WO1997043796A1 - Membrane reactor for producing co- and co2-free hydrogen - Google Patents

Membrane reactor for producing co- and co2-free hydrogen Download PDF

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Publication number
WO1997043796A1
WO1997043796A1 PCT/DE1997/000880 DE9700880W WO9743796A1 WO 1997043796 A1 WO1997043796 A1 WO 1997043796A1 DE 9700880 W DE9700880 W DE 9700880W WO 9743796 A1 WO9743796 A1 WO 9743796A1
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Prior art keywords
hydrogen
chamber
membrane
methanol
reactor
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Application number
PCT/DE1997/000880
Other languages
German (de)
French (fr)
Inventor
Josefin Meusinger
Lambertus G. J. De Haart
Ulrich Stimming
Original Assignee
Forschungszentrum Jülich GmbH
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Publication date
Application filed by Forschungszentrum Jülich GmbH filed Critical Forschungszentrum Jülich GmbH
Priority to AU29496/97A priority Critical patent/AU2949697A/en
Priority to JP09540374A priority patent/JP2000510433A/en
Publication of WO1997043796A1 publication Critical patent/WO1997043796A1/en
Priority to US09/185,228 priority patent/US6129861A/en

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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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • 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
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2475—Membrane reactors
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0407—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds
    • B01J8/0411—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds the beds being concentric
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00504—Controlling the temperature by means of a burner
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00117—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00157—Controlling the temperature by means of a burner
    • 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
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • 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
    • C01B2203/0475—Composition of the impurity the impurity being 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 invention relates to a reactor for converting methanol into hydrogen.
  • Such reactors are intended for use in connection with fuel cells, in particular with PEM fuel cells. In the future, the latter are to be used as components of electrical drive systems in vehicles.
  • PEM fuel cells In comparison to other fuel cells, a solid polymer electrolyte can be used in PEM fuel cells, which enables simple handling and the construction of compact cells.
  • PEM fuel cells have a high power density of approx. 1 W / cm at operating temperatures of 80 ° C.
  • Platinum (Pt) has proven to be the most effective electrocatalyst for the oxidation of pure hydrogen in acidic electrolytes, such as in the PEM fuel cell. But since the existing infrastructure for the car will also be used in the future, i.e. liquid fuel to be sold, liquid methanol must be converted to hydrogen in the vehicle by a reforming reaction.
  • the object of the invention is to provide a reactor which converts methanol into hydrogen in such a way that the hydrogen can be used directly as fuel gas in a PEM fuel cell.
  • the task is solved by a reactor with the features of the main claim. The reactor is used to carry out the method according to the independent claim.
  • the reactor has a membrane which divides the reactor into two chambers.
  • the membrane filters C0 2 out of a hydrogen-CO-C0 2 mixture. It is consequently practically impermeable to CO 2 . CO and especially hydrogen can cross the membrane.
  • Ceramic membranes in particular are provided in the invention.
  • Methanol is introduced into the first chamber, where it is converted into hydrogen.
  • the conversion takes place, for example, using a suitable catalyst at the conversion temperatures required for this.
  • Means for heating the first chamber provide the required transition temperatures.
  • CO and hydrogen permeate through the membrane into the second chamber. Here the CO is now converted into methane.
  • a conventional burner for example, is suitable as a means of generating the heat of reaction.
  • the reactor consists of a tubular membrane which is located in the interior of a further tube (reaction tube).
  • This annular gap is filled with a reforming catalyst and takes over the function of the first chamber (first zone).
  • Required heat of reaction in the first chamber is provided by heating the outer wall of the reaction tube.
  • the second chamber (second zone) is located within the tubular membrane and is filled with a methanation catalyst.
  • (Oxygen-containing) reaction products in the first chamber leave the reactor through the annular gap.
  • Means are advantageously provided which lead the residual gases out of the first chamber and feed them to a heating medium (burner).
  • the residual gases are burned in a mixture with fresh methanol, if necessary, and the heat of reaction for the methanol reforming reaction, ie the heating of the first reaction zone, is thus generated.
  • the hydrogen-CO mixture in the second chamber is (sufficiently) free of CO 2 . It will go directly to the methanation catalyst in the second chamber
  • a strongly endothermic reaction is advantageously coupled to a strongly exothermic reaction via the permeable membrane: an undesired rise in temperature in the methanation catalyst is prevented by the reforming reaction taking place in the shell.
  • the reactor is made in particular from ceramic materials.
  • the membrane advantageously consists of an oxide based on Al 2 O 3 and / or SiO. These materials have high separation factors for hydrogen / CO 2 under the reaction conditions of methanol reforming. They do not age, are easy to shape and inexpensive.
  • the invention is explained in more detail with reference to the figure and the following data.
  • the figure shows in cross section a tubular membrane 1, which is surrounded by an enveloping tube 2.
  • the annular gap 3 forms the first chamber.
  • the second chamber 4 is located inside the tubular membrane 1.
  • the membrane is closed at one end of the tube.
  • the product gases are fed via a discharge line 5 to a PEM fuel cell.
  • Methanol is fed to the first chamber of the reactor via a feed line 6.
  • Residual gases arising in the first chamber are fed via line 7 to a burner (not shown here) which, if necessary, heats the reactor from the outside.
  • a 70 kW passenger car needs a fuel cell that delivers 170 kW of electrical power. This results in a value for the hydrogen flow to be made available of approximately 0.158 mol / s. This hydrogen must be obtained in pure form (less than 10 ppm CO) after the second chamber. Based on experimentally determined permeation rates for ceramic membranes at 200 ° C. for hydrogen (20 * 10 "7 mol / m 2 / s / Pa), a minimum membrane area of at least 5 * 10 Pa is required 15.8 dm 2 .
  • the generation of hydrogen is based on methanol reforming in the first zone.
  • the necessary reforming catalyst volume can be determined from the experimentally determined rate of formation of hydrogen (2-4 Nm / h / dm cat ): 3.16 dm. If 4 liters of a highly active noble metal catalyst are placed in the second reaction zone, comes it at a temperature around 180 ° C for methanation of the CO contained in the permeate. The proportion of 2% by volume of CO produced during the reforming is thus reduced to 10 ppm at sufficiently low space velocities.

