EP4334508A1 - Installation d'électrolyse comprenant une pluralité de cellules d'électrolyse - Google Patents

Installation d'électrolyse comprenant une pluralité de cellules d'électrolyse

Info

Publication number
EP4334508A1
EP4334508A1 EP22732073.6A EP22732073A EP4334508A1 EP 4334508 A1 EP4334508 A1 EP 4334508A1 EP 22732073 A EP22732073 A EP 22732073A EP 4334508 A1 EP4334508 A1 EP 4334508A1
Authority
EP
European Patent Office
Prior art keywords
electrolysis
supply unit
control electrode
electrical
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.)
Pending
Application number
EP22732073.6A
Other languages
German (de)
English (en)
Inventor
Marc Hanebuth
Markus Ungerer
Peter Utz
Richard Wagner
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.)
Siemens Energy Global GmbH and Co KG
Original Assignee
Siemens Energy Global GmbH and Co KG
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 Siemens Energy Global GmbH and Co KG filed Critical Siemens Energy Global GmbH and Co KG
Publication of EP4334508A1 publication Critical patent/EP4334508A1/fr
Pending legal-status Critical Current

Links

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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/10—Electrodes characterised by the structure
    • 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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal

Definitions

  • the invention relates to an electrolysis system with a multiple number of electrolysis cells.
  • electrolysis systems have a large number of electrolysis cells, which are used in the conversion of chemical substances under the action of electricity into other chemical substances.
  • a chemical reaction i.e. a material conversion, is brought about with the help of an electric current.
  • PEM proton exchange membrane
  • alkaline electrolysis For example, hydrogen is now generated by proton exchange membrane (PEM) electrolysis or alkaline electrolysis. These electrolysis systems then use electrical energy to produce hydrogen and oxygen from the water supplied.
  • PEM proton exchange membrane
  • An electrolysis system has a large number of electrolysis cells, which are arranged adjacent to one another.
  • water electrolysis for example, water is broken down into hydrogen and oxygen in the electrolysis cells.
  • distilled water is typically fed to the anode side as a reactant and split into hydrogen and oxygen on a proton-permeable membrane (“proton exchange membrane”; PEM).
  • PEM proton-permeable membrane
  • the water is oxidized to oxygen at the anode.
  • the water is generally conveyed from the underside into the anode compartment and/or cathode compartment.
  • water electrolysis water is broken down into its components, namely hydrogen and oxygen, using electricity.
  • starting materials can also be used as starting materials in electrolysis and are ter Struktur, for example carbon dioxide or the like.
  • the electrolysis products are usually fluid substances that can be fed to the electrolysis cells in an electrolysis system via corresponding supply lines, in which the actual electrolysis is carried out.
  • the electrolysis products are often also in fluid form and are discharged from the electrolysis cells via additional supply lines.
  • the supply lines are usually connected to a cell supply unit, which serves to supply the electrolytic cells with the respective substances or at least one operating substance for proper operation.
  • Supply means not only supplying the operating material or the substance to be electrolyzed, but also discharging the respective electrolysis product, i.e. it includes the supplying of the educt fluid and the discharging of the product fluid that is obtained from the electrochemical conversion process.
  • Hydrogen can be provided with an electrolysis system, also known as an electrolyser, using regeneratively generated electrical energy.
  • an electrolysis system also known as an electrolyser
  • One way of generating hydrogen is to use an electrolysis system whose electrolysis cells are based on proton exchange membranes (PEM).
  • PEM proton exchange membranes
  • An electrolytic cell for generating hydrogen and oxygen from water is disclosed, for example, by DE 102011 007 759 A1. But DE 102019 205 316 A1 also describes a corresponding electrolytic cell for energy-efficient hydrogen production.
  • the electrolytic cells are also arranged one after the other in a stacking direction, so that a cell stack is formed.
  • the stacked arrangement makes it possible for the electrolysis cells arranged one after the other to be electrically contacted directly, for example by mechanical pressure, so that separate electrical connections of the electrolysis cells can be largely reduced.
  • a supply line system (manifold) is also provided within the cell stack, which is used to supply or discharge the at least one fuel to the electrolysis cells.
  • the operating substance can, for example, include the supplied fluid, for example water, and/or the reaction product, for example hydrogen and oxygen.
  • the cell stack is usually operated with a certain electrolysis capacity in such a way that the electric current is as small as possible, but the electric voltage is as high as possible.
