WO2002092500A1 - Membranes separatrices catalytiquement actives pour la production d'hydrogene a haut degre de purete - Google Patents

Membranes separatrices catalytiquement actives pour la production d'hydrogene a haut degre de purete Download PDF

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Publication number
WO2002092500A1
WO2002092500A1 PCT/EP2002/004910 EP0204910W WO02092500A1 WO 2002092500 A1 WO2002092500 A1 WO 2002092500A1 EP 0204910 W EP0204910 W EP 0204910W WO 02092500 A1 WO02092500 A1 WO 02092500A1
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Prior art keywords
membrane
composite membrane
composite
metallic layer
hydrogen
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PCT/EP2002/004910
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German (de)
English (en)
Inventor
Christian Hying
Gerhard HÖRPEL
Christian Herkt-Bruns
Dierk Landwehr
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Creavis Gesellschaft Für Technologie Und Innovation Mbh
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Publication of WO2002092500A1 publication Critical patent/WO2002092500A1/fr

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    • 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
    • B01D67/0046—Inorganic membrane manufacture by slurry techniques, e.g. die or slip-casting
    • 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
    • B01D71/02232—Nickel
    • 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
    • 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
    • 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
    • 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
    • B01D71/0213—Silicon
    • 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
    • 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
    • B01D71/0221—Group 4 or 5 metals
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B01J35/59—Membranes
    • 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
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—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
    • C01B3/40—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 characterised by the catalyst
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • 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
    • B01J2219/00132—Controlling the temperature using electric heating or cooling elements
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to the use of a special membrane as a carrier membrane in a composite membrane for a membrane reactor, a special composite membrane and a membrane reactor.
  • Membrane reactors are known from the prior art. Membrane reactors are devices with which a reaction and a separation process can be carried out simultaneously on a membrane in the same reaction space. Reformers which generate hydrogen by reforming fuels are also known from the prior art. Such reformers can be used to generate hydrogen for the operation of a fuel cell. It is already known from the prior art to use a membrane reactor as a reformer. For example, Volker Formanski (Hydrogen gas production for supplying fuel gas to low-temperature fuel cells using a membrane reactor for methanol reforming. Schwier.-Ber. VDI, Erasmus 3 (2000), 632 I-III.
  • VX pages 84 to 92 in front of a membrane reactor which produces hydrogen by reforming fuels and which consists of a reaction chamber which is filled with a catalytic bulk material, the hydrogen generated under pressure being separated from the reaction chamber by a Pd / Ag membrane.
  • the membrane described is a metal tube that is inserted into the reaction chamber.
  • the metal tube must have sufficient stability so that it is not damaged or destroyed under the operating conditions in the reaction chamber.
  • membrane technology promises an increase in energy efficiency by separating off the product gas and shifting the chemical equilibrium to the hydrogen side
  • no practical membranes are known from the prior art for the following reasons that would be suitable for use with fuel cells that use Can operate automobile.
  • the membranes described by Formanski are able to separate high-purity hydrogen.
  • the membrane must withstand a high pressure differential between the inside and the outside of the reactor. This requirement can only be achieved by using a large layer thickness.
  • a membrane with a large layer thickness is sufficiently stable, but only has a low hydrogen permeability, so that the hydrogen produced can penetrate such a membrane only slowly. This is the dilemma that cannot be solved by the prior art.
  • the present invention uses a flexible, porous membrane as a carrier membrane in an electrically heatable composite membrane for a membrane reactor in which hydrogen is generated by reforming fuels, the composite membrane comprising the carrier membrane and a metallic layer catalyzing the reforming and for the selective separation of the hydrogen produced from the membrane reactor.
  • Another aspect of the present invention is an electrically heatable, composite membrane, comprising a flexible, porous carrier membrane and a metallic layer, characterized in that
  • the electrically heatable, flexible, porous membrane is a composite that has an openwork support, preferably a woven and / or nonwoven, and a porous one
  • the membrane according to the invention catalyzes the synthesis gas reaction, separates high-purity hydrogen from the reaction mixture and is mechanically sufficiently stable against large pressure differences. Furthermore, the membrane according to the invention can be heated electrically. A membrane according to the invention is therefore particularly suitable for synthesis gas reactors for generating high-purity hydrogen, which is required, for example, for electricity generation in a fuel cell.
