EP4139500A1 - Procédé de fonctionnement de système de piles à oxyde solide - Google Patents

Procédé de fonctionnement de système de piles à oxyde solide

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Publication number
EP4139500A1
EP4139500A1 EP21719920.7A EP21719920A EP4139500A1 EP 4139500 A1 EP4139500 A1 EP 4139500A1 EP 21719920 A EP21719920 A EP 21719920A EP 4139500 A1 EP4139500 A1 EP 4139500A1
Authority
EP
European Patent Office
Prior art keywords
solid oxide
cell system
hydrogen
oxide cell
stack
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
EP21719920.7A
Other languages
German (de)
English (en)
Inventor
Oliver Borm
Oliver Posdziech
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.)
Sunfire Se
Original Assignee
SunFire 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 SunFire GmbH filed Critical SunFire GmbH
Publication of EP4139500A1 publication Critical patent/EP4139500A1/fr
Pending legal-status Critical Current

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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • H—ELECTRICITY
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0637—Direct internal reforming at the anode of the fuel cell
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    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
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    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
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    • 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
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    • 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
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    • H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • H01M8/04074—Heat exchange unit structures specially adapted for fuel cell
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    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
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    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow of fuel cell reactants
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    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
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    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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    • C01B2203/0495—Composition of the impurity the impurity being water
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    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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    • C01B2203/08—Methods of heating or cooling
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B15/00—Operating or servicing cells
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
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    • 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
    • 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
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a solid oxide cell system operating method in which an electrochemical conversion by means of electrical current from water vapor hhC g) or a mixture comprising water vapor hhC g) and carbon dioxide CO 2, hydrogen H 2 or synthesis gas CO + H 2 is generated.
  • the method according to the invention is suitable for use in solid oxide electrolysis cell systems (Solid Oxide Electrolyzer Cell, SOEC) and in reversible solid oxide cell systems (English Reversible Solid Oxide Cell, rSOC) in electrolysis.
  • Solid Oxide Electrolyzer Cell SOEC
  • reversible solid oxide cell systems English Reversible Solid Oxide Cell, rSOC
  • the conversion efficiency of such SOEC or rSOC is particularly high if the cells or cell stacks of the solid oxide cell system are operated in a thermally neutral manner over their entire service life.
  • thermo-neutral mode of the stack is described by the fact that the heat production through the ohmic losses of the electrolysis cells is in equilibrium with the heat requirement for splitting the water.
  • PEM low-temperature electrolysis systems
  • the thermo-neutral mode the temperature of the stack changes with the load point. The efficiency remains consistently high. If the current strength is increased or the resistance of the cells increases due to degradation, a maximum temperature is reached at some point at which the cells can be operated continuously.
  • a further increase in the current strength or the resistance leads to the fact that the heat production in the stack exceeds the heat absorption due to the endothermic splitting of water.
  • the stack must then be cooled to avoid overheating. Cooling usually takes place by increasing the air flow on the side of the oxygen electrode.
  • the inlet temperature of the supplied gases can be reduced.
  • the operating voltage and thus the electrical power to be generated increase.
  • the efficiency of the system is disadvantageously reduced depending on the degree of exotherm, characterized by the increase in the stack voltage and the need for cooling air.
  • Low temperature electrolysis systems always work in exothermic mode and therefore have an inherently lower degree of efficiency.
  • the subject of this invention is the supply of hydrocarbons in electrolysis mode, whereby on the one hand the stack is additionally cooled by the endothermic reforming reaction and on the other hand an increased amount of hydrogen is generated as a component of a synthesis gas, whereby the total amount of hydrogen / synthesis gas produced, also referred to as product gas, can be kept constant and / or an overload of hydrogen or synthesis gas can be achieved.
  • Different operating methods are known from the prior art for operating SOEC or rSOC systems.
  • the publication WO 2006/001863 A2 describes an rSOC system which, depending on the electricity and gas price, can be operated in the fuel cell or electrolysis operating modes.
  • a larger amount of hydrocarbon is also fed to the system in order to use the waste heat generated by the exothermicity of fuel cell operation to produce hydrogen.
  • the endothermic reforming reaction required for this takes place either in a pre-reformer or directly on the hydrogen electrode of the stack.
  • Different operating modes are described, which are started depending on the cost of electricity and natural gas as well as the expected production volume of hydrogen.
  • the publication does not describe how hydrocarbons can be used in electrolysis mode to compensate for the degradation.