  • the electrolysis power for the operation of the electrolysis system is provided by the energy source that is connected to it
  • Purpose can be connected to respective opposite ends of the cell stack.
  • a large number of electrolytic cells can be arranged in a cell stack, for example more than 100 electrolytic cells, in particular several hundred electrolytic cells, but preferably no more than about 400 electrolytic cells.
  • the electrical voltage at one of the respective electrolytic cells is around 1.5 V to 2.5 V. This results in the electrical voltage at the cell stack correspondingly, so that the electrical voltage at the cell stack is often 100 V exceeds, can even amount to several hundred volts.
  • the electrolysis system includes other components such as pumps, heat exchangers, separator tanks that are required for the intended operation of the electrolysis system or the electrolysis cells.
  • these components are summarized by the cell supply unit for supplying the electrolytic cells for normal operation with at least one fuel.
  • the cell supply unit is connected to the electrolytic cells arranged sequentially in a stacking direction via supply lines connected to the opposite ends of the electrolytic cells arranged sequentially.
  • the supply lines are usually made of a material such as metal or the like.
  • a correspondingly high electrical voltage occurs between the ends of the cell stack or the electrolytic cells arranged one after the other.
  • the Versor supply lines which are usually formed of a metal, it is therefore necessary that they have respective electrical cal insulating sections that serve to provide a good electrical connection between the ends of the successively arranged electrolytic cells and thus to avoid giequel between the electrical connections of the electrical energy.
  • the invention is based on the object of specifying an electrolytic system which further reduces the aforementioned corrosion problem and is equipped with an improved protection concept compared to the known solutions.
  • an electrolysis system with a plurality of electrolysis cells which are electrically connected in series and which are at least partially arranged one after the other in a stacking direction, where the series connection can be electrically coupled to an electrical energy source, comprising a cell supply unit for supplying the Electrolytic cells for intended operation with at least one operating fluid, and comprising supply lines connected to the cell supply unit and to opposite ends of the electrolytic cells arranged one after the other, wherein a material of the supply lines comprises metal, and wherein at least one of the supply lines comprises an electrical insulating section with an at least partially protruding into the interior of the insulating control electrode with a catalyst material, which is connected to a metallic pipe section of the supply line is electrically contacted on the anodic shear side.
  • the invention is based on the knowledge that previous operating concepts for electrolysis systems with regard to the avoidance and elimination of degradation phenomena, especially with regard to damaging corrosion effects on layers, are technically complex and economically significant have disadvantages.
  • effective and sustainable solutions have not yet been proposed in conventional approaches. Rather, the problem of corrosion remained, which is disadvantageous for the service life of an electrolysis system.
  • MEAs membrane electrode assemblies
  • H 2 O 2 formed at the electrodes can be converted into radicals when they come into contact with metal ions, which chemically attack the membrane structure of the MEAs and can thus impair the service life.
  • the present invention comes in specifically by avoiding the formation and release of a critical foreign ion concentration of damaging cations in the supply line in the area of the insulation section in an electrolysis system as far as possible and taking appropriate precautions.
  • the control electrode provided for this purpose, which partially protrudes into the interior of the insulating section and has a catalyst material, a stray current is achieved, in particular on the anodic side of the insulating section does not flow off via the metal pipe material of the supply line, but rather via the catalytically active control electrode. Corrosion on the anode side is thus suppressed, since no damaging metal cations, such as Fe 3+ from the ferrous material of the supply line, can go into solution.
  • the damaging processes in particular those processes on the anodic side, as explained above, can be suppressed very efficiently and, above all, sustainably and practically completely avoided with the control electrode with the catalyzer material.
  • the service life of the electrolysis system is advantageously increased.
  • the insulating section has a tubular design and is connected in a flow-tight manner to the supply line, for example as a connecting flange.
  • the insulating section has an axial extent in the axial direction, i.e. in the flow direction of the service fluid.
  • the control electrode partially protrudes into the interior of the insulating section. Depending on the design and the control efficiency that can be achieved, the control electrode can protrude between 30% and 70%, preferably about 40% to 60%, in the axial direction into the interior of the insulating section to reduce stray current consumption, measured from the anodic side of the insulating section.
  • the control electrode is in electrical contact with the metal pipe section of the supply line on the anodic side and is set to a corresponding potential, so that the release of metal cations, such as Fe 3+ , from the metal pipe material of the connec tion line in the anodic section of the supply line is efficiently avoided and corrosion protection is achieved.
