EP0201837A1 - Process and apparatus for the readjustment of the operational setting in an electrolysis cell - Google Patents
Process and apparatus for the readjustment of the operational setting in an electrolysis cell Download PDFInfo
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- EP0201837A1 EP0201837A1 EP86106133A EP86106133A EP0201837A1 EP 0201837 A1 EP0201837 A1 EP 0201837A1 EP 86106133 A EP86106133 A EP 86106133A EP 86106133 A EP86106133 A EP 86106133A EP 0201837 A1 EP0201837 A1 EP 0201837A1
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 230000000737 periodic effect Effects 0.000 claims description 31
- 238000012937 correction Methods 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 2
- 150000003378 silver Chemical class 0.000 claims description 2
- 230000001360 synchronised effect Effects 0.000 claims 2
- 0 CCC[C@@](*(C)C(C)CNCC)C1=CC=CC1 Chemical compound CCC[C@@](*(C)C(C)CNCC)C1=CC=CC1 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 241001124532 Bubalus depressicornis Species 0.000 description 1
- JAQREQLLCYKTMX-UHFFFAOYSA-N CCC1C(C2)C2CCC1 Chemical compound CCC1C(C2)C2CCC1 JAQREQLLCYKTMX-UHFFFAOYSA-N 0.000 description 1
- FLRFGFQMWBVYER-VIFPVBQESA-N CC[C@@H](CNCC)C(C)C Chemical compound CC[C@@H](CNCC)C(C)C FLRFGFQMWBVYER-VIFPVBQESA-N 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 230000035987 intoxication Effects 0.000 description 1
- 231100000566 intoxication Toxicity 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical compound [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
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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
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- 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 with a current-voltage characteristic of such a cell.
- the recovery of the silver can also be carried out using cells with a porous, or volumetric, cathoae, such as those found in European Patent No. 37,325 issued in the name of Eastman Kodak Company.
- 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 electrolyzed fixer.
- the present invention therefore aims to provide a method and a device for regulating the position of the operating point of a cell in which electrolysis of the current plate type described above takes place, which makes it possible to fix this point. in the best yield area. without using a reference electrode.
- the method of the invention is a procedure for regulating the position of the operating bridge of a cell where electrolysis is carried out with current-voltage characteristic having a plate on which this point must be maintained. process by which a DC electrolysis voltage corresponding to a point on the plate is superimposed. a periodic tension of amplitude and shape. waveforms. We deduce from a possible deformation of the waveform of the periodic component of the cell output current, a drift of the operating point and we correct the DC supply voltage of the cell so as to reduce this drift and maintain the operating point of the cell on the platform.
- 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) an electrical supply for establishing a stabilized DC voltage between the anode and the cathoce and b) a means for adjusting this voltage.
- the device further comprises c) a source of periodic voltage auxiliary to the wire superimposing on the stabilized anode-cathode voltage a periodic voltage of determined amplitude and shape and (d) a regulator sensitive to the anode-cathode current to form a significant output signal of a difference between the waveform of the periodic comoosante of the anode-cathode current and that of the periodic voltage
- FIG. 1 where there is shown in A the graph of the current-voltage characteristic of a cell with a porous cathode where electrolysis of silver salts takes place.
- the operating point a of the cell be placed on the plateau of this characteristic, in its middle region.
- 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 compared to that of the applied penetration voltage. so as to bring together the whole periodic excursion of tension on the characteristic olateau.
- 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 power 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 penetration 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 includes first and second means (7, 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 plateau, 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 servomotor 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 cell several anoaes 1 '. 1 ". 1" '. etc. are associated with a common 2 'cathode.
- a generator of functions 6 ′ and a common stabilized power supply 5 ′ feed the anodes via regulators 7 ′. 7 ", 7" ', etc. according to the invention, which act separately on a separate anode, in order to polarize the latter optimally as a function of 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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Abstract
Description
La présente invention est relative à un procédé et un dispositif de régulation de la position du point de fonctionnement d'une cellule d'électrolyse et. plus particulièrement, à un tel procédé et un tel dispositif conçus pour maintenir ce point de fonctionnement sur un plateau d'une carctéristique courant-tension d'une telle cellule.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 with a current-voltage characteristic of such a cell.