  • the document EP 1 115908 B1 describes a natural gas-assisted steam electrolyser in which the anode side (oxygen electrode) is operated with a reformate from a catalytic partial oxidation of natural gas.
  • the aim of the arrangement is to reduce the cost of hydrogen production and at the same time to increase the efficiency of the electrolysis.
  • the supply of a fuel gas to the oxygen electrode is not regarded as technically feasible. It is not stated that this will result in a degradation of the stack could be compensated, although this cannot be inferred in an obvious manner, even for a person skilled in the art, since the publication does not give any suggestions in this direction.
  • a high-temperature electrolysis system is known from the publication EP 3 168 330 B1, which provides a constant hydrogen output with fluctuating energy input.
  • a hydrogen storage medium is used for this. Disadvantages of such an arrangement are the limited storage capacity, higher costs and possible degradation of the storage material.
  • the publication WO 2013/078142 A2 also describes a fuel cell system (Solid Oxide Fuel Cell, SOFC) which, in addition to electricity, also produces hydrogen and carbon dioxide.
  • SOFC Solid Oxide Fuel Cell
  • a mixture comprising a hydrocarbon and steam is fed to an SOFC system.
  • the residual anode gas is mixed with hydrocarbon and fed to a pre-reformer in order to produce a hydrogen-rich synthesis gas therefrom.
  • rSOC have been used in the prior art to generate electricity (from H2 or hydrocarbons) in the SOFC mode and / or hydrogen in the SOEC mode by means of electrolysis, as required.
  • the stacks used in the prior art are subject to degradation. In this case, the degradation of the stacks must either lower the efficiency in the electrolysis (exothermic mode) or reduce the hydrogen / synthesis gas generation capacity with constant efficiency (thermo-neutral mode). The latter management is more attractive for the user, since the electricity costs play an essential role in the economic efficiency. This creates a gap in demand that can only be eliminated by an external hydrogen / synthesis gas source in the state of the art.
  • a high-temperature electrolysis system has become known from WO 2015/116964 A1, which has at least one electrolytic fuel cell with an anode and cathode separated from one another and a reserve voltage is applied.
  • the electrolysis system is oversized in order to be able to provide the required amount of hydrogen / synthesis gas even at the end of the life of the electrolysis stack. This is associated with high investment costs, since the electrolysis system can only be operated (with a decreasing) partial load at the beginning and during the course of its operation. Alternatively, depending on the degradation-dependent amount of product gas, additional electrolysis modules can be added or degraded modules can be replaced. This is also associated with additional investment costs and poor utilization of the electrolyzer capacity.
  • the electrolysis system is operated in exothermic mode with increasing degradation. This is unfavorable because the cooling effect of the exothermic mode is limited, the system has to be dimensioned for the low purge air quantities in the thermo-neutral mode as well as for very high air quantities in the exothermic mode and the power electronics are designed for the higher operating voltages in the exothermic mode got to. Operation in the exothermic mode is associated with higher operating costs, the design for larger air volumes and operating voltages is associated with higher investment costs. In addition, the cells are more thermo-mechanically stressed at higher temperatures, which can lead to increased cell breakage or failure of glass seals.
  • Another hydrogen source is connected, for example an inexpensive low-temperature electrolysis system, an SMR system (Steam Methane Reforming) or logistical hydrogen is made available via trailer. All of these cases are associated with higher investment or operating costs and with comparatively low levels of efficiency in generating the additional hydrogen.
  • the present invention is based on the object of specifying a solid oxide cell system operating method which makes it possible to operate a solid oxide electrolytic cell system or a reversible solid cell system in the electrolysis mode in a highly efficient manner and in particular to address the economic and technical problems identified above to solve. In particular, the subtask of keeping the amount of hydrogen / synthesis gas constant when the stack is degraded must be solved.
  • the solid oxide cell system operating method in which in an electrochemical conversion, by means of electrical current from water vapor FhC g) or a mixture comprising water vapor FhC g) and carbon dioxide CO 2 , hydrogen H 2 and / or synthesis gas CO + H 2 is generated characterized in that the water vapor FhC g) or the mixture comprising water vapor H 2 0 (g) and carbon dioxide C0 2 an additional amount of at least one of the substances from the group natural gas, methane CH 4 or another hydrocarbon C m H n additionally for A conversion into synthesis gas CO + H 2 can be added, with an endothermic reforming of the added hydrocarbons by coupling in waste heat from the electrochemical conversion.
