WO2022161595A1 - Procédé de fonctionnement d'un empilement électrolytique - Google Patents

Procédé de fonctionnement d'un empilement électrolytique Download PDF

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Publication number
WO2022161595A1
WO2022161595A1 PCT/EP2021/051707 EP2021051707W WO2022161595A1 WO 2022161595 A1 WO2022161595 A1 WO 2022161595A1 EP 2021051707 W EP2021051707 W EP 2021051707W WO 2022161595 A1 WO2022161595 A1 WO 2022161595A1
Authority
WO
WIPO (PCT)
Prior art keywords
operating
pressure
electrolysis stack
electrolysis
operating time
Prior art date
Application number
PCT/EP2021/051707
Other languages
German (de)
English (en)
Inventor
Stefan Höller
Original Assignee
Hoeller Electrolyzer Gmbh
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 Hoeller Electrolyzer Gmbh filed Critical Hoeller Electrolyzer Gmbh
Priority to PCT/EP2021/051707 priority Critical patent/WO2022161595A1/fr
Publication of WO2022161595A1 publication Critical patent/WO2022161595A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to a method for operating an electrolysis stack of the PEM type and a device for generating a product gas using at least one electrolysis stack.
  • the present invention relates to electrolysis stacks of the PEM type, ie electrolysis stacks which are formed from a large number of electrolytic cells of the PEM type arranged one above the other to form a stack.
  • electrolytic cells are typically those that work with a polymer electrolyte membrane, ie a proton exchange membrane, but can also be those that work with an alkaline membrane, ie an anion exchange membrane.
  • a PEM electrolysis stack can fall under the application of such a regulation if the prerequisites, for example, a pressure vessel are given.
  • a pressure vessel For example, since the titanium used as the bipolar plate material in the electrolysis stack is in what is known as a creep range when used in the pressure vessel, its maximum permissible service life is limited. However, an electrolysis stack can often still be operated safely even after this maximum permissible operating time has been reached if certain boundary conditions are observed.
  • the invention according to the application is based on the object of improving the operation of such an electrolysis stack in terms of safety and, if possible, extending it.
  • the method according to the invention for operating an electrolysis stack of the PEM type provides that at least the operating time of the electrolysis stack is recorded and the operation is controlled as a function of the recorded operating time.
  • the basic idea of the solution according to the invention is to use suitable operating time recording and appropriate control of the operation of the electrolysis stack to ensure that it always complies with the rules of technical safety and is therefore either switched off after a predetermined operating time has been reached or operated at reduced power so that its Operational safety is reliably guaranteed even after this predetermined time has been exceeded.
  • the operating time is recorded as a function of time and the operation is then controlled as a function of the recorded operating times and operating pressures.
  • the operating pressure within the meaning of the invention is to be understood as the pressure that is present at the product outlet of the electrolysis stack.
  • hydrogen is typically the product gas.
  • the oxygen produced during electrolysis is mostly discharged unused into the atmosphere.
  • the oxygen can also be the product gas, in which case the pressure can be detected on the hydrogen and/or oxygen side and the control can be designed accordingly.
  • the method according to the invention is preferably used for the electrolytic production of hydrogen from water.
  • the time- and pressure-dependent control of the stack can be implemented in suitable control and/or regulation.
  • the operating time-dependent control ensures that an electrolysis stack does not exceed a specified permissible operating time or, if it is exceeded, adjusts its operation accordingly. If a PEM electrolysis stack falls under the Pressure Equipment Directive due to its size and operating pressure, then the inventive appropriate procedures ensure that the operation of the electrolysis stack is either switched off after reaching the maximum permissible operating time according to the regulations applicable to pressure vessels or is limited in such a way that the rules applicable to pressure vessels no longer apply.
  • Product gas pressures of up to 120 bar are realistic with a stack volume of between 1 and 30 liters, for example.
  • the operating time is to be recorded in which an electrolysis stack is operated with a pressure vessel operating pressure and, after this predetermined maximum permissible operating time has been reached, the electrolysis stack is to be controlled in such a way that the operating pressure is below the pressure vessel operating pressure.
  • the application of the regulations relevant to pressure vessels is not only determined by the pressure alone, but can also be determined by a product, for example Operating pressure and volume must be determined, which must be less than a certain value in order to no longer have to be operated according to the rules for pressure vessels.
  • This pressure vessel pressure is only to be understood as an example and can also be determined by another pressure value.
  • the pressure can be determined by one or more pressure sensors, but it is particularly advantageous if the method is operated without sensors.
