WO2002085777A2 - Dispositif permettant de produire et / ou de preparer un combustible pour une pile a combustible - Google Patents

Dispositif permettant de produire et / ou de preparer un combustible pour une pile a combustible Download PDF

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Publication number
WO2002085777A2
WO2002085777A2 PCT/EP2002/004411 EP0204411W WO02085777A2 WO 2002085777 A2 WO2002085777 A2 WO 2002085777A2 EP 0204411 W EP0204411 W EP 0204411W WO 02085777 A2 WO02085777 A2 WO 02085777A2
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WIPO (PCT)
Prior art keywords
layer
cooling
channel
heating
medium
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PCT/EP2002/004411
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German (de)
English (en)
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WO2002085777A3 (fr
Inventor
Peter Prechtl
Markus HÖHN
Sven Theisen
Armin Bartsch
Günter HAUSINGER
Original Assignee
Peter Prechtl
Hoehn Markus
Sven Theisen
Armin Bartsch
Hausinger Guenter
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Application filed by Peter Prechtl, Hoehn Markus, Sven Theisen, Armin Bartsch, Hausinger Guenter filed Critical Peter Prechtl
Priority to AU2002319143A priority Critical patent/AU2002319143A1/en
Priority to EP02748669A priority patent/EP1383599A2/fr
Publication of WO2002085777A2 publication Critical patent/WO2002085777A2/fr
Publication of WO2002085777A3 publication Critical patent/WO2002085777A3/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01B—BOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
    • B01B1/00—Boiling; Boiling apparatus for physical or chemical purposes ; Evaporation in general
    • B01B1/005—Evaporation for physical or chemical purposes; Evaporation apparatus therefor, e.g. evaporation of liquids for gas phase reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • 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
    • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D9/00—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D9/0093—Multi-circuit heat-exchangers, e.g. integrating different heat exchange sections in the same unit or heat-exchangers for more than two fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30—Micromixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00783—Laminate assemblies, i.e. the reactor comprising a stack of plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00835—Comprising catalytically active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/0086—Dimensions of the flow channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00873—Heat exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—Mixing
    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • 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
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2260/00—Heat exchangers or heat exchange elements having special size, e.g. microstructures
    • F28F2260/02—Heat exchangers or heat exchange elements having special size, e.g. microstructures having microchannels
    • 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
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • 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 present invention relates to a device for producing and / or processing a fuel for a fuel cell, which has a number of individual components.
  • Fuel cells have been known for a long time and are becoming increasingly important in the automotive industry, for example. Of course, other possible uses for fuel cells are also conceivable. Examples include fuel cells for mobile devices such as computers or the like, right up to power plants. Here, fuel cell technology is particularly suitable for the decentralized energy supply of houses, industrial plants or the like.
  • a fuel cell for example a PEM fuel cell
  • electricity is generated by a chemical reaction.
  • a fuel such as hydrogen and an oxidizing agent such as oxygen from the air are converted into electrical energy and a reaction product such as water.
  • a fuel cell essentially consists of an anode part, a membrane and a cathode part.
  • the membrane consists of a gas-tight and proton-conducting material and is arranged between the anode and the cathode in order to exchange ions.
  • the fuel is supplied on the anode side, while the oxidant is supplied on the cathode side.
  • Protons or hydrogen ions are generated at the anode by catalytic reactions and move through the membrane to the cathode.
  • the hydrogen ions react with the oxygen and water is formed.
  • the electrons released during the reaction can be conducted as electrical current through a consumer, for example the electric motor of an automobile. If one wants to operate the fuel cell with a readily available or storable fuel, such as natural gas, methanol, gasoline or the like, the hydrocarbon must first be converted into a hydrogen-rich gas in an arrangement for producing and / or processing a fuel. This essentially decomposes to hydrogen and carbon dioxide.
