EP4558662A2 - Électrolyseur et procédé pour faire fonctionner un électrolyseur - Google Patents

Électrolyseur et procédé pour faire fonctionner un électrolyseur

Info

Publication number
EP4558662A2
EP4558662A2 EP23765223.5A EP23765223A EP4558662A2 EP 4558662 A2 EP4558662 A2 EP 4558662A2 EP 23765223 A EP23765223 A EP 23765223A EP 4558662 A2 EP4558662 A2 EP 4558662A2
Authority
EP
European Patent Office
Prior art keywords
hydrogen
electrolysis
cathode
water
anode
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
EP23765223.5A
Other languages
German (de)
English (en)
Inventor
Erik Wolf
Christian Reller
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 EP4558662A2 publication Critical patent/EP4558662A2/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
    • 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
    • C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
    • C25B15/027—Temperature
    • 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
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/085—Removing impurities
    • 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
    • C25B9/05—Pressure 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
    • C25B9/77—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 an electrolyzer for splitting water into hydrogen and oxygen by means of electrical current, comprising a plurality of electrolysis cells which form a plurality of electrolysis stacks, each electrolysis cell having a proton-permeable polymer membrane on both sides of which electrodes are applied to which an external voltage is applied during operation, a water supply line being provided on the anode side for supplying water to an anode chamber, an oxygen product line being connected for discharging the oxygen produced from the anode chamber, and a hydrogen product line being provided on the cathode side for discharging the hydrogen produced from the cathode chamber, further comprising a control system for controlling the operation of the electrolysis stacks.
  • the invention further relates to a method for operating an electrolyzer for splitting water into hydrogen and oxygen by means of electric current, comprising a plurality of electrolysis cells which form a plurality of electrolysis stacks, each electrolysis cell having a proton-permeable polymer membrane on which electrodes are located on both sides, to which an external voltage is applied during operation, water being added to an anode chamber on the anode side and the oxygen produced being discharged from the anode chamber, and the hydrogen produced being discharged from a cathode chamber on the cathode side through a hydrogen product line.
  • a component of a PEM electrolysis cell is a proton-permeable polymer membrane (Proton Exchange Membrane), which is contacted on both sides by porous platinum electrodes (anode and cathode). An external voltage is applied and water is added to the anode side of the electrolyzer. The catalytic effect of the platinum causes the water on the anode side to decompose. This produces oxygen, free electrons and positively charged hydrogen ions H+. The hydrogen ions H+ diffuse through the proton-conducting membrane to the cathode side, where they combine with the electrons from the external circuit to form hydrogen molecules H 2 .
  • PEM electrolysis for example.
  • a component of a PEM electrolysis cell is a proton-permeable polymer membrane (Proton Exchange Membrane), which is contacted on both sides by porous platinum electrodes (anode and cathode). An external voltage is applied and water is added to the anode side of the electrolyzer. The catalytic effect of the platinum causes the water
  • the electrolysis cells described above are grouped together in stacks. Water is introduced into the stack, which is under direct voltage, and after passing through the electrolysis cells, two product streams emerge, consisting of water and gas bubbles as oxygen and Hydrogen f. It is inherent in the system that in the product stream of one product gas the other product gas is only present in small quantities. In practice, there are small amounts of hydrogen in the oxygen gas stream and small amounts of oxygen in the hydrogen gas stream.
  • the quantity of the respective foreign gas depends on the electrolysis cell design and also varies under the influence of current density, catalyst composition, aging and, in the case of a PEM electrolysis system, the membrane material. Under certain circumstances it may be necessary to reduce the concentration of foreign gases, directly on or off. directly after the electrolytic cell or the electrolysis stack, e.g. B. in a gas separation device connected downstream of the electrolyzer. The problem is exacerbated in part-load operation and with aged membranes and leads to restrictions in operation.
  • Gas separation is therefore necessary in the following. It is common practice for several electrolysis cells and several electrolysis units to be connected to one another via piping and for the gas-water mixture emerging in each case to be fed to a central gas separator. An advantageous embodiment for this is known, for example, from WO 2020/020611 Al. The invention is therefore based on the object of ensuring safe operation of the electrolyzer and minimizing the negative consequences of membrane damage during operation of an electrolyzer.
  • an electrolyzer for splitting water into hydrogen and oxygen by means of electric current comprising a plurality of electrolysis cells which are divided into electrolysis stacks, each electrolysis cell having a proton-permeable polymer membrane on which electrodes are applied on both sides, to which an external voltage is applied during operation, a first water supply line being provided on the anode side for supplying water to an anode chamber, an oxygen product line being connected for discharging the oxygen produced from the anode chamber and a hydrogen product line being provided on the cathode side for discharging the hydrogen produced from a cathode chamber, further comprising a control system for controlling the operation of the electrolysis stacks, the control system being set up to set a higher pressure in the anode chamber than in the cathode chamber, the pressure in the anode chamber being 2-fold to 20-fold, in particular 4 to 7 times higher than the pressure in the cathode chamber.
  • the object is further achieved according to the invention by a method for operating an electrolyzer for splitting water into hydrogen and oxygen by means of electric current, comprising a large number of electrolysis cells which are divided into electrolysis stacks, each electrolysis cell being a proton-permeable polymer.
  • each electrolysis with a differential pressure.
  • the pressure on the anode side is set higher than on the cathode side.
  • the pressure ratio between the anode side and cathode side is 2 to 20 bar, in particular 4 to 7 bar. This means that if z. B.
