EP0630426B1 - Procede et dispositif de maintien d'une protection cathodique contre la corrosion - Google Patents

Procede et dispositif de maintien d'une protection cathodique contre la corrosion Download PDF

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EP0630426B1
EP0630426B1 EP92919515A EP92919515A EP0630426B1 EP 0630426 B1 EP0630426 B1 EP 0630426B1 EP 92919515 A EP92919515 A EP 92919515A EP 92919515 A EP92919515 A EP 92919515A EP 0630426 B1 EP0630426 B1 EP 0630426B1
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current
potential
intensity
value
anode
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EP0630426A1 (fr
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Gino Cadignani
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Cgr Di Cadignani Pi Gino
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/04—Controlling or regulating desired parameters

Definitions

  • the present invention relates to a process for mantaining a cathodic protection agaist corrosion.
  • the present invention relates to a galvanic process for mantaining a cathodic protection against corrosion on metallic objects, particularly on boilers, using an electrode acting as anode which is crossed by an external current and an electronic control potentiometer.
  • the invention relates to a device suitable for carrying out said process.
  • the invention may be mainly applied in the fields of thermo-mechanical and electrochemical industries.
  • Italian patent n. IT-A-1.079.586 discloses a device for carrying out a method which provides for the use of two electrodes, respectively an anode and a reference electrode which, together with the boiler wall, are connected to the three input terminals of an electrical generator; more precisely, the anode is connected to the positive pole, the boiler wall is connected to the negative pole, and the reference electrode is connected to the connecting pole of a reverse feedback circuit.
  • the system continuously gauges the potential difference appearing between the reference electrode and the boiler wall, without reducing nor interrupting the current.
  • the gauged potential difference is compared with a reference value which is seeked for by means of suitable adjustments of the current which is delivered between the anode and the boiler wall.
  • the reference electrode is provided with a particular structure, according to which said electrode should be mounted close to the boiler wall.
  • EP-A-0 018 522 discloses a further cathodic protection method according to which a single electrode is used, acting as anode, which is connected to the positive pole of an electrical generator whose negative pole is connected to the boiler.
  • the current which is delivered is periodically interrupted (i.e. its value is set to zero) and, during this phase, the potential difference existing between anode and boiler wall is gauged.
  • the anode acts as reference electrode.
  • the gauged potential difference is compared with a reference value by means of a comparator, and the deviation between the values is used for determining the intensity of the current to be delivered during the next phase.
  • Measuring the potential difference between anode and boiler wall during a zero current phase aims to avoid the cited drawbacks due to the presence of a ohmic drop in the water.
  • This drop depends on intermediate desorbing processes which are carried out during the normal current operation, and on a superficial pH variation, the pH passing from an acid value, which is typical of the situation when current is flowing, to an alkaline value, which is typical of water.
  • Document WO 88/08462 discloses a process for measuring the polarised potential of a buried pipeline having impressed current cathodic potential. In particular, it relates to the measurement of the potential of a pipe which has more than one protection circuit.
  • each of the protection circuits are periodically pulsed on and off.
  • the voltage is sampled over both the on and off pulse periods.
  • the sampling technique used enables the problems of IR drop and inductive transients to be overcome. Furthermore, it permits an accurate measurement of the polarise potential, even when current is flowing in the pipe from other protection circuits.
  • this document does not disclose adjusting the protection current to a value between 10 and 50% or 200% of the steady condition value.
  • the use of altered currents as opposed to zero current to determine the polarised potential which makes it possible to reduce the effect of the IR drop and transients on the measurements is not suggested in this document; rather, WO 88/08462 overcomes these problems by using a complex pulsing and sampling technique.
  • the present invention aims to obviate to the disadvantages and drawbacks of the background art, and to provide, thus, for a cathodic protection process which, while making use of a single electrode, allows a reproduceable current measurement to be carried out, and which therefore allows the intensity of the protection current to be reliably controlled.
  • claims 6 to 11 describe a device suitable for carrying out the process according to the invention.
  • the cathodic protection process against corrosion features a single electrode, the anode, which is connected to the positive pole of an electrical power supply, whose negative pole is connected to the object to be protected, e.g. to a boiler.
  • the intensity of the current necessary for mantaining the process is periodically raised or lowered for a predetermined lapse of time about a predetermined percentage value relative to the steady condition value, and during this phase in which a higher or a lower current is delivered the potential difference between boiler and anode is gauged.
  • This potential difference is compared, by means of a comparator, with a predetermined reference value, and the deviation is used for determining the current intensity during the next steady condition phase.
  • measuring the potential difference during a phase in which a lower current is delivered allows the ohmic drop value in the water to be substantially decreased up to a negligible value; this value is otherwise difficult to be gauged, since it varies from place to place and it depends on temperature.
  • the intensity of the protection current is periodically reduced to a fraction relative to the steady condition value for a predetermined lapse of time, and a voltage measurement is carried out during this phase.