Abstract

The invention concerns a reactor for converting methanol into CO- and CO2-free hydrogen. The reactor comprises a membrane (1) which divides it into two chambers. The membrane filters CO2 out of a hydrogen-CO-CO2 mixture. Methanol is introduced into the first chamber (3) and is converted into hydrogen there by means of a catalyst. During this conversion, CO and CO2 are produced as by-products. A burner heats the first chamber, so ensuring that the required conversion temperatures are provided. CO and hydrogen are diffused through the membrane (1) into the second chamber (4) in which CO is converted into methane by means of a catalyst. The resultant hydrogen is now sufficiently free from CO and CO2 and can be fed directly as fuel gas to the anode side of a PEM fuel cell.

Description

B e s c h r e i b u n gDescription
Membranreaktor zur Erzeugung von CO- und C02-freiem WasserstoffMembrane reactor for the production of CO and CO 2 -free hydrogen
Die Erfindung bezieht sich auf einen Reaktor zur Um¬ wandlung von Methanol in Wasserstoff.The invention relates to a reactor for converting methanol into hydrogen.
Gedacht sind solche Reaktoren für einen Einsatz in Ver¬ bindung mit Brennstoffzellen und zwar insbesondere mit PEM-Brennstoffzellen. Die letzteren sollen zukünftig als Komponenten von elektrischen Antriebssystemen in Fahrzeugen eingesetzt werden.Such reactors are intended for use in connection with fuel cells, in particular with PEM fuel cells. In the future, the latter are to be used as components of electrical drive systems in vehicles.
Vorteilhaft kann in PEM-BrennstoffZeilen im Vergleich zu anderen Brennstoffzellen ein polymerer Festelektro- lyt verwendet werden, der eine einfache Handhabung und die Konstruktion von kompakten Zellen ermöglicht. PEM- Brennstoffzellen zeigen eine hohe Leistungsdichte von ca. 1 W/cm bei Betriebstemperaturen von 80 °C.In comparison to other fuel cells, a solid polymer electrolyte can be used in PEM fuel cells, which enables simple handling and the construction of compact cells. PEM fuel cells have a high power density of approx. 1 W / cm at operating temperatures of 80 ° C.
Für die Oxidation von reinem Wasserstoff in sauren Elektrolyten wie in der PEM-Brennstoffzelle erweist sich Platin (Pt) als der effektivste Elektrokatalysa- tor. Da aber die für das Auto vorhandene Infrastruktur auch zukünftig genutzt werden, also flüssiger Brenn- stoff vertrieben werden soll, muß flüssiges Methanol im Fahrzeug durch eine Reformierungsreaktion zu Wasser¬ stoff umgesetzt werden.Platinum (Pt) has proven to be the most effective electrocatalyst for the oxidation of pure hydrogen in acidic electrolytes, such as in the PEM fuel cell. But since the existing infrastructure for the car will also be used in the future, i.e. liquid fuel to be sold, liquid methanol must be converted to hydrogen in the vehicle by a reforming reaction.
Nachteilhaft treten bei der Umsetzung von Methanol zu Wasserstoff Nebenprodukte wie CO auf, die als Katalysa¬ torgifte für den Elektrokatalysator Pt wirken. Enthält also das Brenngas neben Wasserstoff auch CO, tritt eine drastische Minderung der Zelleistung ein.By-products such as CO, which act as catalyst poisons for the electrocatalyst Pt, occur disadvantageously in the conversion of methanol to hydrogen. So if the fuel gas contains CO as well as hydrogen, the cell capacity is drastically reduced.
Daher muß eine Gasnachbehandlung zur Erzeugung von Was- serstoffbrenngas mit einem CO- Gehalt kleiner 10 ppm zwischen Reformer und PEM-Brennstoffzelle durchgeführt werden. Die gewünschte Reinheit kann derzeit nur durch Nutzung einer Pd/Ag-Membran erreicht werden. Die An¬ schaffungskosten für eine solche Membran sind nachteil- haft sehr hoch.For this reason, a gas aftertreatment to generate hydrogen fuel gas with a CO content of less than 10 ppm must be carried out between the reformer and the PEM fuel cell. The desired purity can currently only be achieved by using a Pd / Ag membrane. The acquisition costs for such a membrane are disadvantageously very high.