  • carbon monoxide is also produced, which is a gas which is harmful to the fuel cell, since it renders the catalyst on the anode side ineffective and must therefore be removed before the fuel enters the fuel cell. From a certain concentration, the carbon monoxide in the fuel cell can result in the power output by the fuel cell being reduced and consequently in the efficiency of the fuel cell being greatly reduced.
  • the arrangement for producing and / or processing fuel generally consists of a number of individual components, which can be, for example, chemical reactors such as reformers, shift reactors, reactors for selective oxidation, evaporators, heat exchangers and the like.
  • exothermic reactions take place, which means that heat is released.
  • This heat must be dissipated, which can be done for example via a heat exchanger.
  • the medium must have a certain reaction temperature, for example, which can also be achieved by using heat exchangers.
  • One of these reactor elements is, for example, the evaporator. Heat must be supplied to the evaporator for operation. This is done, for example, using an appropriate heating element.
  • a starting material is reformed, for example, into a hydrogen-rich gas.
  • the reformer is used, for example, to make one from a hydrocarbon serving as a starting material, for example gasoline To produce fuel for the fuel cell.
  • a hydrocarbon serving as a starting material, for example gasoline
  • reactors which are filled with a catalyst based on bulk material (pellets).
  • Reactors are also known in which the catalyst is applied to monoliths (cf. exhaust gas catalyst in a motor vehicle).
  • monoliths cf. exhaust gas catalyst in a motor vehicle.
  • a heat exchanger is required to cool the process medium.
  • a mixing unit is also required in order to be able to meter air into the process medium.
  • a mixing section is required for homogeneous mixing of the very small volume of air.
  • the actual chemical reactor is also required, which is usually designed without its own cooling.
  • at least one further heat exchanger is required to cool the process medium upstream of the fuel cell. If necessary, the above-described required individual components of the device for generating and / or processing the fuel can form a system, with several such systems being able to be connected in series, depending on the embodiment.
  • the individual components of the device are initially available as components which are independent of one another and which, with the disadvantages described above, then have to be combined to form an overall system via corresponding line systems.
  • the present invention has for its object to provide a device for generating and / or processing a fuel for a fuel cell, with which the disadvantages described can be avoided.
  • a device is to be provided which can be manufactured compactly and with little space requirement and which at the same time is particularly powerful. Furthermore, an advantageous use of such a device is to be specified.
  • the invention is based on the basic idea that a device for producing and / or processing fuel for a fuel cell, which has a number of individual components, is designed as a layer sequence of individual layers with a channel structure, the device being designed as a single component in microstructure technology and whereby all individual components are integrated in the one, single component.
  • a device for generating and / or preparing a fuel for a fuel cell which has a number of individual components.
  • the device according to the invention is characterized in that the device is designed as a layer sequence of individual layers, with at least one first layer for passing a process medium through it, which at least in some areas has a channel structure with at least one channel, and with at least one second layer that has at least one component for Treatment of the process medium flowing through the at least one first layer has that the device is designed as a single component in microstructure technology and that all individual components are integrated in the one, single component.
  • microstructure technology is usually understood to mean structures which are in the size range in the range of less than one millimeter (1 ⁇ m to 1000 ⁇ m).
  • the sizes of the structures are not limited to these dimensions.
  • structures on the order of one may be required Represent zenith meter.
  • the systems are preferably particularly efficient today if the structures are in the order of magnitude between 100 ⁇ m and 1000 ⁇ m. It is important that a dimension of the duct dimension is already decisive for performance (eg duct height).
  • the channels have dimensions such as
  • Channel width 0.2 mm to 5 mm (or several centimeters)
  • Width or thickness of the channel walls 50 ⁇ m to 500 ⁇ m (or also in the range of
  • Length of the channels 1 mm to a few cm (10 cm, 20 cm)
  • the microstructures are built up by stacking the same or different layers on top of each other and connecting them using a suitable joining process (e.g. soldering, welding, gluing, clamping, ).
  • a suitable joining process e.g. soldering, welding, gluing, clamping, .
