WO2023245220A2 - Système de pile à combustible, installation de pile à combustible et procédé de production de gaz de synthèse - Google Patents

Système de pile à combustible, installation de pile à combustible et procédé de production de gaz de synthèse Download PDF

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Publication number
WO2023245220A2
WO2023245220A2 PCT/AT2023/060198 AT2023060198W WO2023245220A2 WO 2023245220 A2 WO2023245220 A2 WO 2023245220A2 AT 2023060198 W AT2023060198 W AT 2023060198W WO 2023245220 A2 WO2023245220 A2 WO 2023245220A2
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WO
WIPO (PCT)
Prior art keywords
anode
fuel cell
gas
heat exchanger
cell system
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PCT/AT2023/060198
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German (de)
English (en)
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WO2023245220A3 (fr
Inventor
Manuel TANDL
Fabian ZAPF
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Avl List Gmbh
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Publication of WO2023245220A2 publication Critical patent/WO2023245220A2/fr
Publication of WO2023245220A3 publication Critical patent/WO2023245220A3/fr

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    • 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
    • C25B1/23—Carbon monoxide or syngas
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
    • H01M8/04022—Heating by combustion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126—Humidifying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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

Definitions

  • the present invention relates to a fuel cell system, a fuel cell system and a method for producing synthesis gas using a fuel cell system.
  • One way to reduce dependence on fossil raw materials and reduce CO2 emissions is to replace crude oil with synthetic hydrocarbons made from carbon dioxide (CO2) and water (H2O).
  • CO2 carbon dioxide
  • H2O water
  • SOE high-temperature electrolysis
  • the synthetic hydrocarbons are obtained from the synthesis gas.
  • a fuel cell system which is designed in particular as an electrolysis system, preferably for carrying out co-electrolysis.
  • the fuel cell system has a fuel cell stack with a cathode section, which has a cathode supply section and a cathode discharge section. section, and an anode section, which has an anode supply section and an anode discharge section.
  • the fuel cell system has an anode gas connection, which is fluidly coupled to the anode supply section by means of an anode supply connection, for supplying anode gas to the anode section.
  • the fuel cell system has an anode discharge connection, which is fluidly coupled to the anode discharge section by means of an anode discharge connection, for discharging anode exhaust gases generated by the fuel cell stack.
  • the fuel cell system has a cathode supply connection that is fluidly coupled to the cathode supply section by means of a cathode supply connection for supplying cathode gas to the cathode section.
  • the fuel cell system has a cathode discharge connection that is fluidly coupled to the cathode discharge section by means of a cathode discharge connection for discharging synthesis gas generated by the fuel cell stack.
  • the fuel cell system also has a residual gas supply connection for providing residual gas, which is separated from synthesis gas generated from the fuel cell stack in a synthesis process for producing synthetic hydrocarbons.
  • the fuel cell system further has a catalyst for the catalytic combustion of the residual gas, which is fluidly coupled to the residual gas connection by means of a residual gas supply connection, wherein a catalyst supply section and a catalyst discharge section of the catalyst are fluidly coupled to the anode discharge connection.
  • the fuel cell system has at least one heat exchanger which is arranged in the anode discharge connection in the flow direction (of the exhaust gases from the catalyst) behind the catalyst discharge section.
  • the efficiency of a fuel cell system is increased by using residual gas from the synthesis process to produce synthetic hydrocarbons for catalytic combustion within the fuel cell system.
  • the heat obtained during catalytic combustion is utilized within the fuel cell system by at least one heat exchanger.
  • the additional heat can be provided at various locations, in particular connections, very special supply connections, such as in particular the anode supply connection and / or cathode supply connection, in the fuel cell system and thus increase the efficiency of the high-temperature electrolysis, in particular high-temperature co-electrolysis, which is produced by the fuel cell stack is carried out to produce the synthetic gas or, in other words, synthesis gas.
  • this description is referred to as a fuel cell stack.
  • several fuel cell stacks are provided in the fuel cell system, which can be connected to one another in any way, for example can be connected to one another in series or in parallel.
  • Each cathode section and each anode section of each fuel cell stack is then fluidly coupled to the connections mentioned herein in the manner described herein.
