Classifications

• • 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
• • 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
  • B01D63/061—Manufacturing thereof
• • 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
  • 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
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/12—Composite membranes; Ultra-thin membranes
  • B01D69/1213—Laminated layers
• • 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
  • B01D69/12—Composite membranes; Ultra-thin membranes
  • B01D69/1216—Three or more layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/02—Inorganic material
  • B01D71/022—Metals
  • B01D71/0223—Group 8, 9 or 10 metals
  • B01D71/02231—Palladium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2313/00—Details relating to membrane modules or apparatus
  • B01D2313/04—Specific sealing means
  • B01D2313/042—Adhesives or glues
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2313/00—Details relating to membrane modules or apparatus
  • B01D2313/13—Specific connectors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2323/00—Details relating to membrane preparation
  • B01D2323/58—Fusion; Welding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/02—Details relating to pores or porosity of the membranes
  • B01D2325/0283—Pore size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/04—Characteristic thickness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
  • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes

Definitions

• the present invention relates to a membrane assembly for permeative
• Gas mixtures with a porous, fluid-permeable, in particular gas-permeable, metallic carrier substrate, a formed on the carrier substrate, selectively for the fluid to be separated (in particular gas) permeable membrane, at least superficially from a fluid-tight (in particular gas-tight) metallic material coupling part, wherein the carrier substrate along an edge portion of the same is materially connected to the coupling part, and with a formed between the carrier substrate and the membrane, ceramic, fluid-permeable (in particular gas-permeable), porous, first intermediate layer.
• the invention further relates to a method for producing such
• Membrane arrangements of this type are generally used for the selective separation of a fluid (liquid, gas) from fluid mixtures, in particular for the selective separation of a gas from gas mixtures, in particular for the separation of hydrogen from hydrogen-containing gas mixtures (eg from steam-reformed natural gas).
• a fluid, a gas or a mixture of a liquid and a gas is referred to as fluid.
• a gas mixture with a certain partial pressure of the gas to be separated such as with a certain H 2 -partial pressure
• the atoms / molecules of the gas to be separated endeavor to pass through the membrane to the other side, until on both sides of the same partial pressure of the gas to be separated consists of the membrane surface, a specific gas flow of the gas to be separated, in particular a specific
• H 2 gas flow are assigned as a so-called performance parameter. It regularly applies that the thinner the membrane is and - at least for metallic Membranes - the higher the operating temperature, the higher the specific gas flow of the gas to be separated (eg H 2 ). Largely appropriate
• thin membranes in the range of several ⁇ have a very low dimensional stability and rigidity, they are often as a layer on a porous, fluid-permeable (especially gas-permeable), rohrformigen or planar carrier substrate, which a fluid supply (in particular gas supply) to and / or fluid removal Guaranteed (in particular gas removal) of the membrane and provides a flat surface for application of the membrane is formed.
• Metallic materials for the carrier substrate are distinguished from ceramic materials by low production costs and are relatively simple with an at least surface-fluid-tight (in particular gas-tight) and metallic coupling part, such as. by welding or soldering, connectable.
• the coupling part via the coupling part, the integration of the membrane assembly in a module (with multiple membrane assemblies of this type) or more generally in a system within which the fluid separation (in particular gas separation) is carried out.
• a ceramic, fluid-permeable (in particular gas-permeable), porous, first intermediate layer is provided, which serves to avoid diffusion effects and, in many cases, to gradually reduce the pore size from the metallic carrier substrate to the membrane.
• transition from the porous carrier substrate via the cohesive connection (eg weld seam) to the dense, metallic surface of the coupling part presents a high challenge in the application of the above-mentioned layers.
• this transition region is a fluid-tight (in particular gas-tight) separation of the two fluid spaces (In particular gas spaces), at least as far as the other, in the fluid mixture (in particular gas mixture) in addition to the fluid to be separated
• this transitional area represents the mechanical weak point and there are always spalling of the layers.
• a variant for producing such a dense transition region is in
• the intermediate layer provided between the carrier substrate and the membrane extends beyond the connection region between the carrier substrate and the coupling part, but extends in the direction of the coupling part in front of the membrane.