  • natural gas preferably has a proportion of 60% -99% by volume, preferably 85% -98% by volume, methane, it also being possible for other hydrocarbon compounds to be contained therein.
  • natural gas is to be understood as a methane-rich gas or as a gas of gas family 2. It is essential for the method according to the invention that the additionally provided gas can provide a large amount of hydrogen when it is reformed.
  • Propane, butane, but also methanol, ethanol or dimethyl ether are also suitable for the process.
  • a synthesis gas (H2 + CO) is generated in SOEC mode.
  • the synthesis gas can be used without further gas aftertreatment.
  • CO and CO2 must be removed.
  • Standard processes of a steam reforming plant are used here:
  • the CO is converted to CO2 via one or more shift stages.
  • the heat generated in the shift reaction can be used within the system for heating the educt or for generating steam.
  • the residual CO can be removed via selective oxidation or selective methanation.
  • PSA pressure swing adsorption
  • TSA Temperature swing adsorption
  • amine scrubbing or cryogenic separation are used.
  • B. electrochemical compression or compression by means of metal hydride accumulators can be used at the same time for gas cleaning.
  • the endothermic reforming of the added hydrocarbons can take place both internally and externally with respect to the stacks of the solid oxide cell system, with internal reforming being able to take place parallel to the electrochemical conversion in the cells and external reforming by means of an additionally provided reformer. It is economically advantageous if an external reformer can be dispensed with and the reforming takes place completely within the solid oxide cells of the solid oxide cell system and an external reformer can be dispensed with.
  • a solid oxide cell system according to the invention can in particular be equipped or operated with a reforming module or internal reforming (or also both) in order to generate a constant amount of the hydrogen-rich gas.
  • a reforming module or internal reforming or also both
  • fossil natural gas natural gas from renewable sources, such as synthetic natural gas (SNG) or other suitable ones are added to the system.
  • SNG synthetic natural gas
  • Hydrocarbon compounds supplied The term constant here refers to the time average of the total amount of hydrogen H 2 or synthesis gas generated by the solid oxide cell system based on operation under nominal load.
  • Waste heat generated in the electrolysis operation can supply an endothermic steam reforming process of the hydrocarbons with heat, so that the conversion efficiency is very high.
  • the additional admixture of natural gas / methane CFU and / or other hydrocarbons C m H n to compensate for the effects of degradation of the cells. Since the reforming produces an additional amount of hydrogen H 2 as part of synthesis gas (CO + H 2 ), the additional supply of a hydrocarbon as a hydrogen source advantageously allows a constant amount of Hydrogen can be provided over the life of the system.
  • the constant amount of hydrogen is preferably based on operation under nominal load.
  • the additional amount of the at least one added substance has a predetermined molar ratio, for example 2 mol H2 to 1 mol carbon for CH4, so that the admixture can provide larger amounts of H2 as required to avoid a degradation-related decrease in the amount of hydrogen released from the electrolytic To compensate for decomposition of the water vapor.
  • the relation of the amount of hydrogen generated to operation under nominal load means that the electrolyser is operated at its design values and in the optimal process window (such as maximum volume flows, process temperature, etc.). Over time, the degradation would lead to these values no longer being achieved.
  • the total amount is kept constant at a value that corresponds to the value at nominal load.
  • the solid oxide cells of the solid oxide cell system can preferably be cooled by the endothermic reforming so that they can be operated thermally neutrally over their entire service life.
  • thermo-neutral operation the voltage adjusts to a characteristic value. The voltage only rises when you drive exothermically, i.e. when you remove heat from the stack. The voltage is therefore unsuitable as a controlled variable.
  • the standard volume or mass flows of the product gases are also not very suitable as a controlled variable.
  • a constant electrical power P can be set for the stack and the standard volume flows of the feed gases can be regulated as a function of the measured standard volume flows of H2 or of the synthesis gas in the products.
  • the composition of the synthesis gas at the stack outlet could also be determined via the measured stack temperature.
  • a measurement of the standard volume flow of the generated hydrogen is technically difficult to implement, since H2 and H2O are at the output of the stack as Mixture of substances are present. This becomes even more complex with co-electrolysis, since the product gas contains at least 4 components.
  • the amount of hydrogen produced and / or the amount of synthesis gas is preferably determined using Faraday's law with the aid of the measured current intensity, which is also suitable as a control variable.