  • the result of the measurement is linearly corrected by extrapolating the zero current value, and then compared with a reference value in order to obtain a value for controlling the current during the next steady condition phase.
  • the intensity of the protection current is periodically doubled during a predetermined lapse of time, and the corresponding potential is gauged.
  • reference sign 10 generally indicates a block diagram representing the component parts of a device suitable for carrying out a process according to the invention.
  • Device 10 generally cooperates with an object 11 to be protected against corrosion, having a metallic surface which contacts water.
  • object 11 is constituted by a boiler; however, the process according to the invention may be also applied to other metallic surfaces which are suitable for being corroded by water, such as boat parts, pipelines, gutters etc..
  • Boiler 11 which is filled with water consituting the electrolyte solution, houses an electrode 12 belonging to device 10, and which is connected to the positive pole of a current generator 20, whose negative pole is connected to the wall of boiler 11.
  • This electrode is generally constituted by a titanium bar activated by noble metals.
  • the electrical power supply for the whole circuit is delivered by a suitable DC source (not shown in the figure), which is generally constituted by a feeder which is connected to the AC mains and which is provided with a transformer, a rectifier circuit and suitable filters.
  • current generator 20 and electrode 10 are connected to a pair of Sample and Hold cells 14, 15, which are push-pull controlled by an oscillator 19.
  • cell 15 is rendered conductive, by means of a suitable control, relative to a current intensity equal to 100% of the steady condition current, while cell 14 is rendered conductive relative to a current intensity equal to 50% of the steady condition current.
  • V 100% (V1) is stored, which represents the potential value which is present on anode 12 when the current intensity is equal to the steady condition current I 100% (I1)
  • V 50% (V2) is stored which represents the potential value which is present on anode 12 when the current intensity is equal to 50% of the steady condition current I 50% (I2).
  • Value V3 corresponds to an extrapolated value of the potential corresponding to zero current, and is compared with a potential reference value V r which is predetermined and stored in a memory.
  • device 10 comprises a first differential amplifier 16 which carries out the substraction (V1-V2) and which, by a suitable choice of the resistance values, is set in order to obtain a total gain equal to two; in this way, the output voltage of differential amplifier 16 is equal to 2(V1-V2).
  • This potential is applied to one of the input terminals of a second differential amplifier 17, which substracts said value from the steadi condition potential V1.
  • potential V3 is applied to an input terminal of a third differential amplifier 18, at the other input terminal of which being applied reference potential V r , which is obtained from a divider module 22 by dividing the supply voltage; the output voltage of amplifier 18 is then applied to current generator 20.
  • module 20 generates a current which is proportional to the output voltage of amplifier 18.
  • the circuit is completed by an electronic switch 21 which, by means of a control signal generated by oscillator 19, and timed with the conduction period (Sample) of cell 14, halves the output current of generator 20 and sets it to a value corresponding to 50% of the steady condition value.
  • the potential value V2 corresponds to a 50% reduction of the current intensity.
  • value V2 may be choosed within wide limits, corresponding to values of current intensity comprised between 10% and 50% of the steady condition current intensity; in any case, very reliable controls of the current intensity are achieved.
  • divider 22 is connected to a water temperature sensor (not shown in the figure).
  • the insertion of a water temperature sensor has the purpose of compensating the potential variation on the anode, due to a water temperature change.
  • reference potential V r is generated by divider 22, which reduces the potential which is stabilized by a Zener diode (not shown in the figure); since V r is fixed, it happens that, by controlling the current delivered by the circuit, the potential between anode and cathode varies in accordance with the different behaviour of the electrolyte solution interposed between anode and cathode at different operating temperatures.
  • V r when V r is also controlled, by providing a water temperature sensor cooperating with the divider circuit 22, this reference potential may be varied in accordance with temperature changes in the electrolyte solution.
  • the potential between anode and cathode is characterised by a more constant behaviour; this limited possibility of ranging of the potential allows a more reliable and homogeneous protection to be achieved; the danger of corrosion due to an overprotection in the case where passive protection materials (enamels, paintings etc.) are used, is also greatly reduced.
  • a indicating device (not shown in the figure), which is generally constituted by a LED display, is connected to current generator 20.
  • This device has the purpose of delivering a visible indication of the operation of the protection circuit against corrosion.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)

Abstract

Selon le procédé de protection cathodique contre la corrosion présenté, on utilise une seule électrode (12), l'anode, qui est reliée au pôle positif d'un dispositif d'alimentation en courant électrique dont le pôle négatif est relié à l'objet à protéger, par exemple à une chaudière. Une caractéristique essentielle de l'invention est que l'intensité de courant nécessaire pour maintenir la protection est périodiquement augmentée ou abaissée pendant un temps prédéterminé et d'une valeur prédéterminée représentant un pourcentage de la valeur de régime permanent, et qu'au cours de cette phase, phase pendant laquelle un courant d'intensité plus élevée ou plus basse est fourni, la différence de potentiel entre la chaudière et l'anode est mesurée. Cette différence de potentiel est comparée, au moyen d'un comparateur, avec une valeur de référence prédéterminée, et l'écart trouvé est utilisé pour déterminer l'intensité de courant à fournir pendant la prochaine phase de régime permanent.