• Membrane arrangement in which a dense layer in the transition region on a porous, ceramic support substrate and a gas-tight, ceramic
• the object of the present invention is a membrane assembly of the type specified above and a method for producing such a
• Transition region between the carrier substrate and the coupling part remains connected over a long period of use areally with the respective substrate.
• a membrane arrangement for the permeative separation of a fluid from fluid mixtures in particular a gas
• the membrane arrangement has a porous, fluid-permeable (in particular gas-permeable), metallic carrier substrate, one on the carrier substrate
• a coupling part consisting at least superficially of a fluid-tight (in particular gas-tight) metallic material, wherein the carrier substrate is materially connected to the coupling part along an edge section thereof, and a formed between the carrier substrate and the membrane, ceramic, fluid-permeable (in particular gas-permeable), porous, first intermediate layer.
• connection layer formed.
• the first intermediate layer exits on or at the bonding layer and has a larger, average pore size than the
• Connection layer on.
• the different layers are in one
• layered sintered layers are particularly pronounced, and the
• Layers / components is referred to, the presence of intermediate layers / components is excluded. If, on the other hand, the term “direct” is not used, other layers / components may also be provided therebetween, as far as technically feasible In the case of range specifications, the specified limit values should be included in each case.
• Fluid is referred to a liquid, a gas or a mixture of a liquid and a gas.
• the fluid is preferably in each case a gas, or in the case of fluid mixtures, in each case gas mixtures.
• each is a "gas-tight" or
• the structure of the claimed membrane assembly is associated with several advantages, which will be explained below with reference to the operation of the individual components.
• the membrane is a thin, selectively for certain types of fluids, in particular gas types (especially for H 2 ), permeable layer of a material referred to.
• the membrane or its material is selected according to the fluid to be separated, in particular gas (eg H 2 ).
• gas eg H 2
• the other fluids contained in the respective fluid mixture (in particular gas mixture) (in particular gases) may also be used in the design and material selection of the components
• diaphragm assembly for example, if a component for all of these fluids (in particular gases) of the fluid mixture (in particular
• Gas mixture must be formed fluid-tight (in particular gas-tight).
• the membrane may in principle be formed as an intrinsically stable foil as well as (at least) one layer on a carrier substrate. With regard to the highest possible
• Performance parameters is used in the membrane assembly according to the invention a regularly planar design carrier substrate for the membrane in order to provide the membrane as a thin layer.
• the carrier substrate must be porous and fluid-permeable, depending on which side of the membrane
• Carrier substrate is used (in tubular design, preferably on the inside of the membrane) to ensure the fluid supply to or fluid removal from the membrane.
• carrier substrate and thus also for the applied thereon membrane there are two common basic forms, namely a planar and a tubular basic shape, the focus more and more on the tubular or
• tubular basic shape lies.
• Both metallic and ceramic materials are used for the carrier substrate, wherein the presently claimed, metallic carrier substrate is distinguished from ceramic carrier substrates in that it is easier to seal in the production, in the transition region to the coupling part and relatively easy with the coupling part, such as over a welding process, connectable.
• the production of such porous, fluid-permeable, metallic carrier substrates takes place, in particular, via a powder-metallurgical production method which comprises the steps of shaping (eg pressing) and sintering of metallic starting powders, whereby porous carrier substrates having a microstructure typical for powder metallurgy production are obtained.
• microstructure is characterized in that the individual grains of the metal powder are recognizable, these individual grains are interconnected depending on the degree of sintering by more or less pronounced Sinterotrolse (recognizable, for example, via an electron micrograph of a microsection).
• Porous, fluid-permeable, metallic carrier substrates in particular such powder-metallurgically produced carrier substrates, however, have a relatively large pore size (in some cases up to 50 ⁇ m), which means sealing with a membrane which is typically only a few micrometers thick (thickness in the case of gas separation membranes, in particular in the range from 5-15 ⁇ ) difficult.