  • a target value for the H2 output or synthesis gas output is set by specifying a start value for the current intensity and slowly increased, with the stack temperature being measured. If the current intensity can no longer be increased, because the stack temperature has reached its target value for thermo-neutral operation or a predetermined maximum value, an additional standard volume flow of a hydrocarbon C m H n is provided, so that a predetermined target value for the standard volume flow of the total hydrogen produced or synthesis gas is achieved.
  • the standard volume flow of the total hydrogen or synthesis gas produced results from the sum of the standard volume flow of the electrolytically produced hydrogen, which is calculated from the measured current according to Faraday's law, and the standard volume flow of the reformed hydrogen.
  • Look-up tables can be specified for the regulation, from which the standard volume flow of the reformed hydrogen is specified by means of reforming rates and substance quantity ratios stored therein from the standard volume flow of the supplied hydrocarbon (s).
  • a ramp can be specified for the standard volume flow of the hydrocarbon or hydrocarbons supplied.
  • the degradation behavior can be statistically determined by measuring the current, voltage and stack temperature over time and the ramp can be stored for the control using an empirical function or a look-up table.
  • an additional supply of natural gas / methane and / or other hydrocarbons C m H n with endothermic reforming can lead to an increase in the hydrogen output H2 and / or the synthesis gas output CO + H2 of the system in thermo-neutral operation, which results in peak loads or short-term and / or have short-term additional requirements for H2 or synthesis gas served by downstream processes.
  • the amount of product can also be increased to achieve an overload or nominal load with less electricity, for example if a reduced amount of renewable electricity can be provided from a renewable generator such as a wind or solar park or the supply of hydrocarbons based on the current electricity price for a Duration is more economical.
  • a short-term and short-term increase in the production quantity of hydrogen is possible by simultaneously increasing the current strength and standard volume flows of the educts proportionally according to a predetermined feed conversion rate while monitoring the stack temperature. If the maximum stack temperature is reached, the current strength is kept constant and hydrocarbons are added. At the same time, the supply of H 2 O / CO 2 is adjusted accordingly in order to keep the feed conversion rate constant and to maintain the desired quality of the synthesis gas.
  • the production quantity of hydrogen can be kept constant at a lower power supply by reducing the current intensity and standard volume flows of the starting materials proportionally at the same time according to a predetermined feed conversion rate and setting the current intensity to a value that the electrical power consumed by the system is still completely exhausted the available supply of renewable electricity can be covered.
  • the stack temperature is monitored. If a minimum stack temperature is reached, the current strength is kept constant.
  • the supply of H 2 O / CO 2 is adjusted accordingly in order to keep the feed conversion rate constant and to maintain the desired quality of the synthesis gas.
  • High temperature SOEC or rSOC in electrolysis mode are preferably operated in thermo-neutral mode.
  • the heat that arises in the stack as a result of OhrrTsche losses and the proportion of heat that can be coupled in to split water vapor and / or CO 2 in the electrolysis are in equilibrium. Since the ohmic losses or the resistance of the stack depend heavily on the current density and the temperature of the stack, the temperature of the stack also changes in thermo-neutral operation depending on the current density. If, in spite of degradation, a constant or short-term and short-term larger amount of hydrogen / synthesis gas is to be generated, the cells according to the invention are supplied with natural gas or other hydrocarbons in addition to water vapor or a mixture comprising water vapor and carbon dioxide.
  • the stack By supplying hydrocarbons and the associated endothermic steam reforming, the stack can be operated thermo-neutrally at a higher current density and more hydrogen / synthesis gas is generated.
  • the method used to compensate for the degradation is therefore also suitable for short-term and short-term efficient provision of a larger amount of additional hydrogen / synthesis gas or a constant amount of hydrogen / synthesis gas with reduced consumption of electrical power.
  • a higher or constant output of hydrogen / synthesis gas can take place even with a lower current input.
  • additional heat to increase the hydrogen output and / or the synthesis gas output CO + H2 of the system can be supplied from external sources as required.
  • hydrocarbons can be added to the system and these can be converted into hydrogen / synthesis gas using endothermic steam reforming.
  • the waste heat is preferably fed to an external reformer.
  • the reforming can then take place as far as possible in the external reformer or catalytic reactor, so that only the portion of the added hydrocarbons that is required to stabilize the temperature at the thermo-neutral operating point is converted endothermically in the cells.
  • a bypass supply can be provided so that steam-reformed gas can be supplied to the stack via the external reformer and unreformed hydrocarbons can be supplied via a bypass.
