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WO2007012388A1 - Membrane structure for the elimination of hydrogen or oxygen - Google Patents

Membrane structure for the elimination of hydrogen or oxygen Download PDF

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Publication number
WO2007012388A1
WO2007012388A1 PCT/EP2006/006581 EP2006006581W WO2007012388A1 WO 2007012388 A1 WO2007012388 A1 WO 2007012388A1 EP 2006006581 W EP2006006581 W EP 2006006581W WO 2007012388 A1 WO2007012388 A1 WO 2007012388A1
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WO
WIPO (PCT)
Prior art keywords
membrane structure
membrane
structure according
hydrogen
cover layer
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.)
Ceased
Application number
PCT/EP2006/006581
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German (de)
French (fr)
Inventor
Christian Zilich
Jens Wartmann
Angelika Henzel
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Universitaet Duisburg Essen
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Universitaet Duisburg Essen
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Publication of WO2007012388A1 publication Critical patent/WO2007012388A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02231—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/522—Aromatic polyethers
    • B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
    • 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
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • 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
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C01B3/505—Membranes containing palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/027—Nonporous membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • 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
    • C01B2203/0465—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
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0053—Hydrogen

Definitions

  • the present invention relates to a membrane structure for the separation of hydrogen or oxygen and to a use of such a membrane structure for the separation of hydrogen or oxygen.
  • the separation of high-purity hydrogen or oxygen from a gas mixture is required in various processes, for example, for the separation of CO from reformate gas before feeding to a fuel cell, for hydrogen recovery in petrochemical plants or ammonia synthesis or for the production of pure oxygen for power plants with internal Coal gasification or for the continuous emergency supply of passengers, for example in airplanes.
  • the present invention has for its object to provide a membrane structure and a use of a membrane assembly for the deposition of hydrogen or oxygen, the deposition of hydrogen or oxygen at high temperatures, as they usually occur in processes at high pressures and in a simple and cost-effective manner allow for high separation or deposition rate.
  • An essential aspect of the present invention is a non-porous polymer membrane which consists in particular of polyimide or polyether ketone and temperature-resistant above 150 0 C, with a very thin cover layer of noble metal or a metal alloy as a separation layer which is permeable to hydrogen or oxygen, to provide.
  • a thickness of the cover layer preferably less than 100 nm, in particular less than 50 nm, very high separation or deposition rates (mass or volume flow of separated hydrogen or oxygen per unit area of the membrane structure at a certain pressure difference) are possible.
  • FIGURE shows: a schematic sectional view of a proposed
  • the figure shows in a schematic section a proposed membrane structure 1 with a polymer membrane 2, a cover layer 3 and an optional carrier 4.
  • the polymer membrane 2 is non-porous and serves for full-surface support of the cover layer 3. It is uninterruptible and preferably at least substantially flat.
  • the polymer membrane 2 is preferably temperature-resistant above 15O 0 C, in particular even above 200 0 C or above 300 0 C.
  • the polymer membrane 2 preferably consists at least substantially of polyimide or polyether ketone (s), with mixtures also being possible in principle.
  • the polymer membrane consists at least substantially of hydrogen-free polyimide or of a polyimide containing amide, ester and / or ether groups.
  • the polymer membrane 2 consists at least essentially of polyether ketones, namely of the normal polyether ketones (PEK), in which in each case an ether group is linked to a keto group, from polyetheretherketones (PEEK), from polyether ketone ketones (US Pat. PEKK) or polyetheretherketone ketones (PEEKK).
  • PEK normal polyether ketones
  • PEEK polyetheretherketones
  • US Pat. PEKK polyether ketone ketones
  • PEEKK polyetherketone ketones
  • the polymer membrane 2 is preferably single-layered or single-layered. However, the polymer membrane 2 may, if necessary, also be multilayered or layered. In this case, at least one layer or layer consists at least essentially of one of the abovementioned materials for the polymer membrane 2.
