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WO2025099110A1 - Système d'électrolyse - Google Patents

Système d'électrolyse Download PDF

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Publication number
WO2025099110A1
WO2025099110A1 PCT/EP2024/081415 EP2024081415W WO2025099110A1 WO 2025099110 A1 WO2025099110 A1 WO 2025099110A1 EP 2024081415 W EP2024081415 W EP 2024081415W WO 2025099110 A1 WO2025099110 A1 WO 2025099110A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
gas
stack
electrolysis system
water tank
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
PCT/EP2024/081415
Other languages
German (de)
English (en)
Inventor
Andreas Genssle
Waldemar KOENIG
Markus BRENK
Frederik Hug
Freya Kiesewetter
Tim Sebastian Entenmann
Annika UTZ
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.)
Robert Bosch GmbH
Original Assignee
Robert Bosch 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 Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of WO2025099110A1 publication Critical patent/WO2025099110A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C25B15/083—Separating products
    • 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
    • C25B9/70—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
    • C25B9/77—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 electrolysis system which can be used for the electrolytic splitting of water into hydrogen and oxygen using electrical energy.
  • Electrical energy can be converted into chemical energy in the form of hydrogen.
  • an electrolyzer which comprises an electrochemical cell with an anode and a cathode compartment.
  • the anode and cathode compartments are separated from each other by a semipermeable membrane.
  • the membrane is coated with an anode electrode on the anode side and a cathode electrode on the cathode side, between which a direct electrical voltage can be applied.
  • the anode compartment and—depending on the type of electrolyzer—also the cathode compartment are filled with water or an electrolytic aqueous solution.
  • Electrolyzers with this operating principle are of the so-called PEM type, meaning that the semipermeable membrane is permeable to protons – i.e., H + ions – while the membrane is largely impermeable to other substances.
  • Other electrolyzers are also known, for example, those in which the membrane is permeable to OH - or O 2 ' ions. is permeable.
  • An example of an electrolysis system is known from DE 10 2021 214 205 A1.
  • the electrolysis system according to the invention has the advantage that it is possible to purge and thus remove the reaction gases from an electrolysis stack without contaminating the desired product gases - in particular the hydrogen - or subjecting the stack to strong chemical or mechanical stress.
  • the electrolysis system comprises an electrochemical stack with an inlet through which water can be introduced, and an outlet through which water and/or gas can be discharged from the stack, wherein the outlet is connected via a line to a gas-water separator in which the gas escaping from the stack is separated from the escaping water.
  • the gas-water separator is connected via a drain line to a water tank for storing the separated water, wherein the water tank is connected to the stack inlet via a purge line.
  • the stack If the stack is shut down, practically no new hydrogen is produced, but hydrogen gas is still present in the stack and can mix with the oxygen that is also present through diffusion processes. To prevent this, the stack must be flushed or inerted with water after shutdown (so-called purging) to prevent the mixing of hydrogen and oxygen.
  • the water separated in the gas-water separator gas liquid separator: GLS
  • GLS gas liquid separator
  • the water is produced directly at the stack or GLS and does not have to be added separately, so that the stack can be flushed and thus safely shut down at any time, regardless of an external supply or the availability of water.
  • a conveying device in particular a pump, can be provided in the flushing line.
  • This pump supplies the water from the water tank to the stack at a predeterminable pressure, so that, in particular, the cathode chamber of the stack can be flushed at a pressure corresponding to the operating pressure in the cathode chamber. Flushing at operating pressure reduces the mechanical stress on the stack and thus increases its service life.
  • the water tank is designed as a pressurized water tank in which the water is stored at the same pressure as in the GLS.
  • multiple water tanks can be filled from the GLS. Purging multiple stacks with water from the water tank(s) is also easily possible, provided the water volume is sufficient.
  • the volume of the water tank connected to the reaction chamber is greater than or equal to the volume in the stack connected to the inlet. If multiple stacks are to be flushed, the volume of the water tank corresponds at least to the sum of all stack volumes. This ensures that the corresponding space in the stack can be completely filled with water and thus flushed at least once.
  • gas-water separator Another advantageous feature of the gas-water separator is a water connection for supplying purified water. Especially at the beginning of operation, only a small amount of water is available in the gas-water separator, as this water is gradually formed, especially in the cathode chamber. Therefore, the electrolyzer must be operated for some time to ensure sufficient water is available for purging. However, to ensure sufficient water is available at all times, the gas-water separator can be filled with a sufficient amount of water via the water connection before operation begins. The water level in the gas-water separator is preferably monitored using a level sensor.
  • the stack has an anode compartment and a cathode compartment separated by a semipermeable membrane. Both reaction compartments can be connected to a GLS, and the water can be used to purge the anode compartment or the cathode compartment.
  • the water from the cathode compartment can be advantageously used to flush the cathode compartment, as it is already under sufficient pressure.
  • the water from the anode compartment can also be used for this purpose, although it may need to be compressed using a pump.
  • drawing schematically shows various embodiments of the electrolysis system according to the invention.
