EP1836744A1 - Reformer for a fuel cell - Google Patents

Reformer for a fuel cell

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Publication number
EP1836744A1
EP1836744A1 EP05825900A EP05825900A EP1836744A1 EP 1836744 A1 EP1836744 A1 EP 1836744A1 EP 05825900 A EP05825900 A EP 05825900A EP 05825900 A EP05825900 A EP 05825900A EP 1836744 A1 EP1836744 A1 EP 1836744A1
Authority
EP
European Patent Office
Prior art keywords
chamber
fuel cell
reformer
heat pipe
heat
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.)
Withdrawn
Application number
EP05825900A
Other languages
German (de)
French (fr)
Inventor
Marco Mühlner
Andreas Lindermeir
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.)
Enerday GmbH
Original Assignee
Webasto SE
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 Webasto SE filed Critical Webasto SE
Publication of EP1836744A1 publication Critical patent/EP1836744A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • 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
    • 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
    • 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
    • H01M8/04059—Evaporative processes for the cooling of a fuel cell
    • 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
    • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0883—Methods of cooling by indirect 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
    • H01M8/04029—Heat exchange using liquids
    • 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 reformer for a fuel cell having a chamber having a chamber inlet to the inlet of a Reaktandengasgemisches and a chamber outlet to the outlet of a reformed gas, wherein in the chamber a catalytically active medium is arranged.
  • Generic reformers have numerous applications. In particular, they serve to supply a hydrogen-rich gas mixture to a fuel cell, from which electrical energy can then be generated on the basis of electrochemical processes.
  • fuel cells are used for example in the automotive sector as additional energy sources, so-called APUs ("auxiliary power unit").
  • the design of the reformers depends on numerous factors. In addition to the consideration of the properties of the reaction system, for example, economic aspects are of importance, in particular the integration of the reformer in its environment. The latter also concerns how the material and energy flows entering and leaving the reactor are treated. Depending on the application and the environment of the reformer thus different reforming methods are used, whereby different reformer designs are necessary.
  • CPOX Catalytic Partial Oxidation
  • Fuel-air mixture the reaction in the flow direction can be divided into two different zones. Upon entry into the catalytic Medium first strong exothermic oxidation reactions take place. Subsequently, the intermediates occurring are reformed in a subsequent region of the catalytically active medium.
  • the reformation process is an endothermic reaction in which the temperatures drop sharply, resulting in losses of revenue.
  • the net heat production in the reforming process of the catalytic partial oxidation in the inlet region of the reformer is so great that damage to the materials involved can occur there.
  • the catalytically active medium can be deactivated or the support materials can be destroyed. Since the liberated heat of reaction from the oxidation zone can not be brought into the reforming zone, the control of the reforming process is problematic, so that in general a polytropic reaction can not be avoided, but which has a lower degree of conversion.
  • the invention provides that the reformer has a heat pipe with an outer cylindrical tube wall and an inner cylindrical boundary wall, wherein the chamber between the outer tube wall and the inner boundary wall is arranged.
  • the basic idea of the invention is to achieve both a radially and axially isothermal temperature distribution in the catalytically active medium with the aid of a heat pipe, which is characterized by rapid heat transport.
  • the chamber inlet is arranged near a first axial end of a heat pipe and the chamber outlet near a second axial end of the heat pipe, so that a temperature compensation can take place over the largest possible axial region of the heat pipe. It is particularly preferred if the chamber between the chamber inlet and the chamber outlet is formed spirally. Due to the small cross-sectional area through which the temperature gradients in the radial direction are thus minimized.
  • FIG. 1 shows a cross section through a reformer in a first embodiment of the invention
  • Fig. 2 shows the axial temperature profile in the reformer in polytroper (dashed curve) and isothermal process control (solid curve), and
  • Fig. 3 shows the fuel cell system with the reformer in a schematic representation.
  • Fig. 1 shows a reformer 10 for a fuel cell system shown below, wherein the reformer 10 has a heat pipe 12 with an outer circular cylindrical tube wall 14 and an inner also circular cylindrical boundary wall 16. At a first axial end 18 of the heat pipe 12 there is a chamber inlet 20 through which a reactant gas mixture, consisting for example of air and vaporized fuel, may enter the reformer. At a second axial end 22 of the heat pipe 12, a chamber outlet 24 is arranged, via which reformed gas can leave the reformer 10. Outer tube wall 14 and inner boundary wall 16 bound a chamber 26 which extends between the chamber inlet 20 and the chamber outlet 24. The chamber 26 is formed in the embodiment shown here between the chamber inlet 20 and the chamber outlet 24 spirally.
  • a channel 28 is milled in that in the inner cylindrical boundary wall 16, a channel 28 is milled.
  • the dimension A of the channel in the radial direction of the heat pipe 12 is small compared to the radium R of the heat pipe 12.
  • the temperature gradient in the radial direction in the chamber 26 is very small.
  • a bed 30 is arranged from a catalytically active medium, wherein the catalytically active medium is present in the form of pellets in the embodiment shown here.
  • the inner boundary wall 16 encloses an inner chamber 32 which has a filling of a liquid metal.
  • Liquid metal fillings are particularly well suited for the temperature range up to 1100 ° C.
  • lithium or sodium is used.
  • the inner boundary wall 16 can be made of stainless steel.