• Particularly suitable materials for the carrier substrate are iron (Fe) -based (ie containing at least 50% by weight, in particular at least 70% by weight of Fe), a high chromium content (chromium: Cr). containing alloys (eg at least 16 wt.% Cr), to which further additives, such as yttrium oxide (Y 2 0 3 ) (to increase the oxidation resistance), titanium (Ti) and molybdenum (Mo) may be added, the proportion of these additives total preferably less than 3% by weight (cf., for example, the material designated as ITM from Plansee SE containing 71.2% by weight of Fe, 26% by weight of Cr and in total less than 3% by weight of Ti, Y 2 0 3 and Mo). Furthermore, at the high operating temperatures (typically operating temperatures for gas separation in the range of
• At least one ceramic, fluid-permeable, porous intermediate layer (eg of 8YSZ, ie of zirconium oxide fully stabilized with 8 mol% yttrium oxide (Y 2 O 3 )) is used between the carrier substrate and the membrane. It suppresses interdiffusion effects between the carrier substrate and the membrane. Furthermore, via them, possibly also in stages (in particular via the
• the pore size can be reduced to a few ⁇ , in particular to a suitable for the gas separation, average pore size in the range of 0.03-0.50 ⁇ , the first
• Intermediate layer (and possibly further intermediate layers) and the membrane preferably extend over the entire, for the fluid separation (in particular
• Gas separation provided surface of the carrier substrate.
• this corresponds to the cylindrical outer surface (or possibly the cylindrical inner surface) of the carrier substrate, wherein optionally at least one axial edge region (for example for attaching a connection component or a sealing end) can be recessed.
• the sealing takes place (apart from the permeability for the fluid to be separated) through the membrane.
• the layer structure is to be connected to corresponding connection lines of the system (for example reactor).
• connection lines of the system for example reactor.
• an at least superficially fluid-tight metallic one is present immediately adjacent to the carrier substrate
• the coupling part can also fulfill other functions, such as merging or splitting several connecting lines. For this purpose, appropriately functionalized Sections formed on the coupling part and / or be connected to this.
• the carrier substrate is integrally connected to the coupling part along an edge section thereof (for example via a welded connection).
• the fluid-tight, metallic region of the coupling part is preferably provided on the same side as the membrane on the adjacent carrier substrate, in tubular form, in particular on the outside. In particular, it is in the
• Coupling part to a metallic material in the solid material In the case of one
• tubular design is also the coupling part, at least in the on the
• Support substrate adjacent region, tubular and the cohesive connection extends around the entire circumference of the adjacent components.
• the transition region between the coupling part and the carrier substrate is at least for the other, in the fluid mixture in addition to the fluid to be separated (in particular gas) fluids or gases (hereinafter: "other fluids” in particular “other gases”) fluid-tight (in particular gas-tight) to design.
• other fluids in particular “other gases”
• other gases fluid-tight
• the membrane itself, but alternatively also a layer which is fluid-tight for the other or all fluids of the fluid mixture, adjacent to the membrane or overlapping thereto, can be pulled out beyond the coupling part, in order to be fluid-tight on the coupling part (for the further or all Fluids of the fluid mixture) complete.
• the invention is based on the finding that the flakes of the layers occurring in this transition region and leading to a failure of the membrane arrangement are due to the following causes: between the first intermediate layer and the fluid-tight, metallic material of the coupling part, which consists in particular of a metallic solid material (such as eg steel), there is only insufficient adhesion. This also applies to the field of
• connection and the cohesive connection at least one (in particular exactly one) applied ceramic bonding layer.
• connection layer extends at least over the cohesive connection and an adjacent section of the
• Coupling part It has a smaller, average pore size than the first intermediate layer, which terminates on the bonding layer on.
• a direct contact of the first intermediate layer with the problematic region of the material connection and the coupling part is reduced, preferably even completely eliminated.
• the bonding layer below or immediately adjacent next to the first intermediate layer is applied directly to the coupling part and the integral connection, a significantly better adhesion is achieved due to the lower porosity.