Eine andere Möglichkeit, den Reinheitsanforderungen ge¬ recht zu werden, basiert auf der chemischen Umsetzung von CO mit Wasserstoff zu Methan (Methanisierungsreak- tion) . Bei niedrigen Reaktionstemperaturen (180 °C) und Verwendung von Edelmetallkatalysatoren gelingt es, den CO-Gehalt in einer derartigen Gasnachbehandlungs- einheit auf 10 ppm abzusenken. Voraussetzung hierfür ist allerdings, daß zuvor das C02 aus dem Gasgemisch entfernt wurde. C02 unterliegt bei analogen Reaktions- bedingungen ebenfalls der Methanisierungsreaktion oder bei geringfügig höheren Reaktionstemperaturen der Kon¬ vertierung zu CO. Aufgabe der Erfindung ist die Schaffung eines Reaktors, der Methanol in Wasserstoff derart umwandelt, daß der Wasserstoff direkt als Brenngas in einer PEM-Brenn¬ stoffzelle eingesetzt werden kann. Gelöst wird die Aufgabe durch einen Reaktor mit den Merkmalen des Hauptanspruchs. Der Reaktor dient der Durchführung des Verfahrens gemäß Nebenanspruch.Another possibility of meeting the purity requirements is based on the chemical conversion of CO with hydrogen to methane (methanation reaction). At low reaction temperatures (180 ° C) and the use of noble metal catalysts, the CO content in such a gas aftertreatment unit can be reduced to 10 ppm. The prerequisite for this is, however, that the CO 2 has been removed from the gas mixture beforehand. C0 2 is also subject to the methanation reaction under analogous reaction conditions or to conversion to CO at slightly higher reaction temperatures. The object of the invention is to provide a reactor which converts methanol into hydrogen in such a way that the hydrogen can be used directly as fuel gas in a PEM fuel cell. The task is solved by a reactor with the features of the main claim. The reactor is used to carry out the method according to the independent claim.
Der Reaktor weist eine Membran auf, die den Reaktor in zwei Kammern unterteilt. Die Membran filtert C02 aus einem Wasserstoff-CO-C02-Gemisch heraus. Sie ist folg¬ lich praktisch undurchlässig für C02. CO und vor allem Wasserstoff können die Membran passieren.The reactor has a membrane which divides the reactor into two chambers. The membrane filters C0 2 out of a hydrogen-CO-C0 2 mixture. It is consequently practically impermeable to CO 2 . CO and especially hydrogen can cross the membrane.
Insbesondere keramische Membranen sind bei der Erfin¬ dung vorgesehen. In die erste Kammer wird Methanol eingeleitet und dort in Wasserstoff umgewandelt. Die Umwandlung erfolgt bei¬ spielsweise durch einen geeigneten Katalysator bei hierfür erforderlichen Umwandlungstemperaturen. Mittel zur Beheizung der ersten Kammer sorgen für die Bereit- Stellung der erforderlichen Umwandlungstemperaturen. CO und Wasserstoff permeieren durch die Membran in die zweite Kammer. Hier wird nun das CO in Methan umgewan¬ delt.Ceramic membranes in particular are provided in the invention. Methanol is introduced into the first chamber, where it is converted into hydrogen. The conversion takes place, for example, using a suitable catalyst at the conversion temperatures required for this. Means for heating the first chamber provide the required transition temperatures. CO and hydrogen permeate through the membrane into the second chamber. Here the CO is now converted into methane.