  • a heat exchanger 34 is arranged in the region of the second axial end 22 of the heat pipe 12.
  • heat energy from the heat pipe 12 to other system components of the fuel cell can be transmitted.
  • the heat energy can be transferred to a liquid or gaseous medium flowing in a pipeline 36 and from there to the other system components. Further details will be described below.
  • FIG. 3 shows the integration of the reformer 10 into a fuel cell system 38.
  • a fuel supply line 39 is connected to a media delivery device 40 which is connected to an evaporator 42.
  • Fuel supply line 39 and an air supply line 46 are connected to a mixture forming device 44, which in turn is connected to the chamber inlet 20.
  • Adjoining the chamber outlet 24 of the reformer 10 is a fuel cell stack 48 followed by a fuel cell stack 48.
  • burner 50 is connected downstream.
  • the fuel cell stack 48 is still provided with a Kathodenluftzu- line 52.
  • Fuel is supplied to the evaporator 42 via the fuel supply line 39 by means of the media delivery device 40, where it is converted into a gaseous phase.
  • the vaporized fuel then flows into the mixture forming device 44, into which air is supplied via the air supply line 46 and mixed with the evaporated fuel.
  • the fuel-air mixture is then introduced via the chamber inlet 20 into the reformer 10 (FIG. 1).
  • the fuel-air mixture now enters the bed 30 with the catalytically active medium. By means of the bed 30 with the catalytically active medium takes place, a conversion of the fuel-air mixture to intermediates, wherein the initially released heat of reaction from the oxidation reactions by means of the heat pipe 12 is transferred to the filling of the inner chamber 32.
  • the heat of reaction released in the region of the first axial end 18 of the heat pipe 12 is then transferred via the filling of the inner chamber 32 to the region of the second axial end 22 of the heat pipe 12.
  • a local overheating at the first axial end 18 of the heat pipe 12 is avoided, as is usual in polytroper reaction (see Fig. 2, dashed curve) and a practically constant temperature over the entire axial extent of the heat pipe 12 is reached (see FIG 2, solid curve).
  • the intermediates formed in the region of the first axial end 18 of the heat pipe 12 are now transported in the channel 28 in the region of the second axial end 22 of the heat pipe 12, where a reforming of the intermediates takes place.
  • FIG. 2 shows how local overheating at the first axial end 18 of the heat pipe 12 in the region of the chamber inlet 20, as occurs in the prior art polytropic reaction guide (see FIG. 2, dashed curve), is avoided, and FIG by the use of the heat pipe 12 a practically constant temperature profile over the entire axial extent of the heat pipe 12 between the chamber inlet 20 and chamber outlet 24 is achieved (see Fig. 2, solid curve).
  • the maximum temperature T ma ⁇ which should not be exceeded in order not to reduce the lifetime of the catalytically active medium and the carrier materials is not exceeded in any area of the heat pipe 12. Local overheating is excluded.
  • the reformed gas leaving the chamber outlet 24 is now supplied to the fuel cell stack 48 (see FIG. 3), in which the electrical energy is released in a known manner.
  • the gases flowing out of the fuel cell stack 48 are now supplied to the afterburner 50, in which they are still used thermally.
  • the fuel cell system 38 Since the fuel cell system 38 overall has a surplus of heat energy dependent on the mass flow of the reactant gas mixture at the chamber inlet 20, it can be used by the heat exchanger 34 for further system components of the fuel cell system 38.
  • system components may be the mixture formation device 44 or the cathode air of the cathode air supply line 52 of the fuel cell stack 48.
  • the pipe 36 of the heat exchanger 34 is then to be connected in a corresponding manner with the air supply line 46 or the cathode air supply line 52.
  • the heat energy from the heat exchanger 34 may also be supplied directly to a heating system in a combined system for providing electrical energy and heat.
  • the control of the conversion processes is considerably simplified and the modulability with regard to the media flows is increased.
  • the yield of reformed gas increases significantly.
  • the reaction can be further optimized. If two reformers 10 are interconnected in a suitable manner via pipelines and valves, an alternating use and regeneration operation of the two reformers can be realized: while one of the two reformers is being regenerated, the second reformer can provide reformed gases for operation of the fuel cell system 38 , After regeneration of the first reformer and after exhaustion of the second reformer is switched and the first reformer can generate reformed gases for the fuel cell system 38 again. For higher gas flow rates, several reformers 10 can be operated in parallel. This also allows the use of various fuels, which may be in both liquid and gaseous form.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Fuel Cell (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

The invention relates to a reformer (10) for a fuel cell, comprising a chamber (26), with a chamber inlet (20) for admission of a reactant gas mixture and a chamber outlet (24), for the exhaust of a reformed gas, whereby a catalytic medium is arranged in said chamber (26). According to the invention, the reformer (10) comprises a heating tube (12) with an outer cylindrical tube wall (14) and an inner cylindrical defining wall (16), whereby the chamber (26) is arranged between the outer tube wall (14) and the inner defining wall (16).

