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  • 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
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2415—Tubular reactors
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
  • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
  • C01C3/00—Cyanogen; Compounds thereof
  • C01C3/02—Preparation, separation or purification of hydrogen cyanide
  • C01C3/0208—Preparation in gaseous phase
  • C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
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  • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
• • 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
• • 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
  • C04B37/008—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of an organic adhesive, e.g. phenol resin or pitch
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L13/00—Non-disconnectable pipe joints, e.g. soldered, adhesive, or caulked joints
  • F16L13/007—Non-disconnectable pipe joints, e.g. soldered, adhesive, or caulked joints specially adapted for joining pipes of dissimilar materials
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L49/00—Connecting arrangements, e.g. joints, specially adapted for pipes of brittle material, e.g. glass, earthenware
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L9/00—Rigid pipes
  • F16L9/10—Rigid pipes of glass or ceramics, e.g. clay, clay tile, porcelain
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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  • 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
  • C04B2237/08—Non-oxidic interlayers
  • C04B2237/086—Carbon interlayers
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  • 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
  • C04B2237/341—Silica or silicates
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C04B2237/32—Ceramic
  • C04B2237/38—Fiber or whisker reinforced
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C04B2237/38—Fiber or whisker reinforced
  • C04B2237/385—Carbon or carbon composite
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  • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
  • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
  • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
  • C04B2237/704—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
• • C—CHEMISTRY; METALLURGY
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  • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
  • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
  • C04B2237/76—Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc
  • C04B2237/765—Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc at least one member being a tube
• • 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
  • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
  • C04B2237/84—Joining of a first substrate with a second substrate at least partially inside the first substrate, where the bonding area is at the inside of the first substrate, e.g. one tube inside another tube

Definitions

• the present invention relates to a gas-tight multilayer composite pipe or regions of a multilayer composite pipe with a heat transfer coefficient of> 500 W / m 2 / K containing at least two layers, a layer of nonporous monolithic oxide ceramic and a layer made of oxide fiber composite ceramic.
• Endothermic reactions are often at the beginning of the value chain of the chemical industry, for example in the separation of petroleum fractions, the reforming of natural gas or naphtha, the dehydrogenation of propane, the dehydroaromatization of methane to benzene or the pyrolysis of hydrocarbons. These reactions are strongly endothermic, ie temperatures between 500 ° C and 1700 ° C are required to achieve technically and economically interesting yields.
• the process of producing synthesis gas and hydrogen from natural gas or naphtha includes endothermic reaction steps conducted at high pressures and temperatures.
• the standard process of the prior art is the reforming of natural gas with steam (water vapor reforming) or with carbon dioxide (dry reforming).
• This process requires a catalyst that is distributed over several reaction tubes.
• the reaction tubes are installed in ovens and fired by burners.
• the function of the tube walls is the transfer of the heat flow from an external heat source into the reaction volume and the hermetic separation of the reaction volume from the surrounding heat source while maintaining the pressure difference between the two spaces.
• the tubes of the fixed bed reactors are typically cylindrical with a uniform diameter over the entire length of the tube.
• the material of the tubes is typically stainless steel; In some cases, ceramic materials are used.
• Technical reforming processes are carried out at pressures up to 30 bar and temperatures up to
• the product composition is mainly determined by the C: 0: H ratio of the starting materials. Thus, there is no need to increase the selectivity of individual reactions by a catalyst.
• fiber-composite ceramics consisting of oxidic fibers embedded in a porous matrix of oxide ceramic.
• the porosity of fiber composite ceramics can be between 25% and 50%.
• the advantages of fiber composite ceramics are high temperature resistance up to 1300 ° C or more, high thermal shock resistance and a quasi-ductile deformation and fracture behavior.
• the fracture toughness of fiber composite ceramics can reach values of K
• C 10 - 50 MPa Vm.
• fiber composite ceramics have lower density, lower modulus of elasticity, and lower thermal conductivity coefficient than monolithic ceramics of the same chemical composition. Table 1 contains a list of the relevant standards for the determination of these parameters.
• Table 1 List of relevant standards for the determination of structural, mechanical and thermophysical parameters for monolithic ceramics and composite ceramics. Parameters Monolithic ceramic fiber composite ceramic
• Thermal conductivity coefficient density x (specific heat capacity) x coefficient of thermal conductivity
• Table 2 contains a comparison between the properties of monolithic ceramics and alumina-based fiber-composite ceramics.
• Table 2 Comparison of physical properties of monolithic ceramics and composite ceramics.
• a disadvantage of the porous structure of fiber composite ceramics is their unsuitability for the production of pressure equipment with a pressure of> 0.5 bar. Further, the inferior thermal conductivity is disadvantageous compared to the nonporous monolithic ceramic having the same chemical composition, i. if a heat flow is to be transmitted through a layer of this material.
• DE 2821595 A1 discloses a high-strength ceramic composite tube which has an inner tube made of ceramic material and at least one outer tube made of a metal or ceramic material shrunk onto the inner tube. There is no indication of a fiber composite ceramic.
• DE 3907087 A1 describes a high-pressure container with a wall of a fiber composite material on an inner tube made of metal-ceramic powder and an outer tube made of metal. There is no indication of a multilayer structure with a ceramic inner or outer tube.
• DE 102006038713 A1 discloses a pressure-resistant body, such as a pressure tube, comprising a steel main body, a first layer of ceramic fiber composite material surrounding the main body and at least one second layer of fiber-reinforced plastic and / or fiber-reinforced ceramic disposed on the first layer , The second layer of plastic prohibits the external heating of the pipe.
