EP4573233A2 - Dispositif d'électrolyse à circulation naturelle - Google Patents

Dispositif d'électrolyse à circulation naturelle

Info

Publication number
EP4573233A2
EP4573233A2 EP23768116.8A EP23768116A EP4573233A2 EP 4573233 A2 EP4573233 A2 EP 4573233A2 EP 23768116 A EP23768116 A EP 23768116A EP 4573233 A2 EP4573233 A2 EP 4573233A2
Authority
EP
European Patent Office
Prior art keywords
cell
cathodic
membrane
electrolysis device
alkaline solution
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
EP23768116.8A
Other languages
German (de)
English (en)
Inventor
Bianca GRABNER
Marie-Gabrielle MACHERHAMMER
Matthias RANZ
Michael Richter
Alexander TRATTNER
Bernd CERMENEK
Philipp Schneider
Dietmar Neubacher
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.)
H2i GreenHydrogen GmbH
Original Assignee
H2i GreenHydrogen 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 H2i GreenHydrogen GmbH filed Critical H2i GreenHydrogen GmbH
Publication of EP4573233A2 publication Critical patent/EP4573233A2/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
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
    • 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 object of the present invention was to overcome the disadvantages of the prior art and to provide a device and a method by means of which particularly advantageous effects with regard to the operational safety and effectiveness of the device can be achieved. This task is solved by a device and a method according to the claims.
  • the membrane or the membrane-electrode unit is not seen as an active means of generating flow.
  • the input of electrical energy to the electrodes and the outgassing or production of products of the electrochemical reaction and the flow induced by the products in the half cells are also not seen as active means of generating flow.
  • the process of electrolysis results in mass transport through the membrane at the membrane-electrode unit due to diffusion processes, which mass transport occurs as a passive effect of the electrochemical reaction or the concentration difference between the anodic half-cell and the cathodic half-cell of the respective solutions or liquids or .Electrolytes in the half cells and the resulting osmotic pressure.
  • Normal operation means an operating state in which a product such as molecular hydrogen is continuously produced by means of an electrochemical reaction. Operating states such as maintenance, flushing and the like are therefore not to be understood as normal operation.
  • the electrolysis device can comprise a cathode inlet and a cathode outlet, wherein the cathode inlet and the cathode outlet can be fluidically coupled to the cathodic half cell.
  • the cathode inlet and the cathode outlet can also be fluidically coupled.
  • the transport of the OH ions can be ensured from the cathodic half cell to the anodic half cell using H2O carrier molecules.
  • H2O carrier molecules Through osmosis or the attempt to equalize the concentration of the system, since the initial filling quantity of electrolytes in the cathodic half-cell is not changed by active agents in normal operation, ultrapure water or water molecules are transported from the anodic half-cell to the cathodic half-cell through the membrane in normal operation . Ultrapure water or water molecules can therefore be provided as a starting material for the production of molecular hydrogen in the cathodic half-cell exclusively via diffusion processes through the membrane. Subsequently, during normal operation of the electrolysis device, the ultrapure water required for the production of hydrogen is supplied exclusively to the anodic half cell.
  • the initial filling quantity of alkaline solution can be accommodated in the cathodic half-cell and in a fluid channel and/or fluid tank fluidically coupled to the cathodic half-cell, whereby a receiving volume is defined, with the alkaline solution in the receiving volume being im Normal operation of the electrolysis device no forced circulation, no forced circulation and / or no forced movement, except for the movement that occurs itself due to the electrochemical reaction.
  • the supply of educts for the electrochemical reaction in the cathodic half cell can be provided exclusively by diffusion processes of the educts through the membrane-electrode unit.
  • the structural design of the electrolysis device is therefore simplified, since fresh water or ultrapure water must be supplied to the electrolysis device exclusively via the anodic half cell during normal operation.
  • the electrolysis device can be manufactured more economically, especially if it is intended for cathode-side printing operation, since fewer components or pressure-safe components are necessary.
  • the cathodic electrode and/or a cathode-side surface of the membrane is/are designed to be hydrophilic. This promotes the diffusion processes already described or the entire process of the electrochemical reaction in the electrolysis device, which increases the effectiveness and subsequently the economy of the electrolysis device.
  • the anodic electrode and/or the cathodic electrode is or are formed by applying catalytically active materials to the membrane and/or by applying catalytically active materials to porous support structures contacted with the membrane.
  • a porous carrier material such as a metal foam or the like improves the diffusion or transport processes of the educts and products of the electrochemical reaction in the electrolysis device.
  • a differential pressure between the anodic half cell and the cathodic half cell can be recorded by the membrane-electrode unit, the differential pressure being in the range between 0 bar and 100 bar, or in particular between 5 bar and 30 bar.
