EP2746429A1 - Électrolyseur - Google Patents

Électrolyseur Download PDF

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Publication number
EP2746429A1
EP2746429A1 EP12198034.6A EP12198034A EP2746429A1 EP 2746429 A1 EP2746429 A1 EP 2746429A1 EP 12198034 A EP12198034 A EP 12198034A EP 2746429 A1 EP2746429 A1 EP 2746429A1
Authority
EP
European Patent Office
Prior art keywords
cathode
anode
gas diffusion
clamped
elastic element
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.)
Withdrawn
Application number
EP12198034.6A
Other languages
German (de)
English (en)
Inventor
Peter Woltering
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Uhde Chlorine Engineers Italia SRL
Original Assignee
Uhdenora SpA
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 SpA filed Critical Uhdenora SpA
Priority to EP12198034.6A priority Critical patent/EP2746429A1/fr
Priority to PCT/EP2013/076174 priority patent/WO2014095507A1/fr
Publication of EP2746429A1 publication Critical patent/EP2746429A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • 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 is in the field of chlor-alkali electrolysis and relates to an improved electrolysis cell with gas diffusion cathode and ion exchange membrane and a method in which this electrolysis cell is operated.
  • Chlor-alkali electrolysis is one of the most energy-intensive industrial production processes.
  • aqueous saline solution is subjected to an electrolysis which proceeds according to the following equation: 2NaCl + 2H 2 O ⁇ Cl 2 + 2 NaOH + H 2
  • the decomposition voltage is theoretically only about 2.25 V, the method requires a significantly higher operating voltage of about 3 V, which is due in particular to ohmic potential losses and the overvoltage at the electrodes.
  • the process uses a much lower decomposition voltage of about 1.14 volts. Taking into account voltage losses and overvoltage, an operating voltage of 2 V is sufficient, which leads to energy savings of around 30% compared to the classical method.
  • the electrolysis is now usually carried out by the two-chamber method:
  • the anode chamber is a metal anode, which is separated from the cathode chamber by an ion exchange membrane.
  • the cathode which is located in the cathode chamber, is a gas diffusion cathode.
  • a technological solution consists in segmenting the cathode gas space and connecting these chambers in a cascade manner via downpipes for the passage of the electrolyte. Representing the extensive state of the art, which includes these so-called "gas pockets" is on the EP 0872578 B1 (Bayer).
  • Such a device in the form of a flexible mat is for example from the publications EP 0050373 A1 and EP 0124125 A1 (Oronzio de Nora) known.
  • the object of the present invention has thus been to provide an electrolysis cell which operates according to the two-chamber method and is free of the disadvantages described above.
  • the hydrostatic pressure of the anode side on the cathode side should be compensated.
  • the components used should be easy to manufacture, assemble and exchange.
  • the invention relates to an electrolytic cell comprising an anode chamber with an anode and a cathode gas chamber with a gas diffusion cathode, which are separated from each other by an ion exchange membrane, and a metallic elastic element which is clamped under compression between the rear wall of the cathode gas chamber and the gas diffusion cathode, wherein said elastic element is clamped in the cathode gas space, that the distance between the element and the rear wall in the direction of gravity increases.
  • the contact pressure which the elastic element exerts on the gas diffusion cathode in the direction of gravity increases from approximately 1 kPa to 20 kPa and in particular from approximately 10 kPa to 18 kPa. It has proved to be particularly advantageous if the difference between the contact pressure, the elastic element on the gas diffusion cathode and the hydrostatic pressure in the anode chamber at two opposite points does not exceed a value of about 2 kPa, preferably of 1 kPa. In this way it is ensured that the cathode lies flat against the membrane, but this can not be damaged by excessive pressure.
  • the task described above is solved in full and in an unexpected manner. If the elastic element is clamped as described so that the distance to the rear wall in the direction of gravity, ie generally directed downwards, becomes larger, this means nothing else than that the contact pressure increases in the same way and in this way the hydrostatic pressure profile of the anode chamber depicts and compensates.
  • the object is achieved satisfactorily by the present invention, because the elastic element is, for example, a single mat which is clamped or pressed obliquely into the cathode gas space, so that the distance between the elastic element and the cathode gas rear wall and thus also the contact pressure in the direction of gravity always gets bigger.
  • elastic, normal, unmodified mats can be used as elastic elements, which are clamped in the cell via a carrier element in such a way that the desired pressure compensation takes place.
  • the electrolytic cell is composed of an anode and a cathode compartment containing the two electrodes, which are separated by the ion exchange membrane. As described above, there is the requirement to leave as little space between the electrodes as possible so that no ohmic resistances occur which would lead to a higher electrolysis voltage.
