WO2010100432A2 - Technologie de scellement - Google Patents

Technologie de scellement Download PDF

Info

Publication number
WO2010100432A2
WO2010100432A2 PCT/GB2010/000395 GB2010000395W WO2010100432A2 WO 2010100432 A2 WO2010100432 A2 WO 2010100432A2 GB 2010000395 W GB2010000395 W GB 2010000395W WO 2010100432 A2 WO2010100432 A2 WO 2010100432A2
Authority
WO
WIPO (PCT)
Prior art keywords
alloy
ceramic
seal
range
oxide
Prior art date
Application number
PCT/GB2010/000395
Other languages
English (en)
Other versions
WO2010100432A3 (fr
Inventor
Jinsong Zhang
Chuanyong Hao
Zhenglin Li
Xianfeng Mao
Jichun Chen
Chunhai Jiang
Original Assignee
Institute Of Metal Research, Chinese Academy Of Sciences
Bp Alternative Energy International Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/CN2009/000239 external-priority patent/WO2010099633A1/fr
Priority claimed from PCT/CN2009/000241 external-priority patent/WO2010099635A1/fr
Priority claimed from PCT/CN2009/000240 external-priority patent/WO2010099634A1/fr
Application filed by Institute Of Metal Research, Chinese Academy Of Sciences, Bp Alternative Energy International Limited filed Critical Institute Of Metal Research, Chinese Academy Of Sciences
Publication of WO2010100432A2 publication Critical patent/WO2010100432A2/fr
Publication of WO2010100432A3 publication Critical patent/WO2010100432A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
    • C04B37/005—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of glass or ceramic material
    • 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
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/062—Tubular membrane modules with membranes on a surface of a support tube
    • B01D63/065—Tubular membrane modules with membranes on a surface of a support tube on the outer surface thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/003—Membrane bonding or sealing
    • 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
    • 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
    • B01D71/0223—Group 8, 9 or 10 metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006—Ag as the principal constituent
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
    • C04B37/006—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of metals or metal salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/04—Specific sealing means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/02—Iron or ferrous alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/02—Iron or ferrous alloys
    • B23K2103/04—Steel or steel alloys
    • B23K2103/05—Stainless steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/18—Dissimilar materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
    • B23K2103/52—Ceramics
    • 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
    • C01B2203/0405—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—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
    • 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
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • 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
    • C01B2203/0495—Composition of the impurity the impurity being water
    • 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
    • C01B2210/0046—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/06—Oxidic interlayers
    • C04B2237/062—Oxidic interlayers based on silica or silicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/06—Oxidic interlayers
    • C04B2237/064—Oxidic interlayers based on alumina or aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/10—Glass interlayers, e.g. frit or flux
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
    • C04B2237/125—Metallic interlayers based on noble metals, e.g. silver
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/343—Alumina or aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/405—Iron metal group, e.g. Co or Ni
    • C04B2237/406—Iron, e.g. steel