• this intermediate layer in the form of the bonding layer reduces the stress due to the different thermal expansion coefficients. In particular, in a sintering of the ceramic
• Bonding layer formed between the finer ceramic particles of this bonding layer and the underlying metallic surface significantly more sintering necks than would be the case between the metallic surface and the first intermediate layer. This improves the adhesion of the bonding layer on the metallic surface.
• the application of the first intermediate layer is not a problem and also leads to good adhesion. The occurrence of flaking, both during sintering in the context of Production as well as in later use, could thereby be avoided.
• the first intermediate layer extends in the direction of
• Coupling part at least up to the end of the carrier substrate, possibly even to over the adjacent region of the coupling part to form a good support for the subsequent layers, especially if they have a finer grain structure than the first intermediate layer and the material of the carrier body , if necessary, could seep into the material of the carrier substrate.
• the first intermediate layer runs on the bonding layer, i. such that in the direction perpendicular to the layer surface (corresponding to the radial direction in the case of a tubular basic shape), an overlapping region is formed between the attachment layer and the first intermediate layer (compare FIGS. 1, 3).
• Adjacent layer adjacent see Fig. 2.
• the average pore size of the bonding layer deviates by at least 0.10 ⁇ , in particular by at least 0.15 ⁇ , preferably even by at least 0.20 ⁇ , from the average pore size of the first intermediate layer.
• the consequent, significantly finer-grained structure of the bonding layer favors a particularly good adhesion of the same on the coupling part.
• the bonding layer is a sintered, ceramic layer.
• a ceramic, sintered layer is characterized by a typical microstructure, in which the individual ceramic grains are recognizable, these being interconnected by more or less pronounced sintering necks, depending on the degree of sintering (in the present, ceramic, sintered layers, the sintering necks can only be very weak).
• the typical microstructure in which the individual ceramic grains are recognizable, these being interconnected by more or less pronounced sintering necks, depending on the degree of sintering (in the present, ceramic, sintered layers, the sintering necks can only be very weak).
• Microstructure is e.g. via an electron micrograph of a
• intermediate layer and possibly further, provided intermediate layers each (a) sintered, ceramic layer (s).
• the attachment layer starting from the cohesive connection, extends directly on the carrier substrate beyond a section of the carrier substrate adjoining the cohesive connection.
• the bonding layer extends from both sides of the bonded joint, i. to the side of the coupling part as well as to the side of the support substrate, the discontinuity in the region of the material connection is compensated on both sides by providing a substantially continuous transition and providing a uniform underlay for the first intermediate layer. This improves the adhesion of the layer structure and reduces the risk of cracking.
• connection layer extends, starting from the integral connection in the direction of the coupling part and / or in the direction of the carrier substrate, in each case over a length in the range from 0.2 to 3.0 cm.
• This length which extends in the axial direction in a tubular or tubular design, is in the direction of the coupling part of the adjacent in this direction end of the cohesive connection (which usually itself over a certain
• Connecting length extends, cf. 1 to 3) and in the direction of the carrier substrate are measured by the end of the material connection which adjoins in this direction Range of 0.2-2.0 cm, more preferably in the range of 0.3-1.0 cm.
• the further area and the narrower areas are selected on the one hand with regard to achieving a good layer adhesion on the one hand, and on the most effective utilization of the available space for the fluid separation (in particular gas separation) on the other hand.
• the bonding layer has a thickness in the range of 1 to 50 ⁇ m.
• the layer thickness is in the range of 2 to 20 ⁇ , more preferably in the range of 3 to 10 ⁇ .
• the layer thickness can vary, this being particularly true in the field of
• a distance of 1 mm from the end of the integral connection in the direction of the coupling part is selected as the reference for the layer thickness (ie offset in each case 1 mm in the direction of the coupling part in FIGS.
• the bonding layer preferably has a substantially constant layer thickness, until it then thins towards its end.
• layer thickness information information pore size and in terms of the particle size in each case to these parameters in the ready State, ie, to be sintered layers on the sintered state.
• the bonding layer is porous and fluid-permeable, in particular gas-permeable.
