EP1417356B1 - Elektrolysezelle, insbesondere zur elektrochemischen herstellung von chlor - Google Patents

Elektrolysezelle, insbesondere zur elektrochemischen herstellung von chlor Download PDF

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Publication number
EP1417356B1
EP1417356B1 EP02794511A EP02794511A EP1417356B1 EP 1417356 B1 EP1417356 B1 EP 1417356B1 EP 02794511 A EP02794511 A EP 02794511A EP 02794511 A EP02794511 A EP 02794511A EP 1417356 B1 EP1417356 B1 EP 1417356B1
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EP
European Patent Office
Prior art keywords
anode
current collector
frame
cathode
electrolysis cell
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.)
Expired - Lifetime
Application number
EP02794511A
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German (de)
English (en)
French (fr)
Other versions
EP1417356A2 (de
Inventor
Fritz Gestermann
Hans-Dieter Pinter
Andreas Bulan
Walter Klesper
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Covestro Deutschland AG
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Bayer MaterialScience AG
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Publication date
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Publication of EP1417356A2 publication Critical patent/EP1417356A2/de
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Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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
    • 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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • 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
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections

Definitions

  • the invention relates to an electrolytic cell, in particular for electrochemical Production of chlorine from aqueous solutions of hydrogen chloride is suitable.
  • hydrochloric acid Aqueous solutions of hydrogen chloride, hereafter called hydrochloric acid, fall as Byproduct in many processes, especially those where Chlorinated organic hydrocarbon compounds with chlorine oxidizing. Economically interesting is the recovery of chlorine from these hydrochloric acids, which can then be used for example for further chlorinations. Chlorine off For example, hydrochloric acids can be recovered electrolytically.
  • the anode compartment must be in the electrolytic cell described in US-A-5,770,035 be kept at a higher pressure than the cathode compartment. This will be the Cation exchange membrane on the gas diffusion electrode and this in turn pressed on the power distributor.
  • the adjustment of the pressure may e.g. by a . Liquid compression occur through which the chlorine gas formed in the anode chamber is directed.
  • a high oxygen pressure in the cathode compartment is advantageous because it is too low Voltage and thus leads to lower energy consumption.
  • US-A-5,770,035 known electrolytic cell has the disadvantage that the pressure in the cathode compartment, i. the oxygen pressure can only be increased if at the same time the pressure in the anode chamber is increased, otherwise the gas diffusion electrode is pushed away from the current collector and no longer on this rests.
  • a simultaneous increase in the pressure in the anode compartment is technically only to ensure by appropriate complex structural changes to the electrolyzer.
  • a one-sided increase in the pressure in the anode compartment can in the known Cell design cause the gap between the anode and cation exchange membrane increases, resulting in an undesirable increase in the operating voltage and thus leads to an increased energy consumption.
  • the object of the invention is to provide an electrolytic cell, in particular for electrochemical Production of chlorine from aqueous solutions of hydrogen chloride, too to ensure that even at a pressure difference between Anode space and cathode space the anode, the cation exchange membrane, the Gas diffusion electrode and the current collector abut each other directly.
  • the electrolysis cell according to the invention has an anode and a current collector each carried by an anode frame or a cathode frame are. Between the anode and the current collector is a cation exchange membrane and between cation exchange membrane and current collector one Gas diffusion electrode arranged. To the occurrence of a gap between them Components also at, for example, pressure differences between the anode and the To avoid the cathode side, the anode and / or the current collector according to the invention elastically connected to the anode frame or the cathode frame.
  • the anode and / or the current collector are preferably held so elastic, that pressure forces act on the anode and / or the current collector. It is the same also possible, the anode and / or the current collector in such a way with the anode or Cathode frame to connect that pulling forces, each in the direction of the other Electrode are directed to act on the anode or the current collector.
  • the anode or cathode frame to be elastic or an elastic element exhibit.
  • at least one elastic retaining element such as a spring, provided with the anode frame or the cathode frame connected is.
  • a plurality of holding elements provide, which are arranged in particular regularly.