Definitions

  • This invention relates to seals between metal and ceramic surfaces, more specifically, but not exclusively, to seals that can be used in hermetically joining a ceramic material used in selective separation, or as a support for a selective separation membrane, with a metallic surface.
  • seals between metal and porous ceramic surfaces are described.
  • the composition of the membrane depends on its application.
  • the porous properties of the zeolite are responsible for the separation, the pores being large enough to allow transport of water through the porous structure, while being too small to allow ingress of alcohol molecules.
  • non-porous ceramic membranes separate oxygen by allowing the transport of oxide ions through the ceramic structure, while simultaneously allowing transfer of electrons to enable charge neutrality across the membrane to be maintained.
  • a non-porous palladium film deposited on a ceramic support acts as a selective hydrogen-permeable membrane.
  • the membrane In the practical application of a selectively permeable membrane, the membrane typically needs to be attached to a reactor or separation vessel, which is usually of metallic construction, for example iron, steel or stainless steel.
  • a reactor or separation vessel which is usually of metallic construction, for example iron, steel or stainless steel.
  • a means of securely attaching the ceramic membrane material or support to the metallic vessel is required.
  • the attachment must be made hermetically so as to prevent leakage of undesired components which would reduce the selectivity of the separation process for which the membrane is used.
  • the attachment of porous ceramic surfaces including a membrane layer to a metallic support can be for example realised by mechanical sealing and metallurgical sealing.
  • a joint obtained from mechanical sealing is likely to show poor gas tightness after a few thermal cycles.
  • Metallurgical sealing for example glass sealing and brazing, can in some examples produce a high quality joint between ceramic membrane and metal supports.
  • WO 2007/054462 describes a process for producing a high temperature ceramic to metal seal, comprising preparing and densifying a pre-form made from 10-90% of a glass mixture and 10-90% of at least one ceramic, which is placed between the metal and ceramic surfaces to be joined and heated to provide the seal.
  • Another method of sealing ceramics to metals is to use a brazing method in which a metal or alloy filler can provide an effective join to the metal, and also to the ceramic.
  • the alloy filler In order to be effective, the alloy filler must have good so-called "wettability" properties, in that it can at least partially interact or react with the ceramic surface.
  • the metallization of the ceramic surface can be used to improve the wettability of the filler material on the ceramic surface.
  • GB 1,151,473 describes a method of sealing a ceramic with a refractory metal in which a non-porous layer of molybdenum and/or tungsten is deposited on a ceramic surface and brazed to provide a bond between the refractory metal surface and the coated ceramic surface.
  • Ruthenium-molybdenum and rhodium molybdenum alloys are stated to have good wettability characteristics.
  • an assembly comprising a first ceramic material, a second ceramic material and a metallic surface, in which the first ceramic material is joined to or sealed with the second ceramic material, and a surface of the first ceramic material is joined to or sealed with the metallic surface.
  • first and second ceramic material By providing a first and second ceramic material, an improved seal or join between the metal surface and the ceramic surface can be obtained.
  • the first ceramic can be chosen having properties favourable to forming a joint or seal with the metal, while second ceramic can have different properties favourable to other requirements.
  • thermal stress induced by the mismatch of linear thermal expansion coefficients of surfaces joined or sealed together can greatly lower the stability of the joint or seal.
  • the second ceramic material may have a higher porosity and/or lower density than the first ceramic material.
  • high porosity and/or low density ceramic materials can be preferred in view of their properties for example for use in a selectively permeable membrane
  • high porosity materials can be disadvantageous in some examples in relation to providing a good seal.
  • the joining of a porous ceramic material to metal using conventional brazing methods can be very difficult.
  • the joint though displaying a good appearance, can show microcracks even after a single thermal cycle to 45O 0 C. Gas leakage can therefore occur at the boundary between the ceramic and the braze alloy. Without wishing to be bound by any particular theory, it is thought that this leakage can be commonly ascribed to the relatively brittle surface of a high porosity ceramic and a large mismatch of the linear thermal expansion coefficients between the metal and the ceramic.
  • the first ceramic may be an alumina.
  • the first ceramic may have a surface area of less than 100 m 2 g '1 and/or a density in the range of from 3.0 to 4.1 g mL "1 at 2O 0 C.
  • a surface of the first ceramic which is joined or sealed with the metal surface has a surface area and/or density within the stated ranges.
  • the second ceramic may have a surface area of 100 m 2 g "1 or more and/or a density in the range of from 0.6 to 1.4 g mL "1 at 2O 0 C.
  • the first ceramic is preferably joined to or sealed to the second ceramic with an oxide seal.
  • the oxide seal may for example include oxides of Ca and/or Ba, Si and Al, and further may include oxides of one or more of Zn, B, Li, As 5 Zr and/or Ti.
  • An example of an oxide comprises BaO and/or CaO in the range of from 20 to 50 wt%, SiO 2 in the range of from 20 to 70 wt%, Al 2 O 3 in the range of from 1 to 25 wt%, ZnO, B 2 O 3 , Li 2 O 3 , As 2 O 3 , each being in the range of from 1 to 15 wt% or in a total amount of from 1 to 15 wt%, and/or ZrO and/or TiO 2 content in the range of from 10 to 30 wt%.
  • the first ceramic or second ceramic may comprise a selectively permeable membrane.
  • the selectively permeable membrane may for example be selectively permeable to hydrogen, water or oxygen.
  • the selectively permeable membrane may have one or more further features as described herein.
  • an apparatus comprising a metal, a first ceramic, and an alloy seal, in which the alloy seal is in contact with the surface of the metal and the surface of the first ceramic, in which the alloy seal has a composition as any one of the alloy compositions described herein.
  • an apparatus comprising a first surface, a second surface and an alloy seal, in which the alloy seal is an alloy as any one of the alloys described herein.
  • Also provided by an aspect of the invention is a process for preparing a seal between a metal and first ceramic surface, which process comprises applying an alloy seal between the two surfaces and heating to a temperature above the melting temperature of the alloy, which alloy is an alloy as any one described herein.
  • the heating may be carried out under vacuum or under an inert atmosphere.
  • the heating temperature may be in the range of from 45O 0 C to 1400 0 C.
  • Also provided by the invention is a process for separating a component from a fluid mixture comprising the component, which process comprises contacting the fluid mixture with any one of the seal arrangements or other apparatus described herein, which apparatus or arrangement comprises a membrane that is selectively permeable to the component, wherein the component permeates the membrane.
  • the component may be hydrogen
  • the membrane may be for example palladium or an alloy of palladium with silver and/or copper.
  • a further aspect of the invention provides An assembly comprising a metal, a ceramic and an alloy seal, in which the alloy seal is in contact with the surface of the metal and the surface of the ceramic, and in which the alloy composition comprises Ag and Cu, the alloy additionally comprising an element X, where X is Al and/or Pd, wherein the ceramic comprises a selectively permeable membrane.
  • a further aspect of the invention provides an assembly comprising a porous ceramic, a low porosity ceramic, and a seal, the porous ceramic having a higher surface area than the low porosity ceramic, and the seal being in contact with the surface of the porous ceramic and the surface of the low porosity ceramic, wherein the seal comprises an oxide composition comprising, in addition to oxygen, Al, Ca and Si, and further comprising one or more of Ba, Zr, Ga, Zn, B, Li, As and Ti.
  • an alloy composition comprising Ag and Cu, characterised by the alloy additionally comprising an element X, where X is Al and/or Pd.
  • Copper is typically present in the alloy in an amount of from 10 to 50 wt%, preferably 20 to 40 wt%, for example 25 to 30 wt%.
  • the Al content is typically in the range of from 0.1 to
  • the Pd content is typically in the range of from 0.1 to 20wt%, for example 0.5 to 10wt%, such as 2 to 8 wt%.
  • balance silver preferably comprising 80wt% or more of the balance.
  • Titanium is also present in the alloy, preferably in an amount of from 0.1 to 20 wt%, for example 1 to 10wt%, such as 2 to 8 wt%.
  • the alloy consists of Ag, Cu, Ti and X, where X is Al and/or Pd, and comprises for example from 25 to 30 wt% Cu, from 2 to 8 wt% Al, from 2 to 8wt% Pd, from 2 to 8 wt% Ti, the balance being silver.
  • the alloy comprises 5wt% Ti, 27wt% Cu, 5wt% Al and 63wt% Ag.
  • an alloy composition comprising Ag, Pd, Ti, wherein the alloy additionally comprises an element X where X is one or more of Cu, Al, and Mn.
  • the titanium content may be in the range of from 1 to 10 wt%.
  • the copper content where copper is present may be in the range of from 0.1 to 30 wt%.
  • the aluminium content where aluminium is present may be in the range of from 0.1 to 10 wt%.
  • the manganese content where manganese is present may be in the range of from 0.1 to 15 wt%.
  • the alloy includes Pd 20-30 wt%, Ti 1-10 wt%, Cu 0.1-30 wt%, Al 0.1-10 wt%, Mn 0.1-15 wt% .
  • the alloy can be placed between a ceramic and a metallic surface which, after melting and setting, provides a hermetic seal that effectively prevents fluids permeating between the metal and ceramic surfaces.