  • Gas diffusion cathodes belong to the gas diffusion electrodes. These are electrodes in which the three aggregate states - solid, liquid and gaseous - are in contact with each other and the solid, electron-conducting catalyst catalyzes an electrochemical reaction between the liquid and the gaseous phase.
  • the solid catalyst - usually a noble or platinum metal - is usually pressed into a porous film having a thickness of about 200 microns. While previously the electrode components were joined together by sintering, gas diffusion electrodes with both hydrophilic and hydrophobic regions are now made using PTFE.
  • PTFE-catalyst mixtures can be prepared by dispersing either water, PTFE and the catalyst, if appropriate in the presence of emulsifiers, or using corresponding dry mixtures of PTFE and catalyst powder.
  • the dispersion route is chosen mainly for polymer electrolyte electrodes. When used in liquid electrolytes, the dry process is more suitable.
  • the electrolyte flows - for example, sodium hydroxide solution or potassium hydroxide solution - in a thin layer between the membrane and the gas diffusion cathode.
  • This thin layer is usually designed as a porous medium;
  • the percolator has a layer thickness of about 0.001 cm to about 0.2 cm.
  • the layer must be made of a hydrophilic material, otherwise it could not fulfill its task.
  • it is required to have high corrosion resistance since it is constantly exposed to high alkalinity and high temperatures (typically 90 ° C).
  • it is a porous material, for example of carbon or a plastic, particularly preferred are carbon fibers, which are formed into a fabric.
  • the so-called "zero gap” technology can be used. This dispenses with a percolator and the membrane lies directly on the gas diffusion cathode.
  • a support can be provided between the gas diffusion cathode and the elastic element, which supports the electrode. This has no immediate significance for the method and the invention, but facilitates the installation of the electrode in the cell and leads to more stability. If the contact surface of the elastic element on the gas diffusion electrode is large enough, it is possible to dispense with such a support. However, if such a carrier is present, it transfers the contact pressure of the elastic element to the cathode, so that it is optionally pressed in contact with the liquid retention layer to the ion exchange membrane.
  • a carrier for example, a metal mesh in question, in which the pore size is about 0.3 to about 3 mm.
  • the carrier also acts as a current collector, which contributes to optimum electrical conductivity in the cell.
  • the support itself is preferably nickel or a corrosion resistant nickel alloy such as Inconel, Hastelloy, Monel or SUS310.
  • the support is coated with gold or, in particular, silver; Also preferably, all contact points at which a current transition occurs, coated with the same material, with a layer thickness of about 1 micron is usually sufficient.
  • the electrolysis cell thus preferably contains a device consisting of 5 layers, namely the anode, the ion exchange membrane, the percolator, the gas diffusion cathode and the cathode support.
  • the elastic members of the present invention may be in the form of spirals, composites, coils or woven, knitted or crocheted mats, sheets, pads or pads. Such components are well known from the above-cited prior art, so that reference is made to their dimensions, configurations and production only by way of reference.
  • the elastic members may comprise an outer tissue and an inner tissue, wherein the inner tissue is in the form of, for example, spirals or coils and has a resilient action, and the outer tissue holds the inner tissue together.
  • the elastic elements are clamped in the cathode gas space via a support element ("support structure"), wherein the support element is designed, for example, in a stepped or planar manner.
  • the elastic element must be made of a material that meets the highest demands on corrosion resistance enough.
  • the elastic element also has the task of deriving the flow from the gas diffusion cathode to the rear wall of the cathode gas chamber.
  • it is made of nickel or one of the above-mentioned nickel alloys. Also coated steel, especially stainless steel can be used.
  • the oxygen required for the electrolysis is passed from the bottom of the gas diffusion cathode into the interior of the cathode gas chamber, which makes it advantageous to form the cathode as slim as possible. It has been found that a cathode depth of about 4 to about 50 mm is sufficient.
  • the typical dimension of an electrolytic cell, consisting of the two chambers, is about one meter in height, which when filled with aqueous saline solution results in a hydrostatic pressure (measured at the bottom of the cell) of about 6 to about 18 kPa.
  • the pressure in the cathode gas chamber is at most 1 to 2 kPa.
  • the invention also includes the use of an electrolytic cell comprising an anode chamber with an anode and a cathode gas chamber with a gas diffusion cathode, which are separated from each other by an ion exchange membrane, and a metallic elastic element, which is under compression between the rear wall of the cathode gas chamber and the gas diffusion cathode is clamped, wherein the elastic element is clamped in the cathode gas space such that the distance between the element and the rear wall in the direction of gravity increases, for performing an electrolysis reaction.
  • the space between the elastic element and the rear wall serves to introduce struts, which fix the elastic element and generate the contact pressure.

