WO2004103537A1 - Kompositmembran - Google Patents
Kompositmembran Download PDFInfo
- Publication number
- WO2004103537A1 WO2004103537A1 PCT/EP2004/004995 EP2004004995W WO2004103537A1 WO 2004103537 A1 WO2004103537 A1 WO 2004103537A1 EP 2004004995 W EP2004004995 W EP 2004004995W WO 2004103537 A1 WO2004103537 A1 WO 2004103537A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite membrane
- membrane according
- layer
- sintered metal
- palladium
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 59
- 239000010410 layer Substances 0.000 claims description 52
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- 239000001294 propane Substances 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 11
- 238000007772 electroless plating Methods 0.000 claims description 10
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 9
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000011241 protective layer Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000005240 physical vapour deposition Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 238000007751 thermal spraying Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000010410 dusting Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010285 flame spraying Methods 0.000 description 2
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
-
- 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
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- 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
-
- 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
- B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02231—Palladium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- C01B3/505—Membranes containing palladium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Definitions
- the invention relates to a composite membrane with a sintered metal carrier and a membrane layer applied thereon or applied to at least one intermediate layer.
- Composite membranes are used, for example, in membrane reactors to separate reaction products.
- hydrogen-permeable membranes can be used selectively in order to be used in hydrogen-generating processes, e.g. B. in synthesis gas production by partial oxidation of methane to separate the hydrogen from other reaction products and as hydrogen gas for further use, for. B. as an energy source.
- membrane reactors will also play an increasingly important role in olefin plants for the production of ethene and propene.
- propene is mainly produced together with ethene in thermal or catalytic cracking plants (olefin plants) from naphtha or natural gas.
- the demand for propene has long been growing faster than the demand for ethene.
- propane dehydrogenation can be represented by the following reaction equation:
- Membrane reactors embody a new, innovative principle for carrying out heterogeneously catalyzed reactions, in which a combination of reaction and material separation or material supply in a multifunctional device is used to try to exploit synergies that do not occur with the conventional arrangement of separate units. In the application considered here, this is a shift in equilibrium by simultaneously removing one of the reaction products from the reaction mixture. The aim is to increase the efficiency of the process, and thus to conserve resources due to the reduced amount of by-products and the lower energy consumption.
- porous sintered metal tubes with thin, gas-tight metal layers (palladium, palladium alloys or alternative metals) in order to achieve the desired high permeation rates and high selectivity for To achieve hydrogen and at the same time to guarantee the strength properties necessary for use in an industrial process (e.g. DE 199 43 409 A1).
- the present invention is therefore based on the object of designing a composite membrane of the type mentioned at the outset in such a way that it is long-term stable even under the conditions of propane dehydrogenation.
- the sintered metal carrier is provided with a material that prevents corrosion.
- the invention is based on the knowledge that, under the usual conditions of propane dehydrogenation at 600 ° C., alternating with dehydration (gases present, propane, propene, hydrogen) and regeneration to eliminate
- Coke deposits oxygen, inert gas, steam
- metal dusting quickly the form of corrosion of the so-called "metal dusting" occurs.
- the sintered metal turns brown on the surface and a loosely adhering, metal-containing dust is created as a corrosion product.
- the invention is further based on the consideration that the reason for this behavior lies in the ratio of the material surface to the volume of the carrier material, which is much larger with porous sintered materials than with pressure-bearing components made of solid, dense metals.
- the reason for this behavior lies in the ratio of the material surface to the volume of the carrier material, which is much larger with porous sintered materials than with pressure-bearing components made of solid, dense metals.
- the sintered metal carrier itself consists of the material that prevents corrosion.
- metallic powders can be used to make metal dusting resistant (i.e., corrosion-preventing) sintered metal supports.
- alloy components that lead to stable oxide layers such as. B. aluminum and / or silicon and / or chrome provide the necessary resistance.
- Another way to achieve this goal is to use metals that are insensitive to "metal dusting", such as. B. copper. It is important to ensure that there is sufficient temperature resistance. With the use of such metals it will also be expected that during e.g. B. the propane dehydrogenation suppresses or slows down the formation of coke in the pores of the sintered metal support.
- the sintered metal carrier is provided with a protective layer made of a material that prevents corrosion. It is therefore a "metal dusting" resistant protective layer applied to the non-"metal dusting" resistant carrier material.
- a protective layer made of a material that prevents corrosion.
- metal dusting resistant protective layer applied to the non-"metal dusting" resistant carrier material.
- Aluminum and / or silicon are suitable for components made of sintered metals. Alitation is an example: Conventional sintered, high-alloy steels are exposed to a gas phase of volatile aluminum compounds at around 1000 ° C, which diffuse into the material and form aluminum-rich phases there or aluminum oxides on the surface. Deposits from the gas or liquid phase are generally suitable for the application of protective layers. Techniques such as the so-called CVD (Chemical Vapor Deposition), PVD (Physical Vapor Deposition) and ELP (Electroless Plating) are particularly noteworthy. Sintered metal supports treated in this way offer the desired long-term stability. By creating "metal dusting" resistant protective layers, too be expected that the coke formation in the pores of the sintered metal carrier - as occurs in the case of propane dehydrogenation - is suppressed or slowed down.