Dans beaucoup d'applications de l'électrolyse, il est nécessaire de contrôler presqu'en perma- nence le courant ou le potentiel d'électrolyse. C'est le cas, notamment. lorsqu'on récupère par électrolyse l'argent contenu dans les bains de traitement photographique usagés. Les brevets des Etats-Unis d'Amérique n°4 018 658 et 4 263 108 décrivent, à titre d'exemple, divers moyens de réglage adaptés à des cellules équipées d'électrodes classiques.In many applications of electrolysis, it is necessary to control almost at p erma- vance current or potential electrolysis. This is particularly the case. when the silver contained in used photographic processing baths is recovered by electrolysis. US Patents 4,018,658 and 4,263,108 describe, by way of example, various means of adjustment suitable for cells fitted with conventional electrodes.
La récupération de l'argent peut aussi s'ooérer à l'aide de cellules à cathoae poreuse, ou volumique, telles que celles décntes dans le brevet européen n° 37 325 délivré au nom d'Eastman Kodak Company. Dans cette application, !a caractéristique courant-tension de l'électrolyse présente l'allure illustrée à la figure 1 A du dessin annexé. Sur cette figure, il apparaît que cette caractéristique comprend une partie médiane approximativement rectiligne, de pente faible, ou "plateau". Si le point de fonctionnement se situe à gauche de ce plateau, le courant d'électrolyse est faible et l'électrolyse est lente. A droite du plateau, la forte intensité relative du courant provoque le dépôt sur les électrodes d'espèces indésirables telles que le sulfure d'argent. La zone de meilleur fonctionnement, du point de vue du rendement et de la pureté du dépôt cathodique, se situe donc sur le plateau du courant, l'intensité de ce dernier variant avec la concentration en argent du fixateur électroiysé.The recovery of the silver can also be carried out using cells with a porous, or volumetric, cathoae, such as those found in European Patent No. 37,325 issued in the name of Eastman Kodak Company. In this application, 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 electrolyzed fixer.
Pour maintenir le point de fonctionnement de la cellule sur ce plateau, on peut penser à appliquer. à l'aide d'une alimentation électrique stabilisée. une tension choisie entre anode et cathode. Cependant la tension établie n'est connue avec certitude qu'aux bornes de l'alimentation. En effet. il est difficile de connaître les chutes ce tension qui s'établissent dans la solution à traiter au sein de la cathode volumique elle-même. Le potentiel de fonctionnement n'est pas alors exactement connu. Pour pallier cet inconvénient. on a pensé à utiliser une électrode de référence plongée dans la cellule. Un potentrostat applique alors aux électrodes de la cellule une tension telle que la différence de ootentiel mesurée entre l'électrode de travail de cette cellule et l'électrode de référence reste constante.To maintain the operating point of the cell on this plate, one can think of applying. using a stabilized power supply. a voltage chosen between anode and cathode. However, the established voltage is known with certainty only at the supply terminals. Indeed. it is difficult to know the drops this voltage which are established in the solution to be treated within the volume cathode itself. The operating potential is therefore not exactly known. To overcome this drawback. we thought of using a reference electrode immersed in the cell. A potentrostat then applies a voltage to the cell electrodes such that the difference in ootential measured between the working electrode of this cell and the reference electrode remains constant.