  • the advantage here is that the intended pressure of the electrolysis product does not have to be generated using another means, since the electrolysis device is already operated under pressure. This is advantageous in relation to the overall efficiency of the electrolysis device when integrated into a generation system for hydrogen, for example.
  • the electrolysis device according to the invention in which Since the half cells are completely flooded with electrolyte, this is an advantage because the gas volume in the half cells is particularly small and the electrolysis device can therefore be operated quickly and dynamically.
  • an electrolysis cell stack which electrolysis cell stack comprises several anodic half-cells, cathodic half-cells and membrane electrode units arranged in a row in accordance with the functional design of the electrolysis device according to the invention in the sense of the electrochemical reaction.
  • the cathodic half-cells can be fluidically coupled by means of at least one flow channel, the cathodic half-cells and the at least one flow channel forming a cathode volume, wherein during operation of the electrolysis cell stack, an initial filling amount of alkaline solution in the cathode volume exclusively through diffusion processes through the membrane electrode units and /or can be changed by electrochemical reaction of educts or the alkaline solution in the membrane-electrode units.
  • the advantage here is that the cathode volume can be made available as a combination of all cathodic half-cells of the electrolysis cell stack to accommodate the alkaline solution. As a result, particularly when the individual electrolysis devices have a high output, transient effects are dampened when they are started up into normal operation. This increases the safety of the electrolysis process.
  • an electrolysis system which electrolysis system comprises several electrolysis cell stacks according to the invention.
  • the electrolysis system comprises at least one connecting line, wherein the cathode volumes of the electrolysis cell stacks can be fluidically coupled by means of the connecting line, the electrolysis system comprising a gas separation device, the gas separation device being fluidically coupled to the cathode volumes and being set up to do so. in order to separate the product produced by means of an electrochemical reaction from the alkaline solution, whereby the discharge of the alkaline solution from the cathode volumes can be prevented by means of the gas separation device.
  • the advantage here is that the fluidically coupled cathode volumes can be provided as a combination of all cathodic half cells of the electrolysis system to accommodate the alkaline solution. As a result, particularly when the electrolysis system has a high output, transient effects are dampened when it is started up into normal operation. This increases the safety of the electrolysis process.
  • the use of the electrolysis system according to the invention is particularly advantageous if the product is molecular hydrogen.
  • a process for producing hydrogen by electrochemical reaction from an aqueous, alkaline solution comprises the following process steps:
  • the electrolysis device comprises an anodic half-cell and a cathodic half-cell, the anodic half-cell and the cathodic half-cell being separated by means of a membrane and the cathodic half-cell being permeable by the alkaline solution and the anodic half-cell by an aqueous, alkaline solution or ultrapure water, the anodic half cell comprising an anodic electrode and the cathodic half cell comprising a cathodic electrode, the anodic electrode, the cathodic electrode and the membrane forming a membrane-electrode unit;
  • the initial filling amount of alkaline solution in the cathodic half cell during normal operation of the electrolysis device or when voltage is applied between the anodic electrode and the cathodic electrode is determined exclusively by diffusion processes through the membrane-electrode unit or through the membrane and / or through electrochemical reaction of the alkaline solution in the membrane-electrode unit is changed.
  • an anion exchange membrane is used as the membrane.
  • the advantage here is that by completely filling the cathodic half cells with the alkaline solution during normal operation, a natural flame barrier is present for the hydrogen produced during hydrogen electrolysis.
  • a further advantage is that during normal operation the membrane is completely wetted with the alkaline solution at all times, so that the membrane is not at risk of drying out and is therefore exposed to local overloads due to overheating, thus improving the service life of the membrane used.
  • the process according to the invention can further comprise the following process step:
  • an operating liquid in the anodic half cell the operating liquid being ultrapure water and/or an aqueous, alkaline solution, the operating liquid being supplied exclusively to the anode side during normal operation of the electrolysis device.
  • the anodic half cell initially contains an alkaline electrolyte or an alkaline solution with a first molar concentration that corresponds at most to the second molar concentration of the electrolyte in the cathodic half cell. It is also conceivable that the anodic half cell can be operated with ultrapure water.
  • Gas separation from the cathodic half cell and differential pressure The product gas is removed from the system at the highest point of the cathode volume.
  • the constructive design or by means of the separation device or the gas separation device prevents the alkaline solution from being discharged from the cathode volume.
