the method of forseeing the short-circuit between the anode and the cathode through a study of the method of detecting precisely and quickly the specific voltage variation caused immediately before the short circuit. More specifically, in the method of foreseeing the short-circuit according to the present invention, the rate of voltage change with respect to the voltage between the anode and the cathode of the electrolytic cell is measured, and when the rate thus measured exceeds a predetermined threshold value, an informational signal is produced and utilized to determine that the anode and the cathode are in the condition which occurs immediately before the short circuit.
  • the logical distance between the anode and cathode for enhancing the electric power efficiency and safety in operation of an ordinary mercury cathode electrolytic cell is slightly greater than the distance between the anode and the cathode at which the anode and the cathode are determined to be immediately before the short-circuit.
  • the method of adjusting or regulating the distance between the anode and the cathode is thus completed by studying the specific phenomenon and the application of the specific phenomenon for precise and rapid adjustment of the distance between the anode and the cathode at which they are in the condition which occurs immediately before the short-circuit.
  • the method of adjusting or regulat ing the distance between the anode and the cathode of the electrolytic cell comprises moving the anode downward toward the cathode at a relatively low speed while observing the rate of voltage change with respect to the voltage between the anode and the cathode, producing an informational signal when the rate of decrease of the voltage exceeds a predetermined threshold value.
  • the anode is moved downward towards the cathode at a relatively low speed while the rate of voltage change with respect to the voltage between the anode and the cathode is observed, and when this rate cx ceeds a predetermined threshold value. an informational signal is produced thereby to stop the downward movement of the anode.
  • the anode Immediately after the stopping of the movement of the anode, the anode is moved upward at a speed higher than the speed of the downward movement of the anode and higher than the rising speed of the cathode surface until the anode reaches a position slightly above its final position, at which the anode will be positioned, in order to effectively eliminate the influence of the rise of the cathode surface, and then the anode is moved downward toward the cathode again at a speed lower than the speed of .the upward movement of the anode until the anode reaches the final position higher by a predetermined distance than the position of the anode where the informational signal has been produced.
  • the specific voltage variation which appears immediately before the shortcircuit of the anode and the cathode, and which is utilized to foresee the short-circuit and is used as a signal for the adjustment of the distance between the anode and the cathode is not a voltage drop phenomenon which simply appears in inverse proportion to the distance between the anode and the cathode, nor a voltage variation, which is slight in variation speed, such as a voltage ripple caused by the incomplete rectification of an alternate current electrical source, nor a voltage drop phenomenon between the anode and the cathode caused by a partial or local contact therebetween.
  • the specific voltage variation may be observed directly by an appropriate observing device, for instance an osciliograph inserted between the lead wires 23 and 27 shown in FIG.
  • FIG. 2(b) shows the pulses obtained by measuring the rate of the voltage variation and are obtained, for instance, by measuring at the lead wires 25 and 27 shown in FIG. 1.
  • the rate of increase of the voltage is shown in the upper part of the x axis
  • the rate of decrease of the voltage is shown in the lower part of the x axis.
  • the pulse of the rate of decrease of voltage is greater and more sharp than that of the rate of increase of voltage. Therefore, it is preferable to use the rate of decrease of the voltage as the informational signal or input signal.
  • the short-circuit of the electrodes is forecast when the rate of decrease of the voltage exceeds the predetermined threshold value. Therefore, by referring to thedifference between these rates it is a simple matter to predetermine the threshold value for the rate of voltage change in order to distingish the spec'ific voltage variation from the ordinary slight voltage variation.
  • FIG. 1 there is schematically shown one example of the electrolytic cell system suitable for carrying out the method of the present invention which will become more apparent from the following description.
  • FIG. 1 illustrates schematically an electrolytic cell'having only one anode.
  • the electrolytic cell comprises a vessel 1 covered with a layer of mercury 2 which is used as a cathode and continuously fed into the vessel 1, and an anode 3 which is properly spaced in an alkali chloride electrolyte 4, which is also supplied continuously into the vessel 1, from the surface of the mercury layer 2.
