EP0201837B1 - Verfahren Und Vorrichtung zum Regeln des Betriebspunktes einer Elektrolysezelle - Google Patents

Verfahren Und Vorrichtung zum Regeln des Betriebspunktes einer Elektrolysezelle Download PDF

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Publication number
EP0201837B1
EP0201837B1 EP19860106133 EP86106133A EP0201837B1 EP 0201837 B1 EP0201837 B1 EP 0201837B1 EP 19860106133 EP19860106133 EP 19860106133 EP 86106133 A EP86106133 A EP 86106133A EP 0201837 B1 EP0201837 B1 EP 0201837B1
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EP
European Patent Office
Prior art keywords
voltage
cell
current
cathode
anode
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Expired
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EP19860106133
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English (en)
French (fr)
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EP0201837A1 (de
Inventor
René KODAK-PATHE Kaufmann
François KODAK-PATHE Mohier
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Kodak Pathe SA
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Kodak Pathe 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
    • C25B15/02—Process control or regulation
    • 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
    • C25C7/06—Operating or servicing

Definitions

  • the present invention relates to a method and a device for regulating the position of the operating point of an electrolysis cell and, more particularly, to such a method and such a device designed to maintain this operating point on a plate. of a current-voltage characteristic of such a cell.
  • the recovery of silver can also operate using cell porous cathode, or volume, such as those disclosed in European Patent No. 37,325 issued to Eastman Kodak Compa- ny.
  • the current-voltage characteristic of electrolysis has the appearance illustrated in FIG. 1A of the appended drawing. In this figure, it appears that this characteristic comprises an approximately rectilinear middle part, of slight slope, or "plateau". If the operating point is on the left of this plate, the electrolysis current is low and the electrolysis is slow. To the right of the plateau, the high relative intensity of the current causes the deposition on the electrodes of undesirable species such as silver sulphide. The best operating zone, from the point of view of the yield and the purity of the cathodic deposit, is therefore located on the current plateau, the intensity of the latter varying with the silver concentration of the electrolysed fixer.
  • the object of the present invention is therefore to provide a method and a device for regulating the position of the operating point of a cell where electrolysis of the current plate type described above takes place, which makes it possible to fix this point. in the best performance zone, without using a reference electrode.
  • the method of the invention is a method of regulating the position of the operating point of a cell where an electrolysis is carried out with current-voltage characteristic having a plate on which this point must be maintained, method according to which is superimposed on a continuous electrolysis voltage corresponding to a point on the plateau, a periodic voltage of determined amplitude and waveform.
  • the invention also makes it possible to produce a device for implementing this method, allowing the regulation of at least one anode-cathode voltage in a cell where electrolysis is carried out with current-voltage characteristic having a current plateau, of the type which comprises a) a power supply for establishing between the anode and the cathode a stabilized DC voltage and b) a means for adjusting this voltage.
  • the device further comprises c) an auxiliary periodic voltage source for superimposing on the stabilized anode-cathode voltage a periodic voltage of determined amplitude and waveform and (d) a regulator sensitive to the anode-cathode current to form a output signal significant of a difference between the waveform of the periodic component of the anode-cathode current and that of the periodic voltage superimposed on the DC voltage, the output signal of the regulator acting on the control means of the power supply (6) to correct the voltage.
  • advantage is taken of the non-linearity of the current-voltage characteristic to detect such drifts and to deduce therefrom a correction of the operating potential of the cell, capable of replacing the operating point of this cell in its position. the most favorable, namely the middle part of the plateau.
  • a periodic voltage of predetermined amplitude and waveform is superimposed on the operating voltage of the cell, the waveform of the periodic component is noted. of the cell current and the supply voltage of the cell is corrected as a function of the measured deformation of this waveform relative to that of the periodic voltage applied, so as to recall the entire periodic excursion of tension on the characteristic plate.
  • the periodic voltage E a (see FIG. 1) is superimposed on a periodic voltage, for example of triangular waveform e of excursion e M - e m .
  • This excursion is chosen so that it is at most equal, in voltage, to that of the plateau of the current-voltage characteristic.
  • the intensity response of the periodic voltage variation will have the shape represented in FIG. 1A, practically triangular and of total excursion l M -l m , due to the quasi-linearity of the current-voltage characteristic in its plateau part.
  • FIGS. 2, 3 and 4 show the means used, according to the present invention, to detect these deformations and to deduce therefrom a correction of the operating voltage of the cell.
  • FIG. 2 illustrates the general arrangement of the adjustment device according to the invention.
  • Electrodes 1, 2 are immersed in a container 3 containing the solution 4 to be electrolyzed.
  • One of these electrodes is a porous cathode.
  • the electrodes 1, 2 are connected to the terminals of a stabilized electrical supply 5.
  • the latter delivers an adjustable direct voltage established between the electrodes, as well as an adjustable periodic voltage having, for example, a triangular waveform.
  • This periodic voltage is supplied to the power supply 5 by a function generator 6.
  • the block diagram of the regulator is shown in FIG. 3. It comprises first and second means (8, 8 ', 9, 10) and (11, 12) respectively, for forming signals in slots.
  • This signal B is then transformed into a slot signal C (FIG. 4), in a comparator 10, the other input of which is grounded, by detection of the passage of the signal to zero.
  • This slot signal has the same frequency as the starting signal A but its duty cycle is a function of the position of the cell operating point relative to the plateau of the current-voltage characteristic.
  • the modulation signal supplied by the function generator 6 is taken in the form of a signal A which is also amplified at 11 and processed at 12 with a comparator for detecting the passage of the signal at zero.
  • the signal in slots D obtained has, by definition, a duty cycle equal to 50%. Its amplitude is made equal to that of signal C by appropriate conventional means.
  • a comparator 13 forms a signal E corresponding to the difference of the signals in slots C and D.
  • this operating point has drifted towards one or the other of the ends of the plate, it appears in the difference signal E series of pulses whose polarity is significant of the direction of the correction to be applied to the power supply 5 to bring the operating point of the cell back to the middle area of the plateau of the current-voltage characteristic.
  • pulses correctly amplified, supply an adjustment means such as a servo motor coupled to a potentiometer adjusting the operating point of the stabilized supply.
  • the regulation is then completely automatic.
  • FIG. 5 shows another embodiment of the invention suitable for regulating a multi-anode cell with a volume cathode.
  • this type of cell several 1 ', 1 ", 1"', etc. anodes are associated with a common 2 'cathode.
  • a common 6 'function generator and a stabilized 5' power supply supply the anodes via regulators 7 ', 7 ", 7"', etc. according to the invention, which each act separately on a separate anode, to polarize the latter in an optimal manner according to the local electrolysis conditions.
  • the present invention also finds application in other type of multi-electrode cells and in particular in those described in the aforementioned European patent n ° 37,325.
  • the present invention is applicable whenever the current-voltage characteristic of an electrolysis cell has a sufficiently large current plateau.