On a observé cenpendant les mesures de potentiel ainsi réalisées étaient peu reproductibles. dès que la cellule d'électrolyse est soumise à un champ électrique. En cutre. les esoèces chimiques contenues dans le fixateur photographique traité provoquent, à plus ou moins long terme, un emcoi- sonnement irréversible de l'électrode de référence. notamment par sulfuration. ce oui entraîne une dérive du ootentiel de travail. Le remolacement de cette éiectrode est relativement onéreux en côuts de matériel et de maintenance.It was observed, however, that the potential measurements thus carried out were not very reproducible. as soon as the electrolysis cell is subjected to an electric field. In cutre. the chemical species contained in the treated photographic fixative cause, in the more or less long term, an irreversible intoxication of the reference electrode. especially by sulfurization. this yes leads to a drift in the working potential. The replacement of this electrode is relatively expensive in terms of equipment and maintenance costs.
La présente invention a donc cour but de fournir un procédé et un dispositif de régulation de la position du point de fonctionnement d'une cellule où s'opère une électrolyse du type à plateau de courant décrit çi-dessus, qui permet de fixer ce point cans la zone de meilleur rendement. sans faire appel à une électrode oe référence.The present invention therefore aims to provide a method and a device for regulating the position of the operating point of a cell in which electrolysis of the current plate type described above takes place, which makes it possible to fix this point. in the best yield area. without using a reference electrode.
Le procédé de l'invention est un orocédé de régulation de la position du pont de fonctionnement d'une cellule où s'opère une électrolyse à caractéristique courant-tension présentant un plateau sur lequel ce point doit être maintenu. procédé suivant lequel on superpose à une tension continue d'électrolyse corresoonoant à un point du plateau. une tension périodique d'amplitude et de forme. d'onde déterminées. On déduit d'une déformation éventuelle de la forme d'onde de la composante périodique du courant de sortie de cellule, une dérive du point de fonctionnement et on corrige la tension continue d'alimentation de la cellule de manière à réduire cette dérive et à maintenir le point de fonctionnement de la cellule sur le plateau.The method of the invention is a procedure for regulating the position of the operating bridge of a cell where electrolysis is carried out with current-voltage characteristic having a plate on which this point must be maintained. process by which a DC electrolysis voltage corresponding to a point on the plate is superimposed. a periodic tension of amplitude and shape. waveforms. We deduce from a possible deformation of the waveform of the periodic component of the cell output current, a drift of the operating point and we correct the DC supply voltage of the cell so as to reduce this drift and maintain the operating point of the cell on the platform.
L'invention permet aussi de réaliser un dispositif pour la mise en oeuvre de ce procédé, permettant la régulation d'au moins une tension anode-cathode dans une cellule où s'opère une électrolyse à caractéristique courant-tension présentant un plateau de courant, du type qui comprend a) une alimentation électrique pour établir entre l'anode et la cathoce une tension continue stabilisée et b) un moyen de réglage de cette tension. Le dispositif comorend en outre c) une source de tension périodique auxfilaire cour superposer à la tension anode-cathode stabilisée une tension périodique d'amplitude et de forme d'onae déterminées et (d) un régulateur sensible au courant anode-cathode pour former un signai de sortie significatif d'une différence entre la forme d'onde de la comoosante périodique du courant anode-cathode et celle de la tension périodiqueThe 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) an electrical supply for establishing a stabilized DC voltage between the anode and the cathoce and b) a means for adjusting this voltage. The device further comprises c) a source of periodic voltage auxiliary to the wire superimposing on the stabilized anode-cathode voltage a periodic voltage of determined amplitude and shape and (d) a regulator sensitive to the anode-cathode current to form a significant output signal of a difference between the waveform of the periodic comoosante of the anode-cathode current and that of the periodic voltage
superposée à la tension conunue, le signal de sortie du régulateur agissant sur le moyen de commande de l'alimentation (6) pour corriger la tension.superimposed on the common voltage, the output signal of the regulator acting on the supply control means (6) to correct the voltage.
Au dessin annexé, donné seulement à titre d'exemple :
- la figure 1 comprend trois graphes utiles à l'explication du fonctionnement du procédé suivant l'invention, pour la régulation de la position du point de fonctionnement d'une cellule à électrolyse.