  • Fig. 1 is a schematic representation of the electrolysis system, showing only the essential components
  • Fig. 2 is a schematic representation of an electrochemical cell as part of a stack
  • Fig. 3, 4, 5, 6, 7 and 8 show further embodiments of the electrolysis system according to the invention in the same representation as Fig. 1.
  • Fig. 1 shows a first embodiment of an electrolysis system according to the invention in a schematic representation, with only the essential components being shown.
  • the electrolysis system comprises an electrochemical stack 1, which comprises at least one, but usually a plurality of electrochemical cells 2.
  • Fig. 2 shows a schematic representation of an electrochemical cell 2.
  • the electrochemical cell 2 comprises two reaction chambers, an anode chamber 3 and a cathode chamber 4, which are separated from one another by a semipermeable membrane 5.
  • An anode electrode 6 is arranged on the side of the semipermeable membrane 5 facing the anode chamber 3 and a cathode electrode 7 is arranged on the side facing the cathode chamber 4, wherein the electrodes 6, 7 can be designed, for example, as a coating of the membrane 5.
  • the anode chamber 3 is flushed with water (not shown in the drawing) and an electrical direct voltage is applied between the anode electrode 6 and the cathode electrode 7.
  • an electrical direct voltage is applied between the anode electrode 6 and the cathode electrode 7.
  • the hydrogen diffuses through the semipermeable membrane 5 into the cathode compartment 4, where IT ions recombine with the electrons of the cathode electrode 7 to form hydrogen and flow out as IT molecules via a drain line 10.
  • the cathode chamber 4 has an inlet 8 and an outlet 9.
  • the hydrogen produced in the cathode chamber 4 and the water diffused in are discharged via the outlet 9 as well as via the inlet 8 and a connecting line 14, whereby a valve 40 in the connecting line 14 is opened.
  • the connecting line 14 may also be omitted.
  • water can also be introduced into the cathode chamber 4 via the inlet 8 and flow out via the outlet 9, whereby the valve 40 is then closed.
  • the anode chamber 3 can also have an inlet and an outlet to supply the anode chamber 3 with water and to discharge gas and/or water from the anode chamber 3.
  • a line analogous to the connecting line 14 is not provided for the anode chamber 3, since it is constantly flushed with water even during normal operation.
  • the cathode compartment 4 can be flushed with pure water, as described below. This can also be applied to the anode compartment 3 in the same way, which can be flushed with water, particularly when the electrochemical stack is shut down.
  • the cathode compartment 4 is connected to a gas-water separator 11 via the drain line 10. Hydrogen gas is generated in the cathode compartment 4 during operation of the electrolyzer—i.e., the electrochemical stack 1.
  • drag water constantly penetrates through the membrane 5 from the anode compartment 3 into the cathode compartment 4 during operation, so that a mixture of hydrogen gas and water escapes via the drain line 10.
  • the gas-water separator 11 serves to separate the hydrogen gas from the water.
  • the hydrogen gas is discharged via a gas outlet 15 and collected for further use, for example, in a pressure vessel (not shown here).
  • the water collected in the gas-water separator 11 is drained into a water tank 20 via a drain line 13, with a drain valve 32 arranged in the drain line 13.
  • Multiple stacks 1 may also be present, illustrated here as an example by a further stack 1a.
  • the further stack 1a is also connected via a line 10a to the same gas-water separator 11, where the separation of gas and water from both stacks 1, 1a takes place.
  • the inlet can be connected to the outlet via a connecting line 14a with a valve 40a.
  • the electrochemical stack 1 If the electrochemical stack 1 has been operated for a while, more and more water collects in the gas-water separator 11. As soon as a maximum water level is reached in the gas-water separator 11, the remaining water is drained via a drain line 13 by opening a drain valve 32 into a water tank 20, where it is stored.
  • a relatively high pressure of, for example, 40 bar (4 MPa) prevails in the cathode chamber 4, and accordingly, this pressure also prevails in the gas-water separator 11 and the water tank 20.
  • the water tank 20 is then designed as a pressurized water tank in which the water can be stored for extended periods of time under a flushing pressure that at least essentially corresponds to the pressure in the gas-water separator 11.
  • a diaphragm pressure accumulator in which the water is always under pressure even when the fill level changes, is useful in this case.
  • the water tank 20 is connected to the inlet 8 of the electrochemical stack 1 via a flushing line 22, wherein a flushing valve 33 is arranged in the flushing line and is opened as needed.
  • the other stack 1a can also be flushed via the flushing line 22. If necessary, additional valves can be provided to selectively flush only one of the stacks 1, 1a or all stacks 1, 1a simultaneously.
  • a minimum volume must be present in the water tank 20 or in the gas-water separator 1. If this is not the case, additional deionized water can be supplied from a water treatment system, for example, an EDI (electrodeionization) device, which can produce ultrapure water.
  • the EDI 25 is connected to the gas-water separator 11 via a line 27, in which a pump 26 is arranged, so that deionized water can be supplied to the gas-water separator 11.
  • An additional line 29 with another pressure pump 28 and a shut-off valve 30 also allows the supply of deionized water to the water tank 20, so that the required amount of water can be supplied to the water tank 20 and the gas-water separator 11 as needed.
  • the fill level 35 in the gas-water separator 11 is monitored by a fill level sensor 36 to ensure that the water level does not exceed or fall below a certain level. If there is an excess of water in the gas-water separator Separator 11 , for example because the water tank 20 is already completely filled, this is drained via a drain line 16 with a drain valve in 17.
  • a drain line can additionally or alternatively also be provided in the water tank 20 in order to drain off excess water.