Description

Reformer für eine Brennstoffzelle Reformer for a fuel cell
Die Erfindung betrifft einen Reformer für eine Brennstoffzelle mit einer Kammer, die einen Kammereintritt zum Einlass eines Reaktandengasgemisches und einen Kammeraustritt zum Auslass eines reformierten Gases hat, wobei in der Kammer ein katalytisch wirkendes Medium angeordnet ist.The invention relates to a reformer for a fuel cell having a chamber having a chamber inlet to the inlet of a Reaktandengasgemisches and a chamber outlet to the outlet of a reformed gas, wherein in the chamber a catalytically active medium is arranged.
Gattungsgemäße Reformer haben zahlreiche Anwendungsbereiche. Insbesondere dienen sie dazu, einer Brennstoffzelle ein wasserstoffreiches Gasgemisch zuzuführen, aus dem dann auf der Grundlage elektrochemischer Vorgänge elektrische Energie erzeugt werden kann. Derartige Brennstoffzellen kommen beispielsweise im Kraftfahrzeugbereich als Zusatzenergiequellen, so genannte APUs („auxiliary power unit"), zum Einsatz.Generic reformers have numerous applications. In particular, they serve to supply a hydrogen-rich gas mixture to a fuel cell, from which electrical energy can then be generated on the basis of electrochemical processes. Such fuel cells are used for example in the automotive sector as additional energy sources, so-called APUs ("auxiliary power unit").
Die Auslegung der Reformer ist von zahlreichen Faktoren abhängig. Neben der Berücksichtigung der Eigenschaften des Reaktionssystems sind zum Beispiel wirtschaftliche Aspekte von Bedeutung, insbesondere auch die Einbindung des Reformers in seine Umgebung. Letzteres betrifft auch, wie die in den Reaktor ein- und austretenden Stoff- und Energieströme behandelt werden. In Abhängigkeit von der Applikation und der Umgebung des Reformers kommen somit unterschiedliche Reformierungsverfahren zum Einsatz, wodurch unterschiedliche Reformerkonstruktionen notwendig werden.The design of the reformers depends on numerous factors. In addition to the consideration of the properties of the reaction system, for example, economic aspects are of importance, in particular the integration of the reformer in its environment. The latter also concerns how the material and energy flows entering and leaving the reactor are treated. Depending on the application and the environment of the reformer thus different reforming methods are used, whereby different reformer designs are necessary.
Ein Beispiel für einen Reformierungsprozess ist die so genannte katalytische Reformierung, bei dem ein Gemisch aus Luft und Kraftstoff mit Hilfe eines katalytisch wirkenden Mediums in einer exothermen Reaktion zu einem wasserstoffreichen Reformat umgesetzt wird, mit dem die Brennstoffzelle betrieben werden kann (CPOX = Catalytic Partial Oxidation). Bei dieser katalytischen Umsetzung desAn example of a reforming process is the so-called catalytic reforming, in which a mixture of air and fuel is converted by means of a catalytically active medium in an exothermic reaction to a hydrogen-rich reformate, with which the fuel cell can be operated (CPOX = Catalytic Partial Oxidation ). In this catalytic implementation of the
Kraftstoff-Luft-Gemisches kann die Reaktion in Strömungsrichtung in zwei unterschiedliche Zonen eingeteilt werden. Beim Eintritt in das katalytisch wirkenden Medium finden zunächst stark exotherme Oxidationsreaktionen statt. Anschließend werden die auftretenden Zwischenprodukte in einem nachfolgenden Bereich des katalytisch wirkenden Mediums reformiert. Der Reformationsprozess ist eine endotherme Reaktion, bei dem die Temperaturen stark abfallen, und damit Um- satzeinbußen entstehen.Fuel-air mixture, the reaction in the flow direction can be divided into two different zones. Upon entry into the catalytic Medium first strong exothermic oxidation reactions take place. Subsequently, the intermediates occurring are reformed in a subsequent region of the catalytically active medium. The reformation process is an endothermic reaction in which the temperatures drop sharply, resulting in losses of revenue.
Die Nettowärmeproduktion ist beim Reformierverfahren der katalytischen partiellen Oxidation im Eintrittsbereich des Reformers so groß, dass es dort zu einer Schädigung der beteiligten Werkstoffe kommen kann. So kann beispielsweise das katalytisch wirkende Medium deaktiviert oder die Trägermaterialien können zerstört werden. Da die frei werdende Reaktionswärme aus der Oxidationszone nicht in die Reformierungszone gebracht werden kann, ist die Steuerung des Reformie- rungsprozesses problematisch, so dass in der Regel eine polytrope Reaktionsführung nicht zu umgehen ist, die jedoch einen geringeren Umsatzgrad aufweist.The net heat production in the reforming process of the catalytic partial oxidation in the inlet region of the reformer is so great that damage to the materials involved can occur there. For example, the catalytically active medium can be deactivated or the support materials can be destroyed. Since the liberated heat of reaction from the oxidation zone can not be brought into the reforming zone, the control of the reforming process is problematic, so that in general a polytropic reaction can not be avoided, but which has a lower degree of conversion.
Um eine verbesserte Umsetzung des Reaktandengasgemisches in das reformierte Gas zu erreichen, ist erfindungsgemäß vorgesehen, dass der Reformer ein Wärmerohr mit einer äußeren zylindrischen Rohrwand und einer inneren zylindrischen Begrenzungswand aufweist, wobei die Kammer zwischen der äußeren Rohrwand und der inneren Begrenzungswand angeordnet ist.In order to achieve an improved conversion of the reactant gas mixture in the reformed gas, the invention provides that the reformer has a heat pipe with an outer cylindrical tube wall and an inner cylindrical boundary wall, wherein the chamber between the outer tube wall and the inner boundary wall is arranged.