  • the pressure can then advantageously also be controlled without sensors and/or limited via valves.
  • the operating time is advantageously recorded as a function of the operating pressure prevailing in the electrolysis stack, so that the operating time is only recorded when the operating pressure exceeds a pressure of 0.5 bar compared to the environment, for example, and only then is the operating time measured. If the maximum permissible operating time is then reached, the electrolysis stack is advantageously continued to be operated according to the method according to the invention, but with an operating pressure which is always lower than, for example, 0.5 bar, the pressure currently relevant for the application of the regulations for pressure vessels. It is understood that this pressure can be different with changing regulations, as well as with operation in countries in which different regulations apply in this respect.
  • the designation pressure vessel operating pressure within the meaning of the present invention is therefore to be understood as synonymous with the respective pressure determined by national or international regulations, which requires compliance with certain rules, for example according to the regulations applicable to pressure vessels in Germany.
  • the detection of the pressure via sensors is precise, but comparatively complex, and such sensors also have a certain sen wear and are often to be provided redundantly. In this respect, it is more favorable to record the operating time when a predetermined minimum voltage is present at the electrolysis stack. Since it is advantageous not only for safety reasons to monitor the total voltage of the electrolysis stack, but also each individual cell of the electrolysis stack, the operating time can advantageously be recorded when at least one of the cells has a previously specified minimum voltage applied to it. In the above-described production of hydrogen from water, a cell is typically operated at 1.7 to 2.0 volts, and with severe aging at up to 2.4 volts.
  • the operating time recording starts counting from the point in time when a minimum voltage of, for example, 1.5 volts is applied to at least one of the cells of the electrolysis stack. It can then be reliably ensured that the operating time recorded is always equal to or greater than the actual time given under the operating pressure to be assumed. This is also an essential safety aspect.
  • means for detecting the operating time are to be provided according to the invention, as well as a controller which depends the recorded operating time switches off the electrolysis stack or activates it in such a way that there is a reduced operating pressure in the electrolysis stack.
  • a control can be implemented in the control and regulation electronics that are already present in such a device.
  • an electronic control/regulation is provided which regulates the voltages present at the electrolysis stacks in accordance with the pressure present at the outlet in relation to a target pressure, be it at a high or at a lower pressure level.
  • preferably redundant pressure sensors can be provided at the product outlet of each stack in order to realize this.
  • means for detecting the voltages present at the electrolysis stacks are provided in addition to or in addition to the pressure sensors.
  • the voltage applied to an electrolysis stack is detected, but also the voltage applied to each cell of an electrolysis stack.
  • This monitoring can thus monitor the internal resistance of the supply line, i.e. the internal resistance from the voltage source via the supply line to the first or last bipolar plate of the electrolysis stack, in order to detect inadmissibly large contact resistances in this way.
  • the operating time is preferably measured not only by means of a central electronic control and regulation system, but according to the invention there is additionally or alternatively an operating time counter permanently connected to each electrolysis stack, in particular an operating hours counter, which is preferably non-detachably mechanically and electrically connected to the stack. that is, it is connected to the stack in such a way that disassembly can only take place when the stack itself is disassembled.
  • the device or system shown in the figure has, for example, three electrolysis stacks 1 of the PEM type, the basic structure of which falls within the prior art and is therefore not described in detail here.
  • Each electrolysis stack 1 has two end plates 2, between which the electrolysis cells are clamped against one another. Each of these metal end plates 2 is joined by one Plastic insulating plate 3 which electrically insulates the end plate 2 from an energization plate 4 lying on the insulating plate 3 on the other side, via which the electrolysis stack 1 is supplied with electrical energy.
  • Each current supply plate 4 has a tongue 5 protruding beyond the cross-sectional contour of the stack 1 on one side as a connection for the power supply.
  • One tongue 5 forms the positive pole of the electrolysis stack 1 and the other tongue 5 forms the negative pole.
  • a corresponding power supply is connected via these tongues 5 .
  • an end plate 2 is provided with a connection plate 6, via which the channels formed in the stack 1 can be connected to corresponding line connections.
  • the connection plate 6 comprises a connection 7 for supplying water, a connection 8 for discharging water and oxygen, and a connection 9 for discharging hydrogen, which here forms the product gas.
