EP3460106B1 - Grue auxiliaire automatique pour la maintenance d'une installation d'électrolyse - Google Patents

Grue auxiliaire automatique pour la maintenance d'une installation d'électrolyse Download PDF

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Publication number
EP3460106B1
EP3460106B1 EP16891325.9A EP16891325A EP3460106B1 EP 3460106 B1 EP3460106 B1 EP 3460106B1 EP 16891325 A EP16891325 A EP 16891325A EP 3460106 B1 EP3460106 B1 EP 3460106B1
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Prior art keywords
electrode
electrolysis
electrodes
crane
installation according
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EP16891325.9A
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German (de)
English (en)
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EP3460106A4 (fr
EP3460106A1 (fr
Inventor
Yves Lefevre
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Zincobre Ingenieria SL
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Individual
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B66—HOISTING; LIFTING; HAULING
    • B66C—CRANES; LOAD-ENGAGING ELEMENTS OR DEVICES FOR CRANES, CAPSTANS, WINCHES, OR TACKLES
    • B66C17/00—Overhead travelling cranes comprising one or more substantially horizontal girders the ends of which are directly supported by wheels or rollers running on tracks carried by spaced supports
    • B66C17/06—Overhead travelling cranes comprising one or more substantially horizontal girders the ends of which are directly supported by wheels or rollers running on tracks carried by spaced supports specially adapted for particular purposes, e.g. in foundries, forges; combined with auxiliary apparatus serving particular purposes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • 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