• fluid transport in particular gas transport, to and from the membrane through the attachment layer is also made possible in the region of the attachment layer.
• the porosity of the bonding layer is preferably at least 20%, wherein the determination of the porosity due to the small layer thickness and due to the most angular shape of the individual
• the bonding layer has an average pore size in the range of 0-0.50 ⁇ m, in particular in the range of 0.01-0.30 ⁇ m, more preferably in the range of
• the pore size distribution is the
• the bonding layer in the range of 0.01 - 10.00 ⁇ .
• the bonding layer has an average particle size in the range of 0.01 to 1, 00 ⁇ m, in particular in the range of 0.01 to 0.75 ⁇ m, more preferably in the range of
• the particle size distribution is the
• Bonding layer in the range of 0.01 - 25.00 ⁇ .
• the other areas for the average pore and particle sizes and the corresponding size distributions and in particular the narrower areas are on the one hand to achieve a good adhesion of the bonding layer on the ground, on the other hand to make a good transition to the expiring, first intermediate layer, which has a larger, average pore size and possibly has a larger average particle size selected.
• the layer thickness of the first intermediate layer is according to a development in the range between 5-120 ⁇ , in particular in the range between 10-100 ⁇ , more preferably in the range between 20-80 ⁇ .
• the layer thickness data for the first and below-mentioned second intermediate layer relate to the region of the carrier substrate with a substantially constant layer thickness profile, while in the transition region to the coupling part due to unevenness and layer thickness variations may occur.
• the pore size or pore length of a single pore is determined as follows: the area of the respective pore in the micrograph is measured and, subsequently, its equivalent diameter, which would result for a circular shape of the same area size, is determined. Accordingly, the particle size is determined.
• a suitable grayscale value is selected as the threshold value.
• the pore size of all the pores of a representative region of the relevant layer previously selected in the micrograph is measured, and then its mean value is formed. Accordingly, the determination of the mean
• Particle size For the individual particles to be measured in each case, its geometric outline is decisive and not the grain boundaries of optionally a plurality of grains connected to a particle, each having a different, crystallographic orientation. Only the pores or particles that are completely within the selected range are included in the evaluation.
• the porosity of a layer can be determined in the micrograph (SEM-BSE image) by determining the area fraction of the pores within a selected area relative to the total area of that selected area, including the areas of the pores only partially within the selected area be involved.
• Intermediate layer an average pore size in the range of 0.20 to 2.00 ⁇ , in particular in the range of 0.31 to 1, 20 ⁇ , more preferably in the range of 0.31 to 0.80 ⁇ on.
• the pore size distribution of the first intermediate layer is in the range of 0.01-25.0 ⁇ . According to a development, the first
• Interlayer an average particle size in the range of 0.70 to 3.50 ⁇ , in particular in the range of 0.76 to 2.50 ⁇ , more preferably in the range of
• the particle size distribution is the first
• the porosity of the first intermediate layer is preferably at least 20%, wherein the determination of the porosity due to the small layer thickness and due to the most angular shape of the individual ceramic particles is associated with a relatively large measurement error.
• a ceramic, fluid-permeable, in particular gas-permeable, porous, second intermediate layer which has a smaller average pore size than the first, extends between the first intermediate layer and the membrane
• the second intermediate layer has an average pore size in the range of 0.03 to 0.50 ⁇ m, in particular in the range of
• the second intermediate layer has an average particle size in the range of 0.01-1.00 ⁇ , in particular in the range of 0.01-0.75 ⁇ , more preferably in the range of 0.03-0.50 ⁇ on.
• the layer thickness of the second intermediate layer is according to a
• Training in the range between 5 - 75 ⁇ , in particular in the range between 5 - 50 ⁇ , more preferably in the range between 10 - 25 ⁇ .
• the same starting material and the same sintering step are used for the second intermediate layer as for the bonding layer, so that it is similar in composition and its microstructure of the bonding layer.
• the second intermediate layer extends in the direction of
• Coupling part beyond the first intermediate layer addition may leak on the bonding layer or alternatively on the coupling part on which it adheres as well as the bonding layer due to the comparable properties.