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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)
EP12198034.6A 2012-12-19 2012-12-19 Électrolyseur Withdrawn EP2746429A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP12198034.6A EP2746429A1 (fr) 2012-12-19 2012-12-19 Électrolyseur
PCT/EP2013/076174 WO2014095507A1 (fr) 2012-12-19 2013-12-11 Cellule électrolytique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP12198034.6A EP2746429A1 (fr) 2012-12-19 2012-12-19 Électrolyseur

Publications (1)

Publication Number Publication Date
EP2746429A1 true EP2746429A1 (fr) 2014-06-25

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ID=47559157

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12198034.6A Withdrawn EP2746429A1 (fr) 2012-12-19 2012-12-19 Électrolyseur

Country Status (2)

Country Link
EP (1) EP2746429A1 (fr)
WO (1) WO2014095507A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021103185A1 (de) 2021-02-11 2022-08-11 WEW GmbH Verfahren zur Abdichtung einer Elektrolysezelle
DE102021103877A1 (de) 2021-02-18 2022-08-18 WEW GmbH Verfahren zur herstellung einer elektrolysezelle und eines entsprechenden elektrolyse-stacks
DE102021103699A1 (de) 2021-02-17 2022-08-18 WEW GmbH Elektrolysezelle
EP4123057A1 (fr) 2021-07-19 2023-01-25 Covestro Deutschland AG Vidange de liquide optimisée des électrolyseurs à membrane
WO2024104622A1 (fr) 2022-11-17 2024-05-23 WEW GmbH Procédé de production d'hydrogène

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US884653A (en) * 1906-11-23 1908-04-14 Bleach & Caustic Process Company Electrolytic cell.
EP0050373A1 (fr) 1980-10-21 1982-04-28 Oronzio De Nora S.A. Cellule d 'electrolyse et procédé pour la fabrication d'halogène
EP0072907A1 (fr) * 1981-08-20 1983-03-02 Uhde GmbH Cellule d'électrolyse
US4377455A (en) * 1981-07-22 1983-03-22 Olin Corporation V-Shaped sandwich-type cell with reticulate electodes
EP0124125A2 (fr) 1983-05-02 1984-11-07 De Nora Permelec S.P.A. Cellule d'électrolyse et méthode de production d'halogène
US5676808A (en) 1995-04-28 1997-10-14 Permelec Electrode Ltd. Electrolytic cell using gas diffusion electrode
US6117286A (en) 1997-10-16 2000-09-12 Permelec Electrode Ltd. Electrolytic cell employing gas diffusion electrode
EP0872578B1 (fr) 1997-04-14 2002-10-16 Bayer Ag Demi-cellule électrochimique
US20020189936A1 (en) * 2001-06-15 2002-12-19 Akzo Nobel N.V. Electrolytic cell
JP2003041388A (ja) 2001-07-31 2003-02-13 Association For The Progress Of New Chemistry イオン交換膜電解槽および電解方法
DE10138214A1 (de) 2001-08-03 2003-02-20 Bayer Ag Elektrolysezelle und Verfahren zur elektrochemischen Herstellung von Chlor
JP2004300554A (ja) 2003-03-31 2004-10-28 Chlorine Eng Corp Ltd 液透過型ガス拡散陰極を使用するイオン交換膜電解槽
US20060042935A1 (en) * 2002-11-27 2006-03-02 Hiroyoshi Houda Bipolar zero-gap type electrolytic cell
EP1882758A1 (fr) 2005-05-17 2008-01-30 Toagosei Co., Ltd. Pile electrolytique a membrane a echange d ions