  • a hermetic seal is meant that the seal is able to prevent greater than 99.50%, preferably greater than 99.90%, and even more preferably greater than 99.99% of a fluid or mixture of fluids permeating through the seal under operating conditions.
  • the alloy of the present invention has good wettability properties for the ceramic, and is able to interact or react effectively with the ceramic material to provide a strong adherence thereto, and is also able to adhere well to a metallic surface, which thus enables an effective seal between a metallic and ceramic surface to be achieved.
  • the seal can be formed by using techniques such as brazing, preferably under inert atmosphere, such as a nitrogen and/or argon atmosphere or under vacuum.
  • a reducing atmosphere is used, such as a hydrogen-containing atmosphere, in which the atmosphere can be pure hydrogen, or optionally hydrogen diluted by an inert gas, such as nitrogen or argon, for example as a mixture of 20% by volume or less in inert gas.
  • additives or fillers are used to help reduce any oxidation, a typical example being borax.
  • Another advantage of the alloy of the present invention is that it can act as an effective seal between a metal and ceramic, and can remain effective at high temperatures. It is also chemically resistant, for example to oxidation. This is important where the seal is in contact with oxidising environments, for example when in contact with oxygen- containing gases or high temperature steam.
  • the alloy of the present invention can be used to prepare a seal between two surfaces, where the sealed surfaces are to be used in high temperature applications.
  • the alloy and alloy seal are stable, for example, under sustained temperatures of up to 700 0 C, for example up to 65O 0 C, preferably up to 600 0 C, most preferably up to 55O 0 C.
  • the alloy can be prepared by melting together the constituent elements in the desired ratio, and then cooling the resulting melt. Cooling can be passive, for example by allowing the melt to cool gradually to ambient temperatures by removing the source of heat, or removing the melt from the heat source. Alternatively, a rapid quenching method can be used, for example by contacting the melt with a cooled surface, such as a water-cooled copper surface as described in US 4,678,720. Melting is usually conducted under an inert atmosphere, for example under an argon atmosphere, to prevent oxidation. In one embodiment, inductive melting is used to melt the metals forming the alloy.
  • an alloy seal can be made between a metal surface and ceramic surface which are to be joined and sealed.
  • a brazing technique is used. Brazing is a joining process in which an alloy is heated to a melting temperature, typically 45O 0 C or more, which enables melted alloy to penetrate the gap between two surfaces. On cooling, the alloy solidifies, sealing the gap. The high temperatures typically involved in brazing often cause alloying to take place between the alloy seal and the metallic surface which is being joined or sealed, which contributes to the high strength and stability of the seal.
  • the alloy to be used as the sealing material will have a lower melting point than the surfaces to be joined.
  • the alloy compositions can be used to provide a seal where at least one of the surfaces is a metallic surface with a greater melting point than the alloy seal, for example iron, steel, and stainless steel.
  • the melting point of the alloy is typically in the range of from 45O 0 C to 1400 0 C, for example in the range of from 600 to 1200 0 C or 850 to HOO 0 C.
  • the alloy is particularly suitable for providing a seal between a metallic surface and a ceramic surface.
  • the ceramic can be porous or non-porous.
  • alumina can be prepared in a porous form, with surface areas of 100 m 2 g '1 or more, for example in the range of from 100 to 300m 2 g "1 .
  • Such forms of alumina generally have a bulk density in the range of from 0.6 to 1.4 g/mL at 2O 0 C.
  • Alumina can also exist in a higher density and lower porosity form.
  • Such high density, low porosity alumina can be prepared by sintering porous, lower density alumina at temperatures in the range of from 1500 to 2000°C, for example in the range of from 1650 to 175O 0 C.
  • the resulting sintered alumina has a density typically in the range of from 3.0 to 4.1 g/mL at 2O 0 C, for example in the range of 3.5 to 4.0 g/mL at 2O 0 C.
  • Surface areas of such materials tend to be less than 100m 2 g "1 , for example less than 50m 2 g *1 , or 20m 2 g '1 .
  • the ceramic is a low porosity ceramic.
  • the surface of high porosity ceramics can be quite loosely bound, and hence can become detached from the bulk relatively easily. Thus, although a seal may be strong, the ceramic surface may be prone to cracking or flaking, thus reducing the effectiveness of the seal.
  • the structure can weaken further when exposed to cycling of high and low temperatures. With lower porosity ceramics, the surface tends to be more strongly bound to the bulk of the material, which makes a seal stronger and less prone to degradation during temperature cycling.
  • the alloy of the present invention is particularly suitable for providing a seal between a metallic surface, and the surface of a low porosity ceramic material, for example a ceramic material having a surface area of less than 100 m 2 g ⁇ ', preferably less than 50 m 2 g ⁇ ', more preferably less than 20 m 2 g * '.
  • the linear thermal expansion coefficient of the alloy is typically in the range of from greater than 5 xlO "6 to less than 20 x 10 "6 m m “1 K “1 at 2O 0 C, and preferably in the range of from greater than 7 x 10 "6 to less than 20 x 10 '6 m m “ ' K “1 at 2O 0 C, for example in the range of from 13 x 10- 6 to 19 x 10 "6 m m "1 K "1 at 2O 0 C.
  • the alloy can be used as a seal between a metal and a ceramic surface.
  • the metal surface can itself be an alloy, for example steel, stainless steel or other iron-containing alloys, for example iron-chromium alloys.
  • stainless steels include those comprising one or more of Cr Ni and Ti (in addition to Fe), such as 1 Cr 18Ni9Ti steel comprising 18wt% Cr, 9wt% Ni, ⁇ 0.8wt% Ti, ⁇ 0.12wt%C, the balance being iron.
  • This material mainly adopts the austenite structure.
  • the metal surface is chosen so as to minimise the differences in the linear thermal expansion coefficient and the ceramic, while maintaining its integrity to perform its own function, for example as a support for attaching the ceramic to a reactor or other vessel.
  • the surface is a lCrl3 martensite steel (comprising ⁇ 0.15wt%C, 13wt% Cr, the balance being iron, and being mainly of martensite structure), which has a relatively low linear thermal expansion coefficient (12 x 10 "6 m m “1 K “1 at 20°C),compared to stainless steels with the austenite structure while maintaining physical and chemical resistance at high temperatures.
  • the metal can be 4J33, which has a composition of 33 wt% Ni,
  • the ceramic is sealed to a low expansion metal, for example 4J33 steel, which in turn is attached to a higher expansivity metal, for example a lower cost steel that is used in or forms part of a reactor or other vessel.
  • a low expansion metal for example 4J33 steel
  • a higher expansivity metal for example a lower cost steel that is used in or forms part of a reactor or other vessel.
  • a process for producing an alloy seal between a first material and a second material which alloy comprises preliminary alloy metals and a further alloy metal
  • which process comprises applying to the gap between surfaces of the first and second materials the further alloy metal, and a preliminary alloy comprising the preliminary alloy metals, and heating the further metal, the preliminary alloy and the first and second materials to a temperature below the melting temperature of the first and second materials, and above the melting temperature of the preliminary alloy.
  • an alloy seal comprising preliminary alloy metals and a further alloy metal (optionally more than one further alloy metal), can be prepared in situ during seal formation, for example during brazing, in which the preliminary and further alloy metals are separately applied to the gap between the surfaces of the two materials to be joined or sealed.
  • the preliminary alloy metals are preferably themselves applied in the form of an alloy, herein a "preliminary alloy", such that the melting temperature of the preliminary alloy is lower than that of the two materials to be sealed.
  • the seal can be formed by heating to a temperature above the melting point of the preliminary alloy, but below the melting temperature of the materials forming the first and second surfaces, for example through brazing at temperatures of 45O 0 C or more, and typically 1400 0 C or below, for example 1200 0 C or below.
  • the method of the present invention is useful where one or more of the further alloy metals has a melting point above that of one of the materials to be joined or sealed.
  • one of the materials is iron, steel, stainless steel or some other alloy of iron
  • titanium can be a further alloy metal (melting point of titanium is
  • the first and the second material can be the same or different.
  • the sealing method is particularly suitable for providing a seal between a ceramic material and a metallic material, the ceramic preferably being a low-porosity ceramic, for example having a surface area of less than 100 m g "1 , preferably less than 50 m g " , more preferably less than
  • the ceramic surface can be, for example, a low-porosity, high density refractory oxide, such as sintered alumina as described above.
  • the metal can be iron or an alloy thereof, for example steel or a grade of stainless steel. The further alloy metal can be applied to one of the surfaces to be joined or sealed.
  • this can be achieved by sputtering the further alloy metal thereon.
  • a foil of the further alloy metal can be used, which can be pressed against one of the surfaces or placed between the two surfaces to be sealed.
  • the layer should be thick enough to ensure sufficient metal is available to form the alloy, while being thin enough to ensure that the desired alloy can be created across the thickness of the layer.
