WO2008006909A2 - Électrolyseur chlore-alcali équipé d'une cathode de diffusion d'oxygène - Google Patents

Électrolyseur chlore-alcali équipé d'une cathode de diffusion d'oxygène Download PDF

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Publication number
WO2008006909A2
WO2008006909A2 PCT/EP2007/057279 EP2007057279W WO2008006909A2 WO 2008006909 A2 WO2008006909 A2 WO 2008006909A2 EP 2007057279 W EP2007057279 W EP 2007057279W WO 2008006909 A2 WO2008006909 A2 WO 2008006909A2
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WO
WIPO (PCT)
Prior art keywords
membrane
oxygen
anode
cell according
compartment
Prior art date
Application number
PCT/EP2007/057279
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English (en)
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WO2008006909A3 (fr
Inventor
Giuseppe Faita
Angelo Ottaviani
Fulvio Federico
Original Assignee
Uhdenora S.P.A.
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 Uhdenora S.P.A. filed Critical Uhdenora S.P.A.
Priority to JP2009518905A priority Critical patent/JP5160542B2/ja
Publication of WO2008006909A2 publication Critical patent/WO2008006909A2/fr
Publication of WO2008006909A3 publication Critical patent/WO2008006909A3/fr

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Classifications

    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • Chlorine and caustic soda are obtained by electrolysis of sodium chloride solutions according to the three technologies making use of mercury cathode, porous diaphragm and cation-exchange membrane-type electrolysers.
  • perfluorinated-type cation- exchange membranes containing sulphonic ion groups on the anode side and carboxylic ion groups on the cathode side commercialised by several manufacturers such as DuPont/USA under the trade-mark Nafion ® , Asahi Glass/Japan under the trade-mark Flemion ® and Asahi Kasei/Japan under the trade-mark Aciplex ® .
  • This framework corresponds to an average consumption of about 2300 kWh/tonne of chlorine, which constitutes a heavy penalty at the present cost of electrical energy. Since further significant improvements of the current technology are not foreseeable, several engineering companies in the field of chlor-alkali electrolysis have been involved in deeply innovative alternative processes, potentially capable of substantially reducing the electrical energy consumption per tonne of product.
  • a first possibility provides the integration of chlor-alkali plants with fuel cell stacks which, taking advantage of hydrogen evolved in the electrolysis, usually considered as a by-product, generate electrical energy to be sent back to the electrolysers with an overall energy saving of about 35%.
  • the two reactions are sensibly different under an energy standpoint, the reaction typical of the depolarised process in particular requiring a substantially reduced amount of energy, with a theoretical saving of 1.23 Volts. Practically, due to unavoidable energy dissipation mechanisms, such as ohmic drops and overvoltage, the achievable cell voltage is 1.9 - 2.1 Volts at current densities of 4000 - 5000 A/m 2 .
  • oxygen-diffusion cathodes may be carried out according to two basic mechanical designs, respectively with the cathode directly contacting the membrane (a design known to those skilled in the art as “zero-gap") or with the cathode spaced apart from the membrane by a 1 - 3 mm gap (design known to those skilled in the art as “finite-gap").
  • the gap may be crossed upwardly by a flow of caustic soda allowing an efficient control of the working temperature and concentration deriving from the mixing of the caustic product with the caustic feed.
  • a porous planar layer wherethrough the externally fed caustic soda percolates downwards is inserted in the gap.
  • the concentration of product caustic soda is determined by the amount of water transported across the membrane by aid of the hydrated Na + ion flow and of the natural diffusion between the two solutions of sodium chloride and caustic soda: at the usual water transport rates, the concentration of generated caustic soda is around 35-40%.
  • concentrations are not compatible with the commercial membranes, which would suffer a performance decay due to the progressive loss of carboxylic groups.
  • the present invention is directed to an electrolytic cell with oxygen-diffusion cathode capable of overcoming the inconveniences of the prior art, in particular to an electrolytic cell requiring no humidification of the oxygen feed or any other form of water injection in the cathodic compartment, and no dilution of the brine in the anodic compartment.
  • the present invention is directed to an electrolyser comprising a multiplicity of electrolytic cells overcoming the above inconveniences.
  • the Invention consists of an elementary cell subdivided by an ion-exchange membrane, provided with an oxygen-diffusion cathode in direct contact with the membrane and with an anode comprising a catalytic coating for chlorine evolution kept at a finite distance, preferably not lower than 1 mm, from the membrane.
  • the anode in contact with the membrane is provided with a catalytic coating for chlorine evolution only on the surface opposite the surface contacting the membrane.
  • the non-activated surface of the anode contacting the membrane may be advantageously provided with notches, which in one embodiment are oriented in the vertical direction.
  • the non-activated surface of the anode contacting the membrane may consist of a porous hydrophilic and catalytically inert film.
  • the surface of the anode facing the membrane is provided with a catalytic coating and is kept at a finite distance from the membrane, optionally by interposition of an inert hydrophilic porous layer.
  • the membrane may be kept in contact with a non catalysed surface of the anodic structure by aid of a pressure differential obtained by setting the pressure in the cathodic compartment at a higher value than the pressure in the anodic compartment.