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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)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (10)

1. Verfahren zum Einstellen der Lage des Arbeitspunktes einer Elektrolysezelle mit einem ein Plateau aufweisenden Strom-/Spannungskurvenverlauf, dadurch gekennzeichnet, daß der einem Punkt des Plateaus entsprechenden Elektrolysen-Gleichspannung eine Wechselspannung von vorbestimmter Amplitude und Wellenform überlagert, von einer möglichen Verzerrung der Wellenform der Wechselspannungskomponente des Zellenstroms eine Verschiebung des Arbeitspunktes abgeleitet und die zur Versorgung der Zelle dienende Gleichspannung korrigiert wird, um das Ausmaß der Abweichung zu reduzieren und dadurch den Arbeitspunkt der Zelle auf dem Plateau zu halten.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß durch Vergleich der Null-Durchgänge der Wechselspannungskomponente des Ausgangsstroms mit denen der der Gleichspannung überlagerten Wechselspannung ein Signal erzeugt wird, welches die mögliche Verzerrung dieser Wechselspannungskomponente anzeigt und, ausgehend von diesem Vergleich, eine Kette von Rechtecksignalen erzeugt werden, deren Arbeitszyklus und Polarität Funktionen der an der Elektrolysen-Gleichspannung vorzunehmenden Korrektur darstellen, um die Verschiebung des Arbeitspunktes der Zelle rückgängig zu machen.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß eine Wechselspannung von dreieckiger, sägezahnförmiger oder sinusförmiger Wellenform gewählt wird.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß bezüglich eines Auswanderns der Wechselspannung ein Wert gewählt wird, der auf die Spannung bezogen die Ausdehnung des Plateaus der Stromspannungskurve nicht übersteigt.
5. Vorrichtung zur Durchführung des Verfahrens nach Anspruch 1, zum Einstellen wenigstens einer Anoden/Kathoden-Spannung in einer Elektrolysezelle mit einem ein Plateau aufweisenden Strom- /Spannungskurvenverlauf, wobei die Vorrichtung a) eine zwischen Anode und Kathode zu schaltende stabilisierte Gleichspannungsquelle und b) Mittel zum Einstellen der Spannung aufweist, dadurch gekennzeichnet, daß die Vorrichtung auch c) eine Hilfs-Wechselspannungsquelle (6) zum Überlagern der stabilisierten Anoden/Kathodenspannung mit einer Wechselspannung von vorbestimmter Amplitude und Wellenform und d) einen auf den Anoden/Kathodenstrom ansprechenden Regler (7) zum Erzeugen eines Ausgangssignals, welches das Auftreten einer Differenz zwischen der Wellenform der Wechseistromkomponente des Anoden/Kathodenstroms und der Wellenform der der Gleichspannung überlagerten Wechselspannung anzeigt, wobei das Ausgangssignal die Stromversorgung (6) zur Korrektur der Gleichspannung steuert, um den Arbeitspunkt der Zelle auf dem Plateau der Spannungskurve zu halten.
6. Vorrichtung nach Anspruch 5, dadurch gekennzeichnet, daß der Regler (9) erste Mittel (7, 8, 9, 10) zur Bildung eines Rechtecksignals (C) aufweist, dessen Null-Durchgänge synchron mit denen der Wechselstromkomponente (B) des Anoden/Kathodenstroms erfolgen, zweite Mittel (11, 12) zur Bildung eines Rechtecksignals, dessen Null-Durchgänge synchron mit denen der Anoden/Kathoden-Gleichspannung überlagerten Wechselspannung (A) erfolgen, und einen Komparator (13) zur Erzeugung eines Signals (E), welches das Auftreten einer Differenz zwischen den Signalen (C) und (D) anzeigt, wobei das Signal (E) das Ausgangssignal des Reglers ist.
