DE19934649A1 - Hydrogen generation in reformer with feed containing hydrocarbons, used in vehicle with fuel cell supplying drive or electricity consumers, uses (partial) recycling of gas containing hydrogen - Google Patents
Hydrogen generation in reformer with feed containing hydrocarbons, used in vehicle with fuel cell supplying drive or electricity consumers, uses (partial) recycling of gas containing hydrogenInfo
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- DE19934649A1 DE19934649A1 DE19934649A DE19934649A DE19934649A1 DE 19934649 A1 DE19934649 A1 DE 19934649A1 DE 19934649 A DE19934649 A DE 19934649A DE 19934649 A DE19934649 A DE 19934649A DE 19934649 A1 DE19934649 A1 DE 19934649A1
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- 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
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- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- 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
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- 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
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- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- 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
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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- C01B2203/1247—Higher hydrocarbons
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- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
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- C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung von Wasser stoff in einem Reformer, dem ein kohlenwasserstoffhaltiges Ge misch zugeführt wird gemäß dem Oberbegriff des Patentanspruchs 1. Insbesondere soll der erzeugte Wasserstoff zur Stromerzeu gung in einer Brennstoffzelle verwendet werden.The invention relates to a method for producing water substance in a reformer to which a hydrocarbon containing Ge Mix is supplied according to the preamble of the claim 1. In particular, the hydrogen generated should generate electricity be used in a fuel cell.
Zur Erzeugung von Wasserstoff wird häufig das katalytische Re
formieren von Kohlenwasserstoffen mit Wasserdampf eingesetzt.
Ziel den Spaltverfahrens ist die möglichst vollständige Um
wandlung der Kohlenwasserstoffe in Wasserstoff und Kohlenmon
oxid, verbunden mit einer Umsetzung des Kohlenmonoxids zu Was
serstoff gemäß den nachfolgenden Reaktionsformeln:
To generate hydrogen, the catalytic reforming of hydrocarbons with water vapor is often used. The aim of the cracking process is to convert the hydrocarbons into hydrogen and carbon monoxide as completely as possible, combined with a conversion of the carbon monoxide to hydrogen according to the following reaction formulas:
CnHm + nH2O → nCO + (n + m/2) H2 (1)
CO + H2O → CO2 + H2 (2)C n H m + nH 2 O → nCO + (n + m / 2) H 2 (1)
CO + H 2 O → CO 2 + H 2 (2)
Die Reaktion (2) wird als Shift-Reaktion bezeichnet. Die Reak tionswärme für die endothermen Spaltreaktionen wird bei der Dampfreformierung durch indirekten Wärmeaustausch aufgebracht. Im autothermen Reaktor liefern simultan ablaufende, stark exo therme Oxidationsreaktionen die notwendige Spaltenergie. Wei terhin ist auch die Reformierung mittels partieller Oxidation ohne Zugabe von Wasserdampf bekannt. The reaction (2) is called the shift reaction. The Reak heat of heat for the endothermic cleavage reactions Steam reforming applied through indirect heat exchange. In the autothermal reactor, simultaneous, strongly exo deliver thermal oxidation reactions the necessary gap energy. Wei also the reforming by means of partial oxidation known without the addition of water vapor.
Bei der autothermen Reformierung wird die zur Spaltung der Kohlenwasserstoffe nötige Energie durch teilweise Verbrennung des Einsatzgases mittels Luft oder reinem Sauerstoff aufge bracht.In the autothermal reforming process, the splitting of the Hydrocarbons required energy through partial combustion of the feed gas by means of air or pure oxygen brings.
Das vom Reformer erzeugte Gas wird in einer Gasreinigungsstufe einer Nachbehandlung unterzogen, aus der beim autothermen, mit Luft betriebenen Reaktor die folgenden Gase als Hauptkomponen ten austreten: H2, CO2, N2, H2O und Spuren von CH4 und CO.The gas generated by the reformer is subjected to a post-treatment in a gas cleaning stage, from which the following gases emerge as main components in the autothermal, air-operated reactor: H 2 , CO 2 , N 2 , H 2 O and traces of CH 4 and CO.