  • electrolytic cells Arranged between the current supply plates 4 are a large number of electrolytic cells which are adjacent to one another and connected in series, each of which has a PEM membrane (polymeric le ktrolyte membrane), i.e. a proton exchange membrane which, in a manner known per se, is coated on both sides with is coated with catalytically active electrodes and is surrounded on both sides by bipolar plates, via which the reactants are brought to the membrane and via which the electrical connection between adjacent electrolytic cells takes place.
  • PEM membrane polymeric le ktrolyte membrane
  • the electrolytic cells formed in this way are arranged in the electrolytic stack 1 in an electrically conductive manner and are thus connected in series.
  • each electrolysis cell is connected to the gang connection 7 for the water, with the outlet connection 8 for oxygen and water and the product gas connection 9 is connected.
  • the electrolysis cells are clamped between the end plates 2 with the incorporation of the insulating plates 3 and the current supply plates 4 via tie rods 10, which are fixed with the incorporation of plate spring assemblies 11 by means of nuts 12 on both sides of the end plates 2.
  • Each electrolysis stack 1 has an electronics box 13 on one side, which adjoins each electrolysis cell laterally in such a way that in this electronics box 13 not only the voltage of the voltage present on the electrolysis stack 1, i.e. on the current supply plates 4, is recorded, but also the voltage applied to each individual cell.
  • This data is recorded by means of digital electronics (not shown here in detail) arranged in the electronics box 13, processed, stored and forwarded to a central control and regulation electronics 14, which controls the electrolysis stacks 1 individually.
  • the digital electronics located in the electronics box 13 each include an operating time counter, which records the operating times using the associated electrolysis stack 1, based on the voltages applied to the individual electrolysis cells.
  • the operating time is measured from the point in time at which a voltage of 1.5 volts is present in at least one electrolytic cell of the stack 1 . Up to this voltage, it is ensured that the hydrogen electrolysis from water at the hydrogen connection 9 does not produce a pressure exceeding 0.5 bar. The end of an operating interval of the operating time measurement is determined by the fact that the operating voltage present at the last electrolytic cell falls below 1.5 volts when the stack is shut down.
  • the electronics box 13 with the electrical connections therein and the electronics for recording the operating time is inseparable connected to the electrolysis stack 1 and can only be removed if the electrolysis stack 1 is dismantled after loosening the nuts 12, which in practice is only done by the manufacturer when the electrolysis stack 1 is overhauled.
  • the three electrolysis stacks 1 of the hydrogen generation plant shown here as an example convey with their product gas outlets 9 each via check valves 15 into a product gas line 16, which opens directly or indirectly into a hydrogen storage tank.
  • a pressure sensor 17 is assigned to each product gas outlet 9 of an electrolysis stack 1 , the signal of which is recorded in the digital electronics of the electronics box 13 , processed and fed to the central control and regulation electronics 14 .
  • the operating time of the electrolysis stacks can be determined independently and in addition to the aforementioned voltage-controlled operating time determination via this pressure measurement.
  • the pressure detection is used to connect the electrolysis stacks 1 to a regulation that is carried out by the central control and regulation electronics 14, which applies a voltage to the electrolysis stacks 1 at their current supply plates 4 so that the desired pressure is present at the product outlet 9.
  • the device shown in the figure and described above is controlled in such a way that the electrolysis stacks 1 work with the highest possible operating pressure at the outlet 9, for example 35 bar.
  • the operating time is recorded as described above in the electronics boxes 13 of each electrolysis stack 1, so that regardless of how many electrolysis stacks 1 are active at what time, the operating time is recorded as a function of voltage and/or pressure in each electrolysis stack 1, with high pressure being used in this operation the electrolysis stacks 1 are subject to the regulations applicable to pressure vessels, since the product of the operating pressure in bar and the volume in liters is greater than 200. Because the electrolytic cells in the bipolar plates contain titanium the electrolysis stacks 1 equipped in this way are subject to a maximum permissible operating time of 50,000 or 100,000 hours in this operation at high pressure.
  • the central electronic control and regulation system 4 which, depending on the regulation, either switches off this electrolysis stack 1 or activates it for operation , in which at the product connection 9 there is a maximum pressure of 0.5 bar above the ambient pressure.
  • the electrolysis stack 1 can continue to be operated in accordance with the applicable safety regulations with a possibly provided further maximum permissible operating time, after which the stack is then finally switched off. Since each of the stacks 1 has its own operating time counter in the electronics box 13 , the central electronic control system 14 controls the operating time separately for each electrolysis stack 1 . It is thus always ensured, regardless of the number of electrolysis stacks 1 and their switching on and off, that safe operation is always guaranteed.