• a sufficiently smooth surface for the application of the membrane is continuously provided up to the coupling part.
• the membrane extends in the direction of the coupling part beyond the bonding layer and the at least one intermediate layer and runs directly on the coupling part.
• at least one of the further fluids of the fluid mixture (in particular of the other fluids) is used Gases of the gas mixture) achieved fluid-tight arrangement.
• the second intermediate layer can adjoin the membrane directly.
• the materials of the attachment layer and the at least one intermediate layer are selected from the group of the following materials:
• Zirconium oxide eg addition of typically 3 mol% yttrium oxide with Y 2 0 3 as a stabilizer
• Other stabilizers of zirconia also come ceria (Ce0 2), scandia (Sc0 3) or ytterbium oxide (Y b0 3) in question.
• the carrier substrate and the coupling part are each tubular or tubular. Its cross-section is preferably circular with a constant diameter along the axial direction. Alternatively, but also a otherwise closed cross-section, such as an oval cross-section, and be provided along the axial direction aufweitender cross-section.
• the cohesive connection can in principle be formed by an integral design of the coupling part and of the carrier substrate, by a solder connection and by a welded connection. According to a development, the cohesive connection is formed by a welded connection, which preferably extends in the case of a tubular basic shape around the entire circumference of the respective, tubular edge section. A welded joint is inexpensive and process reliable to produce. Due to the porosity of the carrier substrate, a depression typically forms in the region of the welded connection.
• the materials used for the membrane are basically pure metals which have a certain permeability to hydrogen but which are a barrier to other atoms / molecules.
• noble metals in particular palladium, palladium-containing alloys (especially more than 50% by weight of palladium), for example palladium - Vanadium, palladium-gold, palladium-silver, palladium-copper, palladium-ruthenium or palladium-containing composite membranes, such as with the layer sequence palladium, vanadium, palladium, used.
• the membrane is accordingly off
• Palladium or a palladium-based metallic material e.g., alloy, composite, etc.
• the Pd content of such membranes is in particular at least 50% by weight, preferably at least 80% by weight. Further, it is preferred that the bonding layer and / or the at least one intermediate layer of
• the present invention further relates to a method for producing a
• Membrane arrangement for the permeative separation of a fluid from fluid mixtures, in particular a gas from gas mixtures, especially for the separation of H 2 from H 2 comprising gas mixtures comprising a porous, fiuid die uses (in particular gas-permeable), metallic carrier substrate and an at least on the surface of a fluid-tight (in particular gas-tight), existing metallic coupling part, wherein the carrier substrate along an edge portion of the same is integrally connected to the coupling part.
• the method has the following steps:
• porous intermediate layer on the carrier substrate (in particular gas-permeable), porous intermediate layer on the carrier substrate (and the overlapping region of the bonding layer), wherein the directly applied to the carrier substrate intermediate layer on or on the
• connection layer and the at least one intermediate layer is the connection layer and the at least one intermediate layer.
• the layer containing an organic binder and ceramic particles is applied by a wet-chemical method and then sintered, and only then the subsequent layer (possibly in
• Fig. 1 a schematic cross-sectional view of an inventive
• Fig. 2 a schematic cross-sectional view of an inventive
• FIG. 3 shows a schematic cross-sectional view of a device according to the invention
• Fig. 4 pore size distribution of the bonding layer according to a
• FIG. 6 Pore size distribution of the first intermediate layer according to FIG. 6
• FIG. 7 Particle size distribution of the first intermediate layer according to FIG.
• Embodiment of the invention. 1-3 are different, differing in construction embodiments of a membrane assembly for the permeative separation of a gas to be separated (eg H 2 ) from a gas mixture (eg steam reformed natural gas containing CH 4 , H 2 0, C0 2 , CO, H 2 , etc.), with only the gas mixture (eg steam reformed natural gas containing CH 4 , H 2 0, C0 2 , CO, H 2 , etc.), with only the
• Transition region is shown by the carrier substrate to the coupling part.