- la figure 2 est un schéma d'un dispositif pour la mise en oeuvre du procédé illustré à la figure 1,
- la figure 3 est un schéma du régulateur formant partie du dispositif de la figure 2,
- la figure 4 représente un groupe de formes d'onde permettant d'expliquer le fonctionnement du régulateur de la figure 3, et
- la figure 5 illustre un deuxième mode de réalisation de l'invention, destiné à une cellule d'électrolyse comprenant plusieurs anodes.
- Figure 1 includes three graphs useful for explaining the operation of the method according to the invention, for regulating the position of the operating point of an electrolytic cell.
- FIG. 2 is a diagram of a device for implementing the method illustrated in FIG. 1,
- FIG. 3 is a diagram of the regulator forming part of the device of FIG. 2,
- FIG. 4 represents a group of waveforms making it possible to explain the operation of the regulator of FIG. 3, and
- FIG. 5 illustrates a second embodiment of the invention, intended for an electrolysis cell comprising several anodes.
On se réfère à la figure 1 où l'on a représenté en A le graphe de la caractéristique courant-tension d'une cellule à cathode poreuse où s'opère une électrolyse de sels d'argent. Pour les raisons développées ci-dessus, il est souhaitable que le point de fonctionnement a de la cellule soit placé sur le plateau de cette caractéristique, dans sa région médiane. Au cours du fonctionnement de la cellule, on peut observer une dérive de la position de ce point, soit vers des intensités plus faibles, comme illustré en bà la figure 1B, soit vers des intensités plus fortes comme illustré en c à la figure 1 C.Reference is made to FIG. 1 where there is shown in A the graph of the current-voltage characteristic of a cell with a porous cathode where electrolysis of silver salts takes place. For the reasons developed above, it is desirable that the operating point a of the cell be placed on the plateau of this characteristic, in its middle region. During the operation of the cell, one can observe a drift of the position of this point, either towards weaker intensities, as illustrated in b in figure 1B, or towards stronger intensities as illustrated in c in figure 1 C .
Suivant la présente invention, on tire parti de la non-linéarité de la caractéristique courant-tension pour détecter de telles dérives et en déduire une correction du potentiel de fonctionnement de la cellule, propre à replacer le point de fonctionnement de cette cellule dans sa position la plus favorable, à savoir la partie médiane du plateau.According to the present invention, 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.
Pour ce faire, suivant le procédé de réglage conforme à la présente invention, on superpose à la tension de fonctionnement de la cellule une tension périodique d'amplitude et de forme d'onde prédéterminées, on relève la forme d'onde de la composante périodique du courant de cellule et on corrige la tension d'alimentation de la cellule en fonction de la déformation mesurée de cette forme d'onde oar rapport à celle de la tension pénodique appliquée. de manière à rappeier l'ensemble de l'excursion périodique de tension sur le olateau de la caractéristique.To do this, according to the adjustment method according to the present invention, 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 compared to that of the applied penetration voltage. so as to bring together the whole periodic excursion of tension on the characteristic olateau.
Pratiouement. on sucercose à la tension continue Ea(voir figure 1 une tension périodique. oar exemple de forme d'onde triangulaire e c'excursion eM-em. On choisit cette excursion de manière qu'elle soit au maximum égaie, en tension, à celle du plateau de la caractéristique courant-tension. Ainsi, lorsque le point de fonctionnement a de la cellule se trouve au voisinage de la partie centrale du plateau, la réponse en intensité de la variation périodique de tension présentera l'allure représentée à la figure 1A, pratiquement triangulaire et d'excursion totale IM-Im, du fait de la quasi- linéarité de la caractéristique courant-tension dans sa partie en plateau.Practice. we sucercose at the continuous voltage E a (see figure 1 a periodic voltage. oar example of a triangular waveform e this excursion e M -e m . We choose this excursion so that it is at the most lively, in tension , to that of the plateau of the current-voltage characteristic. Thus, when the operating point a of the cell is in the vicinity of the central part of the plateau, the intensity response of the periodic voltage variation will have the shape represented at FIG. 1A, practically triangular and of total excursion I M -I m , due to the quasi-linearity of the current-voltage characteristic in its plateau part.