• a pressure-resistant body such as a pressure tube
• a first layer of ceramic fiber composite material surrounding the main body and at least one second layer of fiber-reinforced plastic and / or fiber-reinforced ceramic disposed on the first layer ,
• the second layer of plastic prohibits the external heating of the pipe.
• Embodiments with purely ceramic outer tubes are not mentioned. There is no indication of a multi-layer structure with a ceramic inner tube or an inner tube made of fiber-reinforced ceramic.
• DE 102012219870 A1 discloses a method for producing a composite body made of steel and a layer of a fiber composite material enclosing the base body at least in sections on the outside.
• the base body is impregnated with a fiber material before or after wrapping with a resin and heated. It is advantageous that this method can be carried out in situ, so that a renovation of marbled pressure lines without interruption of operation is possible.
• DE 102004049406 A1 describes a multilayer molded part of at least one long fiber reinforced composite material (1) and at least one short fiber reinforced composite material (2), characterized in that the long fiber reinforced composite material (1) contains endless ceramic fibers and ceramic matrix material, the short fiber reinforced composite material (2) ceramic Contains fibers having a mean length in a range of 1 to 50 mm and ceramic matrix material, wherein the long-fiber-reinforced composite material (1) and the short-fiber reinforced composite material (2) are firmly bonded together flat. There is no indication of a combination of a ceramic layer with a fiber composite layer.
• No. 6,733,907 describes a composite of an internal ceramic carrier structure and an external ceramic thermal barrier coating.
• the thermal barrier coating has a thickness of 2 to 5 mm and a porosity of> 20%.
• the porosity of the structure gives both monolithic ceramics and fiber composite ceramics poorer thermal conductivity over non-porous monolithic ceramics having the same chemical composition.
• the ceramic support structure may consist of continuous fibers in a ceramic matrix structure and has a thickness of 3 to 10 mm. It is described that the modulus of elasticity and the thermal conductivity coefficient of the thermal barrier coating are each lower than the corresponding value of the ceramic carrier structure.
• US 2015/078505 describes a gas-tight, two-layered composite tube of silicon carbide for the disposal of nuclear nuclear fuels comprising a dense monolithic SiC layer and a porous SiC-SiC fiber composite ceramic layer.
• the advantage of SiC ceramics within the family of ceramics is the comparatively high thermal conductivity and high thermal shock resistance.
• the disadvantage of SiC ceramics is the comparatively low chemical resistance with respect to oxidizing or carburizing atmospheres.
• the thermodynamic analysis of Eckel et al. (NASA Technical Memorandum, Wyoming, September 12-16, 1989) and Hallum et al.
• US 2012/0003128 describes a connecting piece between a tube made of nonporous monolithic ceramic and metallic leads.
• the ceramic tube has a porosity of ⁇ 5%.
• US 2012/0003128 is based on a frictional connection between the ceramic tube and the metallic connecting part, which surrounds the end portion of the ceramic tube. The frictional connection is ensured by two concentrically arranged metal rings, wherein the inner ring is part of the connecting cable.
• the outer shrink ring has a lower thermal expansion see than the inner ring; This is to suppress the tendency of the inner shrink ring to detach from the ceramic tube when heated.
• a disadvantage of this solution is that, due to the choice of metallic shrink rings, the radial contact pressure between the ceramic tube and the inner shrink ring varies with temperature.
• a tube containing at least two layers, a layer of nonporous monolithic oxide ceramic and a layer of oxide fiber composite ceramic is not to be confused with a ceramic hollow fibers according to JP 2003053166:
• the ceramic hollow fiber which is used in membrane technology, has a capillary tube with an outer Diameter of approx. 0.5 to 4 mm.
• the documents US4222977 and US5707584 describe the production of ceramic hollow fiber membranes.
• the tube wall can have a wall thickness between 30 ⁇ and 500 ⁇ and is monolithic, ie their mechanical properties are identical to the properties of ordinary monolithic ceramics. This means that ceramic hollow fibers are rigid and brittle and therefore unsuitable for achieving a quasi-ductile deformation behavior as with fiber composite ceramics.
• the combination of nonporous and porous ceramics described in JP 2003053166 leaves the capillary tube brittle and susceptible to breakage.
• reaction tubes which can be used at operating pressures of 1 to 50 bar, reaction temperatures up to 1400 ° C. and which can be heated by an external heat source, usually a heating chamber.
• the delimitation of the reaction volume from the surrounding heating chamber is achieved in the prior art depending on the required temperature in the following ways.
• polymers are typically used as sealing elements.
• metallic sleeves are used, which are firmly bonded using solder or adhesive.
• the metallic sleeves are shrunk in a form-fitting manner (for example DE 1995105401).
• the said metal sleeves must be thin-walled in the range of 0.3 to 1 mm for this purpose. With such metal sleeves could at high temperatures above 800 ° C only pressure differences of max. 3 bar, otherwise the metal starts to flow.
• the object of the present invention was therefore to provide a suitable material for reaction tubes, which have the following property profile: (i) heat-permeable with a heat transfer coefficient> 500 - ⁇ , (ii) temperature-resistant up to 1400 ° C, (iii) pressure-resistant up to ca. 50 bar or resistant to pressure differences up to approx. 100 bar, (iv) cor- Resistant to rosin against reducing and oxidizing atmospheres with an oxygen partial pressure of 10 25 bar to 10 bar and (v) temperature change resistant according to DIN EN 993-1 1.
• connection unit / a connecting piece between the material, ie the Reactor tube, on the one hand and the metallic gas-carrying lines for the products and reactants on the other hand show the (i) temperature resistant to above 1 100 ° C, (ii) pressure resistant to 40 bar, (iii) corrosion resistant to oxidizing and against reducing atmosphere and (iv ) is temperature change resistant.
