EP1519894A2 - Procede de demarrage d'un systeme generateur de gaz - Google Patents

Procede de demarrage d'un systeme generateur de gaz

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Publication number
EP1519894A2
EP1519894A2 EP03763585A EP03763585A EP1519894A2 EP 1519894 A2 EP1519894 A2 EP 1519894A2 EP 03763585 A EP03763585 A EP 03763585A EP 03763585 A EP03763585 A EP 03763585A EP 1519894 A2 EP1519894 A2 EP 1519894A2
Authority
EP
European Patent Office
Prior art keywords
starting materials
devices
starting
gas
hydrogen
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Withdrawn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
EP03763585A
Other languages
German (de)
English (en)
Inventor
Marc Sommer
Bernhard Vogel
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.)
Mercedes Benz Group AG
Original Assignee
DaimlerChrysler AG
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 DaimlerChrysler AG filed Critical DaimlerChrysler AG
Publication of EP1519894A2 publication Critical patent/EP1519894A2/fr
Withdrawn legal-status Critical Current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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • 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
    • 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
    • H01M8/0687—Reactant purification by the use of membranes or filters
    • 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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • 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
    • C01B2203/0405—Purification by membrane separation
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • 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
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1604—Starting up the process
    • 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 method for starting a gas generation system for generating a hydrogen-containing gas for operating a fuel cell, with devices for converting starting materials into the hydrogen-containing gas, with devices for conditioning at least some of the starting materials, with devices for cleaning the hydrogen-containing gas from undesired gas components and with a start burner.
  • a hydrogen-containing gas can be generated by converting hydrocarbon-containing compounds into so-called reformers, which gas e.g. can be used to operate a fuel cell.
  • the required hydrogen can be made on-board from a hydrocarbon-containing compound, such as Gasoline, diesel, naphtha, natural gas or from an alcohol, e.g. Methanol.
  • a hydrocarbon-containing compound such as Gasoline, diesel, naphtha, natural gas or from an alcohol, e.g. Methanol.
  • the gas generation system can be started in the shortest possible time.
  • the components which ensure the reforming of the hydrocarbon-containing compound and the cleaning of the hydrogen-containing gas from undesired gas components must be brought into their normal operating state as quickly as possible.
  • a starting method for a gas generation system in a fuel cell system is known from US Pat. No. 4,820,598.
  • the fuel reformed during the later operation in the plant is provided in the starting phase of the gas generation system with the thermal energy required for heating the gas generation system by direct combustion of this fuel in the region of at least individual components of the gas generation system.
  • the temperature of the thermal energy generated by the combustion cannot be controlled, or can only be controlled with difficulty, in a disadvantageous manner.
  • catalytically active materials such as, for example, reformers, selective oxidation stages and the like
  • Another disadvantage also lies in the components to be specially designed for direct heating, so that optimization of the components and possibly thermal insulation of the same is made more difficult.
  • a further disadvantage is certainly also to be noted that the heating of further components which require a lower temperature cannot be provided by the proposed starting method.
  • Temperature control solutions e.g. Under- or over-stoichiometric combustion could be considered in principle, but they would have the disadvantage of very high emissions of soot and / or unburned residues of the fuel, generally certainly a hydrocarbon or the like, or the provision of large amounts of air.
  • catalytic burners are used to heat the components of the gas generation system.
  • the disadvantage of using catalytic burners in this way means that only comparatively low-boiling fuels can be used.
  • Use with higher-chain and therefore correspondingly heavier-boiling hydrocarbon mixtures, such as diesel, is not possible or only with considerable wall for the preparation of the fuel before the actual implementation in the catalytic burners.
  • the object of the invention is a starting method for a gas generation system for generating a hydrogen-containing gas for operating a fuel cell, with devices for converting starting materials into the hydrogen-containing gas, with devices for conditioning at least some of the starting materials, with devices for cleaning the hydrogen-containing gas To create gas from undesirable gas components and with a start burner, which avoids the disadvantages mentioned at the outset and which reduces the residues of the fuel which have not been converted during the start-up process and any soot which may form.