Die Grundidee der Erfindung besteht darin, mit Hilfe eines Wärmerohrs, das sich durch einen schnellen Wärmetransport auszeichnet, sowohl eine radial als auch axial isotherme Temperaturverteilung im katalytisch wirkenden Medium zu erzie- len.The basic idea of the invention is to achieve both a radially and axially isothermal temperature distribution in the catalytically active medium with the aid of a heat pipe, which is characterized by rapid heat transport.
In einer bevorzugten Ausführungsform ist der Kammereintritt nahe einem ersten axialen Ende eines Wärmerohrs und der Kammeraustritt nahe einem zweiten axialen Ende des Wärmerohrs angeordnet, so dass über einen möglichst großen axialen Bereich des Wärmerohrs ein Temperaturausgleich stattfinden kann. Besonders bevorzugt ist, wenn die Kammer zwischen dem Kammereintritt und dem Kammeraustritt spiralförmig ausgebildet ist. Durch die kleine durchströmte Querschnittsfläche werden somit auch die Temperaturgradienten in radialer Richtung minimiert.In a preferred embodiment, the chamber inlet is arranged near a first axial end of a heat pipe and the chamber outlet near a second axial end of the heat pipe, so that a temperature compensation can take place over the largest possible axial region of the heat pipe. It is particularly preferred if the chamber between the chamber inlet and the chamber outlet is formed spirally. Due to the small cross-sectional area through which the temperature gradients in the radial direction are thus minimized.
Weitere Ausführungsformen der Erfindung sind den Unteransprüchen zu entnehmen.Further embodiments of the invention can be found in the dependent claims.
Die Erfindung wird nachfolgend anhand von Ausführungsbeispielen näher erläu- tert, wobei auf Zeichnungen Bezug genommen wird. Die Zeichnungen zeigen:The invention will be explained in more detail with reference to exemplary embodiments, reference being made to drawings. The drawings show:
Fig. 1 einen Querschnitt durch einen Reformer in einer ersten Ausführungsform der Erfindung,1 shows a cross section through a reformer in a first embodiment of the invention,
Fig. 2 den axialen Temperaturverlauf im Reformer bei polytroper (Gestrichelte Kurve) bzw. isothermer Prozessführung (durchgezogene Kurve), undFig. 2 shows the axial temperature profile in the reformer in polytroper (dashed curve) and isothermal process control (solid curve), and
Fig. 3 das Brennstoffzellensystem mit dem Reformer in einer schematischen Darstellung.Fig. 3 shows the fuel cell system with the reformer in a schematic representation.
Fig. 1 zeigt einen Reformer 10 für ein im Folgenden dargestelltes Brennstoffzellensystem, wobei der Reformer 10 ein Wärmerohr 12 mit einer äußeren kreiszylindrischen Rohrwand 14 und einer inneren ebenfalls kreiszylindrischen Begrenzungswand 16 aufweist. An einem ersten axialen Ende 18 des Wärmerohrs 12 befindet sich ein Kammereintritt 20, durch den ein Reaktandengasgemisch, das zum Beispiel aus Luft und verdampftem Kraftstoff besteht, in den Reformer eintreten kann. An einem zweiten axialen Ende 22 des Wärmerohrs 12 ist ein Kammeraustritt 24 angeordnet, über den reformiertes Gas den Reformer 10 verlassen kann. Äußere Rohrwand 14 und innere Begrenzungswand 16 begrenzen eine Kammer 26, die sich zwischen dem Kammereintritt 20 und dem Kammeraustritt 24 erstreckt. Die Kammer 26 ist in der hier gezeigten Ausführungsform zwischen dem Kammereintritt 20 und dem Kammeraustritt 24 spiralförmig ausgebildet. Dies ist dadurch realisiert, dass in die innere zylindrische Begrenzungswand 16 ein Kanal 28 eingefräst ist. Das Maß A des Kanals in radialer Richtung des Wärmerohrs 12 ist klein gegenüber dem Radium R des Wärmerohrs 12. Damit ist der Temperaturgradient in radialer Richtung in der Kammer 26 sehr klein. In dem spiralförmi- gen Kanal 28 ist eine Schüttung 30 aus einem katalytisch wirkenden Medium angeordnet, wobei das katalytisch wirkende Medium in der hier dargestellten Ausführungsform in Form von Pellets vorliegt. Durch den in die innere Begrenzungswand 16 eingefrästen Kanal 28 erhöht sich die wirksame Wärmeübertragungsfläche zwischen der Schüttung 30 des katalytisch wirkenden Mediums und der als Wär- metransportvorrichtung dienenden inneren Begrenzungswand 16, da insgesamt drei Kontaktflächen für den Wärmetransport zur Verfügung stehen. Die innere Begrenzungswand 16 umschließt eine Innenkammer 32, die eine Füllung aus einem flüssigen Metall aufweist. Flüssigmetallfüllungen sind insbesondere für den Temperaturbereich bis 11000C sehr gut geeignet. Vorzugsweise wird dabei Lithium oder Natrium verwendet. Bei