  • the membrane according to the invention consists of a mechanically stable, ceramic, preferably electrically conductive, carrier membrane. This is equipped with a coating that is both catalytically active and stores hydrogen.
  • the present invention offers the advantage that the reaction enthalpy required for the syngas process can be introduced to the catalytically active centers in the reforming process in a controlled manner by heating the membrane.
  • this makes it possible to handle possible load change processes and cold start phases without any problems, particularly in mobile use.
  • the membranes according to the invention can in particular catalyze the generation of hydrogen from hydrocarbons and can separate hydrogen gas in such a way that highly pure hydrogen is produced as the product.
  • Partial oxidation means that the synthesis gas reaction is carried out in the presence of oxygen, with at least some of the hydrocarbons being burned to produce the necessary enthalpy of reaction, so that coking of the fuels occurs.
  • the membranes according to the invention offer sufficient mechanical stability in relation to the pressure difference between the interior of the synthesis gas reactor and the exterior.
  • the membranes according to the invention are preferably used in membrane reactors for the production of high-purity hydrogen.
  • the use of a high-purity hydrogen gas is advantageous for the operation of a fuel cell in mobile and stationary use in two ways.
  • the energy efficiency of the fuel cell can be increased considerably.
  • the catalyst poisons, such as carbon monoxide and sulfur-containing compounds, which are present in traces in the reforming technologies used to date are missing, so that the service life of the fuel cell can be increased compared to the current status.
  • the composite membrane according to the invention can in particular comprise a composite material according to DE 19741498 AI or DE 19640461 AI as the carrier membrane, which is coated with a thin metallic layer consisting of a hydrogen-storing material with sufficiently good adhesion, uniformly strong.
  • Suitable materials for the metallic layer are all materials which are capable of reversibly depositing hydrogen in their interior with a proportion of 1% by weight to 30% by weight.
  • the metallic layer comprises in particular one or more of the following metals: palladium, silver, gold, copper, cobalt, nickel, ruthenium, rhodium, zinc, aluminum, titanium, indium, vanadium, tungsten, rhenium, tungsten, molybdenum and / or rare earth metals ,
  • Palladium is preferred, to which silver or copper is particularly preferably added for the purpose of improving the hydrogen permeability and its mechanical properties while absorbing hydrogen in a concentration range of 15 to 25% by weight, preferably 20% by weight.
  • the thickness of the metallic layer is 0.1 ⁇ m to 1000 ⁇ m, preferably less than 5 ⁇ m.
  • the selection of the metallic layer for the membrane according to the invention is preferably to be made such that the surface of the metallic layer is catalytically sufficiently active for the synthesis gas reaction.
  • highly active catalyst centers can additionally be applied to the surface in order to increase the catalytic activity.
  • These highly active catalysts which require the synthesis gas reactions are applied in the form of submicron-sized dots with a size of 20 nm to 1 ⁇ m, preferably 100 nm, regularly with average lateral distances of 0.1 ⁇ m to 50 ⁇ m. The following materials are used:
  • the elements platinum, palladium, rhodium, rhenium, nickel, copper and / or cobalt can be used as catalysts for the synthesis gas reaction. These elements can be in metallic form alone or in alloy with other metals or in oxidized or reduced form can be used in catalytically active compounds with other elements.
  • the composition of the catalyst centers provided on the surface of the metallic layer is different from the composition of the metallic layer.
  • the metallic layer of the flexible composite membrane can have a pattern of alternating concave and convex regions in order to compensate and / or to avoid stresses due to volume changes due to hydrogen absorption.
  • the volume changes always occur when hydrogen is sorbed by the selective layer, and this is the case in the separation process. Because the volume change due to hydrogen absorption leads to a change in the surface of the membrane, which can go so far that cracks form in the membrane, and then separation is no longer possible with this membrane. This problem comes to the fore the thinner and more sensitive the hydrogen-selective layers become. This also occurs with tubular membranes, but is not quite as problematic as with plate-shaped systems, since the geometry of the tubular design means that many stresses can be absorbed. This means that changes in the surface only occur after 10 times more cycles with tubular membranes than with plate-shaped membranes. But the problem as such is not negligible.