  • the polymer membrane 2 can also be fiber-reinforced, for example by glass or carbon fibers, in order to be able to achieve a high compressive strength and pressure swing loadability with a small thickness.
  • the thickness of the polymer membrane 2 is preferably 1 to 50 ⁇ m, in particular 5 to 20 ⁇ m.
  • the polymer membrane 2 is permeable at least to hydrogen and / or oxygen, possibly also unselective generally for gases.
  • the actual separation or separation takes place through the thin cover layer 3 of noble metal or a precious metal alloy.
  • the thickness of the cover layer 3 is preferably less than 100 nm, in particular less than 50 nm and in particular substantially 25 nm or less.
  • the thickness of the cover layer 3 is preferably less than 10%, in particular less than 1%, of the thickness of the polymer membrane 2.
  • the covering layer 3 for hydrogen deposition preferably consists at least essentially of palladium and / or platinum or an alloy with palladium and / or platinum.
  • the cover layer 3 preferably consists at least substantially of silver or a silver alloy.
  • the cover layer 3 is preferably on the entire surface of the primary membrane 2.
  • the cover layer 3 is applied directly to the polymer membrane 2 without an intermediate layer or adhesion promoter.
  • the cover layer 3 is sputtered or vapor-deposited onto the polymer membrane 2.
  • the cover layer 3 is applied to the polymer membrane 2 by plasma coating, evaporation by means of an arc or the like.
  • the cover layer 3 is only very selectively permeable to hydrogen or oxygen.
  • the cover layer 3 of palladium or a palladium alloy allows deposition of hydrogen having a purity of 99.999% by weight.
  • the proposed membrane structure 1 allows very high Separations at. Deposition rates. Further, the according to the proposal membrane structure 1 can also be used at relatively high temperatures, for example for the separation of hydrogen from a still hot reformate gas at temperatures of 300 to 400 0 C. The separated hydrogen can then a downstream arranged fuel cell can be fed directly.
  • the membrane structure 1 preferably has a support 4 for supporting the polymer membrane 2, in particular on the side facing away from the cover layer 3.
  • the carrier 4 is preferably formed porous or lattice-like, as indicated in the schematic section, to allow a good gas discharge of the permeate.
  • the carrier 4 is preferably made of ceramic, metal or other suitable material, in particular a composite material.
  • the carrier 4 is preferably firmly connected to the polymer membrane 2, so that the membrane structure 1 forms a structural unit. This is in particular a good pressure swing resistance of the membrane structure 1 beneficial.
  • the schematic section indicates by way of example how a gas stream or gas mixture 5 is supplied to the membrane structure 1 on the cover layer side, for example with a flow according to arrow P parallel to the flat side of the membrane structure 1 or the cover layer 3.
  • the membrane structure 1 is permeable to hydrogen or oxygen in particular due to a corresponding partial pressure difference of, for example, about 1 MPa, preferably about 3 MPa, in particular about 5 MPa, from the gas mixture 5 as permeate - in the representation down, ie on the side of the carrier 4 - is deposited.
  • the remaining gas mixture as retentate 5 has a correspondingly reduced concentration of hydrogen or oxygen.
  • the membrane structure 1 can be used for the separation of hydrogen from in particular still hot reformate gas.
  • the reformate gas is produced by a hydrocarbon reformer.
  • the carbon monoxide contained in the reformate gas must be removed. Due to the high selectivity of the proposed membrane structure 1, the carbon monoxide is retained and separated (essentially exclusively) hydrogen gas which can be used directly for the supply of fuel cells.
  • Oxygen can be separated directly from the air with the aid of the proposed membrane structure 1 and used, for example, for internal coal gasification in power plants or for continuous oxygen supply for other purposes.
  • the proposed membrane structure 1 can be used in the petrochemical and ammonia industry for the efficient recovery of hydrogen from product gases, in particular at elevated temperatures and / or pressures.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Disclosed are a membrane structure and a use of a membrane structure for eliminating hydrogen or oxygen from a gas mixture. Said membrane structure comprises a temperature-resistant, non-porous polymer membrane made of polyimide or polyetherketone as well as a coating that is less than 100 nm thick and is made of precious metal or a precious metal alloy.

Description

Membranaufbau zur Abscheidung von Wasserstoff oder Sauerstoff Membrane structure for the separation of hydrogen or oxygen

Die vorliegende Erfindung betrifft einen Membranaufbau zur Abtrennung von Wasserstoff oder Sauerstoff sowie eine Verwendung eines derartigen Mem- branaufbaus zur Abtrennung von Wasserstoff oder Sauerstoff.The present invention relates to a membrane structure for the separation of hydrogen or oxygen and to a use of such a membrane structure for the separation of hydrogen or oxygen.