• the object was achieved with a multilayer composite pipe or with a multilayer composite pipe section with a heat transfer coefficient of> 500 W / m 2 / K containing at least two layers, a layer of nonporous monolithic oxide ceramic and a layer of oxide fiber composite ceramic.
• the inner layer of the multilayer composite pipe of nonporous monolithic oxide ceramic and the outer layer of oxide fiber composite ceramic are provided.
• non-positive or cohesive connections are for example screw or press connections.
• Relevant integral bonds for this invention are soldering, gluing, sintering. All types of connection belong to the state of the art (W. Mitchell, F. Bodenstein: Design Elements of Mechanical Engineering, Part 1: Fundamentals; Fasteners; Housing, Containers, Pipelines and Shut-off Devices Springer-Verlag, 1979).
• the wall of the multilayer composite pipe advantageously comprises at least two layers, a layer of non-porous monolithic oxide ceramic and a layer of oxide fiber composite ceramic; i.e. it may also be a composite pipe section in the multilayer composite pipe.
• a zoned or punctiform composite pipe consisting only in two parts of a layer may be mentioned.
• the multi-layered composite pipe advantageously has no metallic layers in the pipe section which is exposed to an external temperature, for example by a heating chamber, of> 1 100 ° C.
• the inner tube is wrapped with a layer of oxide fiber composite ceramic.
• the two layers can be positively or materially connected to each other and form a component. The properties of this component are due to the temperature resistance and determines the deformation behavior of the layer of oxide fiber composite ceramic.
• the tightness is given by the inner tube of oxide ceramic.
• the inside of the tube wall has a high chemical resistance and abrasion resistance, with a hardness> 14000 MPa for aluminum oxide,> 12000 MPa for zirconium oxide.
• alumina and magnesia are stable throughout the range of 10 to 25 psi oxygen partial pressure, while all other ceramic materials undergo transition between reduction and oxidation (Darken, LS, & Gurry, RW (1953) .Physical chemistry ofmetals.
• the tube inner diameter of the multilayer composite tube is advantageously 20 mm to 1000 mm, preferably 50 mm to 800 mm, in particular 100 mm to 500 mm.
• the total wall thickness of at least two layers is advantageously 0.5 mm to 50 mm, preferably 1 mm to 30 mm, in particular 2 mm to 20 mm.
• the thickness of the layer of oxide-fiber composite ceramic is less than 90%, preferably less than 50%, in particular less than 25% of the total wall thickness;
• the thickness of the layer of oxide fiber composite ceramic is at least 10% of the total wall thickness.
• the thickness of the layer of monolithic oxide ceramic is advantageously from 0.5 mm to 45 mm, preferably from 1 mm to 25 mm, particularly preferably from 3 mm to 15 mm.
• the thickness of the layer of oxide-fiber composite ceramic is advantageously from 0.5 mm to 5 mm, preferably from 0.5 mm to 3 mm.
• the length of the multilayer composite pipe is advantageously 0.5 to 20 m, preferably 1 to 10 m, in particular 1, 5 to 7 m.
• the multilayer composite pipe according to the invention comprising at least one layer of nonporous monolithic oxide ceramic and at least one layer of oxide fiber composite ceramic advantageously has an open porosity of ⁇ ⁇ 5%, preferably ⁇ ⁇ 4%, more preferably ⁇ ⁇ 3%, further preferably ⁇ ⁇ 2%, in particular ⁇ ⁇ 1%.
• the multilayer composite pipe is particularly advantageous gas-tight.
• gas-tight is understood as meaning a solid which has an open porosity of zero according to DIN EN 623-2 The permissible measurement inaccuracy is ⁇ 0.3%.
• the density of the nonporous monolithic oxide ceramic is advantageously greater than the density of the oxide fiber composite ceramic.
• the density of the non-porous monolithic oxide ceramic is advantageously between 1000 and 7000, in particular between 2000 and 5000, for example 2800 for mullite (about 70% aluminum oxide) or 3700 for aluminum oxide with
• the density of the layer of fiber composite ceramic is between 500 and 3000 - ⁇ .
• Ceramic in the composite structure is advantageously between 1: 1 and 3: 1, in particular between 1: 1 and 2: 1.
• the material-dependent elastic modulus of the nonporous monolithic oxide ceramic is advantageously greater than the modulus of elasticity of the oxide fiber composite ceramic.
• the elastic modulus of the non-porous monolithic oxide ceramic is advantageously between 100 GPa and 500 GPa, in particular between 150 GPa and 400 GPa, for example 150 GPa for mullite (about 70% aluminum oxide) or 380 GPa for aluminum oxide with a purity of> 99.7%.
• the modulus of elasticity of the fiber composite ceramic layer is between 40 GPa and 200 GPa. These values are valid at 25 ° C.
• the ratio of the elastic moduli of the monolithic ceramic and the fiber composite ceramic in the composite structure is advantageously between 1: 1 and 5: 1, in particular between 1: 1 and 3: 1.
• the material-dependent coefficient of thermal conductivity of the nonporous monolithic oxide ceramic is advantageously greater than the coefficient of thermal conductivity of the oxide fiber composite ceramic.
• the coefficient of thermal conductivity of the non-porous monolithic oxide ceramic is advantageously between 1 and 50, in particular between 2 and 40, for example m-K m-K m-K m-K m-K
• the coefficient of thermal conductivity of the layer of fiber composite ceramic is between 0.5 and 10, preferably between 1 and 5. These values were at 25 ° C.