  • the metallic layers which preferably have a pattern of alternating concave and convex regions, can better absorb stresses that arise from changes in volume of the selective layers and thereby show a significantly improved long-term stability. These tensions are guaranteed by the special static of the metallic layer on the carrier membrane, which has a perforated carrier.
  • the "corrugated" structure of the surface with "hills” at the uninterrupted areas and “valleys” at the open areas of the openwork support leads to this effect.
  • the fact that the entire membrane is a "mountain and Valley structure "at irregular or preferably regular intervals, ie a structure with alternating concave and convex areas, can be degraded better by the volume changes induced by hydrogen sorption.
  • the metallic layer must not be too thick, so that these advantages are canceled out by the disadvantage of an excessively thick layer.
  • the metallic layer should be less than 5 ⁇ m thick, particularly preferably thinner than 2 ⁇ m and very particularly preferably less than 1 ⁇ m.
  • the coefficient of thermal expansion of the carrier membrane and the coefficient of thermal expansion of the metallic layer differ by less than 15%, preferably less than 10%.
  • the thermal expansion coefficient of the carrier membrane and the thermal expansion coefficient of the metal layer are very particularly preferably approximately the same size. This is ensured by the suitable choice of the openwork carrier, which is preferably made of metal. In this way, cracks in the metallic layer due to temperature changes can be avoided.
  • the surface of the membrane according to the invention is active as a catalyst.
  • the synthesis gas reaction takes place on the surface of the hydrogen-storing metallic layer or, in a further embodiment of the invention, also on specially applied, highly active, submicron-scale catalyst dots.
  • the membranes according to the invention for producing high-purity hydrogen from the reforming process have the property of depositing hydrogen — usually atomically — into the crystalline structure at interstitial sites at high hydrogen gas partial pressure until chemical equilibrium is reached. When the hydrogen gas partial pressure is reduced, the gas is released again. A high hydrogen gas pressure prevails within the membrane reactor during operation. In contrast, a greatly reduced hydrogen pressure prevails outside the reactor.
  • the metallic Layer, consisting of the hydrogen-storing material, thus represents a suitable membrane for the separation of high-purity hydrogen.
  • the perforated support of the composite material of the composite membrane according to the invention comprises a metal mesh, preferably a stainless steel mesh and / or stainless steel fleece.
  • the metal mesh can be easily contacted electrically, so that an electrical current to be applied creates ohmic heat in the immediate vicinity of the reaction. This heat generated in this way reaches the catalytically active areas of the membrane according to the invention and can provide the endothermic reaction enthalpy required for the synthesis gas reaction.
  • This type of energy supply allows targeted heating of the reactive centers, so that losses due to the heating of gases inside the reactor can be largely avoided.
  • the electrical heating can be regulated in a very short time.
  • the generation of hydrogen can thus be regulated in a finely adjustable manner. This property is of great advantage for the needs of the fuel cell automobile, because it makes it particularly easy to manage load change processes.
  • cold start phases can be greatly shortened by rapid electrical heating of the reactive centers.
  • the rate of hydrogen formation when using the composite membrane according to the invention in the reforming preferably corresponds essentially to the rate of hydrogen passage through the composite membrane.
  • the membrane according to the invention offers sufficient stability due to the perforated support inside, in particular with respect to the high pressure difference between the inside and the outside of the reactor.
  • the flexible, openwork support of the composite membrane according to the invention can be a
  • a carrier which has been made permeable to matter by treatment with laser beams, ion beams or an etchant can also be used as a flexible, openwork carrier.
  • the openwork carrier preferably comprises fibers and / or filaments with a diameter of 1 to 150 ⁇ m, preferably 1 to 20 ⁇ m, and / or threads with a diameter of 5 to 150 ⁇ m, preferably 20 to 70 ⁇ m.
  • the openwork carrier is a woven fabric
  • this is preferably a woven fabric made of 11-Tex yarns with 5-50 warp or weft threads and in particular 20-28 warp and 28-36 weft threads. 5,5-Tex yarns with 10-50 warp or weft threads are particularly preferred, and 20-28 warp and 28-36 weft threads are preferred.