Die Abscheidung von hochreinem Wasserstoff oder Sauerstoff aus einem Gasgemisch ist bei verschiedenen Prozessen erforderlich, beispielsweise zur Abtrennung von CO aus Reformat-Gas vor Zuleitung zu einer Brennstoffzelle, zur Wasserstoffrückgewinnung in petrochemischen Anlagen oder bei der Ammoniaksynthese oder zur Gewinnung von reinem Sauerstoff für Kraftwerke mit interner Kohlevergasung oder für die kontinuierliche Notversorgung von Passagieren, beispielsweise in Flugzeugen.The separation of high-purity hydrogen or oxygen from a gas mixture is required in various processes, for example, for the separation of CO from reformate gas before feeding to a fuel cell, for hydrogen recovery in petrochemical plants or ammonia synthesis or for the production of pure oxygen for power plants with internal Coal gasification or for the continuous emergency supply of passengers, for example in airplanes.

Grundsätzlich ist es bekannt, Wasserstoff oder Sauerstoff durch eine Polymermembran oder eine Metallmembran, die für Wasserstoff bzw. Sauerstoff durchlässig sind, abzuscheiden.In principle, it is known to deposit hydrogen or oxygen through a polymer membrane or a metal membrane, which are permeable to hydrogen or oxygen.

Der Artikel "Separation of Hydrogen from H2-CO Gas Mixtures Using amorphous Ca-Ni Alloy Films" von H. Sakaguchi et al., Journal of the Less- Common Metals, 171 (1991), Seiten 353 bis 356, beschreibt die Untersuchung der Wasserstoffabscheidung bei einem Membranaufbau mit einer Polymermembran aus Polyimid mit einer Dicke von 40 μm, mit einer Zwischenschicht aus Nickel mit einer Dicke von etwa 1 μm und mit einer Wasserstofftrenn- membran aus einer Calcium-Nickel-Legierung mit einer Dicke von 0, 1 bis 0,5 μm bei Temperaturen von 318 bis 388 K und bei Drücken bis 2,5 MPa.The article "Separation of Hydrogen from H2-CO Gas Mixtures Using Amorphous Ca-Ni Alloy Films" by H. Sakaguchi et al., Journal of the Less-Common Metals, 171 (1991), pp. 353-356, describes the study of Hydrogen deposition in a membrane structure with a polymer membrane of polyimide with a thickness of 40 microns, with an intermediate layer of nickel with a thickness of about 1 micron and with a hydrogen separation membrane of a calcium-nickel alloy with a thickness of 0, 1 to 0 , 5 μm at temperatures of 318 to 388 K and at pressures up to 2.5 MPa.

Der Artikel "Separation of a Gas Mixture through a Polymer Membrane Me- tallized with Palladium" von P.V. Mercea et al., Gas Separation & Purificati- on, 1990, Vol. 4, September, Seiten 137 bis 140, beschreibt Untersuchungen eines Membranaufbaus mit einer PTFE-Membran mit einer Dicke von 70 μm und mit einer Deckschicht aus Palladium oder anderen Metallen mit einer Dicke von 0, 1 μm bei Temperaturen von 26 bis 6O0C und bei Drücken bis 1 MPa. Bis heute sind keine brauchbaren Membranaufbauten verfügbar, die den Anforderungen hoher Temperaturbeständigkeit, hoher Druckbeständigkeit und hoher Separations- bzw. Abscheidungsraten gerecht werden.The article "Separation of a Gas Mixture through a Polymer Membrane Metallized with Palladium" by PV Mercea et al., Gas Separation & Purification, 1990, Vol. 4, September, pages 137 to 140, describes investigations of a membrane structure with a PTFE membrane with a thickness of 70 microns and with a top layer of palladium or other metals having a thickness of 0, 1 micron at temperatures of 26 to 60 0 C and at pressures up to 1 MPa. To date, no useful membrane assemblies are available that meet the requirements of high temperature resistance, high pressure resistance and high separation or deposition rates.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, einen Membranaufbau und eine Verwendung eines Membranaufbaus zur Abscheidung von Wasserstoff oder Sauerstoff anzugeben, die auf einfache und kostengünstige Weise eine Abscheidung von Wasserstoff oder Sauerstoff bei hohen Temperaturen, wie Sie üblicherweise bei Prozessen auftreten, bei hohen Drücken und bei hoher Separations- bzw. Abscheidungsrate ermöglichen.The present invention has for its object to provide a membrane structure and a use of a membrane assembly for the deposition of hydrogen or oxygen, the deposition of hydrogen or oxygen at high temperatures, as they usually occur in processes at high pressures and in a simple and cost-effective manner allow for high separation or deposition rate.

Die obige Aufgabe wird durch einen Membranaufbau gemäß Anspruch 1 oder eine Verwendung gemäß Anspruch 14 gelöst. Vorteilhafte Weiterbildungen sind Gegenstand der Unteransprüche.The above object is achieved by a membrane assembly according to claim 1 or a use according to claim 14. Advantageous developments are the subject of the dependent claims.