  • the fuel cell stack can particularly be a solid oxide fuel cell stack.
  • the fuel cell system can therefore in particular be a solid oxide fuel cell system or solid oxide electrolyzer cell system (also SOFC system for “Solid Oxide Fuel Cell System”).
  • the fuel cell stack in the fuel cell system is in particular operable in an electrolysis mode or is operated in an electrolysis mode, in particular in a co-electrolysis mode, in order to achieve the electrolysis of water (H2O) and carbon dioxide (CO2).
  • the electrolytes in the fuel cell stack can produce hydrogen gas (H2), carbon monoxide (CO) and oxygen (02). It is advantageous if the fuel cell stack for generating the synthesis gas is connected to a power supply source for providing electricity from a renewable energy source. With such a power supply source, which is powered by renewable energy sources, high-temperature electrolysis operation can be made ecologically sustainable.
  • the fuel cell system is also understood to mean, in particular, an electrolysis system, preferably a co-electrolysis system, and/or a reversible fuel cell system.
  • an electrolysis system preferably a co-electrolysis system
  • a reversible fuel cell system it is possible to advantageously switch between fuel cell operation and electrolysis operation.
  • anode gas in particular air, especially fresh air, or oxygen
  • cathode gas is supplied to the cathode section.
  • cathode gas in particular carbon dioxide
  • the cathode supply connection can be connected to different carbon dioxide sources. It is possible, for example, to remove carbon dioxide from the air, from biogas processes, from industrial exhaust gases, etc.
  • Water can be supplied to the cathode supply section via a first additional supply connection for supplying water.
  • the first additional supply connection which can be fluidly coupled to the cathode supply connection or the cathode supply section by means of a first additional supply connection, can supply water, preferably in the form of water vapor, to the cathode supply section.
  • the water can be evaporated into water vapor in the fuel cell system.
  • the water vapor can be regarded as part of the cathode gas because it is supplied to the cathode supply section.
  • Any protective gas that is supplied to the cathode supply connection can also be regarded as part of the cathode gas because it is supplied to the cathode supply section.
  • the anode exhaust gases are discharged to the anode discharge connection by means of the anode discharge connection.
  • the anode exhaust gases removed in the anode discharge connection include, in particular, exhaust air or oxygen removed from the fuel cell system, especially air enriched with oxygen, as well as catalyst exhaust gases behind the catalyst, i.e. combustion products of the catalytic combustion of the residual gas mixed with the anode exhaust gas. These can be released into the environment, for example, from the anode discharge connection.
  • the generated cathode exhaust gas which is synthesis gas, which in particular mainly contains hydrogen gas and carbon monoxide, is fed to the cathode discharge connection.
  • This can be connected to a synthesis plant with a corresponding synthesis system in order to provide the synthetic gas for producing the synthetic hydrocarbons.
  • the synthesis gas can be converted in this synthesis process.
  • short-chain hydrocarbons are created during the synthesis process.
  • This separated gas portion is referred to herein as residual gas. It was surprisingly found that this residual gas has a high calorific value and can be used advantageously to provide heat in high-temperature electrolysis, which is particularly useful in the invention The efficiency of the fuel cell system can be increased in a proper manner.
  • first component second component
  • third component or elements
  • the compounds mentioned herein are fluid-carrying, in particular gas-carrying, connections.
  • the connections can be made via various paths or lines, such as pipes or hoses, which are each coupled to one another.
  • Various flow-influencing devices can be arranged in the connections, as mentioned herein, such as shut-off devices.
  • the heat exchanger exchanges the heat from two streams in the respective connections with each other, for example in countercurrent.
  • the heat exchanger is actually arranged in each of the two connections and the heat exchanger also thermally couples both connections to one another.
  • shut-off device As far as control or controlling is spoken of here, especially in connection with a shut-off device, this means controlling and/or regulating. stood. Even if this is not explicitly mentioned, appropriate control electronics and control devices that go beyond shut-off devices, such as flow meters, can be provided for monitoring.