  • this object is achieved in that, in a first method step, at least one fuel is burned in the starting burner, the hot exhaust gases from the combustion first heating the devices for conditioning at least some of the starting materials and heating at least one further component with the residual heat still remaining
  • the devices for converting the starting materials are heated by an electric heater, after which in a second process step the starting materials are added to the respective components of the devices after a starting temperature has been reached, and after that in a third process step the quantity ratios are continuously changed the starting materials take place in the direction of the proportions intended for the intended operation.
  • This starting method which relates to a gas generation system in its entirety, uses the energy from direct combustion of a fuel to heat the devices for conditioning at least some of the starting materials. Because this conditioning at least part the starting materials are usually very energy-intensive, since this generally involves at least also the evaporation of water, the high energy content and the good efficiency of direct combustion are very advantageous for this. Since the devices for conditioning at least some of the starting materials are usually designed as heat exchangers and usually contain no catalytic materials, the risk of damage to the devices from overheating is also comparatively small. This then also makes it possible not to regulate the combustion in terms of temperature, but to optimize it with regard to minimal emissions.
  • the possibility is also created of using the components, that is to say in general the heat exchangers, as they exist anyway, since the hot exhaust gases only come from one Part of the heat exchanger must be passed, through which a heat-emitting medium will later flow during regular operation of the gas generation system.
  • the fuel used is irrelevant. According to a very favorable further development of the invention, however, a fuel can be used which is also later used as a starting material for the generation of the hydrogen-rich gas.
  • the hot exhaust gases from the combustion in the starting burner will have cooled significantly. However, they will still have a temperature level that is significantly above the ambient temperature of the gas generation system.
  • the at least one further component can therefore also be heated with the residual heat contained in the exhaust gases.
  • the at least one further component can only be a component which is able to work regularly from a significantly lower temperature than the devices for converting the starting materials into the hydrogen-containing gas or the devices for conditioning the at least part of the starting materials.
  • the devices for cleaning the hydrogen-containing gas from undesired gas components, the fuel cell itself or a cooling circuit of the fuel cell could be mentioned here as examples of such a component, which are not restrictive of the invention.
  • the starting materials arrive at least warmed up by the abovementioned measures for their conditioning and are then approximately ideally conditioned in the further course of the starting process, which generally means vaporized and overheated.
  • the devices for converting the starting materials are thus already heated to a certain extent by the starting materials themselves. Because of their comparatively small heat capacity, they are further heated by electrical heating.
  • This electrical heating which heats the devices for converting the starting materials before the first inflow of the starting materials and then continues until the transition to regular operation of the gas generation system, can be controlled and / or regulated very simply and effectively.
  • the input of thermal energy can be controlled or regulated in such a way that ideal, fastest possible heating takes place without the catalytically active materials normally used in the devices for converting the starting materials experiencing thermal damage.
  • An exemplary solution could, for example, provide a reformer with at least one downstream shift stage in which the starting materials are converted, for example, by autothermal reforming or steam reforming.
  • the starting materials of the respective components of the devices are added as soon as the respective component has reached its starting temperature.
  • the starting temperature is not to be understood as the temperature that guarantees an ideal conversion, but rather the temperature above which a conversion is possible in principle and possibly also with poor efficiency and poor utilization of the starting materials.
  • This non-optimal implementation during the start-up phase is reacted to by means of an appropriate composition of the starting materials with regard to the quantitative ratio.
  • This can mean, in particular, that comparatively little hydrocarbon-containing starting material is added in order to keep starting emissions and soot formation low.
  • suitable measures for example a stoichiometric combustion in the area of the autothermal reformer, an additional heating effect can be achieved by generating thermal energy with such a conversion of the starting materials.
  • the quantitative ratios of the starting materials just described to one another are continuously changed in such a way that they increasingly adapt to the quantitative ratios intended for the intended operation.
  • the transition from the start phase to the intended operation is therefore continuous or at least quasi-continuous.
  • the method according to the invention can thus be used to achieve a very quick and effective start, which enables the gas generation system to operate as intended with a minimal start time and with minimal emissions.
  • water, an oxygen-containing medium, such as air or possibly pure oxygen, and a hydrocarbon-containing compound are used as starting materials.