  • a lower pressure on the cathode side compared to the anode side brings several advantages. On the one hand, the migration of water molecules through the membrane is supported. On the other hand, if the membrane breaks through, less foreign gas comes through. And last but not least, there is an improvement in the foreign gas concentration during operation.
  • the control system is designed to enable circulation of water in the anode chamber.
  • the oxygen discharge line also serves as a water discharge line. If the water only circulates on the anode side, a humidified cell is present on the hydrogen side. Operating a PEM electrolyzer with only one water circuit is less complex than with two circuits.
  • the control system is designed to enable circulation of water in the cathode chamber.
  • the hydrogen product line is also used in particular to drain water. The water circulation improves the inherent safety of the electrolysis cell.
  • the circulation rate in the cathode chamber is in particular smaller than that in the anode chamber.
  • the ratio of water circulation on the hydrogen side to the oxygen side is 0.9 to 0.01.
  • the cell Preferably there is a horizontal cell structure in which the anode space is arranged above the cathode space.
  • the cell can also be oriented vertically.
  • a recombination catalyst for recombining hydrogen and oxygen to form water is integrated in the hydrogen product line.
  • the recombination catalyst prevents a reactive product gas mixture from reaching a downstream gas separator or downstream areas such as compressors due to the oxygen content in the hydrogen product stream.
  • the control system is preferably set up to detect at least one temperature value in the hydrogen product line and to compare the temperature value or a temperature correlated with the temperature value with a threshold value and to block the hydrogen product line and open a bypass line when the threshold value is exceeded .
  • the captured temperature value can be, for example, an absolute temperature in or after the recombination catalyst, a temperature change over time, an inlet and outlet temperature based on the recombination catalyst or a difference between two temperature values from the hydrogen product line. An exothermic reaction with an increase in temperature takes place in the recombination catalyst.
  • the control system is preferably set up to switch off the electrical current to the electrolysis stack when the threshold value is exceeded. In this way, an increase in the concentration of foreign oxygen on the hydrogen side is prevented in good time.
  • control system is advantageously set up to introduce an inert gas into the cathode spaces of the switched off electrolysis stack.
  • nitrogen is used to flush the electrolysis stack through on the cathode side.
  • FIG 1 shows a first embodiment of an electrolysis cell in vertical orientation
  • FIG. 2 shows a second exemplary embodiment of an electrolytic cell in a horizontal orientation
  • FIG. 3 shows a third exemplary embodiment of an electrolytic cell in a horizontal orientation
  • FIG 4 a fourth embodiment of an electrolysis cell in horizontal orientation
  • FIG. 5 shows a fifth exemplary embodiment of an electrolytic cell in a horizontal orientation
  • FIG 6 a vertically aligned electrolysis cell with components shown.
  • FIG. 1 shows a vertically oriented electrolysis cell 2, which is part of an electrolyzer (not shown here) for splitting water into hydrogen f H 2 and oxygen f 0 2 by means of electric current.
  • electrolysis cells 2 are connected one behind the other in electrolysis stacks.
  • Each electrolysis cell 2 has a proton-permeable polymer membrane 4, on which electrodes 6, 8 rest on both sides, to which an external voltage is applied during operation.
  • a first water supply line 10 is provided for supplying water to an anode space 12.
  • the oxygen f O 2 generated in the electrolysis cell 2 is removed from the anode space 12 via an oxygen f product line 14.
  • a hydrogen product line 16 is provided for discharging the hydrogen produced from a cathode space 18.
  • a second water supply line 20 is also connected on the cathode side. Water therefore circulates not only through the anode space 12, but also through the cathode space 16.
  • a control system 22 is provided for controlling the operation of the electrolysis stacks, which is symbolically indicated by the block 22.
  • a higher pressure p a is set in the anode chamber 12 than the pressure p k in the cathode chamber 18, the anode-side pressure p a being approximately 2 to 20 times higher.
  • the pressure p a in the anode chamber 12 is in particular 4 to 7 times higher than the pressure p k in the cathode chamber 18. In this way, the negative consequences of membrane damage during operation of an electrolyzer are minimized, since less foreign gas gets through if the membrane 4 breaks through.
  • the electrolysis cell 2 in FIG. 2 has a horizontal structure in which the anode space 12 is arranged above the cathode space 18.
  • the cathode space 18 is only partially flooded, i.e. H .
  • water is introduced into the cathode space 18 via the second water supply line 20, the space is not completely filled with water.
  • the horizontal electrolysis cell 2 according to FIG. 3 differs from the electrolysis cell 2 in FIG. 2 only in that the anode chamber 12 and the cathode chamber 18 are not the same size, but the anode chamber 12 is larger than the cathode chamber 18, i.e. there is an asymmetrical arrangement of the polymer membrane 4 with the electrodes 6, 8.
  • FIG 6 shows further components of the electrolyzer and how they interact during operation.
  • a recombination catalyst 24 for recombination in which the hydrogen H 2 and the oxygen O 2 are recombined to form water, is integrated in the hydrogen product line 16.
  • temperature sensors 26, 28 are installed before and after the recombination catalyst 22, each of which records a temperature value T 2 , T 2 in the hydrogen product line 16.
  • the temperature values T 2 , T 2 are made available to the control system 22, and from this the control system 22 forms a temperature difference value AT, which is compared with a predetermined threshold value T s .
  • a measured temperature value such as T 2 or another temperature correlated with the temperature value T 2 can be used directly. In this way, a temperature development of the exothermic reaction in the recombination catalyst 24 is monitored.
  • the hydrogen product line 16 is blocked by the valve 30 and a bypass valve 32 is opened so that the mixture of hydrogen H 2 and oxygen O 2 via a bypass line 34 is directed out. If the threshold value T s is exceeded, the electrical current to the respective electrolysis stack is also switched off for safety reasons. In addition, a nitrogen valve 36 installed in the second water supply line 20 is opened so that nitrogen N 2 or another inert gas is introduced into the cathode spaces 18 of the switched-off electrolysis stack.