  • the control electrode acts electrically and catalytically and, due to its dimensions and geometry with a correspondingly low flow resistance for a fluid flowing around, does not impair the promotion of the fuel in the supply line, or does so only to an insignificant extent.
  • the catalyst material is applied to the base body of the control electrode.
  • the catalyst material of the coating is at is chosen such that it favors, for example, the electrochemical decomposition of water into protons and oxygen. In addition to the positioning and arrangement of the control electrode in the insulating section, its catalytic effect combined with the catalyst material ensures particularly efficient protection against corrosion.
  • control electrode projects between 30% and 70%, in particular between about 40% and 60%, in the axial direction into the interior of the insulating section, measured from the anodic side of the insulating section.
  • the electrolysis cells be arranged in at least two sub-stacks, with each of the at least two sub-stacks being connected by means of at least one first supply line connected to the cell supply unit and at a first end of the respective sub-stack and at least one to the cell supply unit and the second supply line connected to a second end of the respective sub-stack opposite the first end in the stacking direction is connected to the cell supply unit, with the first supply line connected to the first end of that sub-stack having a negative electrical potential of the electrical Energy source can be coupled, is electrically conductively connected to the cell supply unit and all other supply lines have respective electrical insulating sections, with a plurality of the insulating sections having a control electrode protruding at least partially into the interior of the insulating section.
  • insulating sections are equipped with a respective control electrode that protrudes at least partially into the interior of the insulating section.
  • a particularly comprehensive protection against corrosion is thus achieved in the electrolytic system, since damaging stray currents are discharged in a majority, if necessary, even in each of the electrical insulating sections, insofar as these corrosion effects are to be feared.
  • the corrosion protection concept of the invention can therefore also be flexibly applied and adapted to electrolysis systems on an industrial scale with a high electrolysis capacity.
  • the electrical insulating sections of the supply lines, which are susceptible to corrosion, are specifically equipped with a control electrode that protrudes at least partially into the interior of the insulating section, in particular on the anodically acting side.
  • the control electrode partially protrudes inside the insulating section.
  • the control electrode can protrude in the axial direction into the interior of the insulating section by between 30% and 70%, preferably between 40% and 60%, in order to reduce stray current consumption by corrosion.
  • a plastic, a ceramic, but also a metal oxide, such as, for example, titanium dioxide, aluminum oxide and/or the like, can be provided as the material for the electrically insulating section.
  • a composite material can also be provided, which can be formed from a plastic, for example, which can be fiber-reinforced, for example.
  • almost any combination of these can also be provided, which are preferably selected in such a way that a chemical reaction with the fuel to be supplied in each case is essentially avoided.
  • the material of the supply line has at least metal.
  • the metal can, for example, be steel, in particular stainless steel.
  • another metal such as titanium or the like, can also be used.
  • Corresponding metal alloys can of course also be provided.
  • the electrical energy source of the electrolysis system can be any voltage source or current source, for example, which is able to provide sufficient power for carrying out the electrolysis through the electrolytic cells.
  • An electrolysis output can be determined at a specific surface current density depending on the dimensions of the respective electrolysis cell, in particular its electrolysis-technically effective areas.
  • the supply lines have a through-opening with a suitable inside diameter or cross-section in order to be able to guide the respective fuel to the electrolytic cells with as little loss as possible and/or to be able to remove it from the respective electrolytic cells or the partial stacks with as little loss as possible.
  • control electrode is arranged in such a way that during normal operation when the fuel is supplied Stray current in the supply line can be derived via the control electrode through its anodic effect.
  • the anode-side electrical connection and action of the control electrode is particularly efficient and therefore advantageous since the release of metal cations due to stray currents is particularly corrosive and therefore damaging in the area of the anodic side of the supply line adjacent to the insulating section.
  • control electrode is designed in the form of a wire, rod or grid.
  • a wide variety of geometric configurations and material compositions are flexibly available. Designing the control electrode from a metal wire and/or with a rod or lattice geometry is particularly advantageous due to the good local adaptability when installed and the low flow resistance that the control electrode opposes to the operating fluid conveyed in the supply line inside the insulating section during operation .