  • the thickness of the further alloy metal is typically 20 ⁇ m or less, and 1 ⁇ m or more, for example in the range of from 1 to 20 ⁇ m or preferably 2 to 10 ⁇ m.
  • An advantage of the method of the present is that it is a relatively simple process to form an alloy comprising a high melting temperature metal, and also enables an effective alloy seal to be prepared in situ, which reduces the complexity of the sealing process.
  • the brazing time is dependent on the individual alloy, but is typically in the range of from 1 minute to 16 hours, for example in the range of from 1 minute to 1 hour.
  • the alloy is an alloy as described above in relation to an aspect of the present invention, and comprises Ti, Ag, Cu and Al.
  • Ti is the further alloy metal.
  • Ti foil (as the further alloy metal) is placed in the gap between the two surfaces to be sealed, for example a ceramic surface, such as a low porosity, high density alumina as herein described, and a metal surface, such as iron, steel or a stainless steel.
  • the preliminary alloy comprising Ag, Cu and Al as the preliminary alloy metals, is also applied to the gap between the two surfaces, and heating is carried out to enable the seal to be formed, typically through brazing.
  • the preliminary alloy melts, enters the gap between the two surfaces (for example through capillary action) either on one side of the further alloy metal foil or both sides.
  • the titanium (as the further alloy metal) and the preliminary alloy combine to produce the desired alloy incorporating the Ti during the heating or brazing process.
  • the further alloy metal is coated onto one or both of the surfaces to be joined, for example by sputtering.
  • the preliminary alloy can be applied between the gap, and heated as previously described.
  • an alloy can be prepared by applying one further alloy metal layer on one of the surfaces to be joined, and a different further alloy metal layer on the other surface, before applying the preliminary alloy before heating or brazing.
  • an alloy composition as a seal.
  • assemblies and apparatus described can be made using one or more of the method features indicated above.
  • membranes for example those used for the purposes of selective separations
  • the membrane material itself is often advantageous for the membrane material itself to be very thin, not least because a thinner membrane generally proffers improved separation kinetics.
  • thin membranes are often fragile and not capable of being self-supported, they are often deposited onto a porous support, for example a porous ceramic support such as alpha- alumina. This provides the mechanical strength required for the membrane to maintain its integrity, while the porosity allows components to flow to and from the membrane.
  • a ceramic membrane or ceramic membrane support is to be connected to a metallic vessel, there remains a need for a metal to ceramic connection of improved stability, in particular improved stability to high temperatures and to thermal cycling.
  • an apparatus comprising a metal, a first ceramic which is porous and a second ceramic with lower porosity than the first ceramic, in which the second ceramic is sealed to the first ceramic by a first seal, and the metal is sealed to the second ceramic by a second seal.
  • the first seal is an oxide seal
  • the second seal is an alloy seal.
  • the seals are hermetic.
  • the process of creating the seal typically involves melting the alloy and allowing it to re-solidify.
  • the molten alloy at least partially reacts with the ceramic surface, which enables the join or seal to be made.
  • the alloy itself partially alloys with the metallic surface to which the ceramic surface is to be joined, which also provides a strong bond or seal.
  • the bond between the alloy and a porous ceramic surface can be quite unstable when subjected to thermal cycling, which is exacerbated where there are imperfections in the ceramic surface.
  • metals and ceramics often have very different thermal expansion coefficients, there is still a large amount of stress on the alloy joint or seal when it is exposed to high temperature conditions, or conditions of thermal cycling.
  • the ceramic material comprises compressed particles of ceramic, typically associated with low density ceramics, such as porous alumina membrane support tubes, the mechanical integrity of the ceramic material itself can be quite low, which also can suffer damage when thermal stresses are applied.
  • a broad aspect of the invention provides the sealing or joining of a ceramic to a metal, in which a dense ceramic, preferably dense alumina, is provided between the ceramic and the metal, for example as a transition layer.
  • the dense ceramic preferably has a lower porosity than the ceramic to be joined to the metal.
  • the invention also provides the use of a low porosity ceramic as a sealing or joining element between a ceramic and a metal to be sealed or joined together.
  • the seal between the first and second ceramic materials can be achieved using an oxide seal, such as a mixed oxide seal.
  • the oxide is often in the form of a glass, preferably one in which there is an even or homogeneous distribution of the different elements of the oxide. Oxides can provide strong seals between two ceramic surfaces, and are effective in preventing passage of fluid compositions (i.e. are hermetic), and also are more resistant to degradation from thermal effects.
  • the low porosity ceramic (second ceramic) preferably has a thermal expansion coefficient similar to that of the high porosity ceramic (first ceramic). This is advantageous in that thermally-induced stresses between the joined and/or sealed ceramic surfaces are reduced or minimised.
  • the low porosity ceramic surface is capable of withstanding thermal expansion differences between it and a metallic surface or support to which it may be attached.
  • the first and second ceramic can be selected from alumina, silica, zirconia, hafnia, titania, magnesia, any lanthanide oxide, or combinations of two or more thereof.
  • the surface area of the first ceramic is typically lOOrt ⁇ g "1 or more, for example in the range of from 100 to 1000m 2 g " ', such as 100 to 300m 2 g ⁇ '.
  • the second ceramic generally has a surface area of less than 100m 2 g " ', for example less than 50m 2 g " ', such as less than 20m 2 g ⁇ '.
  • the first and second ceramic can be of the same or different compositions.
  • the first ceramic can be porous alumina, with a surface area of 100m 2 g '1 or more, for example in the range of from 100 to 300m 2 g "1 , with a typical density in the range of from 0.6 to 1.4 g/mL (at 2O 0 C)
  • the second ceramic can be a sintered alumina, with a surface area of less than 100 m 2 g "J , for example less than 50 m 2 g "! , such as less than 20 m 2 g " ', and having a typical density in the range of from 3.0 to 4.1 g/mL, for example 3.5 to 4.0 g/mL (at 20 0 C).
  • the second seal i.e. the seal between the second ceramic and the metal
  • the alloy is an alloy as herein described in relation to an aspect of the present invention.
  • the first seal i.e. between the first ceramic and the second ceramic, is preferably in the form of an oxide.
  • the oxide is in the form of a glass, in which there is little or no long-range crystalline structure, but wherein the elements in the oxide are evenly distributed.
  • the seal is created by applying oxide sealing material, for example as glass granules, powder or beads, in the gap between the first and second ceramic surfaces, and heating to high temperature, for example temperatures in the range of from 800 to 2000 0 C.
  • the temperature should be lower than the sintering temperature of the first ceramic, for example a temperature of 1500 0 C or lower and/or 1000 0 C or more, such as in the range of from 1000 to 1500 0 C or 1100 to 1400 0 C.
  • Producing the seal does not require an inert atmosphere, although one can be used if desired.
  • As the formation of the oxide (first) seal is usually conducted at higher temperatures than those used for producing the second (alloy) seal, it is usually advantageous to prepare the first seal before the second seal, to prevent excessive temperatures affecting the stability and integrity of the second seal.
  • the metal is preferably chosen from those that melt at higher temperatures than the alloy seal material.
  • the melting point of the metal is preferably greater than about 1200 0 C. Examples include alloys of titanium, alloys of nickel, iron, steel, stainless steel and other alloys of iron.
  • the alloy seal can be an alloy as herein described in relation to an aspect of the present invention.
  • the alloy seal may be an alloy of for example copper, silver, titanium and/or other metal.
  • the first ceramic supports a membrane that is used for selectively separating one or more compounds from a fluid mixture.
  • the membrane can be a zeolite, for example for example zeolite 3 A or 4 A as used in removing water from organic liquids, such as a mixture of water with one or more alcohols such as C 1 to C 4 alcohols.
  • the membrane can be palladium, optionally additionally comprising silver and/or copper, which can be useful in the selective separation of hydrogen from a gaseous mixture, for example a mixture additionally comprising one or more of CO, CO 2 , nitrogen, water, oxygen and one or more hydrocarbons such as one or more Ci to C 6 hydrocarbons.
  • the membrane can be a selective oxygen separation membrane, having a composition comprising electronic and oxide conducting properties, for example an oxide with both electronic and oxide conducting properties, or a composite of different oxides having separate oxide conducting and electronic conducting properties, and which is capable of separating oxygen from a mixture of gases, for example those additionally comprising hydrogen, nitrogen, water, CO, CO 2 and one or more hydrocarbons, such as one or more Ci to Ce hydrocarbons.
  • a composition comprising electronic and oxide conducting properties for example an oxide with both electronic and oxide conducting properties, or a composite of different oxides having separate oxide conducting and electronic conducting properties, and which is capable of separating oxygen from a mixture of gases, for example those additionally comprising hydrogen, nitrogen, water, CO, CO 2 and one or more hydrocarbons, such as one or more Ci to Ce hydrocarbons.