Die in der zweiten Kammer entstandenen Produktgase sind praktisch frei von CO und C02. Sie können nun direkt der Anodenseite einer (PEM-)Brennstoffzelle zugeführt werden. Vorteilhaft sind Mittel vorgesehen, mittels derer aus den Restgasen (=nicht in die zweite Kammer diffundierte Reaktionsprodukte sowie nicht umgesetztes Methanol) Reaktionswärme für die Methanol-Reformierungsreaktion erzeugt wird. Als Mittel zur Erzeugung der Reaktions¬ wärme ist beispielsweise ein konventioneller Brenner geeignet .The product gases generated in the second chamber are practically free of CO and CO 2 . They can now be fed directly to the anode side of a (PEM) fuel cell. Means are advantageously provided by means of which reaction heat for the methanol reforming reaction is generated from the residual gases (= reaction products not diffused into the second chamber and unreacted methanol). A conventional burner, for example, is suitable as a means of generating the heat of reaction.
Bei einem vorteilhaft einfachen Aufbau besteht der Re¬ aktor aus einer röhrenförmigen Membran, die sich im In- neren eines weiteren Rohres (Reaktionsrohr) befindet.In the case of an advantageously simple construction, the reactor consists of a tubular membrane which is located in the interior of a further tube (reaction tube).
Es entsteht so ein Ringspalt zwischen der Außenwand der Membran und der Innenwand des Reaktionsrohres. Dieser Ringspalt ist mit einem Reformierungskatalysator ge¬ füllt und übernimmt die Funktion der ersten Kammer (erste Zone) . Erforderliche Reaktionswärme in der er¬ sten Kammer wird durch Beheizen der Außenwand des Reak¬ tionsrohres zur Verfügung gestellt . Die zweite Kammer (zweite Zone) befindet sich innerhalb der röhrenförmi¬ gen Membran und ist mit einem Methanisierungskatalysa- tor gefüllt.This creates an annular gap between the outer wall of the membrane and the inner wall of the reaction tube. This annular gap is filled with a reforming catalyst and takes over the function of the first chamber (first zone). Required heat of reaction in the first chamber is provided by heating the outer wall of the reaction tube. The second chamber (second zone) is located within the tubular membrane and is filled with a methanation catalyst.
Aufgrund des bestehenden Konzentrations- und Druckge¬ fälles zwischen erster und zweiter Reaktorkammer wan¬ dern die in der ersten Kammer erzeugten Wasserstoff- und CO-Gase durch die Membran hindurch in die zweite Kammer. Nicht umgesetztes Methanol und die anderenDue to the existing concentration and pressure gradient between the first and second reactor chambers, the hydrogen and CO gases generated in the first chamber migrate through the membrane into the second chamber. Unreacted methanol and the others
(sauerstoffhaltigen) Reaktionsprodukte in der ersten Kammer verlassen den Reaktor über den Ringspalt . Vorteilhaft sind Mittel vorgesehen, die die Restgase aus der ersten Kammer wieder heraus- und einem Heizmit¬ tel (Brenner) zuführen. Hier werden die Restgase erfor¬ derlichenfalls im Gemisch mit frischem Methanol ver- brannt und so die Reaktionswärme für die Methanol-Re- formierungsreaktion, also hier die Beheizung der ersten Reaktionszone erzeugt.(Oxygen-containing) reaction products in the first chamber leave the reactor through the annular gap. Means are advantageously provided which lead the residual gases out of the first chamber and feed them to a heating medium (burner). Here, the residual gases are burned in a mixture with fresh methanol, if necessary, and the heat of reaction for the methanol reforming reaction, ie the heating of the first reaction zone, is thus generated.
Das Wasserstoff-CO-Gemisch in der zweiten Kammer ist (hinreichend) frei von C02. Es wird direkt mit dem Methanisierungskatalysator in der zweiten KammerThe hydrogen-CO mixture in the second chamber is (sufficiently) free of CO 2 . It will go directly to the methanation catalyst in the second chamber