Der in diesem Gemisch enthaltene Wasserstoff kann entweder zur Gewinnung reinen Wasserstoffs abgetrennt oder beispielsweise zur Stromerzeugung als Brennstoff einer Brennstoffzelle zuge führt werden. Das aus der Brennstoffzelle austretende Gas ent hält neben den genannten Komponenten noch etwa 20% der Ein gangskonzentration Wasserstoff.The hydrogen contained in this mixture can either be used Obtaining pure hydrogen separated or for example to generate electricity as fuel of a fuel cell leads. The gas emerging from the fuel cell ent holds about 20% of the A in addition to the components mentioned hydrogen concentration.
Ruß-Bildung ist eine unerwünschte Nebenreaktion bei der Dampf
spaltung, da dieser die eingesetzten Katalysatoren deakti
viert. Hierbei spielt die folgende, als Boudouard-Gleichge
wicht bezeichnete Reaktion eine Rolle:
Soot formation is an undesirable side reaction in steam splitting, since this deactivates the catalysts used. The following reaction, known as Boudouard equilibrium, plays a role here:
2CO ↔ CO2 + C (3)2CO ↔ CO 2 + C (3)
Es handelt sich hierbei um ein druck- und temperaturabhängiges chemische Gleichgewicht. Im allgemeinen wird der Ruß-Bildung durch eine ausreichend hohe Zumischung von Wasserdampf begeg net, der die thermodynamischen Bedingungen verschlechtert, un ter denen Ruß, d. h. Kohlenstoff wie auch schwere Kohlenwasser stoffe, entstehen kann. It is a pressure and temperature dependent chemical equilibrium. Generally the soot formation counteracted by a sufficiently high admixture of water vapor net, which worsens the thermodynamic conditions, un the soot, d. H. Carbon as well as heavy hydrocarbon substances that can arise.
Heutzutage besteht das Bedürfnis, mittels Reformierung von Kohlenwasserstoffen den für wasserstoffbetriebene Fahrzeuge notwendigen Wasserstoff bereitzustellen. Dies kann im Fahrzeug selbst geschehen, wobei üblicher Kraftstoff wie Benzin dem Re former zugeleitet wird. Das den Reformer verlassende wasser stoffhaltige Gasgemisch wird dann einem Brennstoffzellensystem zugeführt, das die bei der Oxidation des Wasserstoffs freiwer dende chemische Energie in elektrische Energie umwandelt. Als Oxidationsmittel kann Luft verwendet werden. Hierbei wird etwa 80% des zugeführten Wasserstoffs in der Brennstoffzelle ver braucht und der verbleibende Rest wird bisher in einem kataly tischen Brenner verbrannt, der katalytisch Wasserstoff und Methan-Reste dieses Gemischs mit Luft vollständig in CO2 und H2O verbrennt und Wärme erzeugt.Nowadays there is a need to provide the hydrogen necessary for hydrogen-powered vehicles by reforming hydrocarbons. This can be done in the vehicle itself, with conventional fuel such as gasoline being fed to the reformer. The hydrogen-containing gas mixture leaving the reformer is then fed to a fuel cell system which converts the chemical energy released during the oxidation of the hydrogen into electrical energy. Air can be used as the oxidizing agent. Here, about 80% of the hydrogen supplied is consumed in the fuel cell and the remainder has so far been burned in a catalytic burner that completely burns the catalytic hydrogen and methane residues of this mixture with air in CO 2 and H 2 O and generates heat.
Aus der US-4240805 ist ein Verfahren zum Regenerieren eines Reaktors für das Dampfreformieren bekannt. Hierzu werden zwei Reaktoren parallel derart geschaltet, daß ein Reaktor regene riert wird, während der andere Wasserstoff erzeugt. Das Rege nerieren erfolgt durch Zuleiten der anodenseitigen Abgase ei ner Brennstoffzelle, wobei die wasserstoffhaltigen Gase zusam men mit Luft im Reaktorinneren verbrannt werden, um die bei der Wasserstoffherstellung verbrauchte Reaktionswärme zurück zugewinnen. Anstelle einer eigens vorzusehenden Luftzuleitung wird auch die Zuleitung der Kathodenabgase der Brennstoffzelle vorgeschlagen, die Sauerstoff und Wasser enthalten. Dieses Verfahren dient alleine zur Regenerierung eines Reaktors und zur Wärmerückgewinnung im Parallelbetrieb und ist für den Dau erbetrieb mit einem einzelnen Reformerreaktor nicht geeignet.From US 4240805 is a method for regenerating a Reactor known for steam reforming. This will be two Reactors connected in parallel so that a reactor is raining is generated while the other produces hydrogen. The brisk nerieren takes place by supplying the anode-side exhaust gases ner fuel cell, the hydrogen-containing gases together can be burned with air in the interior of the reactor the heat of reaction consumed in the production of hydrogen to win. Instead of a dedicated air supply line is also the supply of the cathode exhaust gases of the fuel cell proposed that contain oxygen and water. This The method is used solely for the regeneration of a reactor and for heat recovery in parallel operation and is for the duration not suitable for operation with a single reformer reactor.