  • Examples of compositions that can be used in the selective separation of oxygen from a mixture of gases or other fluids comprising oxygen are described in WO 2008/074181.
  • the apparatus described herein can be part of a larger apparatus, for example
  • the metal can be joined, for example through brazing or welding, to a metallic vessel wall.
  • the vessel can be a separation vessel, for example for allowing selective separations using a selectively permeable membrane, the membrane being on the first ceramic.
  • the vessel is a combined reactor and separation vessel, in which a chemical reaction takes place in the reactor, and one or more products are separated by the selectively permeable membrane.
  • the membrane may be a palladium membrane (or a Ag and/or Cu-modified palladium membrane) deposited on the first ceramic, e.g. porous alumina, which enables hydrogen produced in a reaction to permeate across the membrane.
  • the reaction can be catalysed, the reactor on one side of the membrane having a catalyst.
  • the reaction is the steam reforming, autothermal reforming or partial oxidation of a hydrocarbon.
  • the first seal typically has a thermal expansion coefficient that is similar to those of the first and second ceramics in order to reduce stresses to the seal during thermal cycling.
  • the first seal has a linear thermal expansion coefficient in the range of from 6 ⁇ lO "6 to lOxlO "6 m m "1 K "1 .
  • the first seal comprises one or more OfAl 2 O 3 , CaO and SiO 2 .
  • an oxide composition comprising, in addition to oxygen, Al, Ca and Si, characterised by the composition further comprising one or more of Ba, Zr, Ti, B, Li and Ga.
  • the oxide composition comprises, in addition to oxygen, Ba, Ca, Al and Si, one or more of B, Ti, Zr, Li and Ga.
  • an oxide composition including CaO, Al 2 O 3 and SiO 2 and further including one or more OfB 2 O 3 , TiO 2 and oxides of Zr, Li and Ga.
  • an oxide composition including B 2 O 3 , CaO, Al 2 O 3 and SiO 2 and further including oxides of one or more of Ti, Zr, Li and Ga.
  • aspects of the invention provide the modification OfCaO-Al 2 O 3 -SiO 2 glass by the presence of B 2 O 3 , TiO 2 and/or other oxides, for example oxides of B, Zr, Li and/or Ga.
  • aspects of the invention provide the modification Of B 2 O 3 -CaO-Al 2 O 3 -SiO 2 glass by the presence of TiO 2 and/o other oxides, for example oxides of Zr, Li and/or Ga.
  • Glass seals made using the above composition and/or other compositions described hereinby can be effective for joining and/or sealing two ceramic surfaces together.
  • At least some of the compositions may be produced by mixing together separate oxides, and then heating to high temperature, typically at temperatures in the range of from 800 to 2000 0 C.
  • the temperature should be lower than the sintering temperature of the first ceramic, for example a temperature of 1600 0 C, 1500 0 C or lower, while ensuring that the oxides are in a molten state, such as at temperatures of 1000 0 C or more.
  • Temperatures in the range of from 1000 to 1500 0 C or 1600 0 C are preferred, for example in the range of from 1400 to 1600 0 C or 1500 0 C.
  • the composition is an oxide, and typically comprises a homogeneous distribution of the non-oxygen elements.
  • the presence of one or more of Ba, Ga , Ti, B, Li and Zr in the Al, Ca and Si mixed oxide enables control over the fluidity, wettability and linear thermal expansion coefficient of the glass to be achieved, without negatively affecting the stability, chemical resistance and effectiveness when used as a seal between a first and a second ceramic surfaces.
  • the composition of the seal composition when used as a (first) seal between a first and second ceramic surface, is in the range of from 30 to 60wt% BaO, ZrO 2 and/or Ga 2 O 3 (combined total where more than one of these are present), in the range of from 1 to 15wt% CaO, in the range of from 1 to 1 Owt% Al 2 O 3 , and in the range of from 20 to 40wt% SiO 2 .
  • the oxide composition comprises BaO, and in one embodiment the oxide composition comprises BaO and ZrO 2 .
  • the BaO content of the oxide can in one embodiment be in the range of 30 to 40 wt%.
  • the ZrO 2 content of the oxide can in one embodiment be up to 15wt%, for example in the range greater than 0 to 15wt%, such as 1 to 15wt%.
  • At least some of the oxide compositions described herein can be prepared by heating together the different oxide components to form a melt, and quenching the melt to form a glass comprising a mixture of the constituent oxides.
  • the heated oxide mixture or melt is in some examples preferably rapidly cooled or quenched. This can have the advantage of preventing the different oxide components from separating out as separate oxide phases, which helps improve homogeneity of the composition and reduces the chances of defects and loss of sealing effectiveness. Rapid quenching can be achieved by contact with cold water, for example by submerging in water. In some cases the method may include spraying water onto the heated mixed oxides.
  • the mixed oxide glass composition can be applied (typically in powdered or bead form) to the gap between the first and second surfaces, and heating to above the melting temperature of the mixed oxide glass, for example in the range of from 800 to 2000 0 C, for example a temperature of 1500 0 C or less, and/or 1000 0 C or more, for example in the range of from 1000 to 1500 0 C, such as a temperature in the range of from 1400 to 1500 0 C, or preferably 1100 to 135O 0 C.
  • an apparatus comprising a metal surface sealed to a porous ceramic surface can be used to support a selectively permeable membrane.
  • the selectively permeable membrane is able to allow the selective permeation of a component in a fluid mixture comprising that component.
  • the membrane is palladium, or palladium modified with Cu and/or Ag. This is able to separate hydrogen from a fluid mixture comprising hydrogen, such as a mixture of hydrogen with one or more of carbon monoxide, carbon dioxide, oxygen and water.
  • the art-skilled person is aware of how to prepare a palladium membrane supported on a porous ceramic.
  • An example of one such method is described in WO 2005/065806, in which a porous ceramic support, such as alumina, is treated with a solution of a palladium salt, such as aqueous Pd(NH 3 ) 2 Cl 2 , in the presence of a reducing agents such as hyrdazine.
  • a palladium salt such as aqueous Pd(NH 3 ) 2 Cl 2
  • a reducing agents such as hyrdazine.
  • the art-skilled person is also aware of how to operate a supported palladium membrane for separating hydrogen from a hydrogen-containing mixture. Examples of such processes are described in WO 2007/129024 and WO 2007/031713.
  • a zeolite membrane for separating water from organic liquids.
  • the zeolite is one with the LTA structure (according to the database of zeolite structures published by the International Zeolite Association), such as silicalite or zeolite-A, e.g. Zeolite 3 A or 4 A (which comprise potassium and sodium cations respectively to balance the negative charge of the zeolite framework).
  • the zeolite membrane can be produced and used to dewater an organic liquid, typical examples being an alcohol, an ester or a mixture of two or more alcohols and/or esters.
  • a method of making a supported zeolite membrane, and its use in alcohol dewatering is exemplified in EP-A-I 980 314, which describes the treatment of a porous support pre-treated with silica and optionally also zeolite-A crystals as crystal nucleation centres, with an aqueous zeolite-A synthesis gel.
  • organic liquids which, when additionally comprising water, can be dried or dewatered using zeolite membranes, for example zeolites with LTA structure include one or more Ci to C 4 alcohols, for example ethanol, isopropanol, or a mixture Of C 2 to C 4 alcohols.
  • the method of separating water from an organic liquid using a selectively permeable membrane is often termed pervaporation.
  • the membrane, the membrane support (i.e. the first, porous ceramic), and the metal to which the first ceramic is sealed (for example via a low porosity ceramic as herein described), are attached to a reactor or vessel wall.
  • the vessel comprising the selectively permeable membrane can be considered to have two zones; a first zone on one side of the membrane, and a second zone on the other side of the membrane.
  • the first zone relates to the zone having the mixture of fluids comprising the component to be selectively separated
  • the second zone relates to the zone into which the selectively separated component enters after permeating the membrane.
  • the mixture of fluids is a mixture of one or more alcohols with water
  • the wet alcohol mixture in gaseous or liquid form
  • water selectively permeates through the membrane into the second zone, leaving an alcohol-rich mixture that can be removed from the first zone.
  • the mixture of fluids is a gaseous mixture comprising hydrogen, such as when in combination with one or more of water, oxygen, carbon monoxide, carbon dioxide and one or more hydrocarbons, for example a gaseous mixture produced from the steam reforming, autothermal reforming or partial oxidation of a hydrocarbon, such as methane or natural gas.
  • the gaseous mixture is fed to the first zone of the separation vessel, hydrogen permeates the selective permeable membrane (typically a Pd membrane, or Pd modified with Ag and/or Cu) into the second zone, leaving a hydrogen deficient mixture in the first zone.
  • membrane separation processes are typically continuous processes, where a mixture of fluids is constantly fed to the first zone of a separation vessel and a mixture deficient in the separated component (or components where applicable) is removed from the first zone, while the component to be separated permeates the membrane into the second zone of the vessel, from which it is removed.
  • a vacuum can be used, or a sweep or flush gas to flush the permeated component therefrom.
  • the component to be separated is generated in situ in the first zone of the separation vessel.