  • the control electrode it is also possible for the control electrode to be configured from a cylindrical or cup-shaped wire mesh. As a result, a larger effective area of the control electrode is provided over the internal cross section of the supply line in order to practically completely divert or prevent damaging, corrosion-promoting stray currents. At the same time, this geometry ensures that the electrical control electrode has a sufficiently low flow resistance to the pumping of the fuel inside the supply line.
  • the control electrode also preferably has a carrier metal of high conductivity, in particular titanium, coated with the catalyst material.
  • the base body of the control electrode can have or be composed of an oxidation-resistant material of high conductivity. Titanium is ideal here by train.
  • a titanium expanded metal can also function as a carrier or base body of the control electrode or, as described, the rod-shaped or wire-shaped configuration.
  • the catalyst material is applied to this base body.
  • the catalyst material of the coating is preferably selected in such a way that it promotes, for example, the electrochemical decomposition of water into protons and oxygen.
  • the catalyst material has a noble metal oxide. More preferably, the coating of the control electrode contains a catalyst material which has a mixed oxide comprising iridium and/or ruthenium.
  • a titanium-based control electrode in the form of a titanium mixed oxide anode can be used, with a titanium carrier that is activated with a mixed oxide layer.
  • the layers mainly consist of noble metal oxides from the platinum metal group with other dopings, so that so-called metal mixed oxide anodes (MMO) are formed.
  • MMO metal mixed oxide anodes
  • an MMO anode can also be used as an anodically acting control electrode in the insulating section of the electrolysis system, for example, as used for an electrophoretic coating process.
  • These are preferably based on iridium-tantalum activation, 12.5 g iridium per square meter, such as titanium expanded metal type A, for example realized with a fastening element, for example in the form of a welded hook, for fastening and electrical contacting of the control electrode on the anodic side of the supply line .
  • a composite material can also be provided, for example may be formed from a plastic which may be fiber reinforced, for example.
  • a plastic which may be fiber reinforced for example.
  • almost any combination of these can also be provided, which are preferably selected in such a way that a chemical reaction with the fuel to be supplied in each case is essentially avoided.
  • the material of the supply line has at least metal.
  • the metal can, for example, be steel, in particular stainless steel.
  • another metal for example titanium or the like, can also be used.
  • Appropriate metal alloys can of course also be provided.
  • the respective ends of the partial stacks facing the respective insulating sections are electrically insulated from the electrolytic cells.
  • the corrosion effect can be largely avoided in the region between the insulating section and the respective end of the partial stack.
  • the effect of the invention can be further improved as a result.
  • a voltage source is provided, which is connected to the cell supply unit, so that the cell supply unit can be subjected to an electrical potential that is negative with respect to ground potential.
  • the cell supply unit is at least indirectly electrically grounded in the electrolysis system. Due to the grounding, the cell supply unit with the supply lines electrically coupled to the cell supply unit can be connected to a predetermined reference potential. At the same time, this also allows the negative potential of the electrical energy source, which is electrically coupled to the cell supply unit via the supply lines is, also indirectly at least be grounded.
  • the cell stack formed from the sub-stacks is therefore at a defined electrical potential with respect to ground potential and is therefore no longer subject to floating potential. A defined electrical potential difference or electrical voltage can thus be achieved at the respective electrical insulating sections. This allows the reliability of the function of the invention to be further improved.
  • the grounding has a sacrificial anode and/or a voltage source, by means of which the cell supply unit can be subjected to an electrical potential that is negative compared to the ground potential.
  • a voltage source is used, the negative electrical potential of the voltage source can be electrically connected to the cell supply unit and to the supply lines connected to it.
  • the negative electrical potential of the voltage source is preferably grounded accordingly at the same time.
  • the voltage source provides an electrical voltage in a range from approximately -2 V to approximately 0 V in relation to the ground potential this electrical voltage is selected in a range from about -1 V to about -0.8 V.
  • an electrical voltage selected in this range corrosion of stainless steel, for example, can also be prevented under maritime conditions, especially in off-shore applications. be avoided ßere corrosion can be reduced or prevented.
  • the partial stacks are connected in parallel to the cell supply unit in terms of supply.
  • the supply can include supplying or removing the fuel or substances produced during the electrolysis.
  • a further electrode to be arranged in the manner of a counter-electrode for cathodic protection against corrosion in the area of the cell supply unit.
  • the internal corrosion phenomenon relates in particular to corrosion effects within the electrolysis system, especially within the cell supply unit.