  • Electrolysis installations include electrolysis cells with pairs of electrodes, cathode and anode, and a tank with a solution in which the electrodes are submerged subjected to a continuous electrical voltage difference in order to produce electrolysis. Electrolysis enables obtaining for example zinc, copper, nickel, cadmium or cobalt deposited in the cathode from the salts of the solution.
  • electrodes are plate-shaped, arranged in rows in the tank such that the anodes and cathodes alternate and the cells are connected electrically in series.
  • an electrode head holds each electrode.
  • the electrode head comprises an electrode rod of an electrically conductive material, usually copper, and during electrolysis, the electrode head holds the electrode in the tank, vertically and in the longitudinal direction of the rod.
  • each rod is arranged abutting in electrical contact on equipotential rails, usually made of copper, that extend to the sides of the tank and perpendicularly to the electrodes.
  • An electrode unit comprises an assembly of the electrode and the electrode head.
  • the electrode units are positioned in the tank as close as possible to each other in order to increase the productivity of the installation, but avoiding the risk of a short circuit.
  • the electrode head comprises handling means for facilitating the extraction or the insertion of the electrode in the tank, or the transport thereof by means of a crane or a bridge crane of the installation, for example in the form of hooks or gripping lugs.
  • Patent EP 1492906 describes this type of arrangement in an electrolysis installation.
  • the installation includes a main overhead crane and an auxiliary crane.
  • the auxiliary crane is used for housekeeping cell house duties to warranty the exclusive permanent duty and preventive maintenance of the main crane.
  • said document does not specify whether the extraction, removal and replacement of the electrodes as well as the repositioning of new electrodes is carried out by means of the auxiliary crane. It does further not specify whether the at least one sensor remains static with respect to the electrolysis tank.
  • Patent document US4028211 discloses an apparatus for automatically replacing anodes and cathodes disposed alternately in an electrolytic cell used for the electrolytic refining of a metal.
  • Document US2006049054 discloses a process for changing an anode of a cell for the production of aluminum by fused bath electrolysis including a plurality of anodes.
  • PCT application number WO2013160542 concerns a transfer apparatus configured to lift and lower anode plates and cathode plates moved to a position above an electrolytic cell to place the anode and cathode plates into the electrolytic cell and to remove the anode and cathode plates from the electrolytic cell.
  • Another PCT application in this case with number WO2014104896 , describes a system and method for post-cleaning of electrolyte from a used carbon anode in aluminum production.
  • Patent document number CH592164 discloses an electrolytic installation for the production of primary aluminum that includes electrolytic cells assembled above ground level, equipment for the main productive operations arranged on guide rails in the floor, and auxiliary equipment for maintenance, cleaning, etc. suspended from overhead from cranes and/or beams, so that there is no interference between the two sets of equipment.
  • Chinese patent document number CN203845728 provides an auxiliary device for mounting a cathode in an electrolytic cell.
  • the present invention relates to an electrolysis installation comprising a main crane for operating the installation and an automatic auxiliary crane for maintenance in an electrolytic cell house.
  • the function of the Automatic Auxiliary Bridge Crane object of this invention for Handling, inspection and maintenance of Electrodes is that of identifying anomalies in the electrodes located in the tanks, such as increase in temperature, anomalous electrical contacts and faults in the morphology of the metal deposited in the electrodes, and enabling extraction, removal and replacement of the anomalous electrodes from the electrolytic tanks of the plant to the repair and replacement area. Once these electrodes have been removed, the load of the tank will be incomplete and this crane will be in charge of repositioning new electrodes, inserting them in their operating positions.
  • the invention is particularly applicable in a zinc electrolysis installation.
  • the electrode units of the electrolysis system can present and/or cause failures during electrolysis, such as short circuits, electrical contacts of the electrolysis rods with the anomalous equipotential rails or faults in the metal deposited in the electrodes especially on the surface of the cathodes in electrowinning processes. These failures can damage the electrodes, the electrode units and the electrolysis installation, ultimately reducing the productivity of the installation.
  • This known maintenance method has the drawback that the use of the crane or bridge crane for the procedure implies the stoppage of normal operations and less preventive maintenance time of the crane of the installation during the time needed to resolve the failures, since the crane or bridge crane is no longer available, consequently implying a reduction in the productivity of the installation.