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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 électrolyseur conçu pour décomposer de l'eau en hydrogène (H2) et en oxygène (O2) au moyen d'un courant électrique, comprenant une pluralité de cellules d'électrolyse (2) qui sont réparties en piles d'électrolyse, chaque cellule d'électrolyse (2) comportant une membrane polymère (4) perméable aux protons, sur laquelle sont appliquées des deux côtés des électrodes (6, 8), auxquelles est appliquée une tension extérieure lors du fonctionnement, une première conduite d'alimentation en eau (10) étant prévue côté anode pour amener de l'eau à un compartiment anodique (12), une conduite de production d'oxygène (14) étant raccordée pour évacuer l'oxygène produit (O2) du compartiment anodique (12) et, une conduite de production d'hydrogène (16) étant prévue côté cathode pour évacuer l'hydrogène produit (H2) d'un compartiment cathodique (18), comprenant en outre un système de commande (22) pour commander le fonctionnement de la pile d'électrolyse. L'objectif de l'invention est de garantir un fonctionnement sûr de l'électrolyseur et de minimiser les conséquences négatives d'un endommagement de la membrane lors du fonctionnement d'un électrolyseur. À cet effet, le système de contrôle (22) est conçu pour régler une pression (pa) plus élevée dans le compartiment anodique (12) que dans le compartiment cathodique (18), la pression (pa) dans le compartiment anodique (12) étant 2 fois à 20 fois, en particulier 4 fois à 7 fois plus élevée que la pression (pk) dans le compartiment cathodique (18).
EP23765223.5A 2022-09-26 2023-09-04 Électrolyseur et procédé pour faire fonctionner un électrolyseur Pending EP4558662A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102022210095.6A DE102022210095A1 (de) 2022-09-26 2022-09-26 Elektrolyseur sowie Verfahren zum Betrieb eines Elektrolyseurs
PCT/EP2023/074104 WO2024068185A2 (fr) 2022-09-26 2023-09-04 Électrolyseur et procédé pour faire fonctionner un électrolyseur