Aufgabe der vorliegenden Erfindung ist es, den Wirkungsgrad der Reformierung von Kohlenwasserstoffen zu erhöhen, wozu ins besondere eine verminderte Ruß-Bildung erzielt werden soll, sowie den Wirkungsgrad der Stromerzeugung einer nachgeschalte ten Brennstoffzelle zu verbessern.The object of the present invention is the efficiency the reforming of hydrocarbons in particular reduced soot formation is to be achieved, as well as the efficiency of power generation downstream to improve the fuel cell.
Diese Aufgabe wird erfindungsgemäß durch die Merkmale des Pa tentanspruchs 1 gelöst.This object is achieved by the features of Pa claim 1 solved.
Erfindungsgemäß wird das von dem Reformer erzeugte wasser stoffhaltige Gas wenigstens zum Teil dem Reformer wieder zuge führt, wobei das von dem Reformer erzeugte wasserstoffhaltige Gas vor der Rückführung ganz oder zum Teil einem Brennstoff zellensystem zur Stromerzeugung zugeleitet worden sein kann. Wie eingangs geschildert, enthält das durch Reformierung von Kohlenwasserstoffen erhaltene Gas neben Wasserstoff einen ho hen Anteil von CO2. Durch die erfindungsgemäße Rückführung ei nes Teils des den Reformer verlassenden Stoffstromes wird folglich eingangsseitig im Reformer die CO2-Konzentration er höht, wodurch das Bodouard-Gleichgewicht (3) nach links ver schoben wird. Die Ruß-Bildung wird folglich verringert und der Anteil an CO erhöht. Dieses CO steht für die spätere Bildung von Wasserstoff durch die Shift-Reaktion (2) zur Verfügung und stellt daher ein Nutzgas dar. Somit wird durch das erfindungs gemäße Verfahren der Bildung von Ruß begegnet, damit die Standzeiten der Katalysatoren erhöht und die Wasserstoffaus beute vergrößert.According to the invention, the hydrogen-containing gas generated by the reformer is at least partly fed back to the reformer, wherein the hydrogen-containing gas generated by the reformer may have been supplied entirely or in part to a fuel cell system for power generation before being recycled. As described at the beginning, the gas obtained by reforming hydrocarbons contains a high proportion of CO 2 in addition to hydrogen. By recycling a portion of the material flow leaving the reformer according to the invention, the CO 2 concentration is consequently increased on the input side in the reformer, as a result of which the Bodouard balance (3) is shifted to the left. The soot formation is consequently reduced and the proportion of CO is increased. This CO is available for the later formation of hydrogen by the shift reaction (2) and is therefore a useful gas. Thus, the process according to the invention counteracts the formation of soot so that the service life of the catalysts is increased and the hydrogen yield is increased .
Bei Dampfreformern wird durch die erfindungsgemäße Rückleitung eines Teils des erzeugten wasserstoffhaltigen Gases die H2O- Konzentration im Reformer erhöht, was bekanntlich ebenfalls zur Verringerung der Ruß-Bildung beiträgt.In steam reformers, the H 2 O concentration in the reformer is increased by returning part of the hydrogen-containing gas produced according to the invention, which is also known to contribute to reducing the formation of soot.
Schließlich wird bei der autothermen Reformierung durch die erfindungsgemäße Rückführung des wasserstoffhaltigen Stoff stromes Wasserstoff als Brennstoff für die exothermen Oxidati onsreaktionen zur Verfügung gestellt, der somit als Energie lieferant dient und zur Verminderung der durch die Kohlenwas serstoffe bereitzustellenden Reaktionswärme beiträgt.Finally, in the autothermal reforming by recycling of the hydrogen-containing substance according to the invention current hydrogen as fuel for the exothermic oxidati ons reactions provided, which is therefore as energy serves and to reduce the amount of coal water contributes to the heat of reaction to be provided.