  • the retaining elements are preferably arranged and / or formed such that on the anode and / or the current collector is applied a substantially uniform pressure. The Force per unit area is thus at substantially flat anodes or Current collectors substantially at any point of the anode or the current collector equal.
  • the holding elements are preferably designed as spring elements, in which it can be leaf or coil springs.
  • the Holding elements either directly to the frame or over a rear wall of the Anode or cathode compartment connected to the corresponding frame.
  • the size of the anode and / or the current collector is selected such that that it can be placed inside the frame and not on the frame or rests.
  • the anode and / or the current collector is thus exclusively of held the one or more holding elements.
  • the electrical contact takes place to the anode and / or the current collector also via the holding elements.
  • a additional electrical connection with anode and / or current collector can at This preferred embodiment is therefore eliminated.
  • the elastic attachment of Anode and / or current collector can for example by means of springs or other electrically conductive, elastic compounds such as e.g. Carbon felts or Metal sponges take place.
  • the elastic attachment by means of metallic springs.
  • springs as holding elements Titanium or titanium alloys used, as these of the in the electrolytic cell existing chemical substances are not damaged.
  • To the electric Conductivity of titanium springs can also be improved e.g. Copper springs with Titanium coated, are used.
  • the cell construction according to the invention ensures that the anode is directly on the cation exchange membrane, this directly on the gas diffusion electrode and this in turn rests directly on the current collector, i. that no gap exists between the named components. This is reliable even then Fall, when the electrolytic cell is operated so that in the anode compartment and in Cathode space different pressures are set.
  • anode frame and the cathode frame are preferably made resistant materials, such as noble metal coated or doped titanium or titanium alloys.
  • gas diffusion electrodes are used which contain a catalyst of the platinum group, preferably platinum or rhodium.
  • a catalyst of the platinum group preferably platinum or rhodium.
  • gas diffusion electrodes from E-TEK (USA) which have 30% by weight of platinum on activated carbon with a noble metal coating of the electrode of 1.2 mg Pt / cm 2 .
  • Suitable cation exchange membranes are those made of perfluoroethylene, which contain sulfonic acid groups as active centers.
  • sulfonic acid groups as active centers.
  • Commercially available membranes from DuPont can be used, such as the Membrane Nafion® 324.
  • membranes with carboxyl groups on the Cathode side conceivable.
  • Suitable anodes are, for example, titanium anodes, in particular with an acid-resistant, Chlorine-developing coating, e.g. based on ruthenium-coated Titanium.
  • the cathode-side power distributor can be made of titanium expanded metal or noble metal-coated titanium, with alternative resistant materials can be used.
  • the electrolysis cell according to the invention is particularly suitable for electrochemical Production of chlorine from aqueous solutions of hydrogen chloride or aqueous solutions of an alkali chloride, especially sodium chloride.
  • the pressure in the cathode compartment is preferred greater than that in the anode compartment when the current collector is held elastic
  • the differential pressure between the anode and cathode compartments may be e.g. between 0.01 and 1 bar, with larger differential pressures are possible.
  • the differential pressure is 20 to 350 mbar.
  • the anode is held elastic, it is advantageous if the pressure in the Anode space is greater than that in the cathode compartment.
  • an oxygen-containing is in the cathode compartment Gas, for example, pure oxygen, a mixture of oxygen and inert gases, in particular nitrogen, or air introduced, preferably oxygen or an oxygen-rich gas.
  • oxygen-containing gas is pure oxygen, in particular a purity of at least 99 vol .-% used.
  • the oxygen-containing gas is preferably supplied in such an amount that oxygen is superstoichiometrically based on the amount theoretically required according to equation (1).
  • the stoichiometric excess is preferably 1.1 to 3 times, preferably 1.2 to 1.5 times, the stoichiometric amount.
  • the surplus oxygen can be recycled, so that the stoichiometric excess is only of subordinate importance.
  • the aqueous solution of hydrogen chloride is introduced, the temperature of the supplied aqueous solution of hydrogen chloride is preferably 30 to 80 ° C, particularly preferably 50 to 70 ° C.
  • aqueous solutions of hydrogen chloride having a hydrogen chloride concentration of 5 to 20 wt .-%, particularly preferably from 10 to 15 wt .-%, are used.
  • Electrolysis preferably at a pressure in the anode compartment greater than 1 bar absolute carried out.
  • the pressure in the cathode compartment is preferably greater than 1 bar absolute, especially preferably 1.02 to 1.5 bar, particularly preferably 1.05 to 1.3 bar. It became namely found that at a higher pressure in the cathode compartment, i. a higher one Oxygen pressure, the electrolysis at the same current density at lower voltage, i.e. with lower energy consumption, can be done.