  • shut-off devices mentioned here serve at least to stop or allow the flow of the respective fluid, in particular gas, flowing therein in the connections. It is also possible to control the flow rate depending on the type of shut-off device used. It is possible to design the shut-off device in a variety of ways, for example as a valve, gate valve, stopcock or butterfly valve.
  • At least two or at least three heat exchangers are arranged in the anode discharge connection in the flow direction behind the catalyst discharge section.
  • This allows the heat of the hot catalyst exhaust gases from the catalytic combustion of the residual gas to be used at several points, in particular feed connections, in the fuel cell system.
  • These multiple heat exchangers can be arranged in a series and/or parallel connection in the anode discharge connection. This not only allows the heat of the exhaust gases from the catalytic converter to be used several times and thus as efficiently as possible with heat exchangers connected in series, but also to control the amounts of heat in heat exchangers arranged in parallel in order to supply more or less heat to different points of the fuel cell system depending on the operation. This means that the amount of heat can be used individually tailored to the operation of the fuel cell stack.
  • a second heat exchanger of the at least one heat exchanger (which is arranged in the anode discharge connection in the flow direction behind the catalyst discharge section) is thermally coupled to the anode supply connection. This allows heat from the exhaust gases of the catalyst to be removed to the anode supply connection and thus to heat the anode gas arriving at the anode supply section to increase the efficiency of high-temperature electrolysis.
  • a third heat exchanger of the at least one heat exchanger (which is arranged in the anode discharge connection in the flow direction behind the catalyst discharge section) is thermally coupled to the cathode supply connection. This- allows to dissipate heat from the exhaust gases of the catalyst to the cathode supply connection and thus heat the cathode gas arriving at the cathode supply section to increase the efficiency of high-temperature electrolysis.
  • the second heat exchanger and the third heat exchanger are arranged in different partial paths of the anode discharge connection that are divided in the flow direction (of the catalyst exhaust gas) behind the catalyst discharge section. This allows the control of heat release as already mentioned above, namely between the anode and cathode supply connection.
  • the two partial paths can be reconnected to one another at a junction in the flow direction of the catalyst exhaust gas behind the heat exchanger and flow together to the anode discharge connection.
  • a shut-off device is advantageously arranged in at least one of the two partial paths.
  • a shut-off device is particularly advantageously arranged in both partial paths.
  • a butterfly valve can be used as a shut-off device. This allows simple yet precise control of the catalyst exhaust gas flow from the catalyst and the amount of heat carried by it.
  • the at least one shut-off element is arranged behind the second heat exchanger or the third heat exchanger in the flow direction (of the exhaust gas from the catalytic converter). If there are two shut-off devices, both shut-off devices can be arranged behind the respective heat exchanger. This makes it possible to use comparatively inexpensive and simple shut-off devices because they do not have to withstand extremely high temperatures, such as those of the exhaust gas behind the catalytic converter. In contrast, the exhaust gas behind the heat exchangers has already cooled down due to the heat exchange, so that the temperatures here are already lower, although this residual temperature in the exhaust gas can still be advantageously used for further heat exchange.
  • a fourth heat exchanger of the at least one heat exchanger (which is arranged in the anode discharge connection in the flow direction behind the catalyst discharge section) is thermally coupled to a first additional supply connection, which connects the cathode supply connection or the cathode supply section with a first additional supply connection for supplying water or water vapor to the cathode feed section.
  • This fourth heat exchanger can be particularly behind the second in the direction of flow Heat exchanger and / or third heat exchanger may be arranged.
  • the residual heat still contained in the exhaust gas in the anode discharge connection after the heat exchange in the second and/or third heat exchanger can be used to heat the water or the water vapor supplied at the first additional supply connection and thereby further increase the efficiency of the fuel cell system.
  • a fifth heat exchanger of the at least one heat exchanger (which is arranged in the anode discharge connection in the flow direction behind the catalyst discharge section) is arranged in the anode discharge connection and is thermally coupled to the anode supply connection.
  • This fifth heat exchanger can be arranged particularly behind the second heat exchanger and/or third heat exchanger in the direction of flow.
  • a first heat exchanger is arranged in the anode feed connection and is thermally coupled to the anode discharge connection in the flow direction upstream of the catalyst feed section.