(Innenraum) des Reaktors kontaktiert und so das CO in Methan umgewandelt. Die Produktgase können dann der Anodenseite der PEM-Brennstoffzelle zugeführt werden.(Interior) of the reactor contacted and thus converted the CO into methane. The product gases can then be fed to the anode side of the PEM fuel cell.
Beim röhrenförmigen Aufbau ist eine stark endotherme mit einer stark exothermen Reaktion über die permeable Membran in vorteilhafter Weise gekoppelt: Ein unerwünschter Tempe¬ raturanstieg im Methanisierungskatalysator wird durch die in der Hülle ablaufende Reformierungsreaktion verhindert.In the case of a tubular structure, a strongly endothermic reaction is advantageously coupled to a strongly exothermic reaction via the permeable membrane: an undesired rise in temperature in the methanation catalyst is prevented by the reforming reaction taking place in the shell.
Der Reaktor wird insbesondere aus keramischen Materia- lien hergestellt.The reactor is made in particular from ceramic materials.
Die Membran besteht vorteilhaft aus einem Oxid auf Ba¬ sis von Al203 und/oder SiO. Diese Materialien weisen bei Reaktionsbedingungen einer Methanolreformierung hohe Trennfaktoren für Wasserstoff/C02 auf. Sie altern nicht, sind unproblematisch bezüglich Formgebung und preiswert .The membrane advantageously consists of an oxide based on Al 2 O 3 and / or SiO. These materials have high separation factors for hydrogen / CO 2 under the reaction conditions of methanol reforming. They do not age, are easy to shape and inexpensive.
Die Erfindung wird anhand der Figur und der nachfolgenden Daten näher erläutert . Die Figur zeigt im Querschnitt eine röhrenförmige Membran 1, die von einem einhüllenden Rohr 2 umgeben wird. Der Ringspalt 3 bildet die erste Kammer. Die zweite Kammer 4 befindet sich im Inneren der röhrenförmigen Membran 1. Die Membran ist an einem Rohrende verschlossen. Am anderen Ende werden die Produktgase über eine Ableitung 5 einer PEM-Brennstoffzelle zugeleitet. Methanol wird über eine Zuleitung 6 der ersten Kammer des Reaktors zugeführt . In der ersten Kammer entstehende Restgase werden über die Ableitung 7 einem hier nicht dargestellten Brenner zugeführt, der den Reaktor erforderlichenfalls von außen beheizt .The invention is explained in more detail with reference to the figure and the following data. The figure shows in cross section a tubular membrane 1, which is surrounded by an enveloping tube 2. The annular gap 3 forms the first chamber. The second chamber 4 is located inside the tubular membrane 1. The membrane is closed at one end of the tube. At the other end, the product gases are fed via a discharge line 5 to a PEM fuel cell. Methanol is fed to the first chamber of the reactor via a feed line 6. Residual gases arising in the first chamber are fed via line 7 to a burner (not shown here) which, if necessary, heats the reactor from the outside.
Ein Personenkraftwagen der Leistungsklasse 70 kW benötigt eine Brennstoffzelle, die 170 kW an elektrischer Leistung liefert. Daraus ergibt sich ein Wert für den bereitzu¬ stellenden Wasserstoffström von ca. 0,158 mol/s. Dieser Wasserstoff muß in reiner Form (weniger als 10 ppm CO) nach der zweiten Kammer anfallen. Ausgehend von experi¬ mentell bestimmten Permeationsraten für keramische Membra- nen bei 200 °C für Wasserstoff (20*10"7 mol/m2/s/Pa) ergibt sich bei einer Druckdifferenz von 5 * 10 Pa eine min¬ destens notwendige Membranfläche von 15,8 dm2.A 70 kW passenger car needs a fuel cell that delivers 170 kW of electrical power. This results in a value for the hydrogen flow to be made available of approximately 0.158 mol / s. This hydrogen must be obtained in pure form (less than 10 ppm CO) after the second chamber. Based on experimentally determined permeation rates for ceramic membranes at 200 ° C. for hydrogen (20 * 10 "7 mol / m 2 / s / Pa), a minimum membrane area of at least 5 * 10 Pa is required 15.8 dm 2 .