  • this hydrocarbon-containing compound is also used as fuel in the burner.
  • the hydrocarbon-containing compound, which is fed to the devices for converting the starting materials during the second process step is evaporated by means of electrical energy at least during a temporal part of the second process step.
  • the reformer By starting the reformer with the oxygen-containing medium, for example air, and / or the water vaporized in the facilities for conditioning the starting materials and an electrically vaporized liquid fuel, the residual hydrocarbons that are inevitable here can be reduced to a minimum in the starting phase of the gas generation system.
  • the addition of water vapor ensures that the risk of overheating of the reformer, which has a catalytically active material, is minimized.
  • Another advantage is that the electrical evaporation of the fuel, which generally requires much less energy to evaporate it than the water also used, makes it possible to use a liquid and easily storable fuel with a high energy content. Evaporation nevertheless achieves a very homogeneous mixture with the air and / or water vapor, which also facilitates implementation, reduces emissions and shortens the start-up time of the gas generation system.
  • the further component can be a cooling circuit, which is heated via a heat exchanger with the remaining residual heat of the starting burner after the devices for conditioning at least some of the starting materials have been heated.
  • this selective oxidation stage can be heated via this cooling circuit already mentioned. Since the selective oxidation levels require a much lower temperature potential before they can be started than a reformer or evaporator, the residual heat of the type mentioned above can be used ideally for this.
  • an autothermal reforming stage and at least one shift stage arranged thereafter can be used as devices for converting the starting materials.
  • This last-described construction with reactive heating of the at least one shift stage by combustion of hydrogen and carbon monoxide considerably speeds up the process of heating the shift stage in addition to its existing electrical heating. This is very important in particular with regard to a rapid connection of the selective oxidation stage which may be arranged below and has already been described above.
  • the fuel cell itself can also be switched on very early if the selective oxidation stage is switched on, since otherwise it cannot be switched on due to the comparatively high carbon monoxide content.
  • a particularly favorable embodiment variant of the inventive method explained at the beginning can also provide that the gas generated in the devices for converting the starting materials bypasses the devices for cleaning the hydrogen-containing gas and / or the fuel cell at least during the initial phase of the second process step and immediately one Catalytic combustion is supplied, which in turn provides energy to operate the devices for conditioning at least some of the starting materials.
  • This process is generally very simple with regard to the system connection, since such a catalytic burner for burning the residues for standard operation is present anyway and thereby takes over the conditioning of at least some of the starting materials. In general, this will be the evaporation and / or overheating of water and possibly also the preheating of the oxygen-containing medium or the air. If the product gases generated at the early stage of the second process step, which have strong impurities, in particular with carbon monoxide and residual hydrocarbons, are fed directly to the catalytic burner, damage to the components for cleaning the hydrogen-containing gas and / or the fuel cell itself can be avoided. The residues can be converted into thermal energy in an almost ideal manner in the catalytic burner.
  • the fuel circuit itself is heated as a further component by the cooling circuit already mentioned several times above.
  • This comparatively gentle heating of the fuel cell via the coolant protects the material of the fuel cell, which is relatively sensitive to thermal voltages, particularly in the area of the membrane electrode assemblies (MEA).
  • the cooling medium which is used anyway in the fuel cell during normal operation, results in a comparatively rapid, yet relatively gentle heating of the fuel cell. This also serves to ensure the operational readiness of the entire system comprising the gas generation system and the fuel cell within a very short time.
  • the catalytic burner supplies part of the energy for the conditioning of at least some of the starting materials.
  • the residual heat of the exhaust gas from the starting burner which also supplies energy, is therefore no longer fully used, so that a higher thermal energy content is available for heating the other components and this heating takes place more quickly. Since the residual energy content slowly increases when the catalytic burner is started up, the heating of the other components by means of the residual heat is nevertheless comparatively gentle.
  • FIG. 1 shows a first possible embodiment of a gas generation system and a fuel cell
  • FIG. 3 shows a schematic illustration of the operation of the first possible embodiment in the event of a cold start
  • FIG. 6 shows a schematic illustration of a possible interconnection of the gas generation system in the event of a cold start.