  • the whole of the anodic structure and the membrane may be spaced apart by a gap occupied by the process brine, the membrane being kept in contact with the oxygen-diffusion cathode by aid of a pressure differential obtained by setting the pressure in the anodic compartment at a higher value than the pressure in the cathodic compartment.
  • the oxygen-diffusion cathode of the electrolytic cell of the invention has a porous hydrophobic structure provided with a catalyst for oxygen reduction, further equipped with an external porous conductive hydrophilic layer, also provided with a catalyst for oxygen reduction.
  • the hydrophilic external layer may be physically separated or it may be integral to the cathode.
  • FIG. 2 side-view of an anode of an electrolysis cell of the prior art.
  • FIG. 3 top-view of a section of an anode for electrolysis cell in accordance with a first embodiment of the invention.
  • FIG. 4 side-view of an anode for electrolysis cell in accordance with a second embodiment of the invention.
  • FIG. 5 side-view of an anode for electrolysis cell in accordance with a third embodiment of the invention.
  • Figure 1 is a side-view of a chlor-alkali elementary electrolysis cell of the prior art wherein 1 indicates the cell as a whole, 2 the membrane, preferably a cation- exchange perfluorinated membrane, subdividing the cell into a cathodic compartment 3 and an anodic compartment 4, 5 the oxygen-diffusion cathode, 6 the anode provided with catalytic coating for chlorine evolution, 7 the chlorine bubbles dispersed in the brine, 8 the elastic supports for keeping the cathode in contact with membrane 2.
  • Cell 1 is further provided with nozzles 9 for feeding oxygen or an oxygen-containing gas, 10 for discharging the exhaust oxygen, 11 for extracting the product caustic soda, 13 for releasing the mixture consisting of chlorine and exhaust brine.
  • Membrane 2 is further supported by the anode 6 under the thrust of pressure differential obtained by setting pressure P 2 of the cathodic compartment 3 at a value higher than pressure Pi in the anodic compartment 4.
  • Figure 2 shows magnified detail B of figure 1 wherein the side-view of an anode of the prior art is shown, for instance consisting of a titanium expanded sheet whose surface is completely coated with a catalytic film 14 for chlorine evolution.
  • the concentration of the brine in the anodic compartment is maintained in the conventional range of 180 - 220 g/l, it can be noticed that the oxygen concentration in chlorine is significantly higher than the value of 1.5 - 2% commonly observed in industrial plants, the current efficiency is lower than 94 - 95% and the cell voltage quickly rises to unacceptable values.
  • This negative behaviour can be correlated to the high concentration of product caustic soda largely exceeding 35%: such high concentrations cause a sensible back-migration toward the anode and the release of carboxylic groups from the membrane, which in this way progressively loses the cationic conductivity required for its correct functioning.
  • the caustic soda emerging on the membrane anodic surface comes in direct in contact with the anode catalytic coating, causing its immediate conversion to oxygen according to the following reaction: 4 OH " ⁇ O 2 + 2 H 2 O
  • the above inconveniences may be overcome by humidifying the oxygen fed to the cathodic compartment and by diluting the brine in the anodic compartment down to a concentration of 150 - 170 g/l: with these measures, the concentration of product caustic soda is reduced to 33 - 35% extending the membrane lifetime and decreasing the oxygen content in chlorine.
  • a first embodiment of the invention as shown in figure 3 is given by an anode whose catalytic coating 14 for chlorine evolution is applied only to the surface opposite the one contacting the membrane: the catalytic coating-free anode surface may be advantageously provided with notches 15, for instance grooves, preferably oriented in the vertical direction. This embodiment leads to a content of oxygen in chlorine below 1.5% and in the most favourable cases below 1 %.
  • the membrane results free from damages such as the release of carboxylic groups or the delamination of the carboxylic and sulphonic layers, keeping the main operative parameters practically constant.
  • the excellent preservation of the membrane is likely due to the concentration of caustic soda which surprisingly turned out to be comprised between 30 and 34%, even with a 180 - 220 g/l brine concentration in the anodic compartment as commonly employed in the industrial electrolysers of the prior art.
  • this result of great practical interest could be associated to the higher fraction of membrane surface accessible by or in contact with the brine, going along with a higher diffusion of water across the membrane.
  • coatings in form of hydrophilic films characterised by high surface roughness, expressed as maximum peak height (R m ) of at least 50 micrometres, prove particularly advantageous.
  • Suitable films comprise titanium dioxide, zirconium dioxide, niobium oxide and mixtures thereof, obtainable by the known methods of thermal decomposition of paints containing appropriate precursors or by thermal spraying, for instance flame-spray or plasma-spray.
  • anode in accordance with the invention has a composite structure consisting of the anode itself, optionally catalysed on the whole surface, and of a layer 17 formed for instance by a mesh of inert hydrophilic material, for example a titanium mesh free of catalytic coating and having a reduced abutment surface with the membrane (a high expansion factor is for instance preferred when expanded sheets are employed for this purpose).
  • a high degree of hydrophilicity of the porous film is preferred in order to prevent the anode gas bubbles from adhering to the anode-membrane interface.
  • the oxygen-diffusion cathode of elementary cells of figures 1 and 6 preferably consists of a porous layer provided with a catalyst and with additives directed to impart a predetermined ratio of hydrophilicity to hydrophobicity as necessary to allow both the passage of product caustic soda at the membrane interface (hydrophilic pores) and the flow of oxygen (hydrophobic pores).
