WO2024068048A2 - Procédé et installation permettant la préparation d'un produit contenant de l'hydrogène en ayant recours à une électrolyse - Google Patents
Procédé et installation permettant la préparation d'un produit contenant de l'hydrogène en ayant recours à une électrolyse Download PDFInfo
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- WO2024068048A2 WO2024068048A2 PCT/EP2023/025411 EP2023025411W WO2024068048A2 WO 2024068048 A2 WO2024068048 A2 WO 2024068048A2 EP 2023025411 W EP2023025411 W EP 2023025411W WO 2024068048 A2 WO2024068048 A2 WO 2024068048A2
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- electrolysis
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 190
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 230000036961 partial effect Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 230000015556 catabolic process Effects 0.000 claims description 32
- 238000006731 degradation reaction Methods 0.000 claims description 32
- 239000012528 membrane Substances 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000002826 coolant Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 230000002596 correlated effect Effects 0.000 claims 1
- 238000004140 cleaning Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 239000003011 anion exchange membrane Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007620 mathematical function Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
-
- 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
- C25B15/021—Process control or regulation of heating or cooling
-
- 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
-
- 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
Definitions
- the invention relates to a method and a system for producing a hydrogen-containing product using electrolysis.
- Hydrogen can be produced by converting gaseous, solid or liquid carbon sources such as natural gas, naphtha or coal.
- Another way to produce hydrogen from corresponding carbon sources includes catalytic partial oxidation (POX, partial oxidation) and catalytic reforming in different configurations such as steam reforming or autothermal reforming. Combined methods can also be used here.
- hydrogen can also be produced electrolytically from water, as explained in the article mentioned in Ullmann's Encyclopedia of Industrial Chemistry, especially in Section 4.2, “Electrolysis”.
- AEL alkaline electrolysis
- AEM anion exchange membrane
- PEM proton exchange membrane
- the present invention relates in particular to water electrolysis and generally to low-temperature electrolysis, whereby any separators (such as diaphragms in alkaline electrolysis and membranes in electrolysis with proton or anion exchange membranes) are used. More specific embodiments of the invention take place either in the form of alkaline electrolysis or using anion- or proton-conducting ion exchange membranes.
- high-temperature electrolysis can also be carried out, which can also be carried out with alkaline electrolytes (i.e. as AEL) with adapted membranes, for example polysulfone membranes, as well as using solid oxide electrolysis cells (SOEC, Solid Oxide Electrolysis Cells) and high-temperature materials that conduct oxygen ions.
- AEL alkaline electrolytes
- SOEC Solid Oxide Electrolysis Cells
- the latter materials include in particular doped zirconium dioxide or doped oxides of other rare earths, which become technically significantly conductive at more than 600 ° C.
- Huhn et. al. “Recent advances in solid oxide cell technology for electrolysis,” Science 2020, Vol. 370, No. 6513, and Ebbesen et. al., “Poisoning of Solid Oxide Electrolysis Cells by Impurities,” J.
- High-temperature electrolysis which is carried out using one or more solid oxide electrolysis cells, can also be used for the electrochemical production of carbon monoxide from carbon dioxide.
- oxygen is formed on the anode side and carbon monoxide on the cathode side.
- the present invention has the object of facilitating the production of hydrogen or hydrogen-containing products (a hydrogen-containing product can be a mixture of hydrogen and other components or pure hydrogen) using electrolysis.
- the present invention proposes a method and a system for obtaining a hydrogen-containing product using electrolysis with the features of the independent patent claims.
- electrolysis or electrolysis cell is referred to below in the singular, it is understood that embodiments of the present invention are implemented with several electrolysis cells, whereby corresponding electrolysis cells can in particular be part of an electrolysis stack (cell stack, etc., English stack) of a known type, in which such electrolysis cells are present in large numbers.
- electrolysis stack a plurality of arrangements consisting of anode, electrolyte and cathode can be provided, with means for feeding in or removing the respective fluids to be processed or processed being provided on the anode and cathode sides. These are equipped with feed-in or
- electrolytic cells experience constant degradation after they are put into operation. This degradation leads, among other things, to the cell voltage increasing over time at a constant current density or to the current density decreasing over time at a constant voltage. To date, the degradation mechanisms that lead to this phenomenon are not fully understood. However, the literature shows that there are clear factors, such as higher operating temperatures and/or greater load fluctuations, that lead to accelerated cell degradation.