  • the heat of the catalyst exhaust gases with the anode exhaust gas, in particular the discharged air, from the anode discharge section can be used to heat the anode gas, in particular the supplied air.
  • this has the advantage that the anode exhaust gases of the anode section are cooled by the heat transfer, whereby the self-ignition temperature of the residual gas-anode exhaust gas mixture is undershot, which is generated by mixing the residual gas and the anode exhaust gas in the flow direction behind the first heat exchanger.
  • anode exhaust gas is very oxygen-rich with approximately 30% oxygen, since oxygen diffuses from the cathode section to the anode section in the fuel cell stack.
  • the reduction below the self-ignition temperature is expedient in that high thermal stress on the components in the fuel cell system is prevented and controlled combustion is ensured via the subsequent catalyst.
  • a second bypass path connects the anode supply connection in the flow direction in front of the first heat exchanger with the anode supply connection in the flow direction behind the first heat exchanger, with a second shut-off element being arranged in the second bypass path surrounding the first heat exchanger and/or in the anode supply connection Flow direction behind a branch from the anode supply connection to the second bypass path and in front of the first heat exchanger a third shut-off device is arranged.
  • This allows the supplied air in the anode supply connection to easily bypass the first heat exchanger. Furthermore, this enables easy control of the temperature of the anode gas and the anode exhaust gas in the respective anode connection.
  • a first heating device can advantageously be arranged in the second bypass path.
  • the first heating device can in particular be an electric heater. In this way, the temperature of the supplied anode gas can be increased even further in order to operate the fuel cell stack in an optimized operating point.
  • the anode discharge connection is advantageously connected to the anode supply connection in the flow direction upstream of the catalyst supply section by means of a first bypass path.
  • a first bypass path In addition to the mixing that already occurs upstream of the catalytic converter, in which the oxygen-rich exhaust air of the anode exhaust gas from the anode discharge section is mixed with the residual gas, additional, cool air can be introduced into the catalytic converter for the catalytic combustion and thus also used for cooling.
  • a first shut-off element is advantageously arranged in the first bypass path. This allows the amount of additional air supplied to be controlled.
  • the catalyst is designed as an oxidation catalyst.
  • An oxidation catalyst can oxidize pollutants such as carbon monoxide and hydrocarbons, but cannot reduce nitrogen oxides. With the help of an oxidation catalyst, the energy contained in the residual gas can be used in the form of heat, whereby the hydrogen still present in the exhaust gas is also converted.
  • the fuel cell system also has a first additional supply connection for providing heated water vapor, which is used during cooling in the synthesis process of the fuel produced by the fuel cell stack. produced synthesis gas is heated. Accordingly, to optimize the efficiency of the fuel cell system, not only the residual gas from the synthesis process, but also the heated water vapor generated during cooling during the synthesis process is made usable, whereby a double and synergistic efficiency optimization of the high-temperature electrolysis is achieved.
  • the present invention also relates to a fuel cell system with a fuel cell system according to the invention and a synthesis system with a synthesis system.
  • the cathode discharge connection is fluidly coupled to the synthesis system by means of a synthesis gas supply connection.
  • the synthesis system is also set up to synthesize the synthesis gas generated by the fuel cell stack and supplied by means of the synthesis gas supply connection.
  • the synthesis system is fluidly coupled to the residual gas supply connection by means of a residual gas discharge connection for providing residual gas.
  • the fuel cell system is to be understood in particular as a complete system, which is preferably designed as a so-called “power-to-liquid system” or PtL system.
  • a fuel cell system according to the invention therefore brings with it the same advantages as have been explained in detail with reference to the fuel cell system according to the invention.
  • the present invention also relates to a method for producing synthesis gas by means of a fuel cell system, in particular the fuel cell system according to the invention and further in particular by means of the fuel cell system according to the invention, comprising the steps:
  • a method according to the invention therefore brings with it the same advantages as have been explained in detail with reference to the fuel cell system according to the invention.
  • the fuel cell system according to the invention and/or the fuel cell system according to the invention can be set up or designed to carry out the method according to the invention.
  • the anode gas is understood to mean the gas supplied to the anode section, i.e. in particular air or oxygen. This excludes the anode exhaust gas, i.e. the exhaust gas discharged from the anode section, in particular air and/or oxygen.