  • the structures are created by various methods. Examples are: etching, embossing, turning, milling, extruding, injection molding, forming, etc.
  • the device according to the invention is initially very powerful. Furthermore, the device requires only a small amount of space, so that it can be made very compact. The device can therefore advantageously be used wherever only a small amount of space is available.
  • a basic idea of the invention is that the device is designed as a layer sequence of individual layers. This has a number of advantages. It is thus possible in a simple and inexpensive manner to initially produce the individual layers of the device separately and then to join them to form the final device. Furthermore, the number and / or arrangement and / or sequence of the individual layers can also be varied, so that the device can be easily adapted to the prevailing requirements.
  • the layered design of the device also ensures that good heat transfer between the individual layers can be achieved.
  • the layer sequence initially consists of at least a first layer for passing the process medium through. Of course, more than one first layer can also be provided per device.
  • the first layer has, at least in regions, a channel structure with at least one channel.
  • the layer sequence consists of at least one second layer, which has at least one component for treating the medium flowing through the at least one first layer.
  • second layers can also be provided for each device. Non-exclusive examples of possible second layers are explained in more detail below.
  • treatment is understood to mean any type of action on the process medium.
  • Treatment can mean, for example, that the process medium changes, for example as a result of a chemical reaction, for example a catalytic reaction.
  • treatment can also mean that the physical state or the external state of the process medium changes without changing its chemical composition.
  • Treatment can therefore also mean that the process medium is merely heated or cooled, that it is evaporated or the like.
  • the invention is not limited to certain forms of treatment. Rather, these result from the respective field of application of the device.
  • the treatment of the process medium therefore includes any direct or indirect, external or internal influence on the process medium.
  • the first and second layers are combined to form a layer sequence or a layer stack.
  • the sequence pattern of the individual layers can be designed as desired. For example, it can be provided that a first and a second layer are always stacked on top of one another. Of course, several first and / or second layers can also be stacked directly on top of one another, then after several first and / or second layers each follow one or more layers of the other type. Irregular sequence patterns of the individual layers can thus also be implemented, so that the design of the device can be adapted precisely to the prevailing requirements.
  • the device is designed as a single component in microstructure technology.
  • the at least one channel of the at least one first layer is designed as a microchannel.
  • the further channels of the device described below can also be designed as microchannels.
  • the design in microstructure technology ensures that a large number of microchannels can be realized in the smallest space, the width and height of which are in the submillimeter range. For this reason, such devices have high specific surfaces, that is to say a high ratio of channel surface to channel volume.
  • appropriately designed devices which in this case are referred to as microreactors - as the name suggests - have a very high performance with only a small space requirement.
  • the advantage of the invention is therefore that the device is designed as a single component in microstructure technology.
  • the individual components are now integrated in the device, for example the connection technology (cooling water to and from the fuel cell), heat exchanger, mixing section, cooled chemical reactor and the like. So there is only a single component that takes up little space.
  • those individual components of the device which were previously separate, are provided by corresponding line systems connected, individual components were formed within the device in the first and second layers.
  • the at least one first layer and the at least one second layer can advantageously be thermally coupled to one another at least in regions. This means that the layers do not necessarily have to be directly connected to one another. In the light of the present invention, thermally coupled only means that heat exchange in the area of the thermal coupling should be possible. If the individual layers are stacked on top of one another as a layer sequence of individual layers, the thermal coupling advantageously comes about in that the individual layers are placed directly on top of one another. The heat exchange can then take place over the respective layer surfaces. This makes it possible in a simple manner that the heat generated in one layer can be easily transferred to or into another layer.
  • the at least one first layer can advantageously have at least one reaction passage, at least one reaction channel being formed in the reaction passage.
  • the reaction passage can act as the actual chemical reactor, for example.
  • the at least one first layer can have at least one cooling / heating passage, at least one cooling / heating channel being formed in the cooling / heating passage and wherein the cooling / heating passage seen before and in the flow direction of the process medium / or is provided after the reaction passage.