  • the adjustment of the pressure in the cathode compartment can be done, for example, by that the oxygen-containing gas supplied to the cathode space by a pressure-holding device is accumulated.
  • a suitable pressure-retaining device is, for example a liquid compression, through which the cathode space is shut off.
  • a throttling About valves also provides a suitable method for adjusting the Print dar.
  • Electrolytic cells shown schematically in FIGS. 1 to 4 are better Clarity because so illustrated that the individual components of the cell have gaps between them.
  • Electrolytic cell the individual components are directly adjacent.
  • Fig. 1 shows a first embodiment of an electrolytic cell according to the invention.
  • the current collector 10 is elastically attached to the cathode frame 12.
  • the cathode frame 12 is further connected to a rear wall 14. Through the current collector 10, the cathode frame 12 and the rear wall 14 is a cathode space 16th educated
  • the current collector 10 is more than one Spiral springs 18 held elastically.
  • the springs 18 are connected via intermediate parts, e.g. Z or Trapezoidal profiles, 20 attached to the rear wall 14.
  • intermediate parts e.g. Z or Trapezoidal profiles
  • the springs 18 are provided, which regularly are arranged distributed.
  • the springs 18 in several rows and Columns arranged to a substantially rectangular current collector 10 to hold.
  • the current collector 10 is of an assembled state on the cathode frame 12 adjacent seal 22 surrounded.
  • the shape of the seal 22 corresponds essentially the shape of the cathode frame 12.
  • the current collector 10 opposite an anode 24 is provided by an anode frame 26 is worn.
  • the attachment can here, for example by suitable provided on the anode frame 26 lugs or on the Rear wall 28 attached Z or trapezoidal profiles (not shown here) done on where the anode 24 rests.
  • an anode compartment 30 is formed.
  • a gas diffusion electrode 32 and a cation exchange membrane 34 are arranged between the anode 24 and the current collector 10 arranged.
  • the dimensions The gas diffusion electrode 32 are preferably such that they Current collector 10 completely covered.
  • the cation exchange membrane 34 is in contrast, larger, so that it is arranged between the two frames 12,26 and held by the frames 12, 26 in the assembled state.
  • the gas diffusion electrode becomes 32 from the current collector 10 to the cation exchange membrane 34th and pressed them onto the anode 24. It is particularly advantageous if the Anode 24 with the seal 36 in the installed state forms a plane
  • the anode compartment 30 is filled with hydrochloric acid via an HCl inlet 38 and the cathode compartment 16 is filled with oxygen or an oxygen-containing gas via an O 2 inlet 40.
  • the temperature of the hydrochloric acid is preferably 50 to 70 ° C in the electrolysis.
  • the electrolysis can also be carried out at a lower temperature.
  • the anode chamber 30 can be flowed through by the hydrochloric acid.
  • the chlorine formed leaves the anode chamber 30, for example, above a Cl 2 outlet 42. It is also conceivable that other flow variants are selected. For example, a flow through the anode compartment 30, from top to bottom is possible. It is also conceivable that no forced flow is given from the outside by means of a pump.
  • the cathode chamber 16 can be flowed through by the oxygen or the oxygen-containing gas. It is also conceivable to influence the oxygen within the cathode space 16 by means of internals in its flow direction. For example, porous materials, electrically conductive as well as non-conductive, can be used in the space behind the current collector 10.
  • the oxygen can, as shown in FIG. 1, be introduced from below via the O 2 inlet 40 and removed again via an O 2 outlet 44 at the top. However, it is also possible that the oxygen flows from top to bottom or that a lateral flow takes place in the cathode compartment 16 from eg bottom left to top right. With regard to the proceeding reaction, hyperstoichiometric oxygen should be offered.
  • the anode 24 can be installed in the electrolytic cell so that they over the Anodenrahmen 26 so far protrudes that when applied seal 36, the anode 24th forms a surface with the seal 36. It is also possible that the anode 24 so far below the seal 36 is that in the assembled state of Cell components, the seal 36 with the anode 24 forms a plane. Here is the compressibility of the seal 36 and the torques during assembly to consider the cell components.
  • the current collector 10 as shown in Fig. 1 is elastic with the rear wall 14th connected, so the pressure in the anode and in the cathode compartment the same size to get voted. It is also conceivable that the pressure in the cathode chamber 16 is greater is than that in the anode chamber 30. This pressure difference can also at higher absolute pressure can be selected.
  • Fig. 2 corresponds in principle to that shown in Fig. 1 Embodiment. Identical or similar components are therefore with the the same reference numerals.
