EP3794165B1 - Elektrolysezelle mit federnden halteelementen - Google Patents

Elektrolysezelle mit federnden halteelementen Download PDF

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Publication number
EP3794165B1
EP3794165B1 EP19734703.2A EP19734703A EP3794165B1 EP 3794165 B1 EP3794165 B1 EP 3794165B1 EP 19734703 A EP19734703 A EP 19734703A EP 3794165 B1 EP3794165 B1 EP 3794165B1
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EP
European Patent Office
Prior art keywords
electrolysis cell
holding elements
elements
anode
electrolysis
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.)
Active
Application number
EP19734703.2A
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German (de)
English (en)
French (fr)
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EP3794165A1 (de
Inventor
Sebastian Austenfeld
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 Nucera AG and Co KGaA
Original Assignee
ThyssenKrupp Uhde Chlorine Engineers GmbH
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Priority to PL19734703T priority Critical patent/PL3794165T3/pl
Publication of EP3794165A1 publication Critical patent/EP3794165A1/de
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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
    • C25B1/24—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
    • 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
    • C25B9/17—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
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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
    • C25B9/63—Holders for electrodes; Positioning of the 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
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • 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
    • C25B9/70—Assemblies comprising two or more 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms

Definitions

  • the present invention relates to an electrolysis cell comprising an anode chamber and a cathode chamber, which are separated from one another by an ion exchange membrane, the electrolysis cell furthermore having an anode, a gas diffusion electrode and a cathodic current distributor, the anode, ion exchange membrane, gas diffusion electrode and cathodic current distributor in each case in the order mentioned are in direct contact with each other and resilient holding elements are arranged on the other side of the anode and / or on the other side of the cathodic current distributor, which exert a contact pressure on the anode and / or on the cathodic current distributor.
  • the present invention relates in particular to electrolysis cells in electrolysers which operate according to ODC technology with an oxygen-consuming cathode.
  • the desired main product chlorine is produced at the anode according to the following equation: 2 Cl - ⁇ Cl 2 + 2 e -
  • the present invention relates in particular to electrolysis cells for hydrochloric acid electrolysis with an oxygen depolarized cathode, referred to in English as "Oxygen Depolarized Cathode” ("ODC" for short), according to the equation given above.
  • Oxygen Depolarized Cathode oxygen depolarized cathode
  • electrolysers have so far generally been designed with a defined gap between the anode electrode and the membrane resting on the oxygen-consuming cathode due to the process pressure. Since the internal components of the cell were all rigid, their tolerance was designed for a resulting gap in order to avoid excessive compression.
  • an electrolysis cell for the electrochemical production of chlorine in which an anode, a cation exchange membrane, a gas diffusion electrode and a current collector are held together so elastically that there is no distance between the individual components.
  • the elastic cohesion is achieved by elastic fastening of the current collector on the cathode frame or the anode on the anode frame.
  • holding elements which are designed as spring elements and extend, for example, in the cathode space between a rear wall and the current collector.
  • Spiral springs are used, which are fastened on the one hand at one end to the rear wall via Z-profiles and on the other hand exert a pressure force on the current collector in their axial direction at their other end.
  • These spiral springs extend with their axial direction in the transverse direction of the electrolytic cell, that is to say perpendicular to the plane of the electrodes.
  • an electrolytic cell is described with an anode chamber and a cathode chamber, which are separated from one another by an ion exchange membrane, the electrolytic cell also having a gas diffusion electrode.
  • the arrangement of the individual components in the electrolysis cell is such that the anode is followed by the ion exchange membrane, then a percolator, then the cathode, an elastic current collector and the cathode back wall.
  • the electrolysis cell is a chlor-alkali cell with an oxygen-consuming cathode.
  • the elastic current collector used here consists of a kind of mat made of nickel. Alternatively, a current collector with elastically resilient tongues in a comb-like arrangement or with protruding resilient plates fastened on one side can be used, which press on the cathode or on the anode and press them against the ion exchange membrane.
