EP0201837A1 - Verfahren Und Vorrichtung zum Regeln des Betriebspunktes einer Elektrolysezelle - Google Patents

Verfahren Und Vorrichtung zum Regeln des Betriebspunktes einer Elektrolysezelle Download PDF

Info

Publication number
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
Authority
EP
European Patent Office
Prior art keywords
voltage
cell
current
periodic
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86106133A
Other languages
English (en)
French (fr)
Other versions
EP0201837B1 (de
Inventor
René KODAK-PATHE Kaufmann
François KODAK-PATHE Mohier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Pathe SA
Original Assignee
Kodak Pathe SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kodak Pathe SA filed Critical Kodak Pathe SA
Publication of EP0201837A1 publication Critical patent/EP0201837A1/de
Application granted granted Critical
Publication of EP0201837B1 publication Critical patent/EP0201837B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/02Process control or regulation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06Operating 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 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.

Landscapes

  • 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 Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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

Publications (2)

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

Family

ID=9319246

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860106133 Expired EP0201837B1 (de) 1985-05-14 1986-05-05 Verfahren Und Vorrichtung zum Regeln des Betriebspunktes einer Elektrolysezelle

Country Status (3)

Country Link
EP (1) EP0201837B1 (de)
DE (1) DE3662279D1 (de)
FR (1) FR2582022B1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0754780A1 (de) 1995-07-15 1997-01-22 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
EP0999296A2 (de) * 1998-09-04 2000-05-10 Gebr. Schmid GmbH & Co. Einrichtung zum Abtrag einer Beschichtung von Gegenständen
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)

* 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

Citations (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
US4263108A (en) * 1980-03-27 1981-04-21 Foresight Enterprises, Incorporated Control system for the electrolytic recovery of silver from photographic fixing solution
EP0035008A2 (de) * 1980-02-21 1981-09-02 Esterol A.G. Verfahren und Apparat zur Aufbereitung photographischer Lösungen

Patent Citations (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
EP0035008A2 (de) * 1980-02-21 1981-09-02 Esterol A.G. Verfahren und Apparat zur Aufbereitung photographischer Lösungen
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0754780A1 (de) 1995-07-15 1997-01-22 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
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 (de) * 1998-09-04 2000-05-10 Gebr. Schmid GmbH & Co. Einrichtung zum Abtrag einer Beschichtung von Gegenständen
EP0999296A3 (de) * 1998-09-04 2000-12-13 Gebr. Schmid GmbH & Co. Einrichtung zum Abtrag einer Beschichtung von Gegenständen
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
DE3662279D1 (en) 1989-04-13
FR2582022B1 (fr) 1988-02-19
EP0201837B1 (de) 1989-03-08
FR2582022A1 (fr) 1986-11-21

Similar Documents

Publication Publication Date Title
Meissner et al. Photocorrosion of cadmium sulfide: Analysis by photoelectron spectroscopy
EP0201837B1 (de) Verfahren Und Vorrichtung zum Regeln des Betriebspunktes einer Elektrolysezelle
FR2666801A1 (fr) Procede et appareil de traitement de l'eau par electrolyse, notamment en vue de sa decarbonatation.
Haak et al. Electrochemical photocapacitance spectroscopy method for characterization of deep levels and interface states in semiconductor materials
NO972014L (no) Fremgangsmåte for å forhindre vekst av organismer på flater til konstruksjoner neddykket i en væske
US4263108A (en) Control system for the electrolytic recovery of silver from photographic fixing solution
EP0035008B1 (de) Verfahren und Apparat zur Aufbereitung photographischer Lösungen
EP0038244B1 (de) Verfahren zur Ablagerung auf leitungsfähigen Oberflächen, insbesondere auf Metalloberflächen, dünner organischer Filme durch Elektropolymerisierung und so erhaltene dünne Filme
KR20120110101A (ko) 태양 전지의 금속 접점용 씨앗층을 형성하는 광-유도 갈바닉 펄스 증착 방법, 상기 씨앗층 또는 상기 금속 접점의 연속 강화방법 및 상기 방법을 실행하기 위한 장치
FR2612437A1 (fr) Procede et dispositif d'usinage electrochemique de pieces a travailler
EP0053564B1 (de) Verfahren zum Überwachen der Diaphragmadurchlässigkeit während der elektrolytischen Vorbereitung mehrwertiger Metalle und Elektrolysezelle zur Durchführung dieses Verfahrens
JPS6433554A (en) Formation of electrochemical signal process image for copying layer
Cattarin et al. Reduction of H 2 O 2 at CuInSe2 (Photo) cathodes: II. Sustained and Triggered Oscillations
SU1392145A1 (ru) Устройство автоматического управлени процессом электролитического извлечени серебра из использованных фиксирующих растворов
EP0006797A1 (de) Elektrolytische Anzeigezelle mit einer Bezugselektrode und gesteuerter Löschspannung
Abd El Rehim The effect of superimposed ac on dc on the electrodeposition of Cu-Zn alloys
EP0198775B1 (de) Verfahren zur kontinuierlichen Überwachung des Gehalts eines in einem geschmolzenen Salzbad aufgelösten Metalls und dessen Anwendung zur kontinuierlichen Zufuhr dieser Metallsalze in einer Elektrolysezelle
WO1991017287A1 (fr) Dispositif et procede d'electrolyse a electrode poreuse
FR2491958A1 (fr) Procede de reglage de la distance entre les deux electrodes des cellules d'electrolyse a cathode de mercure
JPH0616507B2 (ja) 陽極酸化方法およびその装置
CN115963103A (zh) 一种超声调控电化学发光显微成像装置及成像方法
Lemasson et al. Discussion of “The Transport and Kinetics of Minority Carriers in Illuminated Semiconductor Electrodes”[WJ Albery, PN Bartlett, A. Hamnett, and MP Dare‐Edwards (pp. 1492–1501, Vol. 128, No. 7)]
JP3020678B2 (ja) 化合物半導体用保護膜の形成方法
SU1761821A1 (ru) Способ контрол средней плотности тока при импульсном питании гальванической ванны
ES8107336A1 (es) Un metodo para controlar un proceso de electrodeposicion de metales

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE GB

17P Request for examination filed

Effective date: 19870430

17Q First examination report despatched

Effective date: 19880519

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE GB

REF Corresponds to:

Ref document number: 3662279

Country of ref document: DE

Date of ref document: 19890413

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940428

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940606

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950505

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950505

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960201