WO1998013892A1 - Installation a piles a combustible pourvue de piles a combustible a haute temperature tubulaires - Google Patents

Installation a piles a combustible pourvue de piles a combustible a haute temperature tubulaires Download PDF

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Publication number
WO1998013892A1
WO1998013892A1 PCT/EP1997/005143 EP9705143W WO9813892A1 WO 1998013892 A1 WO1998013892 A1 WO 1998013892A1 EP 9705143 W EP9705143 W EP 9705143W WO 9813892 A1 WO9813892 A1 WO 9813892A1
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WO
WIPO (PCT)
Prior art keywords
fuel cell
gas
fuel
cell device
tubes
Prior art date
Application number
PCT/EP1997/005143
Other languages
German (de)
English (en)
Inventor
Wolfgang Winkler
Original Assignee
Wolfgang Winkler
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 Wolfgang Winkler filed Critical Wolfgang Winkler
Priority to EP97910312A priority Critical patent/EP0870343A1/fr
Publication of WO1998013892A1 publication Critical patent/WO1998013892A1/fr

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Classifications

    • 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
    • H01M8/0606—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
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/243—Grouping of unit cells of tubular or cylindrical configuration
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a fuel cell device with tubular high-temperature fuel cells.
  • Fuel cells are increasingly being used for the direct generation of electricity from the combustion reaction of the fuel in energy technology.
  • the largely isothermally available cell waste heat with cell temperature can be used for further electricity generation in a thermal power process if the fuel cells are operated at high temperature (high-temperature fuel cells).
  • This gradual use of the thermodynamic potential of the combustion reaction by means of the combination of the fuel cell and the thermal power process means that electrical efficiencies of up to 80% can be expected.
  • ⁇ Winkler W. Possibilities of designing combined cycle power plants with high-temperature fuel cells.
  • Winkler W Analysis of the system behavior of power plant processes with fuel cells.
  • SOFC Solid Oxide Fuel Cell
  • one electrode is on the inside and the other on the outside of the fuel cell tube, both electrodes being electrical and separated on the gas side but connected to one another with regard to the transport of oxygen ions.
  • the term "electrical” refers here and below to the transportation of Electrons. All materials used must have approximately the same thermal expansion in order to avoid inadmissible thermal stresses. Air is applied to the cathode and fuel gas to the anode.
  • the individual cells are used to build structures, stacks or stacks, which are suitable for use in power plants.
  • the fuel cells are electrically connected in series to achieve technically usable voltages.
  • a simultaneous parallel connection of the individual cells or stacks of the same voltage level ensures the necessary redundancy in the event of failure of individual cells or stacks.
  • a step-by-step combustion of the fuel gas in cells connected in series ensures that, as far as advanced concepts are concerned, the working capacity of the fuel gas is utilized as much as possible.
  • the second u.a. The solution known from US-A-5 273 839 is based on an electrolyte which is open in the longitudinal direction of the tube and which forms the necessarily gastight tube only when the connection is made (see Westinghouse concept, for example in: The Westinghouse solid oxide fuel cell program - A 1992 progress report, Westinghouse Electric Corporation, Pittsburgh, 1992).
  • the cathode is applied to the inside of the tube and is contacted via the connection contact. On the outside, the anode is applied with corresponding openings so that there is no electrical connection to the connection contact.
  • the tube is closed on one side.
  • the construction is reminiscent of a longitudinally welded tube and the cell is not rotationally symmetrical.
  • the combustion air is introduced into the cell tube near the closed end through an internal ceramic tube and flows out along the cathode side of the cell.
  • the fuel gas is supplied outside.
  • the individual cells are connected in series via the contacting of a cell through the connection contacting with nickel felt on the anode side of the next cell. By adding the fuel gas in the direction of flow of the electric current, this construction also enables cascading.
  • the desired redundancy can be achieved by contacting the individual cells of the same voltage level with nickel felt on the anode side.
  • the electrolyte does not form a closed tube and the fuel cell is therefore no longer rotationally symmetrical.
  • the contacts made on the outside of the tube relate to a total of three voltage levels.
  • the inner tube for air supply limits the tube diameter downwards and thus the power density upwards. Serial electrical connection and cascading is only possible with several pipes.