der Verwendung von Natrium als Flüssigmetallfüllung ergibt sich der Vorteil, dass die innere Begrenzungswand 16 aus Edelstahl gefertigt werden kann.Fig. 1 shows a reformer 10 for a fuel cell system shown below, wherein the reformer 10 has a heat pipe 12 with an outer circular cylindrical tube wall 14 and an inner also circular cylindrical boundary wall 16. At a first axial end 18 of the heat pipe 12 there is a chamber inlet 20 through which a reactant gas mixture, consisting for example of air and vaporized fuel, may enter the reformer. At a second axial end 22 of the heat pipe 12, a chamber outlet 24 is arranged, via which reformed gas can leave the reformer 10. Outer tube wall 14 and inner boundary wall 16 bound a chamber 26 which extends between the chamber inlet 20 and the chamber outlet 24. The chamber 26 is formed in the embodiment shown here between the chamber inlet 20 and the chamber outlet 24 spirally. This is realized in that in the inner cylindrical boundary wall 16, a channel 28 is milled. The dimension A of the channel in the radial direction of the heat pipe 12 is small compared to the radium R of the heat pipe 12. Thus, the temperature gradient in the radial direction in the chamber 26 is very small. In the spiral-shaped channel 28, a bed 30 is arranged from a catalytically active medium, wherein the catalytically active medium is present in the form of pellets in the embodiment shown here. By virtue of the channel 28 milled into the inner delimiting wall 16, the effective heat transfer area between the bed 30 of the catalytically active medium and the inner delimiting wall 16 serving as a heat transport device increases, since a total of three contact surfaces are available for heat transport. The inner boundary wall 16 encloses an inner chamber 32 which has a filling of a liquid metal. Liquid metal fillings are particularly well suited for the temperature range up to 1100 ° C. Preferably, lithium or sodium is used. When using sodium as a liquid metal filling, there is the advantage that the inner boundary wall 16 can be made of stainless steel.
Im Bereich des zweiten axialen Endes 22 des Wärmerohrs 12 ist ein Wärmetau- scher 34 angeordnet. Mittels des Wärmetauschers 34 kann Wärmeenergie vom Wärmerohr 12 auf weitere System komponenten der Brennstoffzelle übertragen werden. Insbesondere kann die Wärmeenergie auf ein in einer Rohrleitung 36 fließendes flüssiges oder gasförmiges Medium und von diesem auf die weiteren Systemkomponenten übertragen werden. Weitere Einzelheiten hierzu werden wei- ter unten beschrieben.In the region of the second axial end 22 of the heat pipe 12, a heat exchanger 34 is arranged. By means of the heat exchanger 34, heat energy from the heat pipe 12 to other system components of the fuel cell can be transmitted. In particular, the heat energy can be transferred to a liquid or gaseous medium flowing in a pipeline 36 and from there to the other system components. Further details will be described below.
In Fig. 3 ist die Einbindung des Reformers 10 in ein Brennstoffzellensystem 38 gezeigt. Eine Kraftstoffzuleitung 39 ist mit einer Medienfördervorrichtung 40 verbunden, die an einen Verdampfer 42 angeschlossen ist. Kraftstoffzuleitung 39 und eine Luftzuleitung 46 sind an eine Gemischbildungseinrichtung 44 angeschlossen, die wiederum mit dem Kammereintritt 20 verbunden ist. An den Kammeraustritt 24 des Reformers 10 schließt sich ein Brennstoffzellenstapel 48 an, dem ein Nach- brenner 50 nachgeschaltet ist. Neben der Verbindung mit dem Kammeraustritt 24 des Reformers 10 ist der Brennstoffzellenstapel 48 noch mit einer Kathodenluftzu- leitung 52 versehen.FIG. 3 shows the integration of the reformer 10 into a fuel cell system 38. A fuel supply line 39 is connected to a media delivery device 40 which is connected to an evaporator 42. Fuel supply line 39 and an air supply line 46 are connected to a mixture forming device 44, which in turn is connected to the chamber inlet 20. Adjoining the chamber outlet 24 of the reformer 10 is a fuel cell stack 48 followed by a fuel cell stack 48. burner 50 is connected downstream. In addition to the connection to the chamber outlet 24 of the reformer 10, the fuel cell stack 48 is still provided with a Kathodenluftzu- line 52.
Im Folgenden soll die Funktionsweise sowohl des Reformers 10 des Brennstoffzellensystems 38 als auch die Einbindung des Reformers 10 in das gesamte System erläutert werden.In the following, the operation of both the reformer 10 of the fuel cell system 38 and the integration of the reformer 10 in the entire system will be explained.