Mit Vorteil läßt sich die Erfindung insbesondere dann einset zen, wenn das durch die Reformierung erzeugte wasserstoffhal tige Gas einer Brennstoffzelle zur Stromerzeugung zugeleitet wird. Es sind mehrere Varianten denkbar, bei denen entweder vor, nach oder sowohl vor als auch nach der Zuleitung des Stoffstroms in die Brennstoffzelle ein Teil dieses Stoffstroms zum Reformer zurückgeführt wird. Vorteilhaft ist es, den ge samten vom Reformer erzeugten Stoffstrom der Anodenseite des Brennstoffzellensystems zuzuführen und einen Teil des die Brennstoffzelle verlassenden Stoffstroms wieder in den Refor mer einzuspeisen. Durch den Verbrauch von Wasserstoff in der Brennstoffzelle ist die CO2-Konzentration in dem die Brenn stoffzelle verlassenden Stoffstrom relativ höher als im Ein gangsstrom. Der die Brennstoffzelle verlassende Stoffstrom kann folglich das Boudouard-Gleichgewicht (3) wirksamer in Richtung auf eine Bildung von CO verschieben.The invention can be used with particular advantage when the hydrogen-containing gas generated by the reforming is fed to a fuel cell for power generation. Several variants are conceivable in which a part of this material flow is returned to the reformer either before, after or both before and after the material flow is fed into the fuel cell. It is advantageous to supply the entire stream of material generated by the reformer to the anode side of the fuel cell system and to feed a portion of the stream of fuel leaving the fuel cell back into the reformer. Due to the consumption of hydrogen in the fuel cell, the CO 2 concentration in the material flow leaving the fuel cell is relatively higher than in the input flow. The mass flow leaving the fuel cell can therefore shift the Boudouard equilibrium (3) more effectively towards the formation of CO.
Das erfindungsgemäße Verfahren eignet sich insbesondere bei autothermer Reformierung von Kohlenwasserstoffen, da hier ein Teil der Reaktionswärme vom rückgeführten Wasserstoff bereit gestellt werden kann.The method according to the invention is particularly suitable for autothermal reforming of hydrocarbons, since here a Part of the heat of reaction from the recycled hydrogen ready can be put.
Der verbleibende, aus der Brennstoffzelle austretende Stoff strom kann nach Rückführung eines Teiles desselbigen zum Re former zur vollständigen Verbrennung einem katalytischen Bren ner zugeführt werden, der ein Teil der für die Verfahrensfüh rung notwendigen Prozeßwärme oder -energie zurückgewinnt. The remaining substance emerging from the fuel cell electricity can be returned to Re former for complete combustion of a catalytic burner ner are supplied, which is part of the procedure for the necessary process heat or energy is recovered.
Das Verfahren ist besonders zum Einsatz in einem Fahrzeug ge eignet, bei dem ein Brennstoffzellensystem zum Antrieb und/oder zur Versorgung elektrischer Verbraucher eingesetzt wird. Die zur Versorgung des Brennstoffzellensystems notwendi gen Wasserstoffmengen werden "on board" beispielsweise durch autotherme Reformierung von üblicherweise zum Verbrennungsmo torbetrieb eingesetztem Benzin erzeugt. Neben Wasserdampf wird dem Reformer als Oxidationsmittel Luft zugeführt.The method is particularly suitable for use in a vehicle is suitable in which a fuel cell system for driving and / or used to supply electrical consumers becomes. The necessary to supply the fuel cell system quantities of hydrogen are "on board", for example autothermal reforming from usually to the combustion engine gasoline used in door operation. In addition to water vapor air supplied to the reformer as an oxidizing agent.
Im folgenden soll ein Ausführungsbeispiel anhand der beigefüg ten Figuren die Erfindung näher erläutern.In the following, an exemplary embodiment is intended to be based on the attached ten figures explain the invention in more detail.
Fig. 1 zeigt den bisherigen Verlauf der Stoffströme in einem Fahrzeug mit Wasserstoffantrieb. Fig. 1 shows the previous course of the material flows in a vehicle with a hydrogen drive.
Fig. 2 zeigt den Verlauf der Gasströme bei einem Fahrzeug mit Wasserstoffantrieb unter Einsatz des erfindungsgemäßen Verfahrens. Fig. 2 shows the course of the gas streams in a vehicle powered by hydrogen using the method according to the invention.