  • the only difference from the one in Fig. 1 illustrated embodiment is that not the current collector 10, but the anode 24 via the springs 8 and the intermediate parts, e.g. Z or trapezoidal profiles, 20 are connected to the rear wall 28.
  • the intermediate parts, e.g. Z or trapezoidal profiles, 20 are connected to the rear wall 28.
  • the current collector 10 but the anode 24 elastically over the rear wall 28 with the anode frame 26 connected.
  • the third embodiment ( Figure 3) is a combination of the methods shown in Figs. 1 and 2 illustrated embodiments.
  • both the anode 24 and the current collector 10 via springs 18 elastically with the rear wall 28th or 14 connected.
  • the anode 24 presses against the cation exchange membrane 34 and the opposite current collector 10 presses against the gas diffusion electrode 32, so that in this embodiment a particularly high security exists that the corresponding components of the electrolytic cell rest against each other without a gap.
  • the substance guide of oxygen and hydrochloric acid can similarly as in the reference to FIGS. 1 and 2 illustrated embodiments.
  • the electrolysis cell can be operated in a wide pressure range in which it is ensured that the gas diffusion electrode 32 on the current collector 10 rests.
  • the fourth embodiment also corresponds in principle to the embodiment described with reference to FIGS. 1 to 3 described electrolytic cell. Same or similar components are therefore again denoted by the same reference numerals.
  • the main difference the electrolytic cell shown in Fig. 4 consists in the type of holding elements used 46.
  • the retaining elements 46 are not helical springs 18, as in the embodiments shown in Figs. 1 to 3, but by a Type leaf spring, on an inner side 48 of the anode frame 26 and the anode 24th is attached.
  • the holding element 46 is also one in the direction of Current collector 10 applied force applied to the anode 24, so that these too Embodiment no gap between current collector 10, gas diffusion electrode 32, Cation exchange membrane 34 and anode 24 consists.
  • the holding elements 46 can also serve as electrical contacts.
  • the current collector 10th to be secured to the cathode frame 12 with corresponding retaining elements 46.
  • the possible pressure differences as well as the material flow guidance are depending on the arrangement the holding elements 46 at least by holding the anode 24 and / or the current collector 10 as described above possible.
  • the anode 24 was built into the electrolysis cell so that it passed over the anode frame 26 protrude so far that when applied seal 36, the anode 24 with the seal 36 formed a surface.
  • the anode 24, the anode frame 26, the Current collector 10, the cathode frame 12 and the electrically conductive springs 18th consisted of a titanium-palladium alloy with 0.2 wt .-% palladium.
  • the Anode 24 was in the form of an expanded metal and was additionally with activated a ruthenium oxide layer. The thickness of the expanded metal was 1.5 mm.
  • the gaskets 36 were made of a fluoroelastomer as available from the company DuPont is sold under the name Viton®.
  • the current collector 10 was also formed in the form of a ruthenium oxide coated titanium expanded metal The contacting of the current collector 10 to the elastic springs 18th was done by spot welding.
  • As the gas diffusion electrode 32 was a gas diffusion electrode from E-TEK, USA, based on carbon with platinum catalyst.
  • the cation exchange membrane 34 was a membrane DuPont based on a Perfluorsulfonatpolymere under the name Nafion® 324 is commercially available. Through the cation exchange membrane 34 the electrolysis cell was separated into an anode and a cathode compartment.
  • the anode compartment was charged with a 14% by weight hydrochloric acid.
  • the temperature of the hydrochloric acid was 53 ° C.
  • the cathode compartment was charged with pure oxygen at a level greater than 99% by volume.
  • the pressure in the cathode compartment was 1 bar.
  • the differential pressure between the cathode space and the anode space was 0 bar.
  • the electrolysis was operated at a current density of 3000 A / m 2 , whereby a voltage of 1.05 V arose.
  • the anode compartment was charged with a 14% by weight hydrochloric acid.
  • the temperature of the hydrochloric acid was 53 ° C.
  • the cathode compartment was charged with pure oxygen at a level greater than 99% by volume.
  • the pressure in the cathode compartment was 1 bar.
  • the differential pressure between the cathode compartment and the anode compartment was 0.3 bar, so that a pressure of 1.3 bar resulted in the anode compartment.
  • the application of a differential pressure was necessary in contrast to the procedure of Example 1, so that the gas diffusion electrode 32 was pressed onto the current collector 10.
  • the electrolysis was operated as in Example 1 at a current density of 3000 A / m 2 . This resulted in a voltage of 1.21 V.
  • Example 1 shows that at a given pressure in the cathode compartment and constant current density set the electrolysis cell according to the invention (Example 1) can be operated at a lower pressure in the anode compartment and thereby a lower voltage occurs, resulting in a significant reduction in energy consumption entails.