  • the stack can be preceded by a reformer or catalytic reactor to regulate the reformer temperature to set the internal reforming in the stack by increasing or decreasing the proportion of hydrocarbons, the reactor being heated from the waste heat of the stack to increase the conversion of the hydrocarbons or from external sources.
  • Fig. 1 the basic operating principle of the solid oxide cell system according to the invention
  • Fig. 2a, 2b show the course of the hydrogen release or the degree of efficiency over time t for methods according to the prior art in which there is no compensation of the degradation and the method according to the invention in which hydrocarbons C m H n are used to compensate for the degradation , and
  • Fig. 3 is a schematic representation of an embodiment of a SOEC
  • Fig. 1 shows the basic principle of the solid oxide cell system operating method according to the invention.
  • the solid oxide cell system shown in principle comprises a stack 1 of SOEC or rSOC, which can be operated in an electrolysis mode.
  • the stack 1 can also be understood as a single cell or as a stack module.
  • the stack 1 comprises an oxygen electrode 2 (anode) and a hydrogen electrode 3 (cathode).
  • the stack 1 is supplied with air 8 as a rinsing medium on the anode side and a gaseous reformate of CFU, H2O, CO2, CO and H224 on the cathode side, and synthesis gas (H2, CO) is generated as product gas 31 via the electrochemical reaction using preferred renewable electricity , while flushing medium 9 enriched with oxygen O2 is released on the anode side.
  • hydrocarbons C m H n are supplied to the solid oxide cell system.
  • the hydrocarbons can be pre-reformed (only partially converted) or completely reformed in an external reformer 23 together with the water vapor or the mixture comprising water vapor and carbon dioxide, which is conventionally provided in high-temperature co-electrolysis.
  • heat QR can be coupled in from the stack 1.
  • internal reforming is possible, in which hydrocarbons, preferably methane here, are converted into H2 and CO directly at the catalytically active hydrogen electrode.
  • heat QE is removed from the electrochemical conversion through the endothermic reforming.
  • the feed gas is fed directly to the stack 1 together with the hydrocarbons C m H n and reformed in the cells of the stack 1.
  • the method shown can always be used when hydrogen / synthesis gas is to be provided and waste heat is available in the stack due to the ohmic losses. This is the case when the stack degrades and the ear resistance increases.
  • the method can also be used when the solid oxide cell system is connected to a synthesis, e.g. Fischer-Tropsch synthesis.
  • a hydrocarbon-rich return / cycle gas is produced, which is converted in the external reformer 23 or directly in the stack into H2 and CO using heat from an exothermic electrolysis.
  • the electrolysis can be operated at a power density at which the stack would otherwise either overheat or the system would be cooled by air, thus reducing the degree of efficiency.
  • the supply of heat to the external reformer 23 can take place in various ways known in the prior art.
  • Fig. 2a and Fig. 2b the relative course of the hydrogen output V or the overall efficiency ETA over time for methods according to the prior art and the method according to the invention, in which hydrocarbons C m H n are used to compensate for the degradation , shown.
  • L2 and L6 represent the time profile of the hydrogen output or the degree of efficiency for methods according to the prior art, in which there is no compensation for the degradation of the cells by an admixture of hydrocarbons.
  • the SOEC system is operated increasingly exothermally over time, whereby an almost constant release of hydrogen can be ensured, but the efficiency decreases as the exothermic process control increases.
  • L3 and L4 represent the time profile of the hydrogen output or the degree of efficiency for methods according to the prior art in which there is no compensation for the degradation of the cells by an admixture of hydrocarbons.
  • the SOEC system continues to operate in its thermo-neutral point, which means that the degree of efficiency can be kept constant over time, but the amount of hydrogen released relative to the nominal value of the hydrogen output decreases over time. If hydrocarbons are now added to the system to compensate for the degradation, this has the effect that, on the one hand, additional hydrogen (and additional synthesis gas) is generated and, on the other hand, the stack is cooled by the endothermic reforming and can thus be operated at its thermo-neutral point.
  • Fig. 3 shows a possible embodiment of a SOEC system that can be operated with the method according to the invention. It consists of a SOEC stack or stack module 1, which in turn comprises an oxygen electrode 2, a hydrogen electrode 3 and an oxygen-conducting electrolyte (not shown).
  • the oxygen electrode 2 of the stack 1 is supplied with temperature-controlled air or another temperature-controlled flushing medium 8 such as nitrogen, CO 2, water vapor or other gases that are inert towards oxygen.