  • hydrogen can be generated by the steam reforming, partial oxidation and/or autothermal reforming of one or more hydrocarbons, such as hydrocarbons selected from one or more Ci to C 4 hydrocarbons, typically in the presence of a catalyst.
  • the separation vessel can be a combined reactor/separation vessel, in which the first zone of the reactor is adapted to allow reactants to be fed thereto, to enable a desired component to be produced therein through a chemical reaction, optionally in the presence of a catalyst, and whereby the desired component permeates into the second zone through the membrane, thus separating it from the other reactants and products.
  • WO 2007/129024 and WO 2007/031713 both describe process in which hydrogen is produced in a combined reactor/separation vessel, in which the first zone of the reactor comprises a catalyst for producing hydrogen from a hydrogen-containing compound, wherein the hydrogen permeates a Pd membrane or a Ag/Cu-modified Pd membrane within the reactor into a second zone, while a hydrogen-deficient product stream is removed from the first zone.
  • reactions include a water gas shift reaction, where water and carbon monoxide react to produce hydrogen and carbon dioxide, or the steam reforming, autothermal reforming or partial oxidation of a hydrocarbon feedstock, such as methane or natural gas, to produce hydrogen and one or more of carbon monoxide and carbon dioxide.
  • reaction and membrane separation is advantageous, particularly in a continuous process, because removal of the desired component continually alters the reaction equilibrium, and enables greater yields of the desired component to be produced.
  • An additional benefit is that product is separated from the remaining reactants and any other products, making purification significantly easier.
  • An aspect of the invention provides a process for producing an alloy seal between a metallic surface and a ceramic, which alloy comprises a preliminary alloy and one or more further alloy metals, which preliminary alloy comprises preliminary alloy metals, which process comprises applying the one or more further alloy metals and the preliminary alloy between the surfaces of the metal and the ceramic, and heating to a temperature above the melting temperature of the preliminary alloy to produce the alloy seal.
  • the one or more further alloy metals may have a melting temperature higher than that of the preliminary alloy.
  • the one or more further alloy metals may have a melting temperature higher than that of the first material and second material.
  • the heating may be carried out to a temperature below the melting temperature of the first material and second material.
  • the seal may be produced by heating at a temperature in the range of from 450 to 1400 0 C.
  • the seal may be produced by brazing under vacuum or under an inert atmosphere.
  • Titanium may be a further alloy metal. There titanium is present in the alloy seal, the titanium content may be in the range of from 0.1 to 20wt%.
  • the preliminary alloy may comprise or may consist of one or more of Ag, Cu, Pd and Al.
  • the Cu content of the alloy seal may be in the range of from 10 to 50wt% and/or the Pd content of the alloy may be in the range of from 0.1 to 20 wt% and/or the Al content of the alloy may be in the range of from 0.1 to 20 wt%.
  • One or more of the further alloy metals may be applied to the surface of the first material and/or second material by sputtering.
  • One or more of the further alloy metals may be applied in the form of a foil.
  • the thickness of each of the one or more further alloy metals may be in the range of from 1 to 20 ⁇ m.
  • the ceramic may be an alumina.
  • the ceramic may have a surface area of less than 100m 2 g "1 and/or a density in the range of from 3.0 to 4.1 g mL "1 .
  • the metal may be selected from iron or an alloy thereof.
  • a flux may also be applied between the first material and second material.
  • Figure 1 is a perspective view of a porous ceramic tube joined to a metal pipe via a ring of a lower porosity ceramic ring.
  • Figure 2 is a view the same apparatus as shown in Figure 1 after an approximately 45° anti-clockwise rotation about axis A-A'.
  • Figure 3 is an exploded view of the apparatus shown in Figures 1 and 2.
  • Figure 4 is a more detailed schematic view of a low porosity ceramic ring, as shown in Figures 1, 2 and 3.
  • FIG. 5 is a more detailed schematic view of a low porosity ceramic plug, as shown in Figures 1, 2 and 3.
  • Figure 6 is a cutaway view of an alloy seal prepared from a metal foil and a preliminary alloy.
  • Figure 7 is a longitudinal section through the apparatus illustrated in Figure 6.
  • Figure 8 illustrates an alternative way of sealing a metal with a ceramic, compared to that illustrated in Figures 6 and 7.
  • Figure 9 is a longitudinal section through a separation vessel comprising a membrane supported on a ceramic tube/metal tube apparatus as shown in Figures 1, 2 and 3.
  • Figure 10 is a longitudinal section through a combined reaction and separation vessel incorporating a membrane supported on a ceramic tube/metal tube apparatus as shown in Figures 1, 2 and 3.
  • Figure 11 is an apparatus having a metal to ceramic seal, where the metal is joined to a different metal with different thermal expansion characteristics.
  • Figure 12 is a photograph demonstrating wettability characteristics of an alloy not according to the present invention on a ceramic surface.
  • Figure 13 is a photograph demonstrating wettability characteristics of an alloy according to the present invention on a ceramic surface.
  • Figures 1 , 2 and 3 show how a metal can be sealed to a first ceramic by means of an intermediate object, in this case a small tube or ring, made of a second ceramic, the first ceramic being porous, and the second ceramic having a lower porosity than the first ceramic.
  • Metal tube, 1 , and a tube made from the first ceramic, 2 are both sealed to a ring of the second ceramic, 3.
  • a passage is formed between the interior, 4, of the metal tube 1, the interior, 9, of the first ceramic tube 2 and the interior, 10, of the ring of second ceramic 3.
  • the tube of first ceramic, 2, is sealed at its other end by a plug, 5, which is also made of a low porosity ceramic, typically made from the same ceramic as the ring of second ceramic, 3.
  • the metal tube is a Kovar alloy, for example 4J33 stainless steel
  • the low porosity second ceramic is sintered alumina
  • the porous first ceramic is porous gamma alumina.
  • the metal tube, 1, is joined and sealed to the ring of second ceramic, 3, with alloy, 6.
  • the first ceramic tube, 2, is sealed to the second ceramic ring, 3, by a glass seal, 7.
  • the first ceramic tube, 2, is also sealed to the plug of second ceramic, 5, using a glass seal, 8.
  • one end of the apparatus is closed, by plug 5, in an alternative embodiment both ends can have hollow interiors, for example where plug 5 more closely resembles the ring of second ceramic 3, which can also optionally be attached to a metal tube, typically one that is similar or identical to metal tube 1.
  • Figures 4 and 5 illustrate respectively in further detail the ceramic ring 3 and ceramic plug 5, each of which has a lip (11 and 12 respectively for ring 3 and plug 5) and a protrusion (13 and 14 respectively for ring 3 and plug 5).
  • the protrusion (13 and 14) extends into the interior, 9, of the tube of first ceramic, 2, maintaining contact with the inner wall of the tube of first ceramic when sealed.
  • the lips (11 and 12) contact the top and bottom edges of the tube of first ceramic when sealed.
  • the ring of second ceramic, 3 is shown after 180° rotation about axis B-B', as identified in Figure 3.
  • Oxide seal is typically applied to the portion of the lip (11 and 12) that makes contact with the edges of the porous ceramic tube 2, and/or the portion of the protrusions (13 and 14) that contact the inner surface of the porous ceramic tube 2.
  • Figures 6 and 7 show how an alloy seal can be made using a metal foil (i.e. a foil of the further alloy metal) and a preliminary alloy.
  • the metal foil of further alloy metal, 15, (for example titanium) is inserted into the gap between metal tube, 1 , and the outer and internal surfaces of the ring of second ceramic, 3.
  • the further alloy metal can be sputtered onto the outer and internal surfaces of ceramic tube, 3, or the outer surface of the metal tube, 1, to produce a metallic layer thereon.
  • the preliminary alloy, 16, comprising the preliminary alloy metals, is then placed at the gap between the second ceramic tube, 3, and the metal tube, 1.
  • the desired alloy forming the seal material is then produced by heating, for example by brazing at a temperature of 45O 0 C or more.
  • the alloy seal is prepared using 5wt% titanium foil, and 95wt% of a preliminary alloy comprising Ag, Cu and Al.
  • the preliminary alloy comprises Cu at 27wt%, Al at 5wt%, the balance being Ag.
  • Figure 8 shows an alternative method of sealing a metal to a ceramic surface.
  • a layer of further alloy metal, 15, (for example titanium) is formed on a portion of the outer surface of ceramic ring, 3, by sputtering.
  • a ring of preliminary alloy, 16, (an example being a Ag, Cu and Al alloy) is placed on top of the further alloy metal surface, and one end of the metal tube placed on top of the further alloy metal ring.
  • the formation of the desired alloy seal can be effected by brazing.
  • Figure 9 shows an apparatus that can be used for a separation process using a selectively permeable membrane supported on a porous first ceramic as described herein.
  • the separation vessel is equipped with metal tubes, 1 and 1 ', integrated into the separation vessel walls.
  • the metal tubes and the vessel can be made from the same metal, or alternatively the metal tubes can be of a different metal or alloy to the vessel. Having the reactor/vessel wall made from a different metal is advantageous where a metal with low expansion coefficient needs to be joined to the ceramic tube, in order to more closely match the expansion coefficient of the ceramic (ceramics tend to have lower thermal expansion coefficients than metals) for reducing stress and degradation of the seal during thermal cycling.