  • the catalytic hydrophilic layer is integral to the cathode.
  • the cathode structure according to the invention is depicted in figure 7 which represents a magnification of detail A in figure 1 , wherein 20 indicates the cathode, pressed against membrane 2 by the current distributor 21 fixed on elastic supports 22, and 23 the conductive and catalytic hydrophilic layer.
  • a suitable porosity of the hydrophilic layer allows discharging the product caustic soda by percolation to the bottom of the cathodic compartment: the cathode may therefore be substantially hydrophobic so as to ensure an optimal oxygen transfer to the catalyst particles.
  • the inventors presume that the presence of catalyst in the hydrophilic layer allows maintaining a homogeneous current distribution also in the critical phase of cell start-up, in which the hydrophilic layer is not yet filled with caustic soda, drained at the time of the previous shut-down. In the course of the start-up, the product caustic soda fills the porosity of the hydrophilic layer and percolates to the bottom part of the cathodic compartment.
  • the catalyst of the hydrophilic layer turns out to be completed flooded by the product caustic soda and stops functioning (start-up catalyst) since the oxygen diffusion is practically blocked: at this stage, the prosecution of the electrolysis is made possible by the intervention of the catalyst contained in the hydrophobic cathode (operation catalyst).
  • operation catalyst The presence of catalyst in the hydrophilic layer is therefore essential, since during the start-up it allows preventing harmful current density inhomogeneities (with the relevant lack of uniformity in the caustic soda concentration and possible hydrogen generation which may lead to formation of flammable mixtures) without having to resort to procedures not compatible with the normal operation of industrial plants.
  • the anodes were welded to stiff supports and configured as follows: - Test 1 : 1 mm thick titanium expanded sheet with rhomboidal meshes (4 x 8 mm diagonals) provided with catalytic coating for chlorine evolution comprising titanium, iridium and ruthenium oxides according to the prior art, only applied to the surface opposite the one facing the membrane, obtained by deposition of the coating on one side of a solid sheet, followed by mechanical expansion and final flattening.
  • Test 2 expanded sheet as in test 1 , added with 5.5 mm high and wide notches, vertically oriented according to the embodiment shown in figure 3.
  • Test 3 expanded sheet as in test 1 , added with a hydrophilic inert film of high superficial roughness consisting of about 500 micrometres of zirconium dioxide
  • Test 5 1 mm thick titanium expanded sheet with rhomboidal meshes (4 x 8 mm diagonals) provided with catalytic coating for chlorine evolution comprising titanium, iridium and ruthenium oxides applied to the whole surface in accordance with the prior art.
  • the cathode consisted of an 80 mesh net made out of a silver thread (0.2 mm diameter) with a layer of catalyst particles applied thereto suitable for oxygen reduction (20% by weight silver-platinum alloy on Shawiningan Acetylene Black carbon produced by Chevron Chemical Co./USA with a total silver loading of 50 g/m 2 ) mixed with polytetrafluoroethylene particles in a 1 :1 weight ratio; the whole assembly was sintered at 350 0 C leading to a final thickness of about 0.5 mm.
  • the structure of the cathode so obtained resulted porous and clearly hydrophobic as indicated by contact angle determinations with water droplet.
  • a porous conductive and hydrophilic layer suitable for allowing the catalytic reduction of oxygen in the early stages of start-up and the percolation of product caustic soda, was interposed between cathode and membrane.
  • This layer was obtained starting from an open cell foam of polyurethane, nickel-plated and further coated with a 5 micrometre silver layer, with an average pore diameter of about 0.2 mm and an initial thickness of 2 mm, in whose meshes a mixture of catalyst particles and zirconium oxide particles (Alfa Aesar GmbH, Germany) was pressed at a 1 :1 weight ratio for a total silver loading of 40 g/m 2 , followed by a final compression to reduce the thickness to a final value of about 1 mm.
  • the current distributor consisted of a 1 mm thick nickel expanded sheet with rhomboidal openings (4 x 8 mm diagonals), fixed to flexible supports, with an additional fine mesh nickel expanded sheet (2 x 4 mm diagonals) welded to the surface facing the cathode. Both of the expanded sheets were provided with a silver coating about 10 micrometre thick, and were subdivided into four portions in order to favour a better adaptation of the cathode-hydrophilic layer assembly to the anode supported-membrane surface.
  • the anodic and cathodic compartments of all cells were respectively fed with sodium chloride brine whose concentration was kept within the range of 190 - 210 g/l and with dry pure oxygen with an about 10% excess. Temperature and current density were respectively set at 86 - 88°C and at 4000 A/m 2 .
  • the product caustic soda was extracted from the bottom of the cathodic compartments. The results obtained are collected in the following table. TABLE
  • Test 4 was repeated, the only difference being the use of a carbon cloth made hydrophilic (Zoltek PWB - 3 boiled in nitric acid) as the interposed catalyst-free conductive layer for oxygen reduction.
  • a carbon cloth made hydrophilic Zoltek PWB - 3 boiled in nitric acid
  • the start-up proved very simple and completely equivalent to that of tests 1 - 5.
  • Test 5 was repeated, the only variation being the dilution of the sodium chloride solution in the anodic compartment to 160 - 170 g/l and the pre-humidification at 85°C of the oxygen feed. With these operative conditions, a sensibly more stable functioning was observed, presumably associated to the lower concentration of product caustic soda (33 - 34%).