Die Erfindung soll anhand des Einsatzes des erfindungsgemäßen Verfahrens für wasserstoffbetriebene Fahrzeuge geschildert werden, bei denen Wasserstoff durch autotherme Reformierung eines kohlenwasserstoffhaltigen Kraftstoffs erzeugt und an schließend einem Brennstoffzellensystem zur Stromerzeugung zu geführt wird. Der autotherme Reformer ist in den Figuren mit der Bezugsziffer 1 gekennzeichnet. Dem Reformer 1 werden aus entsprechenden Zuleitungen oder Reservoiren Luft 4, Wasser 5 und Benzin 6 in geeigneten Druck- und Temperaturbereichen zu geführt. Wie eingangs geschildert, dient der in der Luft ent haltene Sauerstoff zur Erzeugung der benötigten Reaktionswärme durch exotherme Oxidationsreaktionen mit Kohlenstoff, Kohlen monoxid, Kohlenwasserstoffen sowie Wasserstoff selbst. Die Kohlenwasserstoffe werden mit Wasserdampf unter Bildung von Wasserstoff umgesetzt und gespalten. Verbleibende Mengen CO werden nach der Shift-Reaktion (2) in Wasserstoff umgewandelt und der resultierende Gasstrom einer Gasreinigung unterzogen.The invention is to be described using the method according to the invention for hydrogen-powered vehicles in which hydrogen is generated by autothermal reforming of a hydrocarbon-containing fuel and is subsequently fed to a fuel cell system for generating electricity. The autothermal reformer is identified by the reference number 1 in the figures. Air 4 , water 5 and gasoline 6 are fed to the reformer 1 from suitable supply lines or reservoirs in suitable pressure and temperature ranges. As described at the beginning, the oxygen contained in the air is used to generate the required heat of reaction through exothermic oxidation reactions with carbon, carbon monoxide, hydrocarbons and hydrogen itself. The hydrocarbons are reacted with water vapor to form hydrogen and split. Remaining quantities of CO are converted into hydrogen after the shift reaction (2) and the resulting gas stream is subjected to gas purification.
Dieses den Reformer 1 verlassende Stoffgemisch wird in diesem Ausführungsbeispiel vollständig einer Brennstoffzelle 2, ge nauer der Anodenseite eines Brennstoffzellensystems 2 zuge führt. Dort wird 80% des enthaltenen Wasserstoffs zur Stromer zeugung umgesetzt, wodurch das Fahrzeug angetrieben und/oder elektrische Verbraucher im Fahrzeug versorgt werden können. Der die Anodenseite des Brennstoffzellensystems 2 verlassende Stoffstrom wird bisher üblicherweise einem katalytischen Brenner zugeführt, um ein Teil der verbrauchten Wärme/Energie zurückzugewinnen.This mixture of substances leaving the reformer 1 is completely supplied in this exemplary embodiment to a fuel cell 2 , more precisely to the anode side of a fuel cell system 2 . There, 80% of the hydrogen contained is converted into electricity, which can drive the vehicle and / or supply electrical consumers in the vehicle. The mass flow leaving the anode side of the fuel cell system 2 has hitherto usually been fed to a catalytic burner in order to recover part of the heat / energy consumed.