- electrolysis plants operate at constant pressure and temperature throughout their entire service life.
- the temperature of the electrolytic cells can be controlled, for example, by the current or the inlet temperature of a cooling medium, for example water, which is supplied to the electrolytic cells.
- a cooling medium for example water
- the electrolysis is carried out using an electrolysis stack having a plurality of electrolysis cells, the electrolysis cells being subjected to an electrolysis voltage applied to the electrolysis stack during a continuous or discontinuous production period between a first time and a second time, and that the electrolysis cells are operated during the production period at an operating temperature set to a preset value.
- the preset value for the operating temperature is increased during a continuous or discontinuous partial period that lies after a preset time during the operating period.
- a “discontinuous” period is understood here in particular to mean an overall period that is made up of partial periods.
- an operating period in which electrolysis is carried out and the electrolysis cells are therefore supplied with electricity and corresponding media can be interrupted by various other periods, e.g. maintenance or repair periods, and yet form an overall period that lies in particular between a beginning of life (BoL) and an end of life (EoL).
- An “increase” of a value can, within the scope of the present invention, be in particular a gradual, step-by-step increase or an increase corresponding to a specific mathematical function. Since this occurs in a discontinuous period, it may also be interrupted by periods of no increase or decrease.
- the service life of the electrolysis stack can be extended and at the same time the maximum voltage and/or power consumption of the electrolysis stack can be limited.
- Electrolysis stacks can be used over a longer period of time without exceeding a certain threshold voltage, whereby the nominal production rate and/or current density of the electrolysis plant can be achieved. Overengineering of power supply units can be reduced, as also explained further below with reference to embodiments of the invention, without thereby shortening the service life of the electrolysis stack.
- the point in time from which the default value for the operating temperature is increased i.e. a corresponding continuous or discontinuous period of time begins, is specified on the basis of at least one parameter that correlates with a degree of degradation of the electrolysis cells of the electrolysis stack. Further details are also explained below. In particular, this makes it possible to precisely select a corresponding point in time and adapt it to real operation.
- an operating voltage with which the electrolysis cells are operated is increased, with the parameter that correlates with a degree of degradation of the electrolysis cells of the electrolysis stack being reached or a threshold value is exceeded by the operating voltage.
- Such an increase can advantageously be provided to compensate for degradation of the electrolytic cells. It can take place depending, for example, on a production rate of the electrolysis product, in particular in order to keep this constant.
- a maximum achievable current intensity at which the electrolytic cells are operated can be reduced during a continuous or discontinuous partial period that lies before the specified time, the parameter being associated with a degree of degradation Electrolysis cells of the electrolysis stack correlate, reaching or falling below a threshold value through the maximum achievable current intensity.
- the maximum achievable operating voltage with which the electrolytic cells are operated is no longer increased during the partial period that lies after the predetermined point in time.
- the same can also be provided for the maximum achievable current strength.
- the corresponding voltage or current can be limited and further degradation can be compensated for by the increase in the operating temperature provided in embodiments of the invention.
- a corresponding threshold value for an operating voltage can be in particular 101 to 150% or 104 to 120% of an initial value of the operating voltage. This makes it possible to provide corresponding power supply units only so powerful that they allow this increase in voltage. Overdesign can be avoided. Accordingly, a corresponding current intensity threshold may be 50 to 99% or 80 to 96% of the initial current intensity value.
- the electrolysis can be carried out using electrolysis membranes, wherein the electrolysis membranes and/or one or more further components of the electrolysis cells are designed to convert hydrogen permeating through the electrolysis membranes with oxygen to form water.
- a corresponding material can be introduced into the arrangement of membrane and electrodes. This is designed to recombine the hydrogen penetrating into the membrane on the anode side of the electrolysis cell with oxygen to form water. Degradation can lead to a thinning of the membrane and thus increase the gas passage through the membrane. In addition, the permeation of hydrogen and oxygen through typical membrane material can be increased at higher temperatures.
- the means for recombination of oxygen and hydrogen may be a catalyst, eg platinum-based, which may be embedded in the membrane, mixed with the anode-side catalyst, or applied as a thin layer between the anode catalyst and the membrane.
- the electrolysis membranes and/or one or more other components of the electrolysis cells which are designed to convert the hydrogen permeating through the electrolysis membranes with oxygen to form water, can comprise a platinum-based catalyst.
- Alternative embodiments of the present invention can also be set up to use alkaline electrolysis, i.e. the electrolysis can be carried out using electrolysis cells that are set up for alkaline water electrolysis, as are basically known from the prior art.