Par contre, si le point de fonctionnement se déplace sur ce plateau vers l'extrémité gauche de la caractéristique, pour venir par exemple dans la position b repérée sur la figure 18, une partie de l'excursion totale eM-em de la tension périodique superposée s'effectuera sur une partie d'épaule non rectiligne de la caractéristique. La réponse en intensité à cette tension périodique présentera alors la forme d'onde représentée sur la figure 1 B, qui s'écarte alors sensiblement de la forme triangulaire du signal de tension périodique d'entrée.On the other hand, if the operating point moves on this plate towards the left end of the characteristic, to come for example in the position b identified in FIG. 18, part of the total excursion e M -e m of the superimposed periodic tension will be carried out on a non-rectilinear shoulder part of the characteristic. The intensity response to this periodic voltage will then have the waveform shown in Figure 1B, which then deviates substantially from the triangular shape of the input periodic voltage signal.
Il en est de même si le point de fonctionnement s'écarte du plateau vers la droite (figure 1C), la réponse en intensité au signal de tension périodique d'entrée triangulaire s'écartant aussi de la forme d'onde de ce dernier.The same applies if the operating point deviates from the plateau to the right (FIG. 1C), the intensity response to the triangular input periodic voltage signal also deviating from the latter's waveform.
Ces déformations de la forme d'onde sont donc significatives d'une dérive du point de fonctionnement de la cellule. On a représenté aux figures 2, 3 et 4 les moyens mis en oeuvre, suivant la présente invention, pour détecter ces déformations et en déduire une correction de la tension de fonctionnement de la cellule.These deformations of the waveform are therefore significant of a drift of the operating point of the cell. 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.
La figure 2 illustre l'agencement général du dispositif de réglage suivant l'invention. Des électrodes 1,2 sont plongées dans un récipient 3 contenant la solution 4 à électrolyser. L'une de ces électrodes est une cathode poreuse. Les électrodes 1,2 sont connectées aux bornes d'une alimentation électrique stabilisée 5. Celle-ci délivre une tension continue réglable établie entre les électrodes, ainsi qu'une tension périodique ajustable présentant, par exemple, une forme d'onde triangulaire. Cette tension pénodique est fournie à l'alimentation 5 par un générateur de fonctions 6. Un régulateur 7, sensible à une tension prélevée aux bornes d'une résistance 8 placée dans le circuit anode-cathode de la cellule, commande la tension continue établie par l'alimentation 5 entre les électrodes 1.2.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
Le schéma de principe du régulateur est représenté à la figure 3. Il comprend des premier et deuxième moyens (7, 8. 9, 10) et (11, 12) respectivement, de formation de signaux en créneaux. La tension prélevée aux bornes de la résistance 7, amplifiée en 8 et filtrée en 9, présente à la sortie du filtre l'une des formes d'onde représentée sur la ligne 8 de la figure 4. On retrouve en a , b, c les formes d'onde représentées à la figure 1, fonctions de la position du point de fonctionnement de la cellule d'électrolyse. Ce signal B est ensuite transformé en un signal en créneaux C (figure 4), dans un comparateur 10 dont l'autre entrée est mise à la masse, par détection du passage du signal à zéro. Ce signal en créneaux a la même fréquence que le signal A de départ mais son rapport cyclique est fonction de la position du point de fonctionnement de la cellule par rapport au plateau de la caractéristique courant-tension.The block diagram of the regulator is shown in FIG. 3. It includes first and second means (7, 8, 9, 10) and (11, 12) respectively, for forming signals in slots. The voltage taken from the terminals of the