  • the cold rinsing medium such as nitrogen, CO 2, water vapor or other gases that are inert towards oxygen.
  • the preheated flushing medium 6 is additionally regulated to the desired stack inlet temperature by means of an electrical heater 7 before it is fed to the oxygen electrode 2.
  • the oxygen-enriched flushing medium 9 leaving the stack via the oxygen electrode 2 is cooled by means of a heat exchanger 10, the heat exchanger
  • the cooled rinsing medium 11 can be fed to a further heat exchanger 12 in order to in turn extract useful heat before it leaves the system as a cold rinsing medium 13.
  • water or water vapor 20 is supplied to the system. When using liquid water, this is first converted into the gaseous state in the evaporator 21.
  • the evaporator 21 can be designed as a heat store in which excess waste heat is stored in order to generate steam energetically with minimal effort. In addition to heat / waste heat, the energy can also be supplied electrically.
  • the water vapor 22 is fed with process gases 27, for example hydrocarbons C m H n , in particular methane CH4, or return gases from a connected synthesis system (not shown), to a catalytic reactor / reformer 23.
  • the catalytic reactor / reformer 23 can be designed in such a way that heat from the stack module 1 can be coupled into it.
  • the catalytic reactor / reformer 23 can be constructed directly as a heat exchanger or can also be designed as a series connection of at least one heat exchanger and reactor stage.
  • the catalytic reactor / reformer 23 generates a reformate 24 from the process gases 27 which contains CH4, H2O, CO2, CO and H2. If necessary, the reformate 24 can be further heated by means of a recuperator 24a before it is fed to the hydrogen electrode 3.
  • an electric heater (not shown) can also be used for this.
  • Hydrocarbon C m H n , CO2, water vapor and / or return gas from a synthesis (hydrocarbons, CO, CO2, H2, H2O) 25 is fed to the catalytic reactor 23 as the medium to be reformed.
  • the starting materials 25 are heated in a recuperator or electric heater 26 and fed to the reactor 23 as superheated process gas 27.
  • the reactor 23 is operated so that with the external pre-reforming and the internal reforming in the SOEC stack 1 hydrocarbons in can be reformed to a large extent and the stack 1 can be effectively cooled.
  • the reactor 23 can also be operated as a methanation reactor.
  • the reformate 24, which is fed to the hydrogen electrode 3, should only contain methane (CFU) as hydrocarbon, which is catalytically very effectively reformed by nickel within the SOEC stack before the starting material is converted electrochemically.
  • CFU methane
  • the internal reforming consumes heat from the ear losses of the electrochemical reaction.
  • the product gas or residual gas 31, which contains H2, H2O, CO and CO2, removed by the hydrogen electrode 3, is first cooled in a recuperator 32 to remove heat.
  • the recuperator 24a and the recuperator 32 can be designed as a common unit.
  • the cooled residual gas 33 is further cooled in a shift stage 34.
  • CO and H2O are converted to CO2 + H2 in a water-gas shift reaction. If necessary, fine CO cleaning is carried out in which residual amounts of CO are converted.
  • the purified residual gas 35 is then purified or conditioned.
  • a purification stage 36 can serve to remove H2O and / or CO2 or other accompanying substances.
  • Pressure swing adsorption (PSA), temperature swing adsorption (TSA), amine scrubbing, membrane processes and / or cryogenic separation processes can be used for purification.
  • a simple condenser or the methods mentioned above can be used to remove water or water vapor.
  • the purified hydrogen / synthesis gas 37 is then discharged from the system and can, for example, be fed to a downstream system for Fischer-Tropsch synthesis.
  • the separated residual gases 38 such as H2O and CO2 are normally reused, e.g. to save water to be treated or to increase the CO2 conversion.
  • the CO2 is recirculated in gaseous form and fed to the starting materials 25.
  • the standard volume flows of the supplied process gases 4, 20, 25 can be monitored and regulated by means of suitable actuators, such as mass flow controllers (MFC) 70.
  • MFC mass flow controllers
  • the amount of the standard volume flow of the purified hydrogen / synthesis gas 37 can also be monitored by means of a mass flow controller 70. For the sake of clarity, these are only indicated by way of example in Fig. 3.
  • At least one temperature sensor 80 is provided on the SOEC stack 1 in order to monitor the outlet temperature of the product gases 31 and thus the operation of the stack 1 in the thermo-neutral point and to be able to regulate the operation of the stack.