• Ratio of the thermal conductivity coefficient of the monolithic ceramic and the fiber composite ceramic in the composite structure is advantageously between 1: 1 and 10: 1, in particular between 1: 1 and 5: 1
• the pressure reactor is designed for the following pressure ranges; advantageous
• the pressure difference between the reaction chamber and the heating chamber is advantageously from 0 bar to 100 bar, preferably from 0 bar and 70 bar, more preferably from 0 bar to 50 bar, in particular from 0 bar to 30 bar.
• the heat transfer coefficient of the multilayer composite pipe is advantageous> 500 preferred> 1000 more preferably> 2000 especially> 3000 superiors ⁇ m 2 K ⁇ m 2 K m is 2 K ⁇ hens, for determining the heat transfer coefficient known in the art (Chapter Cb: heat transfer, VDI Heat Atlas, 8th edition, 1997). According to this definition:
• R w thermal resistance of a multilayer cylindrical wall in
• ⁇ thickness of a homogeneous layer in m
• n number of layers of a multilayer cylindrical wall
• the multilayer composite pipe according to the invention can have over its length a variable cross-section and a variable wall thickness.
• the multilayer composite pipe can increase or decrease in a funnel shape in the flow direction of the gas, with a cross-section which narrows in the direction of flow being advantageous for fixed beds and a further cross-section advantageous for fluidized beds.
• the edge portion of the outer layer may be advantageously sealed.
• the sealed ends serve as transitions to the gas-tight connection of the composite pipe with metallic gas-carrying lines, distributors, collectors or bushings through the shell of the surrounding heating chamber.
• nonporous monolithic oxide ceramics it is possible to use all oxide ceramics known to the person skilled in the art, in particular analogously to the Information Center for Technical Ceramics (IZTK): Brevier Technische Keramik. Fahner Verlag, Lauf (2003). Preference is given to nonporous monolithic oxide ceramics having at least 99% by weight of Al 2 O 3 and / or mullite.
• Haldenwanger Pythagoras 1800Z TM mullite
• the fiber composite materials are characterized by a matrix of ceramic particles between the ceramic fibers, especially long fibers, are embedded as a wound body or as a textile. It is spoken of fiber-reinforced ceramics, composite ceramics or fiber ceramics.
• matrix and fiber may consist of all known ceramic materials, in which context carbon is also treated as a ceramic material.
• oxidic fiber composite ceramic is meant a matrix of oxidic ceramic particles containing ceramic, oxidic and / or non-oxidic fibers.
• Preferred oxides of the fibers and / or the matrix are oxides of an element from the group: Be, Mg, Ca, Sr, Ba, rare earths, Th, U, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Ga, Si, Ge, Sn, Li, Na, K, Rb, Cs, Re, Ru, Os.lr, Pt, Rh, Pd, Cu, Ag, Au, Cd, in, Tl, Pb, P, As, Sb, Bi, S, Se, Te, as well as mixtures of these oxides.
• the mixtures are advantageously suitable both as material for the fiber and for the matrix.
• Fiber and matrix generally need not be the same material.
• the individual components can occur in the same molar amount, but advantageous are mixtures with greatly different concentrations of the individual components of the mixture, up to dopings in which a component occurs in concentrations of ⁇ 1%.
• binary and ternary mixtures of alumina, zirconia and yttria e.g., zirconia-reinforced alumina
• Mixtures of silicon carbide and alumina Mixtures of alumina and magnesia (MgO spinel); Mixtures of alumina and silica (mullite); Mixture of aluminum and magnesium silicates, ternary mixture of aluminum oxide, silicon oxide and magnesium oxide (cordierite); Steatite (magnesium silicate); Zirconia-reinforced alumina; Stabilized zirconium oxide (ZrO-2): stabilizers in the form of magnesium oxide (MgO), calcium oxide (CaO) or yttrium oxide (Y2O3).
• ZrO-2 Stabilized zirconium oxide
• ZrO-2 stabilizers in the form of magnesium oxide (MgO), calcium oxide (CaO) or yttrium oxide (Y2O3).
• Ceria CeO2
• scandium oxide ScO-3
• YbO3 ytterbium oxide
• 3) as stabilizers for use aluminum titanate (stoichiometric mixture of alumina and titania); Silicon nitride and aluminum oxide (silicon aluminum oxynitrides SIALON).
• zirconium oxide-reinforced aluminum oxide it is advantageous to use Al 2 O 3 with 10 to 20 mol% of ZrC 2 O.
• ZrO 2 advantageously 10 to 20 mol% CaO, preferably 16 mol%, 10 to 20 mol% MgO, preferably 16, or 5 to 10 mol% Y 2 O 3 , preferably 8 mol% ("fully stabilized zirconium oxide") or 1 to 5 mol% Y 2 O 3, preferably 4 mol% (“partially stabilized zirconium oxide”) 80% Al 2 O 3, 18.4% ZrO 2 and 1, 6% Y 2 O 3 are advantageous.
• fibers of basalt, boron nitride, tungsten carbide, aluminum nitride, titanium dioxide, barium titanate, lead zirconate titanate and / or boron carbide in an oxide-ceramic matrix are also conceivable.
• the fibers of the fiber-reinforced carbon can be arranged radially encircling and / or crossing on the first layer of the non-porous ceramic.
• Suitable fibers are reinforcing fibers which fall into the classes of oxide, carbidic, nitridic fibers or C fibers and SiBCN fibers.
• the fibers of the ceramic composite are alumina, mullite, silicon carbide, zirconia and / or carbon fibers.
• Mullite consists of mixed crystals of alumina and silica.
• the use of fibers of oxide ceramic (Al 2 O 3, SiO 2, mullite) or of non-oxide ceramic (C, SiC) is preferred.