- embodiments of the present invention can in particular provide that a hydrogen concentration on the anode side is monitored and the operation of the electrolysis is adapted depending thereon.
- the operation can be adapted in particular by changing the operating conditions, e.g. the cell voltage and the cell temperature, so that a threshold value of the hydrogen concentration at the anode is not exceeded.
- the threshold value can in particular be below the lower explosion limit of 4%.
- threshold values can also be 2% or lower in order to provide an appropriate safety buffer.
- the hydrogen concentration on the anode side is particularly high at high temperatures and low current densities. Therefore, the measured concentration can be used to set an upper limit on temperature or a lower limit on cell voltage and/or current density. Especially when operating at low load, ie at low Voltage and current density is desired, lowering the temperature to limit the hydrogen concentration at the anode can be advantageous.
- the operation of the electrolysis can be adjusted or further adjusted according to embodiments of the invention if the hydrogen concentration on the anode side exceeds a value of 2% or 4%.
- the electrolysis can be operated at least temporarily during the operating period with subnominal current densities, with the operating temperature being set depending on the current densities.
- the temperature can be varied depending on the temporarily applied voltage.
- the electrolysis stack can be operated at a lower temperature than the operating temperature used at the same degradation or level of degradation and at the rated current density. Operation at this lower current density may be possible despite the given degradation level without increasing the temperature or exceeding the predetermined threshold voltage. Operating at a lower temperature can reduce gas transfer, which can be critical at low current densities, and can reduce degradation.
- the operating temperature can be increased by reducing a coolant flow through and/or increasing a coolant inlet temperature into the electrolysis cells.
- an electrolysis stack is operated at temperatures higher than the nominal temperature, the higher operating temperature can be achieved by reducing the coolant flow and/or increasing the temperature of the coolant entering the electrolysis stack.
- superstoichiometric water is used to control the cell temperature, this water can be purified, e.g. by using an ion exchange resin.
- the The temperature of the water entering the cleaning unit must not exceed a threshold temperature, e.g. 60°C.
- the electrolysis stack temperature can be controlled by a bypass via the heat exchanger that cools the water.
- water supplied to the electrolysis cells can be supplied in an adjustable first proportion beforehand to a temperature control and a cleaning device, and in a remaining remainder it can be guided around the temperature control and cleaning device (or only the temperature control or the cleaning device) and downstream from it again with the first share to be combined.
- the temperature control and cleaning device or only the temperature control or the cleaning device
- at least part of the water that is led around the temperature control unit can also be led around the cleaning unit, so that the water at the inlet of the electrolysis stack can have a higher temperature than the water at the inlet of the cleaning unit.
- Any bypasses of a corresponding type are possible and can be provided in embodiments of the present invention.
- At least part of the water may be directed to the heat exchanger and resin at an initial time, while at least another part of the water bypasses the heat exchanger and resin.
- part of the anode and/or cathode current may be diverted from the system or bypass the heat exchanger and water purification unit.
- the system proposed according to the invention for producing a hydrogen-containing product is set up to carry out electrolysis and has an electrolysis stack having a large number of electrolysis cells for carrying out the electrolysis. It is designed to apply an electrolysis voltage applied to the electrolysis stack to the electrolysis cells during a continuous or discontinuous production period between a first point in time and a second point in time and to operate the electrolysis cells during the production period with an operating temperature set to a default value.
- means are provided which are designed to increase the default value for the operating temperature during a continuous or discontinuous sub-period that occurs after a predetermined point in time during the operating period.
- FIGS. 1 to 5 show diagrams illustrating the background and features of embodiments of the present invention.
- Figure 6 illustrates a system according to an embodiment of the invention.
- Different embodiments of the invention may include, have, consist of, or consist essentially of other useful combinations of the described elements, components, features, parts, steps, means, etc., even if such combinations are not specifically described herein.
- the disclosure may include other inventions that are not currently claimed, but that may be claimed in the future, particularly if they are included within the scope of the independent claims.
- the splitting of water into oxygen and hydrogen in electrolysis is an energy-intensive process.
- the energy required for the water splitting reaction is provided by applying an electrical current to an arrangement of electrolysis cells, the electrolysis stack just explained.
- the electrical energy consumed by the electrolysis stack can be calculated as the product of the current flowing through each electrolysis cell, the voltage across each electrolysis cell, and the number of electrolysis cells in the electrolysis stack.