Ein wesentlicher Aspekt der vorliegenden Erfindung liegt darin, eine nicht poröse Polymermembran, die insbesondere aus Polyimid oder Polyetherketon besteht und über 1500C temperaturbeständig ist, mit einer sehr dünnen Deckschicht aus Edelmetall oder einer Metallegierung als Trennschicht, die für Wasserstoff oder Sauerstoff durchlässig ist, zu versehen. Bei einer Dicke der Deckschicht von vorzugsweise weniger als 100 nm, insbesondere von weniger als 50 nm, sind sehr hohe Separations- bzw. Abscheidungsraten (Massen- oder Volumenstrom an abgeschiedenem Wasserstoff oder Sauerstoff pro Flächeneinheit des Membranaufbaus bei einer bestimmten Druckdifferenz) möglich.An essential aspect of the present invention is a non-porous polymer membrane which consists in particular of polyimide or polyether ketone and temperature-resistant above 150 0 C, with a very thin cover layer of noble metal or a metal alloy as a separation layer which is permeable to hydrogen or oxygen, to provide. With a thickness of the cover layer of preferably less than 100 nm, in particular less than 50 nm, very high separation or deposition rates (mass or volume flow of separated hydrogen or oxygen per unit area of the membrane structure at a certain pressure difference) are possible.

Weitere Aspekte, Merkmale, Eigenschaften und Vorteile der vorliegenden Erfindung ergeben sich aus der folgenden Beschreibung eines bevorzugten Ausführungsbeispiels anhand der Zeichnung. Die einzige Figur zeigt: eine schematische Schnittdarstellung eines vorschlagsgemäßenFurther aspects, features, characteristics and advantages of the present invention will become apparent from the following description of a preferred embodiment with reference to the drawing. The sole FIGURE shows: a schematic sectional view of a proposed

Membranaufbaus.Membrane structure.

Die Figur zeigt in einem schematischen Schnitt einen vorschlagsgemäßen Membranaufbau 1 mit einer Polymermembran 2, einer Deckschicht 3 und ei- nem optionalen Träger 4. Die Polymermembran 2 ist nicht porös und dient einer vollflächigen Abstützung der Deckschicht 3. Sie ist unterbrechungsfrei und vorzugsweise zumindest im wesentlichen eben ausgebildet.The figure shows in a schematic section a proposed membrane structure 1 with a polymer membrane 2, a cover layer 3 and an optional carrier 4. The polymer membrane 2 is non-porous and serves for full-surface support of the cover layer 3. It is uninterruptible and preferably at least substantially flat.

Die Polymermembran 2 ist vorzugsweise über 15O0C temperaturbeständig, insbesondere sogar über 2000C oder über 3000C. Entsprechendes gilt für den gesamten Membranaufbau 1, der entsprechend universell zur Abscheidung von Wasserstoff oder Sauerstoff aus noch heißen Prozeßgasen, Reformat- Gasen oder dgl. einsetzbar ist.The polymer membrane 2 is preferably temperature-resistant above 15O 0 C, in particular even above 200 0 C or above 300 0 C. The same applies to the entire membrane assembly 1, the corresponding universal for the separation of hydrogen or oxygen from still hot process gases, reformate gases or the like can be used.

Die Polymermembran 2 besteht vorzugsweise zumindest im wesentlichen aus Polyimid oder Polyetherketon(en), wobei grundsätzlich auch Mischungen möglich sind.The polymer membrane 2 preferably consists at least substantially of polyimide or polyether ketone (s), with mixtures also being possible in principle.

Gemäß einer Ausführungsvariante besteht die Polymermembran zumindest im wesentlichen aus wasserstofffreiem Polyimid oder aus einem Polyimid, das Amid-, Ester- und/oder Ether-Gruppen enthält.According to one embodiment, the polymer membrane consists at least substantially of hydrogen-free polyimide or of a polyimide containing amide, ester and / or ether groups.

Gemäß einer anderen Ausführungsvariante besteht die Polymermembran 2 zumindest im wesentlichen aus Polyetherketonen, und zwar aus den normalen Polyetherketonen (PEK), bei denen jeweils eine Ether-Gruppe mit einer Keto- Gruppe verknüpft ist, aus Polyetheretherketonen (PEEK), aus Polyetherketon- ketonen (PEKK) oder aus Polyetheretherketonketonen (PEEKK).According to another embodiment variant, the polymer membrane 2 consists at least essentially of polyether ketones, namely of the normal polyether ketones (PEK), in which in each case an ether group is linked to a keto group, from polyetheretherketones (PEEK), from polyether ketone ketones (US Pat. PEKK) or polyetheretherketone ketones (PEEKK).