  • the present invention aims to provide a maintenance method that enables increasing the productivity of the installation.
  • the present invention provides a maintenance method of an electrolysis installation as set forth in claim 1 and explained below. Furthermore, the dependent claims reflect advantageous embodiments as disclosed below.
  • the invention comprises both the maintenance method of an electrolysis installation and the electrolysis installation.
  • Said electrolysis installation in turn comprises a main crane for operating the installation and an automatic auxiliary crane for maintenance of the electrolysis installation.
  • the maintenance method of an electrolysis installation comprises the stages of:
  • the maintenance method according to the invention comprises repositioning or removing the faulty electrode unit from the tank and/or inserting the spare electrode unit into the gap by means of an automatic auxiliary crane or bridge crane of the installation.
  • the crane used conventionally for normal operations of the installation is called the main crane in order to distinguish it from the auxiliary crane.
  • the use of the automatic auxiliary crane allows increasing productivity of the installation since it enables using the main crane for the normal operations of the installation while being able to proceed with the handling, repositioning or replacing of the faulty electrode units.
  • the execution of the maintenance method of the installation enables eliminating any short circuits that may occur, inserting electrodes in the gaps of the tank due to the removal of those that were faulty, reducing the time needed to resolve the problems or anomalies that can occur frequently in the electrolysis installation, such as, for example, poor contact between the electrodes and the equipotential rail or a fault in the surface of the metal deposited in the electrode.
  • the stage of detecting the faulty electrode unit, repositioning or removing the same and/or inserting the spare electrode unit is carried out automatically, at least partially, that is, at least in some stages. This way, the productivity of the installation is further improved as the processing time for each stage can be reduced.
  • the invention anticipates the use of a detection system having at least one sensor for checking the status of the electrodes, such as electrode temperature sensors, electrode voltage drop sensors, display sensors of the metal deposited on the electrode and/or electrode weight sensors
  • a detection system having at least one sensor for checking the status of the electrodes, such as electrode temperature sensors, electrode voltage drop sensors, display sensors of the metal deposited on the electrode and/or electrode weight sensors
  • the detection system comprises at least one sensor that remains static with respect to the electrolysis tank.
  • a control unit of the installation can be used, programmed to receive information from the detection system, process said information and command the auxiliary crane to reposition or remove the faulty electrode unit and/or insert the spare electrode unit.
  • the electrolysis installation comprises a main crane for operating the installation and an automatic auxiliary crane used in the maintenance method according to the invention, for repositioning the faulty electrode unit (anode or cathode unit) in the tank or removing it from the tank leaving a gap therein, and/or inserting the spare electrode unit in the gap.
  • Said automatic auxiliary crane comprises: A Main Structure (1), made up of two box girders and two headwalls joined thereto, as well as a grid floor, gangway and railing for supporting and maintaining equipment.
  • a Longitudinal Translation System (2) made up of two motors and four wheels, that enable translation with respect to the electrolysis tanks of the installation, in a direction perpendicular to the longitudinal direction of the electrolysis rods on rails (8) abutting on rail beams (9)
  • a Main Lifting System (3) mainly made up of a lifting geared motor and two drums.
  • An Electrode Collection System (4) made up of A Load-bearing structure of the electrode collection trolley (4a) and a centering and guiding System (4b), centering the crane and guiding the load-bearing structure of the electrode collection trolley (4a).
  • An Anti-Oscillation System A Contact Temperature Checking System
  • An Electrode Voltage Checking System A Morphological Analysis System of the deposited metal
  • An Auxiliary Lifting Mechanism A Feeding System (6) An Electrical Installation, a Control System and an Air Conditioning and Cabinet Pressurization System (7).
  • the supports (9) and rails (8) of the main bridge corresponding to the bridge crane of the main crane can be used, thus minimizing the cost of the auxiliary bridge and thereby the operational costs of the maintenance method.
  • the automatic auxiliary crane can accommodate auxiliary means for the operation thereof in order to carry out the method, such as a control unit or PLC for controlling the movements of the auxiliary bridge, electrical systems, refrigeration equipment and pressurization equipment.
  • the automatic auxiliary bridge can also have access platforms for maintenance and supervision of said means. Access to these platforms from the transit areas of the electrolysis installation can be carried out by means of a ladder (10).