Parallèlement, le signal de modulation fourni par le générateur de fonctions 6 est prélevé sous la forme d'un signal A qui est aussi amplifié en 11 et traité en 12 avec un comparateur à détection du passage du signal à zéro. Le signal en créneaux D obtenu a, par définition, un rapport cyclique égal à 50%. Son amplitude est rendue égale à celle du signal C par des moyens classiques appropriés.In parallel, the modulation signal supplied by the
Un comparateur 13 forme un signal E correspondant à la différence des signaux en créneaux C et D.A
Si le point de fonctionnement de la cellule est situé dans la partie médiané du plateau, la différence des signaux est nulle (figure 4, a). La sortie E du régulateur 7 n'applique alors aucune correction à l'alimentation stabilisée 5. Le point de fonctionnement de la cellule ne bouge pas.If the operating point of the cell is located in the median part of the plate, the difference in signals is zero (Figure 4, a). The output E of
Si au contraire ce point de fonctionnement a dérivé vers l'une ou l'autre des extrémités du plateau, il apparat dans le signal de différence E des séries d'impulsions dont la polarité est significative du sens de la correction à appliquer à l'alimentation 5 pour ramener le point de fonctionnement de la cellule dans la zone médiane du plateau de la caractéristique courant-tension.If, on the contrary, this operating point has drifted towards one or the other of the ends of the plateau, 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
Ces impulsions, correctement amplifiées, alimentent un moyen de réglage tel qu'un servomoteur couplé à un potentiomètre réglant le point de fonctionnement de l'alimentation stabilisée. La régulation est alors totalement automatique.These pulses, correctly amplified, supply an adjustment means such as a servomotor coupled to a potentiometer adjusting the operating point of the stabilized supply. The regulation is then completely automatic.
On a représenté à la figure 5 un autre mode de réalisation de l'invention adapté à la régulation d'une cellule multi-anodes à cathode volumique. Dans ce type ce cellule plusieurs anoaes 1'. 1". 1 "'. etc. sont associés à une cathode 2' commune. Un générateur de fonctions 6' et une alimentation staoilisée 5'communs alimentent les anodes par l'intermédiaire de régulateurs 7'. 7", 7"', etc. suivant l'invention, qui agissent cnacun séparément sur une anode distincte, pour polariser celle-ci de manière optimale en fonction des conditions locales d'électrolyse.FIG. 5 shows another embodiment of the invention suitable for regulating a multi-anode cell with a volume cathode. In this type this cell several anoaes 1 '. 1 ". 1" '. etc. are associated with a common 2 'cathode. A generator of
La présente invention trouve aussi application dans d'autre type de cellules multi-électrodes et notamment dans celles décrites au brevet européen n ° 37 325 précité.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.
On pourrait, sans sortir du cadre de l'invention, utiliser une tension périodique de forme d'onde autre que triangulaire. par exemple en dents de scie ou sinusoïdale. L'homme de métier adaptera aisément le procédé de détection décrit à la forme d'onde choisie pour cette tension périodique.Without departing from the scope of the invention, it is possible to use a periodic voltage with a waveform other than triangular. for example sawtooth or sinusoidal. Those skilled in the art will easily adapt the detection method described to the waveform chosen for this periodic voltage.