Die Erzeugung des Wasserstoffes basiert auf der Methanol- reformierung in der ersten Zone. Bei einer Temperatur von 250 °C kann von der experimentell bestimmten Bildungsge¬ schwindigkeit von Wasserstoff (2-4 Nm /h/dm kat) ausgehend, das notwendige Reformierungskatalysatorvolumen ermittelt werden: 3,16 dm . Werden 4 1 eines hochaktiven Edelmetall- katalysators in der zweiten Reaktionszone plaziert, kommt es bei einer sich einstellenden Temperatur um 180 °C zur Methanisierung des im Permeat enthaltenen CO's. Der bei der Reformierung entstehende Anteil von 2 Vol.-% CO wird so bei hinreichend kleinen Raumgeschwindigkeiten auf 10 ppm abgebaut . The generation of hydrogen is based on methanol reforming in the first zone. At a temperature of 250 ° C, the necessary reforming catalyst volume can be determined from the experimentally determined rate of formation of hydrogen (2-4 Nm / h / dm cat ): 3.16 dm. If 4 liters of a highly active noble metal catalyst are placed in the second reaction zone, comes it at a temperature around 180 ° C for methanation of the CO contained in the permeate. The proportion of 2% by volume of CO produced during the reforming is thus reduced to 10 ppm at sufficiently low space velocities.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Reaktor zur Umwandlung von Methanol in Wasserstoff1. Reactor for converting methanol to hydrogen
- mit einer Membran (1) zur Unterteilung des Reak¬ tors in zwei Kammern (3, 4) , wobei die Membran eine Herausfilterung von C02 aus einem Wasser- Stoff-CO-C02-Gemisch bewirkt,with a membrane (1) for dividing the reactor into two chambers (3, 4), the membrane filtering out C0 2 from a hydrogen / CO 2 mixture,
- mit Mitteln zur Einleitung von Methanol in die er¬ ste Kammer und zur Umsetzung des Methanols in Was¬ serstoffhaltige Gase in dieser ersten Kammer,with means for introducing methanol into the first chamber and for converting the methanol into hydrogen-containing gases in this first chamber,
- mit Mitteln zur Umwandlung von CO in Methan in der zweiten Kammer.- With means for converting CO to methane in the second chamber.
2. Röhrenförmiger Reaktor nach vorhergehendem Anspruch mit einer röhrenförmigen Membran (1) , die die erste Kammer (3) von der zweiten Kammer (4) trennt.2. A tubular reactor according to the preceding claim with a tubular membrane (1) which separates the first chamber (3) from the second chamber (4).
3. Verfahren zur Umwandlung von Methanol in Wasserstoff mit den Schritten:3. Method for converting methanol to hydrogen with the steps:
- Umwandlung von Methanol in ein aus Wasserstoff, Kohlendioxid und Kohlenmonoxid bestehendes Gasge- misch,Conversion of methanol into a gas mixture consisting of hydrogen, carbon dioxide and carbon monoxide,
- Entfernung des Kohlendioxids aus dem Gasgemisch,Removal of the carbon dioxide from the gas mixture,
- Umwandlung des Kohlenmonoxids in Methan. - Conversion of carbon monoxide to methane.
PCT/DE1997/000880 1996-05-10 1997-04-26 Membrane reactor for producing co- and co2-free hydrogen WO1997043796A1 (en)

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JP09540374A JP2000510433A (en) 1996-05-10 1997-04-26 Membrane reactor for producing hydrogen that does not contain CO or CO2
US09/185,228 US6129861A (en) 1996-05-10 1998-11-03 Membrane reactor for producing CO- and CO2 -free hydrogen

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DE19618816A DE19618816C2 (en) 1996-05-10 1996-05-10 Membrane reactor for the production of CO and CO¶2¶ free hydrogen

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US6582499B2 (en) * 1998-11-10 2003-06-24 Ati Properties, Inc. Fluid separation assembly
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DE19618816C2 (en) 1999-08-26

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