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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)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

L'invention concerne une cellule électrolytique subdivisée en deux compartiments par une membrane échangeuse de cations, le compartiment cathodique contenant une cathode de diffusion d'oxygène en contact avec la membrane par l'intermédiaire d'une couche poreuse hydrophile catalysée et le compartiment anodique comprenant une anode pourvue d'un revêtement catalytique pour le dégagement de chlore, cette anode étant espacée de la membrane. La cellule de l'invention permet de produire du chlore présentant une teneur en oxygène réduite et un produit caustique de concentration appropriée sans qu'il soit nécessaire de diluer l'alimentation en saumure ou d'humidifier le flux d'oxygène.
PCT/EP2007/057279 2006-07-14 2007-07-13 Électrolyseur chlore-alcali équipé d'une cathode de diffusion d'oxygène WO2008006909A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2009518905A JP5160542B2 (ja) 2006-07-14 2007-07-13 酸素拡散陰極を備えたクロロ−アルカリ電解槽

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2006A001374 2006-07-14
IT001374A ITMI20061374A1 (it) 2006-07-14 2006-07-14 Elettrolizzatore cloro-soda equipaggiato con catodo a diffusione di ossigeno

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WO2008006909A2 true WO2008006909A2 (fr) 2008-01-17
WO2008006909A3 WO2008006909A3 (fr) 2008-11-27