  • this can be a titanium electrode or titanium anode, which can be coated with a mixed oxide.
  • the anode formed in this way is preferably arranged in a liquid phase of an oxygen separation tank of the cell supply unit.
  • the partial stacks are particularly advantageously connected in parallel to the cell supply unit in terms of supply. In this way, a good supply of the at least one fuel can be achieved for the sub-stacks.
  • the supply can include supplying or also discharging the fuel or substances produced during the electrolysis.
  • the exemplary embodiments explained below are preferred embodiments of the invention.
  • the features and combinations of features specified in the description above, as well as those specified in the following description The features and feature combinations mentioned in the description of exemplary embodiments and/or shown alone in the figures can be used not only in the combination specified in each case, but also in other combinations.
  • the invention also encompasses or is to be regarded as disclosed embodiments that are not explicitly shown and explained in the figures, but that result from the explained embodiments and can be generated through separate combinations of features.
  • the features, functions and/or effects illustrated in the exemplary embodiments can each represent individual features, functions and/or effects of the invention that are to be considered independently of one another and that further develop the invention independently of one another. Therefore, the exemplary embodiments are also intended to include combinations other than those in the illustrated embodiments.
  • the described embodiments can also be supplemented by further features, functions and/or effects of the invention that have already been described.
  • FIG. 1 shows an electrolysis system for the electrolysis of water in a schematic block diagram
  • FIG. 2 shows a schematic sectional illustration of a supply line of the electrolysis system according to FIG. 1 in the area of an insulating section;
  • FIG. 3 shows a schematic sectional illustration of a supply line of the electrolysis system according to FIG. 1 in the area of the insulating section with a control electrode;
  • Electrolysis plant for electrolyzing water a cell stack is divided into four sub-stacks.
  • FIG. 1 shows a schematic block diagram of an electrolysis system 10 which has a cell stack 54 which has a plurality of electrolysis cells 12 which are arranged one after the other in a stacking direction 14 .
  • the electrolytic cells 12 presently serve to decompose water into its components oxygen and hydrogen by electrochemical means.
  • the electrolysis system 10 is therefore used in the present case to generate hydrogen and oxygen from water.
  • the electrolysis cells 12 are arranged directly adjacent to one another, so that respective electrodes of the electrolysis cells 12 arranged adjacent can make electrical contact with one another. It is provided that in each case an anode of a first of the electrolysis cells 12 makes electrical contact with a cathode of the second electrolysis cell 12 which is arranged immediately adjacent in each case. As a result, the Elect rolysezellen 12 are electrically connected in series.
  • the electrolysis cells 12 are on the one hand supplied with water to be electrolyzed and on the other hand discharge lines for the substances produced, hydrogen and oxygen, are provided via an internal supply structure of the cell stack 54, which is not shown in any more detail. This supply can be connected to opposite ends 20, 22 of the cell stack 54 in each case.
  • an electrical energy source 16 is also connected via an electrical line 52, which provides a suitable electrical voltage with an appro Neten electrical power before lying, so that the electrolysis cells 12 can be supplied with sufficient electrical energy for normal operation .
  • the electrolysis system 10 also includes a cell supply unit 18, which is used to supply the electrolytic cells 12 or the cell stack 54 with the respective fuels, which in the present case relate to the supply of water and the removal of hydrogen and oxygen.
  • a discharge line 46 for what hydrogen and a further discharge line 48 for the oxygen in the cell supply unit 18 are provided for discharging the products.
  • a corresponding supply 50 for water is connected to the cell supply unit 18 for the supply of water as the educt of the electrolysis.
  • the cell supply unit 18 also includes a number of components that are required for the intended operation of the electrolysis system 10, such as pumps, heat exchangers, separation tanks and/or the like, which are not further illustrated here.
  • the cell supply unit 18 is connected to the cell stack 54 in terms of supply via supply lines 24 which are connected to the cell supply unit 18 and the opposite ends 20, 22 of the cell stack 54.
  • the supply lines 24 thus fluidly couple the supply structure of the cell stack 54.
  • the supply lines 24 are formed from a metal such as stainless steel.
  • each of the supply lines 24 has an electrically insulating section 38. This ensures that the ends 20, 22 are designed to be electrically isolated from the cell supply unit 18 and thus also electrically isolated from one another.
  • the supply lines 24 are located outside of the cell stack 54.