  • the electrolysis system works as follows: During operation of the electrochemical stack 1, hydrogen gas is produced in the cathode compartment 4. Additionally, water from the anode compartment 3 passes through the membrane 5 into the cathode compartment 4, so that a mixture of water and hydrogen gas from the cathode compartment 4 passes through the outlet 9 and the line 10 into the gas-water separator 11. At the same time, oxygen gas is produced in the anode compartment 3. This oxygen gas is removed from the anode compartment 3 dissolved in water and fed to another gas-water separator (not shown in Fig. 1), where the oxygen is separated from the hydrogen. The oxygen can simply be vented to the atmosphere or used for other purposes, while the water, which is essentially at ambient pressure, can be pumped back into the anode compartment 3. The water separated in the gas-water separator 11 is further conveyed to the water tank 20 via the drain line 13 by opening the drain valve 32 as soon as a sufficient fill level is reached in the gas-water separator 11. The water is stored there for flushing the stack 1.
  • the hydrogen gas must be removed from the cathode compartment 4 of all electrochemical cells to prevent hydrogen and oxygen from mixing over time in the stack 1 or in the lines and valves. Hydrogen is very diffusive and, if left idle for a long time, can pass through the semi-permeable membrane 5 into the anode compartment 3.
  • the pressure in the water tank 20 is practically the same as in the gas-water separator 11 or in the cathode compartment 4, so that after the purge valve 33 is opened, the water is forced via the purge line 22 into the inlet 8 of the stack 1, where it flows through the cathode compartment 4 of the electrochemical cell 2 or all electrochemical cells 2 in the electrochemical stack 1.
  • the cathode chamber 4 can, for example, be flushed with a volume of water that corresponds to twice the volume of the cathode chamber 4. If the water that flushes the cathode chamber 4 returns directly to the pressurized water tank 20 via the gas-water separator 11, the flushing process can be restarted immediately. Otherwise, after the flushing valve 33 is closed, the water tank 20 is refilled with water from the gas-water separator 11 during normal operation of the electrolyzer.
  • Fig. 3 shows a further exemplary embodiment of the electrolysis system according to the invention, the essential difference compared to the exemplary embodiment according to Fig. 1 being a flushing pump 21 in the flushing line 22 and a bypass line 18, with which the water tank 20 can be bypassed.
  • a connecting line 14 analogous to the exemplary embodiment according to Fig. 1 is not shown here. If the high pressure of the gas-water separator 11 does not prevail in the water tank 20, but the water is stored there under a lower pressure, in particular ambient pressure, the water must be compressed with the aid of a flushing pump 21 in order to flush the stack 1.
  • the exemplary embodiment shown here also allows a flushing process bypassing the water tank 20, for example because it is already full and only a small amount of water is required for flushing, which can be taken directly from the gas-water separator 11.
  • a 3/2-way drain valve 32' is arranged in the drain line 13, so that the water from the gas-water separator 11 can be directed either into the water tank 20 or via the bypass line 18 directly to the pump 21.
  • the bypass line 18 enables the stack 1 to be flushed several times if the volume of the water tank 20 is smaller than the amount of water to be used for flushing. In this case, the water is directed through the stack 1 into the gas-water separator 11 and from there flows again into the stack 1 via the bypass line 18.
  • Fig. 4 shows a further embodiment in which each stack 1, 1a is connected to the water tank 20 via a separate flushing line 22, 22a. If necessary, a separate flushing pump 21a is provided in each flushing line 22, 22a, so that the water from the water tank 20 can be used to flush multiple stacks 1, 1a, with only two electrochemical stacks 1, 1a being shown here as an example. This is particularly advantageous if the stacks are operated at different operating points and the flushing should, for example, only be carried out for individual stacks.
  • Fig. 5 shows another embodiment of the electrolysis system.
  • the gas-water separator 11 is connected via several drain lines 13, 13a to a water tank 20, 20a (here, two water tanks are shown as an example), each of which can be filled with water.
  • both water tanks 20, 20a can be filled with deionized water from the EDI.
  • the water from the two water tanks 20, 20a is fed to a respective associated electrochemical stack 1, 1a when a rinsing process is intended.
  • Fig. 6 several water tanks 20, 20a can be connected together with a common flushing line 22, as shown in Fig. 6.
  • This flushing line 22 connects both water tanks 20, 20a with the electrochemical stacks 1, 1a, so that a more compact structure can be achieved.
  • the electrochemical stacks 1, 1a not to be flushed with water in parallel, but rather to be connected in series, so that the water first flows through the cathode compartment of the first electrochemical stack 1 and then the cathode compartment of the second electrochemical stack 1a.
  • the use of several water tanks 20, 20a is possible, as shown in Fig. 8.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Automation & Control Theory (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un système d'électrolyse comprenant une pile électrochimique (1) qui présente un orifice d'entrée (8) à travers lequel de l'eau peut être introduite et comprenant un orifice de sortie (9) à travers lequel de l'eau ou du gaz peut être évacué de la pile (1). L'orifice de sortie (9) est relié, par l'intermédiaire d'une conduite (10), à un séparateur gaz-eau (11) dans lequel le gaz sortant de la pile (1) est séparé de l'eau sortante. Le séparateur gaz-eau (11) est relié à un réservoir d'eau (20) par l'intermédiaire d'une conduite d'évacuation (13) afin de stocker l'eau séparée, le réservoir d'eau (20) étant relié à l'orifice d'entrée (8) de la pile (1) par l'intermédiaire d'une conduite de rinçage (22).
PCT/EP2024/081415 2023-11-07 2024-11-07 Système d'électrolyse Pending WO2025099110A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102023211004.0A DE102023211004A1 (de) 2023-11-07 2023-11-07 Elektrolysesystem
DE102023211004.0 2023-11-07