In Fig. 2 sind dieselben Komponenten aus der Fig. 1 mit den selben Bezugsziffern bezeichnet. Erfindungsgemäß wird ein Teil des vom Reformer 1 erzeugten wasserstoffhaltigen Gasstroms zum Reformer zurückgeführt, wobei in diesem Ausführungsbeispiel das wasserstoffhaltige Gas aus dem Reformer vollständig dem Brennstoffzellensystem 2 zugeleitet wird und erst anschließend die Rückführung zur Eingangsseite des Reformers 1 erfolgt. Diese Rückführung erfolgt durch die Leitung 7, durch die der kleinere Teil des die Brennstoffzelle verlassenden Stoffstroms zum autothermen Reformer 1 geleitet wird. Die in diesem zu rückgeleiteten Stoffstrom enthaltenen Komponenten CO2, H2 und H2O bewirken die folgenden Verbesserungen in der Prozeßführung: die Erhöhung der CO2-Konzentration im autothermen Reformer be günstigt die Bildung von CO gemäß dem Boudouard-Gleichgewicht (3), was zur Verminderung der Ruß-Bildung und zur erhöhten Ausbeute von 1% nach der Shift-Reaktion (2) führt. Der rückge führte Wasserstoff vermindert den Anteil des für die autother me Reformierung bereitzustellenden Brennstoffs, der von den zu spaltenden Kohlenwasserstoffen gebildet wird, wodurch der Wir kungsgrad der Wasserstofferzeugung weiterhin erhöht wird. Die gesteigerte H2O-Konzentration führt in bekannter Weise zu einer weiteren Verringerung der Ruß-Bildung. Insgesamt erzielt das erfindungsgemäße Verfahren bei dem hier vorgestellten Einsatz eine Erhöhung des Gesamtwirkungsgrades des Systems sowie des sen Lebensdauer.In FIG. 2, the same components in FIG. 1 are designated by the same reference numerals. According to the invention, part of the hydrogen-containing gas stream generated by the reformer 1 is returned to the reformer, in this exemplary embodiment the hydrogen-containing gas from the reformer is fed entirely to the fuel cell system 2 and only then is the return to the input side of the reformer 1 . This return takes place through line 7 , through which the smaller part of the material flow leaving the fuel cell is passed to autothermal reformer 1 . The components CO 2 , H 2 and H 2 O contained in this returned material flow result in the following improvements in the process control: the increase in the CO 2 concentration in the autothermal reformer favors the formation of CO according to the Boudouard equilibrium (3), which leads to a reduction in soot formation and an increased yield of 1% after the shift reaction (2). The recirculated hydrogen reduces the proportion of the fuel to be made available for autothermal reforming, which is formed by the hydrocarbons to be split, which further increases the efficiency of the hydrogen production. The increased H 2 O concentration leads in a known manner to a further reduction in the formation of soot. Overall, the method according to the invention achieves an increase in the overall efficiency of the system and in its service life when used here.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934649A DE19934649A1 (en) | 1999-07-23 | 1999-07-23 | Hydrogen generation in reformer with feed containing hydrocarbons, used in vehicle with fuel cell supplying drive or electricity consumers, uses (partial) recycling of gas containing hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934649A DE19934649A1 (en) | 1999-07-23 | 1999-07-23 | Hydrogen generation in reformer with feed containing hydrocarbons, used in vehicle with fuel cell supplying drive or electricity consumers, uses (partial) recycling of gas containing hydrogen |
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| DE19934649A1 true DE19934649A1 (en) | 2001-01-25 |
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| DE19934649A Ceased DE19934649A1 (en) | 1999-07-23 | 1999-07-23 | Hydrogen generation in reformer with feed containing hydrocarbons, used in vehicle with fuel cell supplying drive or electricity consumers, uses (partial) recycling of gas containing hydrogen |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10062965A1 (en) * | 2000-12-16 | 2002-06-20 | Bayerische Motoren Werke Ag | Fuel cell system in a vehicle with an internal combustion engine and method for its operation |