  • the composite membrane according to the invention can preferably be operated at a temperature between 300 ° C. and 900 ° C., particularly preferably at more than 500 ° C., very particularly preferably at more than 800 ° C.
  • the fuel which is preferably used when the composite membrane according to the invention is used in a membrane reactor for reforming fuels comprises a hydrocarbon or an alcohol.
  • the fuel particularly preferably comprises methane, ethane, propane and / or butane or methanol and / or ethanol.
  • the metallic layer can be heated.
  • the metallic layer is very particularly preferably indirectly heated by resistance heating.
  • the composite membrane according to the invention is preferably used in a membrane reactor which is a reformer for a fuel cell for stationary or mobile applications.
  • a composite membrane according to the invention can be operated in a membrane reactor at a pressure of 0.5 to 200 bar (0.5 to 200 ⁇ 10 5 Pa).
  • the composite membrane according to the invention is obtainable from
  • step (F) optionally repeating steps (A) through (E) with the composite from step (E) using mixtures containing particles of smaller particle size to create a multilayer composite.
  • sols such as titanium nitrate sol, zirconium nitrate sol or silica sol or a sol of aluminum oxide can be used as dispersions.
  • the dispersions can also be obtained by hydrolysis of a metal compound, semimetal compound or mixed metal compound in a medium, such as water, alcohol or an acid.
  • the compound to be hydrolyzed is preferably a metal nitrate, a metal chloride, a metal carbonate, a metal alcoholate compound or a semimetal alcoholate compound, particularly preferably at least one
  • the hydrolyzed compound can be peptized with an acid, preferably with a 10 to 60% acid, preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids.
  • an acid preferably with a 10 to 60% acid, preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids.
  • An inorganic component with a grain size of 1 to 10,000 nm can be suspended in the sol.
  • At least one inorganic component which comprises at least one compound from the oxides of the subgroup elements or from the elements of the 3rd to 5th main group, preferably oxides, selected from the oxides of the elements Sc, Y, Ti, Zr, Nb, Ce, V , Cr, Mo, W, Mn, Fe, Co, B, AI, In, TI, Si, Ge, Sn, Pb and Bi, such as B. Y 2 O 3 , ZrO 2 , Fe 2 O 3 , Fe 3 O 4 , SiO 2 , Al 2 O 3 , suspended.
  • the inorganic component can also be aluminosilicates, aluminum phosphates, zeolites or partially exchanged zeolites, such as, for. B.
  • ZSM-5, Na-ZSM-5 or Fe-ZSM-5 or amorphous microporous mixed oxides which can contain up to 20% non-hydrolyzable organic compounds, such as. B. vanadium oxide, silicon oxide glass or aluminum oxide-silicon oxide-methyl silicon sesquioxide glasses.
  • the mass fraction of the suspended component is preferably 0.1 to 500 times the hydrolyzed compound used.
  • the metal oxide which is mixed with the dispersion in step (C) is preferably selected from the group consisting of titanium oxide, aluminum oxide, silicon oxide and zirconium oxide or from their mixed oxides and the hydrolyzable metal compound is preferably a compound of titanium, zirconium, silicon, or aluminum.
  • the suspended compound When using a mesh fabric with a mesh size of z. B. 100 microns as an openwork carrier can preferably be used to increase the freedom from cracks, the suspended compound with a grain size of at least
  • the composite material can preferably be a
  • Thickness from 5 to 1000 microns, particularly preferably from 50 to 150 microns.
  • the mixture of dispersion and compounds to be suspended preferably has a ratio
  • the mixture can be solidified by heating the composite of mixture and openwork carrier to 50 to 1000 ° C., preferably about 100 ° C. In a particular embodiment, the composite is exposed to a temperature of 50 to 100 ° C. for 10 minutes to 5 hours. In a further particular embodiment, the composite is exposed to a temperature of 100 to 800 ° C. for 1 second to 10 minutes.
  • the composite can be heated with heated air, hot air, infrared radiation, microwave radiation or electrically generated heat.
  • the mixture can be solidified by the mixture being applied to a preheated carrier and thus being solidified immediately after the application.