  • the process medium can, for example, be brought to the temperature required for the reaction in the reaction passage via the cooling / heating passage.
  • the cooling / heating passage is a cooling passage when the medium is to be cooled and a heating passage when the medium is to be heated.
  • the cooling / heating passage can be designed in different ways. Some non-exclusive examples are discussed in more detail below. Design variants are also conceivable in which the process medium leaving the reaction passage is in one subsequent cooling / heating passage is brought to a temperature required for further process steps.
  • the first layer has at least two individual components of the device, namely at least one reaction passage and at least one cooling / heating passage. At least one channel is provided for each passage.
  • the invention is not limited to a certain number of channels. In the simplest case, a single channel is provided for each passage. However, several channels can also advantageously be provided, which are then preferably arranged parallel to one another. The more channels are provided, the larger quantities of process medium can be passed through the device at the same time. On the one hand, this can significantly improve throughput. Furthermore, the installation space requirement of the device can be reduced, since the individual channels can be made significantly shorter compared to a single channel.
  • the invention is not restricted to a specific configuration and / or arrangement of the channels. Rather, the channel structure can have any dimension. In particular, the individual channels can have any size and cross-sectional shape.
  • the at least one reaction channel and / or the at least one cooling / heating channel can advantageously be coated with a reaction medium, preferably with a catalyst material.
  • the cooling / heating duct is advantageously used as a heating duct.
  • the at least one first layer can preferably have at least one mixing zone for mixing at least one further medium into the process medium have, the mixing zone seen in the flow direction of the process medium is provided before and / or after the reaction passage.
  • the mixing zone can be connected to the channel inlet of a reaction channel.
  • the process medium then enters the at least one reaction channel via the mixing zone.
  • the process medium can first be mixed with at least one further medium, for example with air, before it enters the reaction channel.
  • the mixing zone can advantageously be provided between the reaction passage and the cooling / heating passage, as seen in the flow direction of the process medium. It is conceivable that the mixing zone is connected to a channel outlet of the cooling / heating passage and to a channel inlet of the reaction passage. In this way, the process medium can first be brought to the desired temperature in the cooling / heating channel and mixed with other media in the subsequent mixing zone. This well-tempered mixture is then introduced into the reaction channel. In the embodiment described above, there are thus at least three individual components of the device on or in the first layer.
  • the at least one second layer can have at least one cooling / heating device for cooling / heating the process medium flowing through the at least one first layer.
  • these components are cooling or heating components, depending on whether the process medium is to be cooled or heated.
  • the invention is not restricted to specific embodiments for the cooling / heating device. It is only important that the device is able to bring the process medium to the required temperature.
  • thermal energy can be provided by means of suitable heating elements, heating cartridges and the like. These elements can then be arranged in the second layer.
  • the cooling / heating device has a channel structure with at least one channel, and that a corresponding cooling medium or heating medium flows through the channel.
  • the invention is not limited to the two exemplary examples mentioned above.
  • the at least one cooling / heating device of the at least one second layer can advantageously be thermally coupled to the reaction passage of the at least one first layer. This makes it possible, for example, to allow heat generated in the reaction passage during the reaction to be dissipated via the device, so that in this case it functions as a cooling device. Likewise, the heat required for a reaction can be supplied via the device, which then functions as a heating device, as required. Since the cooling / heating device is thermally coupled to the reaction passage, the required heat exchange can take place without any problems. The cooling / heating device is then a further individual component of the device, for example a heat exchanger.
  • At least one cooling / heating device of the at least one second layer can be thermally coupled to the cooling / heating passage of the at least one first layer.
  • a heat exchanger can be realized, for example, which cools or heats the process medium flowing through the cooling / heating passage to the required temperature.
  • the cooling / heating device can advantageously have at least one channel for passing a cooling / heating medium through it.
  • the cooling / heating device is constructed in a similar manner to the cooling / heating passage or the reaction passage, so that in this regard reference is also made to the corresponding statements above and reference is hereby made.