  • the insulating sections 38 are essentially formed from an electrical insulating material, which can be, for example, a suitable ceramic material or also a suitable plastic or composite material.
  • 2 shows a schematic sectional view of one of the supply lines 24 from FIG. 1 in the area of the insulating section 38. In FIG Area 56 of the cell supply unit 18 faces. The areas 56 and 58 are electrically isolated from one another by the insulating section 38 .
  • This arrangement is designed to be fluid-tight overall and has an essentially constant inner diameter 62 through which the corresponding fluid can be guided, which in this case is water.
  • Corrosion occurs in a region 64 due to the electrical voltage applied to the electrical insulating section 38 .
  • This can be considered to be due to the fact that in the area of a transition from area 56 to the electrical insulation section 38, negative hydroxide ions are formed due to the absorption of electrons from the metal of the wall of the supply line 24 into the water flowing in the inner diameter 62 electric field to Be rich out 58 and there react electrochemically with the metal of the wall of the supply line 24, as shown in FIG.
  • the wall of the supply line 24 corrodes in this area 64. This is undesirable and disadvantageous for the operation of the electrolysis system for the service life.
  • the hydrogen formed in this way can be dissolved in water or it can also be present in the form of tiny bubbles and be transported away with the water.
  • the quantities produced are usually so small that the hydrogen itself does not have any disruptive effects.
  • Rouging means the finest iron-containing particles that can be distributed in the supply lines 24 and the components of the electrolysis system 10 . They can be observed above all in the supply lines 24, in which hydrogen is also fed. If this rouging gets into the oxygen-carrying ing part of the electrolysis system 10, the rouging can dissolve again with the formation of ions.
  • cations can then get into the electrolytic cells 12 from the oxygen side and accumulate there. This process can lead to higher cell voltages and therefore to lower efficiency of the electrolysis system 10 .
  • Wei terhin damaging mechanisms for the Elektrolysezel len 12 can be associated with these cations. For example, hydrogen peroxide formed at the electrodes can be converted into free radicals upon contact with metal ions, which chemically attack a membrane structure of the electrolytic cells 12 and can thus adversely affect the service life of the electrolytic cells 12 .
  • FIG. 3 shows a schematic sectional view of a supply line 24 in which the disadvantageous corrosion effect in the area of the insulating section 38, which was explained with reference to FIG. 2, is very effectively and sustainably avoided.
  • the supply line 24 shown in FIG. 3 is part of an electrolysis system 10, roughly corresponding to FIG. 1 with an insulating section 38.
  • FIG. 3 shows the supply line 24 with a first area 58, which faces the end 22 of the cell stack 54. whereas an opposite second area 56 faces the cell supply unit 18 .
  • the areas 56 and 58 are electrically isolated from one another by the insulating section 38 .
  • This arrangement is designed to be fluid-tight overall and has an essentially constant inner diameter 62, through which the corresponding fluid, the fuel, can be guided in the axial direction inside the supply line.
  • the fluid or fuel is water for the water electrolysis.
  • the supply line 24 has an electrical insulating section 38 with a control electrode 66 which projects at least partially into the interior of the electrical insulating section 38.
  • the control electrode 66 is in the form of a wire loop made with a titanium base material. This results in high electrical conductivity.
  • the control electrode 66 is also coated with a catalyst material 68, which comprises a mixed oxide comprising iridium and/or ruthenium.
  • the catalyst material 68 is applied to the titanium base body so that a catalytically active layer is formed on the control electrode 66 .
  • the control electrode 66 is electrically contacted via the first region 58 of the supply line 24, which forms the anodic side, and is set to a corresponding positive potential, so that stray currents can be derived.
  • the control electrode 66 is arranged and aligned rich tet that in normal operation when supplied with the fuel, in this case water, for the water electrolysis, an unwanted stray current in the supply line 24 is derived via the control electrode 66 by the anodic effect. On the anode side, ie in area 58, the stray current then no longer flows in a damaging manner via the material of the supply line 24, but instead via the control electrode 66.
  • the catalyst material 68 has a catalytic effect on the control electrode 66, which causes the electrochemical decomposition of water into oxygen and protons.