  • the DE 10 2007 042 171 A1 describes an electrolysis cell in which pneumatic pressure mechanisms are provided on the anode side, which are formed from pneumatically inflatable pressure hoses. These pressure hoses are connected to a pneumatic system and are inflated to the extent necessary for the pressure.
  • the pressure hoses are made of silicone rubber and are therefore not electrically conductive.
  • the contact pressure is generated by means of a pressurized auxiliary medium.
  • Such pressure hoses do not consist of a material which is at least partially plastically deformable as a result of the contact pressure.
  • WO 2017/217427 A1 , DE 102 54 379 A1 , U.S. 4,664,770 and US 2009/0071820 A1 relate to certain holding elements for electrolytic cells.
  • the object of the present invention is to provide an electrolysis cell with the features of the type mentioned at the outset, in which an effective mechanical pressing of the ion exchange membrane against the oxygen-consuming cathode to generate a zero-gap configuration is ensured .
  • the solution to the aforementioned problem is provided by an electrolysis cell of the type mentioned at the beginning with the features of claim 1.
  • the resilient holding elements comprise ring elements or at least one tubular section, the axis of which is oriented in the vertical direction or in the longitudinal direction of the electrolytic cell.
  • the solution according to the invention thus differs significantly from the prior art cited above, since resilient retaining elements are used in the prior art, which are designed similar to spiral springs and which are arranged in the electrolytic cell so that their axis extends in the transverse direction of the electrolytic cell.
  • the ring elements or tubular sections in the electrolysis cell experience, in addition to elastic deformation, at least partially a plastic deformation and are designed to be elastoplastically resilient.
  • a plastic deformation arises from the contact pressure, since the ring elements or tubular sections in the electrolytic cell are subjected to compression in the radial direction.
  • the aforementioned plastic deformation is a permanent deformation, for example a radial compression of the ring elements due to radial impact.
  • spiral spring-like elements are used which, although temporarily deformed under compression pressure, due to their elasticity, deform again when the compressive force decreases and thus take up their original shape again.
  • the expansion of the electrolysis cell in the three mutually perpendicular spatial directions is defined in the present application in such a way that the direction parallel to the mostly flat electrodes and the flat membrane is referred to as the longitudinal direction.
  • the direction perpendicular to the longitudinal direction, also parallel to the extension of the flat electrodes, in the electrolytic cell from the lower end to the upper end, is referred to as the height direction.
  • the direction transversely to the electrodes, that is to say in the direction of the surface normal to the electrodes and to the membrane and thus transversely to the longitudinal direction and height direction, is referred to as the transverse direction.
  • the electrolysis cells according to the invention can thus, for example, have an approximately cuboid basic shape, the extent of the electrolysis cell in the transverse direction defined above being generally less than the extent in the longitudinal direction.
  • several electrolysis cells are also preferably arranged in a series connection next to one another or one behind the other, in such a way that the cathode chamber of one cell is always followed by the anode chamber of the next electrolysis cell in the series connection, with between the cathode chamber of the first electrolysis cell and the anode chamber of the next adjacent electrolysis cell, the ion exchange membrane is arranged in each case.
  • the object solution according to the invention provides that the ring elements or the tubular section of the resilient holding elements are arranged between the anode and the cathodic current distributor in such a way that they are subjected to compression in the radial direction.
  • the radial direction of the ring elements in the solution according to the invention corresponds to the transverse direction of the electrolysis cell, that is to say the direction in which the pressure of the ion exchange membrane against the oxygen-consuming cathode is desired.
  • the ring element or the tubular section is therefore flexible in its radial direction.
  • the pressing of the flat membrane / electrode structure is generated by the compression of the ring elements or tubular sections in their radial direction, the electrode being shifted in the direction of the rear wall of the chamber without simultaneous lateral displacement, because the latter would result in the risk of membrane damage.