Die Polymermembran 2 ist vorzugsweise einschichtig bzw. einlagig ausgebildet. Jedoch kann die Polymermembran 2 bedarfsweise auch mehrschichtig bzw. -lagig ausgebildet sein. In diesem Fall besteht zumindest eine Schicht oder Lage zumindest im wesentlichen aus einem der vorgenannten Materialien für die Polymermembran 2.The polymer membrane 2 is preferably single-layered or single-layered. However, the polymer membrane 2 may, if necessary, also be multilayered or layered. In this case, at least one layer or layer consists at least essentially of one of the abovementioned materials for the polymer membrane 2.

Zusätzlich oder alternativ kann die Polymermembran 2 auch faserverstärkt sein, beispielsweise durch Glas- oder Kohlefasern, um eine hohe Druckfestigkeit und Druckwechselbelastbarkeit bei geringer Dicke erreichen zu können.In addition or as an alternative, the polymer membrane 2 can also be fiber-reinforced, for example by glass or carbon fibers, in order to be able to achieve a high compressive strength and pressure swing loadability with a small thickness.

Die Dicke der Polymermembran 2 beträgt vorzugsweise 1 bis 50 μm, insbesondere 5 bis 20 μm. Die Polymermembran 2 ist zumindest für Wasserstoff und/oder Sauerstoff durchlässig, ggf. auch unselektiv generell für Gase. Die eigentliche Trennung bzw. Separation erfolgt durch die dünne Deckschicht 3 aus Edelmetall oder einer Edelmetallegierung.The thickness of the polymer membrane 2 is preferably 1 to 50 μm, in particular 5 to 20 μm. The polymer membrane 2 is permeable at least to hydrogen and / or oxygen, possibly also unselective generally for gases. The actual separation or separation takes place through the thin cover layer 3 of noble metal or a precious metal alloy.

Die Dicke der Deckschicht 3 beträgt vorzugsweise weniger als 100 nm, insbesondere weniger als 50 nm und insbesondere im wesentlichen 25 nm oder weniger. Die Dicke der Deckschicht 3 beträgt vorzugsweise weniger als 10%, insbesondere weniger als 1%, der Dicke der Polymermembran 2.The thickness of the cover layer 3 is preferably less than 100 nm, in particular less than 50 nm and in particular substantially 25 nm or less. The thickness of the cover layer 3 is preferably less than 10%, in particular less than 1%, of the thickness of the polymer membrane 2.

Vorzugsweise besteht die Deckschicht 3 zur Wasserstoffabscheidung zumindest im wesentlichen aus Palladium und/oder Platin oder einer Legierung mit Palladium und/oder Platin.The covering layer 3 for hydrogen deposition preferably consists at least essentially of palladium and / or platinum or an alloy with palladium and / or platinum.

Zur Sauerstoffabscheidung besteht die Deckschicht 3 vorzugsweise zumindest im wesentlichen aus Silber oder einer Silber-Legierung.For oxygen deposition, the cover layer 3 preferably consists at least substantially of silver or a silver alloy.

Die Deckschicht 3 liegt vorzugsweise vollflächig auf der Primärmembran 2 auf.The cover layer 3 is preferably on the entire surface of the primary membrane 2.

Vorzugsweise ist die Deckschicht 3 ohne Zwischenschicht oder Haftvermittler unmittelbar auf die Polymermembran 2 aufgebracht. Vorzugsweise ist die Deckschicht 3 auf die Polymermembran 2 gesputtert oder aufgedampft. Insbe- sondere ist die Deckschicht 3 durch Plasmabeschichtung, Verdampfung mittels eines Lichtbogens oder dgl. auf die Polymermembran 2 aufgebracht.Preferably, the cover layer 3 is applied directly to the polymer membrane 2 without an intermediate layer or adhesion promoter. Preferably, the cover layer 3 is sputtered or vapor-deposited onto the polymer membrane 2. In particular, the cover layer 3 is applied to the polymer membrane 2 by plasma coating, evaporation by means of an arc or the like.