  • the cathode gas is understood to mean the gas supplied to the cathode section, in particular carbon dioxide, water vapor and/or a protective gas. This excludes the cathode exhaust gas, i.e. the synthetic gas removed from the cathode section.
  • the catalyst exhaust gas stream of the catalytic combustion is divided into two sub-paths and in a first sub-path of the two sub-paths heat is transferred from the at least one heat exchanger to the anode gas by means of a second heat exchanger and in a second sub-path of the two Partial paths by means of a third heat exchanger from which at least one heat exchanger heat is transferred to the cathode gas.
  • This allows the control of heat release as already mentioned above, namely between the anode and cathode supply connection.
  • the catalyst exhaust gas flow in the two partial paths is controlled by means of a shut-off device in each of the two partial paths behind the respective heat exchanger of the respective partial path.
  • catalyst exhaust gas stream is brought together again in the two partial paths after heat transfer to the anode gas and cathode gas becomes. This allows the catalyst exhaust gas stream to be discharged together at the anode discharge connection.
  • the combined catalyst exhaust gas stream flows for further heat transfer through a fourth heat exchanger for heating water or water vapor supplied to the fuel cell system and/or through a fifth heat exchanger for heating the anode gas. This makes it possible to use any remaining heat in the catalyst exhaust gas stream to further increase the efficiency of the fuel cell system.
  • the residual gas is mixed with anode exhaust gas of the fuel cell stack before the catalyst feed section to form a residual gas-anode exhaust gas mixture.
  • the oxygen-rich air of the anode exhaust gas can thus raise the temperature of the residual gas-anode exhaust gas mixture and be used for controlled catalytic combustion.
  • the anode exhaust gas transfers heat to the supplied anode gas by means of a first heat exchanger before it is mixed with the residual gas.
  • the supplied anode gas can be heated with the air and, on the other hand, the anode exhaust gas can be cooled with the air, in particular below the self-ignition temperature of the residual gas-anode exhaust gas mixture.
  • anode gas is added to the residual gas-anode exhaust gas mixture. This can be done through the first bypass path mentioned previously. The amount of air can thus be further increased by anode gas containing fresh air in the residual gas-anode exhaust gas mixture.
  • the residual gas-anode exhaust gas mixture has a temperature in the range from 300 to 550 °C, in particular in the range from 400 to 500 °C. This refers to the temperature at the catalyst supply section. The highest increase in efficiency when producing the synthesis gas was observed in this temperature range.
  • the catalyst exhaust gases from the catalytic combustion have a temperature in the range from 800 to 1,000 °C, in particular in the range from 850 °C to 950 °C. This refers to the temperature at the catalyst discharge section. The highest increase in efficiency when producing the synthesis gas was observed in this temperature range.
  • the synthesis gas produced is fed to the synthesis process, from which the residual gas is separated and fed to the catalyst.
  • the synthesis process is a Fischer-Tropsch process.
  • the coupling of high-temperature electrolysis, in particular high-temperature co-electrolysis, and Fischer-Tropsch synthesis (FTS for short) has proven to be a particularly promising variant for the production of different hydrocarbons.
  • FTS Fischer-Tropsch synthesis
  • synthesis gas resulting from high-temperature co-electrolysis is produced at comparatively moderate temperatures, particularly in the temperature range of 200 to 300 °C, and elevated pressures, particularly in the pressure range of 10 to 30 bar, using a catalyst, in particular Co- or Fe - based, converted into hydrocarbon molecules with different chain lengths.
  • the FTS process is highly exothermic.
  • cooling can be carried out along the length of a reactor in the synthesis plant. Cooling can be done with water evaporation at the specified pressure level. The water vapor can then be used for further process steps and, as mentioned above, for the high-temperature electrolysis itself by supplying the water vapor to the cathode gas.
  • the hydrocarbon chain length distribution resulting from FTS is described by a chain growth probability (with a high chain growth probability, large molecules and thus a shift towards liquid fuels). However, the synthesis gas is not completely converted. In addition, depending on the probability of chain growth, short-chain molecules are created that cannot be used as liquid fuel.