• creep-resistant fibers are used, d. H. Fibers that show no or minimal increase in the duration of permanent deformation, ie creep, in the creep range - in the temperature range up to 1400 ° C.
• 3M specifies the following limit temperatures for the NEXTEL fibers for the residual elongation of 1% after 1000 h under a tensile load of 70 MPa: NEXTEL 440: 875 ° C, NEXTEL 550 and NEXTEL 610: 1010 ° C, NEXTEL 720 : 1 120 ° C (Reference: Nextel TM Ceramic Textiles Technical Notebook, 3M, 2004).
• the fibers advantageously have a diameter between 10 and 12 pm. They are advantageous to each other - usually with linen or satin weave - woven into textile webs, knitted into tubes or wrapped as a fiber bundle around a mold.
• the fiber bundles or fabrics are, for example, infiltrated with a slip containing the components of the later ceramic matrix, advantageously Al 2 O 3 or mullite (Schmücker, M. (2007), Fiber-reinforced Oxide Ceramics, Materials Science and Materials Engineering, 38 (9), 698-704).
• the ceramic fiber composite used is preferably SiC / Al 2 O 3, SiC / mullite, C / Al 2 O 3, C / mullite, Al 2 O 3 / Al 2 O 3, Al 2 O 3 / mullite, mullite / Al 2 O 3 and / or mullite / mullite.
• the material before the slash designates the fiber type and the material after the slash designates the matrix type.
• a matrix system for the ceramic fiber composite structure it is also possible to use siloxanes, silicon precursors and a wide variety of oxides, for example zirconium oxide.
• the ceramic fiber composite material preferably contains at least 99% by weight of Al 2 O 3 and / or mullite.
• Fiber composites based on oxide-ceramic fibers for example 3M TM NEXTEL TM 312, NEXTEL TM 440, NEXTEL TM 550, NEXTEL TM 610 or NEXTEL TM 720, are preferably used in the present invention. Particularly preferred is the use of NEXTEL 610 and / or NEXTEL 720.
• the matrix has a degree of filling of fibers (volume fraction of the fibers in the composite structure) of 20 to 40%, the total solids content of the composite structure is between 50 and 80%.
• Fiber-composite ceramics based on oxidic ceramic fibers are chemically resistant in oxidizing and reducing gas atmospheres (ie no change in weight after storage in air at 1200 ° C. for 15 h (reference: Nextel TM Ceramic Textiles Technical Notebook, 3M, 2004)) and thermally stable until over 1300 ° C.
• Have fiber composite ceramics a virtually ductile deformation behavior. Thus, they are temperatur grillbestig and have a quasi-tough fracture behavior. Thus, the failure of a component announces itself before it breaks.
• the fiber composite material advantageously has a porosity of 20% to 50%; it is therefore not gas-tight as defined in DIN 623-2.
• the fiber composite material advantageously has a long-term use temperature of up to 1500 ° C., preferably up to 1400 ° C., particularly preferably up to 1300 ° C.
• the fiber composite material advantageously has a strength of> 50 MPa, preferably> 70 MPa, more preferably> 100 MPa, in particular> 120 MPa.
• the fiber composite material advantageously has a yield strength of elastic deformation of 0.2 to 1%.
• the fiber composite material advantageously has a thermal shock resistance according to DIN EN 993-1 1.
• the fiber composite material advantageously has a thermal expansion coefficient [ppm / K] of 4 to 8.5.
• the fiber composite material advantageously has a thermal conductivity of 0.5 to 5 ⁇ .
• the ceramic fiber composite material can be produced by CVI (Chemical Vapor Infiltration) method, pyrolysis, in particular LPI (Liquid Polymer Infiltration) method or by chemical reaction such as LSI (Liquid Silicon Infiltration) method.
• a seal can be achieved.
• the sealed areas serve as sealing surfaces.
• This variant can be used up to a temperature range of ⁇ 400 ° C.
• the composite pipe is coated only in the edge region to the metallic connector.
• Edge area means the last section before the transition to another material, preferably to a metallic material, having a length corresponding to the 0.05 to 10 times the inner diameter of the composite pipe, preferably corresponding to the 0.1 to 5 times the inner diameter
• the thickness of the impregnation advantageously corresponds to the complete layer thickness of the fiber-composite ceramic in the edge region
• the processes for impregnation are known to the person skilled in the art.
• the present invention accordingly comprises a multilayer composite pipe comprising at least two layers, a layer of nonporous monolithic ceramic, preferably oxide ceramic, and a layer of fiber composite ceramic, preferably oxide fiber composite ceramic, wherein the outer layer of the composite tube in the edge region before the transition to another material , preferably metallic material, impregnated or coated with polymer, nonporous ceramic, (pyro-) carbon and / or metallic material.
• the sleeve of metal contains one or more of the following materials: chromium, titanium, molybdenum, nickel steel 47Ni, alloy 80Pt20lr, alloy 1 .3981, alloy 1 .3917 or a tri-metal copper / invar / copper.
• the ratio of the length of the lap joint (5) to the inner diameter of the composite tube in the range of 0.05 to 10, preferably from 0.1 to 5, in particular from 0.2 to 2.
• the sleeve is made of metal the outside of the inner layer connected in a gas-tight manner with joining techniques, which are known in the art (Information Center for Technical Ceramics (IZTK): Brevier technical ceramics, Fahner Verlag, Lauf (2003)).
• the outer layer is connected by a material connection with the sleeve made of metal.
• the length of the ceramic overlap i. the area including outer layer and metallic shell without inner layer, from 0.05 times to 10 times, preferably from 0.1 times to 5 times, especially from 0.2 times to 2 times the Inside diameter of the composite pipe.