  • the object of the invention is to design the construction of the fuel cell and the stack so that the serial circuit and the cascading in one Fuel cell tube is made so that the parallel connection of the individual voltage levels takes place in a stack, that the fuel cell tube and its components on the outer surfaces that are important for production and handling are completely rotationally symmetrical even during the production steps, that there is a downward design limitation of the diameter of the fuel cell tube does not exist and that the stack ensures the favorable integration of the required external cooling of the fuel cell tubes.
  • stack also refers here to an arrangement of fuel cell tubes connected in parallel.
  • the electrodes on the outside of a rotationally symmetrical high-temperature fuel cell element are electrically conductively connected to one another by a felt that is resistant to high temperatures and thus form a single voltage level of parallel-connected cell elements;
  • the electrodes of the inner sides of the parallel connected fuel cell elements of a voltage level are electrically connected to the electrodes of the outer sides of the corresponding fuel cell elements of a further voltage level by gas-tight connection contacts, the respective outer spaces of the parallel connected cell elements of both voltage levels filled with the electrically conductive felt by electrically insulating but gas-permeable intermediate floors or other suitable gas-permeable separating elements are separated in order to avoid short circuits.
  • the number of voltage levels that are electrically connected in series is determined by the desired design voltage of the stack.
  • Fuel cell elements form the finished fuel cell tube.
  • the main flow direction of the fuel gas and the combustion air is parallel to the pipe axis.
  • a preferred form of training is the direct current arrangement and Another form of training is the countercurrent arrangement.
  • a uniform distribution of the fuel gas flow is ensured by means of resistance elements at the inlet and / or by means of fuel injection at several points.
  • the gas flow on the anode side is also referred to as anode gas and on the cathode side also as cathode gas, regardless of the type of local gas composition.
  • the cathode side that is exposed to air lies on the inside and outside the anode side that is exposed to fuel gas and that is contacted with nickel felt or another material with a similar structure. If only nickel felt is used in the following, another material with a similar structure is also included, i.e. an electrically conductive felt resistant to the high temperatures of the fuel cell.
  • Another embodiment is the formation of the outside of the cell elements of the fuel cell tube as a cathode. Felts with fibers made of cathode material are used for contacting. The rest of the description refers to the design with the external anode side and the contact with nickel felt, since there is no difference in the construction of the two variants, apart from the exchange of the gas flows and the necessary other materials for the felt.
  • Fuel cell elements of different voltage levels are preferably connected to one another in a gas-tight manner by means of annular connection contacts, the cathode side of the fuel cells of the first voltage level and the anode side of the fuel cell of the next voltage level in the flow direction of the fuel gas being conductively connected to one another via the connection contacts.
  • the fuel cells / ears are softly stored in the nickel felt surrounding them and are not braced with the intermediate floors, but the intermediate floors allow slight compensatory movements.
  • the fuel cell tubes of the stack are expediently fitted gas-tight at their ends facing the inlet side in a perforated plate. In this way, the passage of air to the anode side of the fuel cells is prevented.
  • the perforated plate consists of electrically conductive material with the same thermal expansion as the material of the fuel cells and is conductively connected to the anodes of the fuel cells and the contacting nickel felt.
  • the series connection of the fuel cell elements begins with a cathode-ready contact on the perforated plate, insulation being provided between the perforated plate and the nickel felt
  • the fuel cell stacks are preferably designed such that both gas flows are routed separately to a post-combustion chamber.
  • nozzle-shaped outlet connection contacts are provided on the outlet sides of the fuel cell tubes, which establish a conductive connection for current dissipation of the fuel cell stack. Precautions have been taken in the arrangement and design of the outlet nozzles that largely avoid the formation of nitrogen oxides during exhaust gas combustion.
  • connection between the outlet connection contacts of the fuel cell tubes at the stack outlet by means of nickel felt is preferably designed such that anode gas is constantly present in the area. This makes oxidation impossible. Additional current leads are preferably movably arranged within the nickel felt to a certain extent in order to reduce the electrical resistance of the current leads. At the anode-side outlet there is an electrically conductive nozzle base or a conductive network in the stack.
  • the fuel gas is added in the area of the air outlet.