  • the hydrogen gas or the entire cathode volume can be kept under pressure using external pressure maintaining devices. The penetration of higher external system pressures into the cathode volume when starting up the electrolysis device can be prevented by a check valve in the gas line.
  • Self-regulating system In contrast to known systems, this difference in substance concentration and mass between the anodic half cell and the cathodic half cell is not compensated for by pumps or pipes, but rather is brought about in a targeted manner.
  • the differential pressure between the anodic half-cell and the cathodic half-cell is established depending on the applied electrical power and the prevailing differential pressure a certain liquid level or filling quantity or an electrolyte concentration in the cathodic half cell.
  • the alkaline liquid in the cathode volume is replaced at regular maintenance intervals. To do this, all of the liquid is drained at the lowest point and the cathode volume is then refilled.
  • the alkaline liquid in the anodic half cell is processed or exchanged centrally in an electrolysis system according to the invention.
  • FIG. 1 shows an electrolysis device with an anodic half cell and a cathodic half cell
  • FIG. 2 shows an electrolysis cell stack comprising several electrolysis devices
  • 3 shows an electrolysis system comprising several electrolysis cell stacks
  • the cathodic half cell 3 and the anodic half cell 2 are separated from each other by means of a membrane 4.
  • the anodic half cell 2 comprises an anodic electrode 5, wherein the anodic electrode 5 can be arranged adjacent to the anode-side surface of the membrane 4.
  • the cathodic half cell 3 comprises a cathodic electrode 6, wherein the cathodic electrode 6 can be arranged adjacent to the cathode-side surface of the membrane 4.
  • the anodic electrode 5, the cathodic electrode 6 and the membrane 4 together form a membrane-electrode unit 7, which membrane-electrode unit 7 can include further elements.
  • the anodic half cell 3 is separated from the cathodic half cell 2 by means of the membrane 4, whereby the membrane 4 can be designed as an anion exchange membrane.
  • the anodic electrode 5 and the cathodic electrode 6 can be formed by a porous metallic conductor such as a metal foam or can be applied directly to the membrane 4.
  • the anodic half cell 2 can be flooded with an aqueous, alkaline solution or ultrapure water during operation of the electrolysis device 1.
  • the cathodic half cell 3 can be flooded with an aqueous, alkaline solution during operation of the electrolysis device 1.
  • the cathodic half cell 3 is filled with an initial amount of alkaline solution.
  • no further alkaline solution is actively supplied to or removed from the cathodic half cell 3.
  • an alkaline solution can be used for the electrolysis process.
  • ultrapure water can also be used in the anodic half cell 2, in particular with a correspondingly adapted membrane 4 or membrane-electrode unit 7.
  • a membrane 4 is to be understood as meaning a separating but electrolytically conductive partition in the electrolysis device 1, which is essentially an electrochemical cell.
  • the diaphragm for example, can be seen as synonymous with membrane 4.
  • the separation of the half cells 2, 3 by the membrane 4 allows operation with different concentrations of the alkaline solution or with different liquids or electrolytes in the half cells 2, 3.
  • the membrane 4 can be designed to be so robust that a differential pressure in the range between 0 bar and 100 bar can be present between the anodic half cell 2 and the cathodic half cell 3.
  • filling both half cells 2, 3 with an electrolyte or with ultrapure water or an alkaline solution promotes the absorption of such differential pressures.
  • the safety of the electrolysis device 1 is improved by filling both half cells 2, 3, since a flame barrier is formed by means of the filling when producing products that are flammable in the open atmosphere.
  • Diffusion processes are understood to mean all those transport processes through the membrane 4 or through the membrane-electrode unit 7, which include gas diffusion, water transport mechanisms, gas permeation or the diffusion of other educts or products of the electrochemical reaction of the electrolysis device 1.
  • the membrane 4 or the membrane-electrode unit 7 is not seen as an active means of generating flow.
  • the input of electrical energy to the electrodes 5, 6 and the outgassing or production of products of the electrochemical reaction and the flow induced by the products in the half cells 2, 3 are also not seen as active means of generating flow.
  • the process of electrolysis creates a mass transport through the membrane 4 on the membrane-electrode unit 7 due to diffusion processes, which mass transport occurs as a passive effect of the electrochemical reaction or the concentration difference between the anodic half-cell 2 and the cathodic half-cell 3 Solutions or liquids in the half cells 2, 3 and a resulting osmotic pressure.
  • Normal operation here means an operating state in which a product such as molecular hydrogen is continuously produced by means of an electrochemical reaction. Operating states such as maintenance, flushing and the like are therefore not to be understood as normal operation.
  • the separation device 10 can be fluidically coupled to the fluid channel 8. By means of the separation device 10 can It can be ensured that a product or product gas resulting from the electrolysis process can be removed without the alkaline solution being discharged from the receiving volume 9.
  • Electrolysis device anodic half cell cathodic half cell membrane anodic electrode cathodic electrode