| WO2002059037A1 (en) * | 2001-01-12 | 2002-08-01 | Emitec Gesellschaft Für Emissionstechnologie Mbh | Method for operating a reforming plant for providing hydrogen-enriched gas, and corresponding reforming plant |
| EP1284235A1 (en) * | 2001-08-15 | 2003-02-19 | Sulzer Hexis AG | Process for reforming fuels, especially fuel oil |
| WO2003062141A1 (en) * | 2002-01-23 | 2003-07-31 | Statoil Asa | Process for preparing synthesis gas by autothermal reforming |
| EP1385615A1 (en) * | 2001-03-09 | 2004-02-04 | Honda Giken Kogyo Kabushiki Kaisha | Micro component hydrocarbon steam reformer system and cycle for producing hydrogen gas |
| DE10237834A1 (en) * | 2002-08-19 | 2004-03-04 | Robert Bosch Gmbh | Security system for a facility for power generation |
| EP1400489A1 (en) * | 2002-09-23 | 2004-03-24 | Kellogg Brown & Root, Inc. | Process and apparatus for autothermal reforming with recycle of a portion of the produced syngas |
| US6872379B2 (en) | 2001-08-15 | 2005-03-29 | Sulzer Hexis Ag | Method for the reformation of fuels, in particular heating oil |
| EP1593731A3 (en) * | 2004-04-09 | 2006-04-26 | Hyun Yong Kim | A high temperature reformer |
| WO2006119952A1 (en) * | 2005-05-12 | 2006-11-16 | Cfc Solutions Gmbh | Process for operating a fuel cell arrangement and fuel cell arrangement |
| DE102005056363A1 (en) * | 2005-11-25 | 2007-05-31 | Süd-Chemie AG | Process for reforming hydrocarbons/hydrocarbon mixtures in hydrogen and carbon mono-oxide/their product gas, includes mixing the educt with oxygen containing gas mixture, and reacting the mixture of hydrocarbon oxidation with catalyst |
| DE102006014196A1 (en) * | 2006-03-28 | 2007-10-04 | Bayerische Motoren Werke Ag | Operating procedure for system with hydrogen producing reformer, includes separating partial-quantity of the reformats withdrawal from the reformer and before entering into processing unit, and feeding back the quantity into reformer inlet |
| DE102006032956A1 (en) * | 2006-07-17 | 2008-02-07 | Enerday Gmbh | Reformer and method for converting fuel and oxidant to gaseous reformate |
| EP1927577A1 (en) * | 2006-12-01 | 2008-06-04 | Casale Chemicals S.A. | Process for producing synthesis gas and related apparatus |
| EP1935848A1 (en) * | 2006-12-20 | 2008-06-25 | Bp Exploration Operating Company Limited | Process for producing synthesis gas |
| EP1935847A1 (en) * | 2006-12-20 | 2008-06-25 | Bp Exploration Operating Company Limited | Process for producing synthesis gas |
| AT505940B1 (en) * | 2008-02-07 | 2009-05-15 | Vaillant Austria Gmbh | HIGH-TEMPERATURE FUEL CELL SYSTEM WITH EXHAUST GAS RECYCLING |
| DE102007054768A1 (en) * | 2007-11-16 | 2009-05-20 | J. Eberspächer GmbH & Co. KG | Reformer, fuel cell and related operating procedures |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4010604A1 (en) * | 1989-04-05 | 1990-10-11 | Piesteritz Agrochemie | METHOD FOR SEPARATELY CONTROLLING THE METHANE AND EDEL GAS CONTENT OF AN AMMONIA CRYSTAL RECYCLING EDEL GAS COMPLEX |
| DE4005468A1 (en) * | 1990-02-21 | 1991-08-22 | Linde Ag | Operation of high temp. fuel cells - using ion-conducting electrolytes, removing cathode and anode off-gases produced and recycling anode off-gas |
| DE19727841A1 (en) * | 1997-06-24 | 1999-01-07 | Fraunhofer Ges Forschung | Method and device for the autothermal reforming of hydrocarbons |
| DE19840216A1 (en) * | 1997-09-04 | 1999-03-11 | Aisin Seiki | Fuel cell reforming device |
-
1999
- 1999-07-23 DE DE19934649A patent/DE19934649A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4010604A1 (en) * | 1989-04-05 | 1990-10-11 | Piesteritz Agrochemie | METHOD FOR SEPARATELY CONTROLLING THE METHANE AND EDEL GAS CONTENT OF AN AMMONIA CRYSTAL RECYCLING EDEL GAS COMPLEX |
| DE4005468A1 (en) * | 1990-02-21 | 1991-08-22 | Linde Ag | Operation of high temp. fuel cells - using ion-conducting electrolytes, removing cathode and anode off-gases produced and recycling anode off-gas |
| DE19727841A1 (en) * | 1997-06-24 | 1999-01-07 | Fraunhofer Ges Forschung | Method and device for the autothermal reforming of hydrocarbons |
| DE19840216A1 (en) * | 1997-09-04 | 1999-03-11 | Aisin Seiki | Fuel cell reforming device |