  • the exit area of the combustion air is designed such that the area of the current discharge on the cathode side - gas-tight - separates the area of the anode side of the fuel cell tubes lined with nickel felt and the exit area on the cathode side to prevent a gas mixture
  • the fuel gas flow takes place against the flow of the combustion air towards the air inlet. This is where the anode-side exhaust gas generated during combustion is deflected. Channels conduct the anode-side exhaust gas to the air outlet area and to the afterburning chamber.
  • Another embodiment of the counterflow arrangement allows separate removal of the anode-side exhaust gas and the exhaust air from the cathode side, an air box being provided at the outlet of the fuel cell tubes for collecting the cathode-side exhaust air.
  • the exhaust air and the anode-side exhaust gas are removed via separate channels.
  • the stack is closed to the outside by solid walls.
  • continuous ceramic walls or combinations of metallic walls with ceramic insulation pieces are preferably provided in the transition area between the voltage levels.
  • the respective stack similar to a flat burner.
  • Other embodiments of the stack floor plan are circular and ring-shaped or hexagonal.
  • the afterburning chamber is designed in particular as a common combustion chamber.
  • the combustion air is supplied via the supply line and air box to the cathode side of the fuel cell tubes.
  • the fuel gas is supplied laterally at several points via a fuel gas line and or via separate nozzles in the perforated plate of the respective stack.
  • This design allows the stack floor plan to be adapted to various required floor plans.
  • the cooling tubes are designed as radiation coolers and are made of electrically insulating material, as a result of which short circuits are avoided.
  • a useful further development of the invention is the use of cooling tubes which are integrated in the stack parallel to the cell tubes.
  • Part of the heat released in the fuel cell stack is preferably immediately available for the endothermic process of fuel processing and or another part of this heat is provided for preheating the combustion air and or reheating cooled exhaust gas for further use in downstream processes.
  • Corresponding catalyst material is provided in the tubes for the cooling tubes which are used for fuel processing.
  • a further developed embodiment of a cooler integrated in the stack consists of an electrically insulating tube, which is closed on the outlet side of the stack and is arranged in central locations parallel to the heat-supplying fuel cell tubes in the stack Open pipe arranged, which supplies the arrangement with cooling gas.
  • the inner pipe is arranged centrally in the outer pipe so that the annular gap created between the pipes is sufficient to ensure that the cooling gas flows out functionally.
  • the cooling gas is combustion air, which after heating up flows into the air box and then to the cathode side of the fuel cell tubes.
  • natural gas or another hydrocarbon-containing fuel gas is the cooling gas.
  • the tube arrangement in which the pre-reforming now takes place, is provided with catalyst material and the previously reformed fuel gas flows through suitable openings in the outer tube, which are arranged on the inlet side of the stack, to the anode side of the fuel cell tubes.
  • An expedient development of the invention also uses the heat released in the afterburning for the fuel preparation and / or the air preheating and / or the reheating of the flue gas for use in downstream processes.
  • Coal or biomass gasification can be provided in an allothermal gasification, the tubes heated by the stacks and / or the afterburning chamber serving as a heat source.
  • the fuel cell tube it is advantageous to use a continuous, porous carrier tube made of non-conductive material with the same thermal expansion as the electrolyte and to apply the individual fuel cell elements with coatings of cathode, electrolyte and anode material to the carrier tube by means of suitable thin-film or sintering technology.
  • the individual cell elements which are formed one behind the other in this way are electrically connected in series by means of suitably applied gas-tight connection contacts.
  • a partially electrically conductive carrier tube which consists of a chain of tube elements made of cathode material, which by means of ring-shaped elements made of electrically insulating material with the same
  • Tube are connected.
  • the outer surfaces of the tube elements are provided with a thin gas-tight layer of electrolyte material except for a small annular section at the end of each tube element made of cathode material, which remains free as a connection.
  • the pipe surface is coated with anode material.
  • the individual cell elements that are formed one behind the other are electrically connected in series by means of suitably applied gas-tight connection contacts in order to form the fuel cell tube.
  • tubular elements from cathode material in such a way that the conductor cross section of the tubular element increases due to internal ribs. With the same conductor cross-section, this permits thinner wall thicknesses of the construction and thus smaller diffusion paths for the combustion air and, during start-up operations, higher permissible temperature change rates than is possible with ordinary pipes. That to build the partially electric conductive support tube necessary annular element made of electrically insulating material is designed so that it is provided on both sides with a number of pin-shaped fitting elements which are fitted into the inner ribs of the tubular element made of cathode material and are equipped with suitable technology.