Claims (11)

  1. Procédé de maintien d'une protection cathodique contre la corrosion où une électrode (12) ayant la fonction d'anode et parcourue par un courant extérieur est immergée dans une solution électrolytique en contact avec un objet métallique (11) à protéger, celui-là ayant la fonction de cathode, ledit procédé utilisant un module (22) aux extrémités duquel il y a un potentiel de référence (Vr) et un circuit électronique pouvant comparer des données concernant la différence de potentiel existant entre l'anode et la cathode et ledit potentiel de référence (Vr), procédé caractérisé en ce qu'il comprend:
    - une phase, répétée périodiquement, de variation au moyen de l'élévation ou l'abaissement de l'intensité de régime (I 100%) du courant de protection jusqu'à une valeur prédéterminée et de toute façon pas égale à zèro, ladite valeur étant comprise entre 10 et 50% par rapport à la valeur du courant de régime, ou bien étant égale à 200% par rapport à la valeur du courant de régime;
    - une phase de mésure de la différence de potentiel (V2) existant entre anode et cathode pendant cette condition d'intensité de courant variée par rapport à l'intensité de régime, et
    - une phase de comparaison entre cette différence de potentiel et ledit potentiel de référence (Vr), la différence entre les valeurs étant utilisée en tant que grandeur de contrôle pour l'intensité du courant de protection.
  2. Procédé selon la revendication 1, caractérisé en ce que les valeurs de potentiel correspondant respectivement à une intensité de courant de régime (V1) et à une intensité de courant réduit (V2) sont élaborés par ledit circuit électronique, lequel réalise une correction linéaire d'extrapolation de la valeur de potentiel (V3) correspondant à un courant égale à zéro dans l'anode (12), ledit potentiel (V3) étant par la suite comparé au potentiel de référence (Vr).
  3. Procédé selon la revendication 2, caractérisé en ce que pendant la phase où l'intensité de régime du courant de protection est portée à une valeur comprise entre10 et 50%, la valeur de potentiel (V3) qui correspond à une intensité de courant égale à zéro dans l'anode (12) qui est extrapolée dudit circuit électronique au moyen de l'application de la formule suivante: V3 = V1 - 2(Vl-V2)
    Figure imgb0007
     où Vl représente le potentiel correspondant à l'intensité de courant de régime et V2 représente le potentiel correspondant à l'intensité de courant réduit.
  4. Procédé selon la revendication 1 est caractérisé en ce que les valeurs de potentiel correspondant respectivement à une intensité de courant à régime (Vl) et à une intensité de courant réduit (V2) sont élaborées par ledit circuit électronique qui réalise une correction linéaire de la valeur du potentiel (V4) qui est, par la suite, comparé au potentiel de référence (Vr).
  5. Procédé selon la revendication 4, caractérisé en ce que ladite valeur de potentiel (V4) corrigée en forme linéaire, est obtenue au moyen de l'application de la formule suivante: V4 = Vl - (V2-Vl)
    Figure imgb0008
     où Vl représente le potentiel correspondant à l'intensité de courant augmentée.
  6. Dispositif (10) pour la mise en oeuvre d'un procédé selon l'une des revendications précédentes, comportant une électrode (12) ayant la fonction d'anode immergée dans une solution électrolytique en contact avec un objet (11) à protéger contre la corrosion lequel agit comme une cathode, caractérisé en ce qu'il comprend un couple de cellules (14, 15) du type Sample and Hold lesquelles enregistrent et mémorisent les données concernant la différence de potentiel existant entre l'anode et la cathode en des conditions différentes d'intensité du courant qui parcourt l'anode, une source (22) de potentiel de référence (Vr), des premiers moyens (16, 17) d'élaboration desdites données, des deuxièmes moyens (18) pouvant réaliser une comparaison entre les données élaborées et ledit potentiel de référence (Vr), un générateur de courant (20) contrôlé par lesdits deuxièmes moyens (19) lequel peut être commuté sur une intensité de courant qui est respectivement majeure ou mineure de 100% par rapport au courant de régime, et des troisièmes moyens (19, 20) pouvant respectivement éléver ou reduir l'intensité du courant à des instants prédéterminés.
  7. Dispositif (10) selon la revendication 6, caractérisé en ce que lesdits premiers moyens (16, 17) comportent un couple d'amplificateurs différentiels disposés en cascade et reliés l'un à l'autre et qui sont opportunemént reliés auxdites cellules (14, 15).
  8. Dispositif (10) selon l'une des revendications 6 et 7, caractérisé en ce que lesdits deuxièmes moyens comprennent un amplificateur différentiel (18), une entrée duquel est reliée à la sortie des premiers moyens (16, 17), l'autre entrée duquel est reliée à la source de potentiel de référence (Vr), la sortie de l'amplificateur (18) étant reliée audit générateur de courant (20).
  9. Dispositif (10) selon l'une des revendications de 6 à 8, caractérisé en ce que des troisièmes moyens de temporisation (19, 21) comprennent un interrupteur électronique (21) et un oscillateur (19).
  10. Dispositif (10) selon l'une des revendications de 6 à 9; caractérisé en ce qu'il est doté, en outre, d'un senseur de la température de la solution éléctrolytique coopérant avec ladite source (22) de potentiel de référence (Vr) dans au but de contrôler la valeur du potentiel de référence (Vr) suivant les changements de température qui se produisent dans la solution éléctrolytique pendant le fonctionnement.
  11. Dispositif (10) selon l'une des revendications de 6 à 10, caractérisé en ce qu'il est doté d'un dispositif permettant de voir l'état du procédé de protection.
EP92919515A 1991-08-14 1992-08-12 Procede et dispositif de maintien d'une protection cathodique contre la corrosion Expired - Lifetime EP0630426B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITVR91007 1991-08-14
ITVR910070A IT1253258B (it) 1991-08-14 1991-08-14 Processo di mantenimento di una protezione catodica contro la corrosione e dispositivo per la messa in opera di tale processo
PCT/IT1992/000105 WO1993004218A1 (fr) 1991-08-14 1992-08-12 Procede et dispositif de maintien d'une protection cathodique contre la corrosion