Publications (1)

Publication Number Publication Date
WO2025099110A1 true WO2025099110A1 (fr) 2025-05-15

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Application Number Title Priority Date Filing Date
PCT/EP2024/081415 Pending WO2025099110A1 (fr) 2023-11-07 2024-11-07 Système d'électrolyse

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DE (1) DE102023211004A1 (fr)
WO (1) WO2025099110A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6375812B1 (en) * 2000-03-13 2002-04-23 Hamilton Sundstrand Corporation Water electrolysis system
KR20030043917A (ko) * 2000-07-26 2003-06-02 신코 판텍 가부시키가이샤 수소·산소 공급 시스템
US20210395116A1 (en) * 2020-06-22 2021-12-23 Hyundai Motor Company Water electrolysis system
DE102021214205A1 (de) 2021-12-13 2023-06-15 Robert Bosch Gesellschaft mit beschränkter Haftung Elektrolysesystem und Elektrolyseverfahren zur Elektrolyse von Wasser
DE102022202398A1 (de) * 2022-03-10 2023-09-14 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zum Betrieb eines Elektrolyseurs
US20230340675A1 (en) * 2022-04-25 2023-10-26 Hydrogenics Corporation Hydrogen degassing using membrane

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017204177A1 (de) * 2017-03-14 2018-09-20 Robert Bosch Gmbh Verfahren zum Betreiben eines Elektrolysestacks, Elektrolysestack und Elektrolysesystem

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6375812B1 (en) * 2000-03-13 2002-04-23 Hamilton Sundstrand Corporation Water electrolysis system
KR20030043917A (ko) * 2000-07-26 2003-06-02 신코 판텍 가부시키가이샤 수소·산소 공급 시스템
US20210395116A1 (en) * 2020-06-22 2021-12-23 Hyundai Motor Company Water electrolysis system
DE102021214205A1 (de) 2021-12-13 2023-06-15 Robert Bosch Gesellschaft mit beschränkter Haftung Elektrolysesystem und Elektrolyseverfahren zur Elektrolyse von Wasser
DE102022202398A1 (de) * 2022-03-10 2023-09-14 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zum Betrieb eines Elektrolyseurs
US20230340675A1 (en) * 2022-04-25 2023-10-26 Hydrogenics Corporation Hydrogen degassing using membrane

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