  • the resilient retaining elements in the electrolytic cell in the anode chamber and / or in the cathode chamber so that their axis does not extend in the vertical direction but in the longitudinal direction of the electrolytic cell.
  • the preferably elastoplastically resilient holding elements would be subjected to compression in the radial direction.
  • the ring elements or the tubular section of the holding elements in the electrolysis cell experience not only elastic deformation, but also at least partially a plastic deformation as a result of the pressing.
  • plastic deformation is understood to be a permanent deformation of a material in which the stress acting in the material exceeds the yield point or 0.2% yield point of the material.
  • the holding elements according to the present invention show an elastoplastic behavior. Therefore, in the following in the present application, elastoplastic holding elements and elastoplastic ring elements are also spoken of.
  • the ring elements or the tubular sections achieve the pressing of the flat membrane / electrode structure by elastoplastic compression in their radial direction.
  • the at least partially plastic deformation of the ring element or tubular section effectively prevents overpressing of the membrane.
  • the ring element or the tubular section can only exert a certain maximum limit force, since permanent deformation occurs before this limit force is exceeded.
  • the resilient holding elements comprise ring elements or at least one tubular section which, in addition to elastic deformation, at least partially undergo plastic deformation in the electrolytic cell and are designed to be elastoplastically resilient.
  • the elastoplastically resilient holding elements can, for example, have a plurality of ring elements which are arranged parallel to one another and at a distance from one another and are connected to one another.
  • ring elements For example, to connect the ring elements to one another, webs can be used which extend in a direction perpendicular to the plane of the ring elements. Such webs enable the holding elements to be better processed during assembly of the electrolytic cell, since the flexible holding elements can then be welded to the rear wall of the anode chamber or cathode chamber and / or the anode or cathode without interruption, for example by means of a laser. Otherwise, additional outlay on equipment would be required.
  • the ring-shaped structure of the holding elements according to the invention has the further advantage that it allows the installation of accessories of the electrolytic cell, such as drain pipes, in the annular space created by the ring element, for example approximately concentrically in its center.
  • the ring elements have an ovalized cross-section that deviates from the circular shape.
  • the ring elements have a cross-section which deviates from the circular shape and is flattened in two regions lying opposite one another on the circumference.
  • Such a symmetrical cross section ensures a displacement of the electrode (anode or cathode) exclusively in the direction perpendicular to the surface of the electrode, that is to say in the transverse direction of the electrolytic cell.
  • the oval or large radii shape also ensures uniform deformation. In the case of plastic deformations in particular, large amounts of plasticization of the material would occur in the case of other geometric shapes such as a diamond shape in the tips. This would encourage the formation of cracks and mechanical straightening of the structure could then lead to damage to the spring structure.
  • a preferred development of the invention provides that the resilient holding elements are welded to at least one adjacent component of the electrolytic cell, in particular to the anode and / or to a rear wall of the electrolytic cell.
  • the welding creates the contact between the flexible holding element to the rear wall of the chamber and the electrode (in particular the anode), whereby an optimal low-loss current transfer is guaranteed.
  • the flattened cross-section of the ring elements on both sides opposite on the circumference improves this contact, since the contact surface is enlarged.
  • the welding can be achieved, for example, by means of a laser weld seam running in the vertical direction of the holding element (height direction of the electrolysis cell).
  • holding elements with two or more spaced-apart ring elements which are connected to one another via webs which run in a direction perpendicular to the ring elements, then there are spaces between the individual ring elements which allow the operating medium of the electrolytic cell to flow through the holding elements, whereby an effective cooling is achieved and the ohmic voltage losses are kept low.
  • An alternative embodiment of the invention relates to holding elements with one or more tubular sections.
  • these holding elements which are tubular at least in sections, can be, for example, polygonal.
  • a diamond shape is advantageous in order to ensure that less material is required.