  • a hydrogen-rich gas H 2 is generated from a hydrocarbon-containing starting material C n H m together with an oxygen-containing medium 0 2 / such as air, and optionally water H 2 0.
  • This hydrogen-rich gas H is fed to a fuel cell 2, which can be designed, for example, as a PEM fuel cell, in which an anode space 3 is separated from a cathode space 5 by a proton-conducting membrane (PEM) 4.
  • PEM proton-conducting membrane
  • the hydrogen-rich gas is generated from the hydrocarbon-containing compound C n H m , air 0 2 and water H 2 0 in a reformer 6, for example by autothermal reforming.
  • the added water H 2 0 is first evaporated and / or superheated in a heat exchanger / evaporator 7, with the air 0 2 already being added here, so that it is also preheated.
  • the hydrocarbon-containing compound C n H m which is, for example, gasoline or diesel can be supplied.
  • the autothermal reformer 6 then leaves a hydrogen-containing gas, which is enriched again in a downstream shift stage 8 with regard to its hydrogen content. This then hydrogen-rich gas then flows into a hydrogen separation module 9 or membrane module 9.
  • the hydrogen-rich gas is divided into almost pure hydrogen H 2 and a residual gas, the so-called retentate R, by means of membranes which are selectively permeable to hydrogen, for example based on palladium alloys.
  • the almost pure hydrogen H 2 is fed to the fuel cell and here in particular to the anode compartment 3 of the fuel cell 2.
  • the retentate R passes into a catalytic burner 10.
  • the hydrogen H 2 and an oxygen-containing medium 0 2 are converted into electrical energy and water.
  • the residual gases or exhaust gases from the area of the fuel cell 2 are likewise fed to the catalytic burner 10 via corresponding lines.
  • the mixture of the exhaust gases from the fuel cell 2 and the retentate R from the membrane module 9 still contains sufficient amounts of oxygen and flammable constituents, such as residual hydrogen and residues of hydrocarbons, carbon monoxide and the like, which could not pass through the membrane module 9.
  • Thermal energy is generated in the catalytic burner 10 from the energy content of these residual gases, the exhaust gases of which, in the exemplary embodiment shown here, are used in particular for heating the heat exchanger / evaporator 7.
  • start burner 11 and further components 12, to which, as well as to the optional addition of air 0 2 to the shift stage 8, the description of the method for starting the gas generation system 1 will be explained in more detail later is received.
  • FIG. 2 shows a further alternative embodiment of a gas generation system l 1 .
  • the gas generation system 1 ' has comparable components to the gas generation system 1 shown above. These components are provided with analog reference numerals. In the following, only the differences between the two gas generating systems 1 and 1 'will be discussed in more detail.
  • the gas generating system l 1 operates on the same principle as the gas generating system 1. Only the purification of the hydrogen-rich gas, which gas was of unwanted residues, where the retentate R realized up over the membrane module 9 as a means for purifying the hydrogen-rich, is executed differently here , After the autothermal reformer 6, the hydrogen-containing gas flows first into a high-temperature shift stage 8a and then into a low-temperature shift stage 8b. The principle of operation is comparable to that of a shift stage 8 present in the gas generation system 1, in each of which an enrichment with hydrogen takes place in a manner known per se.
  • the gas generation system 1 'for gas cleaning is followed by a selective oxidation stage 13, in which impurities in the hydrogen-rich gas are oxidized to carbon dioxide with the addition of air or an oxygen-containing medium 0 2 .
  • a hydrogen-rich gas H 2 which will still contain residues of the hydrocarbon-containing compound and carbon dioxide, then flows into the area of the anode 3 of the fuel cell 2.
  • the exhaust gases flow from the area of the fuel cell 2 into the catalytic burner 10, so that the residual energy contained in them, as already described analogously above, can be fed to the heat exchanger / evaporator 7.