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US884653A (en) * 1906-11-23 1908-04-14 Bleach & Caustic Process Company Electrolytic cell.
EP0050373A1 (fr) 1980-10-21 1982-04-28 Oronzio De Nora S.A. Cellule d 'electrolyse et procédé pour la fabrication d'halogène
US4377455A (en) * 1981-07-22 1983-03-22 Olin Corporation V-Shaped sandwich-type cell with reticulate electodes
EP0072907A1 (fr) * 1981-08-20 1983-03-02 Uhde GmbH Cellule d'électrolyse
EP0124125A2 (fr) 1983-05-02 1984-11-07 De Nora Permelec S.P.A. Cellule d'électrolyse et méthode de production d'halogène
US5676808A (en) 1995-04-28 1997-10-14 Permelec Electrode Ltd. Electrolytic cell using gas diffusion electrode
EP0872578B1 (fr) 1997-04-14 2002-10-16 Bayer Ag Demi-cellule électrochimique
US6117286A (en) 1997-10-16 2000-09-12 Permelec Electrode Ltd. Electrolytic cell employing gas diffusion electrode
US20020189936A1 (en) * 2001-06-15 2002-12-19 Akzo Nobel N.V. Electrolytic cell
JP2003041388A (ja) 2001-07-31 2003-02-13 Association For The Progress Of New Chemistry イオン交換膜電解槽および電解方法
DE10138214A1 (de) 2001-08-03 2003-02-20 Bayer Ag Elektrolysezelle und Verfahren zur elektrochemischen Herstellung von Chlor
US20060042935A1 (en) * 2002-11-27 2006-03-02 Hiroyoshi Houda Bipolar zero-gap type electrolytic cell
JP2004300554A (ja) 2003-03-31 2004-10-28 Chlorine Eng Corp Ltd 液透過型ガス拡散陰極を使用するイオン交換膜電解槽
EP1882758A1 (fr) 2005-05-17 2008-01-30 Toagosei Co., Ltd. Pile electrolytique a membrane a echange d ions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021103185A1 (de) 2021-02-11 2022-08-11 WEW GmbH Verfahren zur Abdichtung einer Elektrolysezelle
WO2022171411A1 (fr) 2021-02-11 2022-08-18 WEW GmbH Procédé d'étanchéification d'une cellule électrolytique
DE102021103699A1 (de) 2021-02-17 2022-08-18 WEW GmbH Elektrolysezelle
WO2022175011A1 (fr) 2021-02-17 2022-08-25 WEW GmbH Cellule électrolytique
DE102021103877A1 (de) 2021-02-18 2022-08-18 WEW GmbH Verfahren zur herstellung einer elektrolysezelle und eines entsprechenden elektrolyse-stacks
WO2022175010A1 (fr) 2021-02-18 2022-08-25 WEW GmbH Procédé de fabrication d'une cellule électrolytique et d'une pile électrolytique correspondante
EP4123057A1 (fr) 2021-07-19 2023-01-25 Covestro Deutschland AG Vidange de liquide optimisée des électrolyseurs à membrane
WO2023001723A1 (fr) 2021-07-19 2023-01-26 Covestro Deutschland Ag Évacuation optimisée de liquide provenant d'électrolyseurs à membrane
WO2024104622A1 (fr) 2022-11-17 2024-05-23 WEW GmbH Procédé de production d'hydrogène
DE102022130401A1 (de) 2022-11-17 2024-05-23 WEW GmbH Verfahren zur Erzeugung von Wasserstoff

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Publication number Publication date
WO2014095507A1 (fr) 2014-06-26

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