  • the aqueous alkali chloride solution is electrolized continuously by a direct current flowing between the anode 3 and the cathode 2.
  • chlorine gas is produced at the anode side, while at a deflocculation part (not shown in FIG. 1), hydrogen gas is produced and an aqueous alkali solution is produced and discharged, the mercury being circulated.
  • the anode 3 is connected to an anode bus bar 7 through a vertical metal rod 5 and a lead wire 6. Furthermore, the anode 3 together with many other anodes is mechanically connected through the metal rod 5 to an anode-supporting frame (not shown in FIG. 1) which is moved up and'down by means of an impellant shaft 8.
  • This shaft 8 is provided with a threaded part which is engaged with a threaded rotary shaft 10 of an operating electric motor 9, whereby the rotary motion of the electric motor 9 is transmitted as a linear motion to the impellant shaft 8.
  • a so-called step motor driven by pulses may be employed as the electric motor 9.
  • the step motor 9 is connected to an output terminal 12 of a driving power source circuit 11.
  • This power source circuit 11 drives the electric motor 9 so as to move the anode 3 downward when a control signal is introduced to a control input terminal 13 ofthe power source circuit 11 and to move the anode 3 upward when another control signal is introduced to anothercontrol input terminal 14 of the power source circuit 11.
  • the control input terminal 13 of the driving power source circuit 11 is connected to the output terminal 16 of a bi-stable multivibrator 15, while the control input terminal 14 is connected to the output terminal 18 of another bi-stable multivibrator 17.
  • a lead wire 23 is connected at its one end to a conductor of the anode side of the electrolytic cell, for instance to a proper point of the lead wire 6, while the other end of the lead wire 23 is connected to one terminal of a capacitor 24.
  • the other terminal of the capacitor 24 is connected through another lead wire 25 to one end of the primary winding of an insulating transformer 26.
  • the other end of the primary winding is connected through another lead wire 27 to a bus bar 28 provided on the cathode 2 side.
  • the secondary Winding of .the insulating transformer 26 is connected to the input terminal of a thresholdvalue-responding circuit 29 whose output terminal is connected to both a resetting input terminal 31 of the bi-stable multi-vibrator 15 and a resetting input terminal 32 of the bi-stable multi-vibrator 17.
  • Reference numeral 33 designates an input terminal through which an anode-lowering command signal is'applied when the voltage of the electrolytic cell is brought to a level higher than a predetermined value or at a predetermined time interval. This input terminal 33 is connected to both a setting input terminal 34 of the bistable multi-vibrator l5 and a resetting input terminal 35 of the counter 21.
  • a short-circuit-foreseeing section which is adapted to detect a specific voltage immediately before the shortcircuit between the anode, and the cathode which is one of the essential features of the present invention, is shown within a broken-line enclosure in FlG. l.
  • the short-circuit-foreseeing section comprises the threshold-value-responding circuit 29 which is connected or correlated electrically with the measuring device, the insulating transformer 26 and the capacitor 24, all of which have been described above.
  • the capacitor 24 differentiates the rate of voltage change with respect to the voltage between the anode and cathode, while and electric current proportional to the differential value of the rate of voltage change is supplied through the insulating transformer 26 to the input terminal of the threshold-value-responding circuit 29.
  • the capacitor 24 serves to interrupt an electrical component (a DC component), which varies slowly, and to pass an electrical component which varies quickly and more abraptly.
  • the electrical component varying abruptly is applied to the input terminal of the threshold-value-responding circuit 29.
  • This threshold-value-responding circuit 29 generates and dispatches and output signal when the input signal exceeds a predetermined value with its polarity corresponding to the reduction of the voltage between the anode and the cathode.
  • the voltage between the anode and the cathode contains a voltage pulsation, or a voltage ripple component originated from the voltage ripple of the rectified power source of the electrolytic apparatus.
  • This voltage ripple component passing through the capacitor 24 has a waveform as shown in FIG. 2(a) and is delivered to the input terminal of the thresholdvalue-responding circuit 29.
  • such a voltage ripple component cannot actuate the circuit 29 because there is a non-sensitive range within which the circuit does not sense the voltage ripple component provided in the circuit 29.