  • the reformer 6 Before the actual generation of the hydrogen-containing gas in the gas generation system 1 begins, the reformer 6 in particular must be brought to its ignition temperature. When water vapor is added for the reforming, it must also be generated, which is done by the heat exchanger / evaporator 7 as a device for conditioning at least some of the starting materials. In order to meet these two requirements, which are necessary for starting the gas generation system 1 and in particular for starting the reforming, in the starting burner 11 by a preferably overstoichiometric combustion of a fuel, in particular the hydrocarbon-containing compound C n H m , which in the gas generating system 1 is used anyway to generate the hydrogen-containing gas, generates a hot exhaust gas.
  • the starting burner 11 is designed according to the exemplary embodiment shown here as a pore burner, since this provides the hot exhaust gas at temperatures of up to 1000 ° C. under ideal conditions in the case of the stoichiometric combustion of the hydrocarbon-containing compound C n H m .
  • This hot exhaust gas is then used to heat the heat exchanger / evaporator 7, in which the conditioning of the starting materials and here in particular the evaporation and overheating of the water H 2 0 and possibly also preheating the autothermal reforming air 0 2 takes place.
  • the hot exhaust gas from the start burner 11 is cooled in the heat exchanger / evaporator 7 to such an extent that it can then be used to heat the further components 12.
  • the further components 12 are in particular the hydrogen separation module 9 and a heat exchanger 14.
  • the hot gas is after the heat exchanger / evaporator 7 be cooled to such an extent that it only enables preheating of the hydrogen separation module 9 and minimal heating of the heat exchanger 14.
  • the reformer 6 and the at least one shift stage 8 are heated electrically in the schematic structure shown here, which is symbolized by the electrical connections indicated in principle in the area of the components 6, 8 mentioned.
  • the heating of the shift stage 8, as soon as reformate flows from the reformer 6 into the area of the at least one shift stage 8, can be carried out by combustion under the supply of an oxygen-containing medium 0 2 , for example air, which is optionally indicated in FIG. 1 ,
  • the combustion of at least some of the contents of the reformate in the at least one shift stage 8 with the oxygen 0 2 can ensure immediate heating of the at least one shift stage 8.
  • the reforming process begins in a second step of the method for starting the gas generation system 1.
  • fuel is added in the form of the hydrocarbon-containing compound C n H m , air 0 2 and / or water vapor H 2 0.
  • the hydrocarbon-containing compound is evaporated, as shown in FIG. 5, via an electric evaporator 15, which is justifiable due to the typically small amount of fuel used and the usually comparatively low energy required for evaporation of electrical energy is possible.
  • the simple injection of the fuel into this hot gas stream is sufficient to ensure adequate evaporation.
  • the electric evaporator 15 then does not have to be operated further.
  • the start of the reforming takes place in the reformer 6 with operating parameters that have changed compared to normal operation, which are then changed with increasing heating of the gas generation system 1 in the direction of the operating parameters in normal operation of the gas generation system 1.
  • oxygen or air is also added to the at least one shift stage 8 during the cold start process, so that the heating is accelerated here too.
  • the reformate is used for heating, and the electrical heating described above is also provided.
  • the representation is analogous to the representation in FIG. 3. Only the heating of the membrane module 9 is omitted here, since this in the Gas generation system 1 'is not present. Since the selective oxidation stage 13 requires a much lower temperature level than the shift stage 8 or the shift stages 8a, 8b, it is not heated directly with the hot exhaust gases, but also via the cooling circuit of the fuel cell 2, the heat input into the cooling circuit in the above already known manner takes place via the heat exchanger 14.
  • the reformate generated cannot be fed directly to the fuel cell 2 when the gas generation system 1 'according to FIG. 2 is being set up, since this contains a very high proportion of carbon monoxide CO, which would lead to poisoning of the electrocatalysts in the fuel cell 2.
  • a gas generation system 1 'in a construction according to FIG. 2 is operated during the starting phase in such a way that a bypass 16 leads the hydrogen-containing gas generated immediately after the high-temperature shift stage 8b into the area of the catalytic burner 10, as shown in FIG. 6 is indicated in principle.
  • the selective oxidation stage 13 and the fuel cell 2 are thus bypassed by this bypass 16, so that they are only included in the operation when a sufficient temperature of the components of the gas generation system 1 ⁇ and a sufficient quality of the reformate are present.