  • Another advantageous further development of the invention is the formation of gas channels parallel to the fuel cell tubes in the external nickel felt, inner rings or porous tubes made of nickel material being introduced in such a way that they exert a slight contact pressure on the nickel felt when heated and thus the contact between the nickel felt and the anode side of the Improve fuel cell tube.
  • a further advantageous development of the invention is the production of individual voltage levels, each provided with the associated gas-permeable intermediate floors, consisting of the required number of cell elements, nickel felt and inner rings which, when soaked in volatile plastic or water glass, result in a compact block.
  • the gas-tight cell elements are designed so that they are equipped with a contact surface on the cathode and anode, as well as the necessary insulation.
  • the assembly into the fuel cell tubes is then carried out in all tubes of the stack in one operation per voltage level by connecting the associated cell elements to one another in an electrically serial and gas-tight manner using a suitable joining method.
  • 1 shows part of a fuel cell device in section
  • 2 shows a fuel cell device with tubular fuel cell elements connected in series in section
  • 3a shows a fuel cell device with an arrangement for the supply of fuel gas in countercurrent
  • 3b shows a fuel cell device with an arrangement for the supply of fuel gas in direct current
  • Fig. 4 shows a fuel cell device with a fuel gas supply in
  • Fig. 6 shows part of the fuel cell device as a section
  • FIG. 7b shows a part of the fuel cell device as a section of a fuel cell tube with a partially electrically conductive carrier tube
  • FIG. 8a shows a part of the fuel cell device as a cross section of a cathode tube provided with inner fins
  • Fig. 8b a part of the fuel cell device as a section of the electrically non-conductive connecting elements of a partially electrically conductive support tube and the fit into the inner ribs of the
  • FIG. 9 is a sectional view through part of the fuel cell device with anode-side gas channel and pressure rings of the nickel felt contact.
  • FIG. 1 shows a fuel cell device 30 of a basic type of rotation-symmetrical high-temperature fuel cells (SOFC) have inner cathodes 2 and outer anodes 3 on the circumference, which are separated by the electrolyte 23.
  • the fuel cells are preferably designed as tubes.
  • the cell elements 1 are acted upon on the inside on the cathode side with air, which is denoted by 2a, and on the outside on the anode side with fuel gas, which is denoted by 3a.
  • the arrows 2a, 3a point in the direction of flow. 1 is rotationally symmetrical with respect to a central axis S.
  • the cell elements 1 are contacted by a high-temperature-resistant, electrically conductive metal felt, which is, in particular, nickel felt 4.
  • a high-temperature-resistant, electrically conductive metal felt which is, in particular, nickel felt 4.
  • nickel felt 4 another material with a similar structure can be used.
  • a voltage level is formed by the electrically conductive connection of cell elements 1 arranged in parallel on the same spatial level.
  • This concept has the advantage that the anode space with the porous layer of nickel felt 4 or the like. Contacting material can be filled without paying particular attention to the location of the felt.
  • the main flow direction of the fuel gas is parallel to the tube axis S, which means that both a cocurrent and a countercurrent arrangement is possible.
  • a uniform distribution of the fuel gas flow is ensured by appropriate resistance elements at the inlet and / or by fuel injection at several points in a fuel cell stack. The structural design of the stacking element of a stress level is thus defined.
  • anodes 3 fuel gas and reaction product gas 3a
  • cathodes 2 combustion air and exhaust air 2a
  • the electrical wiring the cascading, so that the structure of the fuel cell tube 100 and the afterburning of anode and cathode exhaust gas, as well as the integration of the fuel gas preparation and the stack cooling.
  • gas flow on the anode side is also referred to as anode gas 3a and on the cathode side also as cathode gas 2a, regardless of the type of local gas composition.
  • Cascading can be achieved very easily by connecting stack elements of several voltage levels to one another in such a way that the elements are electrically connected in series.
  • the individual cell elements 1 are gas-tightly connected with annular connection contacts 5 such that the cathodes 2 of the stacking element n are contacted with the anodes 3 of the stacking element n + 1 via the connection contacts 5.
  • the connection contact material e.g. lanthanum chromite
  • the connection contact material must be electrically conductive and chemically stable at the operating temperature and have the same thermal expansion as the electrolyte material (ytterium-doped zirconium oxide).