- CVD Chemical Vapor Deposition
- PVD Physical Vapor Deposition
- ELP Electroless Plating
- the sintered metal carrier preferably has an asymmetrical porosity.
- Asymmetrical sintered metal pipes guarantee a high flow and at the same time good coatability of the surface.
- a ceramic intermediate layer with high porosity is applied to the sintered metal carrier under the thin, hydrogen-permeable membrane layer made of palladium, palladium alloys or alternative metals.
- This ceramic intermediate layer should be sufficiently thick to prevent interdiffusion of the metals on the one hand and to compensate for surface defects of the sintered metal carrier on the other hand.
- the deposited layer is intended to create a new surface and not only depict the sintered metal surface.
- the ceramic intermediate layer expediently consists of ZrO 2 or another oxide layer. While the ceramic intermediate layer made of ZrO 2 can be applied by means of thermal spraying, other oxide layers could also be applied by means of powder coating (wet powder spraying). As an alternative, asymmetrical porous sintered metal tubes made of ordinary high-alloy steels can also be treated by alitizing.
- the actual membrane layer preferably has a high hydrogen selectivity.
- a palladium film is expediently applied as the membrane layer.
- the palladium film can be applied, for example, by means of electroless plating (ELP).
- ELP electroless plating
- a thickness of the palladium film of 0.5-25 ⁇ m is advantageous.
- the membrane layer can also consist of a palladium / silver alloy or a palladium / copper alloy.
- the membrane layer can also be applied by thermal spraying.
- the invention is particularly suitable for multifunctional reactor concepts for heterogeneously catalyzed reactions.
- the invention can be used to obtain hydrogen from gas mixtures.
- On-board generation for fuel cell vehicles is also a preferred application.
- the invention can be used for a more efficient manufacturing process for propene. reduced raw material and energy consumption. This means that resources can be saved and production-integrated environmental protection can be practiced.
- the figure shows a composite membrane made of an asymmetrical porous sintered metal carrier 1, a ceramic intermediate layer 2 and a palladium film 3 applied thereon.
- a firmly adhering ceramic layer of e.g. B. ZrO 2 or another oxide layer by means of powder coating or thermal spraying e.g. B. ZrO 2 or another oxide layer by means of powder coating or thermal spraying.
- a thin ceramic layer (thickness 0.1-1 ⁇ m) made of ZrO 2 or another oxide layer by means of PVD (Physical Vapor Deposition), not shown in the figure, can additionally be applied to the ceramic intermediate layer in order to ensure a micro-roughness on the one with the actual one Membrane layer (palladium film) surface to be coated for better anchoring of the palladium layer without changing the porosity.
- the actual membrane layer is applied as a thin palladium film with a thickness of approx. 0.5 - 25 ⁇ m by means of electroless plating (ELP).
- ELP electroless plating
- This coating method enables a closed palladium layer.
- the activation is not carried out conventionally by successive baths in SnCI 2 / PdCI 2 solutions, but by means of a CVD (Chemical Vapor Diposition) method for finely divided palladium.
- CVD Chemical Vapor Diposition
- This method creates firmly anchored hemispherical palladium particles in the size range from 2 to 10 nm, which sit within the porous layer on the pore walls. It can be controlled at which point on the outer surface or how deep into the pore structure the palladium is deposited.
- the location of the palladium seed crystals in the porous layer (instead of on the
- the palladium layer can also be applied by atmospheric plasma spraying (APS) or high-speed oxygen flame spraying (HVOF).
- APS atmospheric plasma spraying
- HVOF high-speed oxygen flame spraying
- Very fine metal powder palladium, suitable palladium alloys
- the method of cold gas spraying can also be used.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Ceramic Engineering (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04731917A EP1626798A1 (de) | 2003-05-20 | 2004-05-10 | Kompositmembran |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10322715A DE10322715A1 (de) | 2003-05-20 | 2003-05-20 | Kompositmembran |
DE10322715.6 | 2003-05-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004103537A1 true WO2004103537A1 (de) | 2004-12-02 |
Family
ID=33441022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/004995 WO2004103537A1 (de) | 2003-05-20 | 2004-05-10 | Kompositmembran |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1626798A1 (de) |
DE (1) | DE10322715A1 (de) |