  • the perforated carrier is rolled off a roll at a speed of 1 m / h to 1 m / s, on an apparatus which Contacted mixture with the carrier and then to another apparatus that allows the mixture to solidify by heating, and the composite material thus produced is rolled up on a second roll. In this way it is possible to manufacture the composite material continuously.
  • a ceramic or inorganic layer is applied to a composite material. This can be done, for example, by laminating a green (unsintered) ceramic layer or an inorganic layer, which is present on an auxiliary film, onto the carrier or by treating the composite material with a further suspension (mixture) as described above. This bond can be solidified by heating.
  • the green ceramic layer used preferably contains a nanocrystalline powder of a semimetal or metal oxide, such as. As aluminum oxide, titanium dioxide or zirconium dioxide.
  • the green layer can contain an organic binder.
  • a composite material is obtained which has a pore gradient.
  • supports for the production of composite materials with a specific pore size the pore or mesh size of which is not suitable for producing a composite material with the required pore size.
  • This can e.g. B. be the case when a composite material with a pore size of 0.25 microns is to be produced using a carrier with a mesh size of over 300 microns.
  • the composite material obtained in this way can now be used as Support membrane with a smaller mesh or pore size can be used.
  • a further suspension can be applied to this carrier membrane, which has a compound with a grain size of 0.5 ⁇ m.
  • the insensitivity to cracks in composite materials with large mesh or pore widths can also be improved by applying suspensions to the carrier which have at least two suspended compounds.
  • Compounds to be suspended are preferably used which have a particle size ratio of 1: 1 to 1:20, particularly preferably 1: 1.5 to 1: 2.5.
  • the weight fraction of the grain size fraction with the smaller grain size should not exceed a proportion of at most 50%, preferably 20% and very particularly preferably 10%, of the total weight of the grain size fraction used.
  • a hydrogen-permeable adhesion-promoting layer is provided between the perforated support and the metallic layer.
  • the composite membrane is preferably elastic and preferably tolerates a bending radius down to 100 m, preferably down to 10 cm, and particularly preferably tolerates a maximum bending radius in the range from 1 to 100 mm without the metallic layer subjected to pressure forming cracks.
  • the composite membrane according to the invention is preferably an asymmetrical composite membrane.
  • the metallic layer is applied to the carrier membrane by known coating methods, such as CVD (chemical vapor deposition); PVD (physical vapor deposition, in particular sputtering or plasma coating); Electroplating or electroless plating. These processes are suitable for applying hydrogen-selective and catalytically active layers in good quality to the support membranes.
  • the catalyst centers (dots) are preferably applied to the metallic layer by spraying on a suspension which contains the catalyst-active component.
  • the catalyst centers can, however, also be applied by the same methods as the application of the metallic layer on the support membrane. Before that, however, a grid-like pattern is applied to the metal layer. The catalyst centers are then applied to the metal layer in the spaces between the grid, at the intervals predetermined by the grid. The grid is then preferably removed again. If the grid is permeable to hydrogen and inert to the reforming and the catalytic activity of the catalyst centers is sufficient, the grid can also remain on the metallic layer.
  • the present invention also provides a membrane reactor comprising a composite membrane according to the invention.
  • the membrane reactor is preferably operated continuously.

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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)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne l'utilisation d'une membrane flexible poreuse comme membrane support dans une membrane composite chauffable électriquement destinée à un réacteur à membrane dans lequel de l'hydrogène est produit par reformage de combustibles. La membrane composite comprend la membrane support et une couche métallique catalysant le reformage et elle permet de séparer sélectivement l'hydrogène produit à partir du réacteur à membrane.