  • the sensor 80 can also be integrated at a suitable point in the stack 1.
  • the SOEC stack 1 is supplied with electrical power P by means of an AC / DC converter 40.
  • the AC / DC converter 39 is set up to receive power from an electrical supply network 41 and as direct current with a suitable voltage and current strength for the provide electrochemical reaction at the electrodes 2, 3 of the SOEC stack.
  • a DC / DC converter (not shown) can be provided in order to be able to supply the SOEC stack 1 with direct current from a DC power source (photovoltaic system) and / or a battery store (also not shown).
  • the DC / DC converter can be structurally standardized with the AC / DC converter 40. For the sake of clarity, individual phases of the electrical lines between the assemblies 1, 40 and 41 are not shown in FIG. 3.
  • a regulating device 50 receives measurement signals 72 from the mass flow controllers 70 and provides signals for the control 71 of the electrolysis process to the mass flow controllers 70.
  • Measurement signals 72 can be, for example, the current standard volume flows of the individual process gases or gas mixtures. The composition of the gases can also be monitored using suitable sensors.
  • the control device 50 receives measurement signals 82 from the AC / DC converter 40 and provides these signals for the control 71 of the electrolysis process. Measurement signals 82 are, for example, the current stack voltage and the current strength of the current.
  • the current density which can be calculated from the current intensity in relation to the active area of the cells, can be used as a variable derived from a measured variable as a measurement signal.
  • the control device 50 also receives measurement signals 72 from the temperature sensor 80; in particular, the temperature sensor provides measurement values for the stack temperature as measurement signal 72. Setpoint values for the stack temperature and standard volume flows are specified in the control device 50, and parameters and look-up tables required for the control are stored.
  • the control device 50 is connected to a higher-level control device 60 and can receive setpoint specifications for the control of the electrolysis process, e.g. the currently required amount of hydrogen, and provide information about the available amount of hydrogen and other status information.
  • the control device 60 can be part of a higher-level SCADA system.
  • the control device 50 is communicatively connected to the exchange of measurement signals and control commands and possibly further information with the AC / DC converter 40, the higher-level control device 60, as well as the mass flow controllers 70 and the temperature sensor 80 via corresponding signal lines (not shown for the sake of clarity).
  • the control device 50 can be selected as a programmable logic controller (PLC) or an industrial computer and includes at least one processor configured to process information including information from the mass flow controllers 70 and the temperature sensor 80.
  • the control device 50 comprises a transitory memory and a non-transitory memory for storing and providing information.
  • the method according to the invention can be stored as software or firmware in the non-transitory memory.
  • the control device 50 can further comprise at least one input / output device, which is any device known in the art for providing input data 72, 82 for the control system 50 and / or for providing output signals 71, 81 to the mass flow controllers 70 and the AC / DC Converter 40, may include.
  • the execution of command sequences is not limited to a specific one
  • the control device 50 can also contain at least one interface which enables the control device 50 to communicate with the mass flow controllers 70, the temperature sensor 80 and the AC / DC converter 40.
  • the sensor interface can, for example, be or contain one or more analog-to-digital converters that convert analog signals into digital signals that can be used by the processor.
  • the sensor interface can also be set up to process information using various data transmission protocols.

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Abstract

L'invention concerne un procédé de fonctionnement de système de piles à oxyde solide dans lequel de l'hydrogène H2 ou du gaz de synthèse CO + H2 est produit à partir de vapeur d'eau H2O(g) ou d'un mélange comprenant de la vapeur d'eau H2O(g) et du dioxyde de carbone CO2 dans une réaction électrochimique faisant intervenir un courant électrique. Une quantité supplémentaire d'au moins un composé est ajoutée à la vapeur d'eau H2O(g) ou au mélange comprenant de la vapeur d'eau H2O(g) et du dioxyde de carbone CO2, ledit composé étant choisi dans le groupe constitué par le gaz naturel, le méthane CH4 ou un autre hydrocarbure CmHn et étant ajouté afin d'effectuer une conversion en gaz de synthèse CO + H2. Un reformage endothermique de l'hydrocarbure ajouté est effectué par couplage dans la chaleur d'échappement en provenance de la réaction électrochimique, et la quantité supplémentaire dudit composé est ajoutée afin de compenser les effets d'une dégradation des piles à oxyde solide du système de piles à oxyde solide en ce qu'une quantité supplémentaire d'hydrogène H2 est produite avec laquelle la quantité totale de l'hydrogène H2 généré par le système de piles à oxyde solide est maintenue constante dans le temps.