  • the control electrode extends noticeably, in the example between about 50% and 60% of the axial extent of the insulating section 38, into the interior thereof, the stray current now flows on the anodic side in the region 58 via the control electrode 66. Furthermore, the catalytic coating with the catalyst material 68 promotes the formation of oxygen at the control electrode 66, since the overvoltage for this electrocatalytically desired reaction is reduced in a targeted manner. Since the stray currents are relatively small, the resulting amounts of oxygen are quite small and do not affect operation, at least as long as these amounts of oxygen do not accumulate in the insulating section 38 or in the adjacent areas 56, 58 of the supply line 24 Kings NEN.
  • FIG. 4 The particularly advantageous application of the invention is illustrated in FIG. 4 in a schematic block diagram of a further electrolysis system 60 for the electrolysis of water.
  • this complex electrolysis system 60 the aforementioned corrosion effect in the area of the insulating section 38, which was explained with reference to FIG. 3, is avoided in a lasting and very effective manner.
  • the following explanations are also based on the previous explanations for FIGS. 1 and 3, which is why reference is made to the relevant explanations.
  • the electrolytic cells 12 are arranged in four partial stacks 26, 28, 30, 32.
  • Each of the four sub-stacks 26, 28, 30, 32 is connected to the cell supply unit 18 by means of two first supply lines 24 and two to the cell supply unit 18 and at a first end 20 of the respective sub-stack 26, 28, 30, 32 a second end 22 of the respective sub-stack 26, 28, 30, 32, which is opposite the first end 20 in the stacking direction 14, is connected to the cell supply unit 18.
  • the statements relating to FIGS. 1 and 2 essentially apply to the cell supply unit 18.
  • the number of the respective electrolytic cells 12 of the sub-stacks 26, 28, 30, 32 is the same for all sub-stacks 26, 28, 30, 32. Depending on requirements, however, this can also be selected differently in other configurations without departing from the spirit of the invention.
  • the sub-stacks 26, 28, 30, 32 are in turn electrically connected in series so that--from an electrical point of view--all the electrolytic cells 12 of the sub-stacks 26, 28, 30, 32 are again connected in series--as in the cell stack 54 according to FIG.
  • This construction of the electrolysis system 60 means that the cell supply unit 18, viewed electrically, has the smallest electrical potential of the entire electrolysis system 60. This electrical potential is also connected to the negative electrical potential 34 of the electrical energy source 16 . In addition, the electrical energy source 16 provides the positive electrical potential 36 . The electrical energy source 16 provides the operating voltage for the intended operation of the electrolysis system 60 between the negative and the positive electrical potential 34, 36.
  • first supply line 24 which is connected to the first end 20 of that partial stack 26 which can be coupled to a negative electrical potential 34 of the electrical energy source 16 to be electrically conductive to the cell supply unit 18 is connected and all other supply lines 24 have respective electrical insulating sections 38 .
  • all insulating sections 38 have a respective control electrode 66 which projects at least partially into the interior of the insulating section and which is arranged and configured in accordance with FIG is.
  • an electrical insulating layer is formed, which is present by a coating of an insulating material is formed.
  • the insulation material is, for example, a suitable synthetic material.
  • a corrosion-resistant metal-containing material can also be provided, for example a metal oxide or the like, in particular a ceramic material, for example.
  • the respective ends 20, 22 of the partial stacks 26, 28, 30, 32, which face the respective insulating sections 38 are designed to be electrically isolated from the electrolytic cells 12. This can further reduce the corrosion effect. It has proven to be particularly advantageous if the cell supply unit 18 is electrically grounded by means of grounding 42, which can be designed as a direct ground fault or--as shown in FIG. 4--indirectly.
  • the grounding 42 is not connected directly to the cell supply unit 18, but using a voltage source 44, by means of which the cell supply unit 18 can be subjected to an electrical potential that is negative compared to the ground potential.
  • the voltage source 44 provides an electrical voltage of approximately -1 V to approximately -0.8 V. That tension can, however, in principle also be selected, for example, in a range from approximately -2 V to approximately 0 volts.
  • the counter-electrode for the cathodic protection against corrosion is also arranged in the area of the cell supply unit 18 .
  • the provided here for the grounding 42 electrode is presently formed by a titanium anode which is coated with a mixed oxide be.
  • the titanium anode with the mixed oxide coating is arranged in an electrically isolated manner from the cell supply unit 18 in a liquid phase of an oxygen separation tank, not further illustrated.
  • the exemplary embodiments show that the invention can be used to reduce corrosion by forming a plurality of partial stacks 26, 28, 30, 32 of the electrolysis cells 12, which are all electrically connected in series. however, are connected separately to the cell supply unit 18 via their own supply lines 24 .