Über die Kraftstoffzuleitung 39 wird mittels der Medienfördervorrichtung 40 Kraft- stoff dem Verdampfer 42 zugeführt und dort in eine gasförmige Phase überführt. Der verdampfte Kraftstoff fließt dann in die Gemischbildungseinrichtung 44, in die über die Luftzuleitung 46 Luft zugeführt und mit dem verdampften Kraftstoff vermischt wird. Das Kraftstoff-Luftgemisch wird nun über den Kammereintritt 20 in den Reformer 10 eingeleitet (Fig. 1 ). Das Kraftstoff-Luftgemisch gelangt nun in die Schüttung 30 mit dem katalytisch wirkenden Medium. Mittels der Schüttung 30 mit dem katalytisch wirkenden Medium findet eine Umsetzung des Kraftstoff- Luftgemisches zu Zwischenprodukten statt, wobei die zu Beginn frei werdende Reaktionswärme aus den Oxidationsreaktionen mittels des Wärmerohrs 12 auf die Füllung der Innenkammer 32 übertragen wird. Die im Bereich des ersten axia- len Endes 18 des Wärmerohrs 12 freiwerdende Reaktionswärme wird dann über die Füllung der Innenkammer 32 dem Bereich des zweiten axialen Endes 22 des Wärmerohrs 12 übertragen. Durch diese Maßnahme wird eine lokale Überhitzung am ersten axialen Ende 18 des Wärmerohrs 12 vermieden, wie sie bei polytroper Reaktionsführung üblich ist (siehe Fig. 2, gestrichelte Kurve) und ein praktisch konstanter Temperaturverlauf über die gesamte axiale Ausdehnung des Wärmerohrs 12 erreicht (siehe Fig. 2, durchgezogene Kurve). Die im Bereich des ersten axialen Endes 18 des Wärmerohrs 12 entstandenen Zwischenprodukte werden nun im Kanal 28 in dem Bereich des zweiten axialen Endes 22 des Wärmerohrs 12 transportiert, wo eine Reformierung der Zwischenprodukte stattfindet. Durch den Transport der Wärmeenergie in der Innenkammer 32 vom ersten axialen Ende 18 des Wärmerohrs 12 im Bereich des zweiten axialen Endes 22 des Wärmerohrs 12 durch die Verschiebung des thermodynamischen Gleichgewichts deutlich erhöht. Die erzeugten reformierten Gase werden dann am Kammeraustritt 24 abgezogen.Fuel is supplied to the evaporator 42 via the fuel supply line 39 by means of the media delivery device 40, where it is converted into a gaseous phase. The vaporized fuel then flows into the mixture forming device 44, into which air is supplied via the air supply line 46 and mixed with the evaporated fuel. The fuel-air mixture is then introduced via the chamber inlet 20 into the reformer 10 (FIG. 1). The fuel-air mixture now enters the bed 30 with the catalytically active medium. By means of the bed 30 with the catalytically active medium takes place, a conversion of the fuel-air mixture to intermediates, wherein the initially released heat of reaction from the oxidation reactions by means of the heat pipe 12 is transferred to the filling of the inner chamber 32. The heat of reaction released in the region of the first axial end 18 of the heat pipe 12 is then transferred via the filling of the inner chamber 32 to the region of the second axial end 22 of the heat pipe 12. By this measure, a local overheating at the first axial end 18 of the heat pipe 12 is avoided, as is usual in polytroper reaction (see Fig. 2, dashed curve) and a practically constant temperature over the entire axial extent of the heat pipe 12 is reached (see FIG 2, solid curve). The intermediates formed in the region of the first axial end 18 of the heat pipe 12 are now transported in the channel 28 in the region of the second axial end 22 of the heat pipe 12, where a reforming of the intermediates takes place. By the transport of heat energy in the inner chamber 32 from the first axial end 18 of the heat pipe 12 in the region of the second axial end 22 of the heat pipe 12 by the shift of the thermodynamic equilibrium clearly elevated. The generated reformed gases are then withdrawn at the chamber exit 24.
In Fig. 2 ist dargestellt, wie eine lokale Überhitzung am ersten axialen Ende 18 des Wärmerohrs 12 im Bereich des Kammereintritts 20, wie sie bei polytroper Reaktionsführung nach dem Stand der Technik auftritt (siehe Fig. 2, gestrichelte Kurve), vermieden wird, und durch die Benutzung des Wärmerohrs 12 ein praktisch konstanter Temperaturverlauf über die gesamte axiale Ausdehnung des Wärmerohrs 12 zwischen Kammereintritt 20 und Kammeraustritt 24 erreicht wird (siehe Fig. 2, durchgezogene Kurve). Die maximale Temperatur Tmaχ, die nicht überschritten werden soll, um die Lebensdauer des katalytisch wirkenden Mediums und der Trägermaterialien nicht zu reduzieren, wird in keinem Bereich des Wärmerohrs 12 überschritten. Lokale Überhitzungen sind damit ausgeschlossen.FIG. 2 shows how local overheating at the first axial end 18 of the heat pipe 12 in the region of the chamber inlet 20, as occurs in the prior art polytropic reaction guide (see FIG. 2, dashed curve), is avoided, and FIG by the use of the heat pipe 12 a practically constant temperature profile over the entire axial extent of the heat pipe 12 between the chamber inlet 20 and chamber outlet 24 is achieved (see Fig. 2, solid curve). The maximum temperature T ma χ, which should not be exceeded in order not to reduce the lifetime of the catalytically active medium and the carrier materials is not exceeded in any area of the heat pipe 12. Local overheating is excluded.
Das am Kammeraustritt 24 austretende reformierte Gas wird nun dem Brennstoffzellenstapel 48 zugeführt (siehe Fig. 3), in dem in bekannter Weise die elektrische Energie freigesetzt wird. Die aus dem Brennstoffzellenstapel 48 ausströmenden Gase werden nun noch dem Nachbrenner 50 zugeführt, in dem sie noch thermisch weiterverwertet werden.The reformed gas leaving the chamber outlet 24 is now supplied to the fuel cell stack 48 (see FIG. 3), in which the electrical energy is released in a known manner. The gases flowing out of the fuel cell stack 48 are now supplied to the afterburner 50, in which they are still used thermally.