  • the polygon geometry is also preferably symmetrical or doubly symmetrical in cross section, perform in order to obtain a deformation perpendicular to the membrane surface as possible. If diamond-shaped cross-sections are selected for the tubular sections, then the holding elements are preferably arranged in one of the chambers of the electrolytic cell so that one of the diagonals of the diamond shape extends approximately in the direction of the surface normal to the flat arrangement of electrodes.
  • openings are provided in the tubular sections that can be arranged in rows, for example, and / or that are mutually exclusive for example extend parallel to the axis of the tubular sections.
  • these openings can be configured in the manner of a slot. The material from which the tubular sections are made is weakened by the openings and the plastic deformability of the holding elements is thus increased.
  • the holding elements according to the invention can be used both on the anode side and on the cathode side of the electrolytic cell.
  • the use on the anode side is particularly advantageous because of the usual differential pressures and the better cooling of the structure.
  • a slightly increased electrical resistance leads to the development of heat and this heat can be dissipated by cooling the medium on the anode side.
  • Due to the intended outlet size the overall height of the anode chamber is greater than that of the cathode chamber. As a result, a greater radial expansion of the elastic holding elements is possible in the anode chamber, which reduces their rigidity.
  • the ring elements and / or the webs connecting them to one another are made from sheet metal strips a material thickness of less than one millimeter, preferably with a material thickness of less than 0.8 mm and more than 0.4 mm, for example in the range from about 0.5 mm to about 0.7 mm.
  • the desired elasticities are achieved with the space available.
  • the current paths in the holding element should also be kept small.
  • a certain minimum material thickness is recommended in order to ensure a sufficient cross-section for a low-loss electrical transition.
  • an electrolytic cell comprises at least two elastoplastically resilient holding elements which are arranged at a distance from one another in the longitudinal direction of the electrolytic cell. This is advantageous in order to achieve a uniform pressing of the flat structure comprising the ion exchange membrane, oxygen-consuming cathode and anode in larger surface areas.
  • the resilient holding elements are preferably made at least partially from a metallic material, in particular from a titanium material.
  • a titanium material is understood to mean titanium or a titanium alloy.
  • a support structure is preferably arranged in the cathode chamber, which comprises at least two Z-profiles extending in the transverse direction of the electrolytic cell, preferably a plurality of such Z-profiles, which are arranged at a distance from one another in the longitudinal direction of the electrolytic cell.
  • the elastoplastically resilient holding elements are arranged in the anode chamber and these are each arranged in such a way that, viewed in the longitudinal direction of the electrolysis cell, the resilient holding elements each to the Z-profiles are arranged offset.
  • An approximately central offset of the holding elements based on the respective distance between two Z-profiles in the Cathode chamber is particularly advantageous.
  • the flexural elasticity of the electrodes can also be used to achieve a zero-gap configuration over the largest possible area and to avoid membrane damage in the contact area between the holding element and the Z-profiles.
  • At least two holding elements viewed in the vertical direction of the electrolysis cell, are arranged one above the other in an axial extension. At least three holding elements are preferably arranged one above the other in an axial extension. In this way it is possible to achieve pressing and support over a predominant part or ideally over the entire height of the electrode.
  • a cell voltage of, for example, 1.30 V at 5 kA / m 2 was initially measured in test cells shortly after switching on. After a longer running time, a further reduced operating voltage of 1.25 V at 5 kA / m 2 could be measured.
  • a voltage reduction in the range from 100 to 150 mV or more is possible. This corresponds to a reduction in energy consumption of around 7.1% to 10.7% compared to a previously conventional cell voltage of 1.4 V at 5 kA / m 2 .
  • the present invention also relates to an electrolyser comprising at least one electrolysis cell with at least one resilient holding element with the features described above.