  • the unreacted synthesis gas and the resulting short-chain hydrocarbons can be separated out as the residual gas in product processing. While some of the residual gas can be recirculated into the FTS, some of it must be discharged. In particular, the discharged part of the residual gas is used in the process according to the invention.
  • 1 shows a first embodiment of a fuel cell system according to the invention
  • 2 shows a second embodiment of a fuel cell system according to the invention
  • FIG. 3 shows a third embodiment of a fuel cell system according to the invention.
  • Fig. 4 shows an embodiment of a method according to the invention.
  • FIG. 1 shows schematically a fuel cell system 30 comprising a fuel cell system 10 with a fuel cell stack 100 and a synthesis system 20 with a synthesis system 900.
  • the fuel cell system 10 and the synthesis system 20 are fluidly coupled to one another, as will be explained in more detail later.
  • the fuel cell stack 100 has a cathode section 110 with a cathode supply section 112 and a cathode discharge section 114. Furthermore, the fuel cell stack 100 has an anode section 120 with an anode supply section 122 and an anode discharge section 124.
  • a power supply source 130 which provides electricity from renewable energies, is connected to the fuel cell stack 100.
  • the fuel cell stack 100 is in the present case designed as a solid oxide fuel cell stack and is used in the electrolysis mode for high-temperature co-electrolysis.
  • Anode gas in the form of fresh air is provided in the fuel cell system 10 by means of an anode gas connection 202.
  • the anode gas is provided to the fuel cell stack 100 for electrolysis via an anode supply connection 200, which is fluidly coupled to the anode gas connection 202 and the anode supply section 122.
  • a filter device 204 in particular in the form of an air filter, for air filtering and a blower 206 for transporting the anode gas are arranged in the anode supply connection 200.
  • a first heat exchanger 220 is arranged in the flow direction of the anode gas from the anode gas connection 202 to the anode supply section 122 behind the filter insert. direction 204 and the fan 206.
  • the first heat exchanger 220 is used for heat exchange with a warm anode exhaust gas, in particular in the form of exhaust air removed from the anode section 120, from the fuel cell stack 100.
  • the first heat exchanger 220 is thermally coupled to an anode discharge connection 300 in front of a catalyst 404 in the form of an oxidation catalyst.
  • the anode discharge connection 300 fluidly connects the anode discharge section 124 to an anode discharge connection 316.
  • the catalyst 404 is arranged in the anode discharge connection 300 in the flow direction of the anode exhaust gas behind the first heat exchanger 220 and is fluidly coupled to a residual gas connection 402 by means of a residual gas supply connection 400.
  • the residual gas connection 402 receives residual gas from the synthesis system 900, as will be described in more detail later.
  • the residual gas supply connection 400 and the anode discharge connection 300 are fluidly connected to one another.
  • the residual gas provided for the catalyst 404 is therefore mixed with the anode exhaust gas in the anode discharge connection 300 to form a residual gas-anode exhaust gas mixture, in particular a residual gas-air mixture, before it reaches the catalyst feed section 406 and is then catalytically burned by the catalyst 404.
  • a first bypass path 208 with a first shut-off element 210 arranged therein connects the anode supply connection 200 in the flow direction of the anode gas in front of the first heat exchanger 220 with the anode discharge connection 300 in front of the catalyst supply section 406 and thus allows the air portion of the residual gas-anode exhaust gas mixture to be removed before entering the catalyst 404 to increase further.
  • a second bypass path 212 with a second shut-off element 214 is provided, which connects the anode supply connection 200 in the flow direction of the anode gas in front of the first heat exchanger 220 with the anode supply connection 200 in the flow direction of the anode gas behind the first heat exchanger 220 and thereby makes it possible to control the temperature of the residual gas anode exhaust gas -To control the mixture in front of the catalytic converter 404 by regulating the amount of anode gas flowing through the first heat exchanger 220. Furthermore, it is in the direction of flow A third shut-off element 218 is arranged in front of the second heat exchanger 220 and behind the second bypass path 212.