Da das Brennstoffzellensystem 38 insgesamt einen vom Massenstrom des Reak- tandengasgemisches am Kammereintritt 20 abhängigen Überschuss an Wärmeenergie aufweist, kann dieser mittels des Wärmetauschers 34 für weitere Systemkomponenten des Brennstoffzellensystems 38 genutzt werden. Derartige System- komponenten können die Gemischbildungseinrichtung 44 oder die Kathodenluft der Kathodenluftzuleitung 52 des Brennstoffzellenstapels 48 sein. Die Rohrleitung 36 des Wärmetauschers 34 ist dann in entsprechender Weise mit der Luftzuleitung 46 oder der Kathodenluftzuleitung 52 zu verbinden. Die Wärmeenergie aus dem Wärmetauscher 34 kann jedoch bei einem kombinierten System zur Bereit- Stellung von elektrischer Energie und Wärme auch direkt einem Heizungssystem zugeführt werden. Neben der bereits erwähnten isothermen Temperaturverteilung im Wärmerohr 12 wird bei dem erfindungsgemäßen Reformer die Steuerung der Umsetzungsprozesse deutlich vereinfacht und die Modulierbarkeit hinsichtlich der Medienflüsse erhöht. Die Ausbeute an reformiertem Gas steigt deutlich an. Weiter kann durch den Einsatz verschiedener katalytisch wirkender Medien im Kanal 28 die Reaktionsführung weiter optimiert werden. Werden zwei Reformer 10 in geeigneter Weise über Rohrleitungen und Ventile miteinander verschaltet, so kann ein abwechselnder Nutzungs- und Regenerationsbetrieb der beiden Reformer realisiert werden: während einer der beiden Reformer regeneriert wird, kann der zweite Refor- mer reformierte Gase zum Betrieb des Brennstoffzellensystems 38 bereitstellen. Nach Regeneration des ersten Reformers und nach Erschöpfung des zweiten Reformers wird umgeschalten und der erste Reformer kann wieder reformierte Gase für das Brennstoffzellensystem 38 erzeugen. Für höhere Gasdurchsätze können auch mehrere Reformer 10 parallel zueinander betrieben werden. Dies erlaubt auch den Einsatz verschiedener Kraftstoffe, die sowohl in flüssiger als auch in gasförmiger Form vorliegen können. Since the fuel cell system 38 overall has a surplus of heat energy dependent on the mass flow of the reactant gas mixture at the chamber inlet 20, it can be used by the heat exchanger 34 for further system components of the fuel cell system 38. Such system components may be the mixture formation device 44 or the cathode air of the cathode air supply line 52 of the fuel cell stack 48. The pipe 36 of the heat exchanger 34 is then to be connected in a corresponding manner with the air supply line 46 or the cathode air supply line 52. However, the heat energy from the heat exchanger 34 may also be supplied directly to a heating system in a combined system for providing electrical energy and heat. In addition to the already mentioned isothermal temperature distribution in the heat pipe 12, in the reformer according to the invention the control of the conversion processes is considerably simplified and the modulability with regard to the media flows is increased. The yield of reformed gas increases significantly. Further, by using various catalytically active media in the channel 28, the reaction can be further optimized. If two reformers 10 are interconnected in a suitable manner via pipelines and valves, an alternating use and regeneration operation of the two reformers can be realized: while one of the two reformers is being regenerated, the second reformer can provide reformed gases for operation of the fuel cell system 38 , After regeneration of the first reformer and after exhaustion of the second reformer is switched and the first reformer can generate reformed gases for the fuel cell system 38 again. For higher gas flow rates, several reformers 10 can be operated in parallel. This also allows the use of various fuels, which may be in both liquid and gaseous form.
BezugszeichenlisteLIST OF REFERENCE NUMBERS
10 Reformer10 reformers
12 Wärmerohr12 heat pipe
14 äußere Rohrwand14 outer pipe wall
16 innere Begrenzungswand16 inner boundary wall
18 erstes axiales Ende des Wärmerohrs18 first axial end of the heat pipe
20 Kammereintritt20 chamber entry
22 zweites axiales Ende des Wärmerohrs22 second axial end of the heat pipe
24 Kammeraustritt24 chamber exit
26 Kammer26 chamber
28 Kanal28 channel
30 Schüttung30 bed
32 Innenkammer32 inner chamber
34 Wärmetauscher34 heat exchangers
36 Rohrleitung36 pipeline
38 Brennstoffzellensystem38 fuel cell system
39 Kraftstoffzuleitung39 fuel supply
40 Medienfördervorrichtung40 media conveyor
42 Verdampfer42 evaporator
44 Gemischbildungseinrichtung44 mixture forming device
46 Luftzuleitung46 air supply line
48 Brennstoffzellenstapel48 fuel cell stacks
50 Nachbrenner50 afterburner
52 Kathodenluftzuleitung 52 cathode air supply line

Claims

Patentansprüche claims
1. Reformer (10) für eine Brennstoffzelle mit einer Kammer (26), die einenA reformer (10) for a fuel cell with a chamber (26) having a
Kammereintritt (20) zum Einlass eines Reaktandengasgemisches und einen Kammeraustritt (24) zum Auslass eines reformierten Gases hat, wobei in der Kammer (26) ein katalytisch wirkendes Medium angeordnet ist, dadurch gekennzeichnet, dass der Reformer (10) ein Wärmerohr (12) mit ei- ner äußeren zylindrischen Rohrwand (14) und einer inneren zylindrischenChamber inlet (20) for the inlet of a Reaktandengasgemisches and a chamber outlet (24) to the outlet of a reformed gas, wherein in the chamber (26) a catalytically active medium is arranged, characterized in that the reformer (10) has a heat pipe (12) an outer cylindrical tube wall (14) and an inner cylindrical
Begrenzungswand (16) aufweist, wobei die Kammer (26) zwischen der äußeren Rohrwand (14) und der inneren Begrenzungswand (16) angeordnet ist.Boundary wall (16), wherein the chamber (26) between the outer tube wall (14) and the inner boundary wall (16) is arranged.