- the voltage across each electrolysis cell is also referred to as the cell voltage Uceii and can be assumed to be approximately the same for each electrolysis cell in an electrolysis stack.
- the cell voltage can be divided into the reversible voltage U rev , i.e. the thermodynamic minimum voltage at which a reaction can take place, and an overvoltage.
- the overvoltage includes the activation overvoltage on the catalyst surface as well as the voltages required to conduct the cell current across the ohmic resistances of the various components of the electrolytic cell, as well as other overvoltages Mass transportation limitations. In contrast to the reversible voltage, the overvoltage increases with the current density.
- the cell voltage of an electrolysis cell is greater than its thermoneutral voltage U tn , i.e. the voltage at which the energy transferred into the electrolysis cell (i.e. the transferred charge multiplied by the applied voltage) is greater than the reaction enthalpy. Accordingly, heat is generated in the electrolysis stack and dissipated via a cooling medium, usually unconverted water.
- Typical curves for the reversible voltage, the thermoneutral voltage and the cell voltage versus current density are shown in Figure 1.
- the relationship between cell voltage and current density is often referred to as the Ui curve.
- Figure 2 which plots current density in A/cm 2 on the horizontal axis versus cell voltage in V on the vertical axis, and from top to bottom corresponding curves for temperatures of 30, 40, 55, 60, 70, 80 and 90°C are shown, there is a temperature dependence of the Ui curve.
- Cell voltage is a function not only of current density, but also of operating temperature. This relationship is particularly relevant in the context of the present invention. As the operating temperature increases, the reversible voltage decreases due to the underlying thermodynamics of the water splitting reaction. In addition, the various resistances within the electrolytic cell decrease as the temperature increases, which also leads to a decrease in overvoltage. As a result, the cell voltage and thus the specific energy consumption of the cell decreases as the operating temperature increases. However, it has been shown that increasing the temperature accelerates the degradation of the electrolytic cell, so a compromise typically has to be made between cell efficiency and service life.
- electrolysis plants are operated at constant pressure and constant temperature throughout their entire service life, whereby the temperature of the electrolysis cells can be controlled, for example, by the current or the inlet temperature of a cooling medium, e.g. water, which is supplied to the electrolysis cells.
- a cooling medium e.g. water
- the voltage required to maintain the nominal hydrogen production of the plant is often cited as a criterion for replacing the electrolysis stack.
- Replacement occurs when a certain threshold is reached.
- This threshold can be a fixed voltage, eg 2.2 V, or a percentage degradation, eg 10%.
- a power supply unit must be able to deliver more power at a higher voltage as the cells age, which requires at least some degree of overdesign of the power supply unit compared to the requirements at the beginning of the plant's lifetime.
- the criterion for replacing the electrolysis stack can therefore also be that the power requirement of the electrolysis stack becomes greater than the maximum output power of the power supply unit at a certain current, or becomes too large for economical operation. More generally, any criterion related to the voltage across the electrolysis stack and/or part of the electrolysis stack reaching a certain upper threshold or the maximum achievable current reaching a certain lower threshold can be considered.
- the present invention proposes an operation of an electrolysis which comprises increasing the operating temperature of an electrolysis stack at a certain point during its service life in order to compensate for its performance deterioration. This can extend the service life of the electrolysis stack and at the same time limit the maximum voltage and/or power consumption of the electrolysis stack. As mentioned, this can comprise increasing the temperature from a certain point up to which degradation is compensated by means of an increase in voltage or a reduction in the maximum achievable current.
- the drop in power can preferably initially be compensated for by increasing the electrolysis stack voltage until a threshold voltage is reached.
- an operating voltage of the electrolysis cells of the electrolysis stack is increased from the beginning of the operating period until a threshold voltage is reached, which is selected depending on a nominal voltage of the electrolysis cells of the electrolysis stack.
- a threshold voltage is reached, which is selected depending on a nominal voltage of the electrolysis cells of the electrolysis stack.
- This increase can in turn take place during a continuous or discontinuous period, ie the voltage can also be increased in the meantime reduced again, for example to reduce a production rate or because the reduction of reversible degradation effects enables a corresponding reduction.
- an increase is made, ie in particular the voltage maxima increase before the start of the operating period until they reach a threshold value. This can take place over a period of years.
- an operating current density of the electrolysis cells of the electrolysis stack can be reduced until a lower threshold current density is reached.