Die Deckschicht 3 ist nur sehr selektiv für Wasserstoff oder Sauerstoff durchlässig. Beispielsweise gestattet die Deckschicht 3 aus Palladium oder einer Palladium-Legierung eine Abscheidung von Wasserstoff mit einer Reinheit von 99,999 Gew.-%.The cover layer 3 is only very selectively permeable to hydrogen or oxygen. For example, the cover layer 3 of palladium or a palladium alloy allows deposition of hydrogen having a purity of 99.999% by weight.

Der vorschlagsgemäße Membranaufbau 1 gestattet sehr hohe Separationsbzw. Abscheidungsraten. Weiter ist der vorschlagsgemäße Membranaufbau 1 auch bei verhältnismäßig hohen Temperaturen einsetzbar, beispielsweise zur Abscheidung von Wasserstoff aus einem noch heißen Reformat-Gas bei Temperaturen von 300 bis 4000C. Der abgeschiedene Wasserstoff kann dann unmittelbar einer nachge- ordneten Brennstoffzelle zugeführt werden.The proposed membrane structure 1 allows very high Separationsbzw. Deposition rates. Further, the according to the proposal membrane structure 1 can also be used at relatively high temperatures, for example for the separation of hydrogen from a still hot reformate gas at temperatures of 300 to 400 0 C. The separated hydrogen can then a downstream arranged fuel cell can be fed directly.

Um auch bei hohen Drücken über 1 MPa, vorzugsweise über 3 MPa, insbesondere über 5 MPa, arbeiten zu können, weist der Membranaufbau 1 vorzugsweise einen Träger 4 zur Abstützung der Polymermembran 2 - insbeson- dere auf der der Deckschicht 3 abgewandten Seite - auf. Der Träger 4 ist vorzugsweise porös oder gitterartig ausgebildet, wie in dem schematischen Schnitt angedeutet, um eine gute Gasabführung des Permeats zu gestatten.In order to be able to work even at high pressures above 1 MPa, preferably above 3 MPa, in particular above 5 MPa, the membrane structure 1 preferably has a support 4 for supporting the polymer membrane 2, in particular on the side facing away from the cover layer 3. The carrier 4 is preferably formed porous or lattice-like, as indicated in the schematic section, to allow a good gas discharge of the permeate.

Der Träger 4 besteht vorzugsweise aus Keramik, Metall oder einem sonstigen geeigneten Material, insbesondere einem Verbundwerkstoff.The carrier 4 is preferably made of ceramic, metal or other suitable material, in particular a composite material.

Der Träger 4 ist vorzugsweise fest mit der Polymermembran 2 verbunden, so daß der Membranaufbau 1 eine Baueinheit bildet. Dies ist insbesondere einer guten Druckwechselbeständigkeit des Membranaufbaus 1 zuträglich.The carrier 4 is preferably firmly connected to the polymer membrane 2, so that the membrane structure 1 forms a structural unit. This is in particular a good pressure swing resistance of the membrane structure 1 beneficial.

In dem schematischen Schnitt ist beispielhaft angedeutet, wie ein Gasstrom bzw. Gasgemisch 5 dem Membranaufbau 1 deckschichtseitig zugeführt wird, beispielsweise mit einer Strömung gemäß Pfeil P parallel zur Flachseite des Membranaufbaus 1 bzw. der Deckschicht 3. Der Membranaufbau 1 ist für Wasserstoff oder Sauerstoff durchlässig, der insbesondere aufgrund einer entsprechenden partialen Druckdifferenz von beispielsweise über 1 MPa, vorzugsweise über 3 MPa, insbesondere über 5 MPa, aus dem Gasgemisch 5 als Permeat - bei der Darstellung nach unten, also auf der Seite des Trägers 4 - abgeschieden wird. Das als Retentat verbleibende Gasgemisch 5 weist eine entsprechend verminderte Konzentration an Wasserstoff oder Sauerstoff auf. Dies ist in der Figur schematisch dadurch angedeutet, daß die Konzentration der nicht ausgefüllten Kreise, die Wasserstoff oder Sauerstoff repräsentieren, im Gasgemisch 5 bei der dargestellten Strömung entsprechend von links nach rechts abnimmt. Entsprechend wird auf der Abscheidungsseite bzw. Träger- seite ein Volumenstrom an Wasserstoff oder Sauerstoff als Permeat abgegeben. Bei Bedarf ist der vorschlagsgemäße Membranaufbau 1 auch umgekehrt betreibbar, also das Gasgemisch 5 trägerseitig zuführbar.The schematic section indicates by way of example how a gas stream or gas mixture 5 is supplied to the membrane structure 1 on the cover layer side, for example with a flow according to arrow P parallel to the flat side of the membrane structure 1 or the cover layer 3. The membrane structure 1 is permeable to hydrogen or oxygen in particular due to a corresponding partial pressure difference of, for example, about 1 MPa, preferably about 3 MPa, in particular about 5 MPa, from the gas mixture 5 as permeate - in the representation down, ie on the side of the carrier 4 - is deposited. The remaining gas mixture as retentate 5 has a correspondingly reduced concentration of hydrogen or oxygen. This is indicated schematically in the figure by the fact that the concentration of the unfilled circles, which represent hydrogen or oxygen, decreases correspondingly from left to right in the gas mixture 5 in the illustrated flow. Accordingly, a volume flow of hydrogen or oxygen is released as permeate on the deposition side or carrier side. If necessary, the proposed membrane assembly 1 is also reversed operable, so the gas mixture 5 carrier side fed.