2. Reformer (10) für eine Brennstoffzelle nach Anspruch 1 , dadurch gekennzeichnet, dass der Kammereintritt (20) nahe einem ersten axialen Ende (18) des Wärmerohrs (12) und der Kammeraustritt (24) nahe einem zweiten axialen Ende (22) des Wärmerohrs (12) angeordnet ist.A fuel cell reformer (10) according to claim 1, characterized in that the chamber inlet (20) is proximate a first axial end (18) of the heat pipe (12) and the chamber exit (24) is proximate a second axial end (22) of the Heat pipe (12) is arranged.
3. Reformer (10) für eine Brennstoffzelle nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Kammer (26) zwischen dem Kammereintritt (20) und dem Kammeraustritt (24) spiralförmig ausgebildet ist.3. reformer (10) for a fuel cell according to claim 1 or 2, characterized in that the chamber (26) between the chamber inlet (20) and the chamber outlet (24) is formed spirally.
4. Reformer (10) für eine Brennstoffzelle nach einem der vorhergehenden An- Sprüche, dadurch gekennzeichnet, dass die Kammer (26) aus einem in die innere zylindrische Begrenzungswand (16) eingefrästen Kanal (28) gebildet ist.4. reformer (10) for a fuel cell according to one of the preceding arrival claims, characterized in that the chamber (26) consists of a in the inner cylindrical boundary wall (16) milled channel (28) is formed.
5. Reformer (10) für eine Brennstoffzelle nach einem der vorhergehenden An- sprüche, dadurch gekennzeichnet, dass die innere Begrenzungswand (16) eine Innenkammer (32) umschließt, wobei die Innenkammer (32) eine Füllung aus einem flüssigem Metall aufweist. 5. A fuel cell reformer (10) according to any one of the preceding claims, characterized in that the inner boundary wall (16) encloses an inner chamber (32), the inner chamber (32) having a liquid metal filling.
6. Reformer (10) für eine Brennstoffzelle nach Anspruch 5, dadurch gekennzeichnet, dass das flüssige Metall Natrium oder Lithium ist.6. reformer (10) for a fuel cell according to claim 5, characterized in that the liquid metal is sodium or lithium.
7. Reformer (10) für eine Brennstoffzelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass nahe dem zweiten axialen Ende (22) des Wärmerohrs (12) ein Wärmetauscher (34) angeordnet ist, wobei mittels des Wärmetauschers (34) Wärmeenergie vom Wärmerohr (12) auf weitere Systemkomponenten (44) der Brennstoffzelle übertragen wird.7. reformer (10) for a fuel cell according to one of the preceding claims, characterized in that near the second axial end (22) of the heat pipe (12), a heat exchanger (34) is arranged, wherein by means of the heat exchanger (34) heat energy from the heat pipe (12) is transferred to other system components (44) of the fuel cell.
8. Reformer (10) für eine Brennstoffzelle nach Anspruch 7, dadurch gekennzeichnet, dass die Brennstoffzelle eine Gemischbildungseinrichtung (44) aufweist, und mittels des Wärmetauschers (34) Wärmeenergie vom Wärmerohr (12) auf die Gemischbildungseinrichtung (44) der Brennstoffzelle übertragen wird.8. reformer (10) for a fuel cell according to claim 7, characterized in that the fuel cell has a mixture forming means (44), and by means of the heat exchanger (34) heat energy from the heat pipe (12) to the mixture forming means (44) of the fuel cell is transmitted.
9. Reformer (10) für eine Brennstoffzelle nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass der Brennstoffzelle Kathodenluft zugeführt wird, und mittels des Wärmetauschers (34) Wärmeenergie vom Wärmerohr (12) auf die Kathodenluft übertragen wird. 9. reformer (10) for a fuel cell according to claim 7 or 8, characterized in that the fuel cell cathode air is supplied, and by means of the heat exchanger (34) heat energy from the heat pipe (12) is transmitted to the cathode air.
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EA200701352A1 (en) 2007-10-26
US20090253005A1 (en) 2009-10-08
DE102004063151A1 (en) 2006-07-06
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CA2589785A1 (en) 2006-06-29
WO2006066545A8 (en) 2007-08-09

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