  • the subject of the invention is preferably an electrolyser comprising at least two, preferably a larger number of electrolysis cells with the features described above, connected in series in an arrangement of the electrolysis cells in their transverse direction next to one another, the cathode chamber of one electrolysis cell being followed by the anode chamber of the adjacent electrolysis cell.
  • Such an arrangement is also referred to as single cells stacked one on top of the other in a back-to-back arrangement or a bipolar or filter press design.
  • FIG. 1 a view of the electrolytic cell seen from the cathode side is shown, but the electrode itself is not shown for reasons of clarity.
  • the electrolytic cell 10 has an approximately rectangular outline in the side view.
  • electrolysis cells 10 a larger number of elements (electrolysis cells 10) of the in Figure 1 shown type combined in one block.
  • a plurality of electrolysis cells can be connected to one another in a bipolar manner in a manner known per se in a series connection, with adjacent individual cells being layered back to back one behind the other.
  • this rigid support structure 11 on the cathode side emerges from the detailed illustration according to FIG Figure 3 .
  • several Z-profiles 12 are arranged in the longitudinal direction of the electrolytic cell 10 at a distance from one another, the longer web of the "Z" extending in the transverse direction of the electrolytic cell and thus towards the anode side.
  • the longitudinal direction With the longitudinal direction, the larger (horizontal) direction of expansion in the rectangular outline of the electrolytic cell 10 in the drawing becomes according to Figure 1 labeled from right to left.
  • the smaller (vertical) direction of extent in the rectangular outline of the electrolytic cell in the drawing according to Figure 1 from bottom to top is defined as the height direction.
  • the expansion of the electrolytic cell perpendicular to the plane of the drawing in Figure 1 is called the transverse direction.
  • the two shorter end legs of the "Z", which run approximately perpendicular to the longer web of the "Z”, thus extend in the longitudinal direction of the electrolytic cell and are usually welded to further support structures which extend in the longitudinal direction.
  • the shorter end legs of the "Z” that are on the outside are as shown in Figure 3 recognizes with the drawn there cathode, which is referred to as current distributor 13 in the present application, for example connected by welding.
  • the actual cathode is the oxygen-consuming electrode, which is why the cathode is referred to herein as the current distributor.
  • the tubular anodic liquid inlet 15 is located in FIG Figure 3 on the right side of the drawing.
  • the anodic liquid outlet 16 extends downward and is in Figure 2 recognizable.
  • the cathodic gas inlet 18a via which, for example, ultra-pure oxygen or an at least oxygen-rich gas can be supplied, is located in Figure 3 on the left-hand side and is thus on the side opposite the anodic liquid inlet 15, viewed in the longitudinal direction of the electrolysis cell 10.
  • the cathodic liquid outlet 19 for the resulting condensate is in Figure 2 can be seen on the lower side of the electrolytic cell 10.
  • the cathodic gas outlet 18b is just like the gas inlet in FIG Figure 1 can be seen in the top view of the cathode chamber.
  • resilient holding elements 30 located in the anode chamber, the function of which will be described below with reference to FIG Figures 4 to 7 are explained in more detail.
  • These resilient holding elements 30 are arranged in the electrolytic cell 10 such that their axis extends in the vertical direction of the electrolytic cell.
  • the cross-section of the resilient retaining elements is approximately oval, somewhat flattened on both sides, and they are located in the electrolytic cell 10 in such a way that the somewhat flattened areas on the periphery lying opposite each other rest on the anode 14 on the one hand and on the anode rear wall 17 on the other.
  • the holding elements 30 thus press the anode 14 against the membrane (see also Figure 8 ) and are on the other hand acted upon by the support structure of the cathode chamber, which comprises the Z-profiles 12.
  • the holding elements 30 are not exactly where the Z-profiles 12 are, but rather offset from the Z-profiles 12, viewed in the longitudinal direction of the cell, in such a way that, viewed in the longitudinal direction, there is always one holding element 30, preferably approximately in the middle between two Z profiles 12 lies.