  • the hot catalyst exhaust gases flow in the anode discharge connection 300 through two individual partial paths 302, 308, into which the anode discharge connection 300 is divided in the flow direction of the catalyst exhaust gas behind the catalyst discharge section 408.
  • a second heat exchanger 304 which is thermally coupled to the anode supply connection 200. This allows the heat of the catalyst exhaust gas to be delivered to the anode gas before the anode supply section 122.
  • a fourth shut-off element 306 for controlling the catalyst exhaust gas flow in the first partial path 302.
  • the third heat exchanger 310 is thermally coupled to a cathode supply connection 500.
  • the cathode supply connection 500 fluidly connects a cathode supply connection 502 to the cathode supply section 112.
  • cathode gas in particular carbon dioxide
  • An ejector 504 is arranged in the cathode supply connection 500 in the direction of flow of the anode gas in front of the cathode section 110.
  • a second heating device 506 in the present case in the form of an electric heater, is arranged behind the ejector 504 in the flow direction of the anode gas.
  • the cathode gas can be heated with the heat from the catalyst exhaust gas.
  • cathode exhaust gas in the form of the synthesis gas generated by the high-temperature co-electrolysis, comprising hydrogen and carbon monoxide, is discharged to the synthesis system 20.
  • cathode discharge connection 600 for example, two heat exchangers 608, 610, namely a sixth heat exchanger 608 and a seventh heat exchanger 610, are thermally arranged and thermally coupled to the cathode supply connection 500 in order to transfer heat from the synthesis gas to the cathode gas and thus increase the efficiency of the Fuel cell system 10 to increase.
  • a second additional supply connection 800 fluidly connects a second additional supply connection 802 for supplying a protective gas to the cathode supply connection 500.
  • the second additional supply connection 800 is divided here, for example, into two sub-paths 804, 806, namely a third sub-path 806 and a fourth sub-path 806.
  • the third sub-path 804 leads to the anode supply connection 500 in the flow direction upstream of the ejector 504 and in particular in front of the heat exchangers 608, 610, while the fourth sub-path 806 leads to the ejector 504.
  • a third bypass path 602 leads from the cathode discharge section 600 to the fourth partial path 806 in front of the ejector 504.
  • a nozzle 604, in particular a Venturi nozzle, and a sixth shut-off element 606, in particular a valve, are arranged in the third bypass path 602.
  • the fuel cell stack 100 supplied in the manner described above with anode gas, comprising air, and cathode gas, comprising carbon dioxide, water vapor and protective gas, generates the cathode exhaust gas in the form of synthesis gas, comprising hydrogen and carbon monoxide, in the electrolysis mode by high-temperature co-electrolysis. and the anode exhaust gas, comprising exhaust air.
  • the anode exhaust gas is catalytically burned by the catalyst 404 together with residual gas, so that catalyst exhaust gases are separated from the fuel cell system 10 at the anode discharge port 316.
  • the synthesis gas is provided to the synthesis system 900 of the synthesis system 20 by a synthesis gas supply connection 906, which fluidly connects a synthesis supply section 902 of the synthesis system 900 to the cathode discharge connection 612.
  • a synthesis gas supply connection 906 which fluidly connects a synthesis supply section 902 of the synthesis system 900 to the cathode discharge connection 612.
  • a reactor there, not explicitly shown, it goes through a a synthesis process, in particular a Fischer-Tropsch synthesis process, and is converted into synthetic hydrocarbons.
  • the hydrocarbons are removed via a hydrocarbon removal connection 908 which is fluidly connected to a synthesis removal section 904.
  • synthesis gas and short-chain hydrocarbons that are not converted in the synthesis process remain, some of which can be fed back to the synthesis process and some of which can be discharged as residual gases by means of a residual gas discharge connection 910 to the residual gas supply connection 402, which are fluidly coupled to one another in this respect.
  • FIG. 2 shows a modification of the embodiment of the fuel cell system 30 of Figure 1.
  • the fourth heat exchanger 314 was omitted in FIG. Instead, a fifth heat exchanger 318 was used in the anode discharge connection 300 in the flow direction behind the two heat exchangers 304, 310, which is thermally coupled to the anode supply connection 200, in particular in the flow direction of the anode gas behind the blower 206 and in front of the first heat exchanger 220.