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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)
  • Primary Cells (AREA)
EP02794511A 2001-08-03 2002-07-22 Elektrolysezelle, insbesondere zur elektrochemischen herstellung von chlor Expired - Lifetime EP1417356B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10138214 2001-08-03
DE10138214A DE10138214A1 (de) 2001-08-03 2001-08-03 Elektrolysezelle und Verfahren zur elektrochemischen Herstellung von Chlor
PCT/EP2002/008132 WO2003014419A2 (de) 2001-08-03 2002-07-22 Elektrolysezelle, insbesondere zur elektrochemischen herstellung von chlor

Publications (2)

Publication Number Publication Date
EP1417356A2 EP1417356A2 (de) 2004-05-12
EP1417356B1 true EP1417356B1 (de) 2005-01-12

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EP02794511A Expired - Lifetime EP1417356B1 (de) 2001-08-03 2002-07-22 Elektrolysezelle, insbesondere zur elektrochemischen herstellung von chlor

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US (1) US6841047B2 (pt)
EP (1) EP1417356B1 (pt)
JP (1) JP2004538365A (pt)
KR (1) KR20040030924A (pt)
CN (1) CN1564878A (pt)
AT (1) ATE286995T1 (pt)
BR (1) BR0211694A (pt)
CA (1) CA2456048A1 (pt)
DE (2) DE10138214A1 (pt)
ES (1) ES2236610T3 (pt)
HU (1) HUP0401578A3 (pt)
PT (1) PT1417356E (pt)
WO (1) WO2003014419A2 (pt)