  • Low expansion metals tend to be rare or expensive, and hence construction of a complete reactor or vessel from such a low expansivity metal can be avoided by connecting the metal tube, 1 , to a reactor or vessel, 20, made of more readily available material, such as iron, or alloys of iron such as steel and stainless steel. Techniques such as welding or brazing can be used to provide a strong, stable and impermeable seal between the different metals.
  • the metal tubes are each joined and sealed with rings, 3 and 3' of a low porosity second ceramic, for example as described above.
  • the low porosity tubes of second ceramic are in turned joined and sealed with a high porosity tube of first ceramic, 2, as described above in relation to Figure 3.
  • the surface of the first ceramic tube is coated with a membrane, 22.
  • the membrane is typically palladium, or palladium additionally comprising Cu and/or Ag.
  • the membrane extends over the entire surface of the porous tube of first ceramic to prevent any fluids other than hydrogen permeating through to the other side of the membrane.
  • this Figure shows the membrane on the outer surface of the porous ceramic tube 2, it is also possible to coat the internal surface of the porous first ceramic either instead of, or in addition to, the outer surface.
  • a fluid mixture enters the first zone of separation vessel 20, through inlet 21.
  • One of the components in the fluid mixture permeates the membrane, 22, and enters the internal portion of the porous ceramic tube, 9.
  • the unpermeated portion of the fluid mixture, deficient in the selectively permeated component, leaves the separation vessel via outlet, 23.
  • the membrane is a palladium membrane
  • the fluid mixture is a mixture of hydrogen, carbon monoxide and carbon dioxide
  • hydrogen permeates the membrane, and the hydrogen-deficient gas mixture comprising predominantly carbon monoxide and carbon dioxide is removed via the outlet 23.
  • the selectively separated component (for example hydrogen), permeates the membrane, 22, and enters the interior 9 of the porous tube of first ceramic 2, where it can diffuse out of the reactor through the interior, 4 or 4' of either of the metal tubes 1 or 1', via the interior, 10 or 10', of the low porosity second ceramic tubes, 3 or 3'.
  • a sweep gas can be used to flush the permeated fluid from the interior of the porous ceramic tube, 2.
  • a flow of sweep gas such as nitrogen, argon or steam, can be fed through metal tube 1 , and a mixed fluid comprising the sweep gas and the permeated component leaves through metal tube 1 '.
  • the second zone of the separation vessel can be defined as the portion of the vessel accessible only to the selectively permeated component, and which comprises the interior of the metal tubes, 4 and 4', the interior of the low porosity tubes of second ceramic, 10 and 10', and the interior 9 of the porous tube of first ceramic 2.
  • the first zone comprises the portion of the vessel on the other side of the membrane 22 and within the walls of vessel 20.
  • the reactor can comprise two or more supported membranes. Having more than one membrane allows increased surface area for permeation, which improves the efficiency of the separation process.
  • Figure 10 is a modification of Figure 9, in that the first zone comprises a catalyst, 24, wherein one or more reactants are fed into the first zone of the combined reactor/separation vessel, 20, through inlet, 21, where they contact catalyst 24 and undergo reaction to produce the separable component, which permeates through membrane 22 and into the second zone of the vessel. Unreacted reactants and other products are removed through outlet 23.
  • the first zone comprises a catalyst, 24, wherein one or more reactants are fed into the first zone of the combined reactor/separation vessel, 20, through inlet, 21, where they contact catalyst 24 and undergo reaction to produce the separable component, which permeates through membrane 22 and into the second zone of the vessel. Unreacted reactants and other products are removed through outlet 23.
  • An example of such a reaction is the steam reforming, partial oxidation or autothermal reforming of a hydrocarbon, such as methane, in the presence of steam and/or oxygen to produce a gaseous mixture comprising hydrogen and one or more oxides of carbon, in the presence of a selective hydrogen-permeable membrane, for example a palladium membrane or Pd-Cu or Pd-Ag alloy membrane.
  • a selective hydrogen-permeable membrane for example a palladium membrane or Pd-Cu or Pd-Ag alloy membrane.
  • the low porosity ceramic ring, 3, is attached to metal tube, 1, using an alloy seal, 6, as shown above in Figures 1, 2 and 3.
  • the metal tube, 1, is in turn attached to a second metal tube, 25, which forms part of a reactor or separation vessel, 20, and which is typically of the same material as the reactor or separation vessel.
  • the join (for example weld) between the metal tube, 1, and a tube of second metal, 25, which is integrated into vessel 20 is shown at 26.
  • Figures 12 and 13 illustrate how an alloy comprising silver as described as an example herein exhibits improved wettability characteristics on a ceramic surface than a corresponding Ag-free alloy.
  • Figure 12 shows a copper based Cu-2Al-3Si-2Ti alloy (i.e. 2wt% Al, 3wt% Si, 2wt% Ti and the balance Cu), 30, on a low density, high porosity alumina surface, 31 , after treatment under vacuum at 1100 0 C.
  • the footprint made by the alloy on the surface is small, and does not spread across the ceramic surface, demonstrating a weak interaction with the surface.
  • This alloy is not in accordance with some aspects described herein of the present invention, as it does not comprise silver.
  • Figure 13 shows an Ag-27Cu-5 Al-5Ti alloy (i.e.
  • a homogeneous oxide mixture comprising 40-45% BaO, 5-10% Al 2 O 3 , 10-15% CaO, and 30-40% SiO 2 powders was prepared by ball-milling. The mixture was then melted at 1450-1480 0 C for 1 to 2 hours in an alumina or Pt crucible, followed by rapid water quenching. The obtained glass was ground into fine powders of about 5-15 ⁇ m in diameter by ball milling. To improve the high temperature stability, ZrO 2 powder at up to 15wt% content was homogeneously mixed into the above powdered glass seal.
  • a bimetallic tube was manufactured through butt welding a lCrl8Ni9Ti 304 stainless steel rod (comprising lwt% Cr, 18wt% Ni, 9wt% Ti) to a 4J33 (Kovar) alloy rod, followed by machining to produce a tube shape.
  • the Kovar alloy (4J33) end of the bimetallic tube was brazed to a low porosity, dense alumina ring using Ag 25-30Cu 2-8Al 2-8Pd 2-8Ti alloy (comprising 25-30wt% Cu, 2- 8wt% Al, 2-8wt% Pd and 2-8wt% Ti, the balance being silver).
  • a Ag 25-3OCu 2- 8Al 2-8Pd preliminary alloy (comprising 25-30wt% Cu, 2-8wt% Al, 2-8 wt% Pd, the balance being Ag) was fabricated by inductive melting method under an argon atmosphere. The obtained preliminary alloy was rolled into a thin plate before use.
  • the titanium was incorporated into the alloy by magnetron-controlled sputtering of a Ti film of about 2-10 ⁇ m thick on the end face of the dense, low porosity alumina ring, followed by brazing.
  • the seal the low porosity alumina plug and ring (with an alumina density 3.5g/cm 3 ) to the two open ends of the high porosity ceramic tube was effected as follows. About 0.06 to 0.12 g of a glass sealing powder was mixed with alcohol to form a sticky paste; then a uniform seal paste layer was put around the two end surfaces of the porous ceramic tube.
  • the low porosity alumina plug and ring were inserted into the two ends of the high porosity ceramic tube, such that the lips were held in contact with the pasted end surfaces of the ceramic tube.
  • the assembly was placed vertically into the air furnace and heated to a temperature of 115O 0 C at a rate of 10°C/min, and held at that temperature for 15 min. The joint was then allowed to cool to room temperature.
  • the brazing of bimetallic tube to the low porosity alumina ring was achieved using a vertical vacuum furnace which capable of reaching temperatures of up to 125O 0 C.
  • a Ti film of about 2-10 ⁇ m thick was sputtered onto the end face of the dense alumina ring; a Ag-Cu-Al-Pd alloy ring (0.15-0.2 g) was inserted into the interface between the Kovar alloy (4J33) end of the bimetallic tube and the dense alumina transition ring.
  • the whole assembly, vertically disposed, was put into a vacuum furnace, and brazed at to a temperature of 96O 0 C at a rate of 10°C/min under vacuum, the being about 5> ⁇ 10 3 Pa.
  • the joint was then allowed to cool to room temperature after brazing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Analytical Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention concerne un appareil comprenant un premier matériau céramique, un second matériau céramique et une surface métallique, le premier matériau céramique étant joint ou scellé au second matériau céramique, et une surface du premier matériau céramique étant jointe ou scellée à la surface métallique. L'appareil peut être utilisé dans une membrane sélectivement perméable. L'invention concerne également une composition d'alliage comprenant Ag et Cu, l'alliage comprenant en outre un élément X, X représentant Al et/ou Pd, et son utilisation pour joindre ou sceller une surface métallique à une surface céramique. L'invention concerne aussi une composition d'alliage comprenant Ag, Pd, Ti et X, X représentant un ou plusieurs des éléments Cu, Al et Mn, et son utilisation comme joint d'étanchéité pour joindre ou sceller une surface métallique à une surface céramique. Dans des exemples, l'invention concerne une composition d'oxyde comprenant, outre de l'oxygène, Al, Ca et Si, et comprenant de plus un ou plusieurs éléments parmi Ba, Zr, Ti, B, Li et Ga. La composition d'oxyde peut être utilisée pour joindre ou sceller deux matériaux céramiques.
PCT/GB2010/000395 2009-03-06 2010-03-05 Technologie de scellement WO2010100432A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CNPCT/CN2009/000239 2009-03-06
CNPCT/CN2009/000240 2009-03-06
CNPCT/CN2009/000241 2009-03-06
PCT/CN2009/000239 WO2010099633A1 (fr) 2009-03-06 2009-03-06 Procédé pour la production d'un joint en alliage
PCT/CN2009/000241 WO2010099635A1 (fr) 2009-03-06 2009-03-06 Composition d'alliage et appareil comprenant celle-ci
PCT/CN2009/000240 WO2010099634A1 (fr) 2009-03-06 2009-03-06 Technique de scellement