  • the individual row elements 1 connected in series form the fuel cell tube 100, through which air flows.
  • a gas-permeable intermediate floor 6 made of insulator material which is designed, for example, as a nozzle bottom, is inserted with corresponding passages for the fuel cell tubes 100 between the individual stacking elements or spacers made of insulator material are used which prevent a short circuit between two voltage levels.
  • the fuel cell tubes 100 are not clamped by these intermediate floors, but rather can move as freely as possible in order to rule out possible expansion problems from the outset.
  • zirconium oxide as the insulator material. This ensures the function of cascading and the anode-side parallel connection of the individual voltage levels within the stack. The electrical and gas connection of the stack to the overall system remains to be solved.
  • the cell elements 1 of the first group of stacking elements on the air side are fitted gas-tight in a perforated plate 7 such that the cathode gas 2a can flow into the fuel cell tubes 100 without coming into contact with the anode gas 3a.
  • the perforated plate 7 consists of electrically conductive material with the same possible thermal expansion as the SOFC (eg lanthanum chromite) and is conductively connected to the anode 3 of the SOFC.
  • the serial connection of the cell elements 1 on the perforated plate 7 begins with a correspondingly modified connection of the cells with a cathode-side contact. Insulation between perforated plate 7 and nickel felt 4 is provided.
  • anode gas space is initially electrically insulated from the outside by a gas-permeable intermediate floor 9 or spacers made of insulator material.
  • the electrical current generated in the stack can then be tapped off on the cathode side.
  • the cathode side of each fuel cell tube 100 is provided for contacting with the nozzle-shaped outlet connection contacts 10.
  • This connection is arranged between outlet connection contact 10 and adjacent fuel cell tubes 100 in such a way that it is always wetted with anode gas 3a and therefore oxidation is excluded.
  • This also allows the use of nickel felt 4 or the like as a material for current dissipation.
  • This type of construction has the advantage of a movable mounting of the fuel cell tubes 100 at the outlet and avoids largely unintentional forces on the fuel cell tubes 100. Additional rigid current leads can be movably attached within the nickel felt 4 in order to minimize the resistance of the lead. To the outside, the construction is completed by the conductive nozzle floor or a conductive mesh 12.
  • the outlet connection contact 10 and the conductive nozzle base 12 are designed and arranged in such a way that nitrogen oxide formation during the combustion of the anode exhaust gas is largely avoided.
  • the anode gas 3a is added as a fuel gas in the counterflow arrangement in the area of the air outlet and the outlet area of the combustion air is designed such that the current discharge on the cathode side - gas-tight - separates the cell area and the outlet area so that a mixture of anode exhaust gas and fresh fuel gas is excluded.
  • the fresh fuel gas flows against the flow of the combustion air in the direction of the air inlet. This is where the exhaust gas product generated during combustion is deflected. Channels guide the exhaust gas product to the air outlet area and to the afterburning chamber 8.
  • FIG. 3b Another embodiment of the counterflow arrangement, which is shown in broken lines in FIG Collection of the cathode-side exhaust air is provided.
  • the exhaust air 2b and the anode-side exhaust gas 3b are removed via separate channels.
  • the direct current arrangement, which has already been described above, is shown in FIG. 3b.
  • the stack must be terminated towards page 13 in such a way that no short circuit can occur between the individual voltage levels. This is solved by continuous ceramic walls. A combination of metallic walls with ceramic insulation pieces in the transition area between the individual voltage levels is another solution.
  • the stacks formed in this way have a modular structure and their size can be designed in such a way that the cooling of the stack from the outside is ensured by suitable heat exchanger devices which can be used to heat the working fluid in a downstream thermal power process or to heat another parallel or downstream endothermic process is.
  • Combustion air as cathode gas 2a comes from a supply line 14 to air box 16 and from there enters the cathode side of fuel cell tubes 100.
  • the fuel gas as anode gas 3a is fed laterally into the stack 17 via the fuel gas line 15.
  • the stack 17 is constructed here similar to a flat burner and the post-combustion chamber 8 is designed as a common combustion chamber.
  • the size of the individual stacks is determined by the cooling conditions in order to ensure that the stacks are operated as isothermally as possible.
  • the cooling tubes 18 are arranged as radiation coolers.
  • Another possible variant is an integration of the cooling tubes parallel to the fuel cell tubes 100 in the stack 17 itself.