  • the at least one channel is particularly advantageously designed as a microchannel.
  • the at least one channel of the cooling / heating device can also be coated with a reaction medium, preferably with a catalyst material, in a manner analogous to the channels of the cooling / heating passage or the reaction passage.
  • the channels of the at least one cooling / heating device and the reaction passage and / or the cooling / heating passage can advantageously be aligned with one another in a cross-flow design.
  • the channels can also be aligned parallel to one another.
  • the device can be operated, for example, in the cocurrent principle or in the countercurrent principle.
  • the at least one second layer can preferably have at least one mixing zone for mixing at least one further medium into the process medium.
  • the individual first and second layers are advantageously layered one above the other in such a way that the mixing zones of the first and second layers come to lie directly one above the other. In this way, the mixing zones of the first and second layer (s) form a mixing room.
  • the mixing room is fed with the process medium via channels of the first layer.
  • the mixing room is additionally fed with another medium via the second layer.
  • the mixing zone of the at least one second layer is preferably connected to a corresponding medium inlet via at least one supply channel (of course, several, in particular, parallel, supply channels can also be provided).
  • the various media are mixed with one another in the mixing room before they enter the at least one reaction channel of the reaction passage as a media mixture from the mixing room.
  • At least one central inlet for the process medium is advantageously provided, the central inlet being connected to the at least one channel of the at least one first layer via a channel inlet.
  • at least one central outlet for the process medium can also be provided, the central outlet being connected to the at least one channel of the at least one first layer via a channel outlet.
  • the device according to the invention can be used particularly preferably in connection with a so-called CO pulser.
  • CO pulser for example, the space velocity can be increased considerably.
  • CO pulser for example, it is easily possible to prevent harmful influence of carbon monoxide (CO) on the fuel cell.
  • Such a CO pulser is described, for example, in DE 197 10 819 C1, the disclosure content of which is included in the description of the present invention.
  • a fuel cell is described in which performance losses due to impurities absorbed on the anode catalyst are to be avoided. This is achieved in that the fuel cell is connected to means which impart a positive voltage pulse to the anode of the fuel cell (CO pulses).
  • a pulse-shaped change in the anode potential is brought about by the stamping of the voltage pulse.
  • This pulsed change in the anode potential means that the carbon monoxide in the fuel cell is oxidized.
  • the voltage pulses can be impressed on the fuel cell, for example, by temporarily connecting an external DC voltage source to the fuel cell via a switch.
  • the fuel cell normally requires a CO concentration of less than 50 ppm. By increasing the space velocity, the component can be reduced enormously at the expense of the purity of the hydrogen generated (for example a factor of 5).
  • the gas stream fed into the fuel cell then typically contains 500 ppm CO, which, by using the CO pulser, leads to behavior comparable to that of 50 ppm CO in the fuel cell. This enables enormous space savings.
  • the device according to the invention described above can be part of a fuel cell system, for example, with at least one fuel cell and with a device for producing and / or preparing a fuel for the fuel cell, which is connected upstream of the fuel cell and - as described above.
  • the fuel cell can also be connected, at least temporarily, to a device for applying voltage pulses (CO pulser), as described above.
  • Such a fuel cell system makes it possible to produce the fuel required for operating the fuel cell in a particularly simple and reliable manner.
  • the fuel cell system can advantageously have more than one fuel cell, the individual fuel cells being combined to form a fuel cell stack, or fuel cell stack.
  • the device for producing and / or processing fuel generally consists of a number of individual components, which can be chemical reactors such as reformers, shift reactors, reactors for selective oxidation or the like. All of these reactors can be realized with the device according to the invention. Of course, embodiments of the device are also conceivable in which several chemical reactors are formed on or in the layers. Additional components such as evaporators, heat exchangers, catalytic burners and the like are also required to operate the chemical reactors. These components can also be implemented within the individual layers of the device according to the invention.
  • a device according to the invention as described above is therefore used particularly advantageously as a chemical reactor.