  • fuel such as the hydrocarbon-containing compound C n H m , which is used in the gas generation system 1 'anyway, can be added in the region of the catalytic burner 10, so that the heat yield of the catalytic burner 10 can be increased if necessary.
  • the gas generating system 1 is brought to its operating pressure with the membrane module 9 and, if necessary, an additional compression device for supplying air to the reformer 6 is started, so that in the already preheated membrane module dul 9 hydrogen can be separated from the reformate and fed to the fuel cell 2.
  • the residual gas from the membrane module 9, the retentate R is fed to the catalytic burner 10, so that this too very soon provides thermal energy during the starting process, which likewise heats the heat exchanger / evaporator 7 serves and the start time for the gas generation system 1 or 1 ⁇ further reduced.
  • the further components, in particular the membrane module 9 and the heat exchanger 14 will continue to be heated.
  • the power or the fuel supply to the starting burner 11 can also be reduced, so that no overheating of the coolant occurs in the area of the heat exchanger 14.
  • the start burner 11 can be integrated very easily in the gas generation system 1 or 1 '.
  • the start burner 11 can be connected, for example, via line elements which only have heat-resistant backflow safeguards, so that the connection to the start burner 11 is automatically prevented with increased system pressure in the gas generation system 1 or 1 '.
  • This measure makes it possible, for example, to dispense with complex high-temperature-resistant valves, proportional valves or the like.
  • the start burner 11 with a high temperature level supplies essentially only one component, namely the heat exchanger and / or evaporator, and that the subsequent switched components can be arranged in the usual flow path of the system.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne un procédé de démarrage d'un système générateur de gaz permettant la génération d'un gaz hydrogéné destiné au fonctionnement d'une pile à combustible. Ce système générateur de gaz comprend des équipements de conversion de matières premières en gaz hydrogéné, des équipements destinés à conditionner au moins une partie des matières premières, des équipements destinés à l'épuration du gaz hydrogéné par enlèvement des constituants de gaz indésirables et un brûleur de démarrage. Dans un première étape, au moins un combustible brûle dans le brûleur de démarrage. Les gaz d'échappement chauds émanant de cette combustion chauffent d'abord les équipements de conditionnement d'au moins une partie des matières premières et les chaleurs résiduelles de ces gaz d'échappement chauffent au moins une autre composante. Parallèlement, les équipements de conversion des matières premières sont chauffés par un chauffage électrique. Dans une deuxième étape, les matières premières sont ajoutées dans les composantes respectifs des équipements susmentionnés dès qu'une température de démarrage a été atteinte. Dans une troisième étape, les rapports volumétriques des matières premières sont modifiés en continu pour approcher les rapports volumétriques prévus pour le fonctionnement adéquat du système générateur de gaz.
EP03763585A 2002-07-10 2003-07-02 Procede de demarrage d'un systeme generateur de gaz Withdrawn EP1519894A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10231126 2002-07-10
DE10231126A DE10231126A1 (de) 2002-07-10 2002-07-10 Verfahren zum Starten eines Gaserzeugungssystems
PCT/DE2003/002199 WO2004007356A2 (fr) 2002-07-10 2003-07-02 Procede de demarrage d'un systeme generateur de gaz

Publications (1)

Publication Number Publication Date
EP1519894A2 true EP1519894A2 (fr) 2005-04-06

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EP03763585A Withdrawn EP1519894A2 (fr) 2002-07-10 2003-07-02 Procede de demarrage d'un systeme generateur de gaz