  • the full extent of travel of the auxiliary crane is limited in one direction by the stops of the rails, while in the other direction it is limited by the proximity of the main crane.
  • the drive of the wheels (11) of the headwalls for moving the auxiliary bridge can be carried out by means of an independent electric motor for each drive wheel that acts through an appropriate reducer and is commanded by means of a converter that makes it possible to use the appropriate translation and approximation speeds.
  • the motors can also incorporate brakes, preferably electrically driven brakes.
  • the displacement system of the described auxiliary bridge enables ensuring a positioning with respect to the electrolysis cells that is sufficiently precise to carry out the maintenance method according to the invention.
  • position detectors can be used on the parts of the crane with respect to which they move, such as markings.
  • the electrode collection system (4) comprises: A load-bearing structure of the electrode collection trolley (4a), and the centering and guiding system (4b). Both elements will have relative movements between them during the lifting and lowering strokes.
  • the load-bearing structure of the electrode collection trolley (4a) which is in charge of handling the electrodes, comprises: A frame that supports both the electrode collection trolley (4c) itself and the guide frame when it is lifted.
  • This Frame incorporates four guide elements at the ends thereof that will enable the relative vertical movement of the Electrode Collection Trolley along the guides that the Guiding Structure will be equipped with.
  • the electrode collection trolley (4c) in charge of handling the electrodes consisting of a frame on four wheels, two of which are motorized, which has four sets of opening and closing mechanisms of the electrode collection lugs.
  • the centering and guiding system (4b) is positioned on the upper part of the tank, ensuring the correct position of the Electrode Collection Trolley with respect to the electrodes for their handling.
  • the load-bearing structure of the electrode collection trolley (4a) will be in charge of the vertical movements of the centering and guiding system (4b) when dragging it in the vertical movements thereof, when abutting with it.
  • the electrode collection trolley (4c), as shown in detail in Figure 4 is configured for managing the electrode units, comprising a frame (17) on four wheels (18), two of which are motorized, which has opening and closing means (14) of the tilting gripping arms (21) with electrode collection lugs (15). These lugs have a coupling hole (16) adapted to engage with the gripping means (19) provided in electrode heads (20) of the installation, thus enabling management and handling thereof.
  • the tilting gripping arms (21) can be built with two rotating arms that support the collection lugs (15), for example, driven in a coordinated manner by a single linear actuator that make up the opening and closing means (14). The use of two types of collection lugs (15) is anticipated, some for anodes and others for cathodes.
  • the electrode collection trolley (4c) can incorporate laser detectors, each corresponding to the position of a collection lug, which enable identifying the presence of the electrode in the support thereof on the electrolysis rod, identifying both the number of electrodes present and the correct polarity thereof.
  • a suitable detector system can be incorporated.
  • the different elements of the auxiliary crane must be adequately protected against acid mist corrosion, especially found in zinc electrolysis installations, for example, by means of specific acid-proof paint.
  • the detection system for detecting faulty electrode units may include a detection system with an electrode temperature sensor system, an electrode voltage drop checking system, a system for analyzing the morphology of the metal deposited on the electrodes and/or a system for balancing or checking the weight of the electrodes.
  • the temperature sensor system may include as many sensors as electrodes in the tank.
  • the electrode voltage drop checking system includes voltage drop sensors, which can include as many voltage probes as the number of cathodes plus a probe, for measuring the voltage between the electrode rod and the electrolysis rail on which it abuts.
  • the system for analyzing the morphology of the metal can comprise fixed cameras intended to take pictures of the surface of the metal deposited on the electrode. These pictures can be analyzed manually by an operator in order to assess possible faults in the deposition or automatically by means of image analysis systems. The pictures have sufficient resolution to enable a global analysis of the electrode and the processing thereof so that they can serve as a basis for comparative and statistical analyses.
  • a control unit can be used programmed to detect information from the sensors on the state of the electrode units, process said information and command the auxiliary crane through displacements of the crane and the components thereof, such as translation of the automatic auxiliary crane, lifting and lowering of the electrode collection system, the auxiliary hoist, the electrode collection trolley or the electrode collection lugs.
  • the control unit can also enable partially automatic or semi-automatic control, allowing one or several of the stages of the method to be carried out manually by an operator.