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DE10148600A1 (de) * 2001-10-02 2003-04-10 Bayer Ag Einbau einer Gasdiffusionselektrode in einen Elektrolyseur
DE10152792A1 (de) * 2001-10-25 2003-05-08 Bayer Ag Methode zur Integration einer Gasdiffusionselektrode in einen elektrochemischen Reaktionsapparat
EP1577424B1 (en) * 2002-11-27 2015-03-11 Asahi Kasei Chemicals Corporation Bipolar zero-gap electrolytic cell
JP3924545B2 (ja) * 2003-03-31 2007-06-06 三井化学株式会社 ガス拡散電極の排電方法
US7261798B2 (en) * 2004-01-28 2007-08-28 Hamilton Sundstrand Corporation Assembly for maintaining compression for electrical contact of the active area of an electrochemical cell
JP4834329B2 (ja) * 2005-05-17 2011-12-14 クロリンエンジニアズ株式会社 イオン交換膜型電解槽
ITMI20060054A1 (it) * 2006-01-16 2007-07-17 Uhdenora Spa Distributore di corrente elastico per celle a percolatore
DE102006023261A1 (de) 2006-05-18 2007-11-22 Bayer Materialscience Ag Verfahren zur Herstellung von Chlor aus Chlorwasserstoff und Sauerstoff
US8940139B2 (en) 2009-05-26 2015-01-27 Chlorine Engineers Corp., Ltd. Gas diffusion electrode equipped ion exchange membrane electrolyzer
JP5785492B2 (ja) * 2009-05-26 2015-09-30 ティッセンクルップ・ウーデ・クロリンエンジニアズ株式会社 ガス拡散電極装着イオン交換膜電解槽
ES2643234T3 (es) 2010-03-30 2017-11-21 Covestro Deutschland Ag Procedimiento para la preparación de carbonatos de diarilo y policarbonatos
US9175135B2 (en) 2010-03-30 2015-11-03 Bayer Materialscience Ag Process for preparing diaryl carbonates and polycarbonates
DE102012102210A1 (de) * 2012-03-15 2013-09-19 Solibro Gmbh Heizsystem für eine Vakuumabscheidequelle und Vakuumabscheidevorrichtung
EP2746429A1 (de) 2012-12-19 2014-06-25 Uhdenora S.p.A Elektrolysezelle
ITMI20130563A1 (it) * 2013-04-10 2014-10-11 Uhdenora Spa Metodo di adeguamento di celle elettrolitiche aventi distanze interelettrodiche finite
CN105675680B (zh) * 2014-04-21 2019-07-19 南通大学 一种双室光电化学电解池
CN103981533A (zh) * 2014-05-30 2014-08-13 李欣 一种电解臭氧发生器的阴极紧固弹簧压板结构
EP2957659B1 (de) 2014-06-16 2019-02-20 Siemens Aktiengesellschaft Gasdiffusionsschicht, PEM-Elektrolysezelle mit einer solchen Gasdiffusionsschicht sowie Elektrolyseur
CN104264183B (zh) * 2014-09-24 2017-02-08 宁波华众和创工业设计有限公司 快连接式电解槽
DE102018209520A1 (de) * 2018-06-14 2019-12-19 Thyssenkrupp Uhde Chlorine Engineers Gmbh Elektrolysezelle
DE102020206448A1 (de) * 2020-05-25 2021-11-25 Siemens Aktiengesellschaft Vorrichtung zum Befestigen einer Elektrode
EP4339335A1 (en) * 2022-09-15 2024-03-20 thyssenkrupp nucera AG & Co. KGaA Electrolysis cell

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ATE286995T1 (de) 2005-01-15
HUP0401578A3 (en) 2005-07-28
KR20040030924A (ko) 2004-04-09
DE50202014D1 (de) 2005-02-17
ES2236610T3 (es) 2005-07-16
US20030047446A1 (en) 2003-03-13
WO2003014419A2 (de) 2003-02-20
JP2004538365A (ja) 2004-12-24
EP1417356A2 (de) 2004-05-12
BR0211694A (pt) 2004-07-13
CA2456048A1 (en) 2003-02-20
DE10138214A1 (de) 2003-02-20
HUP0401578A2 (hu) 2004-11-29
CN1564878A (zh) 2005-01-12
PT1417356E (pt) 2005-05-31
WO2003014419A3 (de) 2003-09-18
US6841047B2 (en) 2005-01-11

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