  • the advantageous replaceability will be illustrated below using a non-exclusive example.
  • the device should be designed as a chemical reactor for selective oxidation. If the device for generating and / or Processing fuel is designed as a reactor for selective oxidation, this can be constructed, for example, as follows:
  • the catalysts within the reaction passage can be selected so that they work with temperatures in the range 90-140 ° C. This enables the device to be automatically tempered with the cooling water drain of the fuel cell (80-90 ° C). The mass flow is large enough to drive the temperature in the integrated selective oxidation in a very narrow temperature range.
  • Such a reactor for selective oxidation can therefore, for example, be flanged directly to a fuel cell without the need for a pipe connection and control unit for cooling (a thermal unit). Furthermore, no piping, no gaps, no regulation and the like are necessary for the cooling.
  • At least one heat exchanger is integrated into the device, which serves to cool the supplied process medium.
  • a micromixer in the device allows the process medium to be mixed homogeneously with at least one further medium, for example with air, in the smallest space (for example 1-3 cm in length).
  • the device has a cooling / heating passage upstream of it (selective oxidation - reactor with water cooling passage). This enables exact temperature control to the cooling water temperature (e.g. 90-100 ° C).
  • the layout of the device also permits multi-stage air metering and reaction passage.
  • FIG. 1 shows a perspective view of an inventive device for generating and / or processing a fuel, which is designed in the form of a reactor for selective oxidation.
  • FIG. 1 shows a device 10 for producing and / or processing a fuel, which is designed as a layer sequence of alternately stacked layers 11, 12 with a channel structure.
  • the device 10 is designed in microstructure technology and consists of a number of individual components, which are also designed in microstructure technology, and all of which are integrated in the device 10, so that it is designed as a single component.
  • a fuel for a fuel cell is brought to the required quality. Since the device 10 is designed as a chemical reactor for selective oxidation, the carbon monoxide content of the fuel is reduced to an acceptable level for the fuel cell.
  • the device 10 can be flanged directly to the fuel cell.
  • a process medium for example the fuel, is passed through the layers 11.
  • the layers 12 serve to treat the process medium flowing through the layers 11.
  • the process medium enters the channel inlet 30 via the central inlet 13 for the process medium and is distributed via this into cooling / heating channels 16 of a cooling / heating passage 15.
  • the cooling / heating passage 15 represents a first individual component of the device 10 and is formed in the layers 11.
  • the process medium flows through the channels 16 of the layers 11, the cooling / heating passage 15 serving in the present example as a cooling passage for the process medium.
  • a channel 18 adjoins the channels 16, in which the process medium is mixed with another medium, for example air. This is a further individual component of the device 10, which is formed in the layers 11.
  • a reaction passage 40 is then provided, as seen in the flow direction S of the process medium, which has a number of parallel reaction channels 17. This is the actual reaction passage, for example selective oxidation.
  • the process medium exits the device 10 via a channel outlet 31 and the central outlet 14.
  • Typical dimensions for the dimensions of the channels are:
  • a cooling / heating device 20 is provided in a layer 12 adjacent to the layer 11, which first consists of a first cooling / heating device 41.
  • the cooling / heating device 41 in turn has a number of channels 23.
  • a cooling medium flows through the channels 23, which enters the channels 23 via a cooling / heating medium inlet 21 and exits the channels 23 via a cooling / heating medium outlet 22.
  • the cooling channels 23 are aligned with the channels 16 for the process medium in a cross-flow construction, but can also be aligned in a parallel construction.
  • a further cooling / heating device 41 is provided, which is constructed in the same way as the device described above.
  • the cooling / heating devices 41 are further individual components of the device 10, for example appropriately designed heat exchangers. Since the layers 11 and 12 are thermally coupled, a sufficient heat exchange between the cooling / heating devices 41 on the one hand and the reaction passage 40 or the cooling / heating passage 15 on the other hand can easily take place.
  • the mixing zone 18 is constructed as follows.