• the present invention accordingly comprises a multilayer composite pipe comprising at least two layers, a layer of nonporous monolithic ceramic, preferably oxide ceramic, and a layer of fiber composite ceramic, preferably oxide fiber composite ceramic, wherein a sleeve of metal at the end of the composite pipe, the area between the inner and the outer layer is located, is arranged.
• the present invention includes a connector including at least one metallic gas-conducting conduit extending longitudinally of the multilayer composite tube, i. in the flow direction of the educts, partially overlapped with at least two ceramic layers, wherein at least one ceramic layer includes a non-porous monolithic ceramic, preferably oxide ceramic, and at least one other ceramic layer a fiber composite ceramic, preferably oxide fiber composite ceramic includes.
• the present invention includes a sandwich structure in the transition region between metallic material and ceramic material including a metallic one
• the present invention comprises a connector having a first tube portion including a metallic tube, e.g. B. at least one metallic gas-carrying line, which has a second adjoining the first pipe region pipe region, which is an outer layer of fiber composite ceramic and an inner metallic
• the sandwich structure of the connecting piece has an inner ceramic layer, a middle metallic layer and an outer ceramic layer.
• the fiber composite ceramic is the outer ceramic layer.
• the nonporous monolithic ceramic layer is the inner layer.
• the fiber composite ceramic is the inner ceramic layer.
• the nonporous monolithic ceramic layer is the outer layer.
• the fiber composite ceramic is oxidic.
• the nonporous monolithic ceramic is an oxide ceramic.
• the length of the first tube region is greater than 0.05 times, preferably greater than 0.1 times, in particular greater than 0.2 times, the inner diameter of the multilayer composite tube;
• the length of the first pipe portion is less than 50% of the total length of the composite pipe.
• the length of the second tube region is from 0.05 times to 10 times, preferably from 0.1 times to 5 times, in particular from 0.2 times to twice, the inner diameter of the multilayer composite tube.
• the length of the third tube region is from 0.05 times to 10 times, preferably from 0.1 times to 5 times, in particular from 0.2 times to 2 times, the inner diameter of the composite tube.
• the wall thickness of the metallic tube i. of the metallic overlap, which is from 0.01 times to 0.5 times the total wall thickness, preferably from 0.03 times to 0.3 times the total wall thickness, in particular from 0.05 times to 0.1 -fold the total wall thickness.
• the wall thickness of the ceramic overlap is 0.05 times to 0.9 times the total wall thickness, preferably 0.05 times to 0.5 times the total wall thickness, in particular 0, 05 times to 0.25 times the total wall thickness.
• the wall thickness of the sleeve is 0.05 times to 0.9 times the total wall thickness, preferably 0.05 times to 0.5 times the total wall thickness, in particular 0.05 times to 0.025 times the total wall thickness.
• the thickness of the monolithic ceramic layer is advantageously from 0.5 mm to 45 mm, preferably from 1 mm to 25 mm, particularly preferably from 3 mm to 15 mm.
• the thickness of the layer of oxide-fiber composite ceramic is advantageously from 0.5 mm to 5 mm, preferably from 0.5 mm to 3 mm.
• connection with the inner layer is gas-tight with joining techniques that are known in the art (Information Center for Technical Ceramics (IZTK): Brevier technical ceramics, Fahner Verlag, Lauf (2003)).
• IZTK Information Center for Technical Ceramics
• the connection with the outer layer is cohesive.
• the present invention comprises a connector having a first tube portion including a metallic tube, e.g. B. at least one metallic gas-carrying line, which has a second adjoining the first pipe portion pipe portion having an outer ceramic layer and an inner metallic layer and having a third adjacent to the second pipe portion pipe portion comprising a sandwich structure comprising an inner metallic layer, a middle and an outer ceramic layer, wherein one of the ceramic layers comprises a nonporous monolithic ceramic layer and the other ceramic layer has a fiber composite ceramic layer and a fourth to the third Having region subsequent tube portion having a Mapschich- term composite tube comprising at least two layers, a layer of nonporous monolithic ceramic and a layer of fiber composite ceramic, ( Figure 1 c).
• a connector having a first tube portion including a metallic tube, e.g. B. at least one metallic gas-carrying line, which has a second adjoining the first pipe portion pipe portion having an outer ceramic layer and an inner metallic layer and having a third adjacent to the second pipe portion pipe portion
• the fiber composite ceramic the outer ceramic layer.
• the nonporous monolithic ceramic layer is the inner layer.
• the fiber composite ceramic is the inner ceramic layer.
• the nonporous monolithic ceramic layer is the outer layer.
• the fiber composite ceramic is oxidic.
• the nonporous monolithic ceramic is an oxide ceramic.
• the length of the first tube region is greater than 0.05 times, preferably greater than 0.1 times, in particular greater than 0.2 times, the inner diameter of the multilayer composite tube;
• the length of the first pipe portion is less than 50% of the total length of the composite pipe.
• the length of the second tube region is from 0.05 times to 10 times, preferably from 0.1 times to 5 times, in particular from 0.2 times to twice, the inner diameter of the multilayer composite tube.
• the length of the dntten pipe region is from 0.05 times to 10 times, preferably from 0.1 times to 5 times, in particular from 0.2 times to
• the wall thickness of the metallic tube, d. H. the metallic overlap which is 0.01 times to 0.5 times the total wall thickness, preferably 0.03 times to 0.3 times the total wall thickness, in particular since 0.05 times to 0.1 times the entire wall thickness.
• the wall thickness of the ceramic overlap is 0.1 times to 0.95 times the total wall thickness, preferably 0.5 times to 0.95 times the total wall thickness, in particular 0.8. times up to 0.95 times the total wall thickness.