• a tubular, porous, gas-permeable, metallic support substrate 2 e.g., ITM
• ITM gas-permeable, metallic support substrate
• integral connection 4 which in the present case is formed by a welded joint, is connected to a tubular coupling part 6 formed in the solid material of a metal (for example steel).
• the weld of the cohesive connection 4 forms a circumferential recess which extends in the axial direction a over a length d.
• Support substrate 2 extends a selectively permeable to the gas to be separated membrane 8 (eg of Pd). Between the carrier substrate 2 and the membrane 8 extends a first ceramic, gas-permeable, porous intermediate layer 10 (eg of sintered 8YSZ) and a second ceramic, gas-permeable, porous
• Interlayer 12 (e.g., sintered 8YSZ).
• the first intermediate layer 10 is formed directly adjacent to the carrier substrate 2 and has a smaller average pore size than the carrier substrate 2. In this area is the second
• Intermediate layer 12 immediately adjacent to the first intermediate layer 10 and formed on its other side immediately adjacent to the membrane 8. It has a smaller average pore size than the first intermediate layer 10.
• a ceramic bonding layer 14 eg of sintered 8YSZ
• the integral connection 4 which extends at least over the integral connection 4 and an adjoining section of the coupling part 6, wherein the first intermediate layer 10 expires on the bonding layer 14.
• the carrier substrate 2 in the region of the carrier substrate 2 it can also be infiltrated into the pores by the bonding layer 14, starting from the cohesive connection 4 and also via an adjoining section of the carrier substrate 2.
• the bonding layer 14 is porous and permeable to gas and extends over the entire (circular) connection length of the bonded joint
• Connection 4 (as well as the adjacent areas of the carrier substrate 2 and the
• the second intermediate layer 12 extends beyond the first intermediate layer 10 in the direction of the coupling part 6, so that a sufficiently smooth underlay for the membrane 8 is provided.
• the second intermediate layer 12 likewise runs out on the bonding layer 14, with the bonding layer 14 also being reduced by virtue of its reduced middle position relative to the first intermediate layer 10
• Pore length provides a sufficiently smooth surface for the membrane 8.
• the membrane 8 extends in the direction of the coupling part 6 over the
• Tie layer 14 (and the two intermediate layers 10 and 12) and runs out directly on the coupling part 6, to which it produces a gas-tight connection for the gas to be separated (eg H 2 ).
• the first intermediate layer 10 thus extends directly on the carrier substrate 2, on which it adheres relatively well.
• the coupling part 6 is made of a porous
• gas-permeable base material in particular of the same material as the carrier substrate 2 (for example ITM), and has a gas-tight surface region 16 only on its outside surface.
• the gas-tight surface region 16 can be produced, for example, by applying a coating or a sealing compound or by superficial melting of the porous base material of the coupling part 6 "
• Tie layer 14 also extends and on the coupling part 6 "expires.
• a support substrate in the form of a porous tube made of ITM with an outer diameter of 6 mm, a length of 200 mm, a porosity of about 40% and an average pore size of ⁇ 50 ⁇ is formed at one axial end thereof with a solid material made of steel , tubular
• Coupling part with the same outer diameter welded by laser welding In order to ensure a homogenization of the weld transition, the resulting component is annealed under a hydrogen atmosphere at a temperature of 1200 ° C. Subsequently, the surface in the area of the welded joint is sandblasted to obtain a more uniform surface. Next, the bonding layer is applied in the area of the weld joint.
• Suspension for example with the addition of dispersant, solvent (eg BCA [2- (2-butoxyethoxy) ethyl] acetate, available from Merck KGaA Darmstadt) and binder.
• solvent eg BCA [2- (2-butoxyethoxy) ethyl] acetate, available from Merck KGaA Darmstadt
• binder eg BCA [2- (2-butoxyethoxy) ethyl] acetate, available from Merck KGaA Darmstadt
• the bonding layer is brushed all over on the weld joint and on the adjacent areas of the carrier substrate and the coupling part.
• the weld is located in the middle of the bonding layer extending around the entire circumference and the layer width extends in each case 1 cm from the respective end of the weld in the direction of the coupling part and in the direction of the carrier substrate.