  • a relatively wide channel 27 aligned with the channels 16 in a cross-flow design.
  • the medium for example process air, enters the channel 27 via a medium inlet 24.
  • Medium not used in the mixing zone 18 can exit from the channel 27 via a medium outlet 25.
  • a number of short supply channels 26 are provided, which are aligned in parallel flow construction with the channels 16 from layer 11 and which are connected to the channel 27.
  • the medium flowing through the channel 27 enters the mixing zone 18 via the feed channels 26.
  • the layers 11 and 12 are arranged one above the other in such a way that the mixing zones 18 of the individual layers 11 and 12 come to lie directly one above the other. In this way, a mixing space 19 is created.
  • the mixing space 19 is charged with process medium via the channels 16 and with another medium, for example with air, via the feed channels.
  • the number and design of the feed channels 26 ensure that the additional medium can enter the mixing space 19 over the entire width of the mixing zone 18, which leads to a particularly good, thorough mixing of the two media.
  • the medium mixture formed in this way is then introduced into the reaction channels 17, where the actual reaction takes place.
  • the heat generated during the reaction taking place in the reaction passage 40 is absorbed and transported away via the cooling / heating device 41 thermally coupled to the reaction passage 40, which in the present example is designed as a cooling device.
  • the heat is transferred to a cooling medium flowing through the channels 23.
  • the channels 23 in passage 20 can be coated with an oxidation catalyst so that unburned exhaust gases from the fuel cell burn and thus release heat.
  • 3 fluids are usually required for the preparation of fuel for fuel cells: 1. fuel (gasoline / natural gas), 2. water (steam), 3. air. These fluids must be mixed very homogeneously before entering the reformer. In order to achieve a very high integration density, it can make sense not only to meter in the air in the mixing passage but also all three necessary fluids (e.g.
  • the layers would then be arranged alternately (for example, 1st water or steam, 2nd gasoline / natural gas, 3rd air: stacking sequence, for example 1st, 2nd, 1st, 2nd 3rd etc.)
  • the passage 27 would then not more would connect the inlets 24 and 25 but would alternately be connected to 24 or 25 and could thus enable the described supply of gasoline / natural gas (for example 24) and air (for example 25) in a mixing unit.
  • the device described allows the high and low temperature shift catalytic converters to be fitted in the passages 16 and 17 and a reaction controlled by the cooling passages to take place.
  • the mixing passage is not absolutely necessary and can therefore be omitted.
  • the mixing passage can also be used to feed additional water vapor into the system in order to improve the mode of operation of the shift reactors.

Abstract

Dispositif (10) permettant de produire et / ou de préparer un combustible pour une pile à combustible, qui comporte un certain nombre de pièces individuelles, qui est particulièrement peu encombrant et qui présente une construction simple. A cet effet, ledit dispositif (10) est conçu en tant que suite de couche individuelles (11, 12) qui comprend au moins une première couche (11) destinée à laisser passer un milieu de travail et possédant au moins dans certaines zones une structure de canaux constituée d'au moins un canal (16, 17), et au moins une deuxième couche (12) possédant au moins un constituant destiné à traiter le milieu de travail s'écoulant à travers la première couche (11) au moins. Ledit dispositif (10) est en outre conçu sous forme d'élément unique à microstructure, les pièces individuelles étant intégrées dans l'élément unique.