Cited By (26)
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| DE10062965B4 (en) * | 2000-12-16 | 2009-06-25 | Bayerische Motoren Werke Aktiengesellschaft | Fuel cell system in a vehicle with an internal combustion engine and method for its operation |
| DE10062965A1 (en) * | 2000-12-16 | 2002-06-20 | Bayerische Motoren Werke Ag | Fuel cell system in a vehicle with an internal combustion engine and method for its operation |
| WO2002059037A1 (en) * | 2001-01-12 | 2002-08-01 | Emitec Gesellschaft Für Emissionstechnologie Mbh | Method for operating a reforming plant for providing hydrogen-enriched gas, and corresponding reforming plant |
| EP1385615A1 (en) * | 2001-03-09 | 2004-02-04 | Honda Giken Kogyo Kabushiki Kaisha | Micro component hydrocarbon steam reformer system and cycle for producing hydrogen gas |
| EP1385615A4 (en) * | 2001-03-09 | 2006-10-04 | Honda Motor Co Ltd | Micro component hydrocarbon steam reformer system and cycle for producing hydrogen gas |
| US6872379B2 (en) | 2001-08-15 | 2005-03-29 | Sulzer Hexis Ag | Method for the reformation of fuels, in particular heating oil |
| EP1284235A1 (en) * | 2001-08-15 | 2003-02-19 | Sulzer Hexis AG | Process for reforming fuels, especially fuel oil |
| WO2003062141A1 (en) * | 2002-01-23 | 2003-07-31 | Statoil Asa | Process for preparing synthesis gas by autothermal reforming |
| DE10237834A1 (en) * | 2002-08-19 | 2004-03-04 | Robert Bosch Gmbh | Security system for a facility for power generation |
| EP1400489A1 (en) * | 2002-09-23 | 2004-03-24 | Kellogg Brown & Root, Inc. | Process and apparatus for autothermal reforming with recycle of a portion of the produced syngas |
| EP1593731A3 (en) * | 2004-04-09 | 2006-04-26 | Hyun Yong Kim | A high temperature reformer |
| US7556659B2 (en) | 2004-04-09 | 2009-07-07 | Hyun Yong Kim | High temperature reformer |
| WO2006119952A1 (en) * | 2005-05-12 | 2006-11-16 | Cfc Solutions Gmbh | Process for operating a fuel cell arrangement and fuel cell arrangement |
| DE102005056363A1 (en) * | 2005-11-25 | 2007-05-31 | Süd-Chemie AG | Process for reforming hydrocarbons/hydrocarbon mixtures in hydrogen and carbon mono-oxide/their product gas, includes mixing the educt with oxygen containing gas mixture, and reacting the mixture of hydrocarbon oxidation with catalyst |
| DE102006014196A1 (en) * | 2006-03-28 | 2007-10-04 | Bayerische Motoren Werke Ag | Operating procedure for system with hydrogen producing reformer, includes separating partial-quantity of the reformats withdrawal from the reformer and before entering into processing unit, and feeding back the quantity into reformer inlet |
| DE102006032956A1 (en) * | 2006-07-17 | 2008-02-07 | Enerday Gmbh | Reformer and method for converting fuel and oxidant to gaseous reformate |
| DE102006032956B4 (en) * | 2006-07-17 | 2010-07-01 | Enerday Gmbh | Reformer and method for converting fuel and oxidant to gaseous reformate |
| EP1927577A1 (en) * | 2006-12-01 | 2008-06-04 | Casale Chemicals S.A. | Process for producing synthesis gas and related apparatus |
| EP1935848A1 (en) * | 2006-12-20 | 2008-06-25 | Bp Exploration Operating Company Limited | Process for producing synthesis gas |
| EP1935847A1 (en) * | 2006-12-20 | 2008-06-25 | Bp Exploration Operating Company Limited | Process for producing synthesis gas |
| DE102007054768A1 (en) * | 2007-11-16 | 2009-05-20 | J. Eberspächer GmbH & Co. KG | Reformer, fuel cell and related operating procedures |
| AT505940B1 (en) * | 2008-02-07 | 2009-05-15 | Vaillant Austria Gmbh | HIGH-TEMPERATURE FUEL CELL SYSTEM WITH EXHAUST GAS RECYCLING |
| EP2088638A2 (en) | 2008-02-07 | 2009-08-12 | Vaillant GmbH | High temperature fuel cell system with exhaust gas reclamation |
| DE102009006983A1 (en) | 2008-02-07 | 2009-08-13 | Vaillant Gmbh | High temperature fuel cell system with exhaust gas recirculation |
| EP2787568A2 (en) | 2008-02-07 | 2014-10-08 | Vaillant GmbH | High temperature fuel cell system with exhaust gas reclamation |
| EP2787569A2 (en) | 2008-02-07 | 2014-10-08 | Vaillant GmbH | High temperature fuel cell system with exhaust gas reclamation |
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