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US (1) US7374591B2 (fr)
EP (1) EP1519894A2 (fr)
JP (1) JP2005538501A (fr)
AU (1) AU2003247248A1 (fr)
DE (1) DE10231126A1 (fr)
WO (1) WO2004007356A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111864237A (zh) * 2020-06-17 2020-10-30 江苏大学 一种基于催化和微燃烧的氢燃料电池尾气后处理装置

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7082753B2 (en) * 2001-12-03 2006-08-01 Catalytica Energy Systems, Inc. System and methods for improved emission control of internal combustion engines using pulsed fuel flow
DE10349075B4 (de) * 2003-10-22 2016-01-07 Airbus Operations Gmbh Vorrichtung zur Zufuhr von Brennstoff zu einem Brenner in einem Brennstoffzellensystem mit einem Reformer
KR100560495B1 (ko) * 2004-01-28 2006-03-14 삼성에스디아이 주식회사 연료 전지 시스템의 개질기 및 이를 채용한 연료 전지시스템
CA2583208C (fr) 2004-10-15 2015-08-25 Seattle Genetics, Inc. Anticorps anti-cd70 et son utilisation pour le traitement et la prevention du cancer et des troubles immunitaires
US7641903B2 (en) 2004-10-15 2010-01-05 Seattle Genetics, Inc. Anti-CD70 antibody and its use for the treatment and prevention of cancer and immune disorders
DE102009037145B4 (de) 2009-08-06 2015-08-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Hochtemperaturbrennstoffzellensystem mit einem Startbrenner
JP5820873B2 (ja) * 2010-04-09 2015-11-24 フラウンホーファー・ゲゼルシャフト・ツール・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファウ 高温燃料電池を有するシステム
DE102020127406A1 (de) 2020-10-19 2021-12-02 Diehl Aerospace Gmbh Katalytische Wärmeerzeugung für die Bordküche

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033133A (en) * 1976-03-22 1977-07-05 California Institute Of Technology Start up system for hydrogen generator used with an internal combustion engine
JP2511866B2 (ja) * 1986-02-07 1996-07-03 株式会社日立製作所 燃料電池発電システム及びその起動方法
JPH0217306A (ja) * 1988-07-04 1990-01-22 Fuji Electric Co Ltd 多孔体バーナ
DE19639150C2 (de) * 1996-09-24 1998-07-02 Daimler Benz Ag Zentrale Heizvorrichtung für ein Gaserzeugungssystem
US6221117B1 (en) * 1996-10-30 2001-04-24 Idatech, Llc Hydrogen producing fuel processing system
EP0924162A3 (fr) * 1997-12-16 1999-10-20 dbb fuel cell engines GmbH Membrane pour la séparation d'hydrogène, dispositif de reformage de méthanol utilisant cette membrane et son procédé de fonctionnement
DE19755814C1 (de) * 1997-12-16 1999-11-18 Dbb Fuel Cell Engines Gmbh Verfahren zum Betrieb einer Anlage zur Wasserdampfreformierung eines Kohlenwasserstoffs
DE19755815C2 (de) * 1997-12-16 1999-12-09 Dbb Fuel Cell Engines Gmbh Verfahren zur Wasserdampfreformierung eines Kohlenwasserstoffs oder Kohlenwasserstoffderivats, damit betreibbare Reformierungsanlage und Brennstoffzellen-Betriebsverfahren
DE19755813C2 (de) * 1997-12-16 2000-09-14 Dbb Fuel Cell Engines Gmbh Verfahren zum Betrieb einer Wasserdampfreformierungsanlage, damit betreibbare Reformierungsanlage und Brennstoffzellensystem-Betriebsverfahren
JP2001295707A (ja) 1999-06-03 2001-10-26 Toyota Motor Corp 車両搭載用の燃料改質装置
JP3678118B2 (ja) * 2000-06-01 2005-08-03 日産自動車株式会社 燃料改質システム
CN1195670C (zh) * 2000-08-25 2005-04-06 松下电器产业株式会社 氢发生装置
US20020064487A1 (en) * 2000-11-30 2002-05-30 Richard Sederquist Compact Multiple tube steam reformer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004007356A2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111864237A (zh) * 2020-06-17 2020-10-30 江苏大学 一种基于催化和微燃烧的氢燃料电池尾气后处理装置
CN111864237B (zh) * 2020-06-17 2021-07-20 江苏大学 一种基于催化和微燃烧的氢燃料电池尾气后处理装置

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WO2004007356A3 (fr) 2004-04-08
AU2003247248A1 (en) 2004-02-02
US7374591B2 (en) 2008-05-20
DE10231126A1 (de) 2004-02-05
WO2004007356A2 (fr) 2004-01-22
JP2005538501A (ja) 2005-12-15
AU2003247248A8 (en) 2004-02-02
US20050260110A1 (en) 2005-11-24

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