  • the bi-stable multivibrators and 17 are initially reset so that there'exists no output signal at their output terminals 16 and 18, that is, flip-flops F and F are in the state of0. Then, a pulse signal having a short time duraton is applied as the anodelowering command signal to the input terminal 33. This signal is applied through the input terminal 35 to the counter 21 so that the counter 21 will be in the 0 state, and at the same time the signal serves to change the states of the bi-stable multi-vibrator 15. As a result, an
  • This output signal at the output terminal 16 is applied through the control input terminal 13 to the driving power source circuit 11 thereby to activate the latter, whereby the driving power source circuit 11 is operated so as to move the anode downward.
  • the pulsive voltage variation componet described before is introduced to the input terminal of the threshold-valueresponding circuit 29 thereby to produce an output signal from the latter.
  • the output signal thus produced is applied to the input terminal 31 thereby to change the states of the bi-stable multi-vibrator 15.
  • the signal introduced to the input terminal 13 of the circuit 11 from the output terminal 16 of the multi-vibrator l5 disappears, and the driving operation of the electric motor 9 to move the anode downward stops.
  • the output signal of the thresholdvalue-responding circuit 29 is applied to the input terminal 32 of the multi-vibrator 17 thereby to change the states of the multi-vibrator 17.
  • an output signal is produced at the output terminal 18 ofthe multi-vibrator 17.
  • the output signal thus produced is introduced to the input terminal 14 of the'driving power source circuit 11 whereby the electric motor 9 is driven to move the anode 3 upward.
  • the AND gate 20 is opened by the output signal from the terminal 18 and a train of pulses having a frequency proportional to the rotational frequency of the electric motor 9 is delivered through the output terminal 19 of the circuitll and the AND gate 20 to the digital counter 21 and is then counted by the counter 21.
  • the count of the counter 21 reaches the predetermined counting value, the counter 21 produces an output signal which resets the bi-stable multivibrator 17.
  • the predetermined counting value of the counter 21 it is preferable to select the predetermined counting value of the counter 21 so that the anode 3 stops at a position for instance 0.] to 1.0 mm above the position of the anode where the condition that both the electrodes are immediately before the short-circuit is detected.
  • FIG. 3 is a graphic diagram illustrating the relationships of a distance r between the electrodes with respect to time t in adjusting the distance between the electrodes of the embodimentshown in FIG. 1.
  • FIG. 4 is also a graphical representation indicating the relationship of the distance r between electrodes with respect to time I in another embodiment (not shown in FIG. 1) of the present invention.
  • the operation of regulating the distance from the time t,. where the anode-lowering command signal is applied, to the time t where the condition that both the electrodes are in the condition which occurs immediately before the short circuit is the same as that in FIG. 3.
  • the anode is moved upward by a distance h A h of, for instance, 1.0 to 2.0 mm, exceeding the appropriate distance 11 of, for instance, 0.1 to 1.0 mm, and during the period of time from the time 1 to the time t, the anode is moved downward by the distance A h to obtain the appropriate distance h.
  • FIG. 1 shows the electrolytic cell having only one anode in order to simplify the description.
  • each electrolytic cell having a number of anodes is divided into a proper number of blocks each of which has an anode-supporting frame for a group of anodes belonging to the block, the anode-supporting frame being provided, at a proper position of the electrolytic cell, with an operating device adapted to move the anodes upward and downward.
  • the input terminal which is the measuring means for the measurement of the rate of voltage change and the forecasting of the short-circuit of the electrodes is settled.
  • the input terminals of all blocks are connected jointly with the threshold value-responding circuit 29 through a'switching circuit (not shown in FIG. 1) which switches the connection between a input terminal of each block and the threshold value-responding circuit one by one alternatively, and the operating devices of all blocks are also connected jointly with the driving power source circuit through a switching circuit which switches alternatively the connection between an operating device of each block and the driving power source circuit thereby the adjustting the distance between the electrodes for all of the blocks of the many electrolytic cells continuously or periodically, using commonly one unit of the control system as shown in FIG. 1.