En outre, bien que conçue pour résoudre un des problèmes liés à l'électrolyse des bains de traitement photographique usagés dans une cellule à électrode volumique, la présente invention est applicable à chaque fois que la caractéristique courant-tension d'une cellule d'électrolyse présente un plateau de courant suffisamment étendu.In addition, although designed to solve one of the problems associated with the electrolysis of used photographic processing baths in a cell with a volume electrode, the present invention is applicable whenever the current-voltage characteristic of an electrolysis cell has a sufficiently large current plateau.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8507269 | 1985-05-14 | ||
| FR8507269A FR2582022B1 (en) | 1985-05-14 | 1985-05-14 | METHOD AND DEVICE FOR REGULATING THE POSITION OF THE OPERATING POINT OF AN ELECTROLYSIS CELL |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0201837A1 true EP0201837A1 (en) | 1986-11-20 |
| EP0201837B1 EP0201837B1 (en) | 1989-03-08 |
Family
ID=9319246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19860106133 Expired EP0201837B1 (en) | 1985-05-14 | 1986-05-05 | Process and apparatus for the readjustment of the operational setting in an electrolysis cell |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0201837B1 (en) |
| DE (1) | DE3662279D1 (en) |
| FR (1) | FR2582022B1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0754780A1 (en) | 1995-07-15 | 1997-01-22 | Agfa-Gevaert N.V. | Process for de-silvering a silver-containing solution |
| US5759377A (en) * | 1995-07-15 | 1998-06-02 | Agfa-Gevaert | Process for de-silvering of a silver-containing solution |
| EP0999296A2 (en) * | 1998-09-04 | 2000-05-10 | Gebr. Schmid GmbH & Co. | Apparatus for removing a coating from objects |
| US6187167B1 (en) | 1998-07-13 | 2001-02-13 | Eastman Kodak Company | Recovery of metal from solution |
| US6207037B1 (en) | 1998-07-13 | 2001-03-27 | Eastman Kodak Company | Recovery of metal from solution |
| WO2006105981A2 (en) * | 2005-04-07 | 2006-10-12 | Industrie De Nora S.P.A. | Method for electrochemical deposition of metals |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013213982A1 (en) * | 2013-07-17 | 2015-03-12 | Bayer Materialscience Ag | Method and system for monitoring the functioning of electrolysis cells |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2296705A1 (en) * | 1974-12-30 | 1976-07-30 | Solvay | Detecting contact between electrolytic anode and cathode - by comparison of impulses superimposed on current and voltage |
| US4263108A (en) * | 1980-03-27 | 1981-04-21 | Foresight Enterprises, Incorporated | Control system for the electrolytic recovery of silver from photographic fixing solution |
| EP0035008A2 (en) * | 1980-02-21 | 1981-09-02 | Esterol A.G. | Process and apparatus for treating photographic baths |
-
1985
- 1985-05-14 FR FR8507269A patent/FR2582022B1/en not_active Expired
-
1986
- 1986-05-05 EP EP19860106133 patent/EP0201837B1/en not_active Expired
- 1986-05-05 DE DE8686106133T patent/DE3662279D1/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2296705A1 (en) * | 1974-12-30 | 1976-07-30 | Solvay | Detecting contact between electrolytic anode and cathode - by comparison of impulses superimposed on current and voltage |
| EP0035008A2 (en) * | 1980-02-21 | 1981-09-02 | Esterol A.G. | Process and apparatus for treating photographic baths |
| 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 (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0754780A1 (en) | 1995-07-15 | 1997-01-22 | Agfa-Gevaert N.V. | Process for de-silvering a silver-containing solution |
| US5759377A (en) * | 1995-07-15 | 1998-06-02 | Agfa-Gevaert | Process for de-silvering of a silver-containing solution |
| US6187167B1 (en) | 1998-07-13 | 2001-02-13 | Eastman Kodak Company | Recovery of metal from solution |
| US6207037B1 (en) | 1998-07-13 | 2001-03-27 | Eastman Kodak Company | Recovery of metal from solution |
| EP0999296A2 (en) * | 1998-09-04 | 2000-05-10 | Gebr. Schmid GmbH & Co. | Apparatus for removing a coating from objects |
| EP0999296A3 (en) * | 1998-09-04 | 2000-12-13 | Gebr. Schmid GmbH & Co. | Apparatus for removing a coating from objects |
| WO2006105981A2 (en) * | 2005-04-07 | 2006-10-12 | Industrie De Nora S.P.A. | Method for electrochemical deposition of metals |
| WO2006105981A3 (en) * | 2005-04-07 | 2007-07-12 | De Nora Elettrodi Spa | Method for electrochemical deposition of metals |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0201837B1 (en) | 1989-03-08 |
| DE3662279D1 (en) | 1989-04-13 |
| FR2582022A1 (en) | 1986-11-21 |
| FR2582022B1 (en) | 1988-02-19 |
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