EP21719920.7A 2020-04-23 2021-04-22 Procédé de fonctionnement de système de piles à oxyde solide Pending EP4139500A1 (fr)

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3901329A1 (fr) 2020-04-23 2021-10-27 sunfire GmbH Procédé de fonctionnement d'un système de cellule à oxyde solide
US12091759B2 (en) * 2021-07-16 2024-09-17 Bloom Energy Corporation Electrolyzer system with steam generation and method of operating same
JPWO2023042590A1 (fr) * 2021-09-16 2023-03-23
WO2023218246A1 (fr) * 2022-05-10 2023-11-16 Seeo2 Energy Inc. Système d'électrolyse modulaire et procédé de génération de carburant dans une cellule d'électrolyse à oxyde solide
CN120641530A (zh) 2023-03-17 2025-09-12 庄信万丰戴维科技有限公司 产生液态烃的方法
AT527535A1 (de) * 2023-08-22 2025-03-15 Avl List Gmbh Brennstoffzellensystem für ein Erzeugen eines Synthesegases
EP4553038A1 (fr) * 2023-11-09 2025-05-14 Linde GmbH Procédé et installation de production d'hydrogène
GB202401332D0 (en) 2024-02-01 2024-03-20 Johnson Matthey Davy Technologies Ltd Fischer-tropsch process and system
WO2026024811A1 (fr) * 2024-07-24 2026-01-29 Chevron U.S.A. Inc. Procédés et systèmes pour des applications de conversion d'électricité en carburant utilisant un gaz résiduaire provenant de la synthèse de carburant et/ou du méthane dans un électrolyseur à haute température

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019097429A1 (fr) * 2017-11-16 2019-05-23 Fuelcell Energy, Inc. Charge suivant la génération d'énergie et stockage d'énergie à l'aide de la technologie rep et pem

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6051125A (en) 1998-09-21 2000-04-18 The Regents Of The University Of California Natural gas-assisted steam electrolyzer
US7575822B2 (en) 2003-04-09 2009-08-18 Bloom Energy Corporation Method of optimizing operating efficiency of fuel cells
US20050112425A1 (en) * 2003-10-07 2005-05-26 Ztek Corporation Fuel cell for hydrogen production, electricity generation and co-production
WO2008033452A2 (fr) * 2006-09-13 2008-03-20 Ceramatec, Inc. Appareil et procédé de co-génération d'hydrogène de haute pureté et d'énergie électrique
US8366902B2 (en) * 2008-03-24 2013-02-05 Battelle Energy Alliance, Llc Methods and systems for producing syngas
JP5279419B2 (ja) * 2008-09-05 2013-09-04 株式会社 ウォーターウェア 水電解装置及び水電解システム
EP2783413B1 (fr) 2011-11-21 2018-10-17 Saudi Arabian Oil Company Procédé et système pour une production combinée d'hydrogène et d'électricité à l'aide de carburants à base de pétrole
CA2937948C (fr) * 2014-01-31 2019-10-01 Fuelcell Energy, Inc. Ensemble reformeur-electrolyseur-purificateur destine a la production d'hydrogene, systemes incorporant ledit ensemble et methode de production d'hydrogene
JP6346013B2 (ja) 2014-07-11 2018-06-20 株式会社東芝 高温水蒸気電解を用いた水素製造装置及び方法
EP3054519B1 (fr) * 2015-02-03 2017-11-08 Technische Universität München Système de pile à combustible réversible et procédé de contrôle d'un tel système
GB201522003D0 (en) * 2015-12-14 2016-01-27 Imp Innovations Ltd Regenerative fuel cells
EP3415661A1 (fr) * 2017-06-12 2018-12-19 SunFire GmbH Production de gaz de synthèse à partir de co2 et h2o dans une co-électrolyse
EP3901329A1 (fr) 2020-04-23 2021-10-27 sunfire GmbH Procédé de fonctionnement d'un système de cellule à oxyde solide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019097429A1 (fr) * 2017-11-16 2019-05-23 Fuelcell Energy, Inc. Charge suivant la génération d'énergie et stockage d'énergie à l'aide de la technologie rep et pem

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US20230155150A1 (en) 2023-05-18
US12412915B2 (en) 2025-09-09
AU2021260101A1 (en) 2022-12-08
WO2021214214A1 (fr) 2021-10-28

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