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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)
  • Analytical Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un procédé de fonctionnement d'un empilement électrolytique PEM (1) et est caractérisé en ce qu'il consiste à mesurer le temps de fonctionnement de l'empilement électrolytique (1) et à commander le fonctionnement en fonction du temps de fonctionnement mesuré.
PCT/EP2021/051707 2021-01-26 2021-01-26 Procédé de fonctionnement d'un empilement électrolytique WO2022161595A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2021/051707 WO2022161595A1 (fr) 2021-01-26 2021-01-26 Procédé de fonctionnement d'un empilement électrolytique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2021/051707 WO2022161595A1 (fr) 2021-01-26 2021-01-26 Procédé de fonctionnement d'un empilement électrolytique

Publications (1)

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WO2022161595A1 true WO2022161595A1 (fr) 2022-08-04

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022211743A1 (de) 2022-11-08 2024-05-08 Siemens Energy Global GmbH & Co. KG Elektrolysesystem, insbesondere zur atmosphärischen Wasserelektrolyse

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060118428A1 (en) * 2004-12-03 2006-06-08 Baltrucki Justin D System for generating hydrogen and method thereof
US20190085477A1 (en) * 2017-09-20 2019-03-21 Kabushiki Kaisha Toshiba Carbon dioxide electrolytic device and method of electrolyzing carbon dioxide
US20190127867A1 (en) * 2017-11-02 2019-05-02 Fujitsu Limited Electrolytic system, electrolytic control circuit, and control method for electrolytic system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060118428A1 (en) * 2004-12-03 2006-06-08 Baltrucki Justin D System for generating hydrogen and method thereof
US20190085477A1 (en) * 2017-09-20 2019-03-21 Kabushiki Kaisha Toshiba Carbon dioxide electrolytic device and method of electrolyzing carbon dioxide
US20190127867A1 (en) * 2017-11-02 2019-05-02 Fujitsu Limited Electrolytic system, electrolytic control circuit, and control method for electrolytic system

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022211743A1 (de) 2022-11-08 2024-05-08 Siemens Energy Global GmbH & Co. KG Elektrolysesystem, insbesondere zur atmosphärischen Wasserelektrolyse

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