WO (1) | WO2004103537A1 (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1849510A1 (de) * | 2006-04-26 | 2007-10-31 | Acktar Ltd. | Anorganische Verbundstoffmembran zur Trennung in Flüssigkeitssystemen |
EP3228380A1 (de) * | 2016-04-06 | 2017-10-11 | Horiba Stec, Co., Ltd. | Wasserstoffreinigungsvorrichtung und wasserstoffreinigungssystem mit der wasserstoffreinigungsvorrichtung |
DE102020207245A1 (de) | 2020-06-10 | 2021-12-16 | Forschungszentrum Jülich GmbH | Verfahren zur Herstellung eines Bauteils mit definierter Porosität und Bauteil |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006051525B4 (de) * | 2006-10-27 | 2008-11-06 | Eads Deutschland Gmbh | Hochpermeable Kompositmembran und Verfahren zum Herstellen einer hochpermeablen Kompositmembran |
DE102009016694A1 (de) | 2009-04-07 | 2010-10-14 | Linde Aktiengesellschaft | Membranrohr und Reaktor mit Membranrohr |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2958391A (en) * | 1958-02-24 | 1960-11-01 | Universal Oil Prod Co | Purification of hydrogen utilizing hydrogen-permeable membranes |
EP1082993A2 (de) * | 1999-09-10 | 2001-03-14 | Linde Gas Aktiengesellschaft | Verbund aus einer Kompositmembran |
-
2003
- 2003-05-20 DE DE10322715A patent/DE10322715A1/de not_active Withdrawn
-
2004
- 2004-05-10 EP EP04731917A patent/EP1626798A1/de not_active Ceased
- 2004-05-10 WO PCT/EP2004/004995 patent/WO2004103537A1/de active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2958391A (en) * | 1958-02-24 | 1960-11-01 | Universal Oil Prod Co | Purification of hydrogen utilizing hydrogen-permeable membranes |
EP1082993A2 (de) * | 1999-09-10 | 2001-03-14 | Linde Gas Aktiengesellschaft | Verbund aus einer Kompositmembran |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1849510A1 (de) * | 2006-04-26 | 2007-10-31 | Acktar Ltd. | Anorganische Verbundstoffmembran zur Trennung in Flüssigkeitssystemen |
EP3228380A1 (de) * | 2016-04-06 | 2017-10-11 | Horiba Stec, Co., Ltd. | Wasserstoffreinigungsvorrichtung und wasserstoffreinigungssystem mit der wasserstoffreinigungsvorrichtung |
US10105641B2 (en) | 2016-04-06 | 2018-10-23 | Horiba Stec, Co., Ltd. | Hydrogen purification device and hydrogen purification system using hydrogen purification device |
DE102020207245A1 (de) | 2020-06-10 | 2021-12-16 | Forschungszentrum Jülich GmbH | Verfahren zur Herstellung eines Bauteils mit definierter Porosität und Bauteil |
Also Published As
Publication number | Publication date |
---|---|
DE10322715A1 (de) | 2004-12-09 |
EP1626798A1 (de) | 2006-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2422851C2 (de) | Katalysator und seine Verwendung bei der Behandlung von Auspuffgasen | |
DE2253745C3 (de) | Schneideinsätze | |
EP1495151B1 (de) | Plasmaspritzverfahren | |
DE69916149T2 (de) | Verbesserte Aluminid-Diffusionsverbundschicht für thermische Sperrschichtsysteme und Verfahren dazu | |
DE2825009C2 (de) | Hartmetallkörper und Verfahren zu dessen Herstellung | |
DE2435989C2 (de) | Verfahren zur Herstellung eines verschleißfesten, beschichteten Hartmetallkörpers für Zerspanungszwecke | |
DD155140A5 (de) | Verfahren zur hochtemperaturbehandlung von kohlenstoffhaltigen materialien | |
EP2439306A1 (de) | Verfahren zum Herstellen eines Wärmedämmschichtaufbaus | |
DE3344343A1 (de) | Verfahren zur herstellung von schalenkatalysatoren | |
AT5008U1 (de) | Hartmetallverschleissteil mit mischoxidschicht | |
DE2844294A1 (de) | Metallischer katalysator und verfahren zur herstellung von metallischen katalysatoren | |
WO2021058719A1 (de) | Cobalthaltige metallschaumkörper und verfahren zu ihrer herstellung | |
WO2004103537A1 (de) | Kompositmembran | |
EP1370712B1 (de) | Hartstoffbeschichtetes bauteil mit zwischenschicht zur verbesserung der haftfestigkeit der beschichtung | |
DE102005011047A1 (de) | Katalysatorformkörper, insbesondere zur Verwendung als Katalysatoren bei der Hydrierung | |
DE1942292B2 (de) | Verfahren zur abscheidung eines ueberzuges | |
DE19815677C2 (de) | Verbundkörper und Verfahren zu dessen Herstellung | |
DE4438625C2 (de) | Umwandlungsdeckschichten auf Keramiken und deren Verwendung | |
EP0018432B1 (de) | Mit einer verschleiss- und korrosionsfesten Wolframkarbid-Schutzschicht versehener Metallteil | |
DE2141100A1 (de) | Verwendung von Zerspanungswerkzeugen zur Bearbeitung von Belag bildenden Stählen | |
EP1900842A1 (de) | Pack auf Zwischenschicht | |
EP3823780B1 (de) | Verfahren zur herstellung eines offenporigen metallkörpers mit einer oxidschicht und ein mit dem verfahren hergestellter metallkörper | |
EP1900854B1 (de) | Verfahren zum Härten von galvanischen Chromschichten | |
DE102015222972A1 (de) | Katalysator und Verfahren zur Herstellung | |
DE3590538T1 (de) | Verfahren zum Aufbringen von Überzügen auf Metalle und dabei erhaltenes Erzeugnis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004731917 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2004731917 Country of ref document: EP |