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EP0630426A1 EP0630426A1 (fr) 1994-12-28
EP0630426B1 true EP0630426B1 (fr) 1995-11-15

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EP (1) EP0630426B1 (fr)
DE (1) DE69206157T2 (fr)
DK (1) DK0630426T3 (fr)
ES (1) ES2082500T3 (fr)
GR (1) GR3018985T3 (fr)
IT (1) IT1253258B (fr)
WO (1) WO1993004218A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008013943B4 (de) 2008-03-12 2018-09-13 Stiebel Eltron Gmbh & Co. Kg Warmwasserspeicher und Testvorrichtung zum Testen einer Anode in einem Warmwasserspeicher
US8226812B2 (en) * 2008-03-19 2012-07-24 Ab Volvo Penta Control of a corrosion protection system
ES2409938B1 (es) * 2011-12-28 2014-08-22 Fagor, S. Coop. Método y dispositivo de protección catódica anticorrosiva
CN104818487B (zh) * 2015-04-22 2017-11-14 中交四航工程研究院有限公司 间断供电开关电源组合式恒电位仪

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477931A (en) * 1965-03-30 1969-11-11 Mitsubishi Heavy Ind Ltd Method and apparatus for automatic electric corrosion-proofing
AT344816B (de) 1976-02-10 1978-08-10 Westfael Elekt Werke Vorrichtung fuer den kathodischen korrosionsschutz mit fremdstromanode
DE2916934C2 (de) 1979-04-26 1981-05-07 Vereinigte Elektrizitätswerke Westfalen AG, 4600 Dortmund Verfahren und Vorrichtung zur Aufrechterhaltung eines kathodischen Korrosionsschutzes
US4823072A (en) 1986-09-04 1989-04-18 Walcott Kenneth J Measurement of the polarized potential of buried pipeline having impressed current cathodic protection
DE3707791C1 (de) * 1987-03-11 1988-03-31 Ver Elek Zitaetswerke Westfale Verfahren und Vorrichtung zur Aufrechterhaltung eines kathodischen Korrosionsschutzes fuer metallische Flaechen mit Fremdstrom

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Publication number Publication date
WO1993004218A1 (fr) 1993-03-04
ITVR910070A0 (it) 1991-08-14
ITVR910070A1 (it) 1993-02-14
DE69206157T2 (de) 1996-07-18
ES2082500T3 (es) 1996-03-16
GR3018985T3 (en) 1996-05-31
DK0630426T3 (da) 1996-05-06
EP0630426A1 (fr) 1994-12-28
IT1253258B (it) 1995-07-14
DE69206157D1 (de) 1995-12-21

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