PCT/EP2002/004411 2001-04-21 2002-04-22 Dispositif permettant de produire et / ou de preparer un combustible pour une pile a combustible WO2002085777A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2002319143A AU2002319143A1 (en) 2001-04-21 2002-04-22 Device for producing and/or preparing a fuel for a fuel cell
EP02748669A EP1383599A2 (fr) 2001-04-21 2002-04-22 Dispositif permettant de produire et / ou de preparer un combustible pour une pile a combustible

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10119609 2001-04-21
DE10119609.1 2001-04-21

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WO2002085777A3 WO2002085777A3 (fr) 2003-10-23

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AU (1) AU2002319143A1 (fr)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004091762A1 (fr) * 2003-04-17 2004-10-28 Behr Gmbh & Co. Kg Dispositif melangeur
WO2004108287A1 (fr) * 2003-06-06 2004-12-16 Micronics, Inc. Systeme et procede pour chauffer, refroidir et creer des cycles thermiques dans un dispositif microfluidique
US7648835B2 (en) 2003-06-06 2010-01-19 Micronics, Inc. System and method for heating, cooling and heat cycling on microfluidic device
DE102005060280B4 (de) 2005-12-16 2018-12-27 Ehrfeld Mikrotechnik Bts Gmbh Integrierbarer Mikromischer sowie dessen Verwendung
AT520976A1 (de) * 2018-02-16 2019-09-15 Avl List Gmbh Wärmetauscher für ein Brennstoffzellensystem und Verfahren zum Betreiben eines Brennstoffzellensystems

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004103897A1 (fr) * 2003-05-23 2004-12-02 Hydrogensource Llc Serpentin pour refroidissement de gaz synthetique et appareil contenant un reacteur a oxydation partielle ainsi qu'un serpentin de ce type

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3926466A1 (de) * 1989-08-10 1991-02-14 Messerschmitt Boelkow Blohm Mikroreaktor zur durchfuehrung chemischer reaktionen mit starker waermetoenung
DE19654361A1 (de) * 1996-12-24 1998-06-25 Behr Gmbh & Co Reaktor in Stapelbauweise
EP0862233A2 (fr) * 1997-02-28 1998-09-02 General Motors Corporation ContrÔle d'une pile à combustion à électrolyte polymère par comparaison ses paramètres opératoires d'une cellue auxiliare
US5811062A (en) * 1994-07-29 1998-09-22 Battelle Memorial Institute Microcomponent chemical process sheet architecture

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3926466A1 (de) * 1989-08-10 1991-02-14 Messerschmitt Boelkow Blohm Mikroreaktor zur durchfuehrung chemischer reaktionen mit starker waermetoenung
US5811062A (en) * 1994-07-29 1998-09-22 Battelle Memorial Institute Microcomponent chemical process sheet architecture
DE19654361A1 (de) * 1996-12-24 1998-06-25 Behr Gmbh & Co Reaktor in Stapelbauweise
EP0862233A2 (fr) * 1997-02-28 1998-09-02 General Motors Corporation ContrÔle d'une pile à combustion à électrolyte polymère par comparaison ses paramètres opératoires d'une cellue auxiliare

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004091762A1 (fr) * 2003-04-17 2004-10-28 Behr Gmbh & Co. Kg Dispositif melangeur
WO2004108287A1 (fr) * 2003-06-06 2004-12-16 Micronics, Inc. Systeme et procede pour chauffer, refroidir et creer des cycles thermiques dans un dispositif microfluidique
US7544506B2 (en) 2003-06-06 2009-06-09 Micronics, Inc. System and method for heating, cooling and heat cycling on microfluidic device
US7648835B2 (en) 2003-06-06 2010-01-19 Micronics, Inc. System and method for heating, cooling and heat cycling on microfluidic device
DE102005060280B4 (de) 2005-12-16 2018-12-27 Ehrfeld Mikrotechnik Bts Gmbh Integrierbarer Mikromischer sowie dessen Verwendung
AT520976A1 (de) * 2018-02-16 2019-09-15 Avl List Gmbh Wärmetauscher für ein Brennstoffzellensystem und Verfahren zum Betreiben eines Brennstoffzellensystems
AT520976B1 (de) * 2018-02-16 2020-04-15 Avl List Gmbh Wärmetauscher für ein Brennstoffzellensystem und Verfahren zum Betreiben eines Brennstoffzellensystems

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DE10217335A1 (de) 2002-10-24
AU2002319143A1 (en) 2002-11-05
WO2002085777A3 (fr) 2003-10-23
EP1383599A2 (fr) 2004-01-28

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