  • the cooling tubes 18 must, however, consist of insulator material in order to avoid short circuits in the stack.
  • a combination of cooling tubes 18 integrated in the stack 17 with external cooling tubes 18 as shown in FIG. 4 is another possible flexible variant.
  • circular, ring-shaped or hexagonal shapes for the stack 17 or also floor plans are possible, which require a specific installation situation if the supply of air and fuel is ensured.
  • the fuel preparation takes place in such a way that the heat released at the fuel cell is used directly for the endothermic process of fuel preparation. Reforming is common today when using natural gas.
  • the arrangements shown in FIG. 4 and the arrangements described above are also suitable for integrating the reforming into the stack 17. For this purpose, only the number of cooling tubes 18, which are necessary to cover the heat requirement of the reforming, are filled with catalyst material.
  • allothermal gasification is a suitable process and here the cooling pipes 18 or the post-combustion chamber 8 serve as a heat source for the allothermal gasification.
  • a further developed embodiment of a cooler integrated in the stack consists of an insulating tube 22, which is closed on the outlet side of the stack 17 and is arranged in central positions parallel to the heat-defying fuel cell tubes 100 in the stack, as shown in FIG. 5.
  • a second tube 24 which is open on the inside and which supplies the arrangement with cooling gas.
  • the inner tube is arranged centrally in the outer tube so that the between the tubes 22, 24 resulting annular gap is sufficient to ensure a functional discharge of the cooling gas.
  • the cooling gas is combustion air as cathode gas 2 a, which after heating up flows into the air box 16 and then to the cathode side of the fuel cell tubes 100.
  • FIG. 1 the cooling gas is combustion air as cathode gas 2 a, which after heating up flows into the air box 16 and then to the cathode side of the fuel cell tubes 100.
  • the tube arrangement consisting of tubes 22 and 24, in which the pre-reforming now takes place, is provided with catalyst material and the pre-deformed fuel gas flows through suitable openings in the outer tube 22, which are arranged on the inlet side of the stack 17, to the anode side of the fuel cell tubes 100.
  • This arrangement is gas-tightly separated from the air side, in particular from the air box 16.
  • FIG. 6 shows a detail of the structure of a fuel cell tube 100 which is applied to a carrier tube 19.
  • a continuous, porous carrier tube 19 made of non-conductive material with the same thermal expansion as the electrolyte 23
  • the individual cell elements located one behind the other in this way are electrically connected in series by means of suitably applied gas-tight connection contacts 5.
  • a useful further development is a partially electrically conductive carrier tube, which is formed from a chain of tube elements made of the material of the cathodes 2, which are connected to the carrier tube by means of annular elements 20 made of electrically insulating material with approximately the same thermal expansion as the electrolyte 23 using a suitable joining technique , as shown in Fig. 7a.
  • the outer surfaces of the tubular elements are provided with a thin gas-tight layer made of material of the electrolyte 23 except for a small annular section at the end of each tubular element made of material of the cathodes 2, which remains free.
  • the portion of the tube surface provided with electrolyte material is with the material of the anodes 3 coated.
  • the individual cell elements which are formed one behind the other in this way are electrically connected in series by means of suitably applied gas-tight connection contacts 5 in order to form the fuel cell tube 100.
  • the part of the cathode 2 that remains free is connected to the anode 3 of the next tubular element, as shown in FIG. 7b.
  • FIGS. 8a and 8b An advantageous further development is shown in FIGS. 8a and 8b. It is advantageous to design the tubular elements from the material of the cathodes 2 in such a way that the internal cross-section 21 increases the conductor cross section of the tubular element. With the same conductor cross-section, this permits thinner wall thicknesses of the construction and thus smaller diffusion paths for the combustion air and, during start-up operations, higher permissible temperature change rates than is possible with ordinary pipes.
  • the annular element 20 made of electrically insulating material, which is necessary for the construction of the partially electrically conductive carrier tube, is designed such that it is provided on both sides with a number of pin-shaped fitting elements 27, which fit into the inner ribs 21 of the tubular element made of cathode material and using suitable technology are decreed.
  • FIG. 9 A further advantageous development of a fuel cell device is shown in FIG. 9.
  • the formation of gas channels 25 parallel to the central axis of the cell elements 1 is provided in the outer nickel felt 4, inner rings 26 or porous tubes made of nickel material being introduced in such a way that they exert a slight contact pressure when heated exert on the nickel felt 4 and thus improve the contact between the nickel felt 4 and the anode side of the fuel cell tube 1.