Publications (2)

Publication Number Publication Date
WO2010100432A2 true WO2010100432A2 (fr) 2010-09-10
WO2010100432A3 WO2010100432A3 (fr) 2010-11-18

Family

ID=42212164

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2010/000395 WO2010100432A2 (fr) 2009-03-06 2010-03-05 Technologie de scellement

Country Status (1)

Country Link
WO (1) WO2010100432A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105013339A (zh) * 2014-04-23 2015-11-04 中国科学院大连化学物理研究所 一种金属钯膜表面制备分子筛膜的方法
AT15435U1 (de) * 2016-06-22 2017-08-15 Plansee Se Membrananordnung
IT201700057132A1 (it) * 2017-05-25 2018-11-25 Getters Spa Assemblaggio tubolare composito ceramico-metallo con giuntura a tenuta di gas e un purificatore di idrogeno che lo comprende
CN109848607A (zh) * 2019-01-16 2019-06-07 阜阳佳派生产力促进中心有限公司 一种用于合金钢和碳化硅陶瓷焊接的钎焊材料的制备方法
CN110709369A (zh) * 2017-05-30 2020-01-17 电化株式会社 陶瓷电路基板和使用其的模块

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1151473A (en) 1966-03-28 1969-05-07 Philips Electronic Associated Improvements relating to Refractory Metal-to-Ceramic Seal
US4678720A (en) 1985-01-04 1987-07-07 Gte Laboratories Incorporated Silver-copper-titanium brazing alloy
US5554296A (en) 1995-05-15 1996-09-10 Crown Cork & Seal Company, Inc. System and method for purifying waste streams containing water reducible paints
US5554286A (en) 1993-12-27 1996-09-10 Mitsui Engineering & Shipbuilding Co., Ltd. Membrane for liquid mixture separation
WO2005065806A1 (fr) 2004-01-09 2005-07-21 Bp P.L.C. Membrane composite de palladium metallique ou membrane composite d'alliage de palladium et procedes de preparation de ces membranes
WO2007031713A1 (fr) 2005-09-14 2007-03-22 Bp P.L.C. Procede de production d'hydrogene
WO2007054462A2 (fr) 2005-11-08 2007-05-18 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de fabrication de joint ceramique/metal a temperature elevee et architecture-microstructure de la composition utilisee
WO2007129024A1 (fr) 2006-05-08 2007-11-15 Bp P.L.C. Procédé de production d'hydrogène
WO2008074181A1 (fr) 2006-12-18 2008-06-26 Bp P.L.C. Membrane de séparation d'oxygène
EP1980314A1 (fr) 2006-01-16 2008-10-15 Mitsubishi Chemical Corporation Procede de fabrication de membrane de separation de zeolite

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344586A (en) * 1965-06-22 1967-10-03 Engelhard Ind Inc Gas separation apparatus
JPS60231474A (ja) * 1984-04-27 1985-11-18 松下電器産業株式会社 セラミツクと金属の鑞付方法
JPH0632869B2 (ja) * 1985-01-23 1994-05-02 田中貴金属工業株式会社 セラミックスと金属とのろう付け方法
JPS61283492A (ja) * 1985-06-07 1986-12-13 Tanaka Kikinzoku Kogyo Kk セラミツクス用ろう材
DE3888380T2 (de) * 1987-04-02 1994-10-13 Toshiba Kawasaki Kk Luftdichter Keramikbehälter.
JPH0829990B2 (ja) * 1988-09-21 1996-03-27 日本特殊陶業株式会社 セラミックスと金属との接合体
DE68911864T2 (de) * 1988-11-07 1994-05-05 Morgan Crucible Co Silber-Kupfer-Aluminium-Titan-Hartlotlegierung.
US5364010A (en) * 1990-07-05 1994-11-15 The Morgan Crucible Company, Plc Joining of metal to ceramic bodies by brazing
NL9001662A (nl) * 1990-07-20 1992-02-17 Velterop F M Bv Werkwijze voor het verbinden van een keramisch materiaal met een ander materiaal.
DE4105596A1 (de) * 1991-02-22 1992-08-27 Degussa Verfahren zur herstellung von hochtemperaturbestaendigen loetverbindungen
US6402156B1 (en) * 1999-04-16 2002-06-11 Eltron Research, Inc. Glass-ceramic seals for ceramic membrane chemical reactor application
ES2254207T3 (es) * 1999-07-30 2006-06-16 Battelle Memorial Institute Material de union vitroceramico y procedimiento de union.
JP2006202727A (ja) * 2004-12-24 2006-08-03 Ngk Spark Plug Co Ltd 固体電解質形燃料電池
JP4995463B2 (ja) * 2006-01-23 2012-08-08 日本特殊陶業株式会社 固体酸化物型燃料電池及びその製造方法
JP5057685B2 (ja) * 2006-03-31 2012-10-24 日本特殊陶業株式会社 水素分離装置および水素製造装置
KR100681007B1 (ko) * 2006-04-04 2007-02-09 한국에너지기술연구원 관형 연료극 지지체식 고체산화물 연료전지용 밀봉재와밀봉 방법
JP4482016B2 (ja) * 2007-06-29 2010-06-16 株式会社ノリタケカンパニーリミテド 複合セラミックスの製造方法、複合セラミックス、およびセラミックフィルタアセンブリ

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1151473A (en) 1966-03-28 1969-05-07 Philips Electronic Associated Improvements relating to Refractory Metal-to-Ceramic Seal
US4678720A (en) 1985-01-04 1987-07-07 Gte Laboratories Incorporated Silver-copper-titanium brazing alloy
US5554286A (en) 1993-12-27 1996-09-10 Mitsui Engineering & Shipbuilding Co., Ltd. Membrane for liquid mixture separation
US5554296A (en) 1995-05-15 1996-09-10 Crown Cork & Seal Company, Inc. System and method for purifying waste streams containing water reducible paints
WO2005065806A1 (fr) 2004-01-09 2005-07-21 Bp P.L.C. Membrane composite de palladium metallique ou membrane composite d'alliage de palladium et procedes de preparation de ces membranes
WO2007031713A1 (fr) 2005-09-14 2007-03-22 Bp P.L.C. Procede de production d'hydrogene
WO2007054462A2 (fr) 2005-11-08 2007-05-18 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de fabrication de joint ceramique/metal a temperature elevee et architecture-microstructure de la composition utilisee
EP1980314A1 (fr) 2006-01-16 2008-10-15 Mitsubishi Chemical Corporation Procede de fabrication de membrane de separation de zeolite
WO2007129024A1 (fr) 2006-05-08 2007-11-15 Bp P.L.C. Procédé de production d'hydrogène
WO2008074181A1 (fr) 2006-12-18 2008-06-26 Bp P.L.C. Membrane de séparation d'oxygène

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105013339A (zh) * 2014-04-23 2015-11-04 中国科学院大连化学物理研究所 一种金属钯膜表面制备分子筛膜的方法
CN105013339B (zh) * 2014-04-23 2017-09-29 中国科学院大连化学物理研究所 一种金属钯膜表面制备分子筛膜的方法
AT15435U1 (de) * 2016-06-22 2017-08-15 Plansee Se Membrananordnung
WO2017219053A1 (fr) * 2016-06-22 2017-12-28 Plansee Se Ensemble à membrane
IT201700057132A1 (it) * 2017-05-25 2018-11-25 Getters Spa Assemblaggio tubolare composito ceramico-metallo con giuntura a tenuta di gas e un purificatore di idrogeno che lo comprende
CN110709369A (zh) * 2017-05-30 2020-01-17 电化株式会社 陶瓷电路基板和使用其的模块
CN109848607A (zh) * 2019-01-16 2019-06-07 阜阳佳派生产力促进中心有限公司 一种用于合金钢和碳化硅陶瓷焊接的钎焊材料的制备方法
CN109848607B (zh) * 2019-01-16 2020-11-27 阜阳佳派生产力促进中心有限公司 一种用于合金钢和碳化硅陶瓷焊接的钎焊材料的制备方法

Also Published As

Publication number Publication date
WO2010100432A3 (fr) 2010-11-18

Similar Documents

Publication Publication Date Title
WO2010100432A2 (fr) Technologie de scellement
US6402156B1 (en) Glass-ceramic seals for ceramic membrane chemical reactor application
JP5057685B2 (ja) 水素分離装置および水素製造装置
US8110022B2 (en) Hydrogen purifier module and method for forming the same
Ryi et al. Development of a new porous metal support of metallic dense membrane for hydrogen separation
EP1487563A1 (fr) Membranes de transport d'hydrogene
CN101172880A (zh) 一种钎焊Si3N4陶瓷的钛基高温非晶钎料及制备方法
JP2008524099A (ja) セラミック−金属または合金の接合アセンブリ
JP5904536B2 (ja) 高温で気密性を保つセラミックス−金属のガラスシール構造体
US8753433B2 (en) Membrane tube and reactor having a membrane tube
CN102040393A (zh) 陶瓷和铝或铝合金的表面金属化连接方法
WO2010099635A1 (fr) Composition d'alliage et appareil comprenant celle-ci
JP2002219341A (ja) 水素選択透過膜支持用基材および水素選択透過部材
US6050478A (en) Composition and process for the reactive brazing of ceramic materials containing alumina
WO2010099634A1 (fr) Technique de scellement
WO2010099633A1 (fr) Procédé pour la production d'un joint en alliage
JP4911917B2 (ja) 水素分離装置
JPH04300265A (ja) セラミック材料に別の材料を結合する方法
JPH05285357A (ja) 水素分離膜
JP3174668B2 (ja) 水素分離膜
JP2001278601A (ja) 燃料電池用改質器
JPH11276867A (ja) 水素透過膜の接合方法
JP2006159108A (ja) 複合積層体、これを用いたガス分離膜ならびにその製造方法
JP4528021B2 (ja) 酸化物イオン混合伝導体、複合構造体、酸素分離装置、及び化学反応装置
EP2451605A1 (fr) Procédé de brasage

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10709026

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10709026

Country of ref document: EP

Kind code of ref document: A2