  • Figure 2 can be recognized as in Figure 3 the circumferential frame 20 of the electrolytic cell 10, which can be detachably connected to the other components and which in particular serves to seal the elements from one another.
  • the frame is designed as a solid steel material, for example, in order to optimally support the flange surfaces of the anode and cathode chambers.
  • the seals, which seal the elements against the clamped-in membrane, are preferably placed on the flange surfaces.
  • the forces required to seal the cell stack are significantly greater than the forces required to deform the preferably elastoplastic components according to the invention.
  • the resilient holding elements 30 described above can also be seen in the anode chamber, the ring elements 31 being recognizable here.
  • the anode chamber has a somewhat greater extent than the cathode chamber in the direction of the width (transverse direction) of the electrolytic cell 10. You can also use Figure 2 recognize the longer web of one of the Z-profiles 12 of the support structure in the cathode chamber.
  • This resilient holding element 30 which in the assembled state also partially deforms plastically in the electrolytic cell, comprises a plurality of ring elements 31 which are aligned parallel to one another and spaced from one another and which, as shown in the cross-sectional view according to FIG Figure 6 recognizable is not circular in outline, but one in two areas 32 opposite one another on the circumference, each have a slightly flattened and thus an overall approximately oval shape.
  • these ring elements 31 can be made entirely of sheet metal strips with a material thickness of, for example, less than 1 mm.
  • All ring elements 31 of a holding element 30 are connected to one another via two webs 33, 34, these webs 33, 34 each extending in an axially parallel direction, that is, in the longitudinal direction of the holding element.
  • This axially parallel extension of the webs 33, 34 thus runs approximately perpendicular to the circumferential direction of the ring elements 31. From the sectional view according to FIG Figure 6 the result is that the two webs 33, 34 each lie opposite one another on the circumference with respect to the individual ring element 31, the webs 33, 34 each being located where the ring elements 31 each have the flattened areas 32.
  • Figure 7 shows a possible development or an exemplary cut of the holding element 30 described above, from which the holding element according to the invention to the in Figure 6 shown two-sided flattened cylindrical shape is bent.
  • the sheet metal strips from which the numerous parallel ring elements 31 arise as well as one of the two webs 33 running in the longitudinal or axial direction.
  • the second web is shown in the blank according to FIG Figure 7 each provided halfway at the edges, so that after bending into the cylindrical shape, the two halves 34a, 34b can be connected to one another and then form the second web 34.
  • FIG. 8 Structure and function of an exemplary electrolyser with several electrolysis cells of the type described above in series connection explained in more detail.
  • four electrolysis cells 10 are shown as an example in series connection, each in a back-to-back arrangement, which are arranged in such a way that the electrolysis cells 10 lie one behind the other in their transverse direction described above, so that anode chamber and cathode chamber always alternate, with one cathode chamber 21 and an anode chamber 22 of two adjacent electrolysis cells 10, each an ion exchange membrane 23 is arranged.
  • the electrical current flow through the arrangement of electrolytic cells is in Figure 8 shown by way of example and schematically simplified by the meandering arrow 24, the current flow actually taking place over the entire electrode surface.
  • FIG. 8 a further details of the arrangement can be seen.
  • One of the resilient holding elements 30 lying in the anode chamber 22 can be seen there in the plan view with its flattened annular structure.
  • the individual components are seen in the transverse direction of the arrangement, starting from the second uppermost electrolytic cell to the first uppermost electrolytic cell in the following order:
  • ODC oxygen-consuming cathode
  • the aim is for the anode, the ion exchange membrane, the gas diffusion electrode and the cathodic current distributor to lie close to one another (on top of one another) so that the so-called "zero-gap" configuration results.
  • This goal is supported by the holding elements 30 according to the invention, since they press the anode against the gas diffusion electrode and the other flat elements of the arrangement due to their elastoplastic spring force and their ability to undergo a certain plastic deformation and thus prevent the formation of a gap between them.