  • the condition that the anode and the cathode are in the condition occurring immediately before the short-circuit can be precisely and quickly detected, whereby the adjustment of the distance between the anode and the cathode is carried out automatically and properly while the short-circuit between the anode and the cathode being avoided, and the operation of the electrolytic cells can be conducted safely and economically.
  • the electrolytic cell voltages of all of the blocks were maintained in a low and narrow voltage range'of 4.00 V to 4.03 V, resulting in a satisfactory electrolytic operation with no short-circuit phenomenon.
  • the efficiency of the electric current is not reduced and is maintained in a range of 94.7 percent to 95.1 percent.
  • a method of adjusting the distance between the anode and the cathode of a mercury cathode electrolytic cell comprises the steps of: lowering the anode toward the cathode at a predetermined speed while observing the rate of voltage change with respect to the voltage between the anode and the cathode; producing an informational signal at a position of the anode with respect to the cathode when the rate of voltage change exceeds a predetermined threshold value; stopping and raising said anode at a speed substantially higher than said predetermined speed immediately after receiving the informational signal; and then stopping said anode at a position remote upwardly by a predetermined distance from said position of the anode with respect to the cathode, where said informational signal is produced.
  • a method of adjusting the distance between the anode and the cathode of a mercury cathode electrolytic cell comprises the steps of: lowering the anode toward the cathode at a predetermined speed while observing the rate of voltage change with respect to the voltage between the anode and the cathode; producing an informational signal at a position of the anode with respect to the cathode, when the rate of voltage change exceeds a predetermined threshold value; stopping and raising said anode at a speed substantially higher thansaid predetermined speed immediately after producing the informational signal to a position higher than the predetermined finally stopping position; then lowering said anode close to the cathode at said predetermined speed; and stopping the anode at a position remote upwardly by a predetermined dis tance from said position of the anode with respect to the cathode where said informational signal is produced.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2296705A1 (fr) * 1974-12-30 1976-07-30 Solvay Procede et dispositif pour deceler un contact entre une anode et la cathode d'une cellule a mercure
US4069118A (en) * 1975-11-10 1978-01-17 Stauffer Chemical Company Electrolysis control apparatus and method
US4174267A (en) * 1972-07-17 1979-11-13 Olin Corporation Method for detecting incipient short circuits in electrolytic cells
US20080213344A1 (en) * 2002-06-14 2008-09-04 Providence Health System- Oregon Wound dressing and method for controlling severe, life-threatening bleeding
US11038363B2 (en) * 2014-09-30 2021-06-15 Cps Technology Holdings Llc Battery system to be implemented in an automotive vehicle, wake-up control unit configured to determine whether a short circuit is expected to be present in an electrical system, and short circuit detection unit of an electrical system

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1513138A (en) * 1974-08-16 1978-06-07 Ici Ltd Equipment for detecting variations in direct current flowing in an electrical conductor
JPS5815275Y2 (ja) * 1979-05-01 1983-03-28 三井造船株式会社 潜水体の回収装置
JPS5625690U (hu) * 1979-08-06 1981-03-09

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174267A (en) * 1972-07-17 1979-11-13 Olin Corporation Method for detecting incipient short circuits in electrolytic cells
FR2296705A1 (fr) * 1974-12-30 1976-07-30 Solvay Procede et dispositif pour deceler un contact entre une anode et la cathode d'une cellule a mercure
US4069118A (en) * 1975-11-10 1978-01-17 Stauffer Chemical Company Electrolysis control apparatus and method
US20080213344A1 (en) * 2002-06-14 2008-09-04 Providence Health System- Oregon Wound dressing and method for controlling severe, life-threatening bleeding
US11038363B2 (en) * 2014-09-30 2021-06-15 Cps Technology Holdings Llc Battery system to be implemented in an automotive vehicle, wake-up control unit configured to determine whether a short circuit is expected to be present in an electrical system, and short circuit detection unit of an electrical system

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IT969351B (it) 1974-03-30
JPS4944998A (hu) 1974-04-27
DE2246567A1 (de) 1974-03-14

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