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2397578A2 (fr) 2010-06-16 2011-12-21 Bayer MaterialScience AG Electrode catalytique consommant de l'oxygène et son procédé de fabrication
DE102010039846A1 (de) 2010-08-26 2012-03-01 Bayer Materialscience Aktiengesellschaft Sauerstoffverzehrelektrode und Verfahren zu ihrer Herstellung
EP2444526A2 (fr) 2010-10-21 2012-04-25 Bayer MaterialScience AG Electrode catalytique consommant de l'oxygène et son procédé de fabrication
EP2495353A2 (fr) 2011-03-04 2012-09-05 Bayer MaterialScience AG Procédé destiné au fonctionnement d'une électrode catalytique consommant de l'oxygène
EP2594665A1 (fr) * 2010-07-13 2013-05-22 Chlorine Engineers Corp., Ltd. Cellule électrolytique pour la fabrication de chlore et d'hydroxyde de sodium et procédé pour la fabrication de chlore et d'hydroxyde de sodium
WO2016081846A1 (fr) * 2014-11-20 2016-05-26 University Of Delaware Système d'électrolyse pour une production de chlore
CN105793473A (zh) * 2013-12-04 2016-07-20 赢创德固赛有限公司 灵活运用电力的装置和方法
CN105793473B (zh) * 2013-12-04 2018-02-09 赢创德固赛有限公司 灵活运用电力的装置和方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2200652A (en) * 1986-12-19 1988-08-10 Olin Corp Electrolytic cell
WO2004005583A1 (fr) * 2002-07-05 2004-01-15 Akzo Nobel N.V. Procede de fabrication d'un chlorate de metal alcalin
WO2004013379A1 (fr) * 2002-07-31 2004-02-12 Bayer Materialscience Ag Cellule electrochimique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2200652A (en) * 1986-12-19 1988-08-10 Olin Corp Electrolytic cell
WO2004005583A1 (fr) * 2002-07-05 2004-01-15 Akzo Nobel N.V. Procede de fabrication d'un chlorate de metal alcalin
WO2004013379A1 (fr) * 2002-07-31 2004-02-12 Bayer Materialscience Ag Cellule electrochimique

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9243337B2 (en) 2010-06-16 2016-01-26 Covestro Duetschland AG Oxygen-consuming electrode with multilayer catalyst coating and process for the production thereof
DE102010024053A1 (de) 2010-06-16 2011-12-22 Bayer Materialscience Ag Sauerstoffverzehrelektrode und Verfahren zu ihrer Herstellung
EP2397578A2 (fr) 2010-06-16 2011-12-21 Bayer MaterialScience AG Electrode catalytique consommant de l'oxygène et son procédé de fabrication
US9315908B2 (en) 2010-07-13 2016-04-19 Chlorine Engineers Corp. Electrolytic cell for producing chlorine—sodium hydroxide and method of producing chlorine—sodium hydroxide
EP2594665A1 (fr) * 2010-07-13 2013-05-22 Chlorine Engineers Corp., Ltd. Cellule électrolytique pour la fabrication de chlore et d'hydroxyde de sodium et procédé pour la fabrication de chlore et d'hydroxyde de sodium
EP2594665A4 (fr) * 2010-07-13 2014-04-30 Chlorine Eng Corp Ltd Cellule électrolytique pour la fabrication de chlore et d'hydroxyde de sodium et procédé pour la fabrication de chlore et d'hydroxyde de sodium
DE102010039846A1 (de) 2010-08-26 2012-03-01 Bayer Materialscience Aktiengesellschaft Sauerstoffverzehrelektrode und Verfahren zu ihrer Herstellung
US10202700B2 (en) 2010-08-26 2019-02-12 Covestro Deutschland Ag Oxygen-consuming electrode and method for producing same
CN103140972A (zh) * 2010-08-26 2013-06-05 拜耳知识产权有限责任公司 耗氧电极及其制备方法
WO2012025503A1 (fr) 2010-08-26 2012-03-01 Bayer Materialscience Ag Électrode consommant de l'oxygène et procédé de fabrication de ladite électrode
DE102010042729A1 (de) 2010-10-21 2012-04-26 Bayer Materialscience Aktiengesellschaft Sauerstoffverzehrkathode und Verfahren zu ihrer Herstellung
EP2444526A2 (fr) 2010-10-21 2012-04-25 Bayer MaterialScience AG Electrode catalytique consommant de l'oxygène et son procédé de fabrication
DE102011005133A1 (de) 2011-03-04 2012-09-06 Bayer Materialscience Aktiengesellschaft Verfahren zum Betrieb einer Sauerstoffverzehrelektrode
US9422631B2 (en) 2011-03-04 2016-08-23 Covestro Deutschland Ag Method of operating an oxygen-consuming electrode
EP2495353A2 (fr) 2011-03-04 2012-09-05 Bayer MaterialScience AG Procédé destiné au fonctionnement d'une électrode catalytique consommant de l'oxygène
CN105793473A (zh) * 2013-12-04 2016-07-20 赢创德固赛有限公司 灵活运用电力的装置和方法
CN105793473B (zh) * 2013-12-04 2018-02-09 赢创德固赛有限公司 灵活运用电力的装置和方法
WO2016081846A1 (fr) * 2014-11-20 2016-05-26 University Of Delaware Système d'électrolyse pour une production de chlore

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Publication number Publication date
JP2009543945A (ja) 2009-12-10
ITMI20061374A1 (it) 2008-01-15
WO2008006909A3 (fr) 2008-11-27
JP5160542B2 (ja) 2013-03-13

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