  • This allows the residual heat in the anode exhaust gas to be made available alternatively for the anode gas.
  • any configuration of the heat exchangers 220, 304, 310, 314, 320, 608, 610 shown is possible, which means that these heat exchangers can each be used alone or in any selection thereof in the fuel cell system 10, so it is not necessary to equip the fuel cell system 10 with all heat exchangers 220, 304, 310, 314, 320, 608, 610.
  • FIG 3 shows a variation of the fuel cell system 30 of the embodiment of Figure 1, in which changes in the synthesis system 20 are provided.
  • a cooling device 914 is shown in the synthesis plant 900, which in particular cools a corresponding reactor in the synthesis plant 900. Steam is used to cool the highly exothermic reaction of the synthesis process. The water vapor heated in this way is advantageously supplied to the first additional supply connection 702 by means of a corresponding fluid connection connected to the first supply.
  • Third additional feed connection 916 connected to set feed connection 702 is provided.
  • FIG. 4 shows the method 1000 for generating synthesis gas by means of the fuel cell system 10, which has already been explained with reference to FIGS , whereby further process steps not explicitly shown can be added.
  • a first method step 1002 of the method 1000 residual gas is separated from the synthesis process taking place in the synthesis system 900, in which the synthesis gas from the cathode discharge connection 612 is converted into hydrocarbons.
  • the residual gas is provided to the residual gas supply port 402 by means of the residual gas discharge connection 910 and is thus provided to the catalyst 404 of the fuel cell system 10.
  • the residual gas is burned catalytically by means of the catalyst 404.
  • Corresponding catalyst exhaust gases emerge from its catalyst discharge section 408.
  • the catalyst exhaust gases can have a temperature in the range of 800 to 1,000 °C. 1 to 3, the residual gas can have previously been mixed with the anode exhaust gas and also with the anode gas, i.e. fresh air, so that a residual gas-anode exhaust gas mixture enters the catalyst feed section 404.
  • the residual gas-anode exhaust gas mixture can have a temperature in the range from 300 to 550 °C.
  • heat from the catalyst exhaust gas stream of the catalytic combustion is transferred by means of one or more of the heat exchangers 304, 310, 314, 320 to the anode gas in the anode supply connection 200 and/or the cathode gas in the cathode supply connection 500, as can be seen in Figures 1 to 3.
  • the anode gases and cathode gases heated in this way are supplied to the fuel cell stack 100 of the fuel cell system 10 in a fourth method step 1008 of the method 1000 with the supply of electrical current.
  • the synthesis gas can be generated by means of the fuel cell stack 100 from the supplied anode gas, cathode gas and electrical current.
  • the method steps 1002 to 1010 of the method 1000 are carried out continuously, as indicated by the arrow from method step 1010 to method step 1002.

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  • Manufacturing & Machinery (AREA)
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  • Automation & Control Theory (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un système de pile à combustible (10), une installation de pile à combustible (30) comprenant un système de pile à combustible (10) et un système de synthèse (20) ainsi qu'un procédé (1000) de production de gaz de synthèse au moyen du système de pile à combustible (10).
PCT/AT2023/060198 2022-06-23 2023-06-22 Système de pile à combustible, installation de pile à combustible et procédé de production de gaz de synthèse WO2023245220A2 (fr)

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ATA50453/2022 2022-06-23
ATA50453/2022A AT526077B1 (de) 2022-06-23 2022-06-23 Brennstoffzellensystem, Brennstoffzellenanlage und Verfahren zum Erzeugen von Synthesegas

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WO2023245220A3 WO2023245220A3 (fr) 2024-04-18

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US9631284B2 (en) * 2013-03-15 2017-04-25 Colorado School Of Mines Electrochemical device for syngas and liquid fuels production
DE102015226111A1 (de) * 2015-12-18 2017-06-22 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung Verfahren zur Erzeugung von Kohlenstoff-basierten Sekundärenergieträgern oder Basischemikalien
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
DE102020128868A1 (de) * 2020-11-03 2022-05-05 Karlsruher Institut für Technologie Umwandlung von CO2 in chemische Energieträger und Produkte

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