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

Claims (16)

  1. Procédé de maintenance d'une installation d'électrolyse, comprenant les étapes suivantes :
    identifier des anomalies dans les électrodes situées dans les cuves, telles que l'augmentation de température, des contacts électriques anormaux et des défauts dans la morphologie du métal déposé dans les électrodes au moyen d'un système de détection ayant au moins un capteur ;
    extraire, retirer et remplacer les électrodes anormales en les déplaçant des cuves électrolytiques de l'installation jusqu'à la zone de réparation et de remplacement ; et
    repositionner les nouvelles électrodes en les insérant dans leurs positions opérationnelles,
    caractérisé en ce que les étapes d'extraction, de retrait, de remplacement et de repositionnement sont réalisées au moyen d'une grue auxiliaire, différente de la grue principale utilisée pour actionner l'installation, et où ledit au moins un capteur reste statique par rapport à la cuve d'électrolyse.
  2. Procédé de maintenance d'une installation d'électrolyse selon la revendication 1, caractérisé en ce que l'étape pour identifier des anomalies dans les électrodes, extraire, retirer et remplacer les électrodes ainsi que repositionner de nouvelles électrodes est réalisée automatiquement.
  3. Procédé de maintenance d'une installation d'électrolyse selon l'une des revendications 1 ou 2, caractérisé en ce que le au moins un capteur est sélectionné dans le groupe comprenant un capteur de température d'électrode, un capteur de chute de tension d'électrode, un système pour analyser la morphologie du métal déposé sur les électrodes, un capteur de poids d'électrode et une combinaison des éléments ci-dessus.
  4. Procédé de maintenance d'une installation d'électrolyse selon la revendication 3, caractérisé en ce qu'il comprend l'utilisation d'une unité de commande programmée pour recevoir automatiquement une information du système de détection, traiter ladite information et commander la grue auxiliaire pour repositionner ou retirer l'unité d'électrode défectueuse et/ou insérer l'unité d'électrode de rechange.
  5. Procédé de maintenance d'une installation d'électrolyse selon la revendication 4, caractérisé en ce qu'afin de repositionner ou de retirer l'unité d'électrode défectueuse et insérer l'unité d'électrode de rechange dans l'espace, la grue à portique de la grue auxiliaire comprend un système de collecte d'unité d'électrode comprenant un chariot de collecte d'unité d'électrode.
  6. Installation d'électrolyse comprenant une grue principale pour actionner l'installation et une grue auxiliaire automatique pour sa maintenance, caractérisée en ce que la grue auxiliaire automatique comprend :
    une structure principale (1) composée de deux poutres à caisson et deux murs de tête assemblés à cette dernière, ainsi qu'un plancher grillagé, une passerelle et un garde-corps pour supporter et maintenir l'équipement ;
    un système de translation longitudinal (2) composé de deux moteurs qui actionnent des roues, permettant la translation par rapport aux cuves d'électrolyse de l'installation, dans une direction perpendiculaire à la direction longitudinale des tiges d'électrolyse sur des rails (8) venant en butée sur des poutres de rail (9) ;
    un système de levage principal (3) principalement composé d'un moteur à train d'engrenages de levage et de deux tambours ; et
    un système de collecte d'électrodes (4) comprenant une structure de support de charge du chariot de collecte d'électrodes (4a) et un système de centrage et de guidage (4b), dans lequel les deux éléments ont des mouvements relatifs entre eux pendant les courses de levage et d'abaissement.
  7. Installation d'électrolyse selon la revendication 6, caractérisée en ce qu'un chariot de collecte d'électrode (4c) manipule les unités d'électrode et comprend un bâti (17) sur quatre roues (18), dont deux sont motorisées, ayant des moyens d'ouverture et de fermeture (14) d'un bras de préhension incliné (21) avec des pattes de collecte d'électrodes (15), ces pattes étant prévues avec un trou de couplage (16) adapté pour se mettre en prise avec un moyen de préhension (19) prévu dans les têtes d'électrode (20) de l'installation, permettant ainsi sa gestion et sa manipulation.
  8. Installation d'électrolyse selon la revendication 7, caractérisée en ce que les bras de préhension inclinés (21) sont construits avec deux bras rotatifs qui supportent les pattes de collecte (15), entraînés d'une manière coordonnée par un seul actionneur linéaire, qui composent les moyens d'ouverture et de fermeture (14).
  9. Installation d'électrolyse selon les revendications 6 à 8, caractérisée en ce que deux types de pattes de collecte (15) sont utilisées, l'une pour les anodes et l'autre pour les cathodes.
  10. Installation d'électrolyse selon les revendications 6 à 9, caractérisée en ce que la présence d'une électrode ou d'un espace dans la cuve d'électrolyse est identifiée au moyen de détecteurs laser, chacun correspondant à la position d'une patte de collecte, qui permettent d'identifier la présence d'une électrode dans son support sur la tige d'électrolyse, identifier à la fois le nombre d'électrodes présentes et leur bonne polarité, ces éléments étant positionnés dans le chariot de collecte d'électrodes (4c).
  11. Installation d'électrolyse selon les revendications 6 à 10, caractérisée en ce qu'afin de commander l'abaissement du système de collecte d'électrodes (4) vers la cellule d'électrolyse, elle comprend un système de détecteur, comprenant en outre d'autres moyens de protection, tels que des moyens anti-oscillation pour empêcher les unités d'électrodes d'osciller ou de se déplacer par rapport au chariot de collecte pendant les mouvements de levage et d'abaissement.
  12. Installation d'électrolyse selon les revendications 6 à 11, caractérisée en ce qu'elle comprend en outre :
    un système de détection pour détecter des unités d'électrodes défectueuses avec un système de capteur de température d'électrode,
    un système de vérification de chute de tension d'électrode,
    un système pour analyser le métal déposé sur les électrodes, et/ou
    un système pour équilibrer ou vérifier le poids des électrodes.
  13. Installation d'électrolyse selon la revendication 12, caractérisée en ce que le système de capteur de température peut comprendre autant de capteurs que d'électrodes dans la cuve d'électrolyse.
  14. Installation d'électrolyse selon la revendication 12, caractérisée en ce que le système de vérification de chute de tension d'électrode comprend des capteurs de chute de tension qui peuvent comprendre autant de sondes de tension que le nombre de cathodes plus une sonde, pour mesurer la tension entre la tige d'électrode et le rail d'électrolyse sur lequel il vient en butée.
  15. Installation d'électrolyse selon la revendication 12, caractérisée en ce que le système pour analyser le métal déposé comprend des caméras fixes prévues pour prendre des photos de la surface du métal déposé sur l'électrode, qui sont analysées manuellement par un opérateur ou automatiquement au moyen de systèmes d'analyse d'image afin d'évaluer des défauts éventuels dans le dépôt.
  16. Installation d'électrolyse selon les revendications 6 à 15, caractérisée en ce qu'elle a une unité de commande programmée pour détecter une information des capteurs concernant l'état des unités d'électrode, traiter ladite information et commander la grue auxiliaire par le biais des déplacements de la grue et de chacun des composants de la grue auxiliaire, comme la translation de toute la grue, celui du levage du système de collecte d'électrodes (4) composé de la structure de support de charge du chariot de collecte d'électrodes (4a), le système de centrage et de guidage (4b), le chariot de collecte d'électrodes (4c) et un mécanisme de levage auxiliaire (5).
EP16891325.9A 2016-02-25 2016-02-25 Grue auxiliaire automatique pour la maintenance d'une installation d'électrolyse Active EP3460106B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2016/070126 WO2017144741A1 (fr) 2016-02-25 2016-02-25 Grue auxiliaire automatique pour la maintenance d'une installation d'électrolyse