Abstract

L'invention concerne une installation à piles à combustible (30) pourvu de piles à combustible à haute température. Les piles à combustible sont conçues, avec une symétrie de révolution, comme des éléments de pile (1) auxquels est appliqué, à l'intérieur, du côté des cathodes (2), de l'air de combustion en tant que gaz de cathode (2a) et, à l'extérieur, du côté des anodes (3), du gaz combustible en tant que gaz d'anode (3a). Les piles à combustible sont, à l'extérieur, du côté des anodes complètement en contact avec un feutre métallique, tel qu'un feutre en nickel (4) ou analogue, conducteur et résistant aux températures élevées et forment ainsi un plan de tension.
PCT/EP1997/005143 1996-09-26 1997-09-19 Installation a piles a combustible pourvue de piles a combustible a haute temperature tubulaires WO1998013892A1 (fr)

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EP97910312A EP0870343A1 (fr) 1996-09-26 1997-09-19 Installation a piles a combustible pourvue de piles a combustible a haute temperature tubulaires

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DE19639517.8 1996-09-26
DE19639517A DE19639517A1 (de) 1996-09-26 1996-09-26 Brennstoffzelleneinrichtung

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WO1999054951A1 (fr) * 1998-04-17 1999-10-28 Siemens Westinghouse Power Corporation Systeme de distribution de combustible dans un empilement de piles a combustible
WO2004107491A1 (fr) * 2003-06-03 2004-12-09 Alpps Fuel Cell Systems Gmbh Microreacteur
US8389180B2 (en) 2006-09-11 2013-03-05 Battelle Energy Alliance, Llc Electrolytic/fuel cell bundles and systems including a current collector in communication with an electrode thereof
EP1273061B1 (fr) 2000-03-29 2016-08-10 Dcns Systeme de pile a combustible a gestion de charge

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DE10342493B4 (de) * 2003-09-12 2008-04-10 Clausthaler Umwelttechnikinstitut Gmbh, (Cutec-Institut) Brennstoffzellenmodul und Brennstoffzellenbatterie
US20090145761A1 (en) * 2007-12-11 2009-06-11 Van Hassel Bart A Oxygen separation element and method
DE102009037148B4 (de) 2009-08-06 2014-02-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Festoxid-Brennstoffzellen-System
DE102022114730B3 (de) 2022-06-10 2023-08-03 Audi Aktiengesellschaft Stapelmodulbox, Brennstoffzellenvorrichtung sowie Brennstoffzellen-Fahrzeug

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999054951A1 (fr) * 1998-04-17 1999-10-28 Siemens Westinghouse Power Corporation Systeme de distribution de combustible dans un empilement de piles a combustible
EP1273061B1 (fr) 2000-03-29 2016-08-10 Dcns Systeme de pile a combustible a gestion de charge
WO2004107491A1 (fr) * 2003-06-03 2004-12-09 Alpps Fuel Cell Systems Gmbh Microreacteur
US8389180B2 (en) 2006-09-11 2013-03-05 Battelle Energy Alliance, Llc Electrolytic/fuel cell bundles and systems including a current collector in communication with an electrode thereof

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DE19639517A1 (de) 1998-04-09

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