• the wall thickness of the sleeve which is 0.05 times to 0.9 times the total wall thickness, preferably 0.05 times to 0.5 times the total wall thickness, in particular 0.05 times up to 0.2 times the total wall thickness.
• the thickness of the layer of monolithic ceramic is advantageously from 0.5 mm to 45 mm, preferably from 1 mm to 25 mm, particularly preferably from 3 mm to 15 mm.
• the thickness of the layer of oxide-fiber composite ceramic is advantageously from 0.5 mm to 5 mm, preferably from 0.5 mm to 3 mm.
• the present invention comprises a connector having a first tube portion including a metallic tube, e.g. At least one metallic gas-carrying conduit having a second tube portion adjacent to the first tube portion having a sandwich structure including an inner ceramic layer, a middle metallic layer and an outer ceramic layer, one of the ceramic Layer has a non-porous monolithic ceramic layer and the other ceramic layer has a fiber composite ceramic layer and a third adjacent to the second tube region tube portion comprising a multilayer composite tube containing at least two layers, a layer of nonporous monolithic ceramic and a layer of fiber composite ceramic, having (Figure 3 b).
• a connector having a first tube portion including a metallic tube, e.g. At least one metallic gas-carrying conduit having a second tube portion adjacent to the first tube portion having a sandwich structure including an inner ceramic layer, a middle metallic layer and an outer ceramic layer, one of the ceramic Layer has a non-porous monolithic ceramic layer and the other ceramic layer has a fiber composite ceramic layer and a third adjacent
• the fiber composite ceramic is the inner ceramic layer.
• the nonporous monolithic ceramic layer is the outer layer.
• the fiber composite ceramic is the outer ceramic layer.
• the nonporous monolithic ceramic layer is the inner layer.
• the fiber composite ceramic is oxidic.
• the nonporous monolithic ceramic is an oxide ceramic.
• the length of the second tube region is from 0.05 times to 10 times, preferably from 0.1 times to 5 times, in particular from 0.2 times to twice, the inner diameter of the multilayer composite tube.
• the wall thickness of the metallic tube ie the metallic overlap, is 0.01 times to 0.5 times the total wall thickness, preferably 0.03 times to 0.3 times the total wall thickness, in particular 0.05 times to 0.1 times the total wall thickness.
• the wall thickness of the ceramic overlap is 0.1 times to 0.95 times the total wall thickness, preferably 0.5 times to 0.95 times the total wall thickness, in particular 0.8. times up to 0.95 times the total wall thickness.
• the wall thickness of the sleeve which is 0.05 times to 0.9 times the total wall thickness, preferably 0.05 times to 0.5 times the total wall thickness, in particular 0.05 times up to 0.2 times the total wall thickness.
• the thickness of the layer of monolithic ceramic is advantageously from 0.5 mm to 45 mm, preferably from 1 mm to 25 mm, particularly preferably from 3 mm to 15 mm.
• the thickness of the layer of oxide-fiber composite ceramic is advantageously from 0.5 mm to 5 mm, preferably from 0.5 mm to 3 mm.
• the present invention comprises a connector having a first tube portion including a metallic tube, e.g. At least one metallic gas-carrying line, which has a second tube region adjoining the first tube region, which has a sandwich structure comprising an inner and a middle ceramic layer and an outer metallic layer, one of the ceramic Layers has a non-porous monolithic ceramic layer and the other ceramic layer has a fiber composite ceramic layer and a third adjacent to the second tube region tube portion comprising a multilayer composite tube containing at least two layers, a layer of nonporous monolithic ceramic and a Layer of fiber composite ceramic, having (Figure 3 c).
• a connector having a first tube portion including a metallic tube, e.g. At least one metallic gas-carrying line, which has a second tube region adjoining the first tube region, which has a sandwich structure comprising an inner and a middle ceramic layer and an outer metallic layer, one of the ceramic Layers has a non-porous monolithic ceramic layer and the other ceramic layer has a fiber
• the fiber composite ceramic is the inner ceramic layer.
• the unpopular monolithic ceramic layer is the outer layer.
• the fiber composite ceramic is the outer ceramic layer.
• the nonporous monolithic ceramic layer is the inner layer.
• the fiber composite ceramic is oxidic.
• the nonporous monolithic ceramic is an oxide ceramic.
• the length of the second tube region is from 0.05 times to 10 times, preferably from 0.1 times to 5 times, in particular from 0.2 times to twice, the inner diameter of the multilayer composite tube.
• the wall thickness of the metallic tube is advantageously from 0.01 times to 0.5 times the total wall thickness, preferably from 0.03 times to 0.3 times the total wall thickness , in particular since 0.05 times to 0.1 times the total wall thickness.
• the wall thickness of the ceramic overlap which is 0.1 times to 0.95 times the total wall thickness, preferably 0.5 times to 0.95 times the total wall thickness, in particular since 0.8- times up to 0.95 times the total wall thickness.
• the wall thickness of the sleeve is 0.05 times to 0.9 times the total wall thickness, preferably 0.05 times to 0.5 times the total wall thickness, in particular 0.05 -fold to 0.2 times the total wall thickness.
• the thickness of the monolithic ceramic layer is advantageously from 0.5 mm to 45 mm, preferably from 1 mm to 25 mm, particularly preferably from 3 mm to 15 mm.
• the thickness of the layer of oxide-fiber composite ceramic is advantageously from 0.5 mm to 5 mm, preferably from 0.5 mm to 3 mm.
• the ends of the multilayer composite pipe are advantageously thermostated to a temperature level within the limits of the thermal resistance of the impregnation or coating, the gasket, the metal-ceramic bond, and the metal shell.