- a maximum achievable current strength at which the electrolysis cells are operated can be reduced, the parameter that correlates with a degree of degradation of the electrolysis cells of the electrolysis stack being whether the maximum achievable current strength reaches or falls below a threshold value.
- an interim increase in the current strength can take place as long as the current strength maxima decrease until the threshold value is reached.
- the threshold voltage may, in embodiments of the invention, as mentioned, be expressed as a percentage of the nominal voltage at the beginning of the operating period, and the criterion may be applied to one or more voltages each measured across one or more cells. Similarly, a current threshold may be expressed as a percentage of an initial value.
- the electrolysis stack temperature can be increased from a corresponding period of time in order to achieve the production target without violating the voltage criterion.
- the proposed strategy makes it possible to achieve production rates that can no longer be achieved within the nominal temperature and voltage range with an electrolysis stack that has experienced a certain degree of degradation. Therefore, the proposed strategy enables an extension of the operating life of the electrolysis stack while maintaining the operating conditions, such as the achievable production rate.
- the resulting temperature and voltage profile over time is shown as an example for stationary operation in Figure 4, in which an operating period in years on the horizontal axis, a temperature difference between the current operating temperature and the operating temperature at the beginning of the service life or the operating period shown in K on the left vertical axis, and a ratio of the used to the nominal operating voltage in percent is illustrated on the right vertical axis.
- the upper curve refers to the voltage ratio, the lower curve to the temperature difference.
- FIG. 6 shows a system according to an embodiment of the present invention using a highly simplified system diagram.
- the system is designated as a whole by 100.
- the system 100 can be designed for electrolysis using proton exchange membranes or anion exchange membranes, which can be supplied with water on the cathode and/or anode side.
- the invention is not limited to this, but can in principle also be used with electrolysis cells that are set up for alkaline electrolysis. Corresponding embodiments are not shown separately here merely for reasons of clarity.
- An electrolysis cell or electrolysis stack is designated 10 and has an anode side A and a cathode side C. A membrane is illustrated with M.
- the system 100 is supplied with a water stream 101 which is mixed with recycle streams 102 and
- recycle streams 102, 103 Portions of these recycle streams 102, 103 shown in dashed lines can be diverted beforehand. Operation without recycle streams 102, 103 is also possible. A return of the recycle streams 102, 103 to a downstream position, as also shown by dashed arrows, can also be provided.
- a variable portion of the correspondingly formed water flow can be branched off as a bypass flow 104.
- a remainder 105 is cooled by means of a heat exchanger 20 and at least part of the outlet stream of the heat exchanger 20 is then cleaned in a cleaning device 30. After reuniting with the bypass stream
- a material stream 108 containing the gaseous anode products, in particular oxygen, and the unreacted water can be removed and fed to a gas-liquid separator 40.
- the water used as the recycle stream 102 can be separated and a gaseous anode product 110 can be obtained.
- the anode product can contain hydrogen which has passed into the anode product due to crossover across the membrane.
- a material stream 109 containing the gaseous cathode products, in particular hydrogen, and the unreacted water can be removed and fed to a gas-liquid separator 50.
- the water used as the recycle stream 103 can separated and a gaseous cathode product 111 is obtained.
- the cathode product analogous to the anode product, if no separation or the like is provided, can contain oxygen which has passed into the cathode product due to crossover across the membrane.