Publications (1)

Publication Number Publication Date
EP4558662A2 true EP4558662A2 (fr) 2025-05-28

Family

ID=87933654

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23765223.5A Pending EP4558662A2 (fr) 2022-09-26 2023-09-04 Électrolyseur et procédé pour faire fonctionner un électrolyseur

Country Status (4)

Country Link
EP (1) EP4558662A2 (fr)
CN (1) CN119948207A (fr)
DE (1) DE102022210095A1 (fr)
WO (1) WO2024068185A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102024102394A1 (de) * 2024-01-29 2025-07-31 Quest One Gmbh Elektrolysevorrichtung, System aus mehreren Elektrolysevorrichtungen und Verfahren zum Betreiben der Elektrolysevorrichtung oder des Systems

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6613215B2 (en) * 2000-09-27 2003-09-02 Proton Energy Systems, Inc. Method for electrolysis of water using a polytetrafluoroethylene supported membrane in electrolysis cells
US20110198232A1 (en) * 2010-02-15 2011-08-18 Hamilton Sundstrand Corporation High-differential-pressure water electrolysis cell and method of operation
EP2554713A1 (fr) * 2011-08-01 2013-02-06 Siemens Aktiengesellschaft Dispositif de rénovation d'un flux de produits d'une installation d'électrolyse
FR3062856B1 (fr) * 2017-02-14 2019-04-12 AREVA H2Gen Entretoise d'electrolyseur et electrolyseur equipe d'une telle entretoise
EP3581683A1 (fr) * 2018-06-15 2019-12-18 Siemens Aktiengesellschaft Dispositif d'électrolyse pourvu d'un recombinateur et procédé de fonctionnement du dispositif d'électrolyse
EP3599292A1 (fr) 2018-07-27 2020-01-29 Siemens Aktiengesellschaft Unité d'électrolyse et procédé de fonctionnement de l'unité d'électrolyse
JP7108010B2 (ja) * 2020-11-24 2022-07-27 本田技研工業株式会社 水素・酸素製造システムの制御方法および水素・酸素製造システム
DE102021102535A1 (de) * 2021-02-03 2022-08-04 Airbus Defence and Space GmbH Vorrichtung zur Bereitstellung einer Gaskomponente sowie Fahrzeug mit einer solchen Vorrichtung
EP4108807A1 (fr) * 2021-06-24 2022-12-28 Siemens Energy Global GmbH & Co. KG Procédé de fonctionnement d'une installation d'électrolyse et installation d'électrolyse
EP4123052A1 (fr) * 2021-07-19 2023-01-25 Siemens Energy Global GmbH & Co. KG Procédé de fonctionnement d'une installation d'électrolyse et installation d'électrolyse

Also Published As

Publication number Publication date
WO2024068185A3 (fr) 2024-06-06
WO2024068185A2 (fr) 2024-04-04
CN119948207A (zh) 2025-05-06
DE102022210095A1 (de) 2024-03-28

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