• Advantageous ranges are: ⁇ 1000 ° C (water glass), ⁇ 500 ° C (brazing / mica seal), ⁇ 400 ° C (brazing / graphite), ⁇ 300 ° C (polymer seals Kalrez), ⁇ 250 ° C (silicone rubber, Viton) ,
• ⁇ 1000 ° C water glass
• ⁇ 500 ° C brazing / mica seal
• ⁇ 400 ° C brazing / graphite
• ⁇ 300 ° C polymer seals Kalrez
• ⁇ 250 ° C silicone rubber, Viton
• the middle region advantageously between 20% and 99% of the total length, preferably between 50% and 99% of the total length, in particular between 90% and 99% of the total length, of the composite tube is arranged in a heating chamber and can be at temperatures up to 1300 ° C or to be heated about it; advantageous 900 ° C to 1700 ° C, preferably 1000 ° C to 1600 ° C, in particular 1 100 ° C to 1500 ° C.
• the multilayer composite pipe is typically arranged vertically, fixed at one end and loosely supported at the other end. Preferably, it is firmly clamped at the lower end and slidably guided at the upper end in the axial direction. In this arrangement, the tube can thermally expand stress-free.
• a variant of the solution consists of two concentric tubes ( Figure 2).
• the inner tube advantageously has an inner tube diameter of 10 mm to 100 mm, preferably 15 mm to 50 mm, in particular 20 mm to 30 mm.
• the inner tube is advantageously open on both sides and the outer tube advantageously closed on one side.
• the outer tube advantageously has an inner tube diameter of 20 mm to 1000 mm, preferably 50 mm to 800 mm, in particular 100 mm to 500 mm.
• the main reaction section is advantageously located in the annular space between the inner and the outer tube. The reactants can either be introduced into the annulus and the product stream can be withdrawn from the inner tube or vice versa.
• connection for the inlet and outlet are located at the open end of the pipe.
• the closed pipe end can loosely (without any guidance) protrude into the boiler room and expand there unhindered. As a result, no temperature-induced in the axial direction Tensions arise.
• This configuration ensures that the multilayer composite pipes must be clamped and sealed only on one side, in the cold and sealed at the closed end unhindered thermal expansion.
• the options shown in Figure 1 b, Figure 1 c and Figure 1 d to seal the open end, are applicable to this variant.
• the present invention thus comprises a double-tube reactor for endothermic reactions, which is characterized in that the reactor comprises two multilayer composite tubes with a heat transfer coefficient of> 500 W / m 2 / K containing at least two layers each, a layer of nonporous monolithic ceramic and a layer of fiber composite ceramic, wherein the one composite tube enclosing the other composite tube and the inner composite tube is open on both sides and the outer tube is closed on one side.
• the fiber composite ceramic, the outer ceramic layer of the multilayer composite pipe comprising two concentric tubes.
• the nonporous monolithic ceramic layer is the inner layer.
• the fiber composite ceramic is the inner ceramic layer.
• the nonporous monolithic ceramic layer is the outer one
• the fiber composite ceramic is oxidic.
• the nonporous monolithic ceramic is an oxide ceramic.
• the double-layered construction allows the tightness and temperature resistance of a monolithic non-porous ceramic tube to be combined with the good-natured failure behavior of the fiber-reinforced ceramic ("crack before breakage.")
• the device according to the invention with sealed edge regions enables the gas-tight connection of the multilayer composite tubes to the conventionally designed periphery.
• the ceramic composite pipes according to the invention are used as reaction tubes in the following applications:
• FIG. 1 a shows a schematic representation of a gas-tight multilayer composite pipe with variable diameter
• Figure 1 b / 1 c / 1 d is a schematic representation of the connectors
• Figure 2 is a schematic representation of a variant of the solution consists of two concentric tubes
• Figure 3a is a schematic representation of a gas-tight multilayer sandwich pipe with variable diameter
• Figure 3b / 3c is a schematic representation of the connecting pieces
• the test specimen was a tube with a monolithic wall of dense corundum (product of Fricktec with the product number 122-1 1035-0) with the following dimensions (outside diameter x inside diameter x length): 35 mm ⁇ 29 mm ⁇ 64 mm.
• the heat transfer coefficient of the pipe wall, based on the inside of the wall, was: ki oc 9200 (W / m 2 / K).
• the tube was exposed to the flame of a welding torch.
• the welding torch was supplied with acetylene and oxygen and equipped with a welding insert type Gr3, A, 6-9, S2.5bar.
• the burner tip was directed at a distance of 50mm perpendicular to the tube wall. After about 3 seconds, the tube broke. This finished the test. This test confirmed the thermal shock sensitivity of monolithic ceramics.
• Example 2 Example 2
• the specimen was a tube with a two-layered wall.
• the wall of the core tube was made of dense monolithic corundum (product of Friatec with the product number 122-1 1035-0) with the following dimensions (outside diameter x inside diameter x length): 35mm x 29mm x 64mm.
• the core tube was wrapped with a layer of fiber composite ceramic (ceramic sheet type FW12) with a layer thickness of approx. 1 mm.
• the tube was exposed to the flame of a welding torch.
• the welding torch was supplied with acetylene and oxygen and equipped with a welding insert type Gr3, A, 6-9, S2.5bar.
• the burner tip was directed at a distance of 50mm perpendicular to the tube wall. It formed within 4 seconds on the outer wall of the tube, a white glowing spot with a length of about 25mm (T> 1300 ° C). The flame was removed from the tube after 20 seconds and returned to the tube for 30 seconds 30 seconds later. The tube survived this thermal shock undamaged.

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