  • the invention is in no way limited to use in the electrolysis of water and can also be used in other electrolyses to be carried out, for example carbon dioxide electrolysis or the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne une installation d'électrolyse (60) comprenant : une pluralité de cellules d'électrolyse (12) qui sont connectées électriquement en série et agencées consécutivement au moins en partie dans une direction d'empilement (14), l'agencement en série pouvant être couplé électriquement à une source d'énergie électrique (16); une unité d'alimentation (18) des cellules pour alimenter les cellules d'électrolyse (12) en au moins un fluide de traitement pour un fonctionnement normal; et des lignes d'alimentation (24) qui sont reliées à l'unité d'alimentation (18) des cellules et à des extrémités opposées (20, 22) des cellules d'électrolyse (12) agencées consécutivement. Un matériau des lignes d'alimentation (24) comprend un métal et au moins l'une des lignes d'alimentation (24) comprend une portion d'isolation électrique (38) présentant une électrode de commande (66) qui fait saillie au moins partiellement à l'intérieur de la portion d'isolation électrique (38). L'électrode de commande (66) comprend un matériau catalytique (68) et est mise en contact électrique avec une section de tuyau métallique de la ligne d'alimentation (24) au niveau de son extrémité d'anode.
EP22732073.6A 2021-07-30 2022-05-31 Installation d'électrolyse comprenant une pluralité de cellules d'électrolyse Pending EP4334508A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21188722.9A EP4124676A1 (fr) 2021-07-30 2021-07-30 Installation d'électrolyse dotée d'une pluralité de cellules d'électrolyse
PCT/EP2022/064726 WO2023006276A1 (fr) 2021-07-30 2022-05-31 Installation d'électrolyse comprenant une pluralité de cellules d'électrolyse

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EP4334508A1 true EP4334508A1 (fr) 2024-03-13

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EP21188722.9A Withdrawn EP4124676A1 (fr) 2021-07-30 2021-07-30 Installation d'électrolyse dotée d'une pluralité de cellules d'électrolyse
EP22732073.6A Pending EP4334508A1 (fr) 2021-07-30 2022-05-31 Installation d'électrolyse comprenant une pluralité de cellules d'électrolyse

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US (1) US20240218535A1 (fr)
EP (2) EP4124676A1 (fr)
CN (1) CN117836471A (fr)
CA (1) CA3227648A1 (fr)
WO (1) WO2023006276A1 (fr)

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DE102023133425A1 (de) * 2023-11-29 2024-10-31 H-Tec Systems Gmbh System aus mehreren Elektrolysevorrichtungen
DE102024209041A1 (de) * 2024-09-20 2026-03-26 Siemens Energy Global GmbH & Co. KG Modul für Elektroanalyseanlage mit verbesserter Stromführung

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DE4136917C1 (fr) * 1991-11-09 1993-02-04 Metallgesellschaft Ag, 6000 Frankfurt, De
US5296121A (en) * 1992-08-24 1994-03-22 The Dow Chemical Company Target electrode for preventing corrosion in electrochemical cells
US9080242B2 (en) * 2008-09-30 2015-07-14 General Electric Company Pressurized electrolysis stack with thermal expansion capability
DE102011007759A1 (de) 2011-04-20 2012-10-25 Siemens Aktiengesellschaft Elektrolysezelle mit einem Blechpaket übereinander gestapelter Bleche mit Ausnehmungen und Verfahren zu deren Herstellung und Betrieb
MY202878A (en) * 2018-03-27 2024-05-28 Tokuyama Corp Electrolysis vessel for alkaline water electrolysis
WO2019210961A1 (fr) 2018-05-03 2019-11-07 Siemens Aktiengesellschaft Système de génération d'hydrogène
DE102019205316A1 (de) 2019-04-12 2020-10-15 Siemens Aktiengesellschaft Energieeffiziente Wasserstoffherstellung
EP3757253A1 (fr) * 2019-06-24 2020-12-30 Siemens Aktiengesellschaft Système d'électrolyse et procédé d'accumulation de l'énergie électrique au moyen du système d'électrolyse

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CA3227648A1 (fr) 2023-02-02
US20240218535A1 (en) 2024-07-04
WO2023006276A1 (fr) 2023-02-02
EP4124676A1 (fr) 2023-02-01

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