PCT/EP2002/004910 2001-05-11 2002-05-04 Membranes separatrices catalytiquement actives pour la production d'hydrogene a haut degre de purete WO2002092500A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10122888A DE10122888A1 (de) 2001-05-11 2001-05-11 Katalytisch aktive Trennmembran für die Erzeugung von hochreinem Wasserstoff
DE10122888.0 2001-05-11

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WO2002092500A1 true WO2002092500A1 (fr) 2002-11-21

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DE102004019263B4 (de) * 2003-04-29 2009-11-26 Presting, Hartmut, Dr.Rer.Nat. Vorrichtung zur Erzeugung von nahezu reinem Wasserstoff durch Reformierung und Verfahren zur Herstellung der Vorrichtung
US7648566B2 (en) 2006-11-09 2010-01-19 General Electric Company Methods and apparatus for carbon dioxide removal from a fluid stream
US7966829B2 (en) 2006-12-11 2011-06-28 General Electric Company Method and system for reducing CO2 emissions in a combustion stream
US8597383B2 (en) 2011-04-11 2013-12-03 Saudi Arabian Oil Company Metal supported silica based catalytic membrane reactor assembly
US9745191B2 (en) 2011-04-11 2017-08-29 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
DE102010010822A1 (de) * 2010-03-10 2011-09-15 Eads Deutschland Gmbh Vorrichtung und Verfahren zur Erzeugung von Wasserstoffgas durch Dehydrogenierung von Kohlenwasserstoff-Brennstoffen

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US3505180A (en) * 1963-09-20 1970-04-07 Energy Conversion Ltd Method of making a thin gas diffusion membrane
EP0140073A2 (fr) * 1983-09-08 1985-05-08 Forschungszentrum Jülich Gmbh Paroi perméable d'hydrogène
US5229102A (en) * 1989-11-13 1993-07-20 Medalert, Inc. Catalytic ceramic membrane steam-hydrocarbon reformer
EP0715880A1 (fr) * 1994-06-28 1996-06-12 Ngk Insulators, Ltd. Separateur de gaz et son procede de production
EP0934772A2 (fr) * 1998-02-04 1999-08-11 DaimlerChrysler AG Réacteur pour effectuer des réactions chimiques catalytiques et réacteur pour le reformage de méthanol en particulier
DE19824666A1 (de) * 1997-09-20 1999-12-09 Creavis Tech & Innovation Gmbh Herstellung und Verwendung eines Keramik-Metallträger-Verbundes
GB2355418A (en) * 1999-10-19 2001-04-25 Ford Global Tech Inc Hydrogen separator

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US3505180A (en) * 1963-09-20 1970-04-07 Energy Conversion Ltd Method of making a thin gas diffusion membrane
EP0140073A2 (fr) * 1983-09-08 1985-05-08 Forschungszentrum Jülich Gmbh Paroi perméable d'hydrogène
US5229102A (en) * 1989-11-13 1993-07-20 Medalert, Inc. Catalytic ceramic membrane steam-hydrocarbon reformer
EP0715880A1 (fr) * 1994-06-28 1996-06-12 Ngk Insulators, Ltd. Separateur de gaz et son procede de production
DE19824666A1 (de) * 1997-09-20 1999-12-09 Creavis Tech & Innovation Gmbh Herstellung und Verwendung eines Keramik-Metallträger-Verbundes
EP0934772A2 (fr) * 1998-02-04 1999-08-11 DaimlerChrysler AG Réacteur pour effectuer des réactions chimiques catalytiques et réacteur pour le reformage de méthanol en particulier
GB2355418A (en) * 1999-10-19 2001-04-25 Ford Global Tech Inc Hydrogen separator

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004019263B4 (de) * 2003-04-29 2009-11-26 Presting, Hartmut, Dr.Rer.Nat. Vorrichtung zur Erzeugung von nahezu reinem Wasserstoff durch Reformierung und Verfahren zur Herstellung der Vorrichtung
US7648566B2 (en) 2006-11-09 2010-01-19 General Electric Company Methods and apparatus for carbon dioxide removal from a fluid stream
US7966829B2 (en) 2006-12-11 2011-06-28 General Electric Company Method and system for reducing CO2 emissions in a combustion stream
US8597383B2 (en) 2011-04-11 2013-12-03 Saudi Arabian Oil Company Metal supported silica based catalytic membrane reactor assembly
US9745191B2 (en) 2011-04-11 2017-08-29 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
US10071909B2 (en) 2011-04-11 2018-09-11 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
US10093542B2 (en) 2011-04-11 2018-10-09 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
US10252910B2 (en) 2011-04-11 2019-04-09 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
US10252911B2 (en) 2011-04-11 2019-04-09 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic systems

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