  • the holding elements 30 are arranged in the anode chamber in such a way that their axis extends in the vertical direction of the electrolytic cell, so that the pressing via the resilient and deformable ring elements 31 takes place more or less in their radial direction and not, as in the case of a spiral spring, for example, via a spring effect in the axial direction Direction of the spring.
  • FIG. 9 a force-displacement diagram is shown, which indicates the average contact pressure in mbar based on the electrode surface that an elastoplastic resilient retaining element according to the invention exerts on the membrane, depending on the respective spring deflection of the ring element in mm.
  • Two curves are drawn in the diagram.
  • the upper curve 35 results from the measurements for a ring element made of titanium sheet with a material thickness of 0.6 mm.
  • the lower curve 36 results from the measurements for a ring element with a smaller material thickness of only 0.5 mm.
  • FIG. 13 is a horizontal sectional view similar to that of an electrolytic cell already referred to with reference to FIG Figure 3 was explained above, so that the analog components are not described again here.
  • the holding elements which are denoted here by the reference numeral 40, are designed differently. These holding elements 40 can, as described above, be arranged between the anode 14 and the anode rear wall 17 in the anode chamber in such a way that they exert a contact pressure on the flat electrode structure, the holding elements in the transverse direction of the anode chamber, i.e.
  • the holding elements 40 have a polygonal, for example an approximately diamond-shaped cross section and are preferably acted upon in the direction of one of the diagonals of this diamond shape.
  • the holding elements 40 can consist, for example, of a sheet metal material made of titanium, nickel or one of the other materials mentioned above.
  • the holding elements 40 have, at least in sections, an elongated tubular shape with an approximately diamond-shaped cross-section, their axial extension in the installed state corresponding to the height direction of the electrolytic cell (see also Figure 10 ).
  • the retaining elements 40 have numerous perforations 42 or punchings in their walls 41, which form tubular sections, which are, for example, slot-like and the rows extending in the longitudinal direction of the retaining element , in particular can be arranged in several rows.
  • the otherwise tubular holding element 40 is somewhat weakened by these openings 42, so that its rigidity decreases and the desired flexibility in the transverse direction (diagonal direction) is achieved.
  • the diamond shape of the cross section has slight flattened areas 43 in the corner area adjacent to the anode 14 and in the opposite corner area, similar to the flattened areas 32 in FIG Figure 3 variant described above.

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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)
EP19734703.2A 2018-06-14 2019-06-12 Elektrolysezelle mit federnden halteelementen Active EP3794165B1 (de)

Priority Applications (1)

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PL19734703T PL3794165T3 (pl) 2018-06-14 2019-06-12 Ogniwo elektrolityczne ze sprężynującymi elementami podtrzymującymi

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DE102018209520.5A DE102018209520A1 (de) 2018-06-14 2018-06-14 Elektrolysezelle
PCT/EP2019/065393 WO2019238780A1 (de) 2018-06-14 2019-06-12 Elektrolysezelle mit federnden halteelementen

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EP (1) EP3794165B1 (pl)
JP (1) JP7167191B2 (pl)
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DE (1) DE102018209520A1 (pl)
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WO2019238780A1 (de) 2019-12-19
DE102018209520A1 (de) 2019-12-19
EP3794165A1 (de) 2021-03-24
US20210222306A1 (en) 2021-07-22
US20220325427A1 (en) 2022-10-13
CN112262231A (zh) 2021-01-22
JP7167191B2 (ja) 2022-11-08
US11697883B2 (en) 2023-07-11
JP2021526588A (ja) 2021-10-07
PL3794165T3 (pl) 2022-05-02
SA520420675B1 (ar) 2023-06-27
CN112262231B (zh) 2023-09-05
RU2768867C1 (ru) 2022-03-25
US11479870B2 (en) 2022-10-25

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