Landscapes

  • 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)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un dispositif d'électrolyse (1) conçu pour produire de l'hydrogène par réaction électrochimique à partir d'une solution aqueuse alcaline, le dispositif d'électrolyse (1) comprenant une demi-cellule anodique (2) et une demi-cellule cathodique (3). La demi-cellule anodique (2) et la demi-cellule cathodique (3) sont séparées par une membrane (4) et la demi-cellule cathodique (3) peut être traversée par la solution alcaline. La demi-cellule anodique (2) comprend une électrode anodique (5) et la demi-cellule cathodique (3) comprend une électrode cathodique (6), l'électrode anodique (5), l'électrode cathodique (6) et la membrane (4) formant un ensemble membrane-électrode (7). En outre, une quantité initiale de solution alcaline dans la demi-cellule cathodique (3) peut être modifiée lors du fonctionnement normal du dispositif d'électrolyse (1) exclusivement par des processus de diffusion à travers l'ensemble membrane-électrode (7) et/ou par réaction électrochimique de la solution alcaline dans l'ensemble membrane-électrodes (7).
EP23768116.8A 2022-08-19 2023-08-17 Dispositif d'électrolyse à circulation naturelle Pending EP4573233A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA50642/2022A AT525914B1 (de) 2022-08-19 2022-08-19 Elektrolysevorrichtung mit Naturumlauf
PCT/AT2023/060278 WO2024036353A2 (fr) 2022-08-19 2023-08-17 Dispositif d'électrolyse à circulation naturelle

Publications (1)

Publication Number Publication Date
EP4573233A2 true EP4573233A2 (fr) 2025-06-25

Family

ID=87973340

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23768116.8A Pending EP4573233A2 (fr) 2022-08-19 2023-08-17 Dispositif d'électrolyse à circulation naturelle

Country Status (5)

Country Link
EP (1) EP4573233A2 (fr)
CN (1) CN119790190A (fr)
AT (1) AT525914B1 (fr)
AU (1) AU2023326035B2 (fr)
WO (1) WO2024036353A2 (fr)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1398498B1 (it) * 2009-07-10 2013-03-01 Acta Spa Dispositivo per la produzione on demand di idrogeno mediante elettrolisi di soluzioni acquose.
ITMI20092139A1 (it) * 2009-12-03 2011-06-04 Industrie De Nora Spa Diaframma a porosità predefinita e metodo di ottenimento
TW201504477A (zh) * 2013-07-17 2015-02-01 Industrie De Nora Spa 電解電池和鹼溶液電解槽以及在電池內之電解方法
US20150349368A1 (en) * 2014-05-29 2015-12-03 Christopher G. ARGES Reversible alkaline membrane hydrogen fuel cell-water electrolyzer
KR102664170B1 (ko) * 2018-07-27 2024-05-10 가부시끼가이샤 도꾸야마 가스 제조 장치 및 가스 제조 방법
DE102019129071A1 (de) * 2019-08-20 2021-02-25 Deutsches Zentrum für Luft- und Raumfahrt e.V. Elektrolyseur und Verfahren zum Aufspalten von Wasser
DE102019123858A1 (de) * 2019-09-05 2021-03-11 Thyssenkrupp Uhde Chlorine Engineers Gmbh Kreuzflusswasserelektrolyse
JP7709754B2 (ja) * 2019-11-21 2025-07-17 エヌイー．エム．イー．エスワイエス．エスアールエル 水電解方法および装置
KR102434620B1 (ko) * 2020-03-23 2022-08-23 한국과학기술연구원 외부 전력 없이 독립적으로 구동되는 태양광을 이용한 수소 생산 및 저장 시스템
DE102020206576A1 (de) * 2020-05-26 2021-12-02 Thyssenkrupp Uhde Chlorine Engineers Gmbh Elektrolysezelle, Verfahren zum Betrieb einer solchen Zelle und Elektrolyseur

Also Published As

Publication number Publication date
CN119790190A (zh) 2025-04-08
AU2023326035B2 (en) 2026-03-12
AU2023326035A1 (en) 2025-03-06
AT525914A4 (de) 2023-09-15
WO2024036353A3 (fr) 2024-05-30
AT525914B1 (de) 2023-09-15
WO2024036353A2 (fr) 2024-02-22

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