7. Vorrichtung nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß die Hilfs-Wechselspannungsquelle (6) eine Spannung von dreieckiger oder sägezahnförmiger Wellenform erzeugt, deren auf die Spannung bezogene Amplitude die Ausdehnung des Plateaus der Spannungskurve nicht übersteigt.
8. Vorrichtung nach einem der Ansprüche 5 bis 7, für eine mehrere Elektrodenpaare aufweisende Elektrolysezelle, gekennzeichnet durch einen sämtlichen Anoden/Kathodenkreisen zugeordneten Regler (7).
9. Vorrichtung nach einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, daß die Zelle wenigstens eine poröse Kathode besitzt.
10. Vorrichtung nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, daß sie in einer Elektrolysezelle mit poröser Kathode zur Rückgewinnung von Silber aus einer Silbersalzlösung verwendet wird.
EP19860106133 1985-05-14 1986-05-05 Verfahren Und Vorrichtung zum Regeln des Betriebspunktes einer Elektrolysezelle Expired EP0201837B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8507269A FR2582022B1 (fr) 1985-05-14 1985-05-14 Procede et dispositif de regulation de la position du point de fonctionnement d'une cellule d'electrolyse
FR8507269 1985-05-14

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EP0201837A1 EP0201837A1 (de) 1986-11-20
EP0201837B1 true EP0201837B1 (de) 1989-03-08

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DE (1) DE3662279D1 (de)
FR (1) FR2582022B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013213982A1 (de) * 2013-07-17 2015-03-12 Bayer Materialscience Ag Verfahren und System zur Überwachung der Funktionsfähigkeit von Elektrolysezellen

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0754780B1 (de) 1995-07-15 2001-11-21 Agfa-Gevaert N.V. Verfahren und Vorrichtung zur Entsilberung von Lösungen
US5759377A (en) * 1995-07-15 1998-06-02 Agfa-Gevaert Process for de-silvering of a silver-containing solution
GB9815168D0 (en) 1998-07-13 1998-09-09 Eastman Kodak Co Recovery of metal from solution
GB9815167D0 (en) 1998-07-13 1998-09-09 Eastman Kodak Co Recovery of metal from solution
DE19840471A1 (de) * 1998-09-04 2000-03-09 Schmid Gmbh & Co Geb Einrichtung zum Abtrag einer Beschichtung von Gegenständen
ITMI20050580A1 (it) * 2005-04-07 2006-10-08 De Nora Elettrodi Spa Metodo di deposizione elettrochimnica di metalli

Family Cites Families (3)

* 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
LU82188A1 (fr) * 1980-02-21 1981-09-10 Esterol Ag Procede et appareil de traitement de bains de fixateurs photographiques
US4263108A (en) * 1980-03-27 1981-04-21 Foresight Enterprises, Incorporated Control system for the electrolytic recovery of silver from photographic fixing solution

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013213982A1 (de) * 2013-07-17 2015-03-12 Bayer Materialscience Ag Verfahren und System zur Überwachung der Funktionsfähigkeit von Elektrolysezellen

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DE3662279D1 (en) 1989-04-13
FR2582022A1 (fr) 1986-11-21
FR2582022B1 (fr) 1988-02-19
EP0201837A1 (de) 1986-11-20

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