Nachfolgend werden beispielhaft einige Einsatzmöglichkeiten des vorschlagsgemäßen Membranaufbaus 1 kurz erläutert:Some possible uses of the proposed membrane structure 1 are briefly explained below by way of example:

Der Membranaufbau 1 kann zur Abtrennung von Wasserstoff aus insbesondere noch heißem Reformat-Gas eingesetzt werden. Das Reformat-Gas wird von einem Reformer aus Kohlenwasserstoffen erzeugt. Für die Verwendung in Brennstoffzellen muß üblicherweise das in dem Reformat-Gas enthaltene Kohlenmonoxyd entfernt werden. Aufgrund der hohen Selektivität des vorschlagsgemäßen Membranaufbaus 1 wird das Kohlenmonoxyd zurückgehalten und (im wesentlichen ausschließlich) Wasserstoffgas abgetrennt, das un- mittelbar für die Versorgung von Brennstoffzellen einsetzbar ist.The membrane structure 1 can be used for the separation of hydrogen from in particular still hot reformate gas. The reformate gas is produced by a hydrocarbon reformer. For use in fuel cells, usually the carbon monoxide contained in the reformate gas must be removed. Due to the high selectivity of the proposed membrane structure 1, the carbon monoxide is retained and separated (essentially exclusively) hydrogen gas which can be used directly for the supply of fuel cells.

Sauerstoff kann mit Hilfe des vorschlagsgemäßen Membranaufbaus 1 unmittelbar aus der Luft abgetrennt werden und beispielsweise für die interne Kohlevergasung in Kraftwerken oder für eine kontinuierliche Sauerstoff- Versorgung für sonstige Zwecke eingesetzt werden.Oxygen can be separated directly from the air with the aid of the proposed membrane structure 1 and used, for example, for internal coal gasification in power plants or for continuous oxygen supply for other purposes.

Der vorschlagsgemäße Membranaufbau 1 kann in der petrochemischen und Ammoniak-Industrie zur effizienten Rückgewinnung von Wasserstoff aus Produktgasen, insbesondere bei erhöhten Temperaturen und/oder Drücken, eingesetzt werden. The proposed membrane structure 1 can be used in the petrochemical and ammonia industry for the efficient recovery of hydrogen from product gases, in particular at elevated temperatures and / or pressures.