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
L'invention concerne un procédé pemettant la préparation d'un produit (111) contenant de l'hydrogène en ayant recours à une électrolyse (10), procédé selon lequel l'électrolyse (10) est mise en oeuvre au moyen d'un ou de plusieurs stack d'électrolyse comprenant une pluralité de cellules d'électrolyse, les cellules d'électrolyse étant soumises à une tension d'électrolyse, appliquée au stack d'électrolyse, pendant une période de production continue ou discontinue entre un premier moment (BoL) et un second moment (EoL), et les cellules d'électrolyse fonctionnant, pendant ladite période de production, à une température de fonctionnement réglée à une valeur de consigne. Selon l'invention, la valeur de consigne de la température de fonctionnement est augmentée pendant une période continue ou discontinue partielle qui est postérieure à un moment prédéfini pendant la période de fonctionnement. La présente invention concerne également une installation (100) correspondante.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP22020474.7A EP4345191A1 (fr) | 2022-09-30 | 2022-09-30 | Procédé et installation de production d'un produit contenant de l'hydrogène par électrolyse |
EP22020474.7 | 2022-09-30 |
Publications (2)
Publication Number | Publication Date |
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WO2024068048A2 true WO2024068048A2 (fr) | 2024-04-04 |
WO2024068048A3 WO2024068048A3 (fr) | 2024-06-20 |
Family
ID=83558319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2023/025411 WO2024068048A2 (fr) | 2022-09-30 | 2023-09-28 | Procédé et installation permettant la préparation d'un produit contenant de l'hydrogène en ayant recours à une électrolyse |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP4345191A1 (fr) |
WO (1) | WO2024068048A2 (fr) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013131778A2 (fr) | 2012-03-05 | 2013-09-12 | Haldor Topsøe A/S | Appareil de production de monoxyde de carbone de haute pureté |
WO2014154253A1 (fr) | 2013-03-26 | 2014-10-02 | Haldor Topsøe A/S | Procédé de production de co à partir de co2 dans une cellule d'électrolyse à oxyde solide |
WO2015014527A1 (fr) | 2013-07-30 | 2015-02-05 | Haldor Topsøe A/S | Processus de production de co à haute pureté par purification par membrane du co produit par une pile à électrolyse à oxyde solide (soec) |
EP2940773A1 (fr) | 2014-04-29 | 2015-11-04 | Haldor Topsøe A/S | Éjecteur pour système d'empilement de cellule d'électrolyse d'oxyde solide |
EP3766831A1 (fr) | 2019-07-18 | 2021-01-20 | Linde GmbH | Procédé de fonctionnement d'un four chauffé et agencement comprenant un tel four |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005028713A1 (fr) * | 2003-09-22 | 2005-03-31 | Hydrogenics Corporation | Systeme d'empilage de cellules d'electrolyseur |
JP2019203174A (ja) * | 2018-05-24 | 2019-11-28 | 本田技研工業株式会社 | 水電解システムの運転方法及び水電解システム |
WO2020208949A1 (fr) * | 2019-04-09 | 2020-10-15 | パナソニックIpマネジメント株式会社 | Système d'hydrogène |
JP2022139785A (ja) * | 2021-03-12 | 2022-09-26 | 株式会社豊田中央研究所 | 水電解システム、水電解システムの制御方法、および水電解方法 |
CN114561668B (zh) * | 2022-03-01 | 2024-04-26 | 国家电投集团氢能科技发展有限公司 | 具有蓄热装置的制氢系统和制氢系统的控制方法 |
-
2022
- 2022-09-30 EP EP22020474.7A patent/EP4345191A1/fr active Pending
-
2023
- 2023-09-28 WO PCT/EP2023/025411 patent/WO2024068048A2/fr unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013131778A2 (fr) | 2012-03-05 | 2013-09-12 | Haldor Topsøe A/S | Appareil de production de monoxyde de carbone de haute pureté |
WO2014154253A1 (fr) | 2013-03-26 | 2014-10-02 | Haldor Topsøe A/S | Procédé de production de co à partir de co2 dans une cellule d'électrolyse à oxyde solide |
WO2015014527A1 (fr) | 2013-07-30 | 2015-02-05 | Haldor Topsøe A/S | Processus de production de co à haute pureté par purification par membrane du co produit par une pile à électrolyse à oxyde solide (soec) |
EP2940773A1 (fr) | 2014-04-29 | 2015-11-04 | Haldor Topsøe A/S | Éjecteur pour système d'empilement de cellule d'électrolyse d'oxyde solide |
EP3766831A1 (fr) | 2019-07-18 | 2021-01-20 | Linde GmbH | Procédé de fonctionnement d'un four chauffé et agencement comprenant un tel four |
Non-Patent Citations (4)
Title |
---|
"Ullmann's Encyclopedia of Industrial Chemistry", article "Electrolysis" |
EBBESEN: "Poisoning of Solid Oxide Electrolysis Cells by Impurities", J. ELECTROCHEM. SOC., vol. 157, no. 10, 2010, XP008158752, DOI: 10.114911.3464804 |
HAUCH: "Recent advances in solid oxide cell technology for electrolysis", SCIENCE, vol. 370, no. 6513, 2020 |
ULLMANN: "Encyclopedia of Industrial Chemistry", 15 June 2000, article "Hydrogen" |
Also Published As
Publication number | Publication date |
---|---|
EP4345191A1 (fr) | 2024-04-03 |
WO2024068048A3 (fr) | 2024-06-20 |
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