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EP3460106A1 EP3460106A1 (fr) 2019-03-27
EP3460106A4 EP3460106A4 (fr) 2020-04-15
EP3460106B1 true EP3460106B1 (fr) 2021-06-23

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EP (1) EP3460106B1 (fr)
ES (1) ES2890827T3 (fr)
MX (1) MX2017000943A (fr)
RU (1) RU2018133681A (fr)
WO (1) WO2017144741A1 (fr)

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CN113814650B (zh) * 2021-09-23 2024-01-26 华能荆门热电有限责任公司 等离子阴阳极安装辅助装置及维护检修方法
CN119530890B (zh) * 2025-01-22 2025-04-25 包头铝业有限公司 一种铝电解槽ptm阳极自动换极装置与方法

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CH592164A5 (en) * 1972-09-28 1977-10-14 Zannini Gianfranco Electrolytic plant for primary aluminium prodn. - is laid out above ground to separate productive from ancillary processes
JPS5296904A (en) * 1976-02-10 1977-08-15 Mitsui Mining & Smelting Co Apparatus for automatic replacement of plate electrode in electrolysis of metals
FR2874934B1 (fr) * 2004-09-08 2007-09-07 Ecl Soc Par Actions Simplifiee Procede de changement d'anode dans une cellule de production d'aluminium par electrolyse incluant un ajustement de la position de l'anode et dispositif pour le mettre en oeuvre
FI124617B (en) * 2012-04-23 2014-11-14 Outotec Oyj transfer System
NO336059B1 (no) * 2012-12-27 2015-05-04 Sinvent As Fremgangsmåte og apparat for rensing av karbonanoder
CN203845728U (zh) * 2014-05-26 2014-09-24 广西百色银海铝业有限责任公司 电解槽上用于安装阴极的辅助装置

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Publication number Publication date
RU2018133681A (ru) 2020-03-25
EP3460106A4 (fr) 2020-04-15
MX2017000943A (es) 2018-02-09
EP3460106A1 (fr) 2019-03-27
RU2018133681A3 (fr) 2020-03-25
ES2890827T3 (es) 2022-01-24
WO2017144741A1 (fr) 2017-08-31

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