Claims

Patentansprüche: claims: 1. Membranaufbau (1) zur Abscheidung von Wasserstoff oder Sauerstoff, mit einer vorzugsweise über 15O0C temperaturbeständigen, nicht porösen Po- lymermembran (2), insbesondere aus Polyimid oder Polyetherketon, und mit einer Deckschicht (3), deren Dicke, vorzugsweise weniger als 100 nm beträgt, aus Edelmetall oder einer Edelmetallegierung.1. Membrane structure (1) for the deposition of hydrogen or oxygen, with a preferably over 15O 0 C temperature-resistant, non-porous polymer membrane (2), in particular of polyimide or polyether ketone, and with a cover layer (3), the thickness thereof, preferably less is 100 nm, made of precious metal or a precious metal alloy. 2. Membranaufbau nach Anspruch 1, dadurch gekennzeichnet, daß der Membranaufbau (1) und die Polymermembran (2) über 2000C, insbesondere über 3000C, temperaturbeständig sind.2. Membrane structure according to claim 1, characterized in that the membrane structure (1) and the polymer membrane (2) above 200 0 C, in particular above 300 0 C, are temperature resistant. 3. Membranaufbau nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Polymermembran (2) aus wasserstofffreiem Polyimid oder aus einem Po- lyimid, das Amid-, Ester- und/oder Ether-Gruppen enthält, besteht.3. Membrane structure according to claim 1 or 2, characterized in that the polymer membrane (2) consists of hydrogen-free polyimide or of a polyimide which contains amide, ester and / or ether groups exists. 4. Membranaufbau nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Polymermembran (2) aus PEK, PEEK, PEKK oder PEEKK besteht.4. Membrane structure according to claim 1 or 2, characterized in that the polymer membrane (2) consists of PEK, PEEK, PEKK or PEEKK. 5. Membranaufbau nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, daß die Dicke der Polymermembran (2) 1 bis 50 μm, insbesondere 5 bis 20 μm, beträgt.5. Membrane structure according to one of the preceding claims, characterized in that the thickness of the polymer membrane (2) 1 to 50 .mu.m, in particular 5 to 20 microns, is. 6. Membranaufbau nach einem der voranstehenden Ansprüche, dadurch ge- kennzeichnet, daß die Polymermembran (2) faserverstärkt ist.6. Membrane structure according to one of the preceding claims, characterized in that the polymer membrane (2) is fiber-reinforced. 7. Membranaufbau nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, daß die Polymermembran (2) ein- oder mehrschichtig ausgebildet ist.7. Membrane structure according to one of the preceding claims, characterized in that the polymer membrane (2) is formed one or more layers. 8. Membranaufbau nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, daß die Deckschicht (3) zur Wasserstoffabscheidung aus Palladium und/oder Platin oder einer auf der Basis von Palladium Legierung mit Palladium und/oder Platin besteht. 8. Membrane structure according to one of the preceding claims, characterized in that the cover layer (3) for hydrogen separation from palladium and / or platinum or based on palladium alloy with palladium and / or platinum. 9. Membranaufbau nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Deckschicht (3) zur Sauerstoffabscheidung aus Silber oder einer Silber-Legierung besteht.9. Membrane structure according to one of claims 1 to 8, characterized in that the cover layer (3) for oxygen deposition consists of silver or a silver alloy. 10. Membranaufbau nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, daß die Dicke der Deckschicht (3) weniger als 50 nm, insbesondere im wesentlichen 25 nm oder weniger, beträgt.10. Membrane structure according to one of the preceding claims, characterized in that the thickness of the cover layer (3) is less than 50 nm, in particular substantially 25 nm or less. 11. Membranaufbau nach einem der voranstehenden Ansprüche, dadurch ge- kennzeichnet, daß die Dicke der Deckschicht (3) weniger als 10% , insbesondere weniger als 1%, der Dicke der Polymermembran (2) beträgt.11. Membrane structure according to one of the preceding claims, characterized in that the thickness of the cover layer (3) is less than 10%, in particular less than 1%, of the thickness of the polymer membrane (2). 12. Membranaufbau nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, daß die Deckschicht (3) auf die Polymermembran (2) gesputtert oder aufgedampft ist, insbesondere durch Plasmabeschichten.12. Membrane structure according to one of the preceding claims, characterized in that the cover layer (3) on the polymer membrane (2) is sputtered or vapor-deposited, in particular by plasma coating. 13. Membranaufbau nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, daß der Membranaufbau (1) einen vorzugsweise porösen oder gitterartigen Träger (4) zur Abstützung der Polymermembran (2) - insbeson- dere auf der der Deckschicht (3) abgewandten Seite - aufweist.13. Membrane structure according to one of the preceding claims, characterized in that the membrane structure (1) has a preferably porous or lattice-like support (4) for supporting the polymer membrane (2) - in particular on the cover layer (3) facing away - has. 14. Verwendung des Membranaufbaus (1) gemäß einem der voranstehenden Ansprüche zur Wasserstoffabscheidung oder Sauerstoffabscheidung, wobei dem Membranaufbau (1) ein Wasserstoff und/oder Sauerstoff enthaltendes Gasgemisch bei einer Temperatur über 2000C, insbesondere über 3000C, und/oder mit einem Druck über 0,1 MPa, vorzugsweise über 3 MPa, insbesondere über 5 MPa, zugeführt wird. 14. Use of the membrane structure (1) according to one of the preceding claims for hydrogen separation or oxygen separation, wherein the membrane structure (1) a hydrogen and / or oxygen-containing gas mixture at a temperature above 200 0 C, in particular above 300 0 C, and / or with a pressure above 0.1 MPa, preferably above 3 MPa, in particular above 5 MPa, is supplied.
PCT/EP2006/006581 2005-07-27 2006-07-06 Membrane structure for the elimination of hydrogen or oxygen Ceased WO2007012388A1 (en)

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