• the obtained component is subsequently sintered under a hydrogen atmosphere at a temperature of 1200 ° C., whereby the organic constituents are burned out, a sintering of the ceramic layer takes place and the porous, sintered, ceramic bonding layer is obtained.
• a typical pore size distribution and particle size distribution of a bonding layer produced in this way is shown in FIGS. 4 and 5.
• the pore size distribution is in the range of 0.03 to 5.72 ⁇ (with an average pore size of 0.13 ⁇ ), as shown in FIG. 4 can be seen (with a few pores having a larger diameter are no longer shown), and the
• Particle size distribution is in the range of 0.03 - 18.87 ⁇ (with an average particle size of 0.24 ⁇ ), as shown in FIG. 5 can be seen (with a few particles are no longer shown with a larger diameter).
• a suspension of 8YSZ powder is again prepared for the first intermediate layer, wherein the information given above to the bonding layer apply mutatis mutandis, except that an overall coarser 8YSZ powder is used and a slightly higher viscosity of the suspension than in the bonding layer is set.
• a ceramic powder exclusively
• the first intermediate layer is formed by dip-coating, i. by immersing the tubular component in the suspension, applied and runs on the bonding layer. Subsequently, the resulting component is under
• FIGS. 6 and 7. A typical pore size distribution and particle size distribution of a first intermediate layer produced in this way is shown in FIGS. 6 and 7.
• the pore size distribution is in the range of 0.08 to 12.87 ⁇ (with an average pore size of 0.55 ⁇ ), as shown in FIG. 6 can be seen (with a few pores are no longer shown with larger diameter), and the Particle size distribution is in the range of 0.08 to 61.37 ⁇ (with an average particle size of 1.27 ⁇ ), as with reference to FIG.
• the second intermediate layer For the second intermediate layer to be applied subsequently, the same suspension as for the bonding layer is applied and applied by dip-coating. The second intermediate layer completely covers the first intermediate layer. Subsequently, the obtained component is sintered under a hydrogen atmosphere at a temperature of 1,200 ° C, whereby the organic components are burned out, takes place sintering of the ceramic layer and the porous, sintered, ceramic second intermediate layer is obtained. Subsequently, a Pd membrane is applied via a sputtering process. It completely covers the second intermediate layer as well as the underlying bonding layer and first intermediate layer.
• a further Pd layer is applied to the Pd sputter layer via a galvanic process in order to seal the latter and to achieve the required gas tightness.
• the cohesive connection is not necessarily realized as a welded joint.
• it can also be designed as a solder joint or adhesive bond.
• the cohesive connection is not necessarily realized as a welded joint.
• it can also be designed as a solder joint or adhesive bond.
• Coupling member and the support substrate also be formed integrally or monolithically and the cohesive connection forms the transition between the
• gas-permeable carrier substrate and the at least superficially gas-tight
• Coupling part For example, in the third embodiment (FIG. 3), a monolithic design of the carrier substrate and the coupling part would also be possible. Furthermore, the structure described is suitable not only for the H 2 separation, but also for the separation of other gases (eg C0 2 , 0 2 , etc.). Further alternative membrane can be used, such as microporous ceramic membranes (A1 2 0 3, Zr0 2, Si0 2, Ti0 2, zeolites, etc.) or dense, proton-conducting ceramics (SrCe0 3- 8, BaCe0 3- 8, etc. ). For the separation of liquids (eg alcohols from water-containing liquid mixtures, wastewater treatment, etc.), nanoporous membranes of carbon, zeolites, etc. can be used as membranes, among other things.
• microporous ceramic membranes A1 2 0 3, Zr0 2, Si0 2, Ti0 2, zeolites, etc.
• dense, proton-conducting ceramics SrCe0 3- 8, BaCe0 3-

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• 2015
  • 2015-12-21 AT ATGM377/2015U patent/AT15049U1/de not_active IP Right Cessation
• 2016
  • 2016-12-19 